Additives in Polymers - Analysis and Applications (2016)

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Additives in Polymers

Additives

Zaikov
Rogovina
Berlin
Additives
Additives Polymers
in in Polymers
Additives

ZaikovBerlin
Rogovina
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Analysis and Applications
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EDITORS

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ISBN: 978-1-77188-128-9 Gennady E. Zaikov, DSc
science journals. ISBN: 978-1-77188-128-9
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ADDITIVES IN POLYMERS
Analysis and Applications
ADDITIVES IN POLYMERS
Analysis and Applications

Edited by
Alexandr A. Berlin, DSc, Svetlana Z. Rogovina, DSc, and
Gennady E. Zaikov, DSc
CRC Press Apple Academic Press, Inc
Taylor & Francis Group 3333 Mistwell Crescent
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© 2016 by Apple Academic Press, Inc.
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ABOUT THE EDITORS

Alexandr A. Berlin, DSc


Professor Alexandr A. Berlin, DSc, is Director of the N. N. Semenov In-
stitute of Chemical Physics at the Russian Academy of Sciences, Moscow,
Russia. He is a member of the Russian Academy of Sciences and many
national and international associations. Dr. Berlin is world-renowned sci-
entist in the field of chemical kinetics (combustion and flame), chemical
physics (thermodynamics), chemistry and physics of oligomers, polymers,
and composites and nanocomposites. He is the contributor to over 100
books and volumes and author of over 1000 original papers and reviews.

Svetlana Z. Rogovina, DSc


Professor Svetlana Z. Rogovina is a well-known specialist in the field of
solid-phase modification of polysaccharides and production of blends of
polysaccharides with synthetic polymers under conditions of the shear de-
formation. She is an author of about 100 papers and reviews dedicated
to these problems. She has shown that in solid phase under conditions
of shear deformations, some derivatives of cellulose (alkali cellulose and
some others), as well as chitosan from natural polysaccharide chitin and
its derivatives, may be produced. These results are very important because
they allow scientists to realize that the polysaccharides modification in the
absence of solvents by ecologically friendly method.
In recent years, Dr. Rogovina’s interest lie with the creation of biode-
gradable compositions on the basis of polysaccharides and synthetic poly-
mers. The blending of polymers under conditions of shear deformation
allows to produce the materials with uniform distribution of components
and as sequence with improving physico-mechanical properties and ca-
pacity to biodegradation.

Gennady E. Zaikov, DSc


Gennady E. Zaikov, DSc, is Head of the Polymer Division at the N. M.
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,
Moscow, Russia, and Professor at Moscow State Academy of Fine Chemi-
vi About the Editors

cal Technology, Russia, as well as Professor at Kazan National Research


Technological University, Kazan, Russia. He is also a prolific author, re-
searcher, and lecturer. He has received several awards for his work, in-
cluding the Russian Federation Scholarship for Outstanding Scientists. He
has been a member of many professional organizations and on the edito-
rial boards of many international science journals. Dr. Zaikov has recently
been honored with tributes in several journals and books on the occasion
of his 80th birthday for his long and distinguished career and for his men-
torship to many scientists over the years.
CONTENTS

List of Contributors..................................................................................... ix
List of Abbreviations................................................................................. xiii
Foreword.................................................................................................. xvii
Preface.................................................................................................... xxiii
1. 5-Ethylidene-2-Norborene-Olefin Copolymers: Synthesis, Structure,
Morphology, Properties, and Functionalization of Copolymers............. 1
I. N. Meshkova, A.N. Shchegolikhin, L. N. Raspopov, E. V. Kiseleva, S. P. Kuznetsov,
V. G. Grinev, and L. A. Novokshonova

2. Insight into New Application Aspects for Photopolymerizable Acrylic


Compositions.............................................................................................. 21
N. L. Zaichenko, B. I. Zapadinskii, A. V. Kotova, I. A. Matveeva, V. T. Shashkova,
L. A. Pevtsova, A. O. Stankevich, R. G. Kryshtal, A. V. Medved, and A. V. Roshchin

3. On the Specific Reactivity of Сarbooligoarylenes: Representatives of


Oligomers with Conjugate System........................................................... 63
V. A. Grigorovskaya

4. Porphyrin–Polymer Complexes in Model Photosensitized Processes


and in Photodynamic Therapy................................................................. 77
A. B. Solovieva and N. A. Aksenova

5. Structure and Properties of Rubber Powder and Its Materials.......... 123


E. V. Prut, O. P. Kuznetsova, and D. V. Solomatin

6. Biodegradable Compositions of Polylactide with Ethyl Cellulose and


Chitosan Plasticized by Low-Molecular Poly(Ethylene Glycol).......... 171
S. Z. Rogovina, K. V. Aleksanyan, A. V. Grachev, A. Ya. Gorenberg, A. A. Berlin, and
E. V. Prut

7. Inorganic Polyoxide Thermoplastics: Their Hybrids and Blends....... 193


A. A. Shaulov and A. A. Berlin

8. Hyperbranched 1,4-Cis+1,2-Polybutadiene Synthesis Using Novel


Catalytic Dithiosystems........................................................................... 237
Shahab Hasan oglu Akhyari, Fuzuli Akber oglu Nasirov, Erol Erbay, and
Nazil Fazil oglu Janibayov
viii Contents

9. A Study on the Formation of the Phase Structure of Silanol-Modified


Ethylene Copolymers with Vinyl Acetate and Vinyl Acetate and Maleic
Anhydride in a Wide Range of Temperatures and Compositions....... 247
N. E. Temnikova, O. V. Stoyanov, А. Е. Chalykh, V. K. Gerasimov, S. N. Rusanova, and
S. Yu Sofina

10. Quantum Chemical Calculation of Molecule 3,4,5,6,7-6,7-Pentadime-


thylindene by Method Ab Initio.............................................................. 259
V. A. Babkin, D. S. Andreev, Yu. A. Prochukhan, K. Yu. Prochukhan, and G. E. Zaikov

11. Cobalt Alkylxhanthogenate + Trialkylaluminum Catalytic Dithiosys-


tems for Synthesis of Syndiotactic 1,2-Polybutadiene.......................... 265
Nemat Akif oglu Guliyev, Fuzuli Akber oglu Nasirov, and Nazil Fazil oglu Janibayov

12. A Study on the Effect of the Phase Structure of the Modified EVA
(EVAMA) on Their Properties................................................................ 275
N. E. Temnikova, А. Е. Chalykh, V. K. Gerasimov, S. N. Rusanova, O. V. Stoyanov, and
S. Yu. Sofina

13. Siloxane Matrix wth Methylpropionate Side Groups and Polymer


Electrolyte Membranes on Their Base................................................... 285
Natia Jalagonia, Izabela Esartia, Tamar Tatrishvili, Eliza Markarashvili,
Donari Otiashvili, Jimsher Aneli, and Omar Mukbaniani

14. Composites on the Basis of Glycidoxy Group Containing


Phenylsilsesquioxanes.............................................................................. 305
Marina Iskakova, Eliza Markarashvili, Jimsher Aneli, and Omar Mukbaniani

15. The Comparative Study of Thermostable Protein Macromolecular


Complexes (Cell Proteomics) from Different Organisms..................... 323
D. Dzidzigiri, M. Rukhadze, I. Modebadze, N. Giorgobiani, L. Rusishvili, G. Mosidze,
E. Tavdishvili, and E. Bakuradze

Index.......................................................................................................... 331
LIST OF CONTRIBUTORS

S. H. O. Akhyari
Institute of Petrochemical Processes of National Academy of Sciences of Azerbaijan,
Baku, Azerbaijan

N. A. Aksenova
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia.
E-mail: [email protected]

K. V. Aleksanyan
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

D. S. Andreev
Sebrykov Department, Volgograd State Architect-build University, Volgograd, Russia

V. A. Babkin
Sebrykov Department, Volgograd State Architect-build University, Volgograd, Russia

E. Bakuradze
Department of Biology, Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State
University, Tbilisi, Georgia

A. A. Berlin
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

А. Е. Chalykh
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow 119991, Russia
D. Dzidzigiri
Department of Biology, Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State
University, Tbilisi, Georgia. E-mail: [email protected]

E. Erbay
Petkim Petrokimya Holding, Izmir, Turkey

V.K. Gerasimov
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow 119991, Russia

N. Giorgobiani
Department of Biology, Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State
University, Tbilisi, Georgia

A. Ya. Gorenberg
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia
x List of Contributors

A. V. Grachev
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

V. A. Grigorovskaya
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia.
E-mail: valgrig3@ mail ru
V. G. Grinev
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

N. A. O. Guliyev
Institute of Petrochemical Processes of National Academy of Sciences of Azerbaijan, Baku,
Azerbaijan

M. Iskakova
Department of Chemical Technology, Аk. Tsereteli Kutaisi State University, I. Chavchavadze Ave. 1,
0179 Tbilisi, Georgia. E-mail: [email protected]

N. F. O. Janibayov
Institute of Petrochemical Processes of National Academy of Sciences of Azerbaijan, Baku,
Azerbaijan. E-mail: [email protected]

A. Jimsher
Institute of Macromolecular Chemistry and Polymeric Materials, I. Javakhishvili Tbilisi State
University, I. Chavchavadze Ave. 13, 0179 Tbilisi, Georgia

E. V. Kiseleva
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

A. V. Kotova
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119991,
Russia

R. G. Kryshtal
Institute of Radio Engineering and Electronics, Russian Academy of Sciences (Fryazino Branch),
pl. Vvedenskogo 1, Fryazino, Moscow 141120, Russia
S. P. Kuznetsov
Lebedev Physical Institute, Russian Academy of Sciences, Moscow, Russia

O. P. Kuznetsova
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

E. Markarashvili
Department of Chemistry, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave. 1,
0179 Tbilisi, Georgia
I. A. Matveeva
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119991,
Russia

A. V. Medved
Institute of Radio Engineering and Electronics, Russian Academy of Sciences (Fryazino Branch),
pl. Vvedenskogo 1, Fryazino, Moscow 141120, Russia

I. N. Meshkova
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia
List of Contributors xi

I. Modebadze
Department of Biology, Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State
University, Tbilisi, Georgia

G. Mosidze
Department of Biology, Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State
University, Tbilisi, Georgia
O. Mukbaniani
Department of Chemistry, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave. 1, 0179
Tbilisi, Georgia; Institute of Macromolecular Chemistry and Polymeric Materials, I. Javakhishvili
Tbilisi State University, I. Chavchavadze Ave. 13, 0179 Tbilisi, Georgia

F. A. O. Nasirov
Institute of Petrochemical Processes of National Academy of Sciences of Azerbaijan, Baku, Azerbai-
jan; Petkim Petrokimya Holding, Izmir, Turkey. E-mail: [email protected]

L. A. Novokshonova
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

L. A. Pevtsova
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119991,
Russia

K. Yu. Prochukhan
Department of Chemistry, Bashkir State University, Ufa, Russia

Yu. A. Prochukhan
Department of Chemistry, Bashkir State University, Ufa, Russia

E. V. Prut
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia.
E-mail: [email protected]

L. N. Raspopov
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
S. Z. Rogovina
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia.
E-mail: [email protected]

A. V. Roshchin
Institute of Radio Engineering and Electronics, Russian Academy of Sciences (Fryazino Branch),
pl. Vvedenskogo 1, Fryazino, Moscow 141120, Russia

M. Rukhadze
Department of Biology, Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State
University, Tbilisi, Georgia

S. N. Rusanova
Kazan National Research Technological University, K. Marx Street, 68, Kazan, Tatarstan 420015,
Russia

L. Rusishvili
Department of Biology, Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State
University, Tbilisi, Georgia
xii List of Contributors

V. T. Shashkova
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119991,
Russia

A. A. Shaulov
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia.
E-mail: [email protected]
A. N. Shchegolikhin
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia

S. Yu. Sofina
Kazan National Research Technological University, K. Marx Street, 68, Kazan, Tatarstan 420015,
Russia

D. V. Solomatin
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

A. B. Solovieva
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia.
E-mail: [email protected]

A. O. Stankevich
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119991,
Russia

O. V. Stoyanov
Kazan National Research Technological University, K. Marx street, 68, Kazan, Tatarstan 420015,
Russia. E-mail: [email protected]

T. Tatrishvili
Department of Chemistry, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave. 3, 0179
Tbilisi, Georgia; Institute of Macromolecular Chemistry and Polymeric Materials, I. Javakhishvili
Tbilisi State University, I. Chavchavadze Ave. 13, 0179 Tbilisi, Georgia

E. Tavdishvili
Department of Biology, Faculty of Exact and Natural Sciences, Iv. Javakhishvili Tbilisi State Univer-
sity, Tbilisi, Georgia

N. E. Temnikova
Kazan National Research Technological University, K. Marx Street, 68, Kazan, Tatarstan 420015,
Russia

N. L. Zaichenko
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119991,
Russia. E-mail: [email protected]

G. E. Zaikov
N.M Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow
119991, Russia. E-mail: [email protected]

B. I. Zapadinskii
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119991,
Russia
LIST OF ABBREVIATIONS

AlkXh-Co cobalt alkylxhantogenate


AOC aluminum organic compounds
APs amphiphilic polymers
BA boric acid
CCU Center of Collective Use
CL caprolactam
COA carbooligoarylenes
COCs cycloolefin copolymers
CP cross polarization
4,4′-DADPS 4,4′-diaminodiphenylsulfone
4,4′-DADPM 4,4′-diaminodiphenylmethane
4,4′-DATPO 4,4′-diaminotriphenyloxide
DEAC diethylaluminumchloride
DEDTC-Co cobalt-diethyldithiocarbamate
DSC differential scanning calorimetry
EADC ethylaluminumdichloride
EDG elastic-deformation grinding
EG extrusion grinding
ENB ethylidene norbornene
EO ethylene oxide
EPDM ethylene-propylene-diene rubbers
ESP elastic-strain powdering
ETS ethyl silicate
EVA ethylene with vinyl acetate
EVAMA modified ethylene copolymers with vinyl acetate
GS (3-glycidoxypropyl)trimethoxysilane
GPC gel permeation chromatography
GRT ground rubber tire
HDPE high-density polyethylene
HIC hydrophobic interaction chromatography
HPHTS high-pressure and high-temperature sintering
HTSD high-temperature shear deformation
xiv List of Abbreviations

IPO inorganic polyoxides


IPP isotactic polypropylene
iPrXh-Co cobalt iso-propylxhantogenate
ISAC&S intensive stress action compression and shear
KW Kruskal–Wallis
LDPE low-density polyethylene
MAO methylaluminoxane
MFI melt flow index
MFR melt flow rate
mp melting point
mPCTPO 4-protio-3-carbamoyl-2,2,5,5-tetraperdeuteromethyl-
3-pyrroline-1-yloxy
MPDA methylphenyldiamine
МТHFА metatetrahydrophtalanhydride
MTT methyltetrazolium blue
MW Mann–Whitney
MV Mooney viscosity
OBOs oligomer boron oxides
o-DCB o-dichlorobenzene
PA polyanthracene
PBS phosphate-buffered saline
PD photoditazine
PDT photodynamic therapy
PEG polyethylene glycol
PEI polyetherimide
PEO polyethyleneoxide
PEPA polyethylenepolyimine
PLA polylactide
PMHS polymethylhydrosiloxanes
PMMA polymethyl methacrylate
PN polynaphtalene
PO propylene oxide
PPh polyphenilenes
PPS porphyrin photosensitizers
PRB plasmon resonance band
PS photosensitization
PVA polyvinyl alcohol
PVP polyvinylpyrrolidone
List of Abbreviations xv

RP rubber powder
SAW surface acoustic wave technology
SDV styrene-divinylbenzene
SEC size-exclusion chromatographic
SPR surface plasmon resonance
SSSE solid-state shear extrusion
SV solution viscosity
τind induction time
TAA trialkylaluminum
TEA triethylaluminum
TFHQ tetrafluorohydroquinone
Tg glass transition temperature
TGA thermogravimetric analysis
THF tetrahydrofuran
TMA thermomechanical analysis
TPEs thermoplastic elastomers
TPP meso-tetraphenylporphyrine
TPVs thermoplastic vulcanizates
TSPC thermostable protein complex
UCPS upper critical point of solubility
VCN very cold neutron
МТHFА metatetrahydrophtalanhydride
FOREWORD

The volume presents the results of investigation made in the past years
at the Department of Polymers and Composite Materials of Institute of
Chemical Physics of the Russian Academy of Sciences.
The Institute of Chemical Physics of the Russian Academy of Sciences
is one of the main chemical institutes of the Russian Academy of Sciences.
It was established in 1931. The first head of the Institute was Nobel Prize
winner academician N. N. Semenov.
The Institute was established with the aim of the “introduction of
physical theories and methods into chemistry, chemical industry, and other
branches of economics.” More than 80 years of the activity of the Institute
has shown that this problem was solved. However, the main achievement
of the Institute’s team and its Head N. N. Semenov was the establishment
of a new branch of natural sciences, chemical physics. N. N. Semenov
defined the chemical physics as a “science describing the fundamentals of
chemical transformations and the associated problems of substance struc-
ture.” This idea indicates that chemical physics has a comprehensive char-
acter, and it is not surprising that its ideas and concepts are being used in
all areas of natural sciences including biology and medicine.
Initially, the basic line of investigation in the Institute was the theory
of chain reactions, processes of combustion and explosion, later chain re-
actions of nuclear fission, and polymerization reactions. At present, in the
Institute, studies of kinetics and mechanism of heterogeneous chemical
reactions and catalysis, liquid-phase oxidation reactions, and kinetics of
chemical reactions in biological systems are being developed.
The current Semenov Institute of Chemical Physics consists of six
large departments, each with its own “face”, namely,
i) Department of Kinetics and Catalysis
ii) Department of Polymers and Composite Materials
iii) Department of Combustion and Explosion
iv) Department of Substance Structure
v) Department of Dynamics of Chemical and Biological Processes
vi) Department of Chemical and Biological Safety
xviii Foreword

The Department of Polymers and Composite Materials of Semenov


Institute, traditionally one of the world leaders in the area of synthesis and
investigation of the polymers and polymer composite materials, had been
organized in 1958. The academician N. S. Enikolopov—a famous scien-
tist in the field of polymers and polymer composites—was the head of the
department from 1963 to 1990. For the past 25 years, academician A. A.
Berlin has beens the head of this department. The team of the department
has experience in the successful development of high-strength composite
materials based on filled polymer composite and nanocomposite materials
with the given functional properties, multicomponent polymer and elas-
tomeric compositions, noncombustible materials based on inorganic and
hybrid polymers and composites, and biodegradable composite materials
based on synthetic and natural polymers. Based on the works currently
performed in the Department of Polymers and Composite Materials in this
field, one can distinguish the following priority areas:
1. Development of high-strength composite materials on the basis
of thermoset and thermoplastic matrices reinforced by glass, carbon,
organic, boron, and other high-modulus fibers.
The study of the influence of numerous factors on the physicomechani-
cal properties of composites allows one to synthesize the composite mate-
rials with increased strength.
The main directions of investigations are related to the study of com-
posites fracture mechanisms: fiber adhesion to binders; development and
modification of polymer binders; use for composite reinforcing of new
types of glass fibers, produced from rocks (basalt, tuff, etc.); and creation
of scientific foundations of technology of prepreg and composite produc-
tion.
2. Development of polymer-filled composite and nanocomposite
materials of new generation based on large-tonnage industrial ther-
moplasts – polyolefins.
Synthesis of composites promotes the improvement of the tradition-
al methods of introduction of fillers into polymer matrix via mixing of
components in polymer melt and progress of the polymerization filling
technology proposed first in the Department of Polymers and Compos-
ite Materials and successfully tested in experimental-industrial scale. The
application of the polymerization filling technology allows one to maxi-
mally realize the properties of the polymer nanocomposites at low and
ultrahigh-filling degrees, especially at the synthesis of composites based
Foreword  

on ultra-high-molecular-weight polyethylene (UHMWPE). These works


are developed in the Department of Polymers and Composite Materials in
the following promising area:
Development of constructional and functional nanocomposite materi-
als of new generation based on polyolefins (polyethylene, polypropylene,
ethylene, and propylene copolymers with vinyl comonomers) and nano-
dispersed fillers (carbon, layered silicates, etc.) with the set of improved
operational characteristics (increased rigidity, thermal stability, barrier
properties, decreased combustibility, controlled electric and radar absor-
bent properties, and improved tribological characteristics) and technology
of their production.
Synthesis of new ultra-high-filled polymer composite materials (up
to 80–85 vol.%) combining heat conducting and dielectric properties and
plasticizing capacity based on binary (micro/nano) heat-conducting fillers
and UHMWPE and polymerization technology of their production.
3. Development of nanofilled compositions cured by UV radiation.
Nanofilled compositions cured by UV based on acrylic, methacrylic,
and urethane monomers, oligomers, photoinitiators, and filler nanoparti-
cles are developed. These compositions are used to produce nanoparticles
of dyes, luminophores, and other photosensitive compounds for optical
and electronic industries and filled by TiO2, SiO2, or Al2O3 – for protective
and abrasion-resistant coatings featuring improved quality.
4. Blending and chemical modification of polymers under condi-
tions of shear deformation using extruders and other mixers. Multi-
component polymer and elastomer compositions.
For production of polymer mixtures, a fundamentally new method of
polymer blending based on joint action of high pressure and shear defor-
mations realized in extruders and some kinds of mixers was developed.
It was shown that under these conditions, the significant structural trans-
formation of the compounds and changes in their reactivity take place, so
some chemical reactions can be carried out in solid phase in the absence
of solvents.
Nowadays, the development of new approaches in the regulation of
structure of the polymer composite materials gains special attention, as a
result, gaining set of new properties required for practical application in
modern articles and constructions. So, among multicomponent polymer
systems, the composite materials related to class of thermoplastic elasto-
mers are widespread. The production of such materials using method of
xx Foreword

blending under conditions of shear deformation gives the possibility to


combine two important characteristics peculiar to each of the components:
preservation of the mechanical properties of the initial polymers at opera-
tion with the processability into articles by a technology applied for linear
thermoplastic polymers. A great advantage of the thermoplastic elastomer-
ic materials is also their ability for multiple processing without substantial
decrease in properties that allows one to almost completely use the wastes
of production and used articles and gives additional economic effect.
5. Noncombustible materials based on inorganic and hybrid poly-
mers and composites.
New priority scientific area developed in the Department of Polymers
and Composite Materials is a production of composite materials based on
one of the most widespread classes of natural polymers – inorganic ther-
moplastic polyoxides with increased elastic and strength characteristics.
The binders of organic–inorganic composites is proposed to use the poly-
oxides based on boron, fluorinated borophosphates of different metals,
blends of polyoxides with different thermoplastic polymers, and hybrid
polymers of boron polyoxides with monomeric and oligomeric nitrogen-
containing compounds. In the presence of inorganic thermoplastic com-
ponents, it is possible to perform molding and chemical modification and
synthesize hybrid organic–inorganic polymers and blends with polyole-
fins noncombustible nonflammable materials. Besides, these materials are
characterized by the absence or substantial decrease of the toxic product
amount released at thermal action and inflammation. The production of the
materials based on hybrid polymer composites assumes the application of
ecologically clean technologies in the absence of solvents.
6. Synthesis of biodegradable composite materials based on blends
of synthetic and natural polymers.
The synthesis of biodegradable composite materials based on the
blends of synthetic and natural polymers is one of the priority areas of
modern polymer chemistry. Among such compositions, the blends based
on industrial large-tonnage thermoplastic polymers and renewable poly-
saccharides characterized by easy biodegradability are of special interest.
With the aim to improve the production methods of biodegradable
polymer compositions and operational properties of the materials based
on them, a method of mixing of the above-mentioned classes of polymers
under action of high-temperature shear deformations in the absence of sol-
vents was used. The distinctive feature of the method proposed is a pos-
 Foreword xxi

sibility to obtain under particular conditions the powders with increased


homogeneity and uniform distribution of the components even in the case
when one of them is infusible polymer (polysaccharides). The application
of the shear deformation method for the production of the powder polymer
blends based on infusible polysaccharides and synthetic polymers is origi-
nal approach to simultaneous utilization and processing of the polymer
wastes of both synthetic and natural origin. Thus, the developing problem
is not only scientific, but promotes the solution of the ecological problems.
7. Theory and computer simulation.
Special attention is given to problems of nonlinear dynamics, struc-
tural transitions, and kinetics of solid-state reactions (soliton regimes).
The mechanical properties and fracture of fibrous and filled composites
as well as the structure, mechanical and relaxation properties of polymeric
and inorganic glasses, crystals, and liquids are also of scientific interest.
In 2014, the Institute, hosted a conference dedicated to the 90th an-
niversary of academician Enikolopov, where the main achievements of
Department were presented.
The papers presented in this book concern most of the above-men-
tioned directions of Department’s investigations and the editors hope that
this book will be very interesting for readers.
Alexandr A. Berlin
Director of Semenov Institute of Chemical Physics
Russian Academy of Sciences
4 Kosygin str., 119991 Moscow, Russia
[email protected]
Svetlana Z. Rogovina
Leader Scientific Researcher
Semenov Institute of Chemical Physics
Russian Academy of Sciences
4 Kosygin str., 119991 Moscow, Russia
[email protected]
Gennady E. Zaikov
Head of Polymer Division
N.M. Emanuel Institute of Biochemical Physics
Russian Academy of Sciences
4 Kosygin str., 119991 Moscow, Russia
[email protected]
PREFACE

Additives are selected depending on the type of polymers to which they


will be added or the application for which they will be used. Appropriate
selection of additives helps develop value-added plastics with improved
durability, as well as other advantages. This research book provides a
range of modern techniques and new research on the use of additives in a
variety of applications.
The methods and instrumentation described represent modern analyti-
cal techniques useful for researchers, product development specialists,
and quality control experts in polymer synthesis and manufacturing. En-
gineers, polymer scientists, and technicians will find this volume useful in
selecting approaches and techniques applicable to characterizing molecu-
lar, compositional, rheological, and thermodynamic properties of elasto-
mers and plastics.
CHAPTER 1

5-ETHYLIDENE-2-NORBORENE-
OLEFIN COPOLYMERS:
SYNTHESIS, STRUCTURE,
MORPHOLOGY, PROPERTIES,
AND FUNCTIONALIZATION OF
COPOLYMERS
I. N. MESHKOVA1, A. N. SHCHEGOLIKHIN2,
L. N. RASPOPOV3, E. V. KISELEVA1, S. P. KUZNETSOV4,
V. G. GRINEV1, and L. A. NOVOKSHONOVA1
1
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow,
Russia
2
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow,
Russia
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
3

Chernogolovka, Russia
4
Lebedev Physical Institute, Russian Academy of Sciences, Moscow, Russia

CONTENTS

Abstract.................................................................................................................. 2
Introduction............................................................................................................ 2
Experimental Procedure......................................................................................... 3
Results and Discussion.......................................................................................... 7
Conclusion........................................................................................................... 17
Acknowledgments................................................................................................ 17
Keywords............................................................................................................. 17
References............................................................................................................ 18
2 Additives in Polymers: Analysis and Applications

ABSTRACT

Copolymers of ethylene (propylene) and 5-ethylidene-2-norbornene (ENB)


containing 5–65 mol% of the cyclic comonomer units (ENB) in the main
chain were synthesized by using homogeneous ansa-zirconocene catalysts
of С symmetry. They are rac-Et(Ind)2ZrCl2 (1), rac-Et(H4Ind)2ZrCl2 (2),
2
rac-Me2Si(Ind)2ZrCl2 (3), Me2C(Ind)2ZrCl2 (4), rac-Me2C(t-BuInd)2ZrCl2
(5), and methylaluminoxane (MAO). It is shown that the ethylidene groups
of ENB do not take part in the copolymerization and the very cyclic como-
nomer unit bears the pendent unsaturated group. According to the obtained
kinetic data (on copolymer output, the specific rate of ethylene consump-
tion, and conversion of ENB), catalyst 1 shows the highest activity in the
copolymerization of ethylene with ENB in comparison with the other cata-
lysts used. The incorporation of ENB into copolymer chain proceeds with
greater difficulty than with unsubstituted norbornene. The values of r1 are
higher and the values of r2 are lower for ENB than those reported for the
copolymerization of ethylene with norbornene. The introduction of t-Bu
substituent into Ind-ligand of ansa-zirconocene (catalyst 5) considerably
complicates the ENB insertion into the copolymer. The copolymers were
characterized by FTIR, DSC, NMR, and X-ray spectroscopy as well as by
the original technique of scattering with very cold neutrons having ener-
gies between 2 × 10–7 and 5 × 10–4 eV. With the growth of ENB content in
the copolymer, its crystallinity, melting enthalpy, and melting temperature
progressively decrease. Embedding of ENB units into the polyethylene
main chain leads to a considerable increase of the Tg value and better opti-
cal transparency of the resulting material. The copolymer with 30 mol%
of ENB, prepared by catalyst 1, was optically transparent in the UV and
visible parts of the spectrum and had the highest Tg (83°C) and density
(ρ > 1,000 kg/m3). Ozonolysis under the mild reaction conditions permits
the conversion of the ethylidene groups of poly(ethylene-co-ENB)s into
polar carbonyl, aliphatic carboxylic, and aldehydes side groups.

INTRODUCTION

Cycloolefin copolymers (COCs) are an interesting and practically impor-


tant family of copolymers synthesized by metallocene catalysts. Copoly-
mers of ethylene1–3 and propylene4–6 with norbornene have unique thermal
5-Ethylidene-2-Norborene-Olefin Copolymers 3

and optical properties. On this basis, the firms Mitsui and Ticona manufac-
ture industrial-grade Apel and Topas polymer materials with the very high
glass transition temperature and transparency.7 To improve compatibility
with other materials and for better adhesive properties, the COC func-
tionalization is carried out by one-step copolymerization of ethylene with
cyclic monomers containing polar groups8–10 or by the copolymerization
of ethylene or propylene and cyclic monomers with double bonds, which
are capable of taking part in post-polymerization polymer-analog trans-
formations, such as 5-vinyl-2-norbornene,11–13 5-ethylidene-2-norbornene
(ENB),14–17 4-vinyl-1-cyclohexene,18 and dicyclopentadiene.19
It is known that the relatively cheap substituted norbornene ENB is
used as termonomer in the ethylene propylene diene terpolymer (EPDM)
synthesis with ansa-zirconcene catalysts.20–23 The maximum content of
ENB in EPDM is 15 (12) mol%. In ethylene–ENB copolymerization by
different types of catalysts (with ansa-zirconocenes of C2 symmetry,14–16
constrained-geometry catalysts17), it is possible to obtain copolymer prod-
ucts containing 50–60 mol% of ENB.
In this chapter, the kinetic parameters of the ethylene–ENB copoly-
merization process and the copolymer composition depending on the na-
ture of C2 symmetry ansa-zirconocene catalyst (bridge, ligands in Ind of
ansa-zirconocene) are considered. For the synthesis of the polymer ma-
terials that combine high glass transition temperature, high density, and
optical transparency with the capability for postpolymerization polymer-
analog transformation, the morphology, density, as well as thermal and
optical properties of synthesized poly(ethylene-co-ENB)s are studied. The
possibility of modifying the copolymers by ozonation of their side groups
>C=CH−CH3 is also investigated.

EXPERIMENTAL PROCEDURE

MATERIALS

The catalyst components rac-Et[Ind]2ZrCl2 (1), rac-Et[Н4Ind]2ZrCl2 (2),


rac-Me2Si[Ind]2ZrCl2 (3) (Aldrich), and methylaluminoxane (Aldrich,
10 wt% in toluene) were used as received. Rac-Me2C[Ind]2ZrCl2 (4) and
rac-Me2C[(t-Bu)Ind]2ZrCl2 (5) were synthesized in the laboratory of Prof.
I. E. Nifantyev (Moscow State University).
4 Additives in Polymers: Analysis and Applications

Spectral-grade toluene (Aldrich) was purified by refluxing over sodium


wire with subsequent distillation under nitrogen. Ethylene and propylene
were of polymerization grade. ENB (Aldrich, 99%; a mixture of exo and
endo isomers) was distilled over Na under vacuum at room temperature.

ETHYLENE (PROPYLENE)–ENB COPOLYMERIZATION

The formation of the catalytic complex and the following olefin copo-
lymerization were carried out in a 0.5 dm3 glass reactor equipped with
units for feeding the solvent, catalyst, comonomers and a stirrer to mix
the reaction mixture. The reagents (toluene, methylaluminoxane [MAO],
zirconocene, and ENB) were introduced into reactor at room temperature.
After heating the reaction mixture up to the copolymerization tempera-
ture, toluene in reactor was saturated by the comonomer. The saturation
time was 1.5–2 min. During copolymerization, the ethylene (propylene)
pressure, the temperature, and the stirring rate of reactive mass were
maintained constant. The cyclic comonomer conversion led to a change
in the ENB:olefin molar ratio in the copolymerization. The copolymer-
ization conditions are presented in Table 1.1. The concentration of ethyl-
ene or propylene in toluene was calculated using the experimental values
of Henry (for ethylene kH  = 0.9 × 10–3Q2990/RTmol/L⋅atm; for propylene
kH = 2.1 × 10–3Q3340/RTmol/L⋅atm. The catalyst activity (A) and the rate of
ethylene (propylene) incorporation into the copolymer chain were charac-
terized by the consumption of olefin during the process (Rp, kg of PE(PP)/
mol of Zr mol comonomer h).

COPOLYMER CHARACTERIZATION

The content of ENB in the samples was estimated via calculations from
the yield of the copolymer products and the consumption of ethylene (pro-
pylene) in copolymerization, as well as by the method of ozonation of the
side double bonds of copolymer,24 which is given the next paragraph.
The composition of some ethylene-ENB copolymers was also deter-
mined by 13C NMR (Bruker/XWIN-NMR, solvent TCE, 103°C). To cal-
culate the ENB content in the copolymer chain, the formula applied for the
determination of copolymer composition with unsubstituted norbornene25
was used:
5-Ethylidene-2-Norborene-Olefin Copolymers 5

mol ENB% = {[2ΙC7 + ΙC1–C4 + ΙC2–C3]/3ΙCH2} × 100,
where ΙCH2, ΙC7, ΙC1–C4, and ΙC2–C3 are the total peak area in the ethylene-
ENB spectrum in the ranges 27.73–28.73, 30.90–31.86, 37.57–40.10, and
45.07–48.85 ppm, respectively.

TABLE 1.1  The Influence of the Catalyst Nature and Conditionsa of the Homo- and
olefin–ENB Copolymerization on the Activity of ansa-Zr-cene Catalysts and Copolymer
Compositions
Run Cat- The Initial [Zr], Mol tpol, Yield, Ab Con- [ENB] in
alyst Mol. ratio mmol/L Ratio min g version Copolymer
ENB: Olefin [Al]: of ENB, mol%
[Zr] %
1 1 Ethylene 0.065 3,000 60 0.6 15,000 – 0
2 1 Ethylene 0.26 1,000 70 5.6 4,400 – 0
3 1 2 0.026 2,550 60 4.6 14,600 100 5.3
4 1 6.5 0.244 1,000 87 5.55 1,760 78 9.5
5 1 8.6 0.106 1,875 85 5.64 2,020 74 28
6 1 7.7 0.035 2,510 110 9.5 2,080 24 30.5
7 1 16 0.143 1,500 160 1.29 1,645 62.7 39
8 1 22.5 0.115 1,850 180 0.98 1,000 9.7 43
9 1 ENB 3.6 120 300 0.25 – 3.5 100
10 2 Ethylene 0.023 4,160 90 2 10,400 – 0
11 2 11.8 0.06 1,800 190 1.89 1,170 24 62
12 3 Ethylene 0.132 1,370 65 4.2 5,800 – 0
13 3 Ethylene 0.4 1,060 53 3.75 5,000 – 0
14 3 2.2 0.084 2,230 50 2.9 4,870 100 9.4
15 3 4.4 0.087 2,030 100 4.7 1,900 100 20
16 3 6.5 0.083 2,010 290 3 1,000 37 31
17 3 6.5 0.31 1,000 90 4.22 1,110 79.4 12.6
18 3 10.4 0.02 2,800 170 0.4 800 23.8 37
19 4 Ethylene 0.107 900 120 3.5 2,040 – 0
20 4 6.5 0.264 1,000 129 6.57 1,820 100 17
21 5 Ethylene 0.245 1,000 30 3 9,700 – 0
22 5 6.5 0.245 1,000 65 2.9 5,580 16.6 3.3
23 1 Propylene 0.056 1,700 20 1 3,000 – –
24 1 1.56 0.056 1,300 190 1 120 100 50.4
25 1 1.65 0.56 1,700 200 1.2 150 120 52
Notes: a In run 1, the ethylene concentration is 0.024 mol/L, Tpol = 33°C. In runs 2–8
and 10–22, the ethylene concentration is 0.058 mol/L, Tpol = 40°C. In run 9, the ENB
concentration is 0.99 mol/L; Tpol = 40°C.
b
The ethylene (propylene) consumption in homo- and copolymerization with ENB, kg of
PE (PP)/mol Zr mol С2Н4∙(С3Н6) h.
6 Additives in Polymers: Analysis and Applications

The obtained results coincide with data of other works. Thus, the ENB
content in sample run 4 (Table 1.1), according to 13C NMR, is 9.02 mol%;
from the copolymer yield and the consumption of ethylene 9.50 mol%;
and by ozonation 9.66 mol%.
The molecular mass of the copolymers was characterized by viscom-
etry in decalin at135°C.
The density of the synthesized samples of homo- and copolymers of
the ethylene with ENB was determined by the flotation method (ASTM
D1505) at 20°C using ethanol/water mixture as working fluid. The mea-
surement accuracy was ±0.1%.
The Fourier transform infrared (FTIR) spectra of the copolymers were
obtained by a Perkin-Elmer FTIR-1720 spectrometer.
X-ray studies of the melt-molded ethylene–ENB copolymer samples
with different contents of ENB were performed on a DRON-2.0 gener-
al-purpose diffractometer (Cu Kα radition, 20  mA, 40  kV, and 14°–28°
range). The degree of crystallinity of copolymer samples was estimated
according to the standard Hermans–Weidinger method,26 which was modi-
fied as described by Raspopov and Belov27 .The size of the copolymer
crystallites was determined from the half-width of the reflections [110]
and [200] and calculated by the Scherrer formula.28 As a reference, we
used the [200] line of graphite with reflection angle 2θ = 24.8°, which is
close to the angles of reflections of copolymers under examination.
The supramolecular structure of the ethylene–ENB copolymers was
also tested by the original technique of very cold neutron (VCN) scatter-
ing with energies 2 × 10–7 to 5 × 10–4 eV.29 The neutron wavelengths were
in the range 1–100 nm. In the order of magnitude, these values coincide
with the characteristic sizes of the supramolecular structure of the poly-
mers. VCN experiments were performed with a time-of-flight spectrom-
eter in the wavelength range 4–60 nm. The measurements were conducted
at 300 K using 150–250 μm copolymer samples with a measured surface
area of 2.5 × 3.5 cm2.
The transparency of ethylene–ENB copolymers in the near-UV and
visible range was investigated using an instrument “Specol UV-vis” (the
spectral width was 2 nm).
Differential scanning calorimetry (DSC) measurements of the copoly-
mer products (for Tm, ΔH, and Tg) were carried out on Perkin-Elmer DSC-
7 calorimeter at a heating rate of 10 K/min.
5-Ethylidene-2-Norborene-Olefin Copolymers 7

The samples of homopolymers and E–ENB copolymers for determina-


tion of their properties were prepared by compression molding.
Functionalization of ethylene–ENB copolymers by ozonolysis reaction
The ozonation procedure is based on the ability of unsaturated com-
pounds to attach ozone to the double bonds at a high rate (one ozone mol-
ecule is attached to one double bond). The bimolecular rate constant of
ozone addition to C=C varies over the range 105–106 L/(mol·s).24 Mea-
surements were performed on a double-bond analyzer ADS-5.30 The
copolymer solution in an organic solvent (carbon tetrachloride or o-di-
chlorobenzene, 1.5–2.5 g of the copolymer per liter) was loaded into the
reactor, and an ozone–oxygen mixture with controlled concentration of
ozone (1 × 10–6 mol/L) was passed through the reactor at 0°C. The amount
of absorbed ozone was proportional to the content of double bonds in the
copolymer. To avoid the degradation of polymer products, the concentra-
tion of ozone in the ozone–oxygen mixture did not exceed 1 × 10−6 mol/L.
The ozonation method has high sensitivity (threshold sensitivity is of 10–11
moles per double bond), accuracy of ±1%, and high performance (0.5–
5 min per measurement).

RESULTS AND DISCUSSION

The copolymerization of ethylene and ENB, catalyzed by the ansa-zircon-


ocene systems, as well as the ethylene11 or propylene13 copolymerization
with 5-vinyl-2-norbornene, proceeds by virtue of regioselective insertion
of an endocyclic double bond of the cyclic comonomer into the main chain
(Scheme 1.1). The ethylidene double bond of the ENB does not participate
in the copolymerization.15

SCHEME 1.1  Main Chain.


8 Additives in Polymers: Analysis and Applications

FTIR spectra of the ethylene–ENB copolymers show absorption bands


at 3,038, 1,687, and 808 cm–1, which are characteristic for the ethylidene
unsaturation.20 Any absorption in the vicinity of 712 cm–1, which is nor-
mally assignable to the endocyclic double bond of the ENB the monomer
molecule, is absent in the spectra of the copolymers (Fig. 1.1).

FIGURE 1.1  FTIR Spectra of Ethylene–ENB Copolymers Before (—) and After (···)
Ozonolysis.

The compositions of the prepared ethylene–ENB copolymers, calcu-


lated from the ethylene consumption and yield of copolymer product, cor-
relate with the results of ozonation of the ethylidene double bonds (Table
1.2). This means that the ansa-zirconocene catalyst systems used produce
copolymers in which every cyclic comonomer unit bears the pendent un-
saturated group.15
5-Ethylidene-2-Norborene-Olefin Copolymers 9

TABLE 1.2  Content of ENB and Ethylidene Double Bonds in the Ethylene–ENB
Copolymers
Run Olefin Catalyst Initial [ENB] × 103 [C=C] × 103
Mol.ratio in Copolymer, in Copolymer,
ENB:Olefin mol/g mol/g
4 Ethylene 1 6.5 2.56 2.62
5 1 8.6 5.27 5.5
7 1 16 6.16 6.02
11 2 11.8 6.95 6.75
14 3 2.2 2.56 2.79
15 3 4.4 4.26 4.38
18 3 10.4 6 6.7
24 Propylene 1 1.56 6.2 5.7
25 1 1.65 7.5 8.2

KINETICS OF ETHYLENE–ENB COPOLYMERIZATION BY C2 SYMMETRIC


ANSA-ZIRCONOCENE SYSTEMS

The consumption of ethylene in the homo- and copolymerization and


conversion of ENB in copolymerization are given in Table 1.1. Catalyst
1 shows the highest activity (on copolymer output, the specific rate of
ethylene consumption, and conversion of ENB) in the polymerization of
ethylene and in the copolymerization of ethylene with ENB in comparison
to the other catalysts used.
At constant ethylene concentration in solvent during copolymerization,
the ENB:ethylene ratio decreases with time due to the ENB consumption,
depending on the catalyst activity and the relative reactivity of the como-
nomers.
The ethylene–ENB copolymerization with the catalysts used is a non-
stationary process. Figure 1.2 shows the kinetic curves of ethylene con-
sumption in ethylene–ENB copolymerization for different metallocenes.
The increase of ethylene consumption rate observed for catalyst 1, 3, and
4 can be associated with the gradual reduction of ENB concentration in re-
action zone (decrease of ENB:ethylene ratio) with time as a result of ENB
consumption in the copolymerization and with the consequent increase of
the fraction of ethylene centers. The effect appears more visible for the
10 Additives in Polymers: Analysis and Applications

more active catalyst 1. At low ENB insertion into the copolymer chain,
which was obtained with catalyst 5, the ENB:ethylene ratio in the reaction
zone changes very little. The reduction of ethylene consumption rate with
time is mainly due to the lowering of activity of the catalyst itself. The
decrease of ethylene consumption rate observed after the rate increase for
catalyst 1, 3, and 4 can have the same reason.

FIGURE 1.2  Change of Ethylene Consumption Rate During Ethylene–ENB


Copolymerization With different ansa-Zirconocene Catalysts. Catalyst: ♦ – 1 (Table 1.1,
no. 4), ∆ – 3 (no. 17), □ – 4 (no. 20), and × – 5 (no. 22).

Ethylene–ENB copolymers with the cyclic comonomer content from


10 to 65 mol% were obtained. Based on the composition of the copo-
lymers, which were prepared under conditions where the conversion of
the cyclic comonomer did not exceed 25 mol%, the reactivity ratios of
comonomers were calculated via the Finemann–Ross and Bohm methods.
As seen from Table 1.3, the insertion of ENB into the copolymer chain
in the presence of the tested ansa-zirconocene catalysts proceeds with
more difficulty than with the unsubstituted norbornene. The values of r1
are higher and the values of r2 are lower for ENB than those reported for
5-Ethylidene-2-Norborene-Olefin Copolymers 11

the copolymerization of ethylene with norbornene. The steric volume and


the flexibility of a bridge in the ansa-zirconocene and the presence of sub-
stituents in the Ind-ligand affect the ability of ENB to be inserted into the
copolymer chain as well as in the case of the unsubstituted norbornene.31

TABLE 1.3  Parameters of Copolymerization of Ethylene with ENB and with Norbornene
(N) According to Fineman–Ross Equation32 and BOHM Method33
Cyclic Como-
Catalyst Тpol, °С r1 r2 r1 r2 References
nomer
1 ENB 40 10.5 0.004 0.042 15
1 N 40 3 0.03 0.09 34
1 N 30 1.9 0.03 0.057 35
1 N 30 2.33 0.031 0.072 36
2 ENB 40 7.20a — —
2 N 25 2.20 a
— — 37
2 N 50 3.20a — — 1
3 ENB 40 8.7 0.007 0.061 15
3 N 30 2.71 0.0525 0.143 36
5 ENB 40 ~190 a
— — —
Notes: Calculated on Bohm method, m2/m1 = 1/r1·M2/M1.
a

Under identical conditions of copolymerization, the ENB content in


copolymers was 9.5 mol% for catalyst 1 with Et-bridge (Table 1.1, no. 4),
12.6 mol% for catalyst 3 with Me2Si-bridge (no. 17), and 14 mol% for
catalyst 4 with Me2C-bridge (no. 20).The introduction of t-Bu substitu-
ent into Ind-ligand of ansa-zirconocene (catalyst 5) leads to a decrease
in ENB insertion into the copolymer chain up to 3.3 mol % ENB (no. 22)
compared to 14 mol% ENB in copolymer obtained by catalyst 4 (no. 20).
For catalysts 1 and 3, the product r1·r2 is equal to 0.042 and 0.061,
respectively. This means that the structure of the produced ethylene–ENB
copolymers is intermediate between block and alternating. According to
the obtained copolymerization constants, the tendency to alternate of the
comonomer molecules in the copolymer macrochain is higher for catalyst
1 than for catalyst 3.
12 Additives in Polymers: Analysis and Applications

The molecular weight (intrinsic viscosity) of the ethylene–ENB copo-


lymers decreases with increase of the cyclic monomer content (Table 1.4).

TABLE 1.4  Intrinsic Viscosity of Ethylene–ENB Copolymers Obtained Catalyst 1


Depending on ENB Content (Decalin, 135°C)
Run [ENB] in Copolymer, mol% [η], dL/g
1 0 (PE) 2.30
5 28.6 0.24
7 39.0 0.18
8 43.0 0.15
Supramolecular structure, transparency, and density of PE and ethylene–ENB copolymers

The results of the study of the ethylene–ENB copolymer supramolec-


ular structure by X-ray diffraction and VCN scattering methods as well
as data on density and transparency are summarized in Table 1.5. It can
be seen that as the content of ENB units in the partly crystalline ethyl-
ene–ENB copolymers increases, the overall degree of crystallinity as well
as the crystallite dimension decreases, and eventually the copolymer be-
comes completely amorphous. In the diffractograms for a series of ethyl-
ene–ENB copolymers (Fig. 1.3), the peaks belonging to a crystalline PE
phase can be seen only for the copolymers having ethylene mass content
above 12 mass% (Fig. 1.3, traces 3 and 4). The partly crystalline copoly-
mer having the ENB content of 50 mass% has shown the amorphous halo
peak at 2Θ = 18.9°, while the amorphous copolymer with the ENB content
of 87 mass% exhibits the maximum at 2Θ = 17.4°. The diffractogram of
an ENB-homopolymer (Fig. 1.3, trace 1) reveals the amorphous halo with
two maxima at 16.3° and 22°, which is similar to that observed for the
unsubstituted norbornene homopolymer.
It is worth noting that the X-ray diffraction and the VCN scattering
methods may give, to some extent, controversial results. Specifically, the
mean dimensions of the supramolecular formations in several copolymers
evaluated by VCN scattering turned out to be higher than those found
by X-ray diffraction (Table 1.5, runs 2 and 11). Further, according to the
X-ray data, the samples 4 and 12 are devoid of any crystalline phase,
while the VCN scattering data for the same samples indicate the pres-
ence of nonuniformities with mean diameters 10.0 and 8.7 nm, the volume
fractions of these being equal to 0.1 and 0.2, respectively. Probably the
5-Ethylidene-2-Norborene-Olefin Copolymers 13

observed discrepancies are related to the fact that, in contrast to X-ray


diffraction, which is mainly sensitive to only strictly ordered crystalline
domains, VCN scattering is capable of detecting some almost amorphous
or highly defective structures as well.

FIGURE 1.3  Wide-Angle X-ray Diffraction Patterns of poly-ENB (1) and the Ethylene–
ENB Copolymers. Intensity is Normalized (104 pulse/s).[ENB] in Copolymer in Mass%:
100 (1), 87 (2), 66 (3), and 50 (4).

Notably, the possibility of the presence of the latter structures in the


studied ethylene–ENB copolymers has been supported also by the ob-
served lower optical transparency of the samples 4 and 12 (Table 1.5) as
compared, for example, to sample 13, which is categorized as perfectly
amorphous material in terms of both the X-ray and the VCN scattering
analyses data. The general optical characteristics of the prepared copo-
lymers in the near-UV and the visible parts of the spectrum have been
studied using optical transmission measurements in the range of l = 200–
750 nm. The data relevant to the optical properties of both PE and the
ethylene–ENB copolymers are presented in Table 1.5. The transmittance
of the copolymers increases with increasing content of the ENB units in
the copolymer main chain. For the copolymer samples containing up to
20 mol% of ENB units, gradual formation of zones of transparency in
the UV and visible parts of the spectrum has been noted, while at higher
14 Additives in Polymers: Analysis and Applications

partial contents of ENB in the copolymer main chain the materials reveal
fairly good transparency (T > 50% at l > 350 nm).

TABLE 1.5  Morphology, Optic Transparency, and Density of PE and Ethylene–ENB


Copolymers
Run Catalyst [ENB] in X-ray Studies Very Cold Neutron Transparency Density,
Copo- Scattering (λ = 750 nm), kg/m3
lymer, %b
mol% χ (L200 + φ l, nm
L110) /2,
nm
1 1 0 (PE) 0.77 12 n.d.a n.d. 56 949

3 1 5.3 0.47 8.5 0.5 13 n.d. 955


6 1 30.5 amorphous 0 0.1 10 77.2 1,024
10 2 0 (PE) 0.64 24 n.d. n.d. 36 956
11 2 62 amorphous 0 transparent 0 n.d. 1,200
14 3 9.4 0.31 8 0.3 12 n.d. 963
15 3 20 amorphous 0 0.2 8.7 73.5 986
16 3 31 amorphous 0 transparent 0 84.7 1,000

Notes: χ, degree of crystallinity; L, dimensions of crystallites by X-ray; φ , volume; l,


dimensions of nonuniformity fractions by VCN. aNot determined. bThe light transmission
through the support = 89.9%.

Density is one of the most important parameters controlling the proper-


ties of homo- and copolymers. This parameter is determined by the poly-
mer composition and the conditions of its preparation. From Table 1.5, it
is seen that the density of the ethylene–ENB copolymers increases with
increase in ENB content in copolymer and depends only insignificantly on
the nature of the used catalyst as well as the density of the PE synthesized.

THERMAL PROPERTIES OF ETHYLENE–ENB COPOLYMERS

The thermal properties of the prepared copolymers show a clear depen-


dence on their composition. The thermal characteristics of the ethylene-
ENB copolymers in comparison with those of homo-PE and homo-poly-
ENB samples were studied by DSC and are given in Table 1.6. According
5-Ethylidene-2-Norborene-Olefin Copolymers 15

to the DSC data, and in good correlation with the above-mentioned X-ray
and VCN scattering data, the partly crystalline ethylene–ENB copolymers
show a sharp decrease of their crystallinity degree with increasing ENB
content in the copolymer. Consequently, the crystal phase melting enthal-
py and the melting temperature progressively decrease. Further increase of
the ENB content in the ethylene–ENB copolymers leads to a fully amor-
phous state of the polymers. As is well known, the glass transition of the
homo-PE takes place at temperatures (Tg) below 0°C. Embedding of 5-eth-
ylidene-2-norbornene units into the polyethylene main chain leads to a
considerable increase of Tg value of the resulting material. Among the co-
polymers studied in this work, the highest Tg value of 83°C was observed
for a copolymer containing 30 mol% ENB and prepared using catalyst 1.
This Tg value is typical for ethylene-substituted norbornene copolymers of
similar composition prepared by the same catalyst.34,38–40

TABLE 1.6  Results of Investigation of PE and Ethylene–ENB Copolymer by DSCa

No. Catalyst Composition of ΔH, J/g Crystallinity,b Тm, °С Тg, °С


Polymer Product %
1 1 0 (PE) 174.42 0.59 133.2 Below 0
3 1 5.3 92.56 0.33 124.7 Below 0
5 1 28 – Amorphous 136.4 81.2
6 1 30.5 – Amorphous 131 83.1
9 1 100.0 (poly-ENB) – Amorphous 121.6 57.6
10 2 0 (PE) – 0.66 100.2 Below 0
11 2 62 175.85 Amorphous – 69
12 3 0 (PE) 78.76 0.6 – Below 0
14 3 9.4 11.3 0.27 131.7 Below 0
15 3 20 – 0.03 119.3 36.5
16 3 31 – Amorphous 134.6 60
17 3 37 226.4 Amorphous 134 72.6
18 4 0 (PE) 36.6 77.3 Below 0
19 4 14 199.2 12 66
20 5 0 (PE) 190.4 68 Below 0
21 5 3.3 65 Below 0
Notes: Second melting. Calculated in view of ΔH of the PE monocrystal = 294 J/g.
a b
16 Additives in Polymers: Analysis and Applications

FUNCTIONALIZATION OF ETHYLENE–ENB COPOLYMERS

The ethylene–ENB copolymers, which intrinsically show a good set of


thermal and optical properties, can further benefit from the availability in
their chains of side double bonds which, as has been mentioned previously,
are able to participate in the ozonolysis reaction. The highest content of the
ethylidene >С=СН–СН3 groups in the copolymers prepared in this work
was 6.9 × 10–3 mol/g. For comparison, the content of the same groups in
a homopolymer of 5-ethylidene-2-norbornene was 8.3 × 10–3 mol/g, while
the content of terminal C=C groups in a homo-PE having, for example,
Mn = 100,000 is only ~5 × 10–5 mol/g.
Ozonation of the ethylene–ENB copolymers is a convenient way of
modifying PE-based polymers by generating polar groups pendent to the
main chain. The rate constants of ozone interaction with double bonds by
several orders exceed those characteristic for reactions of O3 with other
groups.24 Ozonides of organic compounds, such as many other derivatives
from the peroxides class, readily decompose during storage or under heat-
ing, the main decomposition products being the corresponding aldehydes
and carbonic acids.41
According to our FTIR data (Fig. 1.1), ozonolysis of the >С=СН–СН3
groups pendent to the main chain of the copolymers under study seems
to be capable of generating plenty of derivative functional groups. For
instance, a series of absorption bands exist in the vicinity of 1,700–1,725,
1,740, and 1,750 cm–1, which obviously originate from the vibrations of
the carbonyl moiety in aliphatic carboxylic acids, ketones, and aldehydes.
One more absorption characteristic for the ozonated material appears in
the range 1,150–1,040 cm–1, which, most probably, belongs to the stretch-
ing vibration of the >C–O– group. However, the asymmetric stretching of
aliphatic ethers bonds (>C–O–C<) is normally observed in the same fre-
quency range (1,140–1,085 cm–1), and one cannot exclude the possibility
of aliphatic ether formation as a result of ozonolysis of such copolymers.
Thus, the obtained results confirm the feasibility of functionalization of
the main chain of PE through copolymerization of ethylene with a cyclic
ENB comonomer, followed by ozonolysis of pendent ethylidene groups.
5-Ethylidene-2-Norborene-Olefin Copolymers 17

CONCLUSION

The main factors controlling the kinetics of the ethylene–ENB copoly-


merization by С -symmetric ansa-zirconocene catalysts, namely, the com-
2
position, morphology, and properties of the obtained ethylene–ENB co-
polymers, depend on the nature of the ansa-zirconocene catalyst (type of
bridge, the presence of substituent in the indenyl ring) and the content of
the cyclic comonomer in the reaction copolymerization mixture.
The modification of crystalline as well as amorphous phases takes
place with the growth of the ENB content in the copolymer. The presence
of the highly defective nano-sized structures in the ethylene–ENB copo-
lymers detected by VCN scattering method decreases the transparency of
the amorphous ethylene–ENB copolymer materials.
The ethylene–ENB copolymer chain with pendent reactive sites is ame-
nable to further polymer-analog transformations, such as the ozonolysis
reaction. By ozonolysis under the mild reaction conditions of ethylidene
double bonds, the carbonyl, carboxy, and ester polar groups can be intro-
duced into ethylene–ENB copolymer. For the first time, we applied the
method of ozonation of ethylidene double bonds for detecting the molecu-
lar compositions and functionalization of the ethylene–ENB copolymers.

ACKNOWLEDGMENTS

We are grateful to Dr. Maria Carmela Sacchi for measurements of the co-
polymers’ 13C NMR spectra, and Prof. I.E. Nifantyev for ansa-zircono-
cenes.

KEYWORDS

•• 5-ethylidene-2-norbornene
•• olefin
•• homogeneous ansa-zirconocenes catalysts
•• copolymerization, ozonolysis
18 Additives in Polymers: Analysis and Applications

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CHAPTER 2

INSIGHT INTO NEW


APPLICATION ASPECTS FOR
PHOTOPOLYMERIZABLE ACRYLIC
COMPOSITIONS
N. L. ZAICHENKO1, B. I. ZAPADINSKII1, A. V. KOTOVA1,
I. A. MATVEEVA1, V. T. SHASHKOVA1, L. A. PEVTSOVA1,
A. O. STANKEVICH1, R. G. KRYSHTAL2, A. V. MEDVED2,
and A. V. ROSHCHIN1
1
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow,
Russia
2
Institute of Radio Engineering and Electronics, Russian Academy of Sciences
(Fryazino Branch), Moscow, Russia
Email: [email protected]

CONTENTS

Abstract................................................................................................................ 22
Introduction.......................................................................................................... 22
Experimental Procedure....................................................................................... 23
Results and Discussion........................................................................................ 25
Conclusions.......................................................................................................... 57
Keywords............................................................................................................. 59
References............................................................................................................ 59
22 Additives in Polymers: Analysis and Applications

ABSTRACT

Aspects of two new applications of photopolymerizable acrylic composi-


tions, namely as a registering medium for optical data recording and a
polymer sensor element for gas analysis, are discussed. The first applica-
tion is based on the possibility of generation of surface plasmon resonance
by gold nanoparticles formed in a 3D network matrix produced by irradi-
ating a liquid acrylic composition containing a dissolved gold salt with a
mercury lamp. It was established that the efficiency of formation of gold
nanoparticles is determined by the parameters of the polymer network and
by the chemical structure of the oligomer block, with the most suitable
matrixes being those having a loose network and containing groups ca-
pable of participating in complexation. The obtained matrixes may serve
as registering media for optical data recording because the agglomeration
of gold nanoparticles is initiated by subsequent external effects (heating
and/or irradiation), and the plasmon resonance band of gold nanoparticles
arises in the visible spectral region (500–600 nm) at the point of exter-
nal effect application. The second application deals with polymer films
containing microcavities with selective absorption centers, which were
obtained from oligoester acrylates. Experimental studies of absorption–
desorption of morpholine as an analyte by a molecularly imprinted poly-
mer film (obtained with morpholine as a template) using surface acous-
tic waves demonstrated significantly increased sensitivity of the polymer
sensor element to morpholine in comparison with other analytes. A new
method to measure the response of the sensitive element based on the mo-
lecularly imprinted polymer, which takes into account the size of output
signal and its relaxation time simultaneously, is proposed.

INTRODUCTION

Application of photopolymerizable oligomers has opened up an important


stage in polymer technology based on the direct transition from the liquid
(oligomer) to the solid state (polymeric product) without the difficult and
labor-intensive stages of synthesis, secretion, purification, granulation,
and processing of high-molecular-weight compounds. Moreover, they are
of low toxicity and volatility, and their transformation into the polymer is
Insight Into New Application Aspects 23

characterized by small shrinkage and takes place without high tempera-


tures and pressures.
All the above-mentioned properties of photopolymerizable oligomers
permit their use in the production of enamels and lacquers for wood and
metal, binders for composite materials, glues, optical devices, contact
lenses, anaerobic sealants, electrical insulating materials, typographic
printing forms, etc. But recently some new applications of photopolymer-
izable oligomers have been proposed, such as the creation of nanocom-
posite materials with unique optical, electronic, magnetic, and catalytic
properties and the development of molecularly imprinted polymers. These
materials can be used as a new generation of sensitive elements for gas and
liquid detectors and as recording media for optical data storage.

EXPERIMENTAL PROCEDURE

Hydrogen tetrachloroaurate(III) tetrahydrate (trihydrate) (HAuCl4·4(3)


H2O) (Merck, analytical grade) with a gold content of 49% and ethylene
glycol monomethacrylate (MEG, Aldrich) with a main component content
of 98% were used as supplied. The methods for synthesizing the oligomers
used have been described previously.1,2

METHOD OF PREPARATION OF OLIGOMERIC


COMPOSITIONS CONTAINING GOLD(III)

1. A 0.03 g (0.073 mmol) portion of HAuCl4⋅4Н2О was dissolved in


0.22 g (0.38 mmol) of MEG in vitro nigro to obtain a solution with
a salt concentration of 12 wt% (as recalculated to HAuCl4). The
solution was stored in the dark at 8–10°С and then used to prepare
the acrylic compositions to be tested.
2. A mixture 0.74 g of acrylate and 0.01 g of Darocur 4265 photoiniti-
ator (a 1:1 mixture of diphenyl(2,4,6-trimethylbenzoyl)phosphine
oxide and 2-hydroxy-2-methylpropiophenon) was placed in vitro
nigro, after which 0.25 g of HAuCl4 solution in MEG was added
under intense stirring; that is, the composition contained 3.0 wt%
HAuCl4. In a similar way, compounds 1–9 and two HAuCl4-free
reference OUM-1 and BDM-based compositions (10 and 11) were
24 Additives in Polymers: Analysis and Applications

prepared from the following acrylates: OUM-1 OUM-2, OUM-3,


OUM-4, OCM-2, DGDA, BDM, EDM, and OTFDM (Table 2.1).
3. To obtain the compositions 23–27, HAuCl4 (3 wt %) was dissolved
directly in a mixture of an acrylic oligomer and the photoinitiator
(1 wt%) , while the composition 33, based on the MEG-incompat-
ible perfluorinated acrylate, was prepared with the use of oligomer
OCM-2 as a cosolvent.

PHOTOINITIATED POLYMERIZATION OF OLIGOMERIC


COMPOSITIONS CONTAINING GOLD(III)

A 1 g portion was applied onto a quartz or silicate glass plate 75 × 35 mm


in size, with a joint sealing insert 0.09 mm in thickness (2 mm for electron
microscopy analysis) and covered with an identical plate, after which the
assembly was irradiated with a DRT_1000 mercury lamp for 2 min from
either side of the sample. The oligomers were analyzed by gel permeation
chromatography (GPC) on a Breeze chromatograph (Waters) equipped
with 100, 500, and 1000 Е Ultrastyrogel columns; the eluent, tetrahydro-
furan, was passed at a flow rate of 1 mL/min.
The electronic absorption spectra of the initial gold(III)-containing
compositions and their time evolution during the reaction were recorded
on a Specord UV–vis spectrophotometer. The absorption spectra of the
test films (on a glass support or between glass plates) after irradiation
were recorded on a Shimadzu vis–NIR 3101PC scanning spectropho-
tometer over the wavelength range 200–2500 nm. The reflection spectra
were recorded using a Shimadzu MPC-310 unit. The size of gold par-
ticles in the polymer matrix were determined by transmission electron
microscopy (TEM) on an LEO912 AB OMEGA instrument (Carl Zeiss,
Germany) with the energy filter integrated into the optical system of
the microscope (resolution of 0.2–0.34 nm). The samples were slices of
the indicated polymers 50–200 nm in thickness, which were prepared
at room temperature by using a Leica Ultracut UCT microtome (Leica,
Germany) with a diamond cutter. The slices were fixed at 300-mesh cop-
per TEM grids (Ted Pella, Canada).
Insight Into New Application Aspects 25

RESULTS AND DISCUSSION

UV-RADIATION-INDUCED FORMATION OF GOLD


NANOPARTICLES IN A 3D POLYMER MATRIX

Among the studies on the development of nanocomposite materials with


unique optical, electronic, magnetic, and catalytic properties, a promis-
ing direction is the synthesis of nanomaterials by means of dispersing a
metal, in particular gold or silver, throughout an olygomer matrix.3,4 The
process of formation of nanosized gold particles has been intensely inves-
tigated in recent years, especially in connection with the discovery of an
absorption band in the visible spectrum associated with localized surface
plasmon resonance (SPR) of metal nanoparticles.5,6 According to the Mie
electromagnetic theory, the position of the plasmon resonance band (PRB)
depends on the aspect ratio, particle size, and dielectric properties of the
medium.7 Many authors have assigned the absorption band in the 500–600
nm range to gold particles of 30–90 nm in diameter.8,9 It was demonstrated
that a number of organic compounds, for example, sulfur-containing com-
pounds,10 specifically influence the size and stability of the nanoparticles
formed.
The main field of applications of the unique properties of gold nanopar-
ticles is the development of sensors for detecting DNA or proteins by mea-
suring the change in the local refractive index caused by the adsorption of
an analyte molecule on the metal surface.11 Gold nanoparticles dispersed
in a polymer matrix have been suggested for use as elements of optical
memory devices12 or as IR-reflecting coatings on organic glasses: eyeglass
lenses or glazing of premises.13 Among the methods for introducing gold
nanoparticles into the matrix of a linear polymer, typically poly(methyl
methacrylate)(PMMA), the most effective one is the photoreduction of
soluble gold-containing salts dispersed throughout the matrix.14
The aim of this work was to examine whether plasmon resonance can
arise in gold nanoparticles dispersed in the 3D network of polyacrylates
and how the parameters of the network influence the kinetics of formation
of nanoparticles and the spectral properties of the synthesized material.
Such matrices have not been studied previously. Gold nanoparticles were
formed during the photoreduction of gold salts dissolved in an acrylic
oligomer composition, the 3D polymerization of which was induced by
photochemical initiation.
26 Additives in Polymers: Analysis and Applications

The structural formulas of the oligomers used (Table 2.1) are given
below:
CH2=C(CH3)COO–R–OOCC(CH3)=CH2 (I)
where R = (CH2)4 for BDM, R = (CH2)20 for EDM, and R = (CH2CH-
2
CH 2
CH2O)m(CH2)4 for OTFDM (m = 15–20); oligo(urethane acrylates)

CH3 CH3

R-OOCNH NHCOO (CH2CH2CH2CH2O)nCO NH NHCOOR'

Here, n = 15–20 and R = R’ = CH2CH2OMet for OUM-1; R =


CH2CH2OMet and R’ = CH(CH3)2 (66 : 33) for OUM-2; R = CH2CH2OM-
et and R’ = CH(CH3)2 (33 : 66) for OUM-3; R = R’ = CH(CH3)2 for OUM-
4; R = R’ =[CH2CH(CH3)O]5–6Met for OUM-5; R = R’ = [CH2CH(CH3)
O]6-7 Met for OUM-6; R = R’ = (CH2CH2O)6–8Met for OUM-7; R = R’
= CH2CH2OAcr for OUA-1; R = CH2CH2OAcr and R’ = CH(CH3)2 (66
: 33) for OUA-2; R = R’ = (CH2CH2O)6-9Acr for OUA-3; and R = R’ =
CH2CH(CH3)OAcr for OUA-4.

Here, n = 15–20 and R = [CH2CH2CH2CH2O]n for OUAIPF.


Here, R = CH2CH2 for OUAIE and R = CH2CH(CH3) for OUAIP.
Insight Into New Application Aspects 27

Here, n = 30–35 and R = MetOCH2CH2 for OUM-2000T.15


MetOCH2CH2OOCO-R-OCOOCH2CH2OMet
Here, R = CH2CH2OCH2CH2 for OCM-2,16
R = (CH2)2O(CH2)2OCOO(CH2)2O(CH2)2OCOO(CH2)2O(CH2)2 for
OCM-2-1,17
R = CH2C(CH2Br)2CH2 for OCMN,

DGDA, n = 5–8

We had established that crystal hydrates of HAuCl4 are highly soluble


in hydroxyl-containing acrylic oligomers.13 For example, the solubility of
HAuCl4 in MEG is 30 wt%; for this reason, this monomer was selected as
an active solvent for HAuCl4 salts. From the experimental point of view,
the optimum concentration of the Au salt in MEG is 12 wt%; so this solu-
tion was used as a stock solution in preparing the acrylic compositions.
When composition 1 was irradiated between quartz plates by unfiltered
light of the mercury lamp, HAuCl4 rapidly disappeared (within 3–4 min),
as evidenced by the vanishing of its absorption band at
28 Additives in Polymers: Analysis and Applications

TABLE 2.1  Structure of Initial Acrylates, Their Basic Properties and Notation of Their
Compositions with a 25 wt% Solution of HAuCl4 in meg
Comp. Notation Name, Block Structure Viscosity, cP d204 , g nD20
Number m -3

– MEG Ethylene glycol mono- 4.0 1071 1.4520


methacrylate
1 OUM-1 Oligourethane methacry- Tm = 29–34°C 1095 1.5000
late (II)
R=R′= –
(CH2)2OOCC(CH3)=CH2
2 OUM-2 Oligourethane methacry- >20,000 1086 1.5012
late (II)
R=–
(CH2)2OOCC(CH3)=CH2
R′=–CH(CH3)2 (66: 33)
3 OUM-3 Oligourethane methacry- >20,000 1078 1.4992
late (II)
R=–
(CH2)2OOCC(CH3)=CH2
R′=–CH(CH3)2 (33: 66)
4 OUM-4 Oligourethane methacry- >20,000 1065 1.4861
late (II)
R=R′= –(CH2CH(CH3)
O)6OC-(CH3)=CH2
5 OCM-2 Oligocarbonate methac- 160 1196 1.4660
rylate
6 DGDA Diphenilopropane glycero- 20 000 1180 1.5590
late diacrylate
7 BDM Butanediol di(meth)acry- 4.7 – –
late [I R=(CH2)4]
8 EDM 1,20-Eicosanediol Tm = 115°C – –
di(meth)acrylate
[I R=(CH2)20]
9 OTFDM Oligotetrahydrofuran-α,ω- Tm = 25–28°C 998 1.4640
diol di(meth)acrylate [I at 30o
R=(CH2)4O)m (CH2)4]
10 OUM-1 Reference sample, without – – –
Au
11 BDM Reference sample, without – – –
Au
Insight Into New Application Aspects 29

320 nm; that is, Au3+ was reduced to Au0 without the formation of prod-
ucts capable of absorbing in visible and near-UV spectral regions (Darocur
4265 photoinitiator has an extinction coefficient of 8.2 × 10–3 M–1 cm–1 at
320 nm) (Fig. 2.1a). Within this time interval, the photopolymerization
of the acrylic components resulted in the formation of a transparent film.

FIGURE 2.1  Absorption Spectra of a HAuCl4 Solution in Acrylic Composition 1 in the


Course of Irradiation: (a) HAuCl4 Consumption: curves 1–12 Correspond to Irradiation
Times from 0 to 5.3 min; (b) PRB Intensity Growth: Curves 1–14 Correspond to Irradiation
Times from 23 to 113 min.

In a number of cases, for example, in OUM-based compositions (No.


1–4 in Table 2.1), 3–5 min after complete consumption of HAuCl4, an
absorption band near 340 nm appeared, the intensity of which increased
for 15–20 min. Only 20–25 min after the beginning of irradiation, an ab-
sorption in the visible spectrum emerged near 550nm (Fig. 2.1b), which is
assigned to a PRB of gold nanoparticles, and its intensity increased for 60–
90 min. Clearly, the formation of gold nanoparticles in the film and their
growth and agglomeration occur at a lower rate compared to the rate of the
reduction of the salt. As a result of these photoinduced processes, a rose-
violet film was formed. When the sample was irradiated between silicate
glass plates (in contrast to quartz plates), the picture was somewhat differ-
ent. The 340 nm absorption band was not observed as an individual peak,
whereas the PRB was shifted to 580 nm and exhibited a shoulder near 640
nm. The above data were obtained for films 20–25 μm in thickness. Note,
30 Additives in Polymers: Analysis and Applications

however, that, under similar conditions of photoinitiated polymerization,


it is possible to obtain transparent, colorless, gold-containing films, 100
μm and more in thickness, which, when irradiated, feature a PRB in the
visible spectrum. It was demonstrated12 that, upon HAuCl4 photoreduction
in a PMMA matrix, the formation of nanoparticles and PRB are observed
only at elevated temperatures and not during irradiation. It is likely that
heating up to the glass transition temperature and above is needed for the
diffusion-controlled growth of the reduced gold phase, which is due to the
thermodynamic incompatibility of PMMA and Au.
Since irradiation with a 1000 W UV lamp is accompanied by signifi-
cant heating due to the irradiation, we studied the effect of temperature
on PRB generation. Table 2.2 lists the results of irradiation (hν) and/or
heating of composition 1, fixed between quartz and silicate glass plates.
To exclude the effect of temperature during irradiation, the assembly with
the test film was cooled with a water flow (10–15°С). In all the above-
mentioned cases, the compositions fixed between quartz plates yielded a
PRB near 550 nm upon irradiation, whereas the 340 nm band manifested
itself as an individual peak only in irradiated oligourethane methacrylates.

TABLE 2.2  Effect of the Conditions on the Formation of Gold Particles after UV
Irradiation of Composition
Conditions Quartz Glass
PRD Wavelength, Color PRD Wavelength, Color
nm nm
90°C 565 Violet Absent Golden
90°C + hν 540 Rose-violet 580 Violet
Hν 540 Rose-violet Absent Colorless

The photoreaction in the respective sample fixed between silicate glass


plates occurred in a different manner. When heated, it produced no PRB;
instead the film turned golden yellow due to the formation of sample up
to 70–90°C depending on the duration of formation of gold particles 1–20
μm in size. When the sample was irradiated without heating, no spectral
changes in the film were observed, and the sample remained transparent
and colorless. Only the joint action of light and heat produced a PRB at
580 nm and the sample turned violet.
When a liquid composition was introduced between the silicate glass
plates and from the very beginning was subjected to the joint action of
Insight Into New Application Aspects 31

UV irradiation and heat (90°C + hν), fairly larges Au particles formed in


100–200 μm films even at early stages of the process, giving rise to golden
color and opalescence. The composition that is homogeneous before cur-
ing becomes optically nonuniform. As double bonds continue to disappear,
gold nanoparticles with a new absorption band near 600 nm are formed. It
was revealed that the polymerization of MEG and its mixture with acrylic
oligomers are markedly inhibited by the gold salt or by the products of its
decomposition. In comparison with the reference (HAuCl4-free) sample,
the rate of the polymerization of composition 5 (Table 2.1) decreased by
2–3-fold. An increase in the salt concentration by 3–13% leads to an in-
crease in the time it takes to cure a film prepared from composition 1 from
12 to 38 min and in the size and concentration of reduced gold particle
that make the sample turn golden yellow. Thus, the photopolymerization
is largely inhibited due to the participation of HAuCl4 in free-radical reac-
tions. Inhibition can also occur due to the reflection of initiation radiation
by the gold particles formed.
As the photoinitiator concentration was increased from 3.2 to 5 wt%,
the inhibiting action of HAuCl4 was overridden and the process of particle
formation was retarded; as a result, the sample remained colorless. When
heated, the cured samples turned violet-golden.
Thus, the photoinduced processes, namely the reduction of gold, po-
lymerization of acrylates, and the growth and agglomeration of gold par-
ticles, are interrelated. In most cases, the polymer matrix formed exhibited
good mechanical properties.
The chemical structure of the acrylic components and the density of
the polymer network markedly affect the photoreduction of HAuCl4 and
emergence of PRB near 580 nm. Figure 2.2 shows the kinetic curves for
the consumption of the gold salt in compositions 1 and 4–6 (numbers at
the curves corresponds to the numbers of the compositions in Tables 2.1
and 2.3). Table 2.3 lists the rate constants for this reaction, whereas Figure
2.3 displays the time evolution of the absorption at 580 nm in the films of
the acrylic compositions, which has been shown to reflect the formation of
Au0 particles ~40 nm in size.14 As can be seen, the interchain length of the
network virtually does not affect the rate of HAuCl4 photoreduction, but
essentially influences the maximum intensity of the PRB. Under a given
condition, the maximum rate of the formation of nanoparticles is observed
for OUM-based low-density networks, whereas, in rigidly cross-linked
OCM-2, BDM, and trimethylolpropane triacrylate matrixes this process
32 Additives in Polymers: Analysis and Applications

occurs much more slowly. Under the same conditions, an increase in the
rigidity of the oligomer block (composition 6) causes a decrease in the rate
of gold reduction and growth of gold particles (Table 2.3).

FIGURE 2.2  Consumption of HAuCl4 During Photoreduction in Acrylic Matrices (λ =


320 nm; Here and Below, the Curve Number Corresponds to the Number of the Respective
Composition in Tables 2.1 and 2.3).

FUGURE 2.3  Time evolution of the intensity of the PRB near 580 nm for the acrylic
compositions tested.
Insight Into New Application Aspects 33

TABLE 2.3  Gold-Containing Acrylic Compositions and Some of the Properties of the
Films Formed in the Course of Photochemical Reactions
Composition Oligomer k × 102, λ, nm Im D/λ
Number s -1 (500–2100
nm)
1 OUM-1 2.53 580/640 1.583 949.6
1a OUM-1 after 14 days – – 1.223 736.4
1b + 5% GDMA – 625 0.423 253.4
2 OUM-2 – 570 0.563 339.1
3 OUM-3 – 560 0.576 345.3
4 OUM-4 2.51 580/620 0.45 267.3
5 OCM-2 1.66 560 – –
5a OCM-2 after 7 days – – 0.27 161.8
5b 5% HAuCl4 – – 0.22 130.7
6 DGDA 0.37 – – –
7 BDM – 580/620 1.13 676.1
8 EDM – – 0.313 187.1
9 DMPF – 600 0.953 570,0

Figures 2.4 and 2.5 show the absorption spectra of 0.2 mm thick films
prepared from gold-containing acrylic matrixes after 20 min of irradia-
tion between silicate glass plates under the same conditions (90°C + hν).
One can claim that the network internodal length in the polymer matrix
is the parameter that governs the formation of gold nanoparticles and re-
sponsible for the appearance of a PRB. Of the systems studied, those with
OUM-based sparse network are most suitable for the formation of gold
nanoparticles capable of generating plasmon resonance: in the case of
OUM-2, OUM-3, and OUM-4, the absorption spectrum of the composites
features only one narrow peak, namely the PRB. This means that, in these
matrixes, gold nanoparticles of approximately the same size, that is, 30–90
nm, are formed. The spectrum of the polymer prepared from composition
1 (Fig. 2.4) differs from the spectra of the other OUM-based polymers,
which suggests that this somewhat more rigid polymer provides the mini-
mum size cell required for the formation of gold nanoparticles exhibiting
a PRB.
On the other hand, under the same condition, the spectra of densely
cross-linked polymers (prepared from compositions 5, 5a, 5b, and 6; Table
34 Additives in Polymers: Analysis and Applications

2.3) feature virtually no absorption in the region of PRB, except for thin
films from composition 5, which exhibits a low-intensity PRB. It appears
that the cell size of these polymers prevents them from acting as reactors
for the processes under study, that is, the accommodation of bulky HAuCl4
molecules and photoreduction to the growth and agglomeration of gold
particles. In these cases, the formation of gold particles most likely occurs
in the defective areas of the polymer network, and the absence of the PRB
shows that, to form 30–90 nm gold particles, the cell walls should act as a
stabilizing factor. Gold-containing, densely cross-linked networks exhibit
a strong absorption over the entire 320–2100 nm range (Figs. 2.4 and 2.5).

FIGURE 2.4  Absorption Spectra of the Films of the Acrylic Nanocompositions after the
Completion of the Photochemical Processes.

The chemical structure of the oligomer block also substantially influ-


ences the formation of gold nanoparticles. Compounds containing groups
capable of complexation with the metal or its ions (e.g., those involving
СH2–O–СH2 ether bonds) promote the formation of nanoparticles. In the
first approximation, the overall absorption within 500–2100 nm (the PRB
and the long-wave shoulder belonging to smaller particles18) can be con-
sidered a measure of the concentration of nanoparticles that give rise to the
PRB. Table 2.3 lists comparative data on the absorption of gold-containing
films, which show that the films prepared from OUM-1 or OTFDM (com-
positions 1 and 9) contain 3–5 times more nanoparticles than the films
Insight Into New Application Aspects 35

prepared from the purely hydrocarbon oligomer with a (СH2)20 block


(composition 8). Differences in the solvating ability of the acrylates also
affect the position of the PRB maximum, which is in the range 560–640
nm. Note that solutions of HAuCl4 in the acrylates are unstable especially
when exposed to light. For example, composition 1 irradiated immediately
after the preparation features a broad band over the entire range covered
(Fig. 2.4, spectrum 1), whereas after being kept in the dark for 14 days and
photoirradiation, the sample exhibits a narrow PRB (spectrum 1a). In the
course of the photoreduction of the completely cured films, the ratio be-
tween the intensity of the bands in the range 500–2100 nm can change, and
consequently the color of the film can also change; but after the comple-
tion of the photochemical reactions, the samples are stable, and the spectra
of the films displayed in Figures 2.4 and 2.5 remain unchanged at room
temperature for 70 days.

FIGURE 2.5  Effect of the Structure of the Oligomer and Conditions of the Photoreactions
on the Generation of the PRB.

The chemical structure of the oligomer block also substantially influ-


ences the formation of gold nanoparticles. Compounds containing groups
capable of complexation with the metal or its ions (e.g., those involving
СH2–O–СH2 ether bonds) promote the formation of nanoparticles. In the
first approximation, the overall absorption within 500–2100 nm (the PRB
and the long-wave shoulder belonging to smaller particles18) can be con-
sidered a measure of the concentration of nanoparticles that give rise to the
36 Additives in Polymers: Analysis and Applications

PRB. Table 2.3 lists comparative data on the absorption of gold-containing


films, which show that the films prepared from OUM-1 or OTFDM (com-
positions 1 and 9) contain 3–5 times more nanoparticles than the films
prepared from the purely hydrocarbon oligomer with a (СH2)20 block
(composition 8). Differences in the solvating ability of the acrylates also
affect the position of the PRB maximum, which is in the range 560–640
nm. Note that solutions of HAuCl4 in the acrylates are unstable especially
when exposed to light. For example, composition 1 irradiated immediately
after the preparation features a broad band over the entire range covered
(Fig. 2.4, spectrum 1), whereas after being kept in the dark for 14 days and
photoirradiation, the sample exhibits a narrow PRB (spectrum 1a). In the
course of the photoreduction of the completely cured films, the ratio be-
tween the intensity of the bands in the range 500–2100 nm can change, and
consequently the color of the film can also change; but after the comple-
tion of the photochemical reactions, the samples are stable, and the spectra
of the films displayed in Figures 2.4 and 2.5 remain unchanged at room
temperature for 70 days.
In the course of the photoreduction of HAuCl4 to Au0, chlorine-contain-
ing products are formed, which can play a significant role in the formation
and agglomeration of nanoparticles. It makes sense to assume that, along
with solvating intermediate products of gold reduction, groups contain-
ing ether bonds in the oligomer block bind chlorine molecules (atoms or
ions), thereby impeding the reverse reaction of dissolution of reduced gold
in the chlorine-containing solution, and thereby promoting the growth of
gold particles. The probability of occurrence of the reversible reaction of
formation of Au0 nanoparticles and their dissolution in “chlorinated water”
with predominant dissolution of nanosized particles due to their higher
surface energy is confirmed by the fast formation of gold nanoparticles
and the emergence of a PRB upon introduction a reducer, for example,
glycidyl methacrylate or oxalic acid (Figure 2.5, spectrum 1b).
It is commonly assumed19 that the ability of gold-containing nanocom-
posites to reflect IR radiation is associated with the presence of ~20 nm
gold particles (such particles give rise to a PRB). Our results show, how-
ever, that films prepared from loose polymers (optimal for the emergence
of a PRB) virtually does not reflect IR radiation (Figure 2.6, spectra 2, 3,
and 4), whereas the densely cross-linked composites exhibit the best re-
flectivity. According to Swanson and Billard,18 the long-wave shoulder of
the PRB in the absorption spectrum is associated with the presence of ~5
Insight Into New Application Aspects 37

nm particles; it seems that such nanoparticles are responsible for the abil-
ity of the material to reflect IR radiation.
The maximum efficiency of IR radiation reflection by the composites
under study, 25–30%, is observed for composites 1 and 7, which are char-
acterized by the most intense absorption within 600–2100 nm. Note that
a marked reflectivity is demonstrated by OUM-2-based matrixes (com-
positions 5, 5a, and 5b in Table 2.3), although they exhibit no absorption
in the visible and near-IR spectrum. One can expect that by selecting a
proper acrylic matrix and conditions for the photoprocess, it is possible to
synthesize nanocomposites with ultrafine gold particles and, consequently,
substantially enhance their IR reflectivity.

FIGURE 2.6  Reflection Spectra of the Films of the Acrylic Nanocomposites.

Electron microscopy analysis showed that the cured acrylic matrixes


contain nanosized gold particles (Fig. 2.7). The concentration of nanopar-
ticles increases after thermal treatment. At temperatures above the glass
transition temperature, the process of secondary formation of fine gold
particles begins.
38 Additives in Polymers: Analysis and Applications

FIGURE 2.7  Gold Nanoparticles Formed upon UV Irradiation of an Acrylic Composition


Containing HAuCl4.

The next step of this work was to investigate in detail the effects of
the structure of acrylic oligomers and the parameters of the network of
a cross-linked polymer – the product of their photopolymerization – on
the formation of gold nanoparticles during the photoreduction of hydro-
gen tetrachloroaurate(III) in solutions of liquid acrylic compounds and to
study the kinetics of consumption of the salt and the kinetics of the forma-
tion of gold nanoparticles characterized by the PRB in the range 500–600
nm.20
We began with the study of the photoinitiator’s influence. An increase
in the photoinitiator concentration from 1 to 3.63 wt% leads, under identi-
Insight Into New Application Aspects 39

cal conditions, to a gain in the rate of photoreduction of HAuCl4 by a fac-


tor of ~4 up to kd = 0.12 s–1 and in the rate of PRB generation, but not in
the maximum optical density (D = 1.18 and 0.97, respectively). Recently,
an efficient method was developed to form gold nanoparticles via the pho-
tolysis of HAuCl4 in aqueous media; the typical polymerization initiator
HO(CH2)2OC6H4COC(CH3)2OH (Irgacure 2959) generating •C(CH3)2OH
radicals was used as reducing agent.21 The latter reduces Au3+ to Au2+ and
then to Au0. It is possible that, in our case, one of the photoinitiator compo-
nents, 2-hydroxy-2-methyl propiophenone [C6H5COC(CH3)2OH], partici-
pates in the reduction of the gold salt and the formation of nanoparticles.
In this case, the consumption of the initiator for the reduction of the gold
salt may determine the inhibiting effect of HAuCl4 on the photopolymer-
ization of acrylates. Thus, the proper choice of the initiator’s structure
and its concentration in an acrylic matrix offers additional possibilities to
control processes leading to the formation of nanoparticles of the desired
shape, as was shown for the reaction in aqueous media.
A much stronger influence on the photolysis rate is related to the spec-
tral composition of the irradiating light; a silicate glass filter sharply de-
creases the rate of photolysis and the rate of acrylate polymerization (Fig.
2.8). Note that, during irradiation of composition 28 placed between two
pieces of transparent KBr glass, the decomposition of the gold salt pri-
marily proceeds in a liquid medium or in a very weakly cross-linked gel.
(For diacrylates, the gel point is reached at a double-bond conversion of
1–5%.) Slower photoreactions simultaneously occur between two pieces
of silicate glass, and the gold salt is mostly reduced in a network polymer
matrix.
On the basis of our data on the suitability of gold nanoparticles in loose
matrixes,13 the effect of 3D network parameters (internodal and interchain
distances) on the generation of the PRB then was studied for oligo(urethane
acrylate) (OUM) compositions with similar structures of the oligomeric
block. The network density in the homo- and copolymers of OUM was de-
termined by using the Cluff and Gladding method for studying the swell-
ing of network polymers from the number-average molecular mass of in-
ternodal subchains (cross-links) of 3D networks.22
40 Additives in Polymers: Analysis and Applications

FIGURE 2.8  Consumption of the Gold Salt in the Media of (1, 2) DMPF and (3, 4)
OUM_1 During Irradiation of the Composition Through (2, 4) Silicate Glass, (1) KBr
glass, and (3) Quartz and the Kinetics of DMPF Photopolymerization During Irradiation
Through (5) Silicate Glass and (6) KBr glass.

Figure 2.9 shows the kinetic curves illustrating variation in the opti-
cal density of the PRB (hereafter, D at the wavelength of the PRB maxi-
mum) in OUM and OUA matrixes with different oligomeric block lengths
(OUM-1, OUA-1, OUA-4, OUM-5, OUM-6, OUM-7, OUA-3, and OUM-
2000T) and internodal distances (OUM-2, OUM-3, and OUA-2) with the
content of functional groups (a partial replacement of acrylic groups with
isopropyl groups; Table 2.4). Note, above all, that in the case of the oligo-
mers under consideration containing the oxyalkylene block, the network
parameters affect the rate of PRB generation, but not the limiting optical
density (Dmax).
Insight Into New Application Aspects 41

TABLE 2.4  Spectral and Kinetic Characteristics of HAuCl4 Photolysis in Acrylic


Compositions

Composition Oligomer lmax, nm kр 102, s-1 lmaxb, nm Dmax (PRB) tindc, min
HAuCl4
Oligomer + MEG + 3% HAuCl4 + 1% photoinitiator
1 ОUM-1 322a 4.39 532/532 1.18 15.7
2 ОUМ-2 325a 4.37 538/532 1.22 15.7
3 ОUМ-3 325a 4.15 535/532 1.15 5.7
4 ОUМ-4 325a 3.22 562/532 1.05 5.7
5 OUM-5 323a 4.05 533/530 1.17 15.7
6 ОUМ-6 323a
5.10 536/533 1.25 5.7
7 OUM-7 326a
4.98 533/530 1.16 5.7
8 ОUМ- 323a
5.24 542/536 1.22 15.7
2000Т
9 ОUМ-4F 320 6.14 535/545 0.45 25.7
10 ОUА-1 323a 4.58 536/533 1.15 15.7
11 ОUА-2 323a
4.80 539/536 1.15 5.7
12 ОUА-3 323a
5.16 530/530 1.17 5.7
13 ОUА-4 323a
5.23 539/533 1.10 5.7
14 ОUAIE 323 5.74 -/521 0.20 35.7
15 ОUАIP 323 5.47 533/524 0.20 35.7
16 ОUАIPF 320 11.71 540/530 1.22 3.7
17 OCM-2 320 10.81 533/528 1.07 5.7
18 ОCМ-2-1 320 6.93 542/535 0.87 5.7
19 ОCМC 320 5.12 560/545 1.04 5.7
20 ОCМN 320 6.30 554/575 1.10 5.7
21 ОCМP 323 7.22 554/566 0.63 0.7
22 ДМPF 323 13.62 560/536 0.91 1.7
Oligomer + 3% HAuCl4 + 1% photoinitiator
23 ОCМ-2 320 8.21 545/535 1.06 5.7
24 DMTG 325 2.57 – – –
25 DMEG 323 6.03 539/536 0.70 20.7
42 Additives in Polymers: Analysis and Applications

TABLE 2.4  (Continued)

Composition Oligomer lmax, nm kр 102, s-1 lmaxb, nm Dmax (PRB) tindc, min
HAuCl4
26 DAHG 323 10.31 542/536 0.94 5.7
27 DAEHG 326 11.57 536/530 0.99 5.7
28 FHAC 320 9.07 550/535 0.62 5.7
ОCМ-2
MEG
Reference samples
29 MEG 320 10.11 525 1.08 3.7
30 MPG 320 9.58 525 0.99 3.7
Notes: aThe band at 340 nm appears. bThe values of lmax at the appearance of the PRB
and the final position of the PRB are in the numerator and denominator, respectively. cThe
induction period (time from the onset of irradiation to the appearance of PRB.

FIGURE 2.9  Effect of the Length of the Oligomer block in Diacrylates on the Kinetics
of PRB Accumulation: (1) OUM-3, (2) OUA-3, (3) OUA1, (4) OUM-2, (5) OUM-1, (6)
OUM2000-T, and (7) OUM-5.
Insight Into New Application Aspects 43

It follows from comparison of the rate of accumulation of the PRB in


acrylic and methacrylic matrixes having identical oligomeric block struc-
tures (Table 2.4) that gold nanoparticles are formed in acrylates at a no-
ticeably higher rate than that in methacrylates (Fig. 2. 9, curves 3 and 5 or
2 and 7). This result is unexpected because the polymerization of acrylates
occurs faster than that of methacrylates, and for polyfunctional acrylic
oligomers the contribution of slower processes generating nanoparticles
in a network matrix is greater than that in the case of methacrylates. In
contrast, the majority of nanoparticles responsible for the PRB are formed
even in the network matrix, and the difference in the rate of accumulation
of the PRB in OUM and OUA matrixes may be determined by the network
density; polyacrylates are more elastic than their methacrylic analogs.
The intensity of the PRB depends on the concentration of the gold salt
in the original composition: at [HAuCl4]0 = 0.085 and 0.12 M for OUM-1,
DmaxPRB = 1.2 and 1.63, respectively. These D values are close to those for
the initial concentration of the salt (0.979 and 1.66). It is known23 that the
PRB of metal nanoparticles is characterized by a large and easily tunable
optical absorption cross section. Thus,24 gold nanoparticles with a diam-
eter of ~40 nm have a calculated absorption cross section of 2.93 × 10–15
m2, corresponding to a molar extinction coefficient of ε = 7.66 × 109 L/
(mol·cm) at the PRB wavelength, a value that is four orders of magnitude
higher than that for HAuCl4 (7.3 × 105 L/(mol cm) at 320 nm). With the
use of common relationships, it may be assumed that the concentration of
nanoparticles is four orders of magnitude lower than the initial concentra-
tion of the salt; that is, each nanoparticle contains ~104 Au atoms.
The value of D attained for the PRB of nanoparticles in the above loose
OUA networks is close to the maximum value for polymer matrixes under
the given experimental conditions: the photolysis of HAuCl4 in solutions
of monomers, that is, MEG or oligo(1,2-propylene glycol) methacrylate,
with n = 5–6 (compositions 35 and 36) leads to a maximum optical density
of the PRB in the matrix of the linear polymer that is close to the above
values for networks: ~1.0.
For oligourethanes with a long oligomeric block, the substitution of
aliphatic isocyanates for aromatic isocyanates leads to a significant in-
crease in the rate of formation of gold nanoparticles responsible for the
PRB: OUAIPF versus aromatic OUA-1 (Fig. 2.10, curves 1, 2).
In the case of OUAIPF, the value of Dmax (1.22) is the highest among
all studied compositions with close interchain distances, while the highest
44 Additives in Polymers: Analysis and Applications

rate of a gain in D is typical for the oligo(ester acrylate) DMPF (Fig. 2.10),
although the attained value of Dmax is noticeably lower than that for other
compositions based on polyfurit.

FIGURE 2.10  Kinetics of PRB Accumulation in Matrices Containing no m-Toluene


Diisocyanate: (1) OUAIPF, (2) OUA-1 (for comparison), (3) DMPF, (4) OUM-4F, (5)
OUAIE, and (6) OUAIP.

At the same time, for “rigid” acrylate networks with short oligomeric
blocks, that is, OUM-4F, OUAIE, and OUAIP (Fig. 2.10, Table 2.4, com-
positions 9, 14, 15), the photolysis of the gold salt occurs in the same man-
ner, but almost no absorption is observed in the visible region.
In summary of the above-described data on the effect of the parameters
of the acrylic polymer network on the generation of gold nanoparticles,
it should be emphasized that, to a certain extent, this effect is leveled off
through the method of introduction of HAuCl4 via its dissolution in MEG
or incomplete consumption of double bonds during 3D polymerization
(Fig. 2.8). The use of MEG as a monomer results in an increase in the
internodal distance, while incomplete polymerization causes an overall
decrease in the network density. In the present work, acrylic oligomer net-
works with glass transition temperatures Тg from –15°С (oligomer OUM-
Insight Into New Application Aspects 45

3) to >80°C (aromatic acrylates) were studied, although most experiments


were performed at a temperature above Tg of the matrix because the tem-
perature of the sample attained 90°С when the samples were irradiated
with the nonfiltered light of the mercury lamp at a power of 1000 W.
The next stage of our study was related to gaining insight into the effect
of groups introduced into the oligomeric block – specifically in terms of
their electronic and steric properties – on the formation of gold nanopar-
ticles (Fig. 2.11). In order to reveal the structure of the block, no MEG,
which is an active solvent for the gold salt, was added to the compositions.
It turned out that, even for the short-chain oligo(carbonate methacrylate)
OCM-2 and its oligomer homologue OCM-2-1, gold nanoparticles may be
generated with approximately the same efficiency as in the case of OUM
and OUA with long oligomeric blocks (Fig. 2.11, curve 1).

FIGURE 2.11  Effect of the Structure of the Oligomer Block in Diacrylates on the
Kinetics of PRB Generation: (1) OCM-2, (2) OCMN, (3) OCMC, (4) OCM-2-1, (5) OCM-
2 + FHAC, (6) DMEG, and (7) DMTG.

This extremely unexpected and efficient formation of the PRB in the


matrix of OCM-2 is probably due to the participation of carbonate groups
in photoprocesses (OCM-2 is one of the best substrates for radiation-
induced or photoinitiated polymerization) or an increase in the network
elasticity due to the “free rotor” effect of the –C(O)–O– group. At the
46 Additives in Polymers: Analysis and Applications

same time, halogenated, perfluorinated, and bulky carborane groups in


the oligomeric block insignificantly affect the generation of the PRB (Fig.
2.11, curves 2, 3, 5). However, in a very “rigid” network based on DMEG,
the formation of nanoparticles is less efficient (Fig. 2.11, curve 6).
A specific behavior is demonstrated by compounds containing sulfide
sulfur: In the DMTG-based composition 24, the gold salt is consumed at
the normal rate, but there is no absorption in the visible region (Fig. 2.11,
curve 7). It may be supposed that 4 nm gold nanoparticles consisting of
~140 Au atoms (according to the mass spectrometry data) are formed in
this case of absorption in the UV region,25 as in the case of DMTG, or a
bimodal distribution of nanoparticles is realized with two PRB bands at
560 nm and a shoulder at 370 nm.26
It turns out that only in OUA matrixes based on m-toluene diisocyanate
does a band at 340 nm (along with the PRB near 530 nm) appear during
generation of gold nanoparticles. The absorption at 340 nm occurs im-
mediately after consumption of the gold salt before the appearance of the
PRB, which then increases together with the PRB and does not disappear.
Figure 2.12 shows the spectra of PRB development in OUMs based on
oligotetrafuran-α,ω-diol and ethylene glycol monoacrylate, which differ
only in the used diisocyanate: m-toluene diisocyanate or isophorone diiso-
cyanate. The indicated band is not seen in the case of aliphatic isophorone
diisocyanate. Moreover, the band at 340 nm is absent in the case of compo-
sition 9, including aliphatic OUM_4F, which is N-phenylsubstituted at the
urethane group. It is possible that in flexible-chain polyurethanes based on
m-toluene diisocyanates, the same electronic interactions are realized as
those in sulfur-containing matrixes,26 which leads to the formation of gold
particles with a bimodal distribution (30–40 and ~4 nm) and two absorp-
tion bands at 560 nm and a shoulder near 340 nm.
Earlier, the effect of regeneration of the gold salt was revealed when
the reduced gold-containing film was heated in the PMMA matrix.27 Fig-
ure 2.13 illustrates the kinetics of evolution in the intensity of the band
of HAuCl4 and of the PRB of gold nanoparticles in the OCM-2-based
network at an initial salt concentration of 3 wt%. The photolysis of the
gold salt was performed photochemically, and, after its complete decom-
position, samples were kept in a thermostat at 70 and 110°С. Heating of
the film at 70 and 110°C leads to the regeneration of the salt and its sub-
sequent slow consumption (Fig. 2.13, curves 1, 2). However, this effect
is not exhibited under our “standard” conditions during simultaneous UV
irradiation and heating at 90°С, owing to the photoreduction of the salt.
Insight Into New Application Aspects 47

FIGURE 2.12  Absorption Spectra of OUM-1 After Irradiation for (5) 15, (3) 40, and (1)
60 min and of OUAIE Containing no m-Toluene Diisocyanate After Irradiation for (4) 20
and (2) 80 min.

FIGURE 2.13  Thermolysis of Gold-Containing Films Based on OCM-2 (composition


5): (1, 2) Changes in the Optical Density of the HAuCl4 Band at 70 and 110°C; (3, 4) the
Same for the PRB at 110 and 70°C.
48 Additives in Polymers: Analysis and Applications

The concentration of PRB-responsible, “photostable” Au nanoparticles


reaches a maximum during heating at 110°С but not at 70°С and then de-
creases; that is, under these conditions, nanoparticles participate in reverse
oxidation reactions up to the regeneration of Au3+. A drop in the intensity
of the PRB is observed only at high [HAuCl4]0 (2–3 wt%) and is not ob-
served at 70°С at any concentrations of the salt.
As was shown above, parallel reactions of acrylate photopolymeriza-
tion and gold salt photoreduction give rise to a transparent, colorless ma-
terial containing dissolved gold. Films based on this material are stable
enough; after 25 months, the samples became only pale yellow without
any PRB traces. The obtained matrix may serve as a registering medium
for optical data recording because a further external effect – heating and/
or irradiation – initiates the agglomeration of gold nanoparticles, and the
plasmon resonance band of gold nanoparticles arises in the visible spectral
region (500–600 nm) at the point of external effect application.
A principal advantage of these registering media is their extremely
high sensitivity. The molar extinction coefficient at the PRB wavelength
is five orders of magnitude higher than that for a typical dye, indocyanine
green (ε = 1.08 × 104 L/(mol·cm) at 778 nm).24
The first experiments demonstrated that gold-containing polyacrylic
films show promise as a registering medium during both thermal and pho-
tochemical external effects. In Figure 2.14a, the image obtained after 5
min UV irradiation of a film based on composition 1 through a metallic
grid with a hole diameter of 200 μm is presented, while in Figure 2.14b
an arbitrary image obtained on the surface of the transparent colorless film
by means of a point heating element with a temperature of 150–160°С is
shown. The colored regions absorb at the PRB wavelength.
Insight Into New Application Aspects 49

FIGURE 2.14  Images obtained (a) during irradiation of the gold-containing transparent
film based on composition 1 through a metallic grid with a hole diameter of 200 μm and (b)
by means of a point heating element with a temperature of 150–160°C. Magnification ×45.

As a result, having no analogous highly sensitive polymeric media, a


3D network polymer containing nanoparticles of Au0 for optical informa-
tion recording was created.28

APPLICATION OF MOLECULARLY IMPRINTED POLYMERS


FOR SURFACE ACOUSTIC WAVE SENSOR ELEMENTS WITH
HIGH SENSITIVITY

Chemical sensors using surface acoustic wave technology (SAW) are


characterized by high reliability and sensitivity, and are easy to produce
and economical at mass production.28 They beneficially differ from other
sensors by their small size, weight, and compatibility with the format of
modern digital devices. Moreover, they can be used in passive and wire-
less regimes.29 The main principle of their action is that the change in the
number of molecules on the acoustic line surface causes a change in the
rates of spreading and decay of signal registered at the end of SAW line.
However, the chemical selectivity of existing sensors based on SAW tech-
nologies is not sufficient to detect with high probability a specified com-
pound with one detector.
In recent years, some new fast methods for detecting vapors of explo-
sives and narcotics have been developed based on molecularly imprinted
polymers.30–32 In this technique, some polymerizable compound (mono-
50 Additives in Polymers: Analysis and Applications

mer, oligomer, or their mixture) that is able to create specific intermolecu-


lar bonds with an analyte (a substance that is to be detected) is chosen.
Then, a liquid mixture of these components is photopolymerized, and the
analyte molecules are removed from the polymer phase by washing, heat-
ing, evacuating, etc. As a result, a special polymer with “nanopores” hav-
ing the size and form of the analyte molecule (solidified imprint of ana-
lyte) is formed. A molecularly imprinted polymer can be characterized as
a “sewed up” polymer phase with predominant absorption selectivity with
respect to the analyte. Depending on the special features of the synthetic
procedures, a distinction is drawn between covalent and noncovalent im-
printing.
The aim of this work was to develop sensitive elements for a SAW gas
detector based on highly sensitive polymeric films obtained from photopo-
lymerizable acrylic compositions.
First, we studied the mechanism of diffusion and absorption processes
of the analyte molecules in polymer films containing microcavities with
selective absorption centers. A complete system of partial differential
equations with initial and boundary conditions that describe the absorp-
tion–diffusion processes was derived, and an algorithm for its solution
was developed.34
Then the experimental study of absorption–desorption of an analyte
by a molecularly imprinted polymer film was performed with the use of
SAWs. The dependence of the phase Δϕ of the SAW on the mass of the
substance absorbed in the film was derived.
Morpholine (C4H8ONH) was selected as the analyte for the absorption
experiments because it is the simplest structural simulator of explosives
with the structure of a cyclic amine, is soluble in most organic solvents,
and has a low boiling point (129°C).
Molecularly imprinted polymer films were obtained by photopolymer-
ization of the diacrylate glicerolate bisphenole

on the surface of the sensitive element of the SAW sensor in the pres-
ence of morpholine as a template following the procedure described by
Binchack et al.30 The film studied had a length of 3 mm, and a thickness
of 1.5 μm.
Insight Into New Application Aspects 51

For experimental studies of the analyte absorption–desorption by a


molecularly imprinted polymer film, we constructed a special installation
unit, schematically shown in Figure 2.15.33

FIGURE 2.15  Units for experimental studies of analyte absorption-desorption by a


molecularly imprinted polymer film with the use of surface acoustic waves. See text for
notation.

It consists of a measuring chamber (а) containing a chemical sensor


based on a SAW delay line and a gas sample preparation block (b). The
sample preparation block is a vaporization chamber (1) placed in a ther-
mostat (2). The membrane (3), made of an elastic silicone polymer mate-
rial, is mounted in the upper part of the vaporization chamber. Through
this membrane, an analyte sample is introduced with the use of a standard
chromatographic microsyringe (4). The analyte is contained in contain-
er (5) in the liquid or gaseous state. The temperature of the vaporization
chamber is maintained at a level higher than the boiling point of the ana-
lyte. The chamber is blown with a carrier gas supplied through the com-
munication line (6) from a cylinder (7). A portion of liquid analyte exiting
from syringe needle vaporizes, and its vapors are carried with a carrier gas
flow into pipeline (8) and thence to the sensor through the entrance pipe
(9). The analyte vapors are absorbed by molecularly imprinted polymer
film (10) on the surface of the SAW sensor (11). They correspond to the
film (16) on the surface of the SAW detector (3) shown in Figure 2.16.
52 Additives in Polymers: Analysis and Applications

FIGURE 2.16  Measuring chamber and chemical detector based on a surface acoustic
wave sensor. See text for notation.

The chemical sensor on the SAW sensor in measuring chamber (a)


has been described by us earlier.34,35 In Figure 2.16, the construction of
the measuring chamber and sensor device used in this work are shown in
more detail.
In this construction, the SAW sensor is situated in a hermetically sealed
chamber (1) on the base (2). The sensor (3) is a delay line with an acoustic
line from a piezoelectric material, e.g., ST quartz or LiNbO3. The delay
line is fastened to the “hot” surface (4) of a Peltier thermoelectric cell (5).
In this variant, the sensor with delay line is fastened to the thermoelectric
cell using a heat-conducting paste (6) usually employed in the production
of radio-electronic equipment. The thermosensitive resistor (7) is placed
on the working surface of the thermoelectric cell to measure its tempera-
ture. The resistor is connected to a temperature control block through con-
tact line (8). A hermetically sealed, heat-insulating gasket (9) is situated
between the base (2) and side walls of the chamber (1). Interdigital trans-
Insight Into New Application Aspects 53

ducers (10) and (11) are situated on the surface of the delay line. Electric
transmitting lines for the introduction (12) and outputting (13) of sinu-
soidal microwave signals are connected to the transducers. In the usual
SAWs, acoustic absorbers (14) and (15) are placed between the ends of
the piezoelectric plate and interdigital transducers for absorbing spurious
SAWs reflected from acoustic line edges. The molecularly imprinted poly-
mer film (16) whose absorption properties are studied is situated between
the input (10) and the output (11) interdigital transducers. Gas pipes for
the introduction (17) and removal (18) of the air flow to be analyzed pass
through the hermetically sealed chamber case.
A SAW excited by the input interdigital transducer delay line propa-
gates along the acoustic line in its surface layer with thickness on the order
of the acoustic wavelength. For this reason, these waves are very sensitive
to the state of the surface and the properties of the medium adjacent to the
surface.
Changes in the physical properties of a molecularly imprinted polymer
film adjacent to the surface of the acoustic line, for instance, in its mass or
viscosity, caused by the absorption of an analyte result in changes in the
parameters of the SAW propagation (the rate of propagation and damping
coefficient). In practice, changes in the phase or amplitude of the electro-
magnetic signal passing through the delay line, caused by changes in the
amplitude and phase of the SAW under the action of sorption processes,
are measured.
In this work, we studied the absorption of analytes by molecularly im-
printed polymer films synthesized from oligoester acrylates in the pres-
ence of one of the analytes as a template. Special attention was given to the
thermal stabilization of delay lines on the SAWs. Commercial single-stage
thermoelectric cells with a standard control circuit provided temperature
stability of at least 0.003°С during 10 min and at least 0.01°С during 10
h over the temperature range 2–67°С at 20–40°С temperature of the me-
dium around the measuring chamber.
During measurements, a flow of dry, chromatographically pure ni-
trogen is passed through the measuring chamber (dew point not higher
than –60 С) at a controlled flow rate of 5–30 cm3/min. The analyte vapors
were introduced into the nitrogen flow using the microsyringe (4) through
membrane (3) of vaporization chamber (1) (Fig. 2.15). The temperature of
vaporization was 130°С, which was higher than the boiling points of all
the analytes used in our experiments. The temperature of the thermostat
54 Additives in Polymers: Analysis and Applications

(2) was also 130°С, and the temperature of the SAW sensor (11) with the
absorbing molecularly imprinted polymer film (10) was 40°С.
A portion of the analyte vapor formed in vaporization chamber (1) after
its injection with the microsyringe passed through gas pipe (8) into the
sensor device and was absorbed by the polymer film (10) on the surface
of the SAW sensor (11). After the absorption was completed and analyte
vapor removed from the sensor device with carrier gas flow, the desorption
of the analyte from the film began.
It was found in the measurements of the amplitude–frequency charac-
teristics of samples with polymer films having various thicknesses without
an adsorbed analyte that, at film thicknesses no larger than 1.5 μm, studies
at frequencies up to 80 MHz could be performed. Subsequently, all mea-
surements with molecularly imprinted polymer films with such a thickness
were performed at an even higher frequency of 120 MHz.
The experimental time dependences of the phase shift Δϕ of the SAW
sensor signal are shown in Figure 2.17. Experiments were performed for a
molecularly imprinted polymer with 10% sewn morpholine with sequen-
tially injecting 0.4 μL acetone, 0.1 μL ethanol, and 0.1 μL morpholine into
the carrier gas. Note that, first, we also studied SAW sensors with 5% sewn
morpholine, but sensors with 10% morpholine were in all respects more
preferable, and, subsequently, only sensors with such molecularly imprint-
ed polymers were made. All the sensors were placed in a vacuum chamber
prior to measurements and held at 40°С in 10–5 Pa vacuum for 3 h.

FIGURE 2.17  Time dependence of signal phase shift Δϕ after the injection of (1) 0.1 μL
morpholine, (2) 0.1 μL ethanol, and (3) 0.4 μL acetone into carrier gas.
Insight Into New Application Aspects 55

Changes in the output signal (response) phase when analyte vapors


passed through the measuring chamber and after analyte vapor left the
chamber, which occurred in approximately 10 s after the largest change in
the response, are shown in Figure 2. 17. It follows from these curves that
the SAW sensor with a molecularly imprinted polymer is several times
more sensitive to morpholine than to acetone or ethanol. We also see that
the phase changes after the removal of morpholine vapor return to the ini-
tial level much more slowly than with the other analytes. Complete sample
restoration at room temperature and atmospheric pressure requires sub-
stantial time, on the order of several hours.
Changes in the phase of surface acoustic waves caused by the injection
of aqueous solutions of morpholine with various concentrations into the
vaporization chamber are shown in Figure 2.18. Each subsequent injection
of the analyte was made without waiting for the complete restoration of
the molecularly imprinted polymer, immediately after heating the sample
for 10 min directly in the measuring chamber in a flow of pure nitrogen.
The experimental conditions were TSAW = 42°С, sample volume = 0.2 μL,
and polymer molecularly imprinted by 10%.

FIGURE 2.18  Time dependence of signal phase shift Dj for aqueous solutions of
morpholine of various concentrations: (1) 10, (2) 5, (3) 1, and (4) 0%.
56 Additives in Polymers: Analysis and Applications

We see from Figure 2.18 that the phase shifts over the whole desorption
region of the time dependence curve is higher when the initial morpholine
concentration in water is higher. Accordingly, the time of restoration of the
molecularly imprinted polymer sample increases. Crude estimates show
that, in the region of slow morpholine desorption from the film, the signal
phase changes are proportional to the concentration of morpholine during
the whole time of desorption.
It was established that it is possible to carry out relative measurements
without full restoration of the molecularly imprinted polymer sample after
its treatment by the analyte. It was enough to get it in the nitrogen flow at
65°C for 10 min; after that, the sample properties practically do not change
for some hours.
The experimental time dependences of phase shifts were approximated
by theoretical curves calculated with the use of optimized kinetic param-
eter values. The kinetic parameter characterizing the selectivity of absorp-
tion was singled out.33
Moreover, we proposed to use a modified method to measure the re-
sponse of the sensitive element based on the molecularly imprinted poly-
mer, which takes into account the size of output signal and its relaxation
time simultaneously. That is, we proposed to use an integral response –
the dependence of phase (amplitude) changes on time. Using this method,
we have tested the selectivity of the developed SAW sensor element to
morpholine as compared with benzene, cyclohexane, and dioxane. The
integral responses (in dB) on analytes containing these substances for in-
tegration time = 300 s are presented in Table 2.5.36 It is evident that the
integral response on the morpholine-containing solution is 10 dB higher
than on other solutions.

TABLE 2.5  Integral Responses in dB for Different Analytes (10 volume % solutions in
ethanol).
Analyte Probe Vol- Sensor Tem- Velocity of Car- Integral Re-
ume, ml perature, °С rier Gas, cm3/ sponse in dB
min.
Benzene 0.4 28 6.1 -23
Insight Into New Application Aspects 57

Cyclohexene 0.4 28 6.1 -15.1

Dioxane 0.4 28 6.1 -10.7

O O

Morpholine 0.4 28 6.1 0

O NH

It should be noted that the described SAV sensitive element with mor-
pholine-modified polymer film is only one example of the potential uses of
molecularly imprinted polymer technology for the fabrication of sensitive
gas detectors.

CONCLUSIONS

1. The possibility of generation of surface plasmon resonance by gold


nanoparticles formed in a 3D network matrix produced by irradiat-
ing a liquid acrylic composition containing a dissolved gold salt
with a mercury lamp is demonstrated for the first time; irradiation
is needed to accomplish the photoreduction of Au3+ to Au0 and pho-
toinduced polymerization of the test acrylates.
2. The efficiency of the formation of gold nanoparticles is determined
by the parameters of the polymer network and by the chemical
structure of the oligomer block, with the most suitable matrixes
being those having a loose network and containing groups capable
of participating in complexation.
3. Chlorine-containing products of HAuCl4 reduction can influence
both the rate of reduction of the salt and the process of forma-
tion of gold nanoparticles. It has been shown that the SPR of gold
58 Additives in Polymers: Analysis and Applications

nanoparticles can be generated in a 3-D network matrix obtained


during UV irradiation of a liquid acrylic composition containing
dissolved gold salt as a result of Au3+ photoreduction accompa-
nied by photoinitiated polymerization of acrylates. Decisive fac-
tors determining the accumulation rate of nanoparticles and their
maximum concentration are the density of the acrylic network and
the complexing ability of the oligomeric block. These parameters
affect the rate of generation of gold nanoparticles but not the limit-
ing optical density of the plasmon resonance band of nanoparticles.
4. The kinetic data on the consumption of HAuCl4 show that, in
oligomeric matrixes with a long oligomeric block, the rates of
salt consumption are close. This process proceeds in the gel and
is completed long before the end of network formation. The gold
salt inhibits the polymerization of acrylates. Nevertheless, in all the
studied cases, we managed to obtain high-quality films in which
the PRB was generated in the visible spectral region after subse-
quent irradiation.
5. It has been found that only in oligo(urethane(meth)acrylate) ma-
trixes based on m-toluene diisocyanate does the band at 340 nm
arise (it increases and does not disappear), along with the PRB near
560 nm, during the generation of gold nanoparticles.
6. The obtained matrixes may serve as registering media for optical
data recording because the agglomeration of gold nanoparticles is
initiated by subsequent external effects – heating and/or irradia-
tion – and the plasmon resonance band of gold nanoparticles arises
in the visible spectral region (500–600 nm) at the point of external
application.
7. Polymer films containing microcavities with selective absorption
centers were obtained from oligoester acrylates.
8. It was found in measurements of the amplitude–frequency charac-
teristics of samples with polymer films having various thicknesses
without a sewed analyte that, at film thicknesses no larger than 1.5
μm, studies at frequencies up to 80 MHz could be performed.
9. Experimental studies of absorption–desorption of morpholine as
an analyte by a molecularly imprinted polymer film (obtained with
morpholine as a template) using the SAWs demonstrated signifi-
cantly increased sensitivity of the polymer sensor element to mor-
pholine in comparison with other analytes.
Insight Into New Application Aspects 59

10. A new method to measure the response of the sensitive element


based on the molecularly imprinted polymer, which takes into ac-
count a size of output signal and its relaxation time simultaneously,
has been proposed.

KEYWORDS

•• Oligomeric composition
•• oligourethane acrylate
•• oligocarbonate methacrylate
•• gold nanoparticles
•• surface plasmon resonance
•• molecularly imprinted polymer
•• acoustic wave sensor

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2005, 50, 651.
CHAPTER 3

ON THE SPECIFIC REACTIVITY


OF CARBOOLIGOARYLENES:
REPRESENTATIVES OF OLIGOMERS
WITH CONJUGATE SYSTEM
V. A. GRIGOROVSKAYA
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow,
Russia; Email: valgrig3@ mail ru

CONTENTS

Abstract................................................................................................................ 64
Introduction.......................................................................................................... 64
Experimental Part................................................................................................. 65
Results and Discussion........................................................................................ 65
Keywords............................................................................................................. 73
References............................................................................................................ 74
64 Additives in Polymers: Analysis and Applications

ABSTRACT

Features of the reactivity of soluble carbooligoarylenes (COA) based on


the condensed aromatic compounds such as naphthalene, anthracene, and
their mixtures with benzene in different chemical processes have been
studied. It has been shown that their increased reactivity in various chemi-
cal processes is due to the presence of long conjugation system in their
structure. This feature leads to the polymeranalogical transformations of
сarbooligoarylenes, which are not possible for corresponding monomeric
and dimeric compounds. Because of the characteristics of dissolving in
organic solvents and softening on heating, oligoaryilenes represent a base
for the synthesis of a series of products of different functions, particularly,
polymer materials resistant to thermal, thermooxydative, thermochemical,
and radiation–thermal influences. It was established that effective stabiliz-
ers of thermal-oxidative degradation for industrial polymers, flame retar-
dants, water-soluble oligomeric cation exchange resins, and antifriction
additives can be obtained by using soluble COA as the base. The totality
of this data suggests that the range of applications of soluble COA can be
much greater.

INTRODUCTION

Being representatives of the polymers with conjugate system, carbooli-


goarylenes (COA) are of great interest due to the increasing demand for
highly resistant polymer materials in different industrial fields. The aim of
this research is to obtain soluble COA by one-stage synthesis from con-
densed aromatic compounds such as naphthalene, anthracene, and their
mixtures with benzene. We have developed two methods for the synthesis
of COA: a thermal dehydropolycondensation 1,2 and the cationic oxida-
tive dehydropolycondensation in the presence of a Friedel–Crafts cata-
lyzer and an oxidizer, proposed initially for the synthesis of polyphenyl-
ene.3 The application of the cationic oxidative dehydropolycondensation
method to a condensed aromatic compounds, first with naphthalene, then
with anthracene, as well as their mixtures with benzene, made it possible
to obtain oligomers that are soluble in organic solvents and that soften on
heating.4,5 We modified this method of synthesis of oligomers by using
copper chloride as an oxidant instead of nitrobenzene, thereby improving
On the Specific Reactivity of Carbooligoarylenes 65

the technological parameters of synthesis.6–8 This research focuses on the


systematic study of chemical properties of COA and their dependence on
the length of oligomeric chains, that is, the value of molecular weight (Mn).

EXPERIMENTAL PART

The aim of this study is to obtain soluble COAs by one-stage synthesis


from the condensed aromatic compounds naphthalene and anthracene
using the method thermal dehydropolycondensation 1,2 or cationic oxida-
tion.4–8 The fractionation of COA was performed by fractional precipita-
tion from benzene–methanol mixture or by exclusion chromatography (to
study the enthalpy of dissolution of COA). The column was filled with
styrene-divinylbenzene (SDV)-gel; tetrahydrofuran was used as an eluent.
The Mn of COA and of their fractions were measured in chloroform by
measuring the condensation heat effects.9 IR spectra were examined using
UR-20 instrument, electronic absorption spectra-SF-4 spectrometer. The
thermomechanical analysis (TMA) curves were recorded under a specific
load of 0.8 kg/cm and a rate of temperature increase of 1.5 deg/min. Ther-
mal stability was estimated by thermogravimetry on an automatic thermo-
balance ATB-2 or Perkin-Elmer. Stabilizing action of COA was studied in
reactions of non-initiated oxidation of ceresin at 170°C and 5% concentra-
tion of COA (above the critical). Content of SO3H groups in sulfonated
COA was measured by means of potentiometric titration. Enthalpies of
dissolution for oligoarylene on the base of naphthalene and its fractions in
benzene, toluene, and 1,2,4-trichlorobenzene were determined on a Calvet
calorimeter with margin error not more than 1%.

RESULTS AND DISCUSSION

THERMAL PROPERTIES OF COA

According to TMA, soluble COA softens on heating, but the repeated


heating after pressing of samples causes increase in their softening tem-
perature resulting in the formation of insoluble and non-fusible products.10
Thus, the insoluble and non-fusible products are the evidence of proceed-
ings of various condensation and polycondensation processes during heat
treatment of COA.
66 Additives in Polymers: Analysis and Applications

The study of COA by thermogravimetric analysis (TGA) method has


shown their property of high thermal stability both in an inert environ-
ment and in the air curing. The temperatures at which intensive weight
loss begin on the air for soluble COA, based on naphthalene, anthracene,
and mixtures of them with benzene, are >450°C–500°C, according to the
TGA data.11 It has been established that the insoluble fractions of the COA
have less resistance to thermooxidative degradation but greater stability
and greater amount of stable balance in inert atmosphere in comparison
with soluble fractions. TGA curves on the air for all soluble COA have
autocatalytic character that indicates the principle distinction of their de-
struction mechanism from that of saturated polymers.12 According to IR
spectroscopy and elemental analysis data, reactions of dehydropolycon-
densation similar to that observed at TMA and leading to the products
with less solubility and less resistant to thermooxydative destruction occur
during the induction period. After accumulating a certain concentration of
these structures, an intensive process of thermal oxidation begins. These
views are confirmed by the results of the absorption of oxygen by the solu-
ble and insoluble fractions of COA on static installation. Analysis of TGA
curves of soluble polymer-homological fractions of COA, differing only
in Mn values, established that in an inert atmosphere, the thermal stability
increases monotonically with increase in Mn and on air, its dependence
on Mn has more complex character: in the beginning, the thermostability
increases due to thermal destruction of COA on low-molecular fragments,
and then, after reaching a certain value of Mn at its subsequent increase,
thermostability on the air begins to decrease.13 This feature is connected
with the proceeding of two kinds of competing processes during heat treat-
ment on the air: thermal destruction with the formation of low-molecular-
weight fragments and thermooxidative destruction of insoluble fractions,
resulting in dehydropolycondensation reactions. Analysis of the products
formed during the heating of the COA samples with different values of
Mn up to the beginning of the intensive mass loss (~350°C) showed that
when the value of Mn of the original oligoarylene was higher, the con-
tent of insoluble fractions obtained was more and Mn of remaining soluble
parts was lower.14 These results indicate that most high molecular-weight
fractions of COA participate in the reactions of polycondensation in the
first instant, which confirms their high reactivity. Thus, these data suggest
that the reactivity in the polycondensation and oxidation processes of both
original COA and their fractions increase with increase in the Mn values.
On the Specific Reactivity of Carbooligoarylenes 67

STABILIZING ACTION OF COA

Previously, it was found that conjugated compounds are capable of show-


ing a stabilizing action in the processes of thermal-oxidative degradation
of various polymer systems.15 So it seemed important to study the influ-
ence of Mn value of soluble COA on their stabilizing activity. Polymer-
homological fractions of polyanthracene (PA) and polynaphtalene (PN)
with various values of Mn, obtained directly after synthesis were studied
as COA. Their stabilizing activity in the reactions of non-initiated oxida-
tion of ceresin at 170°C was studied.16 Fractions of the PA and PN with a
variety of Mn were identical among themselves, according to the data of IR
and electronic spectra, as well as the results of element analysis. Charac-
teristics of fractions of the PA, as well as 9,9′-bianthryl, which can be con-
sidered as the first member of the homologous series of oligoanthracenes,
are shown in Table 3.1.

TABLE 3.1  The Characteristics of the Fractions of Polyanthracene and Induction Time
(τind) of the Ceresin Oxidation at 170°C in the Presence of 5% PA

Polymer Matrix Tem-


Composite Con- perature of
Samples Mn τind, min
centration, ×10−17, Softening,
spin/g °C
1 2230 67 380 20
2 1620 31 320 23
3 1080 8.7 270 44
Fractions of polyanthra-
4 920 3.3 240 225
cene
5 780 1.6 210 2450
6 680 1.5 185 2060
7 – 1.5 165 1250
9,9′ -bianthryl 354 <10 −3
308 ~650

During the study of stabilizing action of PA fractions, it was found that


they can be both weak and strong inhibitors depending on their Mn values.
Strong inhibitors are characterized by occurrence of the critical concentra-
tions. The data from Table 3.1 show that at the inhibitor concentration of
5% (above the critical), the dependence of the induction period (τind) on Mn
68 Additives in Polymers: Analysis and Applications

value has a sharply defined extreme character with the maximum value of
τind (2450 min) at Mn = 780, which corresponds to 4–5 monomeric units
in the chain of the molecule. This value is more than 100 times greater
than the relevant values for PA with Mn = 2230 and 1620. It is interesting
to note that at Mn increase for PA from 550 to 780, the induction period is
increased from 1250 to 2450 min, while the concentration of PMC in the
inhibitor practically does not change (Table 3.1). It is also evident from
Table 3.1 that 9,9′-biantryl, characterized by the absence of paramagnet-
ism, provides induction period of 650 min. These results suggest that Mn
value is the determining factor for the stabilizing activity in the PA studied.
This assumption is confirmed by the data for PN, according to which when
the Mn value of PN is increased from 1100 to 1250, τind. also increases
from 21 to 124 min. By comparing the results of the PA and PN, it can be
observed that the stabilizing activity of COA depends significantly on the
structure of the basic unit, evidently on the conjugation extent in the seg-
ment. The extreme character of τind dependence on the Mn value of inhibi-
tor (COA) can be explained, as in the case of thermal-oxidative stability of
COA, by proceedings of two types of competitive processes. On the one
side, the increase of length of conjugate system causes decrease of excita-
tion energy of polymeric inhibitor molecules that increases the effective
rate constant of interaction between inhibitor and peroxidate radicals and,
hence, a speed of deactivation of these radicals. The last depresses the crit-
ical concentration of inhibitor and increases τind during thermooxidation.
On the other hand, during the process of increase in Mn, the probability of
oligomeric inhibitor interaction with air oxygen also increases. The first
consequence of that is the reduction of the effective concentration of the
inhibitor, and the second consequence is the appearance of the initiating
action of ex-inhibitor. At certain Mn value, the second factor starts to pre-
vail and an extremum appears on the curve of τind dependence on Mn. A po-
sition of the last depends on the structure of the oligomeric inhibitor chain.

SULFONATION OF COA

Interesting and significant results on the influence of Mn value on the reac-


tivity of COA were obtained during the study of COA sulfonation reaction,
which is characteristic of aromatic compounds.17 Sulfonation reaction was
examined for PN, main structural unit of which is 1,4–disubstituted naph-
On the Specific Reactivity of Carbooligoarylenes 69

tylene link.18 The analysis of the IR spectra of formed oligomeric products


has shown that they are sulfonic acids of oligoarylenes and joining of sul-
furic groups occurs, first of all, in 1,4-disubstituted rings of naphtylene
segments.19 Sulfonic acids of OA are readily soluble in water and insoluble
in organic solvents and are not softened or sublimated at high tempera-
tures. In the air, sulfonic acids of OA are stable up to 250°C.
It was noticed that polyphenilenes (PPh) show much less reactivity in
sulfonation process than PN. It is connected, apparently, with the differ-
ence in the degree of сonjugation of PPh and PN links. At the same time,
reactivity of COA is largely determined by the total length of oligomeric
chain, that is, Mn value, which can be observed from the data of Table 3.2.
It is evident from Table 3.2 that not all initial PNs participate in sulfona-
tion reaction at temperatures below 100°C. As one can expect, in less time
and lower temperature, the smaller part of the initial product reacts. It
should be noted that in all cases, the degree of sulfonation increases with
the decreasing of reacted PN part. The detected peculiarity is connected,
obviously, with unequal reactivity polymer-homological fractions, which
are parts of initial OA fractions being characterized by highest molecular
weight and possessing the highest reactivity that participate in the reac-
tion of substitution for the first time leading to the formation of products
with the highest degree of substitution of aromatic rings. If the reaction
conditions are hard, the most part of initial OA would enter the reaction of
substitution, but the average degree of sulfonation of resulting oligomeric
product decreases. At the same time, the tendency of decrease in the Mn
value of unreacted oligomer is observed (Table 3.2).

TABLE 3.2  Influence of Temperature and Time of Sulfonation of PN with Mn = 870 on


the Yield and Degree of Sulfonation of Oligomeric Products

Content of SO3H
Mn of
Temperature Share of Reacting Groups on a Link
Time (h) Unreacted
(°C) Oligomera in a Reaction
Oligomera,b
Product
40 0.5 0.10 5.20 790
60 0.5 0.23 1.70 740
60 4.0 0.61 1.3 720
80 0.50 0.73 1.20 720
80 4.0 0.93 0.81 700
70 Additives in Polymers: Analysis and Applications

100 0.5 1.00 0.64 –


100 19.0 1.00 0.74 –
140 0.5 1.00 2.21 –
Notes: It is defined as the difference between the unit (1) and a share of unreacted
a

PN, insoluble in water, but soluble in chloroform; bThe variability in all cases
does not exceed ±5%.

The conclusion about increase in reactivity of COA with the increase in


Mn value is confirmed also in the conditions when COA participates com-
pletely in the sulfonation reaction. So, sulfonation of PN with Mn = 870 at
100°C for 19 h results in a product containing 0.74 SO3H groups on a link,
which is contrary to a result of processing for PN with Mn = 1890, where
SO3H group contents in the final product reaches only 1.7 on a link. Thus,
from the totality of the above data, it can be concluded that the reactivity
of COA in sulfonation reaction increases with the increase in Mn value. It
is interesting to note that although it is impossible to reach such high de-
grees of sulfonation, this can be obtained in the soft conditions for PN for
the monomer naphthalene even under the most severe conditions.17
So, the data presented proves that as for the original COA and their
fractions with increasing value of Mn, their reactivity increases in different
processes such as polycondensation, thermal oxidation, interaction with
peroxidate radicals, and sulfonation.

COMPLEXING OF COA

It is known that polymers and oligomers with conjugate system, pos-


sessing high donor-acceptor activity, tend to form complexes before the
chemical reaction. Moreover, during different chemical transformations
of COA in organic solvent, the last may also complex with oligoarylene.
In this respect, the results of the influence of Mn value on the enthalpy of
dissolution of COA in solvents of different polarity are interesting. PN
and its fractions with various Mn values, obtained by exclusion chroma-
tography method, were the focus of this study. Dissolution enthalpies in
benzene, toluene, and 1,2,4-trichlorbenzene were determined on a Calvet
calorimeter with a margin error not more than 1%.20 Polymer homologity
of studied fractions is confirmed by the data of electronic and IR spec-
On the Specific Reactivity of Carbooligoarylenes 71

tra, as well as monotonous character of T softening dependency on Mn


value. Besides, according to the data of exclusion chromatography, all the
studied fractions are very homogeneous in composition and close to each
other. Enthalpy of dissolution of PN and its fractions in solvents of differ-
ent polarity are presented in Table 3.3.

TABLE 3.3  Thermal Effects of Dissolution of PN and its Fractions


∆H comm (cal/g)
Oligoarylene Mn In 1,2,4-trichlor-
In Benzene In Toluene
benzene
PN Original 790 + (3.3 ± 0.1) +(4.1 ± 0.2) +(6.4 ± 0.1)
450 −(3.5 ± 0.4) −(3 ± 0.1) −(0.7 ± 0.1)
490 – −(1.72 ± 0.14) –
550 −(2.7 ± 0.7) – +(0.4 ± 0.2)
640 −(2.1 ± 0.2) −(1.5 ± 0.2) –
Fractions of PN
Obtained by Meth- 710 – −(0.49 ± 0.1) –
od of Exclusion 780 – +(2.1 ± 0.2) +(5.0 ± 0.1)
Chromatography
850 – +(5.8 ± 0.1) –
1010 +(6.5 ± 0.1) +(6.5 ± 0.9) +(8.1 ± 0.7)
1260 – +(7.8 ± 0.7) +(10.4 ± 0.2)
1320 – +(11.4 ± 0.1) –

From Table 3.3, the following conclusions can be made:


i) A thermal effect of dissolution of initial unfractionated PN is high-
er than that of narrow PN fraction with similar Mn value.
ii) For each OA, the thermal effect of dissolution increases with the
increase in solvent polarity.
iii) The thermal effects of dissolution always increase with an increase
in fraction Mn.
The obtained results can be explained on the basis of the following
equation:

-DH comm = DH s–s +DH p–p – DH p–s ,



72 Additives in Polymers: Analysis and Applications

where ∆Hcomm is common enthalpy of dissolution of the polymer. ∆Hs–s


is enthalpy of disconnection of solvent molecules, ∆Hp–p is enthalpy of
disconnection of polymer molecules, and ∆Hp–s is enthalpy interaction of
polymer with the solvent.
Thus, the increase in the thermal effect of dissolution, observed with
the increase in solvent polarity, can be explained by a significant increase
of energy of the interaction of COA with the solvent. In order to compare
the dissolution results for various PN fractions in the same solvent, the
observed increase of the heat effect with the increase in Mn should also
be connected with a significant increase in the energy of the interaction of
PN with the solvent. The dependence of the enthalpies of COA dissolution
on Mn value is, obviously, connected with the features of COA electronic
structure, in particular, with the presence of conjugated double bonds in a
chain.
It should be noted that the dependence of soluble COA reactivity on
Mn value is not trivial. Indeed, according to the results of the construction
of molecular models of the COA, as well as the data from NMR of wide
lines, the structure of COA molecules is not coplanar, and the angle of
rotation between neighboring links increases from PPh to PA: if for PPh, it
is ~20°, then for PA, it is ≥45°.21 Nevertheless, the totality of the obtained
data let us to declare unequivocally that the effect of the conjugation is
sufficiently pronounced for soluble COA, owing to what a clear depen-
dence of reactivity of the last on chain length, that is, values of Mn, takes
place. This feature of COA reactivity makes it possible to achieve on their
basis a variety of polymeranalogic transformations, including that which
is basically impossible for corresponding monomeric and dimeric com-
pounds. Reaction products of interaction of soluble COA with n-diethy-
nylbenzene,22,23 polyethyleneglycol, and oligomers on its basis,24 and ep-
oxy compounds such as epichlorohydrin, glycidol, glycidilmethacrilat,25–28
and polyoximethylenes 29–32 after hardening allow to obtain various poly-
meric materials with the desired set of properties, particularly, high stabil-
ity to thermal, thermooxidizing, thermochemical, and radiation-thermal
influences. It should be noted that the analysis of fractionated samples of
oligomeric products of COA transformations has shown that the higher
is the fraction Mn, the larger is the degree of substitution in the aromatic
link.23,25 The specific reactivity of soluble COA allows to synthesize effec-
tive stabilizers of thermooxidative degradation of industrial polymers,33,34
On the Specific Reactivity of Carbooligoarylenes 73

fire retardants,35 oligomeric sulfoacids, including water soluble,36 antifric-


tional additives 37,38 as their base
The analysis of literature data allows us to assume that the dependence
of reactivity on chain length has enough general character for polymers
with a system of conjugated bonds contrary to polymers with saturated
bonds in chains. So, Hutareva et al39 and Jandarova et al40 reported that
at decarboxylation of polypropiolic acid, the increase in chain length es-
sentially influences the process course. A change of a rate and a direction
of polyoxiarylenes reactions in comparison with model compounds were
also obtained by Liogon et al.41
In conclusion, we note that results obtained in the present study ex-
hibit the clear dependency of reactivity of soluble COA on their molecular
weight value. This property allows us to synthesize different products with
soluble COA as a base. Finally, it can be observed that these results give
the grounds to believe that the range of use of soluble COA and products
of their polymeranalogic transformations can be expanded in future.

KEYWORDS

•• Carbooligoarylene
•• conjugate system
•• benzene
•• naphthalene
•• anthracene
•• dehydropolycondensation
•• thermooxydative
•• thermochemical
•• thermoradiative stability
•• solubility
•• molecular weight sulfonation
•• polymer
•• homolog
•• oligomer
74 Additives in Polymers: Analysis and Applications

REFERENCES

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2. Berlin, A. A.; Grigorovskaya, V. A.; Kushnerev, M. Ya; Skachkova, V. K. Structures
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goarylenes. USSR Inventor’s Certificate №. 298613, B. I. 11, 1971.
6. Astrakhantseva, N. I.; Brikenstein, A. A.; Berlin, A. A.; Grigorovskaya, V. A.;
Skachkova, V. K. Influence of synthesis conditions on the yield, molecular weight and
structure of oligoarelenes obtained in the presence of aluminium chloride and cupric
chloride. Polym. Sci. A” (in Rus.). 1973, 15, 54.
7. Astrahanceva, N. I.; Brikenstein, A. A.; Berlin, A. A.; Grigorovskaya, V. A.; Sh-
vetsova, S. I. Method of Producing of Oligoarylenes. USSR Inventor’s Certificate, №
358325, B.I .№ 34, 1972.
8. Kostenkova, L. S.; Iotkovskaya, L. A.; Kuznetsov, V. V.; Siling, M. I.; Grigorovskaya,
V. A. Improved technology of oligoarelene synthesis. Plastics (in Rus.). 1986, 5, 10.
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study of oligomeric arylenes. Polym. Sci. B (in Rus.). 1970, 12(11), 793.
11. Berlin, A. A.; Belova, G. V.; Grigorovskaya, V. A. Thermostability of of oligomeric
arylenes. Polym. Sci. A (in Rus.). 1970, 12(10), 2351.
12. Berlin, A. A.; Grigorovskaya, V. A.; Selskaja, O. G. Thermostability of fractionationed
samples of some oligoarylenes. Polym. Sci. A (in Rus.). 1970, 12(11), 2541.
13. Grigorovskaya, V. A.; Selskaja, O. G.; Khakimova, D. K.; Berlin, A. A. Thermal
transformations of oligoarylenes. J. Therm. Anal., (in Rus.). 1975, 8, 431.
14. Grigorovskaya, W. A.; Selskaya, O. G.; Astrachanzeva, N. I.; Berlin, A. A. Influence
of some factors on the thermostability of oligoarikebes. Plastic Kautchuk, (in Rus.).
1974, 21, 897.
15. Berlin, A. A.; Bass, S. I. Ageing and stabilization of polymers, Moscow, “Khimia”
(“Chemistry”, in Rus); Publishing House: Moscow, 1966; p 129.
16. Firsov, A. P.; Grigorovskaja, V. A.; Pazhitnova, N. V.; Ivanov, A. A.; Berlin, A. A.
Some factors influence on the stabilizing activity of oligoarylenes. Polym. Sci. A (in
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17. Vorozhtsov, N. N. Bases of Intermediate Products and Dyes. Izdatel’stvo nauchno-


texnicheskoi literaturi, (“Science-Technology”, in Rus.); Publishing House: Moscow,
1955; p 98.
18. Berlin, A. A.; Grigorovskaya, V. A.; Kissin, J. V. Study of oligoarilenes structure using
IR- spectroscopy. Polym. Sci. A (in Rus.). 1970, 12, 1497.
19. Grigorovskaya, V. A.; Davydova, G. I.; Berlin, A. A. Some peculiarities of sulfonation
reaction of oligomeric arylenes. Polym. Sci. B (in Rus.). 1980, 22, 315.
20. Grigorovskaya, V. A.; Miroshnichenko, E. A.; Kuzaev, A. I.; Vorobjeva, V. P.; Lebedev,
Y. A. On the influence of average moleculae nass on dissolving enthalpy of fractioned
oligoarylenes. Reports of Russian Academy of Sciences. Ser. Chem. (in Rus.,). 1985,
284, 647.
21. Berlin, A. A.; Grigorovskaya, V. A.; Kushnerev, M. Ja; Urman, Ja. G. Structure of
oligomers on the base of benzene, napthaline and anthracene. Proc. Acad. Sci. USSR,
Ser. Chem. (in Rus.). 1969, 11, 2568.
22. Berlin, A. A.; Skachkova, V. K.; Grigorovskaya, V. A.; Khoroshilova, I. P. et al. Meth-
od of producing of compositions. USSR Inventor’s Certificate №473727, BI №22,
1975.
23. Berlin, A. A.; Skachkova, V. K.; Grigorovskaya, V. A.; Kuzaev, A. I.; et al. Interaction
of oligoarylenes with p- diethylbenzene. Polym. Sci. A” (in Rus.). 1979, 21.
24. Masenkis, M. A.; Khoroshilova, I. P.; Avrasin, J. D.; Berlin, A. A.; Grigorovskaya, V.
A.; Skachkova, V. K. et al. About compositions preparation. USSR Inventor’s Certifi-
cate №77639, 1974.
25. Grigorovskaya, V. A.; Mordvinova, N. M.; Begun, B. A.; Yartseva, I. V. Interaction of
oligoarylenes and epichlorohydrin. Polym. Sci. B” (in Rus.). 1992, 33, 29.
26. Grigorovskaya, V. A.; Mordvinova, N. M.; Begun, B. A.; Yartseva, I. V.; Kuznetsov,
Y. L. Synthesis and properties of chlorohydrine-substituted oligoarylenes. Plastics (in
Rus.). 1993, 6, 8.
27. Grigorovskaya, V. A.; Yartseva, I. V. Polymers based on fluoro(meth)acrylates and
fluropolyimides. Polym. Sci. B, (in Rus.). 2000, 42, 534.
28. Grigorovskaya, V. A.; Begun, B. A.; Yartseva, I. V.; Tikhomirova, I. V.; Tugov, I. I.
Interaction of oligoarylenes with epichlorhydrin. Plastics (in Rus.). 1991, 2, 51.
29. Grigorovskaya, V. A.; Lazareva, O. L.; Selskaya, O. G. Oligomethylolnaphthylenes
for thermostable materials and method of their production. USSR Inventor’s Certifi-
cate № 860479, 1981.
30. Aseeva, R. M.; Grigorovskaya, V. A. Modified carbooligoarylenes as a base for ther-
mostable and combustible materials, Proceedings of International Conference on
“Composite-2004", Moscow, 2004, p 157.
31. Aseeva, R. M.; Grigorovskaya, V. A. Thermochemical properties of cured carbooli-
goarylenes, Proceedings of 6th International Conference on “Polymer materials of
reduction flammability”, Vologda, Russia, 2011, p 90.
32. Grigorovskaya, V. A.; Zaichenko, N. L.; Aseeva, R. M. About interaction of
oligoarylenes with polyoxymethylenes. Plastics (in Rus.). 2005, 9.
33. Zelenetskaya, T. V.; Grigorovskaya, V. A.; Aseeva, R. M.; Berlin, A. A. Stabilization
of three dimensional polyestermethacrylates on the base of α, ω-dimethacrylate
diethyleneglicole. Plastics (in Rus.). 1974, 1, 60.
76 Additives in Polymers: Analysis and Applications

34. Berlin, A. A.; Shutov, F. A.; Aseeva, R. M.; Grigorovskaya, V. A. Method of stabiliza-
tion of polymeric materials. USSR Inventor’s Certificate №. 328725, 1972.
35. Aseeva, R. M.; Grigorovskaya, V. A.; Ruban, L. V.; Zaikov, G. E. Oligobromoarylenes
as fusible and soluble product for production of polymer materials with law combusti-
bility. USSR Inventor’s Certificate № 1413930, 1988.
36. Grigorovskaya, V. A.; Pikalov, A. E.; Davydova, G. I. et al. Sulfonic acids of oli-
goarylenes as catalysts of ion-exchanging type. USSR Inventor’s Certificate №
603647, B.I. №15, 1977.
37. Denisova, O. V.; Rutman, P. A.; Lobanzova, V. S.; Fanstein, I. V.; Grigorovskaya,
V. A.; Kostenkova, L. S. Antifrictional lubricant for mechanical treatment of metals.
USSR Inventor’s Certificate № 1778164, B.I. № 44, 1992.
38. Grigorovskaya, V. A.; Lobancova, V. S.; Rutman, P. A. Study of different carbooli-
goarylenes as antifriction compounds in solid lubricating compositions, Proceedings
of 6th Conference of Chemistry and Physics-chemistry of Oligomers, Kazan, Russia,
1997, p 74.
39. Hutareva, G. V.; Jandarova, M. L.; Shishkina, M. V. Polym. Sci. B (in Rus.). 1970,
12(7), 515.
40. Jandarova, M. L.; Gejderih, M. A.; Krenzel, B. A. Study of decarboxylation reaction of
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41. Liogon′kij, B. I.; Alexanyan, R. Z. On the specific of interaction of polyoxyarylenes
with electrophylic reagents on the example of aryldiazonium salts. Reports of Academy
of Sciences of USSR” (in Rus.). 1983, 270(2), 364.
CHAPTER 4

PORPHYRIN–POLYMER COMPLEXES
IN MODEL PHOTOSENSITIZED
PROCESSES AND IN
PHOTODYNAMIC THERAPY
A. B. SOLOVIEVA and N. A. AKSENOVA
Semenov Institute of Chemical Physics of Russian Academy of Sciences, Moscow,
Russia
E-mail: [email protected], [email protected]

CONTENTS

Abstract.................................................................................................... 78
Introduction.............................................................................................. 78
Experimental Part..................................................................................... 81
Results and Discussion............................................................................ 90
Results of Histological Examinations.................................................... 109
Conclusions.............................................................................................117
Keywords................................................................................................118
References...............................................................................................118
78 Additives in Polymers: Analysis and Applications

ABSTRACT

We have studied the effect of amphiphilic polymers (APs) with differ-


ent structures (polyvinylpyrrolidone, polyethyleneoxide, and a triblock
copolymers of ethylene- and propyleneoxide – Pluronics) on the photo-
activity of porphyrin photosensitizers, disodium salt of protoporphyrin
(dimegin), and diglutamic salt of chlorine e6 (photoditazin), in the pro-
cesses of singlet oxygen photogeneration. The photooxidation of trypto-
phan and histidine were chosen as model systems. Also, we studied the
activity of APs and photoditazin complexes in photodynamic treatment
of cancer cell culture and purulent wounds in rats. We showed that APs,
especially block copolymers of ethylene oxide and propylene oxide, can
increase the photocatalytic activity of porphyrin photosensitizers (PPS)
– dimegin and photoditazine – an N-methylglucamine salt of chlorine e6
both in model experiments in water solution and in biological systems.
In fact, AP may enhance the phototoxicity of photoditazin in cell cultures
and wound healing by photodynamic therapy. We attribute the observed
effect of the APs on the photoactivity of dimegin to the presence of poly-
mer–porphyrin interactions resulting in the porphyrin disaggregation in
aqueous phase. Using 1H NMR spectroscopy, we have found that dimegin
binds to the polymers via the PPS interaction mainly with the hydrophobic
fragments of polymeric macromolecules. Among the studied polymers,
polyvinylpyrrolidone appeared to have the most significant influence onto
the photoactivity of dimegin in model systems and by photodynamic treat-
ment of purulent wounds in rats.

INTRODUCTION

Photodynamic therapy (PDT) is a quickly emerging treatment modal-


ity employing the photochemical interaction of three components: light,
photosensitizer, and oxygen. Tremendous progress has been made in the
past two decades in new technical development of all components, as well
as understanding of the biophysical mechanism of PDT.1 This technique
permanently entered the clinical practice for the treatment of superficial
tumors and festering wounds.1,2
Porphyrins and its analogues – chlorines – are commonly used as pho-
tosensitizers due to their high activity and nontoxicity. The studies con-
Porphyrin–Polymer Complexes in Model Photosensitized Processes 79

ducted so far have shown that excited triplet state molecules of porphyrin
photosensitizers (3PPS*) are capable of initiating photochemical reactions
of two types.3,4 First, a direct 3PPS* interaction with biomolecules is pos-
sible (detachment of an electron or hydrogen atoms), leading to the for-
mation of free radicals. As a result of interactions of free radicals with
molecular oxygen, reactive oxygen species are created. In the reactions of
the second type, an energy transfer from 3PPS* to oxygen molecules takes
place, and singlet oxygen 1O2, an active oxidant, is generated. Besides, 1O2
is capable of accepting electrons from a substrate leading to the generation
of superoxide anion-radicals. At the final stage of the PDT action, both
types of photochemical reactions result in the destructive processes in the
vital cell structures and their death.5 The treatment with the PPS applica-
tion produces positive results, but sometimes, it causes side effects, such
as temperature elevation, muscle weakness, and prolonged skin photosen-
sitivity.6
Therefore, the studies on the reduction of PDT side effects, primar-
ily by lowering the dose of the applied photosensitizers and reducing the
duration of illumination, are of significant importance. The evolution of
the PDT techniques is associated with the creation of new photosensitizer
drug formulations of improved bioavailability and reduced nonspecific
toxicity. In particular, to attain these objectives, it has been suggested that
complexes composed of photosensitizers and amphiphilic polymers (APs)
differing in nature, such as polyoxyethylene, polyvinylpyrrolidone, Plu-
ronics, and polyvinyl alcohol, should be used for the PDT purposes. In
experiments with other polymers forming complexes with photosensitiz-
ers, positive biological effects were also noted. To illustrate, when using
a chlorine e6–polyvinylpyrrolidone complex, Chin et al4,7,8 observed an
increased selectivity of accumulation of this complex in the cancerous tis-
sues and its accelerated removal from the normal tissues. In addition, the
binding of photosensitizers to polymers frequently allows the photophysi-
cal properties of the complexes obtained to be substantially improved as
compared with the original photosensitizers.9–11 Of special interest is the
possibility of using Poloxamers (also known as Pluronics) – triblock copo-
lymers based on ethylene oxide (EO) and propylene oxide (PO) – for PDT
applications. Pluronics, which are tissue compatible emulgators, were ear-
lier demonstrated to have properties of immune adjuvant, show antithrom-
botic activity, and be capable of modifying the activity of neutrophils. One
of the most promising approaches is the development of complexes based
80 Additives in Polymers: Analysis and Applications

on a bis-N-methyl-glucamine salt of chlorine e6. It features a broad ab-


sorption band, low toxicity, water solubility, amphiphilic properties, and
substantial photodynamic activity, even in small doses. We have recently
demonstrated a substantial enhancement of the photocatalytic activity of
photoditazine (PD) when combined with Pluronics and also the depen-
dence of this property on the hydrophilicity of the polymer used. Obvi-
ously, the emergence of new photosensitizer formulations has a number of
merits as applied to the PDT of infected, festering, and persistent wounds,
burns, and trophic ulcers but requires, at the same time, that an insight be
gained into the mechanisms governing the action of such preparations and
that adequate PDT regimens be developed. However, despite the growing
interest in the issue and the appearance of first positive clinical experi-
ence reports, there is practically no morphological and pathophysiological
substantiation for the PDT of wounds and burns using photosensitizers
modified with APs.
Recently, it has been shown that a number of APs can improve thera-
peutic properties of different photosensitizers. It has been shown that non-
covalent8,9 or chemical10 attachment of a photosensitizer to hydrophilic
polymers or APs improves its photophysical properties. Covalent attach-
ment of Zn-protoporphyrin to polyethylene oxide led to the increase in
the triplet state lifetime in cell suspension by an order of magnitude.11
Encapsulation of protoporphyrin IX into methoxy poly (ethylene glycol)-
b-poly (caprolactone) diblock copolymers micelles markedly increased
photocytotoxicity over that of free protoporphyrin IX, by nearly an order
of magnitude at the highest light dose used.12 Moreover, singlet oxygen
quantum yield of such conjugate also increased from 0.05 up to 0.17. Ob-
viously, it means that poly(ethylene oxide) coils impede collision of the
porphyrin with surrounding molecules thus hampering idle losses of triplet
state energy. Formulation of chlorine e6 with polyvinylpyrrolidone (PVP)
was proved to increase photosensitizer tumor tissue selectivity, obviously
due to the facilitation of its clearance from normal tissues.13 Tremendous
(nearly 10-fold) increase in the triplet state lifetimes were observed when
hematoporphyrin was adsorbed on the surface of polysaccharide Percoll
microparticles. In contrast to this, attachment of Sn-chlorine e6 to dextran
and further conjugation of this polymer to anti-melanoma antibodies led
to the decrease in the triplet state lifetime.14 These facts show that the
lifetime of the sensitizer triplet state can be modulated by the properties of
its microenvironment, and optimal pairs “photosensitizer-polymer carrier”
should be selected in each case.
Porphyrin–Polymer Complexes in Model Photosensitized Processes 81

Among biologically compatible polymers, a large family of polyalkyl-


ene oxides is of particular importance due to a large variety of properties
of these polymers, their commercial availability, and simplicity of their
synthesis. EO and PO block copolymers (also referred to as Pluronics,
Fig. 4.1) are nowadays used in pharmacy and medicine as immunoad-
juvants15 and biologically compatible emulsifiers.16 They were shown to
inhibit thrombosis17 and modulate neutrophil activity.18 Pluronics micelles
have already been studied as possible vehicles for hydrophobic photosen-
sitizers. In this regard, Pluronic F127 micelles were studied for their abil-
ity to facilitate transcytosis of highly hydrophobic meso-tetraphenyl por-
phyrin through Caco-2 cells monolayer.19 The same Pluronic was found
to assist transdermal penetration of a hydrophilic prodrug aminolevulinic
acid.20 More hydrophobic Pluronic P123 was found to favor delivery of a
hydrophobic photosensitizer verteporfin to plasma lipoproteins.21
Our own studies22–32 revealed that application of PPS in the complexes
with Pluronics could increase the activity of photosensitizers upon their
photodynamic action onto tumor cells and tumors of laboratory animals,
thus reducing the applied PPS doses by 10–20 times22–24 and also in the
PDT of extended purulent wounds.25–27 In the previous work, we also dem-
onstrated that Pluronics augmented the activity of dimegin and PD in the
model photooxidation processes in aqueous phase.28–32 These phenomena
are likely caused by the enhancement of singlet oxygen generation quan-
tum yield upon porphyrins solubilization in Pluronic micelles. To verify
the above-mentioned statement, we have studied the influence of Pluronic
F127 (the least toxic one of polymeric surfactants) and other APs on the
activity of a hydrophobic tetraphenylporphyrin (TPP) and water-soluble
dimegin and PD in the photogeneration of singlet oxygen and photooxida-
tion of histidine and tryptophan in water and D2O. In addition, we inves-
tigated the activity of complexes PPS–AP in malignant cells by photoir-
radiation and in PDT of infected wounds in rats.

EXPERIMENTAL PART

MATERIALS

Meso-TPP (Fig. 4.1b), l-tryptophan, and l-histidine were purchased from


Sigma-Aldrich Corp. (USA). Disodium salt of 2,7,12,18-tetrame-thyl-3,8-
di(1-methoxyethyl)-13,17-di(2-oxycarbon-ylethyl) porphyrin, (Dimegin,
82 Additives in Polymers: Analysis and Applications

DMG; Fig. 4.1b) was synthesized and kindly gifted by Prof. G. Ponomarev.
N-methyl-bisglucamine salt of chlorine e6 (trade name: Photoditazine,
PD, Fig. 4.1c) was generous gift of Veta-Grand Corp. (Russia).We used
PVP with Mw = 40,000 by Sigma-Aldrich Corp., polyethyleneoxide (PEO)
with Mw = 40,000 by Serva (Germany; Fig. 4.3), tri-block copolymers of
ethylene (m)- and propylene-oxide (n) Pluronics by BASF (USA) – F127
with Mw = 12,600 (m = 100, n = 60), P85 with Mw = 4500 (m = 52, n = 40),
Pluronic F87 with Mw = 7700 (m = 61, n = 40), and F108 with Mw = 14,600
(m = 133, n = 50).

FIGURE 4.1  Structure of (a) Tetraphenylporphyrin, (b) Dimegin, and (c)


PHOTODITAZINE.

Water soluble DMG–AP and PD–AP complexes were prepared by the


following procedure. PPS (10.0 g) was dissolved in 80 mL of water at a
temperature of ∼900°C while stirring for 30–40 min. After cooling it to the
room temperature, 20 mL of PPS water solution with 5 mg/mL concentra-
tion was added to the mixture and stirred to complete the homogenization.
This method of complex preparation was applied for all studied polymers.
Solubilization of hydrophobic TPP were prepared by mixing the TPP
and Pluronics in a chloroform solution with the porphyrin concentration of
1 × 10−4 M and the polymer concentration of 1.7 × 10−4 M. The porphyrin
to Pluronic ratio q  = 0.6 provided the optimal degree of solubilization.
For the AFM imaging, thin films of Pluronics (pure and containing TPP)
Porphyrin–Polymer Complexes in Model Photosensitized Processes 83

on silicon substrates were prepared from the chloroform solution by spin


coating at a rotation speed of 7000 rpm.

SINGLET OXYGEN MEASUREMENTS

Singlet oxygen photogeneration by DMG was detected directly by mea-


suring time-resolved luminescence at 1270 nm, in D2O solutions, after
excitation of the photosensitizer at 532 nm. Samples in 1 cm fluorescence
cuvettes (QA-1000, Hellma Optik, Germany) were excited with 750 ps
microjoule pulses generated by a microchip Nd:YAG laser (Pulselas-P-
1064-FC, Alphalas GmbH, Germany) operating with 2–10 kHz repetition
rate. To filter out first and third harmonics of laser radiation, 50 cm water
filter and dichroic mirrors (BK7 series, Eksma Optics, Lithuania) were
used. Near-infrared luminescence was measured perpendicularly to the
excitation beam in a photon counting mode using a thermoelectric cooled
NIR PMT module (model H10330-45, Hamamatsu, Japan) equipped with
a 1100 nm cut-off filter and a narrow-band filter centered at 1270 nm (NB
series, NDC Infrared Engineering LTD, UK). The data were collected us-
ing a computer-mounted PCI-board multichannel scaler (NanoHarp 250,
PicoQuant GmbH, Germany). The data collection was synchronized with
laser pulses using an ultrafast photodiode (UGP-300-SP, Alphalas GmbH)
as a trigger. The data analysis, including first-order luminescence decay
fitting by the Levenberg-Marquardt algorithm, was performed using a cus-
tom-written software. The quantum yield for singlet oxygen photogenera-
tion by DMG was determined as relative to that of Rose Bengal by mea-
suring initial intensities of the 1270 nm phosphorescence, extrapolated to
zero time after laser pulses, as a function of laser pulse energy, which was
varied by using a series of optical filters with different transmission at
532 nm.
Porphyrin photosensitizing activity in D2O was evaluated based on the ki-
netics of the decrease in oxygen concentration (oxygen consumption). The
effective rate constants of histidine photooxidation kHIS were determined in
accordance with kHIS = ACO2/CHISCphAt, where Cph is the PPS concentration,
CHIS is the substrate concentration, and ACO2 is the change in the oxygen
concentration for the time At. The error of the effective rate constant mea-
surements was estimated as 10%.
84 Additives in Polymers: Analysis and Applications

EPR OXIMETRY

Photosensitized oxygen consumption in the presence of histidine was mea-


sured by EPR oximetry employing 4-protio-3-carbamoyl-2,2,5,5-tetraper-
deuteromethyl-3-pyrroline-1-yloxy (mPCTPO) as a spin probe and using
Bruker EMEX-AA spectrometer (Bruker BioSpin, Germany). The spectral
parameters of the mPCTPO spin probe were calibrated for dissolved oxy-
gen concentration in a water solution at room temperature.32 EPR samples
in flat quartz cells were irradiated in situ in the resonant cavity with yellow
light derived from a Cermax PE300CE-13FM 300 W lamp in air-cooled
housing (Perkin Elmer, USA) using a combination of filters (5 cm of aque-
ous solution of 5 g/L CuSO4, green dichroic and a cut-off <500 nm filter).
The sample irradiance, measured by a calibrated photodiode (Hamamatsu,
Photonics, Japan), was in the range of 151–174 W/m2.
Porphyrin photosensitizing activity in H2O was evaluated based on the ki-
netics of the decrease in l,d-tryptophan concentration upon irradiation with
a phototherapeutic LED apparatus by Polyronic Ltd. (X = 400 nm, power
of 210 mW) in the presence of the porphyrin or its mixtures with the poly-
mers at the temperatures of 23 ± 1°C. The effective rate constants of tryp-
tophan photooxidation kTRP were determined in accordance with kTRP = ACTRP/
CTRPCphAt, where Cph is the PPS concentration, CTRP and ACTRP are the substrate
concentration and its change for the time At, respectively. UV-visible ab-
sorption spectra of the solutions were obtained using a Cary50 spectropho-
tometer (Varian, Austria), the error of measurements being 10%.
*H NMR spectra were recorded using a Bruker AVANCE III 500 MHz
spectrometer. The samples solutions of dimegin, polymers, and PPS-AP
systems (in mass ratio 1:1) in D2O (Aldrich, 99 atom% D) were placed
into standard ampoules (with the outer diameter of 5 mm). 1H NMR
spectra were obtained at a temperature of 20.5  0.1°C and the instrument
working frequency of 500 MHz. The frequencies of NMR shifts were cali-
brated using the residual signals of the protons from the deuterated water
(4.71 ppm). The 1H NMR data interpretation was performed in accordance
with the literature data,33 13C NMR (working frequency of 125.8 MHz)
data, and 2D spectra correlations 1H–1H COSY, 1H–1H NOESY, 1H–13C
HSQC, and 1H–13C HMBC.
Size distributions of Pluronic micelles, porphyrines aggregates, and
their mixtures were estimated with dynamic light scattering technique
using PhotoCor goniometer (USA) equipped with He-Ne laser (10 mW,
Porphyrin–Polymer Complexes in Model Photosensitized Processes 85

633 nm). Autocorrelation functions of scattered light intensity were evalu-


ated with 288-channel correlation device PhotoCor-SP at scattering angle
90o. Mathematical treatment of autocorrelation functions to obtain size
distribution of scattering particles was performed using Dyna L.S. soft-
ware.

ATOMIC FORCE MICROSCOPY DATA

Atomic force microscopy imaging of the prepared films was performed


in the semicontact mode with a Solver P47 AFM instrument (NT-MDT,
Russia). We used NSG10 probes (NT-MDT, Russia) with a nominal spring
constant of 5.1 N/m, nominal resonant frequency of 150 kHz, and nominal
tip radius of 10 nm. Typically, we obtained 6 × 6 µm images at a scan rate
of 1 Hz, with a 512 × 512 pixels resolution. The images were flattened us-
ing the instrument built-in image processing software.
TPP and Pluronics were mixed in a chloroform solution with the por-
phyrin concentration of 1 × 10−4 M and the polymer concentration of
1.7 × 10−4 M. The porphyrin to Pluronic ratio q = 0.6 provided the optimal
degree of solubilization, according to the previous studies.5 For the AFM
imaging, thin films of Pluronics (pure and containing TPP) on silicon sub-
strates were prepared from the chloroform solution by spin coating at a
rotation speed of 7000 rpm.
Photosensitizing activity of PD–AP complexes in the cell experiments
was carried out in Malignant Mouse Fibroblast Cells NIH-3T3-EWS-
FLI1. These cells simulate the behavior of Uing human sarcoma (granted
by Dr Claude Malvy, Institute Gustave Roussy, Villejuif, France). These
cells were made from normal cells with a gene EWS-FLI1 transfection.
Cells were cultivated in DMEM (Sigma) medium, which contained
10% newborn calf serum, 4 mM glutamine, 100 units/mL penicillin,
100 mkg/mL streptomycin, and 2.5 mkg/mL puromycin in CO2-incubator
“NAPCO” (USA) (37єC, 5% CO2, and 95% humidity). The seeding den-
sity of the cells was 5 × 104  cell/mL, and they were reseeded when the
density value was reduced to 0.4 billion/mL (usually, it happened in 3 days
period). All cells were counted in the Goriachev chamber (microscope
“Axiovert 25”, “Zeiss”, Germany).
For photocytotoxicity measurement experiments, PD and cell suspen-
sion (3 × 104 cell/mL) were seeded into 96-hole plane-table (Costar, USA).
86 Additives in Polymers: Analysis and Applications

Sterile solution of PD with polymer was charged into the plane-table holes
after 24 h. Cells were incubated for 3 h and then illuminated with the laser
Atkus-0,4 (by the closed corporation of the Scientific-Production Associa-
tion of Space Instrument Making, Russia; kex = 660 nm, 65 mWt/cm2) for
3 min. Later, the plane-table was again placed in the incubator and left
undisturbed for 24 h. Each sample was measured in four identical probes.
PD–AP complexes for cell experiments were prepared by the follow-
ing procedure. PD (10.0 g) was dissolved in 80 mL of water at a tempera-
ture of ∼900°C, while stirring for 30–40 min. After cooling it to the room
temperature, 20 mL of PD water solution with 5 mg/mL concentration was
added to the mixture and stirred to complete the homogenization. This
method of complex preparation was applied for all studied polymers.
PD–AP complex activity was defined as a ratio of survived cells. Pho-
totoxicity of PD with or without the presence of polymer was determined
by using a method based on the ability of mitochondrial ferments to reduce
methyltetrazolium blue to formazan that have deep blue color. The number
of viable cells was proportional to the quantity of the reduced formazan,
which was determined using spectrophotometric analysis (Xex = 550 nm).
PDT therapy of gunshot wounds of rats was carried out in the follow-
ing method. Animal purulent wounds were washed out with the topical
antiseptic and were treated with 0.5% and 1% PD water solution or PD–AP
(1% PD) gel drifted on gauze pad. Gauze pad was removed after 24 h of
depositing, and wound surface was illuminated for 6 min with the low-
energy semiconductor laser Atkus-2 (X = 660 nm, power = 1 W/cm2, and
energy density = 50 J/cm2). This treatment was carried out for three times.
Each time a new gauze pad was used.

STUDY DESIGN BY EARLY STAGES OF THE WOUND HEALING


IN RATS

In our experiments on rats, we replicated the standard planar full-thickness


skin wound model.34 The next day after wounding, one of the following six
substances, isotonic sodium chloride solution, aqueous photoditazin solu-
tion, aqueous PVP solution, aqueous Pluronic F127 solution, photoditazin-
PVP complex, and photoditazin Pluronic F127 complex, was injected into
the wound bed of animals in the experimental groups. The wounds of the
animals in the control group were left untreated. Fifteen minutes after the
injection, the wounds were exposed to the laser radiation. The procedure
Porphyrin–Polymer Complexes in Model Photosensitized Processes 87

was repeated 3 days after the wounding. Clinical observations were made
during the 4 days following the 5 wounding, and then the animals were
sacrificed, wound tissue fragments were excised, and sent for the morpho-
logical analysis to study the structure of the wound bed and specifics of in-
flammatory and reparative reactions in the different experimental groups.
The histological characteristics of the wounds were evaluated semiquan-
titatively, and the results of the numerical score of the morphological fea-
tures were analyzed statistically.
The experiment was performed on laboratory male albino rats with the
body mass of 120–140 g. The experiment was approved by the Local Ethi-
cal Committee of the I.M. Sechenov First Moscow State Medical Univer-
sity. The animals were housed one per cage under standard animal housing
conditions and given laboratory pelleted feed and unrestricted water. The
standard planar full-thickness skin wound model was replicated as de-
scribed earlier by Solovieva and Timashev35. A concentric (approximately
10 mm diameter) skin graft, complete with the subcutaneous fat down
to the fascia proper, was excised from the preliminarily depilated dorsal
skin in the interscapular area. A Teflon collar with a 3 mm wide flange at
the bottom was inserted into the skin defect that had formed so that the
flange was fit under the skin and the 10 mm high cylindrical portion of the
collar projected above it. Standard-size wounds (300 mm2 in area) were
thus obtained in all the animals. The top of the collar was covered with a
cellophane film to protect the wound from drying and extraneous contami-
nation. The experimental wounding was performed under combined anes-
thesia with intramuscular injection of a zoletil solution (Zoletil 100, Virbac
S.A., Italy) at a rate of 6.0 mg of zolazepam hypochloride per kilogram of
the animal body mass and 0.5 mL/kg of a xylazine hydrochloride solution
(Rometar, Spofa, Praha). The wound PDT sessions were conducted with
an Atkus-4 semiconductor laser with the wavelength of 661 nm.
All the materials used for the PDT purposes were investigated with
respect to their local effect on the wound surface. Depending on the active
factor combination to be studied, the animals were arranged in the follow-
ing seven groups of three animals each: group I – control, untreated; group
II – isotonic sodium chloride solution + irradiation; group III – aqueous
PD solution + irradiation; group IV – aqueous PVP solution + irradiation;
group V – aqueous Pluronic F127 solution +  irradiation; group VI – PD–
PVP complex + irradiation; group VII – PD–Pluronic F127 complex + ir-
radiation. Experimental groups I through V served as controls for the main
88 Additives in Polymers: Analysis and Applications

experimental groups VI and VII. The control experiments were aimed at


revealing the morphological characteristics of the early stage of the wound
healing process taking place under the effect of each of the following PDT
agents: laser radiation (group II) and its combinations with the aqueous
PD solution (group III) and with each of the polymers used as a base/ve-
hicle in the preparation of the PD–PVP (group IV) and PD–Pluronic F127
(group [VII]) complexes.
The treatment of the wounds was started on the next day after the
wounding. The procedures included were as follows:

INJECTION OF THE SUBSTANCES UNDER STUDY INTO THE


WOUNDS:

With the protective cellophane film remaining in place on top of the


Teflon collar, 0.2–0.3 mL of the solution under study was injected with
an insulin administration syringe into the soft tissues of the wound bed
at 4–5 equally spaced points, so as a to have a total of 1.0 mL of the so-
lution injected. When the injected solution contained PD or PD-amphi-
philic polymer complexes, the wound with the collar was covered with
a black cloth after the injections in order to exclude illumination with
extraneous light.

LASER TREATMENT OF THE WOUNDS:

The procedure was started 15 min after the injections. The wound bed
was irradiated with a defocused CW laser beam (with the light spot di-
ameter of around 0.5–0.8 cm) by moving the light guide in scanning
circles for 5 min. The radiation power was 11 mW, and the dose came
to 1.45 J/cm2. The procedure was repeated within 3 days after wound-
ing. Thus, the total irradiation dose amounted to 2.9 J/cm2. In 4 days
after the wounding (the next day after the last irradiation session), the
animals were sacrificed by an intraperitoneal injection of 2.0 mL of 25%
magnesium sulfate solution. The bordering Teflon collars were removed,
and the tissues filling the wounds were completely excised down to the
superficial fascia.
Porphyrin–Polymer Complexes in Model Photosensitized Processes 89

PROCEDURE OF MORPHOLOGICAL ANALYSIS

Tissue samples intended for the morphological analysis were fixed for
3 days in a 10% neutral formalin solution, passed through a series of al-
cohols of gradually increasing concentration, and embedded in paraffin.
Paraffin sections of 4–5 µm thickness were stained with hematoxylin and
eosin and picrofuchsin by the Van Gieson method (to reveal collagen fi-
bers). The microslides thus obtained were examined using an Olympus
BX51 optical microscope (Olympus, Japan) equipped with a SDU-252
digital camera (Special Technik, Russia).
Examination of each microslide included evaluation of several charac-
teristics on a 10-point scale, whereon a score of 0 represented the absence
of a morphological feature and that of 10 represented the maximum inten-
sity of the feature. We evaluated the intensity of inflammation (edema, ex-
udation, cellular infiltration, and microcirculation injuries), hemorrhagic
reaction (erythrocyte concentration in the exudate and tissue), and repara-
tive processes (angiogenesis, fibroblast proliferation, and abundance and
maturity of the granulation tissue).

STATISTICAL ANALYSIS OF THE RESULTS

The statistical analysis of the results was performed using the standard
program package SPSS 13.0 for Windows. The intensities of morpho-
logical features in animals belonging to different groups were compared
by means of nonparametric tests for several independent samples (the
Kruskal-Wallis [KW] test) and by the way of pairwise comparison of the
groups (the Mann–Whitney [MW] test), provided that statistically signifi-
cant differences were revealed to exist at the stage of group comparison
(the KW test). The significance level p of differences was taken at 0.05. In
all cases, we used two-way tests.
90 Additives in Polymers: Analysis and Applications

RESULTS AND DISCUSSION

PORPHYRIN-POLYMER COMPLEXES IN MODEL


PHOTOSENSITIZED PROCESSES

PLURONIC F127 EFFECT ON THE EFFICIENCY OF SINGLET


OXYGEN PHOTOGENERATION IN THE PRESENCE OF DIMEGIN

As seen from Figure 4.2, the intensity IA of 1O2 phosphorescence (pro-


portional to 1O2 concentration in the system) in the presence of dimegin
(5  × 10–6 M) increases upon introduction of Pluronic into the reaction
mixture (illumination with λ = 532 nm).

FIGURE 4.2  (a) Dependence of the Intensity I∆ of Singlet Oxygen Phosphorescence


(λ = 1270 nm) on the Pluronic F127 Concentration CPL in D2O in the Presence of Dimegin.
(b) Singlet Oxygen Phosphorescence Kinetics. (1) in the Presence of 5 × 10−6 М of Dimegin;
(2) in the Presence of 5 × 10−6 М of Dimegin and 1.5 ×10−3 М of Pluronic.

The growth of the singlet oxygen concentration in the presence of


dimegin with Pluronic may be related to the process of dimegin disaggre-
gation. Like all natural porphyrins with a planar spatial structure, dimegin
forms tightly bound aggregates in water, which do not noticeably dissoci-
ate even at high concentrations of surfactants.27,28
For instance, it was shown by Solovieva et al and Zhientaev et al 27,28
that an average size of dimegin aggregates (∼1 × 10−6 M) in aqueous buffer
solutions (PBS) was 50–100 nm and was only slightly reduced (up to ∼50–
Porphyrin–Polymer Complexes in Model Photosensitized Processes 91

70 nm) in the presence of Pluronic F127 (∼8 × 10–5 M). Such aggregates


of porphyrin molecules have a lower specific (per molecule) photoactiv-
ity.27,35 This is due to the fact that for a “face-to-face” position of porphyrin
rings’ characteristic for the nonmetallic porphyrins association, an energy
transfer can occur between the macrocycles, resulting in the vibration de-
activation of the 3PPS* triplet state and the corresponding decrease in the
photosensitizing efficiency of porphyrins.28
Indeed, it has been shown that introduction of Pluronic increases the
quantum yield Φ∆ of 1O2 photogeneration in the presence of dimegin by
20% (Φ∆ = 0.55 in the presence of DMG and Φ∆  = 0.67 in the presence
DMG with Pluronic F127). Since the intensity of 1O2 phosphorescence
does not depend on the Pluronic concentration at the DMG:F127 molar
ratio of 1:50 and higher, as shown in Figure 4.2a, the Φ∆ measurements
were performed at the corresponding concentrations of the components. .
The analysis of time dependencies of I∆ (decay phase of phosphores-
cence) has shown that introduction of Pluronic did not affect the 1O2 life-
time τ∆ (Fig. 4.2b). For example, τ∆ in D2O in the presence of dimegin
(curve 1) is 55 µs, in agreement with the data reported elsewhere,36 while
in the presence of dimegin and Pluronic, it is ∼50 µs independently of the
F127 concentration (curve 2). This fact obviously indicates that Pluronic
does not quench singlet oxygen at the concentration tested.

INFLUENCE OF THE NATURE OF APS ON THE


PHOTOSENSITIZING ACTIVITY OF DIMEGIN IN AQUEOUS
MEDIUM

The increase of the singlet oxygen concentration upon photoexcitation of


dimegin in the solution containing Pluronic obviously accounts for the
observed growth of the rate of histidine photooxidation in D2O (Fig. 4.3a).
Introduction of Pluronic into the dimegin solution in D2O elevates the ef-
fective rate constants of histidine photooxidation kHIS by ∼2.3 times. The
rate constant of histidine photooxidation rises sharply at lower concentra-
tions, while at higher concentrations, kHIS increases only insignificantly,
which is in a good agreement with the data in Figure 4.2a, where essential
rise of I∆, that is, of the singlet oxygen concentration, is observed only at
lower concentrations of Pluronic.
92 Additives in Polymers: Analysis and Applications

FIGURE 4.3  Dependences of the Effective Rate Constants of DMG-Sensitized Photooxidation


of (a) Histidine (kHIS) in D2O and (b) Tryptophan (kTRP) in Water on the Concentration of (1) F127,
(2) PVP, and (3) PEO. The Dimegin Concentration is (a) 2.5 Ч 10–6 M and (b) 5 Ч 10–6 M.

It is noteworthy that if sodium azide (a physical quencher of singlet ox-


ygen) is added to the dimegin–histidine system in D2O, then the reaction
of the substrate photooxidation almost stops. This fact is obviously an ad-
ditional evidence (besides the 1O2 phosphorescence measured at 1270 nm)
for the singlet oxygen 1O2 formation in the systems under study.37
A similar effect of the increase of the rate of dimegin-photosensitized
tryptophan photooxidation was observed in water in the presence of Plu-
ronic, PVP, and PEO (Fig. 4.3b). As seen from Figure 4.3b, the highest
effect (increase of the rate constant kTRP by ∼2.1 times) was found in the
presence of PVP. The increase in the efficiency of singlet oxygen generation
and in the PPS photocatalytic activity in the presence of the polymers in
D2O and H2O may be related to the porphyrin disaggregation resulted from
the interactions of PPS with AP. PVP appears to affect the PPS photoactiv-
ity and, hence, the size of the porphyrin aggregates to the greatest extent.
Previously, we observed a high activity of hydrophobic PPS solubilized
with Pluronics in the oxidation of tryptophan.38
PVP containing both hydrophobic (vinyl) and hydrophilic (pyrrolidone)
fragments is known to form hydrogen bonds and complexes with a number
of aromatic compounds—amines, dyes bearing a negative charge.39 Since
the studied porphyrin molecules contain hydrophobic porphyrin core and
hydrophilic peripheral oxygen-containing anionic groups, it can be ex-
Porphyrin–Polymer Complexes in Model Photosensitized Processes 93

pected that the interaction of PPS with PVP proceeds most efficiently. It is
also known that hydrophobic interactions determine the solubilization of
low-molecular weight substances by Pluronics.27,28,40 One can assume that
the PPS binding to the other APs is also accounted for by hydrophobic
interactions. However, the interaction with the vinyl fragments in PVP is
apparently more efficient than that with the propyleneoxide or methylene
fragments of Pluronic or PEO. Besides, as mentioned before, in the case
of PVP, not only binding to the hydrophobic fragments but also binding to
the hydrophilic (pyrrolidone) fragments is possible.39 The value of 1:10 of
the porphyrin/polymer molar ratio corresponding to the highest kTRP also
points out to a stronger binding in the DMG–PVP systems (Fig. 4.3b).
This value is two times greater than the molar ratios (∼1:20) correspond-
ing to the highest effect of porphyrin “disaggregation” for the dimegin–
Pluronic and dimegin–PEO systems. Thus, the more efficient interaction
of the photosensitizer with the polymer in the dimegin–PVP system leads
to a more intensive disaggregation and to enhancement of the porphyrin
photoactivity. Previously, we saw the same effect of increasing the activity
of tetrephenylporphyrins in photooxidation of cholesterol upon binding to
fluoropolymers.41–43

DETAILS OF PPS INTERACTIONS WITH APS

The interactions between the water-soluble porphyrin and APs’ hydropho-


bic fragments have been detected by 1H NMR spectroscopy. We studied 1H
NMR spectra of dimegin, polymers, and dimegin-AP systems in D2O.44,45
The chemical shifts of the proton signals are presented in Table 4.1.

TABLE 4.1  Signals of DMG, Polymers, and DMG–AP Systems Protons (ppm)

DMG DMG–F127 DMG–PVP DMG–PEO


–CH-meso 10.43 (1H) 10.43 10.45 10.46
9.87 (1H )
a
9.99 10.02 a
9.94a
8.93 (1Ha) 9.16 9.08a 9.05a
7.25 (1H) 7.77 7.80a
7.48
–CH–CH3 6.31 (2H) 6.25 6.29 6.34
–O–CH3 3.59 (6H) 3.57 3.59 3.63
3.81 (3H) 3.74 3.78 3.83
94 Additives in Polymers: Analysis and Applications

–CH3-cycle 3.59 (3H) 1 3.56 3.62


–CH2–CH2– 3.28 (6Ha) 2.65 > About L 2.8–3.4a 3.33a 2.78a
(4Ha) 2.79a
2.37 (2H) 2.49 2.51 2.44
2.09 (2H) 2.26 2.25 2.18
–CH–CH3 2.50 (6H) F-127 2.42 2.42 2.51
EO–CH2 3.65 3.52 – –
PO–CH2–/–CH– 3.43–3.59 3.52 – –
PO–CH3 1.11 PEO 0.61 – –
–CH2–CH2– 3.66 PVP – – 3.57
–CH2-vinyl 1.67 1.52 – «1.5a

–CH-vinyl 3.72 3.59 – «3.5a –
–CH2 (2) pyrrolidone 2.39 – 11.9–2.3 a

2.27 2.25
–CH2 (3) pyrrolidone 1.96 – «1.9a –
–CH2 (4) pyrrolidone 3.24 – 2.9–3.2 a

Notes: Signal broadening.
a

Abbreviations: DMG, Dimegin; AP, amphiphilic polymer; PVP, polyvinylpyrrolidone; PEO,


polyethyleneoxide

It was shown that in all the cases, a downfield shift of the porphyrin
cycle meso-protons and propionic acid residues was observed in the1H
NMR spectra of DMG–AP systems, as well as an upfield shift of the pro-
ton signals of the polymers’ hydrophobic fragments (as compared with
the signal positions in the spectra of initial components). These findings
indicate disaggregation of initially associated DMG molecules in water
and DMG binding to polymer. Note that the 1H NMR spectrum of initial
dimegin contained four signals (singlets) of the meso-protons in the range
of ∼10.5–7.2 ppm and two signals of the methyl group protons of the por-
phyrin ring at 3.59 ppm and 3.28 ppm. Three signals at 2.09–2.65 ppm cor-
responded to the protons of the peripheral methyl groups of the propionic
acid residues in the DMG molecule.
In the1H NMR spectra of Pluronic F127, PEO, and PVP, 30,33 we ob-
served the signals of the protons of the methine (CH–) and methylene
(CH2) groups in the range of 3.43–3.65 ppm. Besides, a signal (triplet) of
the methyl group protons of the hydrophobic propyleneoxide block was
seen for the Pluronic F127 in the strong field (1.11  ppm), while in the
Porphyrin–Polymer Complexes in Model Photosensitized Processes 95

PVP spectra, we observed the signals of the methylene group protons of the
hydrophilic pyrrolidone fragments in the range of 1.96–2.39 ppm and at
3.24 ppm.
As mentioned before, a downfield shift of the signals of the porphyrin
cycle meso-protons and of the protons of –CH2–CH2–COON groups was
found in the1H NMR spectra of the system DMG–AP, which apparently
indicates disaggregation of dimegin.30 At the same time, in the1H NMR
spectrum of the DMG complex with F127, the greatest variations, namely,
broadening and upfield shift up to 0.61 ppm, were observed for the sig-
nal of the methyl group protons of the polypropyleneoxide block. Such
changes testify the presence of interactions between the porphyrin and the
hydrophobic block of the polymer. This conclusion is confirmed by the
results obtained earlier, having shown that, in the process of solubilization,
DMG localizes in the hydrophobic core of Pluronic micelles.27,28 A similar
upfield shift was observed for the signals of the methylene group protons
of PEO in the1H NMR spectra of the DMG complex with PEO. In the 1H
NMR spectrum of PVP, the greatest variations were detected for the sig-
nals of the methylene group protons of the vinyl fragment: the signals in
the range of 1.52–1.67 ppm degenerated into one signal at 1.5 ppm. This
fact pointed out the interaction of PPS mainly with the hydrophobic frag-
ments of the polymer macromolecules. However, besides the mentioned
shifts in the spectrum of the DMG–PVP systems, we observed also a shift
of the methylene group’s signal of the pyrrolidone ring, which obviously
indicates the presence of the PPS interactions with the hydrophilic frag-
ments of macromolecules, as well. The obtained data correlated well with
the above-noted fact of the highest activity of the PPS–PVP systems in the
tryptophan photooxidation compared with that of the PPS complexes with
other APs.
The PPS disaggregation and interaction with the polymers were also
indicated by the changes in the UV-Vis absorption and fluorescence spec-
tra of dimegin in the presence of AP.29,36 Indeed, in the presence of AP,
we observed mostly bathochromic shifts (by 5–10 nm) and increase in
the intensity of bands (by 10–70%) in the UV-Vis absorption and fluores-
cence spectra of dimegin.29 It should be noted that the concentrations of
the polymers, at which the shifts and intensity increase were observed, de-
pended on the nature of the polymer. For example, PVP affects the inten-
sity of the bands and their positions in the UV-Vis spectra of DMG to the
greatest extent (at the porphyrin concentration of 5 × 10−6 M), causing the
96 Additives in Polymers: Analysis and Applications

bands (Soret, I and II) shift by 10 nm and the growth in their intensity by
50–80% already at the polymer concentration of 1 × 10−5 M. In the pres-
ence of Pluronic at the concentration of 1 × 10−5 M, we observed only a
Soret band shift (5 nm); the intensity grew by 20%–50%. With the further
increase of Pluronic concentration, the changes in the UV-Vis spectrum
of PPS are similar to those found in the presence of PVP. In the presence
of PEO (at the polymer concentration of 1 × 10−5 M), the changes in the
UV-Vis spectrum of dimegin were similar to those found in the presence
of Pluronic at the same concentration, but increasing the polymer concen-
tration resulted only in a higher intensity growth. These results confirm
the above-mentioned data on the stronger DMG binding to PVP compared
with PEO and Pluronic F127.
Study of Pluronic–Porphyrins Interaction Using DLS and AFM Tech-
nique
Aggregation of porphyrins in water solution is mainly due to hydro-
phobic and stacking interactions between porphyrins molecules. There-
fore, it is more pronounced for highly hydrophobic TPP (Fig. 4.4a) in
comparison with DMG containing two anionic groups (Fig. 4.4b).27 In
both cases, aggregates of about 100 nm were observed, and TPP aggre-
gates were characterized by the broader size distribution (Fig. 4.4a) than
DMN aggregates (Fig. 4.4b). No light scattering particles were observed
in water solutions (from 1 × 10−6 mole/L to 1 × 10−4 mole/L) of even more
hydrophilic PD, containing three anionic groups (data not shown). Size
of Pluronic micelles was found to be about 7 nm and 11 nm for P85 (Fig.
4.4c) and F127 (Fig. 4.4d) micelles, respectively. Size distribution of the
micelles was rather narrow in both cases. These data are consistent with
the previously published results obtained by pulse-NMR technique and
small-angle neutron scattering.
Addition of Pluronics to the porphyrines induced considerable de-
crease in the size of particles observed in the solution. Thus, Pluronic P85
caused decrease in the size of TPP aggregates from ~100 nm to 10 nm that
was comparable with the size of undisturbed Pluronic micelles. Similarly,
addition of Pluronic F127 decreased the size of DMN aggregates from
80 nm to 10 nm. However, in both cases, considerable broadening of size
distribution in comparison with empty micelles was observed. Hydrophil-
ic PD did not form aggregates in solution and did not alter size distribution
of Pluronic F127 micelles.
Porphyrin–Polymer Complexes in Model Photosensitized Processes 97

FIGURE 4.4  Size Distribution of (a) TPP and (b) DMN Aggregates (1 × 10−6 mole/L);
(c) Pluronic P85 (1.1 × 10−5 mole/L) and (d) Pluronic F127 (7.9 × 10−5 mole/L) Micelles;
(e) TPP/Pluronic P85 Mixture, (f) DMN/Pluronic F127 Mixture, and (g) PD/Pluronic F127
Mixture. Buffer PBS, 37°С.

Thus, the question “why PD photocatalytic activity increases in the


presence of Pluronics, while no aggregates are detected in its water solu-
98 Additives in Polymers: Analysis and Applications

tion?” arises. We suppose that the observed effect is mainly due to the
concentration of photocatalyst and the substrate within micellar volume.
Previously, we have shown that l-tryptophan did not solubilize in Pluronic
micelles; therefore, the “micellar catalysis” mechanism seems to be very
realistic.28
So, we found that either water-insoluble porphyrins (meso-TPP) and
its derivatives, protoporphyrin IX derivatives) or hydrophilic porphyrins
dimegin and PD can be efficiently solubilized in the Pluronic micelles,
a process that is accompanied by a marked improvement in the catalytic
activity of photosensitizers.27,28 Although only water-soluble porphyrins
are generally considered in the PDT drugs development, combination of
photosensitizers with Pluronics gives an opportunity to consider very ac-
tive but water-insoluble porphyrins (Fig. 4.5a, b) as potential PDT drugs.
Solubilization of TPP by Pluronics increases its photocatalytic activity by
a factor of 50–60.28 An exceptionally high increase in the photocatalytic
activity of TPP is primarily related to its dissolution: in the absence of
a Pluronic, TPP produces only dispersion with a vanishingly low photo-
catalytic activity. Second, solubilization can reduce the sizes of porphyrin
aggregates, which are characterized by a lower photocatalytic activity than
that of individual molecules. The aggregates are formed in the aqueous
medium and stabilized by the hydrophobic and π–π interactions of aro-
matic rings. The above-mentioned data of dynamic light scattering have
shown that, even at 1 × 10−6 mol/L, TPP produces large associates; their
dimensions vary from 200 nm to several microns. In contrast, only indi-
vidual porphyrin molecules or small aggregates are contained within a
Pluronic micelle, apparently inside the hydrophobic core.
Finding the characteristic features of PPS–AP interactions is impor-
tant in order to expand the spectrum of potential PPS–AP systems and to
develop novel pharmaceutical formulations. It is reasonable to suppose
that porphyrines also influence the structure of Pluronic micelles. We used
atomic force spectroscopy imaging to assess the details of the structures
grown from Pluronics and Pluronic–TPP solutions on silicon substrates.
We attribute the observed alterations in the Pluronic crystals to the forma-
tion of complexes between the polymer and TPP, which account for en-
hanced photocatalytic activity of such systems in the generation of singlet
oxygen.27,28,46,47
Porphyrin–Polymer Complexes in Model Photosensitized Processes 99

FIGURE 4.5  Structures of (a) A Pluronic Polymer, and (b) A Hypothetical Structure of A
Pluronic Micelle Containing Solubilized Aggregates of TPP.

The spin-coating technique allows the preparation of ultrathin (5–


20 nm) films of Pluronics with controllable thickness and shapes of poly-
mer crystals, depending on the speed of the spinner and the polymer solu-
tion concentration. In the conditions used in this study, we observed the
formation of similar dendritic structures (Fig. 4.6) for all the three Pluron-
ics, despite their difference in the degree of crystallinity and hydrophobic-
ity (defined by the ratio of EO to PO units). The film thicknesses measured
11–13 nm for F87 and F108 and 9–14 nm for F127.47

FIGURE 4.6  Typical Appearance of Thin PLURONIC Films Grown from 1 × 10−4 M
Chloroform Solutions on Silicon Substrates: (a) Pluronic F87, (b) Pluronic F127, and (c)
Pluronic F108.

The observed dendritic patterns of crystallization are characteristic for


thin films of PEO48 and may be attributed to crystallization of PEO units of
a Pluronic. It has been shown49 that in very thin (~15 nm) films, flat-on la-
100 Additives in Polymers: Analysis and Applications

mellae of the polymer branch to form dendritic structures. In such dendrit-


ic structure, we observed that by crystallization under certain conditions,
dewetting of the polymer may occur in thin films leading to the formation
of separate “islands”.47,50 Indeed, occasionally, we observed crystallization
of Pluronics in the form of “islands” with an elevated rim.
In the presence of TPP, the structure of thin films of Pluronics under-
went marked changes (Fig. 4.7, a–c). For all the three Pluronics under
study, particular convex structures appeared on top of the dendrites of
TPP-containing Pluronics. Such convex structures typically grew to 20–
50 nm in height, depending on the Pluronic type, while their diameters
measured up to 1000 nm at the base.

FIGURE 4.7  Effect of TPP on the Growth of Pluronic films. (a) F87, (b) F127, and
(c) F108. The Concentration of TPP is 1 × 10−4 M, and the Pluronics’ Concentration is
1.7 × 10−4 M.

The biggest “lumps” were usually observed in the case of F87 (Fig. 4.7
and 6a). The convex structures in F127 (Fig. 4.7b) were typically rather
small but much more abundant as compared with those in the other two
Pluronics. Various analyses of individual convex particles reveal that they
consist of multiple flat layers positioned on top of each other (Fig. 4.8,
a–b). High resolution topography and phase imaging shows that while the
convex particles are apparently formed by the same polymer lamellae as
the underlying dendrites, they have a distinct manner of multilayer pack-
ing and an invariably rough top surface.
Porphyrin–Polymer Complexes in Model Photosensitized Processes 101

FIGURE 4.8  Convex Particles Formed in the Presence of TPP Consist of Multiple Flat
Layers Located on Top of Each Other. (a and b) High Resolution Topography and Phase
Images of a F108-TPP Film, (c) Quasi-3D image of an Individual Particle in a F87-TPP
Film, (d) Height Histogram Taken Around An Individual Particle. (1) Substrate, (2) Film
(Dendrite) Surface, (3) Steps of Multiple Flat Layers Over the Main (Dendrite) Surface.

In Figure 4.8b, a close-up of an individual particle’s topography is pre-


sented in a coloring regime with gradient lighting (quasi-3D image). At
least four flat layers are seen over the basic (dendrite) film level, and the
top surface differs from the other layers by increased roughness. Obvi-
ously, the polymer packing in the last finishing layer proceeds in a more
disordered manner, leaving loose polymer chains on top of the flat crystal
and giving rise to the observed rough structure of the top layer. The cross-
sections of the convex structures show a stepwise character of the height
change, which can be seen even better if a histogram of heights within the
102 Additives in Polymers: Analysis and Applications

area of an individual “lump” is calculated (Fig. 4.8c). The observed steps


have a typical height of 10–13 nm, suggesting that they are formed by the
same polymer lamellae as those in the dendrites. In some cases, though,
we detected thinner (4–5 nm) or thicker (20 nm) steps between the layers
in the multilayered convex structures. Interestingly, in the case of rela-
tively small particles in the Pluronic F127, the thickness of the layers was
the same as that in the other Pluronics, while the number of layers was
diminished to two to three, or even only one flat layer was seen above the
surface of the dendrites.
The mechanism of the formation of a thin film for PEO includes ad-
sorption of a monolayer followed by the growth of flat-on lamellae from
random nucleation sites.51 Since Pluronics contain rather long PEO frag-
ments (≈22 nm for F87, ≈36 nm for F127, and ≈47 nm for F108), their
crystallization apparently proceeds by the same mechanism. On hydro-
philic surfaces, Pluronics adhere through their PEO units in a pancake
manner, in contrast to hydrophobic surfaces which cause them to adopt a
brush-like conformation.52 The silicon wafers we used had a contact angle
for water of ~40°, characteristic for silicon oxide, so the first adsorbed
polymer layer was formed by extended polymer chains tightly bound to
the surface via their hydrophilic PEO ends. The following crystallization
of PEO fragments proceeds through the formation of flat-on lamellae,
which grow with branching or seaweed-like tip-splitting,51 resulting in the
large dendritic structures. The growth of dendritic structures of a uniform
height (10–13 nm) appears to be an almost exclusive way of Pluronics
crystallization in a thin film. It should be noted that we observed same
dendritic structures with different Pluronic concentrations, different sub-
strates, and also during crystallization from aqueous solutions. Only very
rarely we found single convex multilayered particles in the AFM images
of pure Pluronics.
The formation of thick multilayered crystals can occur at a certain ele-
vated temperature53 but is apparently strictly unfavorable in the conditions
of Pluronics crystallization from a chloroform solution at room tempera-
ture.
However, the presence of a relatively small number of TPP molecules
(compared with the number of the polymer units – 275 units of F87, 442
units of F127, and 537 units of F108 per TPP molecule) causes a marked
change in the growing pattern of the Pluronic crystals. The three-dimen-
sional multilayered structures form in abundance in the presence of the
Porphyrin–Polymer Complexes in Model Photosensitized Processes 103

porphyrin despite the unfavorable conditions for their growth. Apparently,


such noticeable alteration of the local crystallization mechanism can be
related to certain specific interactions between TPP molecules and mac-
romolecules of a Pluronic. Porphyrins are capable of rather strong com-
plexation with Pluronics, as seen from the studies of their partitioning
coefficients (defined as the ratio of porphyrin concentrations in aqueous
solution and in micelles).28 In particular, the partitioning coefficient for
TPP in F127 was found to be 3 × 104, a result which indicates a high affin-
ity between the porphyrin and Pluronics. Porphyrin–Pluronic complexes
have been recently directly observed in our group by NMR spectroscopy.44
The interactions most likely occur between the hydrophobic PPO parts
of the amphiphilic Pluronic molecules and small TPP aggregates, which
are always present in porphyrin solutions.54 Both individual and aggre-
gated TPP moieties were found within the hydrophobic layer of a Lang-
muir-Blodgett film prepared from an amphiphilic copolymer containing
TPP pendants.55 A direct spectroscopic evidence of ZnTPP aggregation in
a polymer film prepared by spin coating from a solution has been obtained
by O’Brien et al.56
We believe that the complexes between TPP and Pluronics create a
micelle core upon their transfer from a solid film into the aqueous phase.
High efficiency of TPP solubilization and small sizes of TPP aggregates
account for the marked improvement of the porphyrin photocatalytic ac-
tivity seen in the experiment.28 The AFM imaging data have shown the
same porphyrin-driven alterations in the structure of the three studied
Pluronics, despite their differences in the molecular weight and degree of
hydrophobicity. Thus, one could expect the same mechanism for the sub-
sequent TPP solubilization by F87, F108, and F127. Indeed, we observed
similar catalytic activity of TPP–F87, TPP–F108, and TPP–127 systems in
the tryptophan photooxidation: the effective rates of oxidation were mea-
sured as 2.0 × 103, 1.9 × 103, and 1.9 × 103 L/(mol.sec), respectively.
Thus, the collection of the presented data leads to a conclusion that in
the presence of APs in aqueous media, a disintegration of the porphyrin
molecular associates takes place, due to the hydrophobic interactions be-
tween AP and PPS. Such PPS disaggregation results in the enhancement
of their photosensitizing activity in the processes of 1O2 generation and
oxidation of substrates. This enhancement of the PPS photosensitizing ac-
tivity in vitro in the presence of APs may be a component of the earlier
104 Additives in Polymers: Analysis and Applications

revealed effect of enhancement of PPS–AP complexes activity in vivo in


the PDT in the treatment in rat’s purulent and firearm wounds.25–27,57,58

PHOTOTOXICAL PROPERTIES OF PORPHYRIN–POLYMER


COMPLEXES

We examined the phototoxic activity of photoditazin–polymer complexes in


cancer cell culture treatment and by PDT of purulent wounds in laboratory rats.
So we analyzed the effects of photoditazin and its complexes with APs, on
the early stage of wound healing in a rat model. A skin excision wound
model with prevented contraction was developed in male albino rats di-
vided into groups according to the treatment mode. All animals received
injections of one of the studied compositions into their wound beds and
underwent low-intensity laser irradiation. The clinical monitoring and his-
tological examination of the wounds were performed. It has been found
that all the PD formulations have significant effects on the early stage of
wound healing. The superposition of the inflammation and/or regeneration
is the main difference between groups. The aqueous solution of PD alone
induced a significant capillary hemorrhage, while its combinations with
APs did not. The best clinical and morphological results were obtained
for the PD–Pluronic F127 composition. Compositions of PD and APs,
especially Pluronic F127, probably have a great potential for therapy of
wounds. Their effects can be attributed to the increased regeneration and
suppressed inflammatory changes at the early stages of repair.
Photosensitizing activity of PD–AP complexes was examined prelimi-
narily in the cell experiments.

CELLULAR EXPERIMENTS

The polymers PVP, PEO, and Pluronic F127 were chosen to determine the
influence of AP on PD phototoxicity in cell experiments. Figure 4.9 shows
dependences of the experimental “survival” results for NIH-3T3-EWS-
FLI1 cells after incubation in dark for 3 h with PD (5Ч10−7 M) and sub-
sequent illumination (with one exception – dependence [2] Fig. 4.1b) with
semiconductor laser (A = 658 nm, 20 mW/cm2, exposure time = 3 min) of
Porphyrin–Polymer Complexes in Model Photosensitized Processes 105

the PD concentration. (The results were estimated in 3 h after illumina-


tion.)

FIGURE 4.9  The NIH-3T3-EWS-FLI1 Cell Survivability Dependence of the PD


Concentration After Incubation in Dark With or Without AP in Medium: (а) Without AP
(1), with 0.1% PVP (2), and 0.1% PEO (3); (b) with 0.5% Pluronic F127 (1), 0.5% F127 in
dark (2), 0.05% Pluronic F127 (3), and 0.1% F127 (4).
In accordance with Figure 4.9, the APs PVP, PEO (Fig. 4.8a, curves
2, 3), and Pluronic F 127 (Fig. 4.8b, curves 1, 3, 4) increase effectively
the photoinductive toxicity of PD, and the Pluronic F 127 turn out to be
the most active among all studded polymers. The activity of the PD–F127
complex did not depend on Pluronic concentration in solution. It is neces-
sary to note that F127 and other APs do not increase the PD dark activity
(Fig. 4.9b).
These results may be connected with the ability of AP to be bound with
lipid membranes, as far as the cell membranes are considered as an impor-
tant target of PDT treatment. The direct bonding of PD and membranes
is caused by low lifetime of singlet oxygen (∼10−6 с), which carries the
photodynamic cellular damage.

PDT EXPERIMENTS IN HEALING WOUNDS IN RATS

Curing of soft tissues pyoinflammatory diseases remains a topical problem


today in spite of significant advances of clinical medicine and pharmacol-
ogy because drug treatment on different stages of wound process is not al-
ways successful. There are many antibacterial and wound healing agents,
but they do not stimulate the processes of regeneration adequately due
106 Additives in Polymers: Analysis and Applications

to the changes of suppurative complication disease-producing factors in


modern time. Generally, anti-infective activity of preparations used is not
sufficient. Of late years, for the therapy of wound formed after suppurative
focus surgical d-bridement, the laser and PDT is applied. PDT is based on
the photosensitization (PS) activation of molecular oxygen. Under the ac-
tion of light, PS gets excited and transfers the molecular oxygen dissolved
in the organism to its chemically active singlet state. The singlet oxygen
oxidizes cell components and initiates a cascade of processes resulting in
the death of the ill cells. Recently, PDT has been used for the treatment of
festering wounds and trophic ulcers.24,57,58 An important advantage of PDT
is its ability to affect bacterial cultures that are resistant to antibiotics.

PD–AP COMPLEX BY PDT OF GUNSHOT WOUNDS IN RATS

The PD–AP complex efficiency was demonstrated in local gunshot wound


treatment of laboratory rats (Table 4.2, Fig. 4.10). The data in Table 4.2
display the wound healing time values depending on the dosage of PD.
The time taken for complete healing of the wound efficiently by PD–
Pluronic gel (containing 1% wt PD with Pluronic F127) is higher (up to
∼40%) compared with using PD corresponding solution.

TABLE 4.2  Pluronic F127 Effect in the Healing of Rat Burn Wounds
Animal Groups and Time of Healing (Days) Acceleration of
Type of Wound
Treatment Granulation Complete Healing Healing Regarding
of Wounds the Control Group
(%)
Control group (the 15.2 ± 1.4 29.8 ± 0.8 –
use of antiseptic
solutions)
First experimental 11.3 ± 0.7 24.2 ± 0.2 18.9
group (1% PD solu-
tion)
Second experimental 7.0 ± 0.5 17.2 ± 1.1 42.3
group (1% gel-com-
plex PD – F127)
Porphyrin–Polymer Complexes in Model Photosensitized Processes 107

FIGURE 4.10  Rat’s Gunshot (a) Wound After 15 Days Conventional Antiseptic Treatment;
(b) The Wound After 15 Days of PDT Treatment with 1% gel PD-Pluronic F127.

The observed effects are illustrated with two photos presented at Figure
4.10: (а) wound after 15 days conventional antiseptic treatment, (b) wound
after 15 days of PDT treatment with 1% gel PD-Pluronic F127.

EARLY STAGE OF THE WOUND HEALING PROCESS BY PDT


USING PD–AP COMPLEXES

The early stage in the healing of wounds has been known to have a princi-
pal effect on the progress and results of the further recovery of the skin and
determine in particular the probability of pathological scarring. It has re-
cently been demonstrated that it is exactly at the initial stage of reparation
that the positive effects of PDT manifest themselves most distinctly.59–61
We believe that the comparative evaluation of the efficacy of the newly
developed photosensitizers with APs on the basis of the results of inves-
tigations into morphological changes taking place in wound tissues at the
initial stage of the healing process can be a valid groundwork for selecting
photosensitizer modification strategies and developing PDT regimens. The
objective of this work was an experimental morphological study of the
specific features of the early stage of the wound healing process in the
case of laser PDT using the photoditazin and its complexes with APs of
different nature.
108 Additives in Polymers: Analysis and Applications

MACROSCOPIC EVALUATION OF THE CLINICAL


PRESENTATION OF THE WOUND CONDITION

One day after the surgical procedure, the clinical condition of the wounds
in all the animals under study was of the same type: the wounds were mod-
erately moist, their bed was covered with a thin whitish fibrin layer; there
was no apparent exudation, and the perifocal reaction in all cases was but
weakly evident.
The next day after the first irradiation session, some differences in the
condition were observed between the wounds, especially evident in groups
III (aqueous PD solution + irradiation) and VI (PD–PVP complex + irra-
diation). Found in the wound collar cavity of two animals in each of these
groups was a hemorrhagic exudate in amounts of 0.5–1.0 mL. The hemor-
rhage intensity and amount of the exudate were greater in the group III
animals. In the rest of the animals of these groups, a small amount of the
ordinary rose-tinted exudate was present in the wound collar cavity. In
groups I (untreated), II (isotonic sodium chloride solution + irradiation),
IV (aqueous PVP solution + irradiation), V (aqueous Pluronic F127 solu-
tion + irradiation), and VII (PD–Pluronic F127 complex + irradiation), the
clinical presentation of the wounds practically did not change.
Prior to the second irradiation session (day 3 after the wounding, and
day 2 after the first irradiation session), the exudative-hemorrhagic reac-
tion in the animals of groups III and VI somewhat intensified: in those
wounds where this reaction in the preceding observation was ambiguous,
the amount of the exudate increased and its color became more marked.
In four animals of these groups, the amount of the exudate was so sub-
stantial that it had to be extracted before the wounds could be irradiated.
With the exudate removed, a cyanotic wound surface was exposed, with
hemorrhage foci at the injection sites (punctures) of the preparations under
study; no fibrin was present. The condition of the wounds in the rest of the
groups (I, II, IV, V, and VII) was “quiet”; only a slight increase of the fibrin
layer, especially at the collar walls, could be observed in some animals. An
insignificant amount of a rose-tinted exudate was found in the wound col-
lar cavities of the animals of group VII (PD–Pluronic F127 complex + ir-
radiation). Not numerous petechial hemorrhages could be observed on the
wound bed in one animal.
Four days after the wounding and two PDT sessions, the tissue layer
excised in the animals of groups III and VI was thicker (≈ 6–8 mm), ge-
Porphyrin–Polymer Complexes in Model Photosensitized Processes 109

latinous (edematous), and impregnated with a hemorrhagic exudate. In


the control animals (groups I, II, IV, and V), the excised wound bed tissue
layer was of ordinary density; it was dark pink in color and thinner than
that in groups III and VI. The wound bed tissue layer in the animals of
group VII (PD–Pluronic F127 complex + irradiation) was thicker, but less
dense and edematous than that in groups III and VI.

RESULTS OF HISTOLOGICAL EXAMINATIONS

The histological examinations of the structure of the tissues developing


in the wound bed, conducted within four days after the wounding and
two PDT sessions, showed that these tissues in all the groups of animals
had a similar structure. It consisted of three layers: a fibrinous-leukocytic
layer (exudate), a layer of the granulation tissue, and a fatty tissue layer.
However, the morphological characteristics of these layers in each of the
groups had certain differences, apparently due to photobiological effects.
The numerical scores of the intensity of these morphological features are
listed in Table 4.3.
Predominant in the wounds in control groups I, II, IV, and V (untreated,
isotonic sodium chloride solution + irradiation, aqueous PVP solution + ir-
radiation, and aqueous Pluronic F127 solution + irradiation, respectively)
were inflammatory processes: exudation, neutrophil infiltration, edema,
blood vessel hyperemia, with stasis and erythrocytic sludge in the lumen,
and erythrocyte diapedesis (signs of microcirculation injuries). In group
I, the developing granulation tissue did not yet form a continuous layer
but was represented by individual foci. In control groups II, IV, and V,
the granulation tissue occupied the entire wound surface, but its layer
was relatively thin. The tissue itself was markedly immature. It consisted
of proliferating spindle-shaped and polygonal fibroblasts, macrophages,
lymphocytes, and few vessels. Neoangiogenesis was weakly expressed,
and vertical capillaries were practically absent. Collagen fibers were thin
and immature (bleak color in Van Gieson staining with picrofuchsin). In
the animals of these groups, the reparative regeneration processes that
manifest themselves in fibroblast proliferation and neoangiogenesis were
much less expressed than the signs of inflammation.
The most significant morphological features of the wound healing pro-
cess were revealed in group III animals (aqueous PD solution  irradiation).
110 Additives in Polymers: Analysis and Applications

The main distinctive feature was the perceptible accumulation of loose


hemorrhagic exudate in the wound. This fact can probably be considered
as the evidence that the permeability of vessels has increased in response
to the PDT procedure combining the photobiological effects of laser radia-
tion and PD. The structure and functional condition of granulation tissues
in group III animals also featured a number of distinctions. The layer of
granulations was thicker than that in control groups I, II, IV, and V. The
tissue showed a greater maturity: the number of vascular elements therein
was increased, which points to intensive neoangiogenesis. Separate verti-
cal capillaries were observed in some areas. The granulation tissue con-
sisted of fibroblasts and thin immature collagen fibers and contained an
increased number of lymphocytes and macrophages. This testifies to the
activation of cellular immunity reactions under the effect of PDT.
Thus, the wounds in the animals of control group III (aqueous PD so-
lution + irradiation) show more pronounced regeneration processes (more
abundant and somewhat more mature granulation tissues) and intensified
neoangiogenesis and fibroblast proliferation. At the same time, the signs of
inflammation and microcirculation injuries do not differ in intensity from
those in the animals of the rest of the control groups. The hemorrhagic
character of the exudate and tissue edema point to increased permeability
of blood vessel walls.

TABLE 4.3  The 0–10 Point Numerical Scores for the Intensity of Morphological
Alterations in the Animals Under Study

Group Animal Intensity of Morphological Alterations, Score


No. Inflammation Hemorrhagic Reaction Reparation
I 1 8 0 2
2 8 1 2
3 7 0 3
II 4 7 2 3
5 7 2 3
6 6 2 4
III 7 6 5 5
8 7 6 4
9 6 5 5
Porphyrin–Polymer Complexes in Model Photosensitized Processes 111

IV 10 6 2 3
11 6 2 3
12 7 2 1
V 13 6 2 3
14 5 2 2
15 6 2 3
VI 16 6 6 3
17 3 4 5
18 3 4 5
VII 19 3 2 5
20 3 2 5
21 3 2 6

In group VI (PD–PVP complex + irradiation), the exudate was of hem-


orrhagic character (Fig. 4.6), but the amount of hemorrhages was percep-
tibly smaller than in group III (aqueous PD solution + irradiation). At the
same time, the granulation tissue occupied a greater volume in the struc-
ture of the wound bed. It was more mature and rich in vascular elements.
Characteristic of this granulation tissue was also the presence of numerous
proliferating fibroblasts and an increased number of macrophages, which
points to activation of the reparative processes, and the signs of inflamma-
tion (edema, neutrophil infiltration, erythrocyte stasis, and sludge in capil-
laries) being less marked than in control groups I (untreated), II (isotonic
sodium chloride solution + irradiation), and III (aqueous PD solution +
irradiation).
The histological study of the wound tissues in group VII animals
(PD–Pluronic F127 complex + irradiation) showed that, in contrast to the
wounds in the animals of group V (PD–PVP complex + irradiation) and
control group III (aqueous PD solution + irradiation), the concentration of
erythrocytes in the fibrinous-leukocytic layer was minimal, which was in
agreement with the macroscopic examination data. The granulation tissue
layer was even thicker than that in the rest of the groups. It is important
to note that the granulation tissue formed a continuous layer and extended
over the entire wound surface, which was uncharacteristic of the control
groups. This tissue was of a sufficiently mature character. Some capillar-
ies assumed vertical orientation. As compared with the control groups,
112 Additives in Polymers: Analysis and Applications

increased number of macrophages was observed. The number of neutro-


phils and edema were less than those in control groups I and II and also
in group VI.
Thus, the main distinctive feature of the early stage of the wound heal-
ing process in the case of PDT using the PD–Pluronic F127 complex is
the absence of the hemorrhagic exudate observed to occur in the wounds
subject to PDT using the PD–PVP complex. Apparently, the complex of
PD and Pluronic F127 reduces the harmful effect of the photosensitizer on
the endothelium and basal membrane of capillaries and, as a consequence,
prevents erythrocytes from egressing into the surrounding tissue. In addi-
tion, inflammatory alterations, microcirculation injuries included, in the
wounds in group VII animals were less marked. The signs of regeneration
(maturing of the granulation tissue) were more pronounced than those in
all the rest of the groups.
The results obtained bear witness to the fact that the photobiological
properties of PD in the PD–Pluronic F127 complex remain unimpaired,
while its histotoxicity, which in the case of PDT using an aqueous PD
solution, manifests itself in the increase of the permeability of capillaries
and development of hemorrhagic reactions decreases. Consequently, the
use of the PD–Pluronic F127 complex in the PDT of wounds proves more
effective than the original PD preparation at the early stage of the wound
healing process.
The statistical analysis of the intensity of morphological features in
the groups of animals under study by the group comparison (KW) proce-
dure demonstrated that statistically significant relations existed between
the kind of substance injected into the wound bed and the intensity of
inflammation (p = 0.014), the hemorrhagic reaction (p = 0.003), and the
reparative reaction (p = 0.018). This evaluation is based on the fact that
the laser treatment conditions were the same for all the groups of animals
under study. The results of the pairwise comparisons of the intensities of
morphological features in the groups of animals under study (the relation
between the mean ranks of values in the groups being compared) are pre-
sented, along with the p values, in Table 4.4.
Injections of sodium chloride into the wound bed tissues, combined
with their laser irradiation (group II), cause no statistically significant
changes in the intensity of inflammation and hemorrhagic and reparative
reactions as compared with group I (untreated).
Porphyrin–Polymer Complexes in Model Photosensitized Processes 113

The use of the aqueous PD solution (group III) for this purpose results
in a statistically significant enhancement of the reparative reaction com-
pared with group I (untreated). At the same time, it is accompanied by
intensification of the hemorrhagic reaction in comparison with groups I,
II, IV, V, and VII.
The morphological effects of injections of aqueous PVP (group IV)
and Pluronic F127 (group V) solutions into the wound bed tissues, com-
bined with the laser treatment, are statistically indistinguishable. At the
same time, for both these polymers, no statistically significant changes
were found in the intensity of the morphological features under study by
comparison with group II (isotonic NaCl solution + irradiation). Com-
pared with group I (untreated), injections of the aqueous PVP and Pluronic
F127 solutions, combined with laser irradiation, somewhat increased the
intensity of the hemorrhagic reaction. Since no statistically significant dif-
ferences in the intensity of the morphological features existed between
groups I and II, it can be assumed that the hemorrhagic reaction owed to
the combined effect of laser radiation and injections. Inasmuch as the laser
treatment regimen in group II was the same as in groups III through VII,
the intensification of the hemorrhagic manifestations can be explained
by the alteration of the osmotic balance in the wound tissues occurring
against the background of the laser-induced dilation of blood vessels.
The use of the PD–PVP complex (group VI) was observed to cause a
statistically significant decrease of inflammation as compared with group
I (untreated). At the same time, the intensity of the hemorrhagic reaction
increased by comparison with groups I, II, IV, and V. No statistically sig-
nificant differences in the intensity of inflammation, hemorrhagic reaction,
and reparative phenomena were found in comparison with group III (aque-
ous PD solution).
The injection of the PD–Pluronic F127 complex (group VII) into the
wound bed tissue is characterized by a statistically significant decrease of
the inflammatory manifestations as compared with groups I, II, III, IV, and
V. Statistically significant increase in the reparative activity was observed
in comparison with groups I, II, IV, and V. The hemorrhagic reaction was
more pronounced than that in group I (untreated), but statistically signifi-
cantly weakened as compared with groups III (aqueous PD solution + ir-
radiation) and VI (PD–PVP complex + irradiation).
114 Additives in Polymers: Analysis and Applications

TABLE 4.4  Comparison of the Intensities of Morphological Features by Means of the


Mann–Whitney Test
Group Morphological II III IV V VI VII
Featuresa NaCl, PD PVP Pluronic PD–PVP PD–Plu-
0.9% F127 complex ronic
F127
Complex
I In II < I, III < I, IV < I, V < I, VI < I, VII < I,
(untreated) p = 0.099 p = 0.068 p=0.068 p = 0.043 p = 0.043 p = 0.034
H II > I, III > I, IV > I, V > I, VI > I, VII > I,
p = 0.099 p = 0.043 p = 0.034 p = 0.034 p = 0.043 p = 0.034
R II > I, III > I, IV > I, V > I, VI > I, VII > I,
p = 0.099 p = 0.043 p = 0.816 p = 0.456 p = 0.068 p = 0.043
II In III < II, IV < II, V < II, VI < II, VII < II,
p = 0.456 p = 0.456 p = 0.099 p = 0.068 p = 0.034
H III > II, IV = II, V = II, VI > II, VII = II,
p  0.034 p = 1.000 p = 1.000 p = 0.034 p = 1.000
R III > II, IV < II, V < II, VI > II, VII > II
p = 0.068 p = 0.197 p = 0.197 p = 0.239 p = 0.043
III In IV = III, V < III, VI < III, VII < III,
p = 1.000 p = 0.197 p = 0.099 p = 0.034
H IV < III, V < III, VI < III, VII < III,
p  0.034 p = 0.034 p = 0.361 p = 0.034
R IV < III, V < III, VI < III, VII > III,
p = 0.043 p = 0.043 p = 0.796 p = 0.197
IV In V < IV, VI < IV, VII < IV,
p = 0.197 p = 0.099 p = 0.034
H V = IV, VI > IV, VII = IV,
p = 1.000 p = 0.034 p = 1.000
R V > IV, VI > IV, VII > IV,
p = 0.96 p = 0.099 p = 0.043
V In VI < V, VII < V,
p = 0.239 p = 0.034
H VI > V, VII = V,
p = 0.034 P = 1.000
R VI > V, VII > V,
p = 0.099 p = 0.043
VI In VII < VI,
p = 0.317
H VII < VI,
p = 0.034
R VII > VI,
p = 0.197
Notes: aMorphological features: In, inflammation; H, hemorrhagic reaction, and R,
reparative reaction. Statistically significant differences are shown in bold type.
Porphyrin–Polymer Complexes in Model Photosensitized Processes 115

In this part, experiments are described, related with carrying out clini-
comorphological studies of the tissue reactions and specific features of
the wound healing process in rats on day 4 after the wounding in the case
of PDT of wounds with the use of the photosensitizer PD and its combi-
nations with APs. The choice of this time period is nonrandom, for it is
exactly during the course of this period that the transition takes place from
the inflammatory to the proliferative phase of the wound healing process.
The histological examination of the superposition of the inflammation
and/or regeneration morphological features developing during this period
under the effect of various extrinsic factors allows one to evaluate the
activity of the wound healing process and the role of these factors, which
either hamper or, conversely, stimulate its course.62
The comparative experimental morphological studies on the effect of
PDT, with numerical scoring being made for the inflammatory, hemor-
rhagic, and reparative (regenerative) manifestations, helped us to reveal
a number of specific features of the healing process in uncomplicated
wounds. Since the laser treatment regimen was the same for all the groups
of animals under study, the differences observed were conditioned by the
choice of the substances used for photochemical treatment purposes (the
compositions injected into the wound bed tissues).
When the isotonic sodium chloride solution was injected into the
wound bed and the wound was thereafter exposed to laser radiation, the
wound was dominated by inflammatory processes manifest in edema, neu-
trophil infiltration, and microcirculation injuries (hyperemia, erythrocyte
stasis, sludge in the lumen of microvessels, and diapedetic hemorrhages).
At the same time, the reparative–regenerative processes (fibroblast pro-
liferation and neoangiogenesis) were but weakly expressed. The absence
of the wound healing effect from a low-intensity laser light61 is appar-
ently explained by the twofold reduction (to 2.9 J/cm2) of the total irradia-
tion dose by comparison with that provided for by the wound treatment
protocol described earlier for a similar model in animals.61 Based on the
fundamental principles of the photodynamic concept of the healing ef-
fect of low-intensity optical radiations [61], it can be suggested that to
achieve photosensitized free-radical activation of the cells participating
in the wound healing process, it is necessary either to increase the wound
irradiation dose or to combine wound irradiation with agents catalyzing
the photochemical reactions; that is, to use exogenous photosensitizers,
for example, PD.
116 Additives in Polymers: Analysis and Applications

The aqueous solution of PD, combined with laser irradiation, caused


perceptible activation of the reparative processes (neoangiogenesis, fibro-
blast proliferation, collagen fibrillogenesis, granulation tissue growth), as
compared with the untreated control. This photosensitizer had no signifi-
cant effect on the inflammatory processes. At the same time, it should spe-
cifically be noted that PD intensified hemorrhagic morphological features,
which can be due to the increase in the permeability of blood vessel walls
or can be due to the difference in osmotic potential between the PD solu-
tion and the tissue fluid. PD has been known to have the ability of accumu-
lating predominantly in neovascular tissues [61], and granulation tissues
are essentially this type. The increase of the permeability of blood vessel
walls can supposedly be due to the damage caused to the endothelium and
basal membrane of the newly formed vessels by the free radicals resulting
from PDT. One of the ways to combat the undesirable toxic complica-
tions and improve the healing effect is to use photosensitizers in combi-
nation with APs.27,63 It is desirable to create the photosensitizer–polymer
complexes using such polymers that do not affect the bioavailability and
photocatalytic activity of the chromophore and do not hamper the devel-
opment of the reparative processes in the wound. In our investigations, we
used PVP and Pluronic F127.
When in our experiments we used the amphiphilic polymer PVP or
Pluronic F127 wound-bed injections (without PD) in combination with
laser irradiation of the wounds, no statistically significant differences were
found in the intensity of the inflammatory and hemorrhagic manifesta-
tions in the wounds by comparison with control group I. At the same time,
a tendency toward weakening of the inflammatory and intensification of
the reparative manifestations was observed in the case of Pluronic F127
application as compared with PVP. This fact allows us to state that the
above polymers used in combination with laser irradiation do not inhibit
the wound reparation process, and at the same time, they even somewhat
activate it, as illustrated by the example of Pluronic F127.
When using the PD–Pluronic F127 complex in the PDT of wounds, we
observed the most clearly pronounced improvement of the wound healing
process at the early stage. The observed improvement involved decrease
of inflammation, activation of reparation, and lowering of the intensity of
the hemorrhagic reaction manifestations to the minimal values among all
the combinations of the therapeutic factors studied (to the level character-
istic of sodium chloride injections combined with laser irradiation). The
Porphyrin–Polymer Complexes in Model Photosensitized Processes 117

comparative analysis of the intensities of the morphological features of


wound healing showed that, when using the PD–PVP complex, the hem-
orrhagic reaction was manifest approximately to the same extent as in the
case of aqueous PD solution. The PDT of wounds with the use of the PD–
PVP complex had practically no effect on the intensity of inflammation
and reparation.

CONCLUSIONS

We showed that APs, especially block copolymers of EO and PO, can


increase photocvatalytic activity of porphyrins photosensitizers – dimegin
and PD – an N-methylglucamine salt of chlorine e6 both in model experi-
ments in water solution and in biological systems. In fact, AP enhances
phototoxicity of photoditazin in cell cultures and wound healing by PDT.
This effect may be due to various reasons. Moreover, the mechanism of
influence of AP on PD photocatalytic activity in water solution and in
biological experiments may be quite different. We suppose that AP-in-
duced activation of PD in water solution is mainly due to disaggregation
of PPS associates by complex between PPS and AP formation. Probably
such mechanism is acting in biological systems too. Besides, we expect
that Pluronic and other AP may suppress reparative processes in the cells,
for example, via inhibition of membrane ATPases located on cell plasma
membranes or causing leakage of intracellular scavengers of singlet ox-
ygen such as glutathione. Anyway, this subject requires further investi-
gation. However, applicability of the observed effect in PDT of infected
wounds has been proved herein and offers the challenges for wide investi-
gation of polymer-based formulations in photodynamic therapy.
The observed clinicomorphological details of the early stage of the
wound healing process under the PDT applying PD–AP complexes lead
us to the conclusion that the polymer Pluronic F127 can weaken (and pos-
sibly eliminate) the adverse effect of PD on microvessels and prevent the
development of local hemorrhagic reactions that complicate the wound
healing process. It is also important to note that laser irradiation in com-
bination with the PD–Pluronic F127 complex is conducive to the weak-
ening of the inflammatory processes and intensification of the reparative
ones by comparison with the PD–PVP complex. In this connection, the
118 Additives in Polymers: Analysis and Applications

PD–Pluronic F127 complex can be used as a photosensitizer for the PDT


purposes.
Establishing the mechanisms of the interactions of the components
within the PD–Pluronic F127 complex and regulation of those reactions
during the light treatment process, as well as the study of the PDT effects
dynamics with the use of this complex, will be the subject of our further
investigations.

KEYWORDS

•• Photodynamic therapy
•• porphyrin photosensitizers
•• singlet oxygen
•• photogeneration
•• tryptophan
•• histidine
•• photooxidation
•• photoditazin
•• cancer cells
•• purulent wounds

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49. Chan, C.-M.; Li, L. Direct observation of the growth of lamellae and spherulites by
AFM. Adv. Polym. Sci. 2005, 188, 1.
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CHAPTER 5

STRUCTURE AND PROPERTIES


OF RUBBER POWDER AND ITS
MATERIALS
E. V. PRUT, O. P. KUZNETSOVA, and D. V. SOLOMATIN
Semenov Institute of Chemical Physics of Russian Academy of Sciences, Moscow,
Russia
Email: [email protected]

CONTENTS

Abstract.............................................................................................................. 124
Introduction........................................................................................................ 124
Effect of Joint Action of High Pressure and Shear Deformation on
Physical and Chemical Properties of Solid........................................................ 128
Elastic-Deformation Grinding........................................................................... 131
High-Pressure and High-Temperature Sintering................................................ 141
Applications of Rubber Powder in Thermoplastics........................................... 147
Conclusion......................................................................................................... 165
Acknowledgments.............................................................................................. 166
Keywords........................................................................................................... 166
References.......................................................................................................... 167
124 Additives in Polymers: Analysis and Applications

ABSTRACT

The treatments, technologies, and materials of rubber are presented in this


review. The review gives a comparative analysis of process characteris-
tics, rheological and mechanical properties, structural transformations,
curing behavior, and diffusion processes taking place in unfilled and filled
rubbers during their treatment by the method of high-temperature shear
deformation (HTSD). Sulfur-cured rubbers are considered, along with de-
tails of degradation mechanisms of the rubber network by mechanical and
thermal exposure. Properties of blends and composites of devulcanized
and virgin rubbers are presented. Future directions and further develop-
ment of the technology HTSD are discussed.

INTRODUCTION

New properties of macromolecules with important practical results have


been discovered in polymer chemistry and physics. Basic advances reveal
key relationships in the development of new materials that exhibit pre-
viously inconceivable combinations of properties. A principal difference
between fundamental science and technologies is intent.
Macromolecular science covers a fascinating field of research, focused
on the creation, understanding, and tailoring of materials formed out of
very high molecular weight molecules. Such compounds are needed for a
broad variety of important applications. Due to their high molar masses,
macromolecules show particular properties not observed in any other class
of materials.
The history of synthetic polymers is incredibly short. Considering the
uneven rate of polymer consumption around the world, polymer produc-
tion has the potential to increase tenfold by the mid-21st century. Polymers
are the fastest growing structural materials. Nowadays, polymers are ex-
tensively used in different fields.
Many new multicomponent polymeric materials have been developed
during the past two decades. Polymer compositions grow to take on a very
significant role in the major application areas for polymers. This is con-
nected with the significant expansion of the polymer applications with
comparatively limited assortment of monomers. The combination of poly-
mers using different methods provides one with a means of varying their
Structure and Properties of Rubber Powder 125

properties. These combinations of polymers allow one to obtain polymer


blends. Mixing of different polymers is an effective and economic way
for production of new materials with desired properties. Performance of
such multicomponent polymeric materials depends on their compatibility
and morphology developed during the processing. The large numbers of
scientific papers, industrial patents, scientific meetings, and exhibitions
devoted to this class of materials are a sufficient witness to their strategic
importance.1–4
Blends based on thermoplastics and rubbers occupy a prominent posi-
tion among multicomponent polymeric materials. The mechanical prop-
erties of these materials can be changed in a wide range by varying the
ratio of blend components. When the content of rubber is small (5–20%),
blends behave as high-impact thermoplastics. If the rubber content var-
ies from ~50% to 80%, thermoplastic elastomers (TPEs) can be prepared.
Both classes of materials find wide application that requires detailed con-
sideration of different factors, such as the influence of the chemical and
molecular structures of the elastomer, the molecular-weight distribution of
the properties of the finished products.
Toughened plastics are usually multiphase polymers; the dispersed
phase consists of rubbery or thermoplastic domains, and the continuous
phase is a thermoplastic polymer matrix. The basic reason for toughen-
ing a plastic via this route is to improve its toughness, or crack resistance,
without significantly decreasing other important properties such as the
modulus and creep resistance. Such toughened plastics that are widely
used in many diverse industries form the basis for engineering plastics,
structural adhesives, and matrices for fiber-composite material.5
The TPEs constitute a commercially relevant and fundamentally inter-
esting class of polymeric materials. The emergence of TPEs provided a
new horizon to the field of polymer science and technology. They combine
the properties of cross-linked elastomers, such as impact resistance and
low temperature flexibility, with the characteristics of thermoplastic mate-
rials, for example, the ease of processing. In general, TPEs are phase sepa-
rated systems consisting of a hard phase, providing physical cross-links,
and a soft phase, contributing to the elastomeric properties. In many cases,
the phases are chemically linked by block or graft copolymerization. In
other cases, a fine dispersion of the hard polymer within a matrix of the
elastomer by blending also results in TPEs like behavior. Consequently,
TPEs exhibit mechanical properties that are, in many ways, comparable
126 Additives in Polymers: Analysis and Applications

to those of a vulcanized rubber, with the exception that the network and
hence the properties of the TPEs are thermally reversible. This feature
makes TPEs ideally suited for high-throughput thermoplastic processes,
such as melt extrusion and injection molding. Mainly three classes of com-
mercial TPEs can be distinguished: polystyrene-elastomer block copoly-
mers, multiblock copolymers, and polymer-elastomer blends. Thus, TPEs
combine the mechanical properties of rubbers at ordinary temperatures
with processability above their melting temperatures inherent of linear
thermoplastic polymers.
The properties of TPEs can be substantially improved by the method
of dynamic vulcanization. The feature of this method is that rubber com-
ponent is chemically cross-linked during the process of mixing. This gives
rise to the heterogeneous structure in which the cross-linked elastomer
particles of the order of 1–3 µm in size are dispersed in the continuous
matrix of the thermoplastic component. TPEs prepared by dynamic vul-
canization are identified as thermoplastic vulcanizates (TPVs). The char-
acteristics of elastomeric phase can have significant impact on the me-
chanical properties of TPVs. At room temperature, the TPVs exhibit the
mechanical properties typical of elastomers, and at temperatures above
the melting temperature of thermoplastics, their rheological behavior is
inherent to thermoplastic polymers. The processing behavior of TPVs is
essentially influenced by the rheological properties of their melt. In order
to reduce the viscosity and to improve the processability of TPVs, some
modifiers (e.g., paraffinic oil) are added to the material.6
One of the various problems of the 21st century is the problem of waste
disposal management.7–9 A lot of waste rubber is produced every year in
the world. The main sources of waste rubber products are discarded waste
tires, rubber pipes, rubber belts, rubber shoes, edge scraps, and waste prod-
ucts that are produced in the rubber processes and others. Since polymeric
materials do not decompose easily, disposal of waste polymers is a serious
environmental problem. The three-dimensional cross-linked structure of
waste rubber makes it infusible, insoluble, and difficult to recycling. Typi-
cal methods have been developed to treat the waste rubber: combustion,
landfilling, biodegradation, and recycling. Among them, recycling is the
most attractive method. Recycling is a major issue for most plastics pro-
cessors and waste disposal authorities in the new century. However, the
technology for recycling of rubbers is complex and costly.
Structure and Properties of Rubber Powder 127

The three-dimensional network of the thermoset polymer system must


be broken down either through the cleavage of cross-links or through the
carbon–carbon linkage of the chain backbone. As was mentioned by To-
bolsky,10 the C–C bond dissociation energy upon peroxide vulcanization is
DC−C = 390 kJ/mol, and in the case of vulcanization with sulfur-containing
agents, the dissociation energy of monosulfide, disulfide, and polysulfide
bonds is DC−S−C  = 210–251 kJ/mol, DC−S−S−C = 172 kJ/mol, and DC−S−S−
S−S
 = 113 kJ/mol, respectively.
At present, the major effort in waste rubber recycling is to reuse it as
a finely crumb rubber, produced by mechanical grinding. A lot of effort is
put into the improvement of the quality of recycled rubber, reflecting, on
the one hand, the high interest in rubber recycling, and on the other hand,
indicating the difficulties of the recycling process. The processes used for
grinding of rubber are based on cutting, shearing, or impact, depending on
the equipment (knife, shredder, granulator, extruder, disk grinder, or im-
pact mill) and the grinding conditions (ambient, wet, or cryogenic grind-
ing). The choice of the process is based on the requirements for the final
product, such as particle size and particle size distribution, morphology of
the particles, and purity of the rubber powder.7,9
Waste rubber has been recycled and reused for a long time, through
the application of various techniques involving size reduction by grind-
ing, at either ambient or cryogenic temperature. Each of these grinding
techniques produces crumb rubber of different particle size, particle-size
distribution, and shape. Crumb rubber is added as a partial replacement of
virgin rubber in various blends and composite. However, the amount of
crumb rubber used in these compositions is limited, due to some loss in
its physical properties. The search for better technologies that will allow
larger quantities of used waste rubber to be incorporated into new products
continues, and several new approaches have been successful.
One of the promising methods developed in the past two decades is
the elastic deformation grinding technique (EDG). This technique is based
on the degradation of a material in a complex strained state by the action
of uniform compression pressure and shear forces under elevated tem-
peratures. EDG makes it possible to obtain fine powders of comminuted
rubbers, thus allowing the valuable properties of elastomer materials to be
realized to a considerable extent.11
128 Additives in Polymers: Analysis and Applications

EFFECT OF JOINT ACTION OF HIGH PRESSURE AND SHEAR


DEFORMATION ON PHYSICAL AND CHEMICAL PROPERTIES OF
SOLID

The pioneer works by R. Bridgman12 initiated the systematic studies on


the high-pressure effect on physical and chemical properties of solid. This
effect, being rather strong, ensured a sufficient improvement of the prop-
erties of materials treated in these conditions. In this respect, it became
necessary to develop basically new technological processes.
Today, the advances in polymeric materials can be achieved through
the development of totally new methods of mechanical treatment that will
result in a sharp rise of productivity and quality of articles with a simulta-
neous reduction of metal consumption and specific power inputs of equip-
ment. A successful implementation of this field is impossible without ap-
plying to the processing technology the latest achievements of polymer
physics and chemistry, rheology, and high-pressure physics.
A highly effective method of controlling polymer properties under pro-
cessing and improvement of articles’ characteristics is an action of me-
chanical fields on the material causing the change in parameters of the
micro- and macrostressed state of the system.13
In 1970, at the Semenov Institute of Chemical Physics of Academy of
Sciences in Moscow, Russia, the scientists under the direction of the aca-
demician, Enikolopyan, studied the behavior of solids under high pressure
and shear deformation.14,15
Possible procedures for physical modification polymer materials in-
volve elastic-deformation grinding and plastic deformation at high pres-
sure using Bridgman anvils.
Experiments under shear deformation and high pressure conditions
were carried out on an anvil-type apparatus, which is based on the fact
that the compression of a solid specimen between two plates did not lead
to the flow out of the substance if a sufficiently thin specimen was taken.
A version of this apparatus is shown in Figure 5.1. The device consists of
a pair of metal anvils, having the form of a truncated cone and made of
a special alloy. The bottom anvil is supported by a ball bearing, permit-
ting rotation of this anvil relative to the top anvil. The sample is placed
between polished working surfaces of the anvil. Shear deformation is cre-
ated by rotation of the bottom anvil. Its magnitude is characterized by the
rotation angle.
Structure and Properties of Rubber Powder 129

FIGURE 5.1  Bridgman Anvils.

The degradation of isotactic polypropylene (IPP) subjected to the joint


action at high pressure and shear deformation on the Bridgman anvils was
studied. It was shown that weight-average molecular weight (Mw) and
number-average molecular weight (Mn) values decrease with shear defor-
mation. The Mn value drops to higher extent with pressure compared with
the value of Mw At 1 GPa, the Mw/Mn ratio is virtually independent of the
shear angle, whereas at pressures of 2 GPa and 5 GPa, molecular-weight
distribution becomes wider and, eventually, takes a bimodal character. The
melting temperature was found to decrease linearly with decrease in Mn
value.16,17
X-ray diffraction measurements of IPP/high-density polyethylene
(HDPE) blend showed that intensive plastic deformations involved in the
solid-state mixing and elastic deformation treatment lead to a breakage of
130 Additives in Polymers: Analysis and Applications

the initial crystalline structure until reaching a grain size of 2−4 nm in the
component representing the dispersed phase.18–21
The effect of intensive plastic deformation on the structure of ther-
modynamically incompatible polymer blends was studied on a mixture
containing IPP and up to 10 wt% HDPE.22 The mixing was carried out
in the following regimes: (i) in the melt at 473 K in the absence of any
significant shear deformation; (ii) in the course of elastic deformation of
components in the rotor disperser under considerable shear deformation,
whereby the mixing occurs during the crystallization of components at
409−411  K (Fig. 5.2); (iii) during the joint action at high pressure and
shear deformation on the Bridgman anvils.
This unit is a rather simple apparatus consisting of a transport screw
and a grinding head. The screw is 32 mm in diameter. The ratio of the
length to diameter L/D is equal to 11. The extruder has two working zones
with autonomic temperature control. The gradual compression of material
(the degree of compression was as high as 3.5) and its heating are real-
ized in the transport zone. The grinding head presents a cam rotor rotating
inside a channeled cylinder, that is, the grinding of material is performed
in a narrow annular gap under shear deformations, which were constant
over the entire surface of the annular gap. The shear deformation level was
determined by the product of the average shear rate and the residence time
in the grinding zone. In this case, the stationary temperature regime in the
head and extruder zones was maintained. Thus, in this unit, the pressure
is produced by screw, and the necessary shear deformations are formed
between the walls of grinding chamber and the rotating rotor.
The intensive shear deformations involved both in the solid-phase
blending of the IPP/HDPE system and in the elastic deformation blending
in the rotor disperser lead to the formation of blends with a homogeneous
structure of the amorphous regions. The critical content at which this phe-
nomenon is manifested depends on the magnitude of shear deformation.
The formation of homogeneous amorphous regions in the blend leads to
an increase in the elongation at break.21
Structure and Properties of Rubber Powder 131

FIGURE 5.2  Schematic Representation of Rotor Disperser: (1) Heating Elements, (2)
Concentric Transport Gap of the Dispersion Chamber, (3) Grinding Rotor.

ELASTIC-DEFORMATION GRINDING

The researchers of the Semenov Institute of Chemical Physics of Academy


of Science of SSSR observed a formation of fine powder in a high-shear
Banbury mixer when a low-density polyethylene (LDPE) was subjected
to high pressure and shear accompanied by cooling (instead of heating).
This discovery resulted in the development of a new grinding process that
was initially termed elastic deformation grinding (EDG). This technique
is based on the degradation of a material in a complex strained state by the
action of uniform compression pressure and shear forces under elevated
temperatures.23,24
Over the years, EDG was also termed elastic-strain powdering (ESP).
When modified single- or twin-screw extruders were used, EDG was also
referred to as extrusion grinding (EG), solid-state shear extrusion (SSSE),
and solid-state shear pulverization (SSSP or S3P). In the more recent past,
we used the term intensive stress action compression and shear (ISAC&S)
or high-temperature shear deformation (HTSD).7
132 Additives in Polymers: Analysis and Applications

The extensive studies have provided a basic understanding of the grind-


ing of polymers under high shear and compression. So, it has been shown
that in the range of the melting of LDPE is observed drop in elongation
at break, that is, a transition from ductile to brittle fracture. Temperature
range depends essentially on the molecular-weight distribution and ther-
mal history of the sample. It was found that on EDG in the melting temper-
ature range, a highly dispersed LDPE powder is formed (Fig. 5.3).25 The
EDG method was characterized by rather low energy consumption, which
was two to three times lower than that of conventional grinding methods.26

FIGURE 5.3  Elongation at Break εb of Low-Density Polyethylene as a Function of the


Temperature.

Solid-state extrusion was successfully employed for rubber powder


production.27 In such materials, elastic deformation dominates over plastic
deformation. The defects shaped as helical cracks arise at some critical
value of accumulated rubberlike strain. Under extrusion of cross-linked
elastomers, the extrudate is not destroyed at the initial stage of the extru-
sion draw ratio λ < λmax (Fig. 5.4a).27 At increased strain, helical defects
become more distinct, after which secondary destruction occurs in the
Structure and Properties of Rubber Powder 133

form of small helical cracks branching from the main helices (Fig. 5.4b).
Fracture in this case has multiple characters, and the extrudate is a loose
agglomerate of small particles. Therefore, at complex loading, when de-
formation is less than its critical value corresponding to a particular tem-
perature–time regime, the deformation is reversible, and there the critical
value, accumulation of macroscopic defects takes place (Fig. 5.4c). This
process is accompanied by a partial release of elastic energy. The remain-
ing energy makes the material strained, which forms the basis for a further
sharp increase of surface in the course of disintegration. Multiple fractures
occur when there are no other ways to release the elastic energy except for
the formation of a new surface. Surface area should increase as the num-
ber of elementary acts of fracture increases, that is, at higher deformation,
lower values of critical deformation, and increased contribution of the rub-
berlike component to the total deformation.28

FIGURE 5.4  Characteristic Structures of Extrudate as a Function of Extrusion Draw


Ratio λ.
134 Additives in Polymers: Analysis and Applications

Pavlovskii and coworkers29 observed some peculiarities during grind-


ing of used tires by the EDG method, where fracture occurred at elevated
temperature under complex deformation of compression and shear. They
used a modified co-rotating twin-screw extruder consisting of five zones
capable of maintaining independent temperature of each zone during pro-
cessing (Fig. 5.5).
Twin screw extruders can be used for the grinding of rubber. A grind-
ing extruder is a twin-screw extruder equipped with two independent co-
rotating screws with a set of grinding elements. Starting with a material
having a granulometry of some millimeters, the final powder can have an
average particle size of a few hundred micrometers.7
In the first zone, the material is subject to compression, and in the re-
maining zones, high shear deformations are realized with cam elements.
The grinding of material occurs in gaps between the rotating faceted cam
elements as well as in gaps between side and end faces of neighbor grind-
ing elements located at different screws. As is shown, the best design of
shear grinding elements is based on the combination of direct and reverse
cams. Such design gives the optimum combination of shear deformations
and the counter pressure effect. In this case, the material is densified as it
passes through extruder. The screw rotation velocity, the rate of material
input, and the grinding temperature influence the degree of grinding and
the energy consumption. Therefore, in the second unit, the pressure is cre-
ated by two screws, and the shear deformation itself is realized between
the shear elements.

FIGURE 5.5  Schematic Representation of Twin-Screw Extruder.


Structure and Properties of Rubber Powder 135

Ground rubber tire (GRT) is a complex composite containing various


elastomers, carbon black, zinc oxide, stearic acid, processing oils, and
other curatives. For producing rubber powders by the HTSD method, the
characterized vulcanizates of ethylene-propylene-diene rubbers (EPDM)
with different cross-link density and paraffin oil contents were also used.
This allowed one to study and analyze physicochemical processes occur-
ring during the grinding of EPDM and to propose a mechanism for grind-
ing. Moreover, the effect of the properties of EPDM vulcanizates on the
characteristics of the resulting rubber powders was estimated.30
The grinding of cross-linked oil-expended EPDM was carried out
by HTSD method in a rotor disperser.31 The operation of this disperser
is based on repeated deformations of grinding material in gaps between
the grinding elements (cams) and the housing walls. It was found that the
compacted material is fed into a grinding head and is subjected to further
grinding.
During grinding, two competitive processes take place: the fracture
and formation of particles smaller in size compared with pristine particles
(grinding) and aggregation of particles (Fig. 5.6).
Chaikun and colleagues used both single- and twin-screw extruders
and obtained powder of various sizes as a function of temperature and
clearance between screws and the barrel. Analysis of rubber powder
showed that finer fractions were agglomerated irrespective of the type of
extruder used.32

FIGURE 5.6  Model of Grinding Process.


136 Additives in Polymers: Analysis and Applications

The analysis of the rubber crumb structure during EDG showed that
in front of the entrance to the rotor disperser head, the compacting of rub-
ber takes place; the smaller its initial particle size, the higher the degree
of compaction. The density of the material before grinding the elements
determines the particle size distribution of the obtained powder to a great
extent. The coarse initial rubber fraction yielded a looser material before
the entrance to the rotor disperser head. This material was comminuted
better. A reduction in the size of the powder particles resulted in a material
with better mechanical characteristics. Upon grinding, at least two com-
peting processes occur: the formation of particles with a size less than the
initial size (disintegration) and agglomeration of particles. Powder par-
ticles were asymmetric in shape and had a fairly developed surface area
from 750 cm2/g to 1200 cm2/g. Two characteristic regions with a distinct
boundary were observed at the surface of particles: a region of plastic fail-
ure with a highly developed surface and the region of brittle fracture with
a smooth surface.
Since during EDG two processes take place simultaneously, namely,
fracture and agglomeration, it was important to determine which of these
processes is dominant. Pavlovskii and coworkers studied the mechanism
of grinding cross-linked elastomers by EDG using twin-screw extruders.33
Two mechanisms of cross-linked rubber using EDG have been suggested.
The first mechanism leads to the formation of small particles, is related to
viscoelastic properties of rubber, and is insensitive to a change in defor-
mation rate. The authors suggested particles and the extruder barrel. The
second mechanism is sensitive to a deformation rate and follows estab-
lished physics of fracture by forming microcracks at the stressed sites, ac-
cumulation of elastic energy, and its release with a creation of new surface
(i.e., powder).
The grinding of cross-linked rubbers occurs under the joint mechanical
and thermal action. The thermal and mechanical degradation of polymer
materials is inevitable under such conditions and results in the degradation
products. During EDG, the action of mechanical factors initiates various
chemical processes, such as oxidation, degradation, secondary structur-
ing, and so on. Intensity of mechanochemical processes during EDG was
studied by analysis of sol- and gel-fractions. It was found that low-molec-
ular-weight compounds of sol-fraction were concentrated on the surface
of particles obtained by the EDG. It was found that the surface of crumb
particles contains up to 80% sol-fraction. This conclusion was confirmed
Structure and Properties of Rubber Powder 137

by the results of determination of the amount of double chemical bonds on


the surface of particles.34 The concentration of double bonds on the par-
ticle surface increases from 2.45 × 10−6 mol/g for the virgin rubber crumb
up to 8.13 × 10−6 mol/g for the powder. Removal of this sol-fraction from
surface of particles significantly improved mechanical properties of the
cross-linked rubber/GRT composites.
It is concluded from a chemical analysis of the powders that grind-
ing leads to the formation of oxidized oligomer products with molecular
weight from 300 to 2000 and causes secondary structuring, which is more
intensive in large particles.33 The presence of oligomer products of degra-
dation in the material strongly affects the mechanism of grinding because
of changes in the character of friction. The results of grinding can also
depend on the structural inhomogeneity of the sample. It is energetically
preferable to fracture through the boundaries of structural inhomogene-
ity. This can lead to fast formation of particles with sizes close to that of
inhomogeneity. In particular, this is the reason for the increased content of
sulfur after the grinding of carbon black-filled vulcanizates.32
These results were also observed for grinding of cross-linked oil-ex-
pended EPDM rubber by the HTSD.30 In this study, EPDM was cured by
a sulfur-based system up to different degrees of cross-linking. The cross-
link density in rubber powder was higher compared with that for cross-
linked rubbers (vulcanizates).
Chaikun and coworkers32 investigated the influence of sulfur as a vul-
canizing agent during EDG on properties of recycled vulcanizates. They
found that presence of sulfur–sulfur bonds resulted in the formation of
finer rubber. The authors obtained rubber with higher tensile strength than
that of the used tire rubber that was ground without the vulcanizing agents.
The results of the work35 suggest that mechanochemical processes oc-
curring during the preparation of rubber powders from EPDM vulcani-
zates are accompanied by the formation of structurally and dynamically
inhomogeneous networks, with the local mobility of polymer chains in
such networks being substantially different in different areas, that is, the
preparation of rubber powders produces a network with an essentially in-
homogeneous degree of cross-linking.
Polyakov and coworkers36 showed properties of recycled vulcanizates
obtained by EDG technique and by conventional milling. They stated that
during EDG, rubber is subjected to multiple shear deformations that allow
production of much finer powder than that produced by using roll mills.
138 Additives in Polymers: Analysis and Applications

The authors indicated that agglomeration of fine powder during EDG was
a function of the particle size of resultant tire rubber powder (the smaller
the particle size, the more agglomerates were observed). Physical proper-
ties of EDG-made rubber were higher for a powder containing finer parti-
cle-size powder.
Trofimova et al34 analyzed used tire rubber crumb ground by two
methods: so-called “ozone-knife” and EDG, and investigated the effect of
grinding method on the mechanical properties of resultant materials. It is
shown that the surface activity of the “ozone-knife” particles is markedly
lower as compared with that of the EDG particles.

FIGURE 5.7  Grinding Process Curves for the Sol-Fraction of (1) the Initial Crumb
Rubber and the Crumb Passed Six Times through the Rotor Disperser and Thermally
Treated for (2) 5, (3) 15, and (4) 25 min. Extraction with Tetrahydrofuran.

The influence of the shear deformation value in EDG and of the heat
treatment time at 150C on the structure of GRT was analyzed by Trofi-
mova et al.37 The value of shear deformations was varied by changing
the number of repeated GRT passes through a rotor disperser. After each
pass through the rotor disperser, GRT was divided into two portions, of
which one was subjected to thermal treatment at 150°C for 5–30 min and
the other was ground further. It is found that the surface of GRT passed
Structure and Properties of Rubber Powder 139

four times through the rotor disperser becomes more developed. The pro-
portion of sol-fraction components with a large molecular mass increases
with an increase in shear deformation and heat treatment time (Fig. 5.7).
Pavlovskii and coworkers38 studied the properties of mixtures of tread
rubber with up to 60% of used rubber obtained by EDG with a rotor dis-
perser. Ground tread rubber (consisting of three different rubbers) was
converted into powder at 140°C with bimodal particle size distribution
from 0.315 µm to 0.8 µm. Intensity of mechanochemical processes during
EDG was studied by analysis of sol- and gel-fractions. The authors found
that gel-fraction was decreased for finer particle-size powder, while sol-
fraction localized on the entire surface of particles; large particles with less
dense networks were capable of absorbing more of the sol-fraction and
had more of toluene extract.
An increase in mechanical properties of materials based on mixtures
of tread rubber with used tire rubber was explained by an interaction of
dispersed phase and a matrix. Recycled rubber obtained by EDG had the
larger surface area, by a factor of two, as compared with that made by
conventional grinding. The authors reported that tear strength and flex-
ural modulus of mixtures containing EDG-made used rubber powder were
higher than those of virgin tread rubber compound, while a small decrease
in plasticity was observed. When sol-fraction was removed from used rub-
ber prior to mixing with virgin rubber, both flexural modulus and elonga-
tion at break were increased.
Their work confirmed results obtained by Pavlovskii’s earlier work29,33
and studies by other researchers that EDG process is not simply mechani-
cal grinding, since several chemical processes such as oxidation take
place. It was concluded that the EDG process is a mechanochemical grind-
ing process by which an application of mechanical energy causes several
chemical changes to occur.
In the work by Prut et al,30 rubber powder was prepared by the HTSD
method via fourfold passing of EPDM through a rotor disperser. While
studying the process of EPDM vulcanizate grinding, it was found that,
on the particle surface, there were two characteristic zones with the well-
defined interface: the zone of plastic fracture with the highly developed
surface and the brittle fracture zone with the smooth surface. It was shown
that in the course of vulcanizate grinding, rubber powder particles charac-
teristic of the gradient of the cross-link density directed from the periphery
140 Additives in Polymers: Analysis and Applications

regions of particle to the particle center with a higher cross-link density


may be formed.
A mechanism of grinding under elastic deformation conditions was
first proposed to describe the extrusion in the solid state.39 Depending on
the temperature, rate, and amplitude of deformation, there are three stages
of imperfection formation: clouding of extrudate, appearance of helical
cracks and small defects, and total fracture of the material. The transition
between these stages depends on the character of plastic flow.
A flow of polymer is accompanied by concurrent processes: accumula-
tion of reversible elastic and irreversible viscous flow. The material can
accumulate reversible elastic deformation only to a certain limit, and after
reaching this limit, a transition takes place to another type of defect, or,
as was formulated by the authors, the flow becomes unstable. Intensity of
this transition depends on the viscoelastic properties of the material. For
example, a rheological explosive is possible.40
It is clear that critical deformation depends on the character of mechan-
ical loading. Reaching this deformation is a necessary but not a sufficient
condition for multiple fractures. For example, deformation of PP using a
Bridgman anvil (pressure 2 GPa and rotation angle 1000°) does not cause
fracture, although the conditions in this case are tougher as compared with
grinding using rotor disperser.41
It follows that a condition no less important is the creation of an opti-
mal temperature regime.
At increased temperature, melting and crystallization start playing an
important role. The formation of defects near the phase transition depends
on the thermal history of the sample.42
The physical principle underlying EDG method consists in the fact that
the energy, accumulated in the sample after the application of pressure, is
consumed on forming new surface under the influence of shear deforma-
tion.
This process is not a gradual grinding of the sample in which particle
sizes gradually decrease. It takes place in confined space and a limited
time interval. This indicates the spontaneous nature of degradation and al-
lows us to suggest a branching mechanism in the evolution of degradation
centers. Under the appropriate conditions of interaction with the mechani-
Structure and Properties of Rubber Powder 141

cal field, the structural elements of the substance can intensively absorb
supplied energy. Then, the grinding can proceed in explosive fashion for
both polymers and low-molecular-weight substances. The sample under-
goes grinding to small, rapidly disintegrating particles.

HIGH-PRESSURE AND HIGH-TEMPERATURE SINTERING

High-pressure and high-temperature sintering (HPHTS) is a novel recy-


cling technique that makes it possible to recycle vulcanized rubber pow-
ders made from waste rubber through only the application of heat and
pressure. The design of new materials using secondary raw materials is a
promising line of research in polymer chemistry. Both economic and envi-
ronmental problems are solved in this case, which is especially important
for the technical rubber goods industry in which wastes amount to millions
of tons.43–45
The influence of the structure of GRT particles and their surface
structure can be analyzed using 100% GRT material prepared by sinter-
ing.46 An inspection of microphotographs has shown that there is no sub-
stantial difference in the surface structure of the crumb rubber particles
examined. For both compositions, the surface of GRT particles exhibited
both mirror and uneven areas. However, there is a small difference in the
amount of the sol-fraction. Consider the effect of this factor on the prop-
erties of a sintered sheet. In this case, a sintered sheet can be obtained
by sintering without the addition of a supplementary vulcanizing agent.
Figure 5.8 shows the scheme of sintering. Step 1 corresponds to the ap-
proach of particles to one another; step 2 corresponds to the intermixing
and repacking of particles and to the degradation of aggregates of par-
ticles; step 3 refers to the mutual displacement (shift) of particles, which
is accompanied by their partial degradation, changes in shape and in-
ternal porosity, and disappearance of boundaries between particles; and
step 4 is the emergence of bonds between particles and the formation of
a monolithic plate.
142 Additives in Polymers: Analysis and Applications

FIGURE 5.8  Scheme of Sintering. (Refer Text for Details.)

When GRT undergoes pressing, particles first approach each other and
the compaction of crumb rubber takes place, which is accompanied pri-
marily by structural deformations, that is, by the mutual displacement and
repacking of particles and the degradation of weak aggregates (associates)
of particles. Basically, only elastic strains develop in this case. As the load
increases, structural deformations slow down and the mutual displacement
(shear) of particles, which is accompanied by their partial degradation and
changes in shape and internal porosity, begins to prevail. The boundary
between the particles disappears. This leads to an increase in the number
of contacts and entanglements between structural elements; as a result, a
monolithic plate should be formed.
It is obvious that the sintering of rubber particles is a rather complex
process. When GRT is pressed in the absence of additional vulcanizing
agents, the strength σb of the final sintered sheet is pressure and temper-
ature-dependent and varies very slightly with time (Table 5.1). There are
two limiting models used to describe the sintering process, the Hertz mod-
el for elastic solids47 and the Frenkel model48 for the coalescence of two
types of viscous spherical particles. According to the Hertz model, the
compaction time should not affect the mechanical characteristics. Accord-
ing to the Frenkel model, the neck radius between particles χ is related to
the compaction time τ by χ ∼ τ1/2. However, as shown in Table 5.1, these
models are not quite appropriate for describing the compaction of ground
rubber particles.
Structure and Properties of Rubber Powder 143

TABLE 5.1  Influence of Ground Rubber Tire Sintering Parameters (Without Additional
Vulcanizing Agents) on the Strength b of the Final Sintered Sheets43,49

T (°C) Time (min) σb (MPa) at Various Pressures (MPa)


10 20 30
160 3 0.6 1.3 1.6
10 0.6 1.0 1.5
20 0.6 1.0 1.7
200 3 0.8 1.3 2.0
10 1.0 1.7 2.1
20 1.0 1.6 2.4
220 3 1.1 1.6 2.0
10 1.0 1.7 2.2
20 1.1 2.0 2.7

The plates produced are often porous and underpressed and have a large
number of imperfections. These defects are removed by several means: in-
creasing the compression of ground rubber, multiple refresh pressings in
the course of sintering, varying the process temperature, and introducing
modifier additives to improve the final sintered sheet.49
The complexity of sintering of ground rubber particles is aggravated
by the fact that molding in the absence of any chemical additives can lead
to degradation processes that will prevail over structuring processes. This
degradation will increase the amount of low-molecular-weight fractions
and decrease the number of cross-links. As the degradation of ground rub-
ber proceeds, the formation of contact between particles is facilitated by
the sol-fraction flow. However, significant degradation of ground rubber is
undesirable because of the strong deterioration of the mechanical proper-
ties of the final sintered sheet. The properties of sintered sheet prepared
with or without the addition of vulcanizing agents are given in Table 5.2.
The initial GRT contains a certain residual amount of vulcanizing agents.
From Table 5.2, it is seen that the strength σb is independent of the size
of GRT particles when no vulcanizing agents are additionally introduced.
However, the Young’s modulus E and the stress at 100% extension σ100
are somewhat greater for the molding compound prepared from particles
size d < 0.4, whereas the extension at break εb is smaller. Measurement of
the equilibrium swelling ratio showed that Q∞ is lower for sintered sheets
144 Additives in Polymers: Analysis and Applications

made from smaller particles; that is, the cross-link density of these materi-
als is higher.

TABLE 5.2  Mechanical Properties of Sintered Sheets


Particle Size (d, mm) E (MPa) σb (MPa) σ100 (MPa) εb (%) Q∞ (%)
< 0.4 3.0/9.0 2.9/5.1 2.1/3.9 150/150 1.9/1.8
0.4 < d < 0.7 2.3/9.1 2.9/6.5 1.8/3.3 180/200 2.4/2.0

Notes: E, Young’s modulus; σb, tensile strength; 100, stress at elongation of 100%; εb,
elongation at break; Q∞, equilibrium swelling ratio. The values given in the numerator and
denominator refer to the presence or absence of additional vulcanizing agents, respectively.

TABLE 5.3  Mechanical Properties of Sintered Sheets (Without Additional Vulcanizing


Agents) Based on EPDM29

Rubber Pow- Cross-link Cross-link E (MPa) σb (MPa) εb (%)


der (RP)a Density of Density of
Rubber Powder Sintered Sheets
(ν×105mol/cm3) (ν×105mol/cm3)
EPDM-4044
 RP-1 5.2 2.2 2.1 0.9 110
 RP-2 5.5 2.5 2.5 0.8 80
 RP-3 6.1 2.6 2.7 0.6 60
 RP-4 6.2 3.0 3.0 0.6 40
EPDM-4334
 RP-1 4.2 1.2 1.6 0.8 160
 RP-2 4.4 1.6 1.7 0.7 130
 RP-3 5.1 1.8 1.9 0.6 90
 RP-4 5.4 2.0 1.9 0.5 90
EPDM-4535
 RP-1 2.9 0.4 0.9 0.6 260
 RP-2 3.1 0.6 0.9 0.6 190
 RP-3 3.6 0.8 1.0 0.55 170
 RP-4 4.1 1.1 1.0 0.5 160
Notes: E, Young’s modulus; σb, tensile strength; EPDM, ethylene-propylene-diene rubbers.
a
Type of RP differs content vulcanizing agent (sulfur) in the original vulcanizates: 1 wt part
(1), 2 wt. part (2), 3 wt. part (3), 4 wt. part (4) per 100 wt. part EPDM.
Structure and Properties of Rubber Powder 145

The addition of vulcanizing agents to GRT favors an increase in the


cross-link density for larger particles and almost does not affect the same
for smaller particles. The introduction of additional vulcanizing agents
leads to an increase in the number of the cross-link density inside the par-
ticles and between the particles, as well as to the enhancement of mechani-
cal properties. The size of the effect in this case depends on the surface
area and the amount of the low-molecular-weight fraction of raw rubbers
at the surface.
However, in practice, the effect of cross-link density of rubber powder
and plasticizer has not been studied. The effect of these factors is present-
ed in Table 5.3. It is seen that the Young’s modulus varies slightly, and the
tensile strength and the elongation at break decreased with increasing of
cross-link density of rubber powder. The presence of paraffin oil leads to
a decrease in modulus, tensile strength and higher elongation at break. In
this case, the density of cross-links is about 2–3 times lower than that for
oil-extended material than in the absence of oil. Therefore, reducing the
cross-link density and increasing the sol-fraction improved microrheology
processes that lead to an increase in elongation at break.

TABLE 5.4  Mechanical Properties of Sintered Sheets Based on EPDM29 Without


Additional Vulcanizing Agents

Rubber Powdera (RP) E (MPa) σb (MPa) εb (%)


EPDM-4044
 RP-1 3.0 1.3 100
 RP-2 3.1 0.8 70
 RP-3 3.1 0.7 50
 RP-4 3.5 0.6 40
EPDM-4334
 RP-1 1.8 0.95 140
 RP-2 1.9 0.8 100
 RP-3 1.9 0.7 80
 RP-4 1.9 0.6 70
EPDM-4535
 RP-1 0.9 0.85 230
146 Additives in Polymers: Analysis and Applications

TABLE 5.4  (Continued)

Rubber Powdera (RP) E (MPa) σb (MPa) εb (%)


 RP-2 0.9 0.7 220
 RP-3 1.0 0.7 200
 RP-4 1.1 0.5 170

Notes: E, Young’s modulus; σb, tensile strength; εb, elongation at break; EPDM, ethylene-
propylene-diene rubbers. aType of RP differs content vulcanizing agent (sulfur) in the
original vulcanizates: 1 wt part (1), 2 wt part (2), 3 wt part (3), 4 wt part (4) per 100 wt
part EPDM.

It was shown that the sintering of the rubber powder in the absence
of any chemical additives leads to the predominance of degradation pro-
cesses. This is reflected in the increase in the proportion of low-molec-
ular-weight fractions and decrease in the cross-link density. The degra-
dation of rubber powder facilitated the formation of the contact between
the particles due to microrheological processes caused by the flow of the
sol-fraction. However, significant degradation of the rubber powder is un-
desirable because of the sharp deterioration in the mechanical properties
of sintered sheets.
Additional introduction of the vulcanizing system does not change the
nature of the dependence of the mechanical properties as the function of
the oil content in the rubber and cross-link density of rubber powder. Thus,
there is a slight increase in the absolute values of the Young’s modulus and
tensile strength (Table 5.4).
Thus, mechanical properties of sintered sheets significantly depend on
plasticizer content and the cross-link density of the rubber powder. At the
same time, the mechanical characteristics of the sintered sheets were about
50% of the initial values of the vulcanizates
It should be noted that in the literature, there are practically no data on
the effect of grinding on the properties of the sintered sheets from the rub-
ber powder. Shape and size of particles significantly affect their packaging
at sintering, as well as the number and size of pores in the materials is
obtained. The particle size is mainly influenced by the speed and tempera-
ture of sintering. Proper distribution of particle size is important for high
packing density.
Structure and Properties of Rubber Powder 147

Most often assemblies are connected in agglomerates and aggregates.


Agglomerates are formed due to the weak mutual attraction between the
particles of the powder and can be destroyed with little external influence.
In aggregates, particles are bonded more strongly, for example, as a result
of mutual attraction in the production process of the powder. Aggregates,
during compaction of powders, behave as large particles with high surface
area. In the step of sintering, the compacts manufactured from the ag-
gregate powder, hard aggregates as well as larger particles, give rise to a
coarse grain structure in the final product.
A problem associated with the aggregation of particles occurs when
sintering. Thus, for compacting the aggregated powder by sintering to
achieve certain material properties, high temperature is required, and the
larger units should be in the powder particles. Due to aggregation and
agglomeration of the particles, it is difficult to obtain compact materials.
Large mechanical forces or an increase in temperature (sintering) are re-
quired to overcome the forces of agglomeration.
The main problem with the compaction of rubber powder in the manu-
facture of bulk samples is the uneven distribution of the density by the
volume of powder products.
Thus, in this section, the experimental results on the preparation of
sintered sheets show the feasibility and promise of this technology for the
production of various rubber-technical products.

APPLICATIONS OF RUBBER POWDER IN THERMOPLASTICS

Considerable efforts have been made in finding new applications for GRT.
Fine GRT particles may be used as fillers and property modifiers in ther-
moplastic, elastomer, and thermoset blends. Addition of rubber to plastics
also improves some of the key properties of the plastics, particularly the
impact resistance. Although the use of GRT as fillers in polymer com-
posites is a potentially attractive approach, it is fraught with a number of
difficulties. Thermoplastics such as polyethylene and polypropylene are
not only cheap, but also are available in a wide range of melt index and mi-
crostructure, which can be used for mixing with recycled rubber. Karger-
Kocsis et al9 recently published a comprehensive review regarding the dif-
ficulties to produce high-quality GRT-filled compounds. The mechanical
properties of such composites depend on the content of GRT, polymer ma-
148 Additives in Polymers: Analysis and Applications

trix type, and adhesion between the GRT and the polymer matrix, as well
as the particle size and their dispersion and interaction between the GRT
and the matrix. However, the incorporation of GRT particles into a number
of polymer matrices significantly deteriorates the mechanical properties
of the composites due to very weak interfacial adhesion between the GRT
particles and the matrix-forming polymer. Similar poor behavior of GRT/
thermoplastic composites is often reported.7,9
Since most polymers and elastomers are thermodynamically immis-
cible with each other, their blends undergo phase separation, with poor
adhesion between the matrix and dispersed phase. Therefore, mechanical
properties of multicomponent polymer systems depend on their two-phase
structure and blending conditions. By varying mixing conditions, espe-
cially, the intensity of shear strains, it is possible to control the level of
heterogeneity of blends at different structural scales and, thus, to prepare
materials that substantially differ in characteristics from their individual
components.
By mixing thermoplastic polymers with GRT, new blends referred to
as thermoplastic rubbers were prepared.50 By their composition, thermo-
plastic rubbers are similar to TPEs in which vulcanized rubber particles
are distributed in the polymer matrix.51 However, by their structure and
properties, thermoplastic rubbers are particulate-filled polymer compos-
ites.52 The dissimilarity between composites containing rubber particles
and mineral filler consists in a difference in the rigidity of disperse phase
and matrix. As was shown by Bazhenov et al and Goncharuk et al,53,54 it
is possible to prepare composites containing up to 90 parts by volume of
rubber particles. In this case, a thermoplastic polymer serves as a matrix.
However, the influence of blending conditions on the mechanical prop-
erties of thermoplastic rubbers containing different amounts of a rubber
component remains an open question.
In the work by Trofimova et al,55 the effect of mixing conditions on
the mechanical properties of thermoplastic rubbers based on IPP and GRT
prepared from the tread rubber by the method of HTSD was studied. Melt
blending of IPP and GRT was carried out using a Brabender internal mixer
at 190°C for 10 min (rotor speed of 100 rpm) and the method of HTSD in
a rotor disperser (temperature 190°).
The mechanical properties of the blend were shown to be indepen-
dent of mixing conditions (Figs. 5.9 and 5.10). Depending on the amount
of crumb rubber, three regions that differ in the mechanism of deforma-
Structure and Properties of Rubber Powder 149

tion of thermoplastic rubbers are distinguished: below 0.1, 0.1–0.75, and


above 0.75 parts by volume. According to Bazhenov et al,53 the successive
change of deformation, a mechanism from plastic macro-heterogeneous
deformation to brittle fracture and then to macro-homogeneous deforma-
tion, takes place when the GRT content in the blend increases.
Thus, the content of GRT is an important factor that influences on the
structure and properties of composites. So, when the content of GRT in
composite is lower than 10−20%, the properties of composite are satisfac-
tory, while the content is higher than 20%, the properties of composite are
not satisfactory.

FIGURE 5.9  (1) Elastic Modulus E and (2, 3) and Tensile Strength σb as Functions of
the GRT Loading φ for the Materials Blended (1, 2) in a Brabender Mixer and (3) by the
Method of High-Temperature Shear Deformation.

It is very interesting to explore the possibility of modifying the surface


of GRT particles so that new reactive groups are introduced for enhanced
miscibility with the thermoplastic phase.
150 Additives in Polymers: Analysis and Applications

FIGURE 5.10  Elongation at Break εb as a Function of the Ground Rubber tire Loading
φ for the Materials Mixed (1) in the Brabender Mixer and (2) by the Method of High-
Temperature Shear Deformation.

Prut et al56 have studied mixing of GRT with functional polymers to


improve the compatibility and extension at break of GRT/polymer com-
posite. Four different polymers have been used: LDPE, ethylene-vinyl
acetate copolymers with content of vinyl acetate 9–14% (EVA-1) and
24–30% (EVA-2), and ethylene-vinyl acetate-maleic anhydride terpoly-
mer OREVAC T 9318 (Orevac). Composites with different ratio compo-
nents, viz., GRT/polymer = 20/80, 30/70, 50/50, 60/40, 70/30, 80/20, were
prepared by melt mixing the components in a Plastograph EC at 160°C,
100 rpm for 10 min.
The addition of the GRT significantly lowered the mechanical proper-
ties. The detailed mechanical properties of all the composites are sum-
marized in Table 5.5. It is observed that incorporation of GRT in polymer
matrix decreases the tensile strength, Young’s modulus, and elongation
at break of all the composites. However, the magnitudes of the tensile
strength, Young’s modulus, and elongation at break are significantly dif-
Structure and Properties of Rubber Powder 151

ferent depending on the polymer matrix. So, the LDPE/GRT composites


have very poor mechanical properties, especially elongation at break. The
elongation at break εb is seen to drop by about 80% even at 20 wt% filler
loading. The εb continues to drop until at 30 wt% filler. The Young’s modu-
lus E and tensile strength b are seen to decrease steadily with increasing
GRT content. At 30  wt% GRT, the tensile strength σb has decreased by
about 46% and the Young’s modulus E by about 21%.
A potentially even more attractive route is the use of matrices that in-
crease interaction (adhesion) between the matrix and the GRT particles.
Data in Table 5.5 indicate that elongation at break decreases with increase
in the GTR content up to 80 wt%. Changes in tensile strength and Young’s
modulus followed the same trend. All the composites have higher elonga-
tion at break compared with the composites without functional polymers
at 70 wt% GTR. This can be explained by the assumption that the func-
tional polymers increase interaction (adhesion) between the matrix and the
GRT particles. Table 5.5 indicates that the highest elongation at break was
obtained with the recipe containing OREVAC. The elongation at break of
the GRT/OREVAC composites containing 70 wt% GRT is more than two
times of that of GRT/LDPE. The enhancement in elongation may suggest
the formation of an interfacial region. The possible chemical interaction
between OREVAC and GRT may lead to improved compatibility and also
to dispersion of the GRT in the matrix, thereby improving the product’s
elongation at break.

TABLE 5.5  Effect of Functional Polymers on the Mechanical Properties (Young’s


Modulus [E], Tensile Strength [σb], Elongation at Break [εb]) and MFI of GRT/Polymer
Blends
Polymer Composition Method of E σb (MPa) εb (%) MFI
Matrix GRT/Polymer, Molding (MPa)
wt part
LDPE 0/100 Compression 140 12.3 380 1.4
20/80 molding 150 7.8 80 2.1
30/70 110 6.6 70 1.8
  100/0 Compression 5.8 1.1 50 −
molding
EVA-1 0/100 Compression 55 16.4 780 3.8
30/70 molding 28 4.7 155 5.4
50/50 25 4.0 115 3.1
70/30 11 2.3 75 0.5
152 Additives in Polymers: Analysis and Applications

EVA-2 0/100 Compression 7.4 6.3 790 Flow


molding with-
Injection mold- out
ing load
30/70 6.5 2.4 230 Flow
50/50 5.8 2.4 170 13.6
70/30 6.4 2.5 135 1
80/20 4.3 1.6 90 0.1
50/50 8.4 2.7 160 12.6
70/30 6.6 2.7 140 1
OREVAC 0/100 Compression 30.5 20.6 880 6–8
60/40 molding 17 5.1 180 1.4
70/30 Injection mold- 11 3.8 130 0.3
ing
80/20 7.5 3.0 120 No
flow
60/40 14.5 5.0 170 1.4
70/30 13.6 4.5 140 0.3
80/20 8 4.1 155 No
flow
Notes: MFI, melt flow index; GRT, Ground rubber tire.

Samples of GRT/EVA-2 and GRT/OREVAC in the composition of


60/40, 70/30, and 80/20 were prepared by injection molding and compres-
sion molding (Table 5.5). As can be seen from Table 5.5, the method of
injection molding allows obtaining the samples with the higher elongation
at break in comparison with compression molding.
Consequently, different mechanical behavior between composites can
be attributed to the difference of bonding between the rubber powders and
polymer matrix. The higher percent vinyl acetate has a good compatibility
with other materials.
In order to maximize the effectiveness, it was desired for the greatest
percentage of GRT possible to be used in the composites.
As can be seen from Table 5.5, the GRT content does not cause sig-
nificant changes in viscosity of GRT/LDPE composites within the experi-
mental error. The melt flow index (MFI) of GRT/LDPE composites can be
explained in terms of the extremely low adhesion in these systems. This
may be attributed to the high cross-link density of a tire, which does not
Structure and Properties of Rubber Powder 153

allow for any interfacial interpenetration, resulting in a sharp interface.


The MFI of the other composites decreases with increasing filler content
(Table 5.5). Decreasing of MFI is ascribed to the formation of an interfa-
cial region.
The composites, in which the GRT content was as high as 70 wt%,
were characteristic of a good processability.
Prut and coworkers57 have studied rheological properties of GRT filled
IPP of different molecular-weight characteristics. IPP of different molecu-
lar weights were used as thermoplastic polymer matrices (Table 5.6).
GRT formed at the output of the rotor disperser was fractionated with
a sieve set. GRT with a particle size of d = 0.1−0.4 mm was incorporated
into the polypropylene by melt blending.

TABLE 5.6  Molecular Weight Values, Polydispersity Index, and MFI for IPP
Polymer M (g/ Mw (g/ Mn (g/mol) IP = Mw/Mn MFI, 190°C, 2.16 kg
mol) mol)
IPP-1 360,000 150,000 40,000 3.8 10.0
IPP-2 535,000 230,000 63,000 3.7 3.0
IPP-3 520,000 280,000 95,000 2.9 0.3
Notes: IP, polydispersity index; MFI, melt flow index, Mz, z-average molecular weight;
Mw, weight-average molecular weight; Mn number-average molecular weight.

The dynamic viscoelastic properties, such as storage and loss moduli,


complex viscosity, and loss tangent of IPP/GRT composites, were deter-
mined in function of GRT loading and compared with those of the parent
IPP. The complex viscosity log η* of the neat IPPs and IPP/GRT compos-
ites decreased with increasing frequency. All the composites and polymers
exhibited a pseudoplastic or shear thinning. The higher the GRT loading
in the composites, greater is the deviation from the Newtonian behavior.
The storage and loss moduli of virgin IPPs and IPP/GRT composites
were shown to increase as the frequency increased. The value of critical
crossover frequency ωc, for which G″ is equal to G′, increased with de-
creasing IPP molecular weight (from 1.6 rad/s for PP-3 to 63.1 rad/s for
IPP-1).
A significant improvement in the melt flowability of IPP/GRT compos-
ites was found to depend on the IPP molecular weight and the content of
GRT. The higher was the GRT loading in the composites, the greater was
the deviation from the Newtonian flow behavior.
154 Additives in Polymers: Analysis and Applications

The addition of a relatively small amount of GRT (5−10 wt%) reduced


G′, G″, and η* of the corresponding two-phase system compared with the
matrix (Figs. 5.11−5.13). This decrease depended on the IPP molecular
weight. The values of log G′, log G″, and η*of IPP–2/GRT and IPP–3/
GRT composites went through a minimum at a loading of about 10 wt%
GRT. The addition of GRT to IPP-1 did not change log G′, log G″, and η*
for all frequencies. The flowability of IPP/GRT composites depended on
the IPP molecular weight and GRT loading.

FIGURE 5.11  Plots of (a) log G′, (b) log G″, (c) log η*, and (d) tan δ versus GRT Loading
for (1) IPP-1, (2) IPP-2, (3) IPP-3. Frequency ω = 1 rad/s; GRT, Ground Rubber Tire; IPP,
Isotactic Polypropylene.
Structure and Properties of Rubber Powder 155

FIGURE 5.12  Plots of (a) log G′, (b) log G″, (c) log η*, and (d) tan δ versus GRT Loading
for (1) IPP-1, (2) IPP-2, (3) IPP-3. Frequency ω = 10 rad/s; GRT, Ground Rubber Tire; IPP,
Isotactic Polypropylene.

FIGURE 5.13  Plots of (a) log G′, (b) log G″, (c) log η*, and (d) tan δ Versus GRT
Loading for (1) IPP-1, (2) IPP-2, (3) IPP-3. Frequency ω = 100 rad/s; GRT, Ground Rubber
Tire; IPP, Isotactic Polypropylene.
156 Additives in Polymers: Analysis and Applications

The dynamic rheological behavior of composites depended strongly


on the degree of agglomeration of the powdery filler. The appearance of a
minimum in the viscosity curve was reasoned by supposing the formation
of additional free volume in the interphase adjacent to filler particles.
A monotonic decrease of the loss tangent tan δ was observed with in-
creasing ω for all composites. The values of tan δ of both the IPP–2/GRT
and the IPP–3/GRT composites went through a maximum at GRT loading
of about 10 wt%. The addition of GTR increased the range of solid-like
behavior in comparison to that of the neat IPP. The shift of the critical
crossover frequency for IPP–3/GTR composites indicated a transition
from a more viscous to a more elastic behavior.
There were significant differences in the low-frequency data between
the composites. The IPP/GRT composites with high molecular weight of
IPP exhibited solid-like behavior. In contrast, the low-frequency response
for the IPP/GRT composites with low molecular weight revealed liquid-
like behavior. The values of the storage modulus G′, the loss modulus G″,
complex viscosity η*, and the loss tangent tan δ of the composites were
controlled by the IPP characteristics.
The rheological properties of the composites showed complex behav-
ior, which is not readily predictable. On the other hand, the rheological
properties are highly sensitive to the structure of the composites, in our
case to the GRT dispersion in the IPP matrix. This study suggests that it is
possible to obtain composites with good rheological properties at low cost.
The influence of dynamic vulcanization on the mechanical properties
of ternary (IPP–rubber–crumb rubber) and binary (rubber–crumb rubber)
blends was studied.58 Two types of ethylene–propylene–diene elastomer
were used as the rubber component, the oil-free elastomer Buna EP G
6470 (EPDM-6470) and the oil-extended elastomer Buna EP G 3569
(EPDM-3569). The blends were vulcanized in the presence of a sulfur
accelerating system.
Five types of crumb rubber that differed in the particle size d were
used:
SAARGUMMI crumb rubber (Germany) prepared via cryogenic treat-
ment from commercial rubber goods, having a particle size of d < 0.1 mm
(GRT-1).
SCANRUB crumb rubber (Denmark) prepared from spent car tires by
ultrasonic treatment; d < 0.4 mm (GRT-2).
Structure and Properties of Rubber Powder 157

SCANRUB crumb rubber (Denmark) prepared from spent car tires by


ultrasonic treatment; 0.4  d < 0.7 mm (GRT-3).
SCANRUB crumb rubber (Denmark) passed at 150–155°C for 5 min
through a rotary disperser designed on the basis of a single-screw extruder
at the Institute of Chemical Physics; 0.4 < d < 0.63 mm (GRT-4).
Crumb rubber (Russia) passed four times at 150–155°C for 5 min
through the rotary disperser;6 0.4 < d < 0.63 mm (GRT-5).
Table 5.7 presents the characteristics of binary blends of EPDM-6470
and EPDM-3569 with GRT.
Vulcanization of the blends leads to the formation of a network struc-
ture in the elastomer phase and to enhancement of interfacial interaction
between the components, a situation that can have an effect on the me-
chanical properties of EPDM blends with crumb rubber.58

TABLE 5.7  Cross-link Density ν and Mechanical Characteristics of EPDM-6470/GRT


and EPDM-3569/GRT Blends (GRT Content of the Blends Is 25 wt%)
GRT Type E (MPa) σ σ300 (MPa) σb (MPa) εb (%) ν×105
100
(MPa) mol/mL
EPDM-6470/GRT
None 4.0/3.3 1.2/1.1 1.8/2.1 7.3/3.7 1130/505 22.6
GRT-1 7.1/12.3 1.75/2.8 3.0/4.7 14.7/5.1 160/330 11.4
GRT-2 4.7/6.9 1.4/2.7 1.9/4.5 4.0/5.15 850/350 3.6
GRT-3 6.25/4.8 1.3/1.5 1.9/1.9 2.6/2.1 610/360 8.3
GRT-4 4.7/4.8 1.2/2.0 1.7/– 3.4/3.1 950/270 5.4
GRT-5 4.6/7.0 1.3/1.9 2.3/2.9 2.9/3.0 510/350 4.5
EPDM-3569/GRT
None 0.6/0.8 0.2/0.4 0.2/0.6 0.7/1.8 >1800/710 7.7
GRT-1 1.4/2.5 0.3/0.9 0.4/1.9 2.2/4.0 1500/750 8.6
GRT-2 0.8/1.5 0.2/0.6 0.2/0.9 0.5/1.7 1730/760 6.3
GRT-3 1.0/1.0 0.25/0.4 0.25/0.5 0.5/1.1 1230/950 8.8
GRT-4 1.0/1.5 0.2/0.45 0.15/0.5 0.3/1.2 >1700/990 8
GRT-5 0.7/1.6 0.1/0.6 0.1/1.0 0.3/1.5 >1800/630 7.1
Notes: The numerator and denominator refer to the characteristics of the material in the
a

absence and in the presence of vulcanizing agents, respectively. E, Young’s modulus, σb,
tensile strength; εb, elongation at break.
158 Additives in Polymers: Analysis and Applications

Figure 5.14 presents tensile stress–strain curves for neat EPDM-6470


and its blends with GRT. When 25 wt% GRT is introduced into EPDM-
6470, the Young’s modulus E of the blends increases relative to the initial
elastomer, and the breaking strength σb and elongation at break εb decrease.
The exception is the uncured blend of EPDM-6470 with GRT-1 having a
particle size of d < 0.1 mm (Fig. 5.14, curve 2; Table 5.7). For this blend,
the parameters E and σb have values 1.8–2.0 times above those for the vir-
gin elastomer. However, the elongation at break εb is practically the same.
It may be assumed that this behavior is due to more homogeneous GRT-1
particles in the elastomer phase. The σ–ε plots for EPDM-6470 blends
with other types of GRT have identical patterns. However, the mechani-
cal parameters differ. For example, for the blend with GRT-3, the Young’s
modulus E is higher and the ultimate strength σb and elongation at break
εb are lower than those for the blends with GRT-4 (0.4 < d < 0.63 mm) and
GRT-2 (d < 0.4 mm). The lowest value of εb is observed for the EPDM-
6470 blend with GRT-5 (0.4 < d < 0.7 mm). It is difficult to analyze these
results, because GRT-3 particles (0.4 < d < 0.7 mm) have a less developed
surface than GRT-4 (0.4 < d  < 0.63 mm) and a larger size than GRT-2
particles (d < 0.4 mm). Furthermore, GRT-4 and GRT-2 particles differ not
only in size but also in the structure of the surface layer owing to different
preparation procedures.

FIGURE 5.14  Tensile Stress–Strain Curves for (1, 3) EPDM-6470 and (2, 4) its Blends
with GRT-1: (1, 2) the Uncured and (3, 4) the Cured Materials. The EPDM/GRT ratio is
75/25. GRT, Ground Rubber Tire; EPDM, Ethylene-Propylene-Diene Rubbers.
Structure and Properties of Rubber Powder 159

The vulcanization of these blends varies in the form of σ–ε curves and
the mechanical parameters (Fig. 5.14, curves 3, 4); the plots lack the por-
tion that corresponds to crystallization during stretching. After vulcaniza-
tion, the Young’s modulus E becomes higher and the elongation at break
becomes smaller relative to the uncured blends. The value of εb depends on
neither the particle size of GRT nor its preparation procedure in this case
(Table 5.7). At the same time, the values of E and εb are higher for blends
not only with GRT-1 (d < 0.1 mm) but also with GRT-2 (d < 0.4 mm) and
GRT-5 (0.4 < d < 0.63 mm). Consequently, the parameters E and σb are
dependent on the particle size of crumb rubber (Table 5.7).
When oil-extended EPDM-3569 is used in blends, the appearance of
–ε curves and the mechanical parameters change as well (Fig. 5.15). The
curve portion corresponding to rubber crystallization is less pronounced
than that for EPDM-6470 (Fig. 5.15, curve 1): σ for EPDM-3569 increases
with an increase in ε to a lesser extent than for EPDM-6470, a difference
that is most likely due to the presence of oil. As a result, EPDM-3569 has
lower values of E and σb and a higher value of εb than EPDM-6470 (Table
5.7). This effect is characteristic of both uncured and cured blends. From
the data presented in Table 5.7, it is seen that, in the presence of crumb
rubber, the Young’s modulus increases and the elongation at break εb drops
relative to those parameters of the uncured initial elastomer EPDM-3569.
The maximal growth in E and σb characterizes the blend with GRT-1
(d < 0.1 mm), as in the case of the EPDM-6470 blend. It is noteworthy
that the particle size of GRT and its preparation procedure have a weak ef-
fect on the other blends, vulcanized or unvulcanized. The lack of the effect
is due to a more homogeneous structure of distribution of crumb rubber in
oil-extended EPDM-3569.
The σ–ε tensile stress–strain curves of the uncured EPDM-3569/GRT
blends exhibit a yield point (Fig. 5.15). A similar effect is observed for
GRT blends with oil-extended Dutral TER 4535 EPDM (Italy).59 Accord-
ing to Nielsen,60 the yield point appears in elastomer compositions with
hard fillers. Its appearance is associated with either the formation of mi-
crocracks or the debonding of the polymer from the filler upon the failure
of the adhesive bond between them and a dramatic decrease in the elastic
modulus of the composition. It is likely that, owing to the presence of oil,
interfacial interaction between EPDM and GRT is very weak in the given
case and drawing causes the formation of vacuoles.
160 Additives in Polymers: Analysis and Applications

Thus, the replacement of 25% elastomer with GRT leads to an increase


in the Young’s modulus of E of blends, regardless of the type of GRT and
the nature of EPDM. The ultimate strength σb and the elongation at break
εb drop in the presence of GRT for both cured and uncured EPDM-6470
blends. However, for the systems with oil-extended elastomer EPDM-
3569, the ultimate strength σb insignificantly increases and a change in the
elongation at break εb depends on vulcanization of the blend.
Ternary IPP/EPDM/GRT blends were obtained at the two component
ratios 50/37.5/12.5 and 30/52.5/17.5. The EPDM/GRT ratio was three in
both cases. The PP/rubber (EPDM blend with GRT) ratios of 50/50 and
30/70 are typical of TPEs.6

FIGURE 5.15  Tensile Stress–Strain Diagrams for Uncured EPDM-3569 and its Blends
with GRT: (1) EPDM, (2) EPDM/GRT-1, (3) EPDM/GRT-2, (4) EPDM/GRT-3, (5) EPDM/
GRT-4, and (6) EPDM/GRT-5. The EPDM/GRT ratio is 75/25. GRT, Ground Rubber Tire;
EPDM, Ethylene-Propylene-Diene Rubbers.

From the results (Tables 5.8 and 5.9), it follows that the presence of
GRT in a blend, regardless of its type, increases the Young’s modulus E
relative to the GRT-free blend and decreases the breaking strength σb and
elongation at break εb, with εb decreasing by a factor of ∼10.
From the data presented in Table 5.7, it is seen that the highest values
of E, σb, and εb were obtained for EPDM-6470 with GRT-1 (d < 0.1 mm).
In this case, vulcanization has almost no effect on εb (Fig. 5.16). When
other types of GRT are used in the uncured PP/EPDM-6470/GRT blends
at a component ratio of 50/37.5/12.5, the elongation at break εb is less than
100% (Table 5.7) and the specimens experience quasi-brittle fracture. The
vulcanization of these blends increases εb to 100% or more. The stress–
Structure and Properties of Rubber Powder 161

strain plots exhibit a small growth in the plastic region, an increase in ε


without a noticeable rise in σ (Fig. 5.15).

TABLE 5.8  Mechanical Characteristics and MFI of 50/37.5/12.5 IPP/EPDM-6470/GRT


and IPP/EPDM-3569/GRT Blends
G RT σ 1 0 σ 3 0 MFI g/10 min
E (MPa) 0 0 σb (MPa) εb (%)
Type (MPa) (MPa) 2.16 kg 10.6 kg

IPP/EPDM-6470/GRT

None 205/250 8.6/11.6 11.4/17.9 15.6/32.0 580/620 0.50/– 7.15/–a


GRT-1 400/430 11.1/11.3 13.9/15.3 16.7/20.1 450/460 0.40/– 6.00/1.05
GRT-2 350/330 –/10.7 – 10.0/11.8 60/185 0.40/– 7.00/0.15
GRT-3 320/300 –/10.3 – 9.4/10.2 35/100 0.55/– 8.70/0.20
GRT-4 380/310 –/10.0 – 10.0/10.0 45/100 0.95/– 11.25/1.00
GRT-5 300/350 10.7/– – 10.9/9.8 120/60 0.40/0.85 –
IPP/EPDM-3569/GRT
None 190/210 7.7/8.8 10.1/12.6 12.2/14.8 450/390 2.00/0.30 59.0/47.8
GRT-1 270/290 9.5/9.5 12.0/– 13.6/10.4 400/180 1.20/1.40 35.0/40.65
GRT-2 250/240 – – 8.9/8.8 40/50 1.40/1.35 43.5/42.6
GRT-3 220/430 – – 7.8/11.7 30/10 2.65/2.15 63.5/43.9
GRT-4 215/240 – – 8.4/8.5 35/40 2.30/1.90 46.05/50.4
GRT-5 200/210 – – 7.6/8.7 30/40 4.30/2.40 –
Notes: GRT, ground rubber tire; E, Young’s modulus; σb, tensile strength; σ100, stress
at elongation of 100%; εb, elongation at break; MFI, melt flow index; IPP, isotactic
polypropylene; EPDM, ethylene-propylene-diene rubbers.

An unusual picture is observed for the MFI of vulcanized blends. The


vulcanized IPP/EPDM-6470 = 50/50 blend in the absence of GRT does
not flow even under a load of 10.6 kg. When GRT is added, the blend be-
gins to flow (Table 5.7). A similar result is obtained for the uncured 30/70
IPP/EPDM-6470 blend, which does not flow under a load of 2.16 kg in the
absence of GRT and begins to flow when GRT is added (Table 5.7). Thus,
partial replacement of rubber with GRT in the IPP/EPDM blend leads to a
decrease in the viscosity of the system, a change that is most likely due to
the character of surface of crumb rubber particles.
162 Additives in Polymers: Analysis and Applications

TABLE 5.9  Mechanical Characteristics and MFI of 30/52.5/17.5 IPP/EPDM-6470/GRT


and IPP/EPDM-3569/GRT Blends

GRT σ100 σ300 σb MFI g/10 min


E (MPa) εb (%)
Type (MPa) (MPa) (MPa) 2.16 kg 10.6 kg
IPP/EPDM-6470/GRT
None 26/61 3.6/6.6 6.0/14.5 8.8/19.0 660/380 –a/–a 2.20/–a
GRT-1 86/139 5.7/7.1 8.6/10.5 10.3/16.2 485/570 0.10/–a 2.20/–a
GRT-2 63/101 5.8/7.6 – 6.8/10.0 210/200 0.20/–a 3.40/–a
GRT-3 44/71 4.4/6.2 – 4.65/8.0 120/190 0.20/–a 3.12/–a
GRT-4 50/64 4.8/5.4 – 5.0/8.2 145/290 0.25/–a 3.84/–a
GRT-5 34/65 4.35/5.7 5.7/8.4 5.8/8.4 260/315 0.30/–a 3.76/0.10
IPP/EPDM-3569/GRT
None 30/58 2.6/4.0 3.8/6.1 4.6/7.0 520/400 0.20/–a 29.0/1.36
GRT-1 69/96 4.2/5.2 5.6/6.7 6.0/7.9 355/430 0.40/0.02 18.0/5.13
GRT-2 60/73 4.1/4.6 – 4.2/4.6 130/90 0.60/–a 28.8/2.50
GRT-3 46/62 – – 2.9/3.6 70/55 0.60/–a 28.9/1.20
GRT-4 43/58 3.3/4.2 – 3.1/4.0 95/75 0.56/– a
32.0/1.12
GRT-5 41/52 3.2/4.3 – 3.3/4.7 125/170 1.00/0.07 36.5/–a
Notes: GRT, ground rubber tire; E, Young’s modulus; σb, tensile strength; 100, stress
at elongation of 100%; εb, elongation at break; MFI, melt flow index; IPP, isotactic
polypropylene; EPDM, ethylene-propylene-diene rubbers.

The MFI of the blends increases with an increase in load. At a IPP/


EPDM-6470/GRT = 50/37.5/12.5, the vulcanized blends flow only under
a load of 10.6 kg (Table 5.8).
In the blends of oil-extended EPDM-3569 with GRT, the MFI dra-
matically increases (Tables 5.8 and 5.9). The oil in the rubber acts as a
plasticizer, and the MFI grows. For the uncured and cured IPP/EPDM-
3569/GRT = 50/37.5/12.5 blends, the MFI is improved to 35–65 and
40–50 g/10 min (at a load of 10.6 kg), respectively. As the IPP content
decreases, the MFI decreases to 18–32 g/10 min for the vulcanized blends
or to 1–5 g/10 min for the uncured blends (Tables 5.8 and 5.9). Upon
Structure and Properties of Rubber Powder 163

vulcanization, the presence of oil in the rubber has no effect on the MFI,
unlike the case of oil–free rubber.

FIGURE 5.16  Tensile Stress–Strain Curves for (a) Uncured and (b) Cured IPP/EPDM-
6470/GRT Blends Having a Component Ratio of 50/37.5/12.5: (1) IPP/EPDM and (2) IPP/
EPDM/GRT-1. GRT, Ground Rubber Tire; IPP, Isotactic Polypropylene; EPDM, Ethylene–
Propylene–Diene Rubbers.

Thus, the use of oil-extended rubber and introduction of GRT into the
blends lead to the situation that the rheological properties of the blends,
and hence the processability of these materials are improved. It is likely
that this effect is due to a change in the interfacial tension and sliding on
the interface.61
Thus, vulcanization improves the mechanical characteristics. This ten-
dency is observed regardless of the type of EPDM rubber or GRT. The
highest values of the mechanical characteristics are observed for the IPP/
EPDM-3569/GRT blends in which the particle size of GRT is d < 0.1 mm.
Consequently, the best mechanical and rheological characteristics
were obtained for the ternary blends using GRT with a particle size of
d < 0.1 mm.
The addition of GRT powder promotes the flowability of uncured IPP/
EPDM = 50/50 and these TPVs (Table 5.10). The MFI values of TPVs-
containing GRT are higher than those of TPVs without GRT. One can see
that blends with IPP/EPDM = 30/70 do not flow at low and medium loads,
but an increase of a load to 10 kg leads to a weak flow.62
As can be seen from Table 5.10, rubber particle size is an important
factor affecting the MFI of TPVs. The reduction of the rubber particle size
increases MFI of uncured blends and dynamically cured TPVs. So, the
164 Additives in Polymers: Analysis and Applications

TPVs processability is strongly influenced by a partial substitution of the


EPDM rubber by the GRT powders. GRT contains mineral fillers such as
carbon black and other additives, which could vary rheological properties
of TPVs. Hence, use rubber powder of cured virgin elastomer without any
additives will be good. For these reasons, Prut et al used the powder of
EPDM-4044 vulcanizates without mineral fillers.
Figure 5.17 shows plots of IPP/EPDM-4044 complex viscosity versus
rubber powder content. One can see that a partial replacement of virgin
EPDM-4044 by rubber powder increases η* value of uncured IPP/EPDM-
4044/RP blends. But growth of rubber powder content in TPVs steadily
decreases their complex viscosity. So, the addition of 25wt% rubber pow-
der results in one order reduction in η* value.
Therefore, the partial replacement of traditional rubbers used in TPV
by GRT will make it possible to improve the processability of TPVs and
reduce the environmental pollution.

TABLE 5.10  MFI Values of Uncured and Dynamically Cured TPV


IPP/EPDM/ Particle Size MFI (dg/min)
GRT of GRT 2.16 kg 5.00 kg 10.00 kg
d, (mm)
Uncured Cured Un- Cured Uncured Cured
cured
50/50/0 − − − − − − −
50/37.5/12.5 without fraction 0.05 0.4 0.4 1.6 2.4 8.4
50/37.5/12.5 d < 0.1 0.3 0.4 0.4 1.5 2.4 8.4
50/37.5/12.5 0.1 < d < 0.4 0.1 0.2 0.2 1.0 1.8 6.0
50/37.5/12.5 0.4 < d< 0.63 − 0.05 0.1 0.6 1.3 5.1
30/70/0 − − − − − − −
30/52.5/17.5 without fraction − − − 0.1 0.1 0.6
30/52.5/17.5 d < 0.1 − − − 0.1 0.1 1.2
30/52.5/17.5 0.1 < d < 0.4 − − − − 0.1 0.4
30/52.5/17.5 0.4 < d< 0.63 − − − − − 0.05
Notes: IPP, isotactic polypropylene; EPDM, ethylene-propylene-diene rubbers; GRT,
ground rubber tire; MFI, melt flow index; TPV, thermoplastic vulcanizates.

Therefore, a partial replacement of a virgin elastomer by rubber pow-


ders can essentially change a rheology of TPVs.
Structure and Properties of Rubber Powder 165

FIGURE 5.17  Plots of Complex Viscosity log η* Versus Rubber Powder Content for
(1) Uncured and (2) Dynamically Cured by Sulfur System IPP/EPDM-4044 = 50/50. IPP,
Isotactic Polypropylene; EPDM, Ethylene-Propylene-Diene Rubbers.

CONCLUSION

This review provides an overview of the science and technology of grind-


ing of waste plastics. The review describes the types of rubbers that are
suitable for recycling, the mechanism of degradation of various rubbers,
and characterization of the grinding products.
Today, the process HTSD is developed as a new size-reduction meth-
od for producing rubber powder. The use of rubber powder has increased
rapidly over recent years due to their unique combination of processabil-
ity and performance. Powders made with the HTSD technology would
enhance the manufacturing of parts due to their unique morphology and
surface characteristics. Because HTSD deals with the behavior of solids,
sometimes referred to as particulates or powders, it is important to study
the relationship between powder properties, such as particle size, shape,
and bulk density and their motions during processing.
In addition to the powder-production capability, it has been demon-
strated that the process allows for blending incompatible polymers and
166 Additives in Polymers: Analysis and Applications

incorporating and homogenizing additives. With HTSD, these processes


occur in the solid state, resulting in powders with properties superior to
those of melt-processed materials. Efficient mixing in the solid state will
permit the development of new polymer blends with stable morphologies
while eliminating phase inversion associated with conventional melt-mix-
ing techniques.
Progress in rubber separation and sorting is a major factor in the future
development of both mechanical and feedstock recycling. As methods of
rubber sorting are improved, the purity and homogeneity of the rubber
wastes are increased, which favor the application of more advanced grind-
ing processes, specific for each type of rubber. Therefore, more intensive
work on rubber separation should be carried out in the next few years.
Increasing the value of the products derived from feedstock recycling
of rubber wastes will also help the process economy.
As a final conclusion, it can be stated that, although feedstock recy-
cling of rubber wastes has been studied for more than 20 years, due to the
need for suitable alternatives for dealing with the increasing generation
of these types of wastes and the number of technological challenges still
present, this topic will continue to be the subject of much research activity
for the beginning of the 21st century.

ACKNOWLEDGMENTS

The authors gratefully acknowledge the Russian Science Foundation


(Contract No 14−13−00803) for the financial support.

KEYWORDS

•• Rubber powder
•• ground rubber tire
•• elastic deformation grinding
•• high-temperature shear deformation
•• blend
•• composite
Structure and Properties of Rubber Powder 167

REFERENCES

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CHAPTER 6

BIODEGRADABLE COMPOSITIONS
OF POLYLACTIDE WITH ETHYL
CELLULOSE AND CHITOSAN
PLASTICIZED BY LOW-MOLECULAR
POLY(ETHYLENE GLYCOL)
S. Z. ROGOVINA*, K. V. ALEKSANYAN, A. V. GRACHEV,
A. YA. GORENBERG, A. A. BERLIN, and E. V. PRUT
Semenov Institute of Chemical Physics of Russian Academy of Sciences, Moscow,
Russia, Email: [email protected]

CONTENTS

Abstract.............................................................................................................. 172
Introduction........................................................................................................ 172
Experimental...................................................................................................... 174
Results and Discussion...................................................................................... 177
Conclusion......................................................................................................... 188
Acknowledgments.............................................................................................. 188
Keywords........................................................................................................... 189
References.......................................................................................................... 189
172 Additives in Polymers: Analysis and Applications

ABSTRACT

Compositions of polylactide (PLA) with polysaccharides ethyl cellulose


and chitosan are obtained at different initial ratios of components under
conditions of shear deformation in a Brabender mixer. It has been shown
that the addition of a given amount of low-molecular poly(ethylene glycol)
(PEG) leads to an increase in the elongation of rigid polysaccharide–PLA
compositions. The influence of molecular weight and amount of PEG
on the thermal behavior of PLA is investigated by differential scanning
calorimetry method. The biodegradability of films prepared from the
blends under investigation is estimated by weight loss after holding in soil
and tests on the fungus resistance, and it is shown that the compositions
have good biodegradability. The changes in the film morphology after
holding in soil revealed by the SEM method additionally confirm that
compositions are subjected to biodegradation.

INTRODUCTION

The aim of this study is to synthesize biodegradable polymer materials for


the utilization of synthetic polymer wastes that can be degraded under the
environmental conditions (sunlight, humidity, microorganisms, etc.) with
formation of water and carbon dioxide1–3, as degradation of polymers is
one of the important problems of modern polymer physics and chemistry.
Among different methods of synthesis of biodegradable polymer
composite materials, the most efficient and economically profitable is
the production of polymer materials via mixing synthetic polymers with
natural biodegradable ones or mixing natural polymers of different classes.
Such polymer compositions in which the properties of each component
are useful can be successfully applied in different areas, especially in the
production of packaging materials, films for foodstuffs, and articles for
short-term application.
There are a lot of works on the production and investigation of
biodegradable compositions based on synthetic polymers and natural
polysaccharides (see, for example, reviews of Arvanitoyannis and
Rinaudo [2006 and 2008] 1,3,4). Under conditions of shear deformation in
the absence of solvents, the biodegradable compositions of low-density
polyethylene with different polysaccharides (starch, cellulose, chitin, ethyl
Biodegradable Compositions of Polylactide with Ethyl Cellulose 173

cellulose, and chitosan) were obtained, and their structure, morphology,


and biodegradability were studied. It was shown that the biodegradability
depends on the blend composition and the nature of polysaccharide.5–7
In recent years, polylactide (PLA) – a product of lactic acid
polymerization – attracts a great interest. PLA is isotactic polymer
with optical activity of polymers and has l- and d-isomers with quite
high degree of crystallinity (30–80%) depending on the production
method. PLA density comprises 1.27 g/cm3; densities of amorphous and
crystalline regions are equal to 1.248 and 1.290 g/cm3, respectively. The
glass transition point of PLA lies in the region of 57–60°C, while the
crystallinity degree and melting point depend on the isomer composition.
The statistic polymers containing different isomers are less crystalline and
soften before melting at lower temperatures.
In comparison with other polyesters based on plant raw material,
thanks to thermal and mechanical properties of the complex, PLA is
most promising for the production of plastics and fibers with the given
characteristics, especially taking into account serious technological and
economic problems at their production, application, and utilization. Due
to its high mechanical characteristics, oil and UV radiation stability,
the capability of retaining the shape, etc., PLA is in competition with
traditional synthetic polymers. However, the possibilities of its application
are restricted by low values of elongation at break (<10%) and impact
strength (∼5 kJ/m2).
The mixing of PLA with synthetic and natural polymers allows one
to impart new properties to the materials based on it. This explains the
wide range of works dedicated to investigation of blends of PLA with
polymers of different classes. For example, the compositions of PLA
with polybutylene carbonate,8 ethylene copolymers,9–11 and thermoplastic
polyurethanes12 were studied. The blends based on PLA and natural
rubber are characteristic of a significant increase in the elongation at break
compared with PLA.13
As is known, pure PLA is biodegradable only under specific conditions
(elevated temperature, humidity, etc.),14,15 unlike its blends with different
polymers. The PLA-based compositions with improved biodegradability
and high mechanical characteristics were produced with the following
polymers: aliphatic polyesters,16,17 poly([R,S]-3-hydroxybutyrate),18
poly(3-hydroxybutyrate-co-4-hydroxybutyrate),19 etc., aliphatic–aromatic
copolyesters,20–22 hyaluronic acid,23 etc.
174 Additives in Polymers: Analysis and Applications

A lot of works is dedicated to the study of the compositions of PLA


with chitosan – a biodegradable polymer formed by deacetylation of a
natural polysaccharide chitin24–28. Chitosan is used as a packaging polymer
or coating owing to its good film-forming capacity. Among the numerous
application areas of the compositions based on chitosan, the medicine is
of great importance. The possibility of using chitosan–PLA compositions
as a nerve conduit was shown by Xie et al, 28 and this composition was
used as a scaffold material in the study by Li et al.25 The compositions
with montmorillonite additives, which can be used for the production of
biodegradable devices, which should not be removed from organism, were
described by Nanda et al.26
One of the most widely used plasticizer for PLA is poly(ethylene glycol)
(PEG).29–33 The PLA–PEG compositions were studied in detail.30,34–36
However, there are no literature data on the influence of different low-
molecular PEG on PLA properties.
The aim of this work was the production of biodegradable binary
compositions of two polysaccharides – ethyl cellulose and chitosan – with
PLA, as well as their ternary compositions containing low-molecular
PEG, and investigation of the mechanical characteristics, thermal
properties, morphology, and biodegradation capacity. The films prepared
from compositions of PLA and chitosan may have increased water
resistance in comparison with the films prepared from pure chitosan that
may improve their performance as packaging materials. The compositions
based on thermoplastic ethyl cellulose and PLA can be used for molding
and casting of the articles for different purposes: spectacle frames, tool
handles, toothbrushes, etc.

EXPERIMENTAL

MATERIALS

Chitosan (deacetylation degree = 0.87, and molecular weight = 4.4 105


[Bioprogress, Russia]), ethyl cellulose (ethoxy group content = 46.6% and
dynamic viscosity = 57), PLA (density = 1.24 g/cm3, Tm = 150−175°C
[Hycail HM 1011, Hycail, the Netherlands]), and PEG of different
molecular weights (600, 1000, and 3000) were used.
Biodegradable Compositions of Polylactide with Ethyl Cellulose 175

BLEND PRODUCTION

Ethyl cellulose and chitosan were blended with PLA in a Brabender mixer
(Brabender GmbH & Co. KG, Dusseldorf, Germany) at 160°C for 10 min.
The ternary compositions with PEG were obtained in the same apparatus
under similar conditions.

METHODS OF INVESTIGATION

PRESSING

For the mechanical tests, the SEM examination, and tests on


biodegradability, the films 0.18–0.25 mm thick were pressed at 160°C and
10 MPa for 10 min followed by cooling under the same pressure at the rate
of 15 K/min. For mechanical tests, the obtained samples were shaped as
dumbbell with the size of gauge of 35 × 5 mm2.

MECHANICAL TESTS

The mechanical tests were performed on an Instron-1122 tensile test


machine in tension mode at the rate of the upper traverse of 50 mm/min at
room temperature. Based on the stress (σ)–strain (ε) diagrams, the initial
elastic modulus (E), ultimate tensile strength (σb), and elongation at break
(εb) were calculated. The results were averaged for 7–10 samples.

THERMOGRAVIMETRIC ANALYSIS AND DIFFERENTIAL


SCANNING CALORIMETRY

The thermal stability of individual polymers and their compositions were


analyzed on a STA 449 F3 Jupiter synchronic thermal analyzer (NETSCH,
Germany) in platinum open pans in the temperature range of 30–560°C
with the rate of temperature change of 10 K/min in air. The sample weight
was of 5–8 mg, and the rate of gas consumption was 10 mL/min.
176 Additives in Polymers: Analysis and Applications

INVESTIGATION OF COMPOSITION BIODEGRADABILITY

INVESTIGATION OF BIODEGRADABILITY BY WEIGHT LOSS


AFTER HOLDING IN SOIL

The biodegradation of the polymer compositions was studied by holding


the samples in soil. The films were placed into a container with wet soil
consisting of biohumus, wood ash, finely grinded clay gravel, etc., at pH =
7.5. The films were placed into soil on different levels that minimizes the
probability of partial loss of films. The containers were kept in a thermostat
at 30°C for several months. The rate of biodegradation was controlled by
the weight losses of samples measured at intervals.

TESTS ON FUNGUS RESISTANCE

The tests on fungus resistance were performed according to the procedure


based on the exposition of the materials infected by fungus spores under
the optimum conditions for their growth in aqueous solutions of mineral
salts followed by the estimation of fungus resistance by the degree of their
growth (State Standard 9.049–91). The samples were shaped as plates 50 ×
50 mm in size. The concentration of different fungus spores in suspension
was 1–2 billion/cm3. The test time was 28 days; the fungus resistance in
terms of the intensity of fungus growth on the samples was evaluated with
a six-number scale.

SCANNING ELECTRON MICROSCOPY

The surface morphology of films prepared from initial binary ethyl


cellulose–PLA and chitosan–PLA compositions and from their ternary
blends with PEG, as well as the film surface morphology after holding
in soil, were analyzed using a JSM-7001F JEOL scanning electron
microscope at accelerating voltages of 1 kV, without any treatment of
surface.
Biodegradable Compositions of Polylactide with Ethyl Cellulose 177

RESULTS AND DISCUSSION

PRODUCTION OF BLENDS AND MECHANICAL TESTS

To endow the biodegradable materials obtained from PLA with new


properties and to extend their application areas, the biodegradable
polymer compositions – ethyl cellulose–PLA and chitosan–PLA – were
produced. The binary compositions of ethyl cellulose and chitosan with
PLA containing 30 wt.% and 70 wt.% of polysaccharide (in the case of
compositions based on chitosan only 70 wt.%) were obtained by a solid-
phase blending of components under conditions of shear deformation in a
Brabender mixer.
The results of mechanical tests of films obtained by pressing of
compositions at 160°C are given in Tables 6.1 and 6.2. As is seen from
Table 6.1, the introduction of 30 wt.% ethyl cellulose practically does not
change the elastic modulus (E), whereas the addition of 70 wt.% ethyl
cellulose leads to a significant drop of E. In the case of chitosan–PLA
composition, E slightly increases, since chitosan is more rigid polymer
than ethyl cellulose (Table 6.2). The introduction of 70 wt.% ethyl
cellulose leads to a decrease in ultimate tensile strength σb (about six times
in comparison with pure PLA); the effect observed is probably explained
by a poor compatibility of these polymers. For compositions containing 30
wt.% ethyl cellulose or chitosan, this parameter decreased insignificantly
compared with PLA. At the same time, as is seen from the data of Tables
6.1 and 6.2, the addition of ethyl cellulose and chitosan to PLA leads
to a substantial decrease of elongation at break εb. Thus, the change of
mechanical characteristics of the polysaccharide blends with PLA depends
both on the blend composition and on the polysaccharide nature.

TABLE 6.1  Influence of Composition of Blends Based on Ethyl Cellulose and PLA on
Mechanical Characteristics
Blend Composition
Composition Е (MPa) σb (MPa) εb (%)
(wt.%)
PLA – 2625 ± 65 52 ± 1.0 4.7 ± 0.05
Ethyl cellulose–PLA 70:30 1650 ± 96 8.7 ± 0.6 0.9 ± 0.09
Ethyl cellulose–PLA 30:70 2620 ± 90 32.7 ± 1.0 1.9 ± 0.15

Ethyl cellulose–PLA– 30:60:10 1500 ± 74 12.9 ± 0.4 1.8 ± 0.13


PEG 20:60:20 252 ± 17 4.9 ± 0.2 20.1 ± 1.60
178 Additives in Polymers: Analysis and Applications

With the aim to increase the elasticity of the films obtained from ethyl
cellulose–PLA and chitosan–PLA compositions, a plasticizer – PEG (M =
600) – was added as a third component into the compositions.
The introduction of 10 wt.% PEG leads to a slight change in the
elongation at break of blends, while the addition of 20 wt.% PEG results
in a significant increase of εb, especially for compositions containing
chitosan. So, the elongation value for chitosan–PLA–PEG (20:60:20
wt.%) composition increases up to 57.5% compared with the binary
chitosan–PLA composition with the elongation at break of 2.5% (Table
6.2). However, further increase in PEG content up to 27 wt.% leads to a
decrease of εb to 29.5% that can be connected with the phase separation of
the components.

TABLE 6.2  Influence of Composition of Blends Based on Chitosan and PLA on


Mechanical Characteristics

Blend Composition
Composition Е (MPa) σb (MPa) εb (%)
(wt.%)
PLA – 2625 ± 65 52 ± 1.0 4.7 ± 0.05
Chitosan–PLA 30:70 3110 ± 90 45.5 ± 2.2 2.5 ± 0.21
30:60:10 1370 ± 61 17.6 ± 0.3 3.2 ± 0.23
Chitosan–PLA–
20:60:20 106 ± 11 8.9 ± 0.1 57.5 ± 2.00
PEG
21:52:27 181 ± 28 3.6 ± 0.05 29.5 ± 2.20

ANALYSIS OF BLENDS BY DIFFERENTIAL SCANNING


CALORIMETRY AND THERMOGRAVIMETRIC ANALYSIS
METHODS

The thermal behavior of PLA in the presence of PEG of different


molecular weight was investigated by differential scanning calorimetry
(DSC) method.
Figure 6.1 shows the DSC thermograms of PLA and its compositions
with PEG600 at different plasticizer contents. Compared with Tg of pure
PLA (69.3°C), Tg of blends diminishes with increase of PEG600 content up
to 44.1°C in the presence of 10 wt.% PEG. The obtained dependence can
be explained by a gain in the segmental mobility of PLA with the number
of plasticizer molecules leading to the enhancement of PLA molecular
Biodegradable Compositions of Polylactide with Ethyl Cellulose 179

mobility. The cold crystallization of both PLA and its blend containing 5
wt.% PEG600 was not observed, but with the increase in PEG content, the
cold crystallization appears. Moreover, the cold-crystallization temperature
Tcc of PLA decreases as the PEG content increases, that is, connected with
a growing number of the crystallization centers. Tm of PLA–PEG600 blends
weakly depending on their composition. The analogous results were
obtained for blends of PLA with PEG1000 and PEG3000.

exo

1
2
DSC (mW/mg)

4
Tg Tcc
Tm

0 50 100 150 200 250


T (oC)

FIGURE 6.1  DSC Curves of PLA (1) and PLA–PEG600 Compositions at Different
Component Ratio: 95:5 (2), 93:7 (3), and 90:10 wt.% (4) Obtained in Air.

The determined Tg values, as well as crystallization and melting


temperatures (Tcc and Tm) of initial PLA and PLA plasticized by PEGs of
different molecular weights (600, 1000, and 3000), are presented in Table
6.3. As is seen from Table 6.3, for PEGs of different molecular weights,
Tg and Tcc of PLA–PEG blends decrease with increase of the PEG content.
The melting temperature weakly depends on the blend composition, but
the heat of melting increases with the increase of content of all PEGs
differing in molecular weight that may be explained by increase of the
composition crystallinity.
180 Additives in Polymers: Analysis and Applications

As was found, molecular weight of PEG influences the thermal


properties of PLA−PEG blends. Thus, the lower the PEG molecular
weight, the stronger the decrease of Tg of PLA−PEG compositions. This
is especially evident when PLA–PEG600 blends are compared with PLA–
PEG1000 and PLA–PEG3000 blends (Table 6.3).

TABLE 6.3  Characteristic Temperatures of PLA and PLA–PEG compositions

Blend Composition
Composition Tg (°C) Tcc (°C) Tm (°C) Hm (J/g)
(wt.%)
PLA – 69.3 – 144.4 4.5
95:5 50.7 – 144.2 1.8
PLA–PEG600 93:7 46.8 113.5 145.0 12.7
90:10 44.1 105.4 145.5 18.6
95:5 52.1 – 143.9 4.1
PLA–PEG1000 93:7 49.3 121.5 144.8 6.4
90:10 46.0 105.9 145.9 21.6
95:5 52.1 – 143.6 4.7
PLA–PEG3000 93:7 49.1 120.5 144.9 11.6
90:10 44.8 110.3 143.1 19.8

Figure 6.2 shows the thermograms of PLA compositions containing 7


wt.% of PEG of different molecular weight. As can be seen from Figure
6.2, the cold crystallization heats depend on PEG molecular weight and
increase with their decrease. This fact can be explained by increase of
number of PEG molecules, which are the crystallization centers for PLA,
with a decrease of PEG molecular weight. On the other hand, a possibility
of interaction of PEG terminal hydroxyl groups with PLA in a Brabender
mixer under conditions of shear deformation cannot be excluded. In this
case, the lower the PEG molecular weight, the greater is the amount of hy-
droxyl groups capable of reacting with PLA and the higher the heat effect
of reaction. The possibility of some chemical reactions in polymers under
these conditions was demonstrated in our previous works37,38. However,
this problem calls for further investigation.
Biodegradable Compositions of Polylactide with Ethyl Cellulose 181

FIGURE 6.2  DSC Curves of (1) PLA–PEG600, (2) PLA–PEG1000, and (3) PLA–PEG3000
(93:7 wt.%) Compositions Obtained in Air.

When considering DSC curves of the chitosan–PLA and ethyl cellu-


lose–PLA compositions, the absence of cold crystallization in the curves
of the binary compositions of PLA with polysaccharides was found, that
is, the PLA crystallization does not occur in the presence of polysaccha-
rides (Fig. 6.3a,b curve 1). However, the addition of PEG leads to the
appearance of a peak of cold crystallization for chitosan–PLA–PEG600 and
ethyl cellulose–PLA–PEG600 compositions (Fig. 6.3a,b curve 2). At the
same time, some decrease in Tg for the binary compositions in comparison
with the initial PLA is observed (Fig. 6.3a,b).

FIGURE 6.3  DSC Curves of Binary and Ternary Compositions Obtained in air: (a) Ethyl
Cellulose–PLA (30:70 wt.%; curve 1) and Ethyl Cellulose–PLA–PEG600 (30:60:10 wt.%;
curve 2); (b) Chitosan–PLA (30:70 wt.%; curve 1) and Chitosan–PLA–PEG600
(30:60:10 wt.%; Curve 2).
182 Additives in Polymers: Analysis and Applications

The compositions obtained were also investigated by thermogravimet-


ric analysis (TGA) method. The TG curves of individual chitosan, PLA,
PEG600, and their binary and ternary compositions are shown in Figure 6.4.
As can be seen from the presented data, the temperatures of the onset of
degradation of binary chitosan−PLA and ternary chitosan–PLA–PEG600
(30:60:10 wt.%) compositions are slightly lower compared with that for
pure chitosan.
Thus, the thermal stability of the investigated compositions depends on
their composition and the polymer nature. The introduction of PEG into
the compositions of polysaccharide with PLA leads to a decrease in the
material thermal stability.

FIGURE 6.4  TG curves of (1) PLA, (2) Chitosan, (3) PEG600, (4) chitosan–PLA (30:
0 wt.%), and (5) Chitosan–PLA–PEG600 (30:60:10 wt.%) Compositions.

INVESTIGATION OF BIODEGRADABILITY

The biodegradability of obtained compositions was studied by three inde-


pendent methods.
Biodegradable Compositions of Polylactide with Ethyl Cellulose 183

The tests on biodegradability were performed on the films prepared


from the binary ethyl cellulose–PLA and chitosan–PLA (30:70 wt.%)
and ternary ethyl cellulose–PLA–PEG600 and chitosan–PLA–PEG600
(20:60:20 wt.%) compositions.

INVESTIGATION OF BIODEGRADABILITY BY WEIGHT LOSS


AFTER HOLDING IN SOIL

The changes occurred in the samples after their holding in soil at 30°C for
several months were estimated through weight losses. Figure 6.5 shows the
weight loss curves for the samples held in soil. As can be seen from Figure
6.5, the weight of a binary film containing ethyl cellulose remains almost
unchanged throughout the entire experiment, while the binary films con-
taining chitosan and ternary films with PEG are subjected to biodegrada-
tion with the weight loss up to 20 wt.%. The appearance of microcracks
and spots on the film surface can be clearly seen by the naked eye, especial-
ly noticeable changes were observed for the samples containing chitosan;
moreover, the samples became significantly more fragile after holding in
soil for 12 months (see insert in Figure 6.5).

FIGURE 6.5  Weight Loss Curves of Films from (1) Ethyl Cellulose–PLA (30:70 wt.%),
(2) Chitosan–PLA (30:70 wt.%), (3) Ethyl Cellulose–PLA–PEG600 (20:60:20 wt.%), and
(4) Chitosan–PLA–PEG600 (20:60:20 wt.%) Blends After Holding in Soil for ∼12 Months.
Insert: Photographs of Films from Chitosan–PLA Blend (30:70 wt.%) After Holding in
Soil.
184 Additives in Polymers: Analysis and Applications

TESTS ON FUNGUS RESISTANCE

The tests on fungus resistance were performed with the films obtained
from the investigated binary and ternary compositions (Fig. 6.6). On ex-
amination of films from the compositions containing ethyl cellulose, the
materials were not subjected to deep degradation by fungi and the inten-
sity of mold fungus growth was measured according to 2 in the six-number
scale. In this case, deep sprouting of the fungus mycelium hyphae inside
the film thickness were not observed at magnification ×40 (Fig. 6.6b,d).

FIGURE 6.6  Micrographs of Surface of Films from (a, b) Ethyl Cellulose–PLA (30:70
wt.%), (c, d) Ethyl Cellulose–PLA–PEG600 (20:60:20 wt.%), (e, f) Chitosan–PLA (30:70
wt.%), and (g, h) Chitosan–PLA–PEG600 (20:60:20 wt.%) Infected with Fungus Spores for
28 days at Different Magnifications: 15× (a, c, e, g), 40× (b, d, f, h).
Biodegradable Compositions of Polylactide with Ethyl Cellulose 185

At the same time, the films from chitosan–PLA (30:70 wt.%) com-
position were subjected to effective degradation by fungi. At the greater
magnification, it is clearly seen that the fungus mycelium hyphae sprouted
deeply into the film structure (Fig. 6.6f). The intensity of fungus growth
was estimated by the maximum value 5. The most efficient degradation
by the mold fungi was noted for the films from ternary compositions of
chitosan: the deep sprouting of the fungus mycelium hyphae into the film
structure was observed (Fig. 6.6h). The fungus growth intensity of these
films was also measured by 5. However, it should be noted that although
in all samples, fungus growth is clearly seen by the naked eye, only the
compositions containing chitosan showed the maximum biodegradability.

RESULTS OF SEM EXAMINATION OF SAMPLES AFTER


HOLDING IN SOIL

The surfaces of the films obtained from compositions of PLA with ethyl
cellulose and chitosan after holding in soil for several months were in-
vestigated by the scanning electron microscopy (SEM; Figs. 6.7 and 6.8).
The cross-sections of films cannot be investigated, since the samples after
holding in soil were highly fragile.
As can be seen from micrographs of chitosan–PLA film surface af-
ter holding in soil, in contrast to the initial compositions, at a low (×50)
magnification, a network of microcracks that apparently leads to further
cracking and fragmentation of the material was observed. At the same
magnification, for chitosan–PLA–PEG600 compositions, the microcracks
are deeper and wider that testifies the more intensive biodegradation of
the ternary compositions in the presence of PEG600 in comparison with the
binary ones (Fig. 6.7c,d). At the medium (×500) and high (×2000) mag-
nifications (Fig. 6.7e,f), the PLA structure as multilayer shell and sponge
is clearly seen. At the same magnifications, in the ternary compositions
with PEG600, it can be seen that the film structure is more uniform (Fig.
6.7g,h). The observed cavities in the PLA matrix suggest the presence of
biodegradation.
Different results were obtained for films from the ethyl cellulose–PLA
compositions (Fig. 6.8). At medium (×300) magnification, the structure of
the PLA matrix containing individual fibrous elements of ethyl cellulose
is observed (Fig. 6.8e). The addition of PEG600 into composition leads to
186 Additives in Polymers: Analysis and Applications

the appearance of microcracks similar to those observed for chitosan–PLA


binary blends, that is, the biodegradability of the compositions based on
ethyl cellulose in comparison with chitosan compositions is pronounced in
the presence of PEG600 (Fig. 6.8f). At high (×1000) magnification, a cavity,
which is apparently formed as a result of PLA biodegradation, is clearly
seen (Fig. 6.8g,h). Hence, the process of biodegradation occurs not only
as a result of polysaccharide degradation, but also is connected with the
biodegradation of PLA.

FIGURE 6.7  Electron Micrographs of Surface of Films Obtained from (a, c, e, g)


Chitosan–PLA (30:70 wt.%) and (b, d, f, h) Chitosan–PLA–PEG (20:60:20 wt.%) Blends
Before (a, b) and After (c, d, e, f, g, h) Holding in Soil at Different Magnifications: ×50
(a–d), ×500 (e, f), ×2000 (g, h).
Biodegradable Compositions of Polylactide with Ethyl Cellulose 187

FIGURE 6.8  Electron Micrographs of Surface of Films Obtained from (a, c, e, g) Ethyl
Cellulose–PLA (30:70 wt.%) and (b, d, f, h) Ethyl Cellulose–PLA–PEG (20:60:20 wt.%)
Blends Before (a, b) and After (c, d, e, f, g, h) Holding in Soil at Different Magnifications:
×50 (a–d), ×300 (e, f), ×1000 (g, h).
188 Additives in Polymers: Analysis and Applications

Thus, the SEM data show the differences in morphology of the films
containing chitosan or ethyl cellulose after their holding in soil, so it can
be concluded that the mechanism and, consequently, the rate of biodegra-
dation are connected with the nature of the polysaccharides used. These
data confirm the results obtained on studying the composition resistance
to fungus action.

CONCLUSION

The biodegradable compositions based on PLA and polysaccharides chi-


tosan and ethyl cellulose were obtained under conditions of shear defor-
mation in a Brabender mixer. The mechanical characteristics of the com-
positions were determined, and it was found that the addition of 20 wt.%
of PEG600 plasticizer leads to a 20-fold increase in εb values. However,
further increase in the PEG content up to 27 wt.% leads to a decrease of εb
that can be connected with the phase separation of the components.
Using DSC method, it was revealed that the introduction of PEG leads
to an increase of the PLA macromolecule mobility resulting in a change
of Tg and Tcc depending on the amount and molecular weight of PEG used.
The study of biodegradability by tests on fungus resistance showed that
the compositions containing chitosan have improved biodegradability
compared with the blends based on ethyl cellulose. Using SEM method
for investigation of the sample morphology after their holding in soil, it
was found that the defects are formed both in the PLA matrix and in poly-
saccharides that proved the biodegradation of both components.

ACKNOWLEDGMENTS

This work was supported by the Russian Foundation for Basic Research,
project no. 13-03-12070-ofi_m. This work was produced using equipment
of MIPT Center of Collective Use (CCU) with the financial support from
the Ministry of Education and SCIENCE OF THE Russian Federation. We
are grateful to Yu. I. Deryabina (Bach Institute of Biochemistry) for help-
ing to do microbiological experiments.
Biodegradable Compositions of Polylactide with Ethyl Cellulose 189

KEYWORDS

•• Biodegradability
•• polylactide (PLA)
•• blends
•• ethyl cellulose
•• chitosan
•• poly(ethylene glycol)

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CHAPTER 7

INORGANIC POLYOXIDE
THERMOPLASTICS: THEIR HYBRIDS
AND BLENDS
A. A. SHAULOV and A. A. BERLIN
Semenov Institute of Chemical Physics, Russian Academy of Sciences,
Moscow, Russia
Email: [email protected]

CONTENTS

Abstract.............................................................................................................. 194
Introduction........................................................................................................ 194
Results and Discussion...................................................................................... 195
Conclusion......................................................................................................... 231
Keywords........................................................................................................... 232
References.......................................................................................................... 232
194 Additives in Polymers: Analysis and Applications

ABSTRACT

Synthesis, structure, and thermal and mechanical properties of hybrids and


blends of inorganic polymers, such as boron oxides, phosphates, sulfo-
phosphates, and fluorophosphates with organic thermoplastics, were in-
vestigated and analyzed. The use of these hybrids presents a very promis-
ing line in the development of polymer materials science. It was shown
that the blends of inorganic polyoxides with organic thermoplastics are of
specific interest due to various valuable properties, such as high thermal
and radiation stability, oxidation resistance, inflammability, and the ab-
sence of volatiles at thermal degradation.

INTRODUCTION

Inorganic, metallorganic, and organic polymers as nonmetallic materials


can be subdivided into polymers of hydrocarbon and inorganic nature, con-
sidering inorganic polymers as compounds without hydrocarbon groups.
Their behavior similar to macromolecular compounds has been well
proved, although the concepts of the polymer nature of inorganic com-
pounds are not widely believed.1–9
Every class of polymers is characteristic of specific chemical, physi-
cal, and technological features. Hydrocarbon polymers with their low re-
laxation times are characteristic of plasticity and elasticity, relatively low
processing temperatures, and low thermal stability due to the tendency of
hydrocarbon groups to oxidation, combustibility, low radiation resistance,
and relatively low elastic parameters.
The intensive development of polymer materials science allowed one
to synthesize materials based on organic polymers with characteristics
close to the theoretical values. However, their service under extreme con-
ditions, in particular, at high temperatures, cannot be realized fundamen-
tally. In other words, their potential development is limited to some extent.
Thus, the use of inorganic polymers and their hybrids and blends with
polyhydrocarbons presents a natural evolution line in the development of
polymer materials science.
By analyzing inorganic compounds from the point of view of polymer
structure, more than 10 classes of polymers can be distinguished: mono-
elemental polymers (Cn, Sin, Gen, Pn, Bn, Asn, Sbn, Bin, Ten, Sen, and Sn),10
Inorganic Polyoxide Thermoplastics 195

polyoxides, borides, nitrides, silicides, carbides, phosphides, chalcogen-


ides (S, Se, and Te copolymers), fluorocarbon polymers, and others. In-
organic polyoxides (IPO; silicates, phosphates, aluminates, borates, ger-
manates, titanates, complex polyoxides − clays, etc.) with the properties
determined by the nature of the basic elements are of the highest interest
for the synthesis and application of hybrid polymers.
IPO, comprising up to 80% of the Earth’s crust, demonstrates a variety
of space structures characteristic of polymers: a wide range of softening
temperatures, high thermal and radiation stability, stability to oxidation,
inflammability, the absence of volatiles at thermal degradation, and low
vapor pressure on processing. Moreover, IPOs are ecologically safe and
can be synthesized under mild conditions.
Polyoxides are also of interest due to further peculiarity: a number of
polyoxides (e.g., silica, phosphates, titanates, aluminates, borides, boron
nitride, graphite, complex layered polyoxides, clays, etc.) have planar
(two-dimensional [2D]) structure, which is typical for low- and high-mo-
lecular inorganic compounds, unlike organic compounds, for which the
planar structure occurs only in a number of low-molecular compounds. At
the same time, IPOs require elevated synthesis and processing tempera-
tures and are characteristic of low fracture toughness and brittleness.
Unlike organic polymers with purely covalent bonds between atoms or
a minor portion of ionic bonds, in polyoxides, the fraction of ionic bonds
is as high as 50% that is related to a great difference in the electric negativ-
ity of oxygen and basic element atoms. This determines the high energy
of internal interactions − the energy of chemical bonds and intermolecular
interactions and, consequently, high melting and glass transition tempera-
tures.

RESULTS AND DISCUSSION

When considering the properties of IPOs in the frame of the energy theory,
the equilibrium interatomic distances and chemical bond energy may be
related to thermal and mechanical characteristics of polymers.10 The com-
parative estimation of the chemical bond energy in monoelemental poly-
mers, in which the ionic component of the bond energy is absent, and in
polyoxides showed that the chemical bond energy in oxides is two times
higher due to the contribution of dipole component
196 Additives in Polymers: Analysis and Applications

Ek monoel ≈ 2Ek oxide.


The objects of investigations were chosen on the basis of the energy
theory related to the energy of internal interactions in solids with their
thermal and elastic characteristics (Figs. 7.1 and 7.2).
It was shown that the melting temperature depends on the chemical
bond energy only for 3D cross-linked polymers, that is, the melting of
these polymers occurs under conditions of thermal degradation, whereas
the melting of linear and branched polymers is determined by intermo-
lecular physical interactions with much lower energy.
The presented data allow one to make a conclusion that boron polyox-
ide and phosphorus polyoxide have the minimum softening temperatures
and may be used as objects of investigation.
Low-softening thermoplastic polyoxides and their hybrids and hybrid
resins can be prepared via the synthesis of oxides in oligomer and polymer
forms, copolymerization, chemical and physical modification by organic
and metallorganic compounds using synthetic procedures typical of the
synthesis and processing technology of hydrocarbon polymers.
They can be used in the preparation of thermoplastic polymer blends,
low- and non-flammable block, and reinforced materials with high heat
resistance and a reduced amount of gaseous products evolved during ther-
mal exposure.
This approach may provide a number of advantages:
i) Co-processing with an organic polymer providing the degree of
filling up to 95 vol%, which allows one to avoid rheology prob-
lems accompanying the polymer filling with dispersed solid par-
ticles.
ii) Preparation of hybrid polymer blends with a combination of both
classes of components at the molecular level.
iii) Chemical modification of inorganic polymers and synthesis of hy-
brid polymers without the use of solvents.
iv) Changes in the morphology of organic polymer in blends.
v) Fiber formation in mineral components during processing through
extrusion and molding technology.
vi) A significant reduction in the content of the hydrocarbon groups,
which determine the flammability of material and present a source
of volatile degradation products that allows one to obtain incom-
bustible materials without flame-retardants.
Inorganic Polyoxide Thermoplastics 197

Ultraphosphates,11,12 fluorophosphates,13,14 sulfophosphates,15 boron


oxides 16 are used as such inorganic polymers.
It was shown that the melting temperature of different organic poly-
mers in compositions with fluorophosphates decreases, up to full amor-
phization,17 whereas the glass transition temperature of some polymers
reduces by 14°.18
It was also demonstrated that a variety of morphologies, such as drop-
lets and fibrils, could be achieved, 19,20 which was previously observed in
mixtures of immiscible organic polymers.
The mechanical properties of various hybrids have also been reported.
It has been shown that sulfophosphate exhibits higher Young’s modulus
and flexural strength than equivalently filled conventional composites,21
and fluorophosphate increases creep resistance of composites and pro-
vides the dimensional stability at high temperatures.18
The rheology of sulfophosphate/polyetherimide (PEI) blends was
qualitatively examined through evaluation of their processing behavior. It
was found that the inorganic polymer modified the flow behavior of PEI
and enhanced the formability of the hybrid and its resultant properties.21
The elongation flow behavior (elongation viscosity at the strain rate of
1.0 s−1) of fluorophosphate/low-density polyethylene (LDPE) 22 and fluo-
rophosphate/polyamide blends 23 was studied as well.

FIGURE 7.1  Melting Temperature of Polyoxides Versus Chemical Bond Energy.


198 Additives in Polymers: Analysis and Applications

FIGURE 7.2  Microhardness of Polyoxides Versus Chemical Bond Energy.

Low-softening polyoxides are not exotic objects. The literature de-


scribes a wide range of such glasses of different compositions and content
of the basic elements, which can be considered as a new class of ther-
moplastic oligomers. The main basic elements used in the preparation of
glasses with Tsoft < 300°°C are B, P, Sn, Pb, F, Bi, and V (Table 7.1).

TABLE 7.1  Low-softening Polyoxides (Тg ≤ 250°С)


Compositions Тg,, °С Тsoft., °С Ref.
Boron oxides 102–253 140–302 Our data
Phosphates
Р2О5-K2O-Na2O-B2O3-MgO-ZnO 122–300 113–180 Our data
SnO-SnF2-P2O5 95–145 160–175 24–27

SnO-SnF2-P2O5-В2О3 – 68.5–181 27

SnF2-SnCl2- PbO-P2O5 58.5–164 – 28

Lead glasses
PbO-B2O3-SiO2-Nd2O3-MgO- Bi2O3 – 300 29,30
Inorganic Polyoxide Thermoplastics 199

TABLE 7.1  (Continued)

Compositions Тg,, °С Тsoft., °С Ref.


Bismuth glasses
Bi2O3-PbO-ZnO-SiO2-B2O3 – 270–300 31

Oxyfluoride glasses 18
МnNbOF5- PbF2 189 – 32

МnNbOF5-BiF2-BaF2 209 –
Phenyl phosphate glasses
SnO-SnF2-P2O5-PhPO3 25–164 – 33

The feature of polyoxides is not only low-temperature processing, but


also the ability of chemical synthesis and modification at mild conditions
(T < 300°°C). This was the basis for the synthesis of a number of low-
softening polyoxides: boron oxides, Si, Ti, Sb, Al, Mg, Zr borates, Al,
Zn, Mg phosphates, and cross-linked phosphates (ultraphosphates) and
fluorinated phosphates of tin and boron in order to choose the objects for
investigation.

BORON OXIDE OLIGOMERS

Boron polyoxides, which are the products of polycondensation of orthobo-


ric acid, are formed by the following scheme:
The process of polycondensation of orthoboric acid − a three-func-
tional monomer of planar structure – includes the stage of synthesis of
metaboric acids with the general formula (HBO2)n. Among them, b-form
of metaboric acid constitutes a linear oligomer with the crystalline struc-
ture composed of six-membered boroxol rings connected by oxygen at-
oms with a hydroxyl group at each boroxol ring (Тm = 200.9°°С).34–36
The final product of boric acid (BA) polycondensation − boric anhy-
dride – has Tg = 300.4°°C.
Oligomer boron oxides (OBOs) used as components of blends
with polyhydrocarbons were obtained via polycondensation of BA at
220−300°°C, reaction time τ = 1−3 h (Figs. 7.3 and 7.4).
The study of the conditions of synthesis of oligomers with Tg < 150°C
resulting in oligomers in the glassy state, which can be characterized as
thermoplastics with rubbery properties (Figs. 7.5 and 7.6), allows one to
200 Additives in Polymers: Analysis and Applications

choose an oligomer, which meets the basic requirements of the inorganic


thermoplastic as a component of blends. The obtained oligomers are stable
in the atmosphere.

FIGURE 7.3  Tsoft and Tflow of OBO Versus Synthesis Temperature (t = 3 h).

FIGURE 7.4  Tsoft and Tflow of OBO Versus Synthesis Time (T = 220°C).
Inorganic Polyoxide Thermoplastics 201

The ideal structure of boric anhydride can be presented as a planar


macromolecule consisting of macrocycles from six-membered boroxol
rings connected by oxygen bridges.37 By the experimental data, the boron
fraction in cycles comprises,38 82 ± 8 39 and 70%.40

FIGURE 7.5  Thermomechanical Curve of Thermoplastic Boron Oxide Oligomer.

FIGURE 7.6  Temperatures of (1) Softening and (2) flow of OBOs Versus Synthesis Time
(T = 220°C).
202 Additives in Polymers: Analysis and Applications

Crystalline boron polyoxide is characteristic of a layered supramolecu-


lar structure characteristic of weak van der Waals interactions between
layers,41,42 whereas the glassy polymer has a weakly branched disordered
structure with folded and chaotically distributed branched macromol-
ecules.43
We carried out the computer simulation of the structure of boron poly-
oxides with different degree of branching. The calculation was performed
using a program package CHARMM v.30b2 under the control of OS Linux
and a computer based on Intel Pentium IV 2.4 GHz processors.
The structure consideration was based on a fragment of continuous
network of the Zakhariasen ideal model 300 ´ 300 nm.
The generation of macromolecules via opening of a fraction of boroxol
rings of the continuous network by random law was carried out. The en-
ergy minimization and geometry optimization were performed at 0 K, as
well as the structure simulation by molecular dynamics method at 300 and
500 K, with the step of 0.001 ps in the range of 10,000–100,000 steps, in
vacuum.
The calculation was carried out for structures with different degrees of
branching and molecular mass close to the value obtained by the measure-
ment of melt viscosity of boric anhydride 44 with 100 (the Zakhariasen
model), 70, 50, 30, and 15% boroxol rings opened. Interatomic potentials
of B2O3 were fitted using the data 45–47 based on the Morse and Bucking-
ham equations for calculation of valence bond parameters and van der
Waals interactions, respectively, with account for the Coulomb forces and
valence angle deviation (Fig. 7.7).

FIGURE 7.7  Computer Simulation Model of Fragment of BORon Polyoxide


Macromolecule with 70% Boroxol Rings Opened (T = 300 K).
Inorganic Polyoxide Thermoplastics 203

The borates of different metals were considered. The observed Tg are


related to high temperature synthesis of polymers and allow one to deter-
mine the modifier concentration and possible changes in Tg (Fig. 7.8).

FIGURE 7.8  Tg of Borates of Uni- and Bivalent Elements (The Literature Data).

It should be noted that the modification allows the control of the relax-
ation properties of boron polyoxides to improve the hydrolytic stability of
polymers. Aluminum borate may be considered as an example.

ALUMINUM BORATE

Thermoplastic based on BA and aluminum hydroxide was prepared by


thermal treatment of powdered homogeneous oxide mixture at B2O3/
Al2O3 ratios of 91.9/8.1 and 83.6/16.4 mol% (T = 230°C, t = 3 h)%. It was
shown that the thermomechanical characteristics of aluminum borate can
be changed by the addition of a third component - magnesium hydroxide.
The reaction products are partially soluble in water. The yield of insoluble
fraction is as high as 74.5%.
204 Additives in Polymers: Analysis and Applications

Figure 7.9 shows the thermomechanical curves for aluminum borates


at the contents of aluminum hydroxide of 10 wt% (8.2 mol%), as well as
for a mixture BA/Al(OH)3/Mg(OH)2 = 80/19/1 wt%.

FIGURE 7.9  Thermomechanical Curves of the Product of BA and Al(OH)3 Interaction


and the Mixture.

BA / Al ( OH )3 / Mg ( OH )2 == 80 /19 /1 wt% (T == 220°C, t == 3 h) : (1) BA / Al ( OH )3 == 90 /10 wt% and ( 2) BA / Al ( OH )3 / Mg ( OH )2 == 80 /19 /1 wt%.

The obtained aluminum borate has Tsoft = 140°C, Tflow = 198°C, DT =


58°C and is stable in air. By comparing these data with the analogous
parameters for OBO synthesized under the same conditions (Tsoft = 112,
Tflow = 159, and DT = 47°C), it can be concluded that the pristine reagent
changes considerably and a product with significantly higher temperature
characteristics and molar mass distribution width is formed.
The data of IR and Raman spectra of the initial reagents and reac-
tion product are also indicative of the transformation of aluminum hy-
droxide: the disappearance of absorption bands after thermal treatment of
aluminum hydroxide in the region of high wave numbers 1018.6, 891.8,
710.4, 570 cm-1 and low wave numbers 147.2, 198.6, 293.2, 476.6 cm-1.
The comparison of the obtained data with the Raman spectra of suggested
reaction products - alumina (263.5, 391.5, 429.4 cm-1) and boehmite [ - O
- Al(OH) - ]n (355.2, 460.2, 494.8, 629.9, 933.9 cm-1) allows one to make
Inorganic Polyoxide Thermoplastics 205

a conclusion on the absence of these compounds in the reaction products


(Fig. 7.10).

FIGURE 7.10  (a) IR and (b) Raman spectra of Al(OH)3, BA, and the Product of Their
Interaction.

The thermal analysis showed that the dehydration of Al(OH)3 begins at


T = 220°C. By comparing the heat of absorption of Al(OH)3 equal to 859.6
J/g and the reaction product (6.4 wt%) in the same temperature range (55.5
J/g) gives the conversion of Al(OH)3 of 95.6% (Fig. 7.11).

FIGURE 7.11  DSC Curves of Initial Reagents and Reaction Product: (1) BA, (2)
Al(OH)3, and (3) Reaction Product; B2O3/Al2O3 = 91.9/8.1 mol%.
206 Additives in Polymers: Analysis and Applications

The possibility of solid-phase synthesis of aluminum borate under


the joint action of mechanical mixing and shear stresses in the Brabender
mixer was studied. Figure 7.12 shows the thermomechanical curves of the
products obtained in the Brabender mixer.

FIGURE 7.12  Thermomechanical Curves of Aluminum Borate (B2O3/Al2O3 = 92/8


°mol%) Prepared Under Different Conditions: (1) Mixing With Blade Stirrer (T = 220°C,
180 min), (2) Mixing in Brabender Mixer of ICP RAS (T = 220°C, 50 min), (3) Mixing in
Brabender Mixer of ICP RAS (T = 220°C, 30 min), (4) Mixing in Brabender GmBh & Co.
KG (T = 250°C, 6 min), (5) Mixing in Brabender GmBh & Co. KG (T = 250°C, 12 min),
and (6) Mixing in Brabender GmBh & Co. KG (T = 250°C, 60 min).

The resulting thermoplastic compositions are of heterogeneous nature.


It was shown that polyphosphates can be synthesized at simple technologi-
cal conditions.

PHOSPHATES: LOW-TEMPERATURE SYNTHESIS

Di-and trivalent metal phosphates were synthesized under mild conditions:


molar ratio Al2O3/ZnO/P2O5 = 1/1/2, Al2O3/ZnO/P2O5 = 3/1/8 (90°°С, 9 h)
(Fig. 7.18), MgO/P2O5 = 1/1 (250°°С, 1.5 h) (Figs. 13 and 14). Tsoft of the
Inorganic Polyoxide Thermoplastics 207

products as high as 230−235°°С and DT = 20°°С suggest the oligomeric


character of the products, as well as high viscosity of aqueous solutions.

FIGURE 7.13  Thermomechanical Curves of Al-Zn-Phosphates.


1 – Al2O3 / ZnO / P2O51/1/ 2 mol, 2 - Al2O3 / ZnO / P2O5 == 3 /1/ 8 mol.

FIGURE 7.14  Thermomechanical Curves of Mg Phosphates (MgO/P2O5 = 1/1 mol/mol).


208 Additives in Polymers: Analysis and Applications

The dried samples are hygroscopic because of which their practical


application is difficult.

ULTRAPHOSPHATES: HIGH-TEMPERATURE SYNTHESIS

The basic structure of cross-linked polyphosphates presents a modifica-


tion of polyphosphoric acid, which allows one to control the temperature
of the phase transition and hydrolytic stability of the polymer (Fig. 7.15).
The methods that reduce glass transition temperature of ultraphosphates
are based on the optimization of R2O5/OMe, simultaneous modification
by two alkali metals, alkaline earth metals, and boron oxide (see Table
7.2). The synthesis was performed at 800°C, 2 h. Thus colorless glasses
are obtained.

FIGURE 7.15  The Structure of Low-Softening Ultraphosphates.


(Ме+- K, Li, Na; Ме2+ - Mg, Ba, Zn).

TABLE 7.2  Compositions of Ultraphosphates, mol%


Р2О5 Li2O K2O Na2O B203 Mgo Zno BaO
70 10 – 10 5 5 – –
70 10 – 10 5 – 5 –
70 10 – 10 5 – – 5
Inorganic Polyoxide Thermoplastics 209

Hydrolytic stability of ultraphosphates was determined by the weight


loss rate of 1 cm3 sample in boiling water for 1 h (Fig. 7.16).

FIGURE 7.16  Hydrolytic Stability of Ultraphosphates (at T = 100°C).

FLUORINATED PHOSPHATES

One of the ways for stabilizing the hydrolytic stability of polyoxides is


getting polyoxides fluorine derivatives. In this connection, fluorinated tin
phosphate [(-Sn-O)n-(PO-(O)d (F) m]k 24 and tin boron phosphate [(-Sn-O)
n
-(PO-(O)d-B-O(O)p (F m] k were synthesized at the reactant ratio SnF2/
SnO/P2O5 = 40/30/30 mol% and SnF2/SnO/P2O5 = 40/30/30 + 7% B2O3.27
The synthesized polymers are durable thermoplastics с Тg. = 127°°С, Тsoft =
162°С, Тflow = 232°°С, and Тg = 166°°С, Тsoft = 181°°С, Тflow = 247°°С. The
synthesis was performed at 500°C for 3 h.

CHEMICAL MODIFICATION

The high activity of OH groups of polyoxides determining their chemi-


cal transformations allows their modification, which is accompanied by
210 Additives in Polymers: Analysis and Applications

a decrease in the number of cross-links and by weakening of the inter-


molecular interactions. The modification may be a means for controlling
relaxation properties and organophilization.
The analysis of the literature data on the effect of chemical modifica-
tion of SiO2, Ge2O3, and B2O3 by univalent elements on Tg of polymer
showed the dependence of Tg change on the macromolecular structure of
modified polymer at low modifier contents16 (Fig. 7.17).

FIGURE 7.17  Tg of Silicon, Germanium, and Boron Polyoxides Versus Modifier


Concentration (Li2O, Na2O, K2O, Rb2O, and Cs2O).

Most desirable modification is the use of phenyl groups characteristic


of high heat resistance and low-energy intermolecular interaction. Thus,
Si, B polyoxides, and Zn phosphate phenyl derivatives were obtained.
Chemical modification was carried out via reaction of tetraethoxysi-
loxane with its phenyl derivative
Inorganic Polyoxide Thermoplastics 211


Si ( OC2 H 5 )4 + + Ph - Si ( OC2 H 5 )3 →  -O - Si ( Ph )( OH ) - O -  n [-O - Si ( OC2 H 5) - O -  .
m

The presence of residual chemically active OH and C2H5O groups al-


lows one to realize further reactions with the formation of cross-linked
polymer by thermal treatment of the product, the modified silica with Tg £
260°C can be obtained (Fig. 7.18).

FIGURE 7.18  Tg of [Ph-Si-O1.5-]n as a Function of Time (Synthesis Temperature 250°C).

The product of the interaction of BA with tetrafluorohydroquinone


(TFHQ) was synthesized by the following reaction: (T = 140 - 200°C,
1 - 15 h).

B ( OH )3 + + HO - PhF4 - OH ( HO )2 - B - O - ( PhF4 ) - O - B - ( OH )2

Thermomechanical curves of reaction products with softening temper-


atures ranged from 50 to 160°C (Fig. 7.19).
The resulting polymers are colored black, insoluble in water, soluble in
organic solvents, and incombustible.
212 Additives in Polymers: Analysis and Applications

FIGURE 7.19 Thermomechanical Curves of Products of BA Reaction with TFHQ. (1: 1,


mol/mol, T = 160°C; t = (1) 3, (2) 10, and (3) 15 h.

ZINC PHENYLPHOSPHONATE

[-O-Zn-O-P(O)(Ph)-O-]n was synthesized via interaction of an aqueous


solution of phenylphosphonic acid with ZnO (2: 1 mol/mol, 90°C, 1 h) un-
der intensive stirring. The product yield was as high as 62%. The resulting
zinc phenylphosphonate is water-resistant compound with Tsoft = 481°C.
By the data of TGA and calorimetry, temperature of the onset of weight
loss constitutes 508°C, and the intensive degradation of phenyl rings be-
gins at 590°C (Fig. 7 20).
Inorganic Polyoxide Thermoplastics 213

FIGURE 7.20  TG and DSC Curves of Zinc Phenylphosphonate Obtained from ZnO and
Phenylphosphonic Acid.

HYBRID RESIN

Among the major disadvantages of organic resins are the flammability


and toxicity of the degradation products. An improvement in these prop-
erties can be achieved by minimizing the content of hydrocarbon groups
in the resin composition. For this purpose, a mixture of miscible reactive
organosilicon oligomers and boron oxide was used. Hybrid resin was pre-
pared from mutually soluble boron oxide oligomer and silicone oligomer
[СН3SiO0.75(СН3О)1.5]n/Н0.3ВО1.7 at a ratio of 1/0.37 mol/mol for 3 h with-
out air access. The mixture is a clear colorless liquid (viscosity is 130 cps
at 20°C, lifetime in the absence of air of 5 days at 20°C).
The resin forms polymers with Tsoft = 300 - 450°C depending on curing
temperature (50 - 150°C), 5% weight loss at heating up to 500°C, and the
oxygen index of 81 (Fig. 7.21).
214 Additives in Polymers: Analysis and Applications

FIGURE 7.21  Thermogravimetric Data for Samples Cured at Different Temperatures:


(1) 50, (2) 100, and (3) 150°С.

Based on the results of 13C NMR spectroscopy, it was shown that the
curing mechanism is associated with the formation of =В - О - Siº bonds.
The cured samples are transparent to visible light and moisture resis-
tant (Fig.7.22).

FIGURE 7.22  Cured Hybrid Resin (T = 120°C, 30 min); Plate is 2 mm Thick. The
Signature is Located Under the Plate.
Inorganic Polyoxide Thermoplastics 215

The hybrid resin was used as a binder of the composite reinforced by


basalt fabric (0.15 mm, 5 layers). The noncombustible composite has flex-
ural strength of 140 MPa, elastic modulus of 8.5 GPa, and relative elonga-
tion at break of 0.9%.

HYBRID COPOLYMERS OF BORON OXIDE OLIGOMERS


WITH NITROGEN-CONTAINING COMPOUNDS

For obtaining hybrid polymers, the sol-gel method based on hydrolysis


of the alkoxy compounds in acetone or alcohol solution followed by
polycondensation of polyoxide nanoparticles and chemical grafting to
the organic polymer is used. Using this method, the synthesis of hybrid
and chemically modified polyoxides and their compositions was carried
out.
The synthesis of the hybrid and chemically modified polyoxides and
their compositions can be also performed in suspensions and melts of mis-
cible compounds. The hybrid copolymers were synthesized via reaction
of BA with imidazole, polyethylenepolyimine (PEPA), and caprolactam
(CL) forming donor-acceptor bonds between electrophilic boron and ni-
trogen atoms (T = 25 - 250°C; Fig. 23). Weight loss of samples during
the reaction of BA polycondensation and the softening temperature of the
resulting products were determined (Fig. 7.24).

FIGURE 7.23  Samples of CL/BA = 60/40 vol%, Imidazole/BA = 70/30 vol%, and PEPA/
BA = 45/55 vol% (Temperature of Syntheses 250, 220, and 150°С, Respectively, 3 h).
216 Additives in Polymers: Analysis and Applications

FIGURE 7.24  Softening Temperatures and Weight Loss of Hybrid Copolymers (a) BA/
PEPA (150°C, 3 h) and (b) BA/Imidazole (220°C, 3 h).

The data of IR spectroscopy confirmed the formation of ВN− bonds and


the chemical identity of the products with the maximum and minimum
Tsoft. It was shown that the stoichiometric ratio of BA and imidazole is
equal to 55/45 wt%.
Abnormal changes in the relaxation properties of the resulting supra-
molecular structures at different ratios of reagents supposedly are related
to their structure.
The formation of donor–acceptor bonds between boron and nitrogen
atoms are also found in the product of BA and CL polycondensation.
The resulting polymers are environmentally stable, water soluble, and
light transparent.

COPOLYCONDENSATION OF MONOMERS

The polycondensation of reagents was carried out in a homogeneous melt


of BA in CL (Tm = 62°C) at a ratio of BA/CL = 70/30 wt% at 200 - 250°C.
It was shown that during heat treatment of the reaction mixture, the poly-
condensation of BA takes place followed by hydrolysis of CL by released
water, formation of e-aminocapronic acid and its polymerization.
Inorganic Polyoxide Thermoplastics 217

O
H2O -H2O
NH NH2 -(CH2)5-COOH (-NH-(CH2)5-OC-)n
-H2O

The product of reaction (Т = 200°С, 1 h) has Тsoft = 200.7°С.


The structure of the reaction products was determined by IR and 13С,
11
В, 1Н solid-state NMR spectroscopy.48
The comparison of the IR spectra of the reaction products obtained
at 200°С and a mechanical mixture showed the presence of bands due to
amino acid groups of starting reagents (1715, 1607, and 1317 cm-1) indica-
tive of the opening of the CL cycle. Moreover, there is an intense donor-
acceptor band due to B+...N- at 1622 cm-1. This conclusion is confirmed by
the 11B NMR spectra shifted upfield explained by increasing coordination
number of boron.
The NMR magic-angle-spinning spectra display bands due to the CL
ring opening at 200°C. The comparison of the 13C NMR spectra with 1H
cross polarization (CP) of the initial crystalline CL and the products of
thermal treatment of BA-CL mixture at 200°C showed a slight change in
chemical shifts of aliphatic carbon atoms that results in the appearance of
an additional line and the shift of the carbonyl C line to a stronger field
(from 181.3 to 177.7 ppm).
The 2D spectrum of [11B - 1H] heteronuclear correlation shows that all
boron atoms contact with all protons of the products obtained at 200 and
255°C.
The full contact of boron atoms with nitrogen atoms and protons indi-
cate that the aforementioned compositions are solid solutions.

POLYMER BLENDS

A new type of composites can be obtained via blending in molten hydro-


carbon and oxide polymers with similar thermomechanical and rheologi-
cal properties using the conventional technologies of plastics processing.
218 Additives in Polymers: Analysis and Applications

The melt processing has several advantages: avoiding the rheological


difficulties encountered in filling of solid dispersions and carrying out the
synthesis of hybrid polymers using the chemical activity of the compo-
nents.
The compositions of BA, OBO, boron polyoxide, and aluminum bo-
rate with PE of different molecular masses, PP, ethylene-vinyl acetate co-
polymers, and polyurethane were prepared by blending in Brabender mix-
ers and a mixer of new type – RMX (elongation flow Reactor and MiXer;
Scamex, France), and two-screw extruder.
During the preparation of the composition, the following effects were
observed:
i) An increase in the flow rate of polymer melts in mixtures of poly-
hydrocarbons with boron oxide explained by the planar structure of
boron polyoxide, which is confirmed by computer simulation of its
macromolecular structure.
ii) The decrease of the pressure on the walls of the extruder and torque
of the screw with an introduction of OBO into the PE melt. These
effects were explained by two factors: i) the larger rigidity of OBO
molecules in comparison with PE chains, and ii) slippage of planar
OBO on the extruder walls, as well as on the interfaces between
OBO and PE. The latter one is in accordance with the tribological
properties of the self-lubricated boric acid.49,50 Further increase in
OBO content leads to the abnormal drop of the pressure at vol-
ume fraction of OBO by 25 vol% (Fig. 7.25). This threshold lies
in the concentration range corresponding to the interpenetrating
structures of incompatible polymer blends. The sharp decrease in
pressure apparently testifies a spontaneous change of the blend
structure due to the violation of connectivity of the inorganic com-
ponent.
Note the absence of a marked effect for PE-PMMA blends of non-
planar structure and PE-BA mixtures having the planar structure at the
molecular level.
Inorganic Polyoxide Thermoplastics 219

FIGURE 7.25  Pressure Drop on the Extruder Walls at Melt Mixing of PE/OBO (10, 15,
20, 30 min). (1) BA and (2, 3) PMMA (15 min).

As a result of the orientation of boron polyoxide in the melt flow, fibrils


are formed at the component ratios of phase inversion accompanied by
changes in the mechanical properties of molded samples of blends (Fig.
7.26).

FIGURE 7.26  Dependence of (a) Tensile Strength and (b) Elastic Modulus of Blends (1)
PE/OBO, (2) PE/PMMA, and (3) Composite PE/TiO2 Versus Composition.

The fibril formation in the injection molding samples is observed on


electron microscopic images (Fig. 7.27).
220 Additives in Polymers: Analysis and Applications

PE++10 vol% OBO PE++40 vol% OBO PE++64 vol% OBO

FIGURE 7.27  SEM Images of PE/Boron Oxide Blends.

VISCOMETRIC TESTS

By analyzing the flow curves of the compositions prepared at 150°C (Fig.


7.28), it was shown that the addition of HBO2 to PE results in the enhance-
ment of the maximum Newtonian viscosity of the two-component system,
at HBO2 concentrations up to ~30 vol%, without any qualitative changes
in the shape of flow curves. However, at a higher HBO2 content, the flow
pattern changes abruptly (curve 6): a clearly pronounced yield stress is
observed, and the blend becomes viscoplastic.

FIGURE 7.28  Viscosity Versus Shear Stress at (a) 150°C and (b) 180°C for (1) Pure PE
and PE/HBO2 Blends with (2) 6.8, (3) 14.1, (4) 21.9, (5) 30.4, and (6) 39.6 vol% HBO2.
Inorganic Polyoxide Thermoplastics 221

As the temperature increases to 180°C, the transition from the New-


tonian flow of PE melt to the viscoplastic behavior of blends is observed,
even for samples with 14.1 vol% HBO2 (Fig. 7.27b). It should be empha-
sized that, at this temperature, the yield stress of the composition with
39.6 vol% HBO2 is lower compared with the composition with 30.4 vol%
HBO2. Moreover, Figure 7.10b shows that, at the shear stresses above the
yield point, the viscosity of these blends becomes lower compared with
the PE viscosity.51
A similar result was obtained for PP/aluminum borate blends contain-
ing a significant amount of boron polyoxide (Fig. 7.29)1.

FIGURE 7.29  Viscosity of Aluminum Borate-PP Blends Prepared on RMX Mixer


(Scamex).

BLENDS OF FLUORINATED POLYMERS

Other interesting systems are blends of polyoxides with fluorinated poly-


mers characteristic of inflammability and hydrolytic and chemical stability.
1
The data were obtained in collaboration with prof. R. Muller, ЕСРМ, Strasburg University,
France.
222 Additives in Polymers: Analysis and Applications

The blends were obtained by extrusion with three types of polyoxides:


oligomers of boron oxide, fluorinated tin and phosphorus oxides [(SnO)
n
-(P(O)(F)m]k (FООP), and fluorinated tin, phosphorus, and boron oxides
[(-Sn-O)n-(P-O-(O)d-В-О(О)р (F)m]k (FOOPB). As fluorocarbon polymers,
polyvinylidenes fluorides with different flow and processing temperatures
(Tmix) F2 (Тflow = 280°°С, Tmix = 280°°С, 15 min) and F2М (Тflow = 215°С, Tmix
= 230°°С, 15 мин) and F2МВ (Tmix = 280°°С, 15 мин) were used (Fig. 7.30).

FIGURE 7.30  Thermomechanical Data of (a) F2М, ОBO and F2М/ОBO Blends and (b)
(1) F2МВ, (2) FOOPB, (3) F2МВ/FOOPB = 50/50 vol% (3).

In the former case, the thermomechanical data are indicative of the


unchanged softening temperature of fluorocarbon polymers and the in-
compatibility of components, and, in the latter case, of a new product of
interaction2.
The mechanical properties of all mixtures were measured and the
stress–strain curves of molded samples were obtained. Figure 7.31 shows
the mechanical properties of F2MB/FOOPB blends.
a b c

FIGURE 7.31  Dependence of (a) Tensile Strength, (b) Young’s Modulus, and (c)
Elongation at Break of F2МВ–FOOPB Blends on FOOPB Content.

The data were obtained in collaboration with V.M. Buznik, L.M. Ignatieva, and N.N.
2

Loginova.
Inorganic Polyoxide Thermoplastics 223

Fluorinated polyoxides in mixtures with F2MB exhibit chemical and


catalytic activity.

STRUCTURE OF BLENDS

The degree of mixing of the components is an important characteristic of


blends. The degree of mixing of the components was studied by different
methods. The level of mixing of PE and PP with OBO was estimated by
the paramagnetic probe method.52
Based on the ESR spectra of a paramagnetic molecule-iminoxyl radi-
cal incorporated into the composition, correlation times (t) inversely pro-
portional to the rotation frequency and characterizing the molecular mo-
bility of the radical environment may be measured.
For this purpose, t values in PE and PP (the paramagnetic probe is
insoluble in boron oxides) were measured and compared with the ESR
spectral patterns and t values for the compositions.
It was found that the ESR spectra of probe in the compositions repre-
sent a superposition of the spectra with different t values (Fig. 7.32).
Previously, no selective adsorption of the stable radical from heptane
solution on a solid surface of boron oxide oligomer was observed, unlike
the adsorption of the particles of Al (OH)3.
This means that the blends contain the zones of a new phase with the
molecular mobility significantly lower as compared with hydrocarbons.
The new phase fraction increases with the oxide concentration up to 45%
(Table 7.3).

TABLE 7.3  Spin Probe Correlation Times in New Phases of BA/LDPE Blends%
Composition, wt % Т, °С t1, 1010, с % t2, 1010, с %
40 27 – –
LDPE 60 16,3 100 – –
80 6,9 – –
40 26 84 130 16
ОBO/LDPE 46/54 60 14 87 138 13
80 6,9 85 130 15
224 Additives in Polymers: Analysis and Applications

TABLE 7.3  (Continued)


Composition, wt % Т, °С t1, 1010, с % t2, 1010, с %
40 27 65 140 35
ОBO/LDPE 69/31 60 13 55 110 45
80 3,9 58 100 42

FIGURE 7.32  ESR Spectra of Spin Probe in OBO/LDPE Compositions.

The degree of blending of boron oxides with polyolefins was also stud-
ied by electron probe X-ray spectral microanalysis.53
The measurements were carried out with polymer films prepared by
pressing at 170°C. The PE-BA-PP samples in the “sandwich” form were
pressed from BA powder between the polymer films at 190°C for 15 min.
The samples were annealed in the range of 190-260°C for 1-6 h.
Along with three-layer films, the phase structure of LDPE and PP
blends with boron oxides prepared by the condensation of orthoboric
acid, which were obtained by blending in a laboratory Brabender mixer at
190°C for 10 min followed by pressing at the same temperature was stud-
ied. The blend composition was ranged from 30 to 100 wt% BA.
Inorganic Polyoxide Thermoplastics 225

The distribution profiles of polyolefins and BA in the contact zone of


phases were determined by electron probe X-ray spectral microanalysis at
different stages of thermal annealing.
The concentrations of C, O, and B elements in the compositions were
analyzed along the line perpendicular to the contact boundary of films.
The profiles of the distribution of the blend components in the contact
zone of phases and their changes in the course of thermal treatment were
obtained.
In the OBO phase, the intensity of the characteristic X-ray radiation of
carbon corresponds to the background level, and as it moves to the poly-
olefin phase, the intensity increases. In monolithic phases of LDPE and PP
contacting with BA particles, an extended transition zone characteristic of
a smooth profile of composition change is observed (Figs. 7.33 and 7.34).

FIGURE 7.33  Evolution of Concentration Profiles in the Zone of OBO and PE Phase
Conjugation at (1) 220 and (2) 260°C in the Annealing Time of 60 min.
226 Additives in Polymers: Analysis and Applications

FIGURE 7.34  Kinetics of BA Diffusion Front Motion into Melt of (1) PE and (2) PP; T
= 210°C.

It was found that the zone of phase conjugation increases with tem-
perature and time of annealing, and at 260°C and annealing time of 60
min, its length achieves ~9 mm and ~10 mm for LDPE-BA and PP-BA
blends, respectively.
The treatment of concentration profiles in the frame of the classical
solution of the second Fick’s law for semi-infinite media showed that the
composition change in the transition zone is of diffusion character. By
extrapolation of the concentration profiles on the interface, the solubility
of BA in polyolefin melts was estimated. As indicated earlier, at 210 and
260°C, the solubilities of BA in LDPE are as high as 30 and almost 50
wt%, respectively.
Inorganic Polyoxide Thermoplastics 227

The BA diffusion coefficients into the polyolefin matrix estimated by


the initial portions of kinetic curves change from 1 × 10-9 cm2/s for PP and
6 × 10-10 cm2/s for LDPE up to 1 × 10-13 cm2/s with the annealing time.
The results obtained are indicative of a partial molecular compatibility
of components, and a diffusion-chemical model of the complex structure
of composites may be proposed.
Another example of the deep mixing is the change of Tsoft of amorphous
phase of PP (Tm = 162°C, Tg = 48°C, Tsoft = 75°C) in blends with boron oxides
(Table 7.4).
The change in Tg of polymer can be used as a parameter reflecting the
degree of mixing of the components.
The increase in Tsoft can be explained by the formation of a new blend
with the other relaxation properties dissimilar to the properties of the ini-
tial components. In both cases, such significant changes are associated
with a deep interpenetration of the components.

TABLE 7.4  Tg of amorphous phase of PP in blends with boron oxide


Concentration of Boron Oxide, vol% 0 8 16 19 27
Тg °C 48 58 70 73 77

It has been reported that Tg of polymers can change by as much as


±30°C due to the addition of a nanofiller.54,55 The decrease of Tg may occur
during
heterogeneous plasticization of organic polymers by nanoparticle fill-
er with a low surface energy, which prevents the interaction between the
polymer chains. This is shown with an example of graphite,54 alumina,56
clay,57 and phosphate.58
It was shown that some blends, namely, samples of boron oxide/poly-
olefin and boron oxide/ethylene-vinyl acetate copolymer blends, are
transparent in the visual light that suggests a high level of mixing (the let-
tering is located beneath the plate, 2 mm thick; Fig. 7.35).
Taking into account that the diffraction of light waves is possible only
when the size of the obstacle is 102-103 nm, one can conclude that the size
of the oxide particles is less than these values.
228 Additives in Polymers: Analysis and Applications

PP + boron oxide, PE + boron oxide PE + ethylene and vinylacetate copolymer


57/43 wt% 47/53 wt% 80/20 wt%
FIGURE 7.35  Transparent Organic/Inorganic Blends.

BORON OXIDE OLIGOMERS AS INHIBITORS OF OXIDATION


PROCESSES

It was shown that in PE/boron oxide blends, the thermal stability of PE


increases along with the changing direction of the reactions of thermal
oxidative degradation of the polymer.59 The temperature of 1% weight loss
for PE-boron oxide blends increased by 140 K at the maximum oxide con-
tent up to 64 vol% (Fig. 7.36).

FIGURE 7.36  Temperature of Onset of Weight Loss for LDPE-Boron Oxide Blend
Versus Oxide Weight Fraction Calculated on Assumption that the Activation Energy of
Degradation is Equal to the Energy of C-C Bond Scission in PE (19.7 kJ/mol).
Inorganic Polyoxide Thermoplastics 229

The following scheme of the inhibition of catalytic oxidation of poly-


hydrocarbons can be presented.
Hydroperoxide formation
R - H + +O 2 → HO 2 + + R * + + O 2 → ROO * + + RH → RO - OH + + R *
The stage of inhibition
RO - OH + + HO - B <<→ RO * + + *Î - Â <<
RO * → R == Î , RO * + + HO - B <<→ R - OH.
It was shown that the retardation of the degradation rate is related to
the effective inhibition of the process via interaction of chemically active
-B-OH groups with hydroperoxides inevitably forming upon hydrocar-
bon oxidation. This is corroborated by the formation of oxygen-containing
products of flash pyrolysis of PE in the presence of boron oxides, which
are virtually absent in the products of pure PE pyrolysis that is in an accor-
dance with the classical scheme of thermal degradation of hydrocarbons.
The scheme under consideration correlates with the mechanism of liquid-
phase oxidation of paraffins in the presence of catalytic amounts of boric
anhydride.60, 61
In all obtained mass spectra of gaseous products of degradation of
LDPE-OBO compositions, no boron-containing compounds were found.
The degradation of PE in the presence of boron oxides is characteristic
of the presence of an additional feature, namely, more intensive formation
of double bonds as a result of PE chain scission that is accompanied by
conjugation and cross-linking processes and, hence, enhanced coke for-
mation.
Thus, a conclusion can be made on a significant decrease in the rate of
thermooxidative degradation of PE in the presence of boron oxides, which
act as high-temperature antioxidants. The effect of thermal stabilization of
polyhydrocarbon by boron oxide was also found for blends with ethylene-
vinyl acetate copolymer.

LOW-TEMPERATURE CARBONIZATION

Powdered blends of BA and poly(vinyl alcohol) (PVA) with the compo-


nent ratio of 50/50 wt% were studied (T = 200-600°C, 3 h). An intensive
carbonization process beginning at 200°C was observed, with the shape
230 Additives in Polymers: Analysis and Applications

and color of carbonized sample being retained at further heating, whereas


the analogous thermal treatment of PVA does not result in the coke resi-
due62 (Fig. 7.37).

FIGURE 7.37  Carbonized Sample of BA and Polyvinyl Alcohol Mixture Obtained at T


= 200°C.

On the examination of processes in powdered compositions, it should


be taken into account that all reactions begin at the interface at temperature
above Tm of BA; in this case, the polycondensation accompanied by water
release with the formation of oligomer oxides.
Inorganic Polyoxide Thermoplastics 231

FIGURE 7.38  Reactions of Catalytic Dehydration and Dehydrogenation of PVA in the


Presence of Boron Oxide.

Supposedly, in the course of thermal treatment, two parallel processes


take place: catalytic degradation and dehydrogenation of PVA in the pres-
ence of boron polyoxide with the formation of diene bonds followed by
their aromatization (Fig. 7.38) and chemical interaction of -B-OH groups
with hydroxyl groups of PVA “retaining” carbon atoms in materials at high
temperatures.

CONCLUSION

In conclusion, it should be noted that the relevant field of research is an


attempt to extend the range of polymeric materials constructing an inter-
mediate region between the hydrocarbon and inorganic polymers.
232 Additives in Polymers: Analysis and Applications

Low-softening inorganic polymers and their hybrids and blends ob-


tained under mild conditions have a wide promise not only as inflammable
block polymers but also as binders for reinforced materials.
Furthermore, the study in this field opens the way to endow inorganic
polymers with the deformability.

KEYWORDS

•• Organic-inorganic hybrids
•• polymer blends
•• polyoxides
•• phosphates
•• thermal stability
•• inflammability

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CHAPTER 8

HYPERBRANCHED 1,4-CIS+1,2-
POLYBUTADIENE SYNTHESIS USING
NOVEL CATALYTIC DITHIOSYSTEMS
SHAHAB HASAN OGLU AKHYARI1, FUZULI AKBER OGLU
NASIROV1,2, EROL ERBAY2, and NAZIL FAZIL OGLU JANIBAYOV1
Institute of Petrochemical Processes of National Academy of Sciences of
1

Azerbaijan, Baku, Azerbaijan; 2Petkim Petrokimya Holding, Izmir, Turkey


Email: [email protected], [email protected]

CONTENTS

Introduction........................................................................................................ 238
Experimental Procedure..................................................................................... 239
Results and Discussion...................................................................................... 240
Keywords........................................................................................................... 246
References.......................................................................................................... 246
238 Additives in Polymers: Analysis and Applications

INTRODUCTION

Branching degree of polydienes (polybutadiene, polyisoprene, and so on)


is a very important parameter with the necessary specifications such as ste-
reoregularity, molecular mass, and molecular mass distribution. Branches
in the structure of polydienes strongly reduce solution viscosity (SV) by
improving its processability and increasing operating ability of vulcani-
zates. On the other hand, the branched polymers easily decompose via
light and by biological factors, which solves the problem of the elimina-
tion of waste polymers from the environment.
By using known catalytic systems, we can achieve high molecular
mass, linear 1,4-cis–polybutadienes of high SV. These easily prevent the
polymer processing and limit using them in preparation of impact resistant
polystyrenes. At the same time, as it is known,1 because of their high crys-
tallization temperature, high stereo, regular 1,4-cis–polybutadienes cannot
be used in the production of tires and technological rubbers, which are em-
ployed in cold climatic conditions. Therefore, it is of critical importance
to obtain cold resistant, hyperbranched, and high molecular 1,4-cis+1,2-
polybutadiene with 20–40% of 1,2-vinyl bonds.1
Earlier, in the Institute of Petrochemical Processes of Azerbaijan Na-
tional Academy of Sciences, we have developed the new bifunctional
nickel- and cobalt-containing catalytic dithiosystems, which have shown
high catalytic activity and stereo selectivity in butadiene polymerization
process. Particularly, by using the cobalt-dithiocarbamate catalytic system
(diethyl­ditiocarbamate cobalt  + alkylaluminummonochloride), it was pos-
sible to obtain linear high molecular 1,4-cis+1,2-polybutadiene of high
SV.1
For the synthesis of hyperbranched 1,4-cis+1,2-polybutadienes, the
new dialkyldithiocarbamate cobalt + alkylaluminumdichloride (or alkyl-
aluminumsesquichloride) catalytic dithiosystems have been prepared and
used in the butadiene polymerization process. It has been shown that by
using the dialkyldithiocarbamate cobalt + alkylaluminumdichloride (or al-
kylaluminumsesquichloride) catalytic dithiosystems, it is possible to syn-
thesize hyperbranched, low SV, and high molecular weight 1,4-cis–poly-
butadiene with 20–40% 1,2-vinyl bond content.
In this chapter, the main results of butadiene polymerization to high
molecular weight hyperbranched 1,4-cis+1,2-polybutadienes using new
Hyperbranched 1,4-cis+1,2-Polybutadiene 239

dialkyldithiocarbamate cobalt + alkylaluminumdichloride (or alkylalumi-


numsesquichloride) catalytic dithiosystems are given.

EXPERIMENTAL PROCEDURE

Butadiene (99.8 wt.%) and aluminum organic compounds (85.0 wt.% – in


benzene) were obtained from Sigma-Aldrich (St. Louis, MO, USA). Or-
ganic dithioderivatives (dithiocarbamates, dithiophosphates, and xantho-
genates) of cobalt were synthesized according to the previously described
procedures.1–3
After drying over metallic sodium for 24 h, polymerization was con-
ducted in toluene, which was distilled and preserved over sodium. Where
necessary, manipulations were carried out in 50–200 mL Schlenk-type
glass reactors under dry, oxygen-free argon or nitrogen with appropriate
techniques and gas-tight syringes. The usual order of addition was solvent,
cobalt component, aluminum organic compound (at -78°C), and finally,
the monomer. Polymerizations were conducted at 25–60°C, and then the
polymerizate was poured to ethanol (or methanol) followed by the ter-
mination. The obtained polymer was washed several times with ethanol
(or methanol) and was dried at 40°C in a vacuum to constant weight and
stored under argon (or nitrogen).
Solution viscosities of polybutadienes were measured using an Ubbelo-
hde viscometer in toluene solution at 30°C at a concentration of 0.2 °g/dL.4
The molecular weight of 1.4-cis+1.2-polybutadienes were determined by
viscometric method1,4 using the following formula:

[h]30(toluene ) = 15.6·10-5 M 0.75


The molecular weights (Mw and Mn) and molecular weight distribu-
tion (Mw/Mn) of polybutadienes were measured by a Gel Permeation Chro-
matograph (GPC) constructed in the Czech Republic with a 6000 A pump,
original injector, R-400 differential refractive index detector, and styragel
columns with nominal exclusions of 500, 103, 104, 105, and 106. The GPC
instrument was calibrated according to the universal calibration method
by using narrow molecular-weight polystyrene standards.5
The microstructure of the polybutadiene was determined using FT-
IR-spectrometry (“Nicholet NEXUS 670” with spectral diapason from
240 Additives in Polymers: Analysis and Applications

400 cm–1 till 4000 cm–1, as a film on KBr, obtained from toluene solu-


tion).6,7
Mooney viscosity (MV) was determined by the means of a SMV-201
Mooney viscometer (Shimadzu Co., Ltd) in accordance with ASTM D
1646.8,9 Branching degree was calculated based on the viscosity of polybu-
tadiene at 25°C in 5% toluene solution. SV in proportion to MV at 100°C
(SV/MV) and its branching index (gM) were calculated from proportional
literature sources.8,9 Branching index for linear polybutadiene is gM  = 1.0
and for branched polybutadienes is gM < 1.0.

RESULTS AND DISCUSSION

In this study, we have used dialkyldithiocarbamate cobalt as the main cata-


lyst component with the structure as shown below:

R1 S S R1
N-C Co C-N
R S S R
where R and R are alkyl, aryl, and alkylaryl radicals, and co-catalysts are
1

the aluminum organic compounds (dialkylaluminumchlorides, alkylalu-


minumdichlorides, alkylaluminumsesquichlorides, and aluminumoxanes)
with formulas AlR2CI2 and/or Al2R23CI3, AlR22 CI (where R2 is methyl,
ethyl, isobutyl radicals, and so on).
We have investigated the peculiarities of dialkyldithiocarbamate co-
balt + alkylalu­minumdichloride (or alkylaluminumsesquichloride) catalyt-
ic dithiosystems in the polymerization of butadiene to highly branched and
high molecular weight 1,4-cis+1,2-polybutadiene. These catalysts were
studied in comparison with a known cobalt-containing catalytic dithiosys-
tems for butadiene polymerization dependence of process outcomes, cata-
lyst activity and selectivity on the nature of ligands of cobalt compounds,
catalyst component concentration and ratios, as well as the influence of
temperature and polymerization time. As may be, in polymerization, the
ligand nature of the transition metal is also crucial for the catalyst activity
and stereoselectivity. Ligands used in this work were mainly dithiocarba-
mates, dithiophosphates, and xanthogenates. As can be seen in Table 8.1.,
Exp. 28–31, that cobalt-dithiophosphates and cobalt-dialkylxanthogenates
in combination with diethylaluminumchloride (DEAC), ethylaluminum-
Hyperbranched 1,4-cis+1,2-Polybutadiene 241

dichloride (EADC), and methylaluminoxane (MAO) allow yield of linear


high molecular weight 1,4-cis polybutadiene with polymer yield of 80.0–
98.0%, catalyst activity of 12.0–34.0 kg PBD/g Co h, intrinsic viscosity
[h] of 1.8–2.5 dL/g, and 1,4-cis content of 90.0–97.0%. Cobalt-dialkyldi-
thiocarbamate catalytic system–cobalt-diethyldithiocarbamate (DEDTC-
Co) + DEAC (or MAO) gives linear high-molecular weight 1,4-cis+1,2-
polybutadiene with polymer yield of 85.0–90.0%, catalyst activity of
20.0–22.0 kg  PBD/g Co h, intrinsic viscosity [h] of 2.3–2.8 dL/g, 1,4-cis
content of 63.0–66.0%, and 1,2-vinyl content of 20.0–25.0% (Table 8.1,
Exp.24–27).
As seen from Table 8.1, Exp. 28–31, cobalt-dithiophosphates and
cobalt-dialkylxanthogenates in combination with DEAC, EADC, and
MAO allow yield of linear high molecular weight 1,4-cis polybuta-
diene with a polymer yield of 80.0–98.0%, catalyst activity of 12.0–
34.0 kg PBD/g Co h, intrinsic viscosity [h] of =1.8–2.5 dL/g, and 1,4-cis
content of 90.0–97.0%.

TABLE 8.1  Results of Butadiene Polymerization to Hyper Branched and Linear


Polybutadienes with Bifunctional Cobalt-containing Catalytic Dithiosystems
Branch- Micro-
Aluminum Organic Com-

ing structure
Kg of PBD/g Co hour
Reaction Time, min.

of PBD%
[Co]× ×104, mol/L
Cobalt Compound

Catalyst activity,
Yield of PBD,%
pounds (AOC)

[М], mol/L

[h], dL/g

Degree (SV/МV)

Mw/Mn
Al:Co

Т,°C

Index (gМ)

1,4-trans
1,4-cis

1,2-

1 2 3 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 DEDTC EADC 1.0 100 5.0 25 60 96.0 44.0 2.5 0.35 2.5 2.3 70 5 25
2 DMDTC EADC 1.0 100 5.0 25 60 92.0 42.0 3.5 0.55 2.7 2.5 60 5 35
3 DBenz- EADC 1.0 100 5.0 25 60 97.0 45.0 3.3 0.40 2.6 2.6 60 10 30
DTC
4 DPhDTC EADC 1.0 100 5.0 25 60 98.0 55.0 3.0 0.52 2.7 2.3 60 7 33
5 DEDTC EASC 1.0 100 5.0 25 60 94.0 33.0 2.9 0.60 3.0 2.6 72 3 25
6 DBDТK EASC 1.0 100 5.0 25 60 92.0 22.0 2.8 0.70 3.4 2.7 71 7 22
7 DЕDТК EADC 1.0 100 5.0 25 60 92.0 42.0 2.5 0.60 3.1 2.6 70 5 25
8 DМDТК EADC 1.0 100 5.0 25 60 97.0 44.0 2.7 0.65 3.25 2.3 72 6 22
9 DBDТК EADC 1.0 100 5.0 25 60 88.0 40.0 2.3 0.55 2.7 2.8 75 5 20
242 Additives in Polymers: Analysis and Applications

10 DEDTC EADC 0.5 100 5.0 25 90 90.0 50.0 3.5 0.65 3.5 2.5 75 5 20
11 DEDTC EADC 2.5 100 5.0 25 60 95.0 44.9 2.9 0.55 2.7 2.3 68 7 25
12 DEDTC EADC 5.0 100 5.0 25 30 98.0 43.0 2.5 0.49 2.5 2.1 65 5 30
13 DEDTC EADC 10.0 100 5.0 25 10 99.0 40.0 2.0 0.42 2.4 2.0 55 5 40
14 DEDTC EADC 1.0 10 5.0 25 60 87.0 39.8 3.0 0.75 3.7 2.4 72 2 25
15 DEDTC EADC 1.0 50 5.0 25 60 95.0 43.5 2.8 0.55 2.8 2.5 72 1 27
16 DEDTC EADC 1.0 100 1.0 25 60 98.0 22.0 2.0 0.22 2.5 2.2 60 10 30
17 DEDTC EADC 1.0 100 3.0 25 60 97.0 26.6 2.8 0.28 3.0 2.3 65 7 28
18 DEDTC EADC 1.0 100 8.0 25 60 90.0 50.0 3.5 0.60 3.6 2.8 70 10 20
19 DEDTC EADC 1.0 100 5.0 45 60 95.0 43.5 2.9 0.40 2.3 2.4 70 3 27
20 DEDTC EADC 1.0 100 5.0 60 60 90.0 41.2 2.7 0.35 2.3 2.3 71 2 27
21 DEDTC EADC 1.0 100 5.0 25 10 86.0 36.1 2.8 0.70 3.6 2.2 62 3 35
22 DEDTC EADC 1.0 100 5.0 25 90 99.0 30.2 3.5 0.45 2.4 2.5 68 4 28
23 DEDTC EADC 1.0 100 5.0 25 120 90.0 20.0 2.5 0.95 9.2 3.2 62 13 25
24 DMDTC DI- 1.0 100 5.0 25 120 85.0 19.5 2.3 0.96 10.0 3.2 65 15 20
BAC
25 DBDTC DEAC 1.0 100 5.0 25 120 92.0 22.0 2.7 0.94 8.8 3.5 66 12 22
26 DBenz- MAO 1.0 100 5.0 25 120 88.0 20.0 2.7 0.95 9.0 3.6 65 13 22
DTC
27 DPhDTC DI- 1.0 100 5.0 25 120 90.0 21.0 2.8 0.96 9.5 3.5 63 12 25
BAC
28 DCDTPh DEAC 1.0 100 3.0 25 60 98.0 12.0 1.8 0.92 8.6 1.8 90 8 2
29 DEDTPh MAO 1.0 100 3.0 25 60 97.0 30.0 2.2 0.93 8.7 2.6 97 2 1
30 DPh- EADC 1.0 100 3.0 25 60 94.0 34.0 2.3 0.98 8.5 3.2 95 3 2
DTPh
31 BuXh EASC 2.0 100 3.0 25 60 80.0 28.0 2.5 1.0 10.0 2.6 95 2 3
32 EtXh TEA 2.0 100 3.0 25 60 93.0 30.0 2.5 1.0 - - 2 2 96
33 i-PrXh TEA 2.0 100 3.0 25 60 98.0 35.0 2.3 1.0 - - 1 1 98
Notes: In experiments 7–9, benzene, chlorobenzene, and hexane were used as solvent,
respectively; In experiments 24, 25, 27, alkylaluminummonochlorides (such as
DEAC and DIBAC) were used as co-catalysts, respectively; In experiments, 28–33
O,O-dialkylsubstituted dithiophosphates and alkylxanthogenates were used as cobalt
compounds, respectively.
Abbreviations: DCDTPh-Co, Cobalt-O,O’-di-4-methylphenyl dithiophosphate; DEDTPh-
Co, Cobalt-Diethyldithiophosphate; DMDTC-Co, Cobalt-Dimethyldithioicarbamate;
DBDTC-Co, Cobalt-Dibutyldithiocarbamate; DBenzDTC-Co, Cobalt-
Dibenzyldithiocarbamate; DPhDTC-Co, Cobalt-Diphenyldithiocarbamate; DPhDTPh-Co,
Cobalt-Diphenyldithiophosphate; EtXh-Co, Cobalt-Ethylxanthogenate; DCDTPh-Co,
Cobalt-O,O’-di-4-methylphenyl dithiophosphate; EASC, Ethylaluminumsesquichloride;
BuXh-Co, Cobalt-Butylxanthogenate; AlkXh-Co, Cobalt-Alkylxanthogenate; TEA,
Triethylaluminum; iPrXh-Co, Cobalt-iso-Propylxanthogenate.
Hyperbranched 1,4-cis+1,2-Polybutadiene 243

The cobalt-dialkyldithiocarbamate catalytic system DEDTC-


Co + DEAC (or MAO) gives linear high molecular weight 1,4-cis+1,2-
polybutadiene with polymer yields of 85.0–90.0%, catalyst activity of
20.0–22.0 kg PBD/g Co h, intrinsic viscosity [h] of 2.3–2.8 dL/g, 1,4-cis
content of 63.0–66.0%, and 1,2-vinyl content of 20.0–25.0% (Table 8.1,
Exp.24–27).
Cobalt-dialkylxanthogenates + TEA catalytic dithiosystems give high
molecular and high crystalline syndiotactic 1,2-PBD (1,2-SPBD). In their
presence, polymer yield was 93.0–98.0%, catalyst activity was 30.0–
35.0 kg PBD/g Co h, and the sythesized 1,2-SPBD had an intrinsic vis-
cosity (135°C, tetralin) of 2.3–2.5 dL/g, and 1,2-vinyl content of 96–98%
(Table 8.1, Exp. 32 and 33).
By using only the dialkyldithiocarbamate cobalt + EADC (or EASC)
as catalyst results in obtaining of hyperbranched high molecular weight
1,4-cis+1,2-polybutadiene with the yields of 92.0–98.0%, intrinsic viscos-
ity [h]  = 2.8–3.5 dL/g, 1,2-vinyl content of 22.0–35.0%, branching in-
dex of 0.35–0.70, and with the capability of regulation of polymers chain
branching in wide intervals. Productivity of these catalysts is 22.0–55.0 kg
PBD/g Co h (Table 8.1, Exp. 1–23).
The influence of the organic solvents (toluene, benzene, chloroben-
zene, and hexane) on the activity and stereoselectivity of the diethyldithio-
carbamate cobalt + ethylaluminumdichloride (DEDTC-Co + EADC) cata-
lytic dithiosystem was studied at [Co] = 1.0 10-4 mol/L, [M] = 5.0 mol/L,
Al:Co = 100:1. The butadiene polymerization reactions were conducted at
25°C for an hour.
From the results shown in Table 8.1, Exp.1 and 7, it seems that when
toluene and benzene were used as the solvent, the polymer yield was
96.0% and 92.0%, and the catalyst activity was 44.0  kg PBD/g Co h and
42.0 kg PBD/g Co h, respectively. The obtained polybutadiene had 1,2-vi-
nyl content of 30.0% and 25.0% and branching index of 0.35 and 0.60,
respectively. The used catalyst showed the same results in terms of activ-
ity and stereoselectivity when chlorobenzene and hexane were used as the
process solvent (Table 8.1, Exp. 8 and 9).
For future investigations, toluene, a largely used industrial polymeriza-
tion process solvent, has been chosen as an optimal solvent in the polymer-
ization of butadiene to hyperbranched polybutadiene. In these experiments,
polymerization of butadiene was carried out at 25°C, and the cobalt-com-
pound concentration was varied within the limits – [Co] = (0.5–10)×10-
244 Additives in Polymers: Analysis and Applications

4
 mol/L at Al:Co = 100:1. The results are shown in Table 8.1, Exp.1, 10–13.
An increase in cobalt-compound concentration from 0.5×10-4 mol/L up to
approximately 10.0×10-4 mol/L resulted in an increase in the yield of poly-
mer from 90.0 to 99.0%. Increase in the concentration of cobalt compound
resulted in a decrease in the branching index of polymer from 0.65 to 0.42
and intrinsic viscosity [h] from 3.5 to 2.0 dL/g. Content of the 1,2-vinyl
chain increased in the range of 20.0–44.0%.
The influence of Al:Co ratio in the interval of (10–100):1 on the ac-
tivity, stereoselectivity, and productivity of catalyst was investigated at
[Co] = 1.0×10-4 mol/L and t = 25°°C. From the results of Table 8.1, Exp.1,
14, 15, it seems that an increase of Al:Co ratio from 10:1 to 100:1 resulted
in an increase of polybutadiene yield of 87.0–95.0% and 1,2- vinyl content
of 25.0–30.0%. It was also observed that the intrinsic viscosity decreased
to 3.0–2.5 dL/g and branching index of polymer decreased to 0.75–0.35.
The influence of monomer concentration in a range of 1.0 to 8.0 mol/L
was studied at [Co] = 1.0×10-4 mol/L, t = 25°C (Table 8.1, Exp.1, 16–18).
Increase in the monomer concentration resulted in a decrease in the poly-
mer yield of 98.0–90.0% and 1,2-vinyl content of 30.0–20.0 with an in-
crease in the catalyst activity to 22.0–50.0 kg PBD/g Co h and branching
index to 0.22–0.60.
The influence of temperature on the yield of the butadiene polymeriza-
tion reaction was investigated between 25°C and 60°C. As it can be seen
in Table 8.1, Exp. 1, 19, and 20, an increase in temperature resulted in
a decrease in polybutadiene yield of 96.0–90.0% and intrinsic viscosity
[h] of =2.9–2.5 dL/g. But this has no influence on the 1,2-vinyl content
(25.0–27.0%) and branching index (0.35–0.40) of the product.
Experimental results show that only the new cobalt alkyldithio-
carbamate  +  alkylaluminumdichloride (or alkylaluminumsesquichlo-
ride) catalytic dithiosystems allow us to obtain high molecular weight
1,4-cis+1,2-polybutadienes with high activity and stereoselectivity, high
cold resistance, and various branching index.
The presence of known catalytic systems, such as cobalt-dithio-
phosphate  + AOC, cobalt-xanthogenate + AOC, and cobalt-dithiocarba-
mate + dialkylaluminumchloride, did not yield branched polybutadienes.
Obtaining of branching polymers in the presence of alkyldithiocarbamate
cobalt  + alkylaluminumdichloride (or alkylaluminumsesquichloride)
could be explained by the cationic nature of an alkylaluminumdichloride
and alkylalumi­numsesquichloride co-catalysts. These co-catalysts act as
Hyperbranched 1,4-cis+1,2-Polybutadiene 245

catalysts in the polymerization process of butadiene (I. Direction) and in


the co-polymerization of the obtained polymer with a new molecule of
monomer (II. Direction) or with another molecule of polymer (III. Direc-
tion), resulting in the formation of branching with various lengths in the
polybutadiene chain as shown in scheme 8.1.

SCHEME 8.1  Formation of Branching in 1,4-cis+1,2-Polybutadiene Molecule.

CONCLUSIONS
High activity and stereo selectivity cobalt-dithiocarbamate catalytic di-
thiosystems for butadiene polymerization process have been developed.
Based on alkyldithiocarbamate cobalt as the main catalyst compound in
combination with alkylaluminumdichloride (or alkylaluminumsesquichlo-
ride) as the co-catalyst, they provide for the preparation of high molecular
hyperbranched 1,4-cis+1,2-polybutadienes with 20–40% 1,2-vinyl bond
content.
Productivity of these catalysts is 20.0–40.0 kg PBD/g Co h with the
yields of polybutadiene 85.0–99.0%. The obtained hyperbranched poly-
butadienes have a branching index of 0.70–0.20 versus the branching in-
dex of linear polybutadienes, which is between 0.96–0.94. Known cata-
lytic systems based on cobalt-dithiophosphates or cobalt-xanthogenates
as the main cobalt compound and aluminum organic compounds (such
as dialkylaluminumchlorides, alkylaluminumdichloride, alkylaluminum-
sesquichloride, and trialkylaluminum) and cobalt-dithiocarbamate + dial-
246 Additives in Polymers: Analysis and Applications

kylaluminumchloride do not lead to the formation of hyperbranched poly-


butadienes.
Synthesized hyperbranched high molecular 1,4-cis+1,2-polybutadiene
can be used in the production of tires, technological rubbers, and impact
resistant polystyrenes.

KEYWORDS

•• Polydienes
•• molecular mass
•• waste polymers
•• environment
•• catalytic systems
•• binders

REFERENCES

1. Nasirov, F. A. Bifunctional Nickel- or Cobalt containing catalyst-stabilizers for poly-


butadiene production and stabilization (Part I): kinetic study and molecular mass ste-
reoregularity correlation. Iran. Polym. J. 2003, 12(4), 217–235.
2. Nasirov, F. A. Organic dithioderivatives of metalls – components and modificators of
petrochemical processes. Petrochemistry. 2001, 6, 403–416. (in Russian).
3. Byrko, V. M. Dithiocarbamates; Nauka: Moscow, 1984; p 342. (in Russian).
4. Rafikov, S. P.; Pavlova, S. A.; Tvyordokhlebova, I. I. Methods of Determination Mo-
lecular Weight and Polydispersity of High Molecular Materials; Academy of Sciences
of USSR: Moscow, 1963; p 336. (in Russian).
5. Deyl, Z.; Macek, K.; Janak, J.; Eds. Liquid Column Chromatography; Elsevier, Am-
sterdam Scientific: Amsterdam, 1975; Vol. 1, p 2.
6. Haslam, J.; Willis, H. A. Identification and Analysis of Plastics; Iliffe Books:
London/D. Van Nostrand Co: Princeton, NJ, 1965; pp 172–174.
7. Bellami, L. J. The Infra-red Spectra of Complex Molecules; Methuen and Co:
London/J. Wiley: New York, 1957; p 592.
8. Grechanovsky, V. A. Branching in polymer chains. Uspekhy Khimii, т. 38, 12, с.2194-
2219, 1969 (Russian).
9. Jang, Y.-C.; Kim, P.-S.; Kwag, G.-H.; Kim, A.-J.; Lee, S.-H. Process for controlling
degree of branch of high 1,4-cis polybutadiene. US Patent 20020016423 A1, 2002.
CHAPTER 9

A STUDY ON THE FORMATION


OF THE PHASE STRUCTURE OF
SILANOL-MODIFIED ETHYLENE
COPOLYMERS WITH VINYL
ACETATE AND VINYL ACETATE AND
MALEIC ANHYDRIDE IN A WIDE
RANGE OF TEMPERATURES AND
COMPOSITIONS
N. E. TEMNIKOVA1, O. V. STOYANOV1, А. Е. CHALYKH2,
V. K. GERASIMOV2, S. N. RUSANOVA1, and S. YU SOFINA1
1
Kazan National Research Technological University, K. Marx street, 68, Kazan,
420015, Tatarstan, Russia
2
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of
Sciences, Leninskii pr. 31, Moscow, 119991, Russia

CONTENTS

Abstract.............................................................................................................. 248
Introduction........................................................................................................ 248
Subjects and Methods........................................................................................ 249
Results and Discussion...................................................................................... 250
Conclusion......................................................................................................... 256
Acknowledgment............................................................................................... 256
Keywords........................................................................................................... 256
References.......................................................................................................... 256
248 Additives in Polymers: Analysis and Applications

ABSTRACT

The solubility of components has been studied in a wide range of tempera-


tures and compositions in the systems of copolymers of ethylene – ami-
noalkoxysilane. Phase diagrams have been constructed. The solubility of
the components in different temperatures and concentration areas has been
identified, and structure of the modified copolymers has been studied.

INTRODUCTION

Copolymers of ethylene are widely used for the synthesis of materials and
products for various purposes including coatings and adhesives. In this
connection, there is a need for continuous improvement in the properties
of existing materials because synthesis of a new polymer is difficult. Thus,
to extend the scope of industrially produced copolymers of ethylene is
possible by their modification. One of the effective ways of modification
is the introduction of organosilicon compounds. Introduction of such addi-
tives allows to achieve various changes in polymer properties],1–3 includ-
ing adhesive characteristics.4,5
So g-aminopropyltriethoxysilane (AGM-9) is used in fiberglass and
paint industries to improve the adhesion of different polymers and coat-
ings (acrylates, alkyds, polyesters, and polyurethanes) to inorganic sub-
strates (glass, aluminum, steel, and others) and to increase water resistance
and corrosion stability of paint materials. AGM-9 is also used as pigment-
ing additives (to enhance the interaction of the pigment with the polymeric
matrix of composite material or paint material).
In order to optimize the composition of the polymer compounds and
conditions of the structure formation of their mixtures, the information
about the phase organization of these systems is of considerable interest.5
Despite the fact that there are studies focused on improving adhesion
to various substrates when modifying copolymers of ethylene by aminosi-
lanes,6,7 the information about the influence of monoaminofunctional si-
lane on phase balance and phase structure of the polyolefin compositions
in the scientific literature is not available.
The aim of this work was to study the formation of the phase structure
of silanol-modified ethylene copolymers with vinyl acetate and vinyl ac-
etate and maleic anhydride in a wide range of temperatures and composi-
tions.
A Study on the Formation of the Phase Structure 249

SUBJECTS AND METHODS

In this study, copolymers of ethylene with vinyl acetate Evatane 2020


(EVA20) and Evatane 2805 (EVA27) with vinyl acetate content of 20
and 27 wt%, respectively, and copolymers of ethylene with vinyl acetate
and maleic anhydride brand Orevac 9307 (EVAMA13) and Orevac 9305
(EVAMA26) with vinyl acetate content of 13 and 26 wt% were used. Main
characteristics of the copolymers are given in Table 9.1.

TABLE 9.1  Characteristics of the Copolymers of Ethylene

Polymer Symbol VA Con- MA Melting МV MFR, Density,


tent,% Con- Temper- g/10 g/cm3
tent, % ature, °С min
125°С
Evatane EVA20 20 – 80 44,000 2.23 0.936
2020
Evatane EVA27 27 – 72 57,000 0.74 0.945
2805
Orevac EVA- 26 1.5 47 20,000 11.13 0.951
9305 MA26
Orevac EVA- 13 1.5 92 73,000 1.1 0.939
9307 MA13
Silane containing an amino group gAGM-9 was used as a modifier. It is a transparent,
colorless liquid with a molecular weight of 221. Density is 962 kg/m3. Refractive index nd20
=is 1.4178, and the content of amine groups is 7–7.5%. The melting temperature is -70°°C.

Determination of the composition of coexisting phases and the inter-


diffusion coefficients were carried out by processing of series of interfero-
grams obtained by microinterference method. Interferometer ODA-3 was
used for the measurements. Measurements were performed at a range of
temperatures from 50 to 150°°C. To construct profiles of concentrations
by interference patterns, the temperature dependencies of the refractive
index of the components are required.6–8 Refractive index measurements
were carried out by an Abbe refractometer IRF-454 BM at a range of tem-
peratures from 20 to 150°°C.
The structure of the modified copolymers was investigated by the trans-
mission electron microscopy. Identification of the phase structure of the
250 Additives in Polymers: Analysis and Applications

samples was carried out by etching of the surface in high-oxygen plasma


discharge with the subsequent preparation of single-stage carbon-platinum
replicas. Samples were viewed using PEM EM-301 (Philips, Holland).

RESULTS AND DISCUSSION

KINETICS OF MIXING OF THE COMPONENTS

Typical interferograms of interdiffusion zones of the systems EVA (EVA-


MA) – modifier are shown in Figure 9.1.
Preliminary studies have shown that at high temperatures, the interdif-
fusion process is completely reversible, that is, the phase structures, which
occurred when the temperature was lowered, dissolved again when the
temperature was increased. This means that the net of the diffusion ex-
periment is not formed or is formed but broken during the diffusion of the
modifier, which is uncommon.
It is known that during the interaction of polymers with a modifier, tran-
sitional zones appear, within which the structure, composition, and proper-
ties vary continuously during the transition from one phase to another.

FIGURE 9.1  The Interferograms of Interdiffusion Zones of the Systems: (a) EVAMA26–
AGM-9 (100°°C); (b) EVAMA26–AGM-9 (60°°C – cooling); (c) EVA20–AGM-9
(120°°C); (d) EVA20–AGM-9 (90°°C – cooling), (e) EVAMA26–AGM-9 (140°°C).
A Study on the Formation of the Phase Structure 251

For all systems, the general picture is characteristic of partially com-


patible systems with a primary dissolution of alkoxysilanes in the melt of
copolymers.
Phase boundary (III), a region of diffusion dissolution of modifiers in
the melt of copolymers (IV), and phases of a pure copolymer (I) and the
modifier (II) are clearly expressed on interferograms. Situation in the sys-
tems changes with decrease in the temperature: near the interface, there
appears a region of opacity in between the dispersed phase in the melt of
the copolymer (V) and the modifier. However, when the temperature in-
creases again, the region of opacity disappears, indicating the reversibility
of phase transformations occurring in the systems.
However, the compatible systems and the temperatures correspond-
ing to this dissolution have been registered. AGM-9 is compatible in the
systems EVA27 – AGM-9 and EVAMA26 – AGM-9 (see Fig. 9.1e) at a
temperature above 100°°C and in the systems EVA20 – AGM-9 (at a tem-
perature above 120°C) and EVAMA13 – AGM-9 (at a temperature above
150°°C).
Typical profiles of the concentration distribution in these systems are
shown in Fig. 9.2.

FIGURE 9.2  Profiles of the Concentration Distribution in the System EVAMA13 –


AGM-9 at 135°C. Diffusion Time: (1) 11 min, (2) 7 min. (I) Diffusion Zone of AGM-9 in
EVAMA13, (II) Diffusion Zone of EVAMA13 in AGM-9, and (III) Phase Boundary.
252 Additives in Polymers: Analysis and Applications

The size of the diffusion zone is influenced by several factors: the tem-
perature and the time of observation.
It can be seen that the sizes of the diffusion zones on both sides of the
phase boundary increase in time, whereas the values of concentrations near
the interphase boundary in isothermal process conditions do not change.
The influence of temperature has a number of characteristic features.
The higher the temperature, the greater the distance the molecules of the
modifier diffuse for equal periods of time and larger the diffusion zone.
This distribution of the concentration profiles when the temperature
changes indicates that the system belongs to a class of systems with upper
critical point of mixing.8
Figure 9.3 shows the kinetic curves of isoconcentration planes moving
at different temperatures for the systems studied.

FIGURE 9.3  The Time Dependence of the Size of the Diffusion Zone EVAMA26 –
AGM-9 at Various Temperatures: (1) 140°°C, (2) 120°°C, (3) 100°C.

Despite the fact that the kinetics of movement of the modifier front
in the matrix of the copolymer has a linear dependence, IR-spectroscopy
showed that all of the systems react chemically.9 We can assume that the
method of interferometry was unable to fix a chemical reaction under the
given observation time. The rate of chemical reaction is comparable or
A Study on the Formation of the Phase Structure 253

slightly higher than the rate of diffusion, and the movement of the modifier
already occurs in a chemically modified matrix, which is the reason for the
lack of bending motion of the modifier front in the copolymer. The result-
ing matrix is soluble in the copolymer; hence, the phase decomposition by
reheating cannot be observed.
As the temperature increases, the nature of the concentration distribu-
tion and mixing of the components is maintained in the zone of diffusion.
Only the velocity of the movement of the isoconcentration planes changes.
The angle of inclination of these relationships varies with temperature: the
higher the temperature, the greater the angle of inclination of the line in
the coordinates X–t1/2. The slope of the kinetic lines is proportional to the
coefficient of the modifier diffusion into the matrix. Therefore, the greater
the angle of inclination, the higher the numerical value of the diffusion
coefficient.

PHASE EQUILIBRIA

Consideration of diffusion zones of interacting copolymers and modifiers


allows us to obtain not only the concentration profiles, but also the phase
diagrams of the studied systems by quantitative analysis of interferograms
obtained at different temperatures.

FIGURE 9.4  Phase Diagrams of the Systems of a Copolymer of Ethylene with


Vinyl Acetate – AGM-9: (1) EVA20; (2) EVA27. (I, II) The Areas of True Solutions,
Heterogeneous Condition; (III) The Area of Preparation of the Compositions; and (IV) The
Area of Study of the Structure and Physical Properties.
254 Additives in Polymers: Analysis and Applications

FIGURE 9.5  Phase Diagrams of the Systems of a Copolymer of Ethylene with Vinyl
Acetate and Maleic Anhydride – AGM-9: (1) EVAMA13; (2) EVAMA26: (I, II) the
Areas of True Solutions, Heterogeneous Condition; (III) The Area of Preparation of the
Compositions; and (IV) the Area of Study of the Structure and Physical Properties.

There are two binodal curves on all phase diagrams: the right branch of
the binodal corresponds to the solubility of the copolymer in the modifier
and is located in the area of infinitely dilute solutions. The second binodal
curve represents the solubility of the modifier in the copolymers and is
located in a fairly wide concentration area. The solubility of the modifier
in the copolymer is increased as the temperature increases.
In all phase diagrams (see Figs. 9.4 and 9.5), there are the areas cor-
responding to temperature-concentration areas of the components mixing
(area III) and the areas corresponding to the structure of the compounds
and their physical properties (area IV). The diagrams show that the prepa-
ration of the mixtures takes place in the single-phase area (area I in the
diagrams). As the temperature decreases, the figurative point of the sys-
tems crosses the binodal curve and the system goes into a heterogeneous
area (area II in the diagrams). The phase decomposition takes place, and
it is uniquely fixed in electron microscopic images (see Figs. 9.6 and 9.7).
Judging from the microphotographs, in the mixtures with EVAMA13, pre-
cipitated phases have a size that ranges from 0.1 to 1 micron, whereas
A Study on the Formation of the Phase Structure 255

for EVAMA26, the dispersed particles have a size that ranges from 50 to
100 micron.

FIGURE 9.6  Microphotograph of EVAMA13 – AGM-9 (10%).

FIGURE 9.7  Microphotograph of EVAMA26 – AGM-9 (10%).


256 Additives in Polymers: Analysis and Applications

Particles, protruding from the surface, etched in plasma of high-oxy-


gen discharge have smaller etching rate compared with the dispersion me-
dium. It has been shown previously10 that the lowest etching rate among
carbo- and heterochain polymers have polysiloxanes. Thus, it can be con-
cluded that the dispersed phase is enriched by siloxanes.
With the increase of the content of vinyl acetate groups both in EVA
and in EVAMA, solubility of AGM-9 increases. In this case, the tendency
in the change of solubility is the same for high and low temperature areas.

CONCLUSION

Thus, comprehensive studies of diffusion, phase, and structural-morpho-


logical characteristics of the compositions allow us to identify the contri-
bution of chemical reactions for the change of phase equilibrium and the
phase structure formation.

ACKNOWLEDGMENT

This work was financially supported by the Ministry of Education and


Science of Russia in the framework of the theme No. 693 “Structured
composite materials based on polar polymer matrices and reactive nano-
structured components.”

KEYWORDS

•• Copolymers of ethylene
•• Aminoalkoxysilane
•• Phase diagrams

REFERENCES

1. Stoyanov, O. V.; Rusanova, S. N.; Khyzakhanov, R. M.; Petykhova, O. G.; Chalykh,


A. E.; Gerasimov, V. K. Modificatsya promyshlennykh etilenvinilatsetatnykh sopo-
A Study on the Formation of the Phase Structure 257

limerov predelnymi alkoksisilanami. Vestnik Kazanskogo tekhnologicheskogo univer-


siteta. 2002, 1-2, 143–147.
2. Chalykh, A. E.; Gerasimov, V. K.; Rusanova, S. N.; Stoyanov, O. V.; Petykhova, O.
G.; Kulagina, G. S.; Pisarev, S. A. Formirovanie fazovoi structury silanolno-modifit-
sirovannykh polimerov etilena s vinilatsetatom. VMS seriya A. 2006, 48(10), 1801–
1810.
3. Stoyanov, O. V.; Rusanova, S. N.; Khuzakhanov, R. M.; Petuhova, O. G.; Deberdeev,
T. R. Structure-mechanical characteristics of ethylene with vinylacetate copolymers
modified by saturated alkoxysilanes. Russ. Polym. News. 2002, 7(4), 7.
4. Temnikova, N. E.; Rusanova, S. N.; Sof’ina, S.Yu; Stoyanov, O. V.; Garipov, R. M.;
Chalykh, A. E.; Gerasimov, V. K. The effect of aminoalkoxy and glycidoxyalkoxy si-
lanes on adhesion characteristics of double and triple copolymers of ethylene. Polym.
Sci. Ser. D. 2014, 7(3), 84–187.
5. Temnikova, N. E.; Rusanova, S. N.; Sofina, S.Yu; Stoyanov, O. V.; Garipov, R. M.;
Chalykh, A. E.; Gerasimov, V. K.; Zaikov, G. E. Influence of aminoalkoxy- and glyci-
doxyalkoxysilanes on adhesion characteristics of ethylene copolymers. Polym. Res. J.
2014, l8(4), 305–310.
6. Osipchik, V. S.; Lebedeva, E. D.; Vasilets, L. G. Razrabotka i issledovanie svoistv
silanolnosshitogo polietilena. Plast. Massy. 2000, 9, 27–31.
7. Kikel, V. A.; Osipchik, V. S.; Lebedeva, E. D. Sravnitelnyi analiz structury i svoistv
sshitykh razlichnymi metodami polietilenov. Plast. Massy. 2005, 8, 3–6.
8. Polimernye smesi. V 2-kh tomakh/Pod red. D.R. Pola i K.B. Baknella/Per. s angl. pod
red. Kulezneva V.N. – Spb.: Naychnye osnovy i tekhnologii, 2009, 1224 s.
9. Rusanova, S. N.; Temnikova, N. E.; Stoyanov, O. V.; Gerasimov, V. K.; Chalykh, A. E.
IK-spektroskopicheskoe issledovanie vzaimodeistviya glitsidoksisilana i sopolimerov
etilena. Vestnik Kazanskogo tekhnologicheskogo universiteta. 2012, 22, 95–96.
10. Temnikova, N. E. Vliyanie amino- i glitsidoksialkoksisilanov na formirovanie fazovoi
structury i svoistva etilenovykh sopolimerov: dis. kand. tekh. nauk. Kazan. 2013;154
s.
CHAPTER 10

QUANTUM CHEMICAL
CALCULATION OF MOLECULE
3,4,5,6,7-6,7- PENTADIMETHYLIN-
DENE BY METHOD AB INITI
V. A. BABKIN1, D. S. ANDREEV1, YU. A. PROCHUKHAN2,
K. YU. PROCHUKHAN2, and G. E. ZAIKOV3
1
Sebrykov Department, Volgograd State Architect-build University, Volgograd,
Russia
2
Bashkir State University, Ufa, Russia
3
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4,
Kosygin Street, Moscow 119991, Russia

CONTENTS

Abstract.............................................................................................................. 260
Aim and Background......................................................................................... 260
Experimental Procedure..................................................................................... 260
Keywords........................................................................................................... 263
References.......................................................................................................... 263
260 Additives in Polymers: Analysis and Applications

ABSTRACT

For the first time, quantum chemical calculation of a molecule of


3,4,5,6,7-pentamethylindene by the method AB INITIO with optimiza-
tion of geometry on all parameters is executed. The optimized geometri-
cal and electronic structure of this compound is obtained. Acid power of
3,4,5,6,7-pentamethylindene is theoretically appreciated. It is observed
that this compound pertains to a class of very weak H-acids (pKa was
equal to +33, where pKa is the universal index of acidity).

AIM AND BACKGROUND

The aim of this work is to study the electronic structure of the molecule
3,4,5,6,7-6,7-pentadimethylindene1 and theoretical estimation of its acid
power by quantum-chemical method AB INITIO in base 6-311G**. The
calculation was carried out with optimization of all parameters by standard
gradient method using built-in PC GAMESS2. The calculation was carried
out by the method of the insulated molecule in gas phase. Program Mac-
MolPlt was used for the visual presentation of the model of the molecule.3.

EXPERIMENTAL PROCEDURE

Geometric and electronic structures and general and electronic energies


of the molecule 3,4,5,6,7-6,7-pentadimethylindene were obtained by the
method AB INITIO in base 6-311G** and are shown in Figure 10.1 and in
Table 10.1. The universal factor of acidity was calculated by the following
formula4,5:

pKa = 49.04 - 134.6*q max H + ,


where qmaxH+ is a maximum positive charge on atom of the hydrogen
qmaxH+ = +0.12 (for 3,4,5,6,7-6,7-pentadimethylindene qmaxH+ alike in Table
10.1). This same formula is used by Вabkin and Zaikov,6 and the pKa was
calculated to be 33.
Quantum Chemical Calculation of Molecule 261

Quantum-chemical calculation of the molecule 3,4,5,6,7-6,7-penta-


dimethylindene by method AB INITIO in base 6-311G** was executed
for the first time. Optimized geometric and electronic structure of this
compound was obtained. Acid power of the molecule 3,4,5,6,7-6,7-pen-
tadimethylindene was theoretically evaluated (pKa = 33). This compound
pertains to the class of very weak H-acids (рКа > 14).

FIGURE 10.1  Geometric and Electronic Molecule Structure of


3,4,5,6,7-6,7-Pentadimethylindene.
(Е0 = -1419471 kDg/mol, Еel = -3740911 kDg/mol)

TABLE 10.1  Optimized Bond Lengths, Valence Corners, and Charges on Atoms of the
Molecule 3,4,5,6,7-6,7-Pentadimethylindene
Bond Lengths R,A Valence Corners Grad Atom Charges on Atoms
C(2)–C(1) 1.39 C(5)–C(6)–C(1) 122 C(1) -0.02
C(3)–C(2) 1.41 C(9)–C(6)–C(1) 110 C(2) -0.09
C(4)–C(3) 1.4 C(1)–C(2)–C(3) 118 C(3) -0.10
C(5)–C(4) 1.4 C(13)–C(2)–C(3) 119 C(4) -0.12
C(6)–C(5) 1.38 C(2)–C(3)–C(4) 121 C(5) -0.09
262 Additives in Polymers: Analysis and Applications

C(6)–C(1) 1.4 C(12)–C(3)–C(4) 119 C(6) -0.15


C(6)–C(9) 1.51 C(3)–C(4)–C(5) 120 C(7) -0.10
C(7)–C(1) 1.5 C(11)–C(4)–C(5) 120 C(8) -0.16
C(8)–C(7) 1.33 C(9)–C(6)–C(5) 128 C(9) -0.06
C(9)–C(8) 1.5 C(4)–C(5)–C(6) 118 C(10) -0.20
C(10)–C(5) 1.52 C(2)–C(1)–C(6) 120 C(11) -0.21
C(11)–C(4) 1.52 C(8)–C(9)–C(6) 102 C(12) -0.21
C(12)–C(3) 1.52 C(10)–C(5)–C(6) 120 C(13) -0.20
C(13)–C(2) 1.52 C(2)–C(1)–C(7) 133 C(14) -0.18
C(14)–C(7) 1.5 C(1)–C(7)–C(8) 109 H(15) +0.08
H(15)–C(8) 1.07 C(14)–C(7)–C(8) 123 H(16) +0.12
H(16)–C(9) 1.09 C(7)–C(8)–C(9) 112 H(17) +0.12
H(17)–C(9) 1.09 C(4)–C(5)–C(10) 122 H(18) +0.11
H(18)–C(13) 1.09 C(3)–C(4)–C(11) 120 H(19) +0.10
H(19)–C(13) 1.08 C(2)–C(3)–C(12) 119 H(20) +0.10
H(20)–C(13) 1.08 C(1)–C(2)–C(13) 123 H(21) +0.10
H(21)–C(11) 1.08 C(1)–C(7)–C(14) 128 H(22) +0.11
H(22)–C(11) 1.09 C(7)–C(8)–H(15) 125 H(23) +0.10
H(23)–C(11) 1.08 C(8)–C(9)–H(16) 112 H(24) +0.11
H(24)–C(10) 1.09 C(8)–C(9)–H(17) 112 H(25) +0.11
H(25)–C(10) 1.09 C(2)–C(13)–H(18) 112 H(26) +0.10
H(26)–C(10) 1.08 C(2)–C(13)–H(19) 112 H(27) +0.10
H(27)–C(12) 1.08 C(2)–C(13)–H(20) 111 H(28) +0.11
H(28)–C(12) 1.09 C(4)–C(11)–H(21) 111 H(29) +0.10
H(29)–C(12) 1.08 C(4)–C(11)–H(22) 112 H(30) +0.11
H(30)–C(14) 1.09 C(4)–C(11)–H(23) 112 H(31) +0.10
H(31)–C(14) 1.08 C(5)–C(10)–H(24) 112 H(32) +0.11
H(32)–C(14) 1.09 C(5)–C(10)–H(25) 112
C(5)–C(10)–H(26) 111
C(3)–C(12)–H(27) 111
C(3)–C(12)–H(29) 112
C(7)–C(14)–H(30) 112
C(7)–C(14)–H(31) 110
C(7)–C(14)–H(32) 112
Quantum Chemical Calculation of Molecule 263

KEYWORDS

•• Quantum chemical calculation


•• Method AB INITIO
•• 3,4,5,6,7-pentamethylindene
•• acid power

REFERENCES

1. Kennedi, J. Cationic Polimerization of Olefins. Nauka (Science) Publisher: Moscow,


1978; p 431.
2. Shmidt, M. W.; Baldrosge, K. K.; Elbert, J.A.; Gordon, M. S.; Enseh, J. H.; Koseki, S.;
Matsvnaga, N.; Nguyen, K. A.; Su, S. J.; and anothers. Advances in electronic struc-
ture theory: GAMESS a decade later. J. Comput. Chem. 1993, 14, 1347–1363.
3. Bode, B. M.; Gordon, M. S. J. Mol. Graphics Mod. 1998, 16, 133–138.
4. Babkin, V. A.; Fedunov, R. G.; Minsker, K. S et al. Oxid. Commun., 2002, 25(1),
21–47.
5. Babkin, V. A.; and others. Oxid. Commun., 1998, 21(4), 454–460.
6. Вabkin, V. A.; Zaikov, G. E. Nobel laureates and nanotechnology of the applied quan-
tum chemistry. Nova Science Publisher: New York, USA, 2010; p 351.
CHAPTER 11

COBALT ALKYLXHANTHOGENATE
+ TRIALKYLALUMINUM CATALYTIC
DITHIOSYSTEMS FOR SYNTHESIS OF
SYNDIOTACTIC 1,2-POLYBUTADIENE
NEMAT AKIF OGLU GULIYEV1, FUZULI AKBER OGLU
NASIROV1,2, and NAZIL FAZIL OGLU JANIBAYOV1
Institute of Petrochemical Processes of National Academy of Sciences of
1

Azerbaijan, Baku, Azerbaijan


2
Petkim Petrokimya Holding, Izmir, Turkiye
E-mail: [email protected]; [email protected]

CONTENTS

Introduction........................................................................................................ 266
Experimental Procedures................................................................................... 266
Results and Discussion...................................................................................... 268
Conclusions........................................................................................................ 272
Keywords........................................................................................................... 272
References.......................................................................................................... 273
266 Additives in Polymers: Analysis and Applications

INTRODUCTION

Syndiotactic 1,2-polybutadiene is a photodegradable polymer with mo-


lecular irregularities – double bonds in its polymeric backbone. Studies
have shown a 95% loss of properties after photodegradable materials have
been exposed to direct sunlight over a year.
It is used in the manufacturing of tires, packing polymer-film materi-
als, microcapsules for the medical purposes, ceramics, semi-permeability
membranes, adhesives, synthetic leather, oil-resistant tubes, coatings for
semi-conductor devices, non-woven materials, and carbon fibers, and so
on.1,2
Syndiotactic 1,2-polybutadienes have been synthesized using various
catalysts based on compounds of Ti, Cr, Pd, Co, V, Fe, and Mo. The re-
sults, relating to the catalysts and processes of syndicotactic 1,2-polybu-
tadiene synthesis, have been described in many studies3–11 and patents.12
Ashitaka H. et al., in a series of articles,3–6 have described the
Co(acac)3+AIR3+CS2 catalyst for the polymerization of butadiene to high
stereoregularity and high melting point syndiotactic 1,2-polybutadiene.
This catalyst had very low catalytic activity that polymer yield is only
10–20% in toluene solution (the mostly used industrial polymerization
processes as solvent).
Chinese researchers have recently focused on the synthesis and charac-
terization of syndiotactic 1,2-polybutadiene,7–11 but catalytic systems have
shown very low catalytic activity and stereoregularity.
Earlier, we have developed the new bifunctional nickel- and cobalt-
containing catalytic dithiosystems for the polymerization of butadiene.13,14
In this article, the results of the polymerization of butadiene to the photo-
degradable highly crystalline syndiotactic 1,2-polybutadiene in the pres-
ence of a new cobalt alkylxhantogenate (AlkXh-Co) + trialkylaluminum
(TAA) catalytic dithiosystems is shown.

EXPERIMENTAL PROCEDURES

Butadiene (99.8% wt) and aluminum organic compounds (85.0% wt in


benzene) were used as obtained from Aldrich.
Cobalt Alkylxhanthogenate + Trialkylaluminum 267

Organic dithioderivatives (dithiophosphates, dithiocarbamates, and


xhantogenates) of cobalt were synthesized according to procedures ex-
plained by Nasirov and Djanibekov.13–16
Polymerization was conducted in toluene, which, after predrying over
metallic Na for 24 h, was distilled and preserved under Na. Where nec-
essary, manipulations were carried out under dry, oxygen-free argon or
nitrogen in 50–200 mL glass reactors. The desired volumes of toluene,
monomer, triethylaluminum (TEA; or DEAC, MAO), and cobalt-com-
pound solutions from the calibrated glass reservoir were added to the reac-
tor under stirring at controlled temperature. The usual order of addition
was solvent, cobalt component, aluminum organic compound (at -78°C),
and finally, the monomer. All polymerizations were conducted at a tem-
perature range of 0–100°C. After polymerization, the polymerizate was
poured into ethanol or methanol and the polymerization reactions were
terminated. The precipitated polymer was washed several times with etha-
nol (or methanol). Polybutadiene was dried at 40°C in a vacuum to con-
stant weight and stored under argon or nitrogen.
The viscosity of dilute solutions of syndiotactic 1,2-polybutadienes
was measured using a Ubbelohde viscometer in tetralin at 135°C or in o-
dichlorobenzene (o-DCB) at 140°C at a concentration of 0.2 g/dL.2,3 The
molecular mass of high molecular weight and high crystalline syndiotactic
polybutadiene was determined by viscometric method17 using the follow-
ing relationship:

[hh ]135(tetralin ) == [hh ]140( o-DCB) == 9.41•10-5 • M 0.854

The molecular masses (Mw and Mn) and molecular mass distribution
(Mw/Mn) were measured by a Gel Permeation Chromatograph (GPC),
which was constructed in Czech Republic, consisting of a 6000 A pump,
original injector, R-400 differential refractive index detector, and styragel
columns with nominal exclusion of 500, 103, 104, 105, and 106. The GPC
was operated at a flow rate of 0.8 mL/min with o-dichlorobenzene as sol-
vent. The sample concentration was kept at about 0.3–0.6% with a sample
volume of 100–200 mL. The GPC instrument was calibrated according to
the universal calibration method by using narrow molecular weight poly-
styrene standards.18
The microstructure of the polybutadiene was determined by a FTIR
spectrometer (Nicholet NEXUS 670, with spectral diapason from 400
268 Additives in Polymers: Analysis and Applications

cm–1 to 4000 cm–1, as a film on KBr, received from THF or o-dichloroben-


zene solution).19,20 Tactisity and crystallinity of polymer were determined
accordingly.21 Melting point (mp) was determined under nitrogen by dif-
ferential scanning calorimeter (DSC Q20 V23.4).21,22

RESULTS AND DISCUSSION

We have investigated the peculiarities of cobalt alkylxhantogenate + tri-


alkylaluminum catalytic dithiosystems in the polymerization of butadi-
ene to syndiotactic 1,2-polybutadiene.23–26 These catalysts were studied in
comparison with known cobalt-containing catalytic dithiosystems for bu-
tadiene polymerization dependence of process outcomes on the nature of
ligands of cobalt-compounds, catalyst components concentration and ra-
tio, as well the influence of temperature on catalyst activity and selectivity.
Apart from the metal chosen for polymerization, the ligand nature is
also of high importance. Ligands that have been used for polymerization
of butadiene were mainly dithiophosphates, dithiocarbamates, and xhan-
thogenates. The results are given in Table 11.1.
It can be observed from Table 11.1 that co-dithiophosphates and co-al-
kylxhantogenates in combination with diethylaluminumchloride (DEAC)
allow obtaining of high molecular mass 1,4-cis polybutadiene with 1,4-
cis contents of 90.0–96.0%. Cobalt alkyldithiocarbamate catalytic system
(DEDTC-Co + DEAC) yields high molecular mass 1,4-cis + 1,2-polybu-
tadiene with 1,4-cis content of 58.0% and 1,2-content of 34.0%.
Only the cobalt alkylxhantogenate catalytic dithiosystems (Cobalt al-
kylxhantogenates + TEA) yield high molecular mass and high crystalline
syndiotactic 1,2-PBD (1,2-SPBD). In their presence, polymer yields are
93.0–99.0%, and the obtained 1,2-SPBD has intrinsic viscosity (135°C,
in tetralin) of 2.2–3.5 dL/g, 1,2-content of 94.0–99.0%, crystallinity of
86.0–95.0%, and mp of 175–208°C.
The effect of the organic solvents (toluene, benzene, chlorobenzene,
methylene chloride, and hexane) on the activity and selectivity of the iso-
propylxhantogenate (iPrXh-Co) + TEA catalytic dithiosystem was studied
at [Co] = 1.0×10 -4 mol/L, [M] = 3.0 mol/L, Al:Co = 100:1. For that, the
Cobalt Alkylxhanthogenate + Trialkylaluminum 269

necessary amount of a particular solvent was mixed with iPrXh-Co fol-


lowed by the addition of TEA and butadiene into reactor at -78°C. The
butadiene polymerization reactions were conducted at 40°C for 120 min.
From the results shown in Table 11.2, it appears that when toluene and
benzene were used as the solvent, the polymer yield was 96.0–99.0%. The
obtained polybutadiene had 1,2-vinyl contents of 96.0–98.0%, mp of 203–
208°C, crystallinity of 93.0–95.0%, and syndiotacticity of 95.0–97.5%.
The known catalytic systems for butadiene 1,2-polymerization showed
very low catalytic activity and stereoregularity in toluene and benzene
solutions. For future investigations, toluene, a commonly used industrial
polymerization process solvent, has been chosen as an optimal solvent in
the 1,2-polymerization of butadiene.
An increase in cobalt concentration from 0.2×10-4 mol/L up to ap-
proximately 10.0×10-4 mol/L resulted in an increase in the initial reaction
rate. As the concentration of cobalt compound was increased, the polybu-
tadiene yield increased from 50.0 to 100.0%, 1,2-vinyl content decreased
from 99.0 to 95.0%, and mp decreased from 212 to 187°C as shown in the
results in Table 11.3.
The increase of Al:Co ratio from 10:1 to 200:1 resulted in an increase
of polybutadiene yield to 65.0–99.0% and a decrease in the intrinsic vis-
cosity to 2.9–1.5 dL/g, 1,2-content of 99.0–94.0%, crystallinity of 96.0–
76.0%, and mp of 212–175°C (Table 11.3).
With an increase in temperature, there was an increase in polybutadi-
ene yield to 26.0–100.0% as expected. This results in decreasing of intrin-
sic viscosity to 3.5–1.3 dL/g, 1,2-content of 99.0–94.0%, crystallinity of
98.0–63.0%, and mp of 215–177°C.
Experimental results show that the high activity and stereoregularity of
the new cobalt alkylxhantogenate + trialkylaluminum catalytic dithiosys-
tems in toluene solution allow for the formation of syndiotactic 1,2-poly-
butadienes of varying crystallinity, syndiotacticity, and molecular mass
when experimental conditions are varied.
270 Additives in Polymers: Analysis and Applications

TABLE 11.1  Comparison of Efficiency of Different Cobalt-containing Catalytic


Dithiosystems CoX2 + AOC in the Butadiene Polymerization Process
Molecular Microstructure%

Polymer Yield% (mass)


Catalytic System (CoX2

Mass

Intrinsic Viscosity [h],


Cobalt-containing

Syndiotacticity%

Yield of Polymer,
Melting Point,°C
Crystallinity%

kg PBD/g Co h
Mw × Mw/Mn 1,4- 1,4- 1,2-
Item No

+ AOC)

10-3 cis trans

dL/g
1 DCDTPh-Co + 95 – – – 2.62 570 2.1 92 6 2 57
DEAC
2 TBDTPh-Co + 98 – – – 2.6 610 2.3 90 7 3 109
DIBAC
3 4m-6-TBPh-Co + 92 – – – 2.5 625 2.5 92 5 3 59
MAO
4 X-Co + DEAC 95 – – – 2.9 610 1.9 93 6 1 57
5 NGDTPh-Co + 88 – – – 3.1 630 1.85 93 5 2 46
DIBAC
6 DEDTC-Co + 58 – – – 2.55 600 2.3 58 8 34 44
DEAC
7 EtXh-Co + DEAC 95 – – – 2,8 540 1.85 96 2 2 127

8 BuXh-Co + 90 – – – 2,5 410 1.65 95 2 3 105


DIBAC
9 EtXh-Co + TEA 95 92 98.5 208 2.2 270 2.1 2 1 99 96
10 i-PrXh-Co + TEA 99 95 97.0 205 2.3 255 1.82 1 1 98 115

11 BuXh-Co + TEA 98 93 95.5 200 2.5 240 1.6 3 1 96 125


12 HeXh-Co + TEA 95 88 94.0 185 2.9 330 1.75 5 1 94 108
13 OcXh-Co + TEA 93 86 94.5 175 3.5 485 2.2 6 2 95 112
The obtained experimental results allow us to establish the optimal parameters for the
synthesis of high molecular mass and highly crystalline syndiotactic 1,2-polybutadiene42–45:
[Co] = (1.0–2.0) × 10-4 mol/L; [M] = 3.0 mol/L; Al:Co = (50–100):1; T = 40–80°C.
Reaction conditions: [Co] = 2.0 × 10–4 mol/L, [M] = 3.0 mol/L; Al:Me = 100; T = 25°C; τ
= 60 min; solvent – toluene.
Notes: In experiments 9–13, an intrinsic viscosity was measured in tetraline at 135°C.
Cobalt Alkylxhanthogenate + Trialkylaluminum 271

TABLE 11.2  The Influence of Organic Solvents Type on the Conversion of Butadiene,
Selectivity and Productivity of iPrXh-Co + TEA Catalytic System [Co] = 1.0 × 10–4
mol/L, [M] = 3.0 mol/L, Al:Co = 100:1, T = 40°C, and τ = 120 min
Solvent Microstructure%

Syndiotacticity,%

Melting point, °C
Crystallinity,%
Yield of PBD,%

[h]135,dL/g

1,4-trans
(mass)

1,4-cis

1,2-
Toluene 99.0 2.5 95 97.5 208 1 1 98
Benzene 96.0 2.3 93 95.0 203 3 1 96
Chlorobenzene 92.0 1.75 91 94.0 194 3 2 95
Methylene chloride 90.0 1.65 90 93.8 185 3 2 95
Hexane 70.0 1.5 76 91.0 190 6 2 92
- 56.0 3.5 93 95.0 195 4 1 95

TABLE 11.3  The Influence of Butadiene Polymerization Parameters on the Conversion


of Butadiene, Selectivity and Productivity of iPrXh-Co + TEA Catalytic System (Solvent–
Toluene)
Microstructure,%
Dura-

Yield of 1,2-SPBD,

Syndiotacticity,%
Temperature, °C

Melting Point, °C
Crystallinity,%
[Co]·104, mol/L

[h]135, dL/g
[M] mol/L

% (mass)
tion, min
Reaction

1.4-trans
1.4-cis
Al:Co

1.2-

0.2 3.0 100 40 180 50 3.0 68 98 212 1 – 99


0.5 3.0 100 40 120 65 2.8 72 98 212 1 – 99
1.0 3.0 100 40 120 95 2.5 76 97 210 1 1 98
2.0 3.0 100 40 60 99 2.3 85 98 205 1 1 98
5.0 3.0 100 40 15 99 2.1 90 96 197 2 1 97
10.0 3.0 100 40 15 99 1.7 95 95 187 3 2 95
2.0 1.5 100 40 60 97 2.0 84 96 207 2 1 97
2.0 6.0 100 40 45 90 3.2 87 98 203 1 – 99
2.0 3.0 10 40 180 65 2.9 96 98 212 1 – 99
2.0 3.0 25 40 90 83 2.7 93 98 208 1 – 99
2.0 3.0 50 40 60 91 2.4 78 97 206 1 1 98
2.0 3.0 150 40 45 99 2.0 73 96 186 3 1 96
2.0 3.0 200 40 30 99 1.5 76 94 175 4 2 94
272 Additives in Polymers: Analysis and Applications

2.0 3.0 100 0 180 26 3.5 98 97 215 1 – 99


2.0 3.0 100 10 120 45 2.8 93 97 212 1 1 98
2.0 3.0 100 25 60 95 2.4 90 96 209 2 1 97
2.0 3.0 100 55 45 99 2.0 81 95 194 4 1 95
2.0 3.0 100 80 45 99 1.5 68 93 180 4 2 94
2.0 3.0 100 100 45 99 1.3 63 93 177 5 1 94

CONCLUSIONS

In this work, novel, highly active, and stereoregular cobalt alkylxhanto-


genate + trialkylaluminum catalytic dithiosystems have been developed.
Activity and stereo regularity of these catalysts were studied in compari-
son with known cobalt-containing catalytic dithiosystems of butadiene po-
lymerization. These experiments were conducted under varied conditions
including catalyst concentration, ratio, and temperature. The developed
catalytic systems allowed for the synthesis of high molecular weight and
high crystalline syndiotactic 1,2-polybutadiene with yields of 50.0–99.0%
and 1,2-contents of 94.0–99.0%, intrinsic viscosity between 1.3 and 3.5
dL/g, crystallinity between 63.0 and 98.0%, and mps between 175 and
212°C in toluene solution.
The optimal conditions for the synthesis of high molecular mass and
highly crystalline syndiotactic 1,2-polybutadiene were established with
the following parameters: [Co] = (1.0–2.0) × 10–4 mol/L; [M] = 3.0 mol/L;
Al:Co = (50–100):1; T = 40–80°C.

KEYWORDS

•• Syndiotactic 1,2-polybutadiene
•• polymerization of butadiene
•• microstructure
•• cobalt alkylxhantogenate
•• trialkylaluminum catalytic dithiosystems
Cobalt Alkylxhanthogenate + Trialkylaluminum 273

REFERENCES

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and viscoelastic properties. Polym. J. 1975, 7(02), 207–216.
2. Junji, K.; Shoko, S. Syndiotactic 1,2-polybutadiene rubber characteristics and applica-
tions. JETI. 1998, 46, 111–115.
3. Ashitaka, H.; Ishikawa, H.; Ueno, H.; Nagasaka, A. Syndiotactic 1,2-polybutadiene
with Co-CS2 catalyst system. I. Preparation, properties, and application of highly
crystalline syndiotactic 1,2-polybutadiene. J. Polym. Sci., Polym. Chem. Ed. 1983, 21,
1853–1860.
4. Ashitaka, H.; Ishikawa, H.; Ueno, H.; Nagasaka, A. Syndiotactic 1,2-polybutadiene
with Co-CS2 catalyst system. II. Catalysts for stereospecific polymerization of buta-
diene to syndiotactic 1,2-polybutadiene. J. Polym. Sci., Polym. Chem. Ed. 1983, 21,
1951–1972.
5. Ashitaka, H.; Ishikawa, H.; Ueno, H.; Nagasaka, A. Syndiotactic 1,2-polybutadiene
with Co-CS2 catalyst system. III. 1H-and 13C-NMR Study of highly syndiotactic
1,2-polybutadiene. J. Polym. Sci., Polym. Chem. Ed. 1983, 21, 1973–1988.
6. Ashitaka, H.; Ishikawa, H.; Ueno, H.; Nagasaka, A. Syndiotactic 1,2-polybutadiene
with Co-CS2 catalyst system. IV. Mechanism of syndiotactic polymerization of Bu-
tadiene with Cobalt compounds-organoaluminum-CS2. J. Polym. Sci., Polym. Chem.
Ed. 1983, 21, 1989–1995.
7. Cheng-zhong, Z. Synthesis of syndiotactic 1,2-polybutadiene with silica gel supported
CoCl2-Al(I-Bu)3-CS2 Catalyst. China Synth. Rubber Ind. 1999, 22(04), 243.
8. Cheng-zhong, Z. Synthesis and morphological structure of crystalline syndiotactic
1,2-polybutadiene. Chem. J. Chin. Univ. 2003, 11.
9. Cheng-zhong, Z. Investigation on synthesis of high vinyl polybutadiene with iron-
based catalysts. I. Effect of Triphenyl Phosphate. Chin. J. Catal. 2004, 08, 1219.
10. Cheng-zhong, Z.; Zhen, D.; Li-hong, N. Research progress of syndiotactic 1,2-polybu-
tadiene. Chem. Propell. Polym. Mater. 2005, 04.
11. Lan-guo, D.; Weijian, H.; Cheng-zhong, Z. Preparation and characterization of high
1,2-syndiotactic polybutadiene/polystyrene in situ blends. China Synth. Rubber Ind.
2005, 28(03).
12. XXX. Patent USA 4751275 A, 1988; Patent USA 5239023 A, 1993; Patent USA
5356997 A, 1994; Patent USA 5677405 A, 1997; Patent USA 5891963 A, 1999; Pat-
ent USA 6720397 B2, 2004; Patent USA 6956093 B1, 2005; Patent USA7186785 B2,
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13. Nasirov, F. A. Dissertation Prof. Doctor (Chemistry). IPCP, Azerbaijan National Acad-
emy of Sciences, Baku, 2003; 376 p (in Russian).
14. Nasirov, F. A. Bifunctional nickel- or cobalt containing catalyst-stabilizers for polybu-
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16. Nasirov, F. A. Organic dithioderivatives of metals – components and modificators of
petrochemical peocesses. Petrochemistry. 2001, 6, 403–416. (in Russian).
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lecular weight and polydispersity of high molecular materials. M.: Acad. Sci. USSR.
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don; J. Wiley: New York, 1957; p 592.
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Guliev, N. A. Method of Producing Syndiotactic 1,2-Polybutadiene. Patent 20010128,
Azerbaijan, 1999 (in Azerbaijanian).
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Catalyst for Obtaining of Syndiotactic 1,2-Polybutadiene, Proceedings of III. Baku
International Mamedaliev Petrochemistry Conference, Baku, 289, 1998.
25. Nasirov, F. A.; Guliev, N. A.; Novruzova, F. M.; Azizov, A. G.; Djanibekov, N. F. Pec-
ularities of Butadiene Polymerization to Syndiotactic 1,2-Polybutadiene in Toluene
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ence, Baku, 266, 2000.
26. Nasirov, F. A.; Azizov, A. H.; Novruzova, F. M.; Guliyev, N. A. Polymerization of Bu-
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Catalytic Systems, Proceedings of Polychar – 10 World Forum on Polymer Applica-
tions and Theory, Denton, USA, 226, 2002.
CHAPTER 12

A STUDY ON THE EFFECT OF


THE PHASE STRUCTURE OF THE
MODIFIED EVA (EVAMA) ON THEIR
PROPERTIES
N. E. TEMNIKOVA1, А. Е. CHALYKH2, V. K. GERASIMOV2,
S. N. RUSANOVA1, O. V. STOYANOV1, and S. YU. SOFINA1
1
Kazan National Research Technological University, K. Marx street, 68, Kazan,
420015, Tatarstan, Russia
2
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of
Sciences, Leninskii pr. 31, Moscow, 119991, Russia
Email: [email protected]; [email protected]

CONTENTS

Abstract.............................................................................................................. 276
Introduction........................................................................................................ 276
Subjects and Methods........................................................................................ 276
Results and Discussion...................................................................................... 278
Conclusion......................................................................................................... 283
Acknowledgment............................................................................................... 283
Keywords........................................................................................................... 284
References.......................................................................................................... 284
276 Additives in Polymers: Analysis and Applications

ABSTRACT

The mutual solubility of the components was investigated, and the phase
diagrams in a wide range of temperatures and compositions in the systems
EVA (EVAMA) – glycidoxyalkoxysilane – were constructed. The effect
of structural heterogeneity of silanol-modified EVA (EVAMA), associated
with the chemical interaction of the components, on the properties of the
compositions was identified.

INTRODUCTION

Introduction of the reactive additives, which chemically interacts with


macromolecules, to the polymer not only changes the chemical nature of
the material, but also naturally affects the properties of the complex.1–4
Graft structures formed in the matrix increase the molecular weight of the
polymer, thereby affecting the process of the melt flow and solutions of
the compositions.
Previously, it has been found5 that the introduction of small amounts
(up to 3%) of ethyl silicate (ETS) into the copolymers of ethylene with vi-
nyl acetate (EVA) leads to the increase in intrinsic viscosity of EVA. Here-
with further increase in the concentration of ETS did not affect the process
of solutions flow. Dependence of melt flow index of modified EVA on the
concentration of the modifier has an extreme character with a minimum.
Minimum amount of the ETS significantly affects the proportion of vinyl
acetate in the copolymer.
The aim of this work was to study the effect of the phase structure of
the modified EVA (EVAMA) on their properties. Thus, the solubility of
the components was studied, and the phase diagrams in a wide range of
temperatures and compositions for the systems EVA (EVAMA) – glyci-
doxyalkoxysilane – were constructed.

SUBJECTS AND METHODS

Copolymers of ethylene with vinyl acetate Evatane2020 (EVA20) and


Evatane2805 (EVA27) with a vinyl acetate content of 20 and 27 wt%,
respectively, and copolymers of ethylene with vinyl acetate and maleic
anhydride brand Orevac9307 (EVAMA13) and Orevac9305 (EVAMA26)
A Study on The Effect of The Phase Structure 277

with a vinyl acetate content of 13 and 26 wt% were used as the objects of
the study. Main characteristics of the copolymers are given in Table 12.1.

TABLE 12.1  Characteristics of the Copolymers of Ethylene


MA Melting МV MFR,
VA Con- Tempera- g/10 min
Polymer Symbol Content,
tent,% ture, °С
% 125°С
Evatane2020 EVA20 20 – 80 44,000 2.23
Evatane2805 EVA27 27 – 72 57,000 0.74
Orevac9305 EVAMA26 26 1.5 47 20,000 11.13
Orevac9307 EVAMA13 13 1.5 92 73,000 1.1

Silane containing glycidoxy group – (3-glycidoxypropyl)trimethoxysi-


lane (GS) – was used as the modifier. It is a clear, colorless liquid with a
molecular weight of 236. Density is 1070 kg/m3, refractive index nD20 is
1.4367, and content of glycidoxy groups is 31%. Melting point is -70°C,
flashpoint is 135°C, and boiling point is 264°C.
Modification of the copolymers was carried out in the melt on labora-
tory micro-rollers for 10 min in the temperature range from 100 to 120°C.
(The rotational speed of the rolls is 12.5 m/min, and friction is 1:1.2.)
The melt flow rate (MFR) was measured in accordance with GOST
11645–73 at 190°C and under a load of 2.16 kg.
Viscosity was measured by viscometric method by dissolving the com-
positions in carbon tetrachloride.
Determination of the composition of coexisting phases and the inter-
diffusion coefficients were carried out by processing of series of interfero-
grams obtained by microinterference method. Measurements were per-
formed at a range of temperatures from 50 to 150°C. To construct profiles
of concentrations by interference patterns, the temperature dependencies
of the refractive index of the components are required.6 Refractive index
measurements were carried out by an Abbe refractometer IRF-454 BM at
a range of temperatures from 20 to 150°C.
The structure of the modified copolymers was investigated by the trans-
mission electron microscopy. Identification of the phase structure of the
samples was carried out by etching of the surface in high-oxygen plasma
discharge with the subsequent preparation of single-stage carbon-platinum
replicas. Samples were viewed using PEM EM-301 (Philips, Holland).
278 Additives in Polymers: Analysis and Applications

RESULTS AND DISCUSSION

The temperature dependencies of the solubility of (3-glycidoxypropyl)


trimethoxysilane (GS) in the initial double and triple copolymers of eth-
ylene were identified in diffusion experiments by directly bringing EVA
(EVAMA) and GS into contact.
Studies of mutual solubility of the components are shown in Figures
12.1 and 12.2.

FIGURE 12.1  Phase Diagrams of the Systems Copolymer of Ethylene with Vinyl
Acetate – GS: (1) EVA20; (2) EVA27. (I, II) The Areas of True Solutions, Heterogeneous
Condition; (III) The Area of Preparation of the Compositions; (IV) The Area of the Study
of the Structure and Physical Properties.

There are two binodal curves on all phase diagrams: the right branch of
the binodal corresponds to the solubility of the copolymer in the modifier
and is located in the area of infinitely dilute solutions. The second binodal
curve represents the solubility of the modifier in the copolymers and is
located in a fairly wide concentration area. The solubility of the modifier
in the copolymer is increased as the temperature increases. In the systems
EVA – GS, the solubility of the modifier reduces with an increase in VA
content. However, for the systems EVAMA – GS, this is not observed. In
A Study on The Effect of The Phase Structure 279

these systems, the solubility of GS in the copolymer increases with the


increase in VA content.

FIGURE 12.2  Phase Diagrams of the Systems Copolymer of Ethylene with Vinyl Acetate
– GS: (1) EVAMA13; (2) EVAMA26. (I, II) The Areas of True Solutions, Heterogeneous
Condition; (III) The Area of Preparation of the Compositions; (IV) The Area of the study
of the Structure and Physical Properties.

It was found that the rate of a chemical reaction is greater than or com-
parable with the diffusion rate, and the movement of the modifier occurs
in a chemically modified matrix, so we cannot see the appearance of the
“hourglass” on the diagram.5 The resulting matrix is soluble in the copo-
lymer, and therefore, we do not observe the phase decomposition during
reheating.7
Thus, it can be argued that these mixtures are characterized by dia-
grams with upper critical point of solubility (UCPS). This is also evi-
denced by the temperature dependencies of the pair interaction parameters
(Fig. 12.3), calculated according to the equation, assuming that the right
branch of the binodal is located on the axis φ2 = 1:
280 Additives in Polymers: Analysis and Applications

r1
φ2,êðèò =
r1 + r2
,
2
1 1 1 
χ=  + 
2  r1 r2 
,
where c is the pair interaction parameter; φ1 and φ2 are the concentration of
EVA and GS, respectively; r1, r2 are their degrees of polymerization.

FIGURE 12.3  Temperature Dependence of the Pair Interaction Parameter of the Systems:
(a) (1) EVA20 – GS; (2) EVA27 – GS; (b) (1) EVAMA13 – GS; (2) EVAMA26 – GS.
Arrows show UCPS.

In all phase diagrams (see Figs. 12.1 and 12.2), there are the areas cor-
responding to temperature-concentration areas of the components mixing
(area III) and the areas corresponding to the structure of the compounds
and their physical properties (area IV). The diagrams show that the prepa-
ration of the mixtures takes place in the single-phase area (area I in the
diagrams) and the study of the part of the system takes place in a hetero-
geneous area (area II in the diagram).
After etching of the cooled samples in plasma of high-oxygen dis-
charge, there appear some particles, which have a lower etching rate
compared with the dispersion medium. Earlier, it has been shown that the
lowest etching rate among carbo- and heterochain polymers have polysi-
A Study on The Effect of The Phase Structure 281

loxanes. Thus, it can be concluded that the dispersed phase is enriched by


siloxanes (Fig. 12.4).

FIGURE 12.4  Microphotograph of EVAMA26 – GS (10%).

Since the reaction mixing was accompanied by intense shear impacts in


the presence of oxygen and air moisture, the composite material obtained
is the result of the processes of diffusion mixing and chemical interactions
between the components. This may explain the presence of the dispersed
phase, although based on the phase diagrams it should not be here.8
Formation of grafted siloxane units affects viscosity and rheologi-
cal characteristics of the compositions. With the introduction of glyci-
doxysilanes, there is a decrease in the melt flow (see Fig. 12.5) of the
modified polymers (by 30%) and an increase in the intrinsic viscosity (in
1.3–1.5 times), indicating that the preferential formation of branching
and intermolecular bridges, increasing the length of the macromolecule,
takes place.
282 Additives in Polymers: Analysis and Applications

FIGURE 12.5  The Dependence of the Intrinsic Viscosity and MFR from the Modifier
Content: EVAMA26 – GS (Viscosity at 40°C, MFR 125°C – 2.16kg).

Isolation of siloxane into a separate phase leads to an enrichment of the


surface of the composition by them, and, consequently, to an increase of
the adhesion characteristics.9
Glycidoxypropyltrimethoxysilane is used as an additive for polyesters,
polyacrylates, polysulfides, urethanes, epoxy, and acrylic resins to improve
their adhesion to glass, aluminum, steel, and other substrates. Aqueous and
alcoholic solutions of glycidoxysilane are used to improve the adhesion of
epoxy resin to aluminum plates.
Thus, the system EVAMA26 - GS has a good adhesion to PET. For this
system, at the moment of the substrate rupture, an adhesion strength of the
content of GS of 1.5 wt.% increased to 3.4 times (see Fig. 12.6). In this
case, the rapture has a cohesion nature and is accompanied by the rapture
of the substrate.1
A Study on The Effect of The Phase Structure 283

FIGURE 12.6  Adhesion Strength of the Polymer – PET: EVAMA26 – GS. Condition of
the Formation: at 160°C for 10 min.

CONCLUSION

Thus, the data of these phase diagrams can be used in the study of the
compositions, as well as selecting regimes for their preparation. From the
diagram, we can define the aggregate state, the amount and chemical com-
position of the phases, as well as structural-phase state of the compositions
according to the temperature and concentration of its constituent compo-
nents.
The triple copolymer, modified by glycidoxysilane, can be used in the
production of laminated multilayer films as it simultaneously has a good
flowability and a high value of the adhesion strength.

ACKNOWLEDGMENT

This work was financially supported by the Ministry of Education and Sci-
ence of Russia in the framework of the theme №693 “Structured compos-
ite materials based on polar polymer matrices and reactive nanostructured
components”.
284 Additives in Polymers: Analysis and Applications

KEYWORDS

•• Copolymers of ethylene
•• aminoalkoxysilane
•• phase diagrams
•• viscosity
•• rheology
•• adhesion strength

REFERENCES

1. Temnikova, N. E.; Rusanova, S. N.; Tafeeva, Yu. S.; Sof’ina, S. Y.; Stoyanov, O. V.
The effect of an amino-containing modifier on properties of ethylene copolymers.
Polym. Sci. Ser. D. 2012, 5(4), 259–265.
2. Temnikova, N. E.; Rusanova, S. N.; Sofina, S. Yu.; Stoyanov, O. V.; Garipov, R.
M.; Chalykh, A. E.; Gerasimov, V. K.; Zaikov, G. E. Influence of aminoalkoxy- and
glycidoxyalkoxysilanes on adhesion characteristics of ethylene copolymers. Polym.
Res. J.. 2014, 8(4), 305–310.
3. Temnikova, N. E.; Rusanova, S. N.; Sof’ina, S. Yu.; Stoyanov, O. V.; Garipov, R. M.;
Chalykh, A. E.; Gerasimov, V. K. The effect of aminoalkoxy and glycidoxyalkoxy
silanes on adhesion characteristics of double and triple copolymers of ethylene. Polym.
Sci. Ser. D. 2014, 7(3), 84–187.
4. Temnikova, N. E.; Rusanova, S. N.; Tafeeva, Yu. S.; Stoyanov, O. V. Study of
modification of ethylene copolymers by aminosilanes by IR spectroscopy FTIR.
Bulletin of Kazan Technological University. 2011, 19, 112–124.
5. Rusanova, S. N.; Stoyanov, O. V.; Gerasimov, V. K.; Chalykh, A. E. Influence of
the phase structure of copolymers of ethylene with vinyl acetate, modified by ethyl
silicate, on their rheological properties. Bulletin of Kazan Technological University.
2006, 1, 156–163.
6. Chalykh, A. E.; Gerasimov, V. K.; Petukhova, O. G.; Kulagina, G. S.; Pisarev, S. A.;
Rusanova, S. N. Phase structure of silanol-modified ethylene-vinyl acetate copolymers.
Polym. Sci. Ser. A. 2006, 48(10), 1058–1066.
7. Temnikova, N. E. Effect of Amino and Glycidoxyalkoxysilanes on the Formation of
the Phase Structure and Properties of Ethylene Copolymers. Thesis PhD, Kazan, 2013,
154 p.
8. Rusanova, S. N.; Temnikova, N. E.; Stoyanov, O. V.; Gerasimov, V. K.; Chalykh, A.
E. IR spectroscopic study of the interaction of glycidoxy silane and copolymers of
ethylene. Bulletin of Kazan Technological University. 2012, 22, 95–96.
9. Chalykh, A. E.; Gerasimov, V. K.; Rusanova, S. N.; Stoyanov, O. V. Еffect of structural
heterogeneity of ethylene-vinylacetate copolymers modified by ethyl silicate on their
stress-strain characteristics. Polym. Sci. Ser. D. 2011, 4(2), 85–89.
CHAPTER 13

SILOXANE MATRIX WITH


METHYLPROPIONATE SIDE GROUPS
AND POLYMER ELECTROLYTE
MEMBRANES ON THEIR BASE
NATIA JALAGONIA, IZABELA ESARTIA, TAMAR TATRISHVILI,
ELIZA MARKARASHVILI, DONARI OTIASHVILI, JIMSHER ANELI,
and OMAR MUKBANIANI
Department of Chemistry, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze
Ave. 3, Tbilisi 0179, Georgia
Institute of Macromolecular Chemistry and Polymeric Materials, Iv. Javakhishvili
Tbilisi State University, Faculty of Exact and Natural Sciences, I. Chavchavadze
Ave. 13, Tbilisi 0179, Georgia
E-mail: [email protected]

CONTENTS

Introduction........................................................................................................ 286
Experimental Procedure..................................................................................... 286
Results and Discussion...................................................................................... 289
Conclusion......................................................................................................... 301
Keywords........................................................................................................... 302
References.......................................................................................................... 302
286 Additives in Polymers: Analysis and Applications

INTRODUCTION

Solvent-free polymer electrolytes may be formed by the interaction of po-


lar polymers with metal ions. Ion transport in polymer electrolytes is ex-
tensively studied since Wright1 discovered that polyethyleneoxide (PEO)
can act as a host for sodium and potassium salts, thus producing a solid
electrical conductor polymer/salt complex. The unique idea of employing
these polymer electrolytes in battery applications belong to Armand et al.2
Transport mechanism models developed by Ratner et al.3 indicated that
polymers with low Tg have extremely high free volumes that favor the
ion transport. Better results are obtained for polymers with highly flexible
backbones, bearing oligo(ethylene glycol) side chains.
Interest in polysiloxane-based polymer electrolytes arose early in the
1980s. PEO-substituted polysiloxanes as ionically conductive polymer
hosts have been previously investigated.4–6 Their relatively high ionic con-
ductivity was ascribed to the highly flexible inorganic backbone, which
produced a totally amorphous polymer host. In recent years, improved
battery performance has been observed for systems containing polymer
electrolytes, with a Li+ transference number close to unity.7 Efforts have
also been made to design and synthesize siloxane-based single-ion con-
ductors.8,9 Polysiloxanes are promising components for comb polyelectro-
lytes because they possess a flexible backbone that enhances the transports
of ions. Their amorphous and highly flexible [Si–O]n backbone produces
glass transition temperatures as low as -100°C and yields little or no crys-
tallinity at room temperature. In addition, each monomer unit has two
sites for cross-links or functional side chains through bond formation with
silicon. Simulations indicate that comb polyelectrolytes should display
higher conductivity values than their analogs to local motion of the bound
anions in comb systems.10–12

EXPERIMENTAL PROCEDURE

MATERIALS

D4H (Aldrich), platinum hydrochloric acid (Aldrich), Karstedt’s catalyst


(Pt2[(VinSiMe2)2O]3) or platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisi-
loxane complex (2% solution in xylene) (Aldrich), vinyltriethoxysilane (Al-
Siloxane Matrix with Methylpropionate Side Groups 287

drich), and methyl acrylate (Aldrich) were used as received. Lithium triflu-
oromethanesulfonate (triflate) and lithium bis(trifluoromethanesulfonyl)
imide were purchased from (Aldrich). Toluene was dried over and distilled
from sodium under an atmosphere of dry nitrogen. Tetrahydrofuran (THF)
was dried over and distilled from K–Na alloy under an atmosphere of dry
nitrogen.

CHARACTERIZATION

FTIR spectra were recorded on a Varian 660/670/680-IR series spectrom-


eter. 1H, 13C NMR and 29Si NMR spectra were recorded by a Varian Mer-
cury 300VX NMR spectrometer, using DMSO and CCl4 as the solvent and
as an internal standard. Differential scanning calorimetric (DSC) investi-
gation was performed on a Netzsch DSC 200 F3 Maia apparatus. Thermal
transitions including glass transition temperatures Tg were taken as the
maxima of the peaks. The heating and cooling scanning rates were 10 K/
min.
Size-exclusion chromatographic (SEC) study was carried out with the
use of Waters Model 6000A chromatograph with an R 401 differential
refractometer detector. The column set comprised 103 and 104 Å Ultra-
styragel columns. Sample concentration was approximately 3% by weight
in toluene, and typical injection volume for the siloxane was 5 mL, and
flow rate was 1.0 mL/min. Standardization of the SEC was accomplished
by the use of styrene or polydimethylsiloxane standards with the known
molar mass.
Wide-angle X-ray analysis was performed on a Dron-2 (Burevestnik,
Saint Petersburg, Russia) instrument. A-CuKa was measured without a fil-
ter; the angular velocity of the motor was w ≈ 2°/min.
Determination of ≡Si–H content was calculated according to the meth-
od described by Iwahara et al.13

HYDROSILYLATION REACTION OF D4H WITH METHYL


ACRYLATE AND VINYLTRIETHOXYSILANE

D4H (5.000 g and 0.0208 mol) were transferred into a 100 mL flask under
nitrogen using standard Schlenk techniques. High vacuum was applied to
288 Additives in Polymers: Analysis and Applications

the flask for half an hour before the addition of methyl acrylate (5.3636 g
and 0.0624 mol) and vinyltriethoxysilane (3.9562 g and 0.0208 mol). The
mixture was then dissolved in 7 mL of toluene, and 0.1 M solution of plati-
num hydrochloric acid in THF (5/9×10-5 g per 1.0 g of starting substance)
was introduced. The homogeneous mixture was degassed and placed in
an oil bath, which was previously set to 60°C and reaction continued at
60°C. The reaction was controlled by decrease of intensity of active ≡Si–H
groups. Then 0.1 wt.% activated carbon was added and refluxed for 12 h
for deactivation of catalysts.
All volatile products were removed by rotary evaporation, and the com-
pound was precipitated at least three times into pentane to remove side prod-
ucts. Finally, all volatiles were removed under vacuum for 24 h to isolate
13.7 g (95.6%) of colorless viscous compound I - 2.4.6.8-tetramethtyl-2.4.6-
tri(methyl propionate)-8-ethyltriethoxysilanecyclotetrasiloxane (D4R,R’).

RING-OPENING POLYMERIZATION REACTION OF D4R,R’

The 1.1365 g (1.4046 mmol) of compound D4R,R’ was transferred into 50


mL flask under nitrogen. High vacuum was applied to the flask for half an
hour. Then the compound was dissolved in 1.8 mL dry toluene, and 0.01%
of total mass powder-like potassium hydroxide was added. The mixture
was degassed and placed in an oil bath that was previously set to 60°C
and was polymerized under nitrogen for 25 h. After the reaction, 7 mL of
toluene was added to the mixture, and the product was washed using wa-
ter. The crude product was stirred with MgSO4 for 6 h, filtered, and evapo-
rated, and the oligomer was precipitated at least three times into pentane to
remove side products. Finally, all volatiles were removed under vacuum to
isolate 1.06 g (93%) colorless viscous oligomer (II).
Ring-opening polymerization reaction of compound I at various tem-
peratures had been carried out in the same manner.

GENERAL PROCEDURE FOR PREPARATION OF CROSS-


LINKED POLYMER ELECTROLYTES

In a typical preparation, 0.75 g of polymer II was dissolved in 4 mL of dry


THF and thoroughly mixed for half an hour before the addition of catalytic
Siloxane Matrix with Methylpropionate Side Groups 289

amount of acid (one drop of 0.1 M HCl solution in ethyl alcohol) to initiate
the cross-linking process. After stirring for another 3 h, required amount
of lithium triflate from the previously prepared stock solution in THF was
added to the mixture and stirring continued for another 1 h. The mixture
was then poured into a Teflon mould with a diameter of 4 cm, and solvent
was allowed to evaporate slowly overnight. Finally, the membranes were
dried in an oven at 70°C for 3 days and at 100°C for 1 h. Homogeneous
and transparent films with average thickness of 200 mm were obtained in
this manner. These films were insoluble in all solvents and only swollen
in THF.

AC IMPEDANCE MEASUREMENTS

The total ionic conductivity of samples was determined by locating an


electrolyte disk between two 10 mm diameter brass electrodes. The elec-
trode/electrolyte assembly was secured in a suitable constant volume sup-
port, which allowed extremely reproducible measurements of conduc-
tivity to be obtained between repeated heating–cooling cycles. The cell
support was located in oven, and the sample temperature was measured
by thermocouple positioned close to the electrolyte disk. The bulk con-
ductivities of electrolytes were obtained during a heating cycle using the
impedance technique (impedance meter BM 507–TESLA for frequencies
50–500 kHz) over a temperature range between 20 and 100°C.

RESULTS AND DISCUSSION

Comb-type polymers for solvent-free solid polymer electrolytes usually


are obtained via hydrosilylation or dehydrocondensation reactions of in-
dustrial linear polymethylhydrosiloxanes (PMHS) with donor group con-
taining vinyl-, allyl- or hydroxyl-containing organic compounds. It should
be noted that often these reactions proceed incompletely resulting in the
formation of irregular defect structures.
The aim of our work is to synthesize organocyclotetrasiloxane with de-
sired propionate donor side groups at silicon via hydrosilylation reaction
of 2.4.6.8-tetrahydro-2.4.6.8-tetramethylcyclotetrasiloxane (D4H) with
methylacrylate and vinyltriethoxysilane at 1:3:1 of initial compounds in
the presence of platinum catalysts; polymerization reactions of organo-
290 Additives in Polymers: Analysis and Applications

cyclotetrasiloxane in the presence of nucleophilic catalysts and obtaining


comb-type polymers with regular arrangement of methyl propionate and
ethoxyl group; obtaining solid polymer electrolyte membranes by the incorpora-
tion of lithium salt into polymer matrices; and investigation of ionic conductivity
of membranes via impedance method.
Preliminary heating of initial compounds separately in the temperature
range of 50–60°C in the presence of catalysts showed that under these
conditions, polymerization of D4H or allyl acetoacetate and scission of si-
loxane backbone does not take place. No changes in the NMR and FTIR
spectra of initial compounds were found. It was established that in melt
condition, the hydrosilylation reaction proceeds vigorously with initiation
of side reactions;14 therefore, for obtaining fully addition product, hydrosi-
lylation reaction have been carried out in dilute solutions.
Hydrosilylation reaction of D4H methylacrylate and vinyltriethoxysi-
lane at 1:3:1 of initial compounds in the presence of platinum catalysts
was carried out in 50% solution of dry toluene or THF at 60–70°C temper-
ature. It was established that hydrosilylation in the presence of Karstedt’s
and platinum hydrochloride acid catalyst proceeds very slowly, so in hy-
drosilylation reaction, we did not use catalyst Pt/C (5%).
In order to increase the reaction rate, the reaction temperature at the
final stage of the reaction mixture was increased up to 80°C.
The reaction generally proceeds according to the following Scheme
13.1:

SCHEME 13.1  Hydrosilylation Reaction of D4H with Methyl Acrylate and


Vinyltriethoxysilane.

From the literature, it is known that hydrosilylation with unsat-


urated bonds may be proceeded according to Markovnikov and anti-
Markovnikov (Farmer) rules.11,12
Siloxane Matrix with Methylpropionate Side Groups 291

In addition, methyl acrylate is a conjugated compound. As it is known


from the literature, in conjugated systems, hydrosilylation might proceed
not only in the direction of 1.2, but also in the direction of 1.4 (Scheme
13.2):

SCHEME 13.2  Possible Addition of ≡Si–H Bonds to Methyl Acrylate.

As it is seen from the possible Scheme 13.2.3, in the case of 1.4-hydride


addition, reaction proceeds with obtaining of intermediate-transition com-
plex. By regrouping of the intermediate product according to the Eltekov
rule (Scheme 13.2.4), the products of 1.2-addition by anti-Markovnikov
rule are obtained.
In addition, in hydrosilylation reaction, the mixture of isomeric cy-
clic compounds (cis– and trans–isomeric mixture) can take place. The ob-
tained substance is a transparent viscous liquid, which is well soluble in
common organic solvents. Compound I was identified by IR, 29Si, 1H and
13
C NMR spectral data, determining the molecular mass and molecular
refractivity: nD20 = 1.4389; d420 = 1.1185; calculated MRD = 153.36; and
found MRD = 152.67.
In the FTIR spectra of compound I absorption bands at 1020 and 1197
cm , characteristic for asymmetric valence oscillation of ≡Si–O–Si≡, Si–
-1

O–C, and CO–O–C bonds were observed. Also, one can observe absorp-
tion bands at 1257 and 2860–2970 cm-1 region, characteristic for valence
oscillation of ≡C–H bonds. In the FTIR spectra of compound I at 2167
cm-1, there is no absorption bands characteristic for unreacted ≡Si–H
292 Additives in Polymers: Analysis and Applications

bonds. In the spectra absorption bands at 1736 cm-1, characteristic for car-
bonyl groups is observed.
In 29Si NMR spectra of compound I, one can see signal with chemi-
cal shift d≈-18.98 and d≈-26.86 ppm corresponding to the presence of
RR’SiO (D) units in cyclotetrasiloxane fragment;15,16 on the other hand,
two signals d≈-46.09÷-47.43 and d≈-58.28÷-61.03 ppm corresponding to
the presence of M(OR)2 და DOR fragments and the signal with chemical
shift d≈-65.66 ppm T units at -55 and –65 ppm are observed,16 which is
confirmed reaction direction, with the formation of above structure. The
direction of the reaction is confirmed by the structure formation.

FIGURE 13.1  29
Si NMR Spectra of Compound I.

In the 1H NMR spectrum of compound I (Figs. 13.1 and 13.2), one can
observe singlet signal with a chemical shift d = 0.1–0.2 ppm characteristic
for protons in ≡Si–Me groups in isomeric mixture of cyclotetra-
Siloxane Matrix with Methylpropionate Side Groups 293

FIGURE 13.2  I 1H NMR Spectra of Compound I.


siloxane fragments, triplet signal for methylene protons in ≡Si–CH2- fragment with
chemical shift d = 0.50 ppm (during addition to anti-Markovnikov rule), and triplet signal
for methyl protons in =CH–CH3 group with chemical shift d = 1.1 ppm (during addition to
Markovnikov rule). Also, one can observe multiplet signals with center of chemical shifts
d = 2.3, 3.6, -3.8 ppm characteristics for proton in CH3CH=, -CH2CO-, and OCH3 group,
respectively.

In the 13C NMR spectra of isomeric mixture of compound I (Fig. 13.3),


the resonance signals with chemical shifts d≈-3.83, -2.45, 1.01, 17.75,
26.38, 30.13, 50.45, and 57.33 ppm characteristic for ≡Si–Me, CH3 to
CH=, ≡Si–CH2-, -CH2CO-, -CH(CH3)- and OCH3, accordingly 13C NMR
spectra correspond to 1H NMR spectra data.
294 Additives in Polymers: Analysis and Applications

FIGURE 13.3  C NMR Spectra of Compound I.


13

The synthesized compound I was used in the polymerization and co-


polymerization reactions. From literature,12 it is known that during polym-
erization reactions of ethoxyl group containing compound D4R,R’ proceeds
with obtaining of cross-linking systems, which may be explained via in-
termolecular condensation reactions of ºSi–OH and -Si(OC2H5)3 groups.
Therefore, we have investigated copolymerization reactions of D4R,R’ with
hexamethyldisiloxane as a terminating agent at 8:1 ratio of initial com-
pounds. In most cases, terminating agent helps to regulate the molecular
masses.17
The polymerization reactions of compound I in the presence of an-
hydrous powder-like potassium hydroxide (0.01 mass%) as a catalyst in
dilute solution of dry toluene (C = 0.8606 mol/L) at 60–80°C temperature
have been investigated. It was established that polymerization reactions
proceed slowly during 80–100 h. The optimal condition of reaction tem-
perature is 80-90°C. During polymerization reaction of D4R,R’ in toluene,
the polymer precipitated from the solvent, but during polymerization in
THF, the polymer remained in the solution. The copolymerization reac-
tion generally proceeds according to the Scheme 13.3:
Siloxane Matrix with Methylpropionate Side Groups 295

SCHEME 13.3  Copolymerization Reaction of Compound I.

Where, m:n = 8:1. II1 (60°C), II (80°C).


The synthesized polymers are vitreous, viscous products, which are
well soluble in ordinary organic solvents with specific viscosity hsp ≈
0.14–0.27. The structure and composition of polymers were determined
by elemental analysis and molecular masses by FTIR and NMR spectra
data. Elemental composition yields and some physical–chemical proper-
ties of oligomers were studied.
In FTIR spectra of polymers, the absorption band at 1080 cm-1 is char-
acteristic for asymmetric valence oscillation of ≡Si–O–Si≡ bonds. In the
spectrum are reserved all the absorption bands characteristic of the initial
monomeric compound I.
In 29Si NMR spectra of polymers (Fig. 13.4), one can see resonance
signal with chemical shifts d≈-19.10 and d≈ -26.97 ppm corresponding to
the presence of D to M(OR)2 and DOR units; on the other hand, the signal at
d≈-65.73 ppm corresponds to T units.
296 Additives in Polymers: Analysis and Applications

FIGURE 13.4  Si NMR Spectra of Polymer II.


29

On the 1H NMR spectra of polymers (Fig. 13.5), singlet signal with


a chemical shift d≈0.1–0.2 ppm characteristic for protons in ≡Si–Me
groups, triplet signal for methylene protons in ≡Si–CH2- fragment with
che-mical shift d≈0.50 ppm (during addition to anti-Markovnikov rule),
triplet signal for methyl protons in =CH–CH3 group with chemical shift
d = 1.1 ppm (during addition to Markovnikov rule) were observed. Also,
one can observe multiplet signals with center of chemical shifts d≈2.3,
3.6, -3.8 ppm characteristics for proton in CH3CH=, -CH2CO-, and OCH3
group, respectively.
In Figure 13.6, 13C NMR spectra of polymer II is presented. The signal
with chemical shifts at d≈ d≈-3.83, -2.45, 1.01, 17.75, 26.38, 30.13, 50.45
and 57.33 ppm characteristic for ≡Si–Me, CH3CH=, ≡Si–CH2-, -CH2CO-,
-CH(CH3)- and OCH3 accordingly is preserved.13C NMR spectra of oligo-
mer I is in accordance with 1H NMR spectra.
Siloxane Matrix with Methylpropionate Side Groups 297

FIGURE 13.5  H NMR Spectra of Polymer II.


1

FIGURE 13.6  13
C NMR Spectra of Polymer II.

For obtaining polymer II, the molecular masses by ebuliometric meth-


ods have been determined`by Mn = 6100. As is known from the literature
298 Additives in Polymers: Analysis and Applications

data, the molecular masses of obtained polymer are sufficient for a solid
polymer membranes electrolytic production.
DSC calorimetric investigation of polymer II was carried out. As it can
be seen from Figure 13.7, the polymer is characterized of only one glass
transition temperature, which is equal to Tg = -81.7°C.

FIGURE 13.7  DSC Curve of Polymer II.

POLYMER ELECTROLYTE MEMBRANES

For obtaining the membranes, we prepared the polymer solutions of


the lithium salts triflate (LiSO3CF3) and lithium-bis(trifluoromethanesul
fonimide) [(CF3SO2)2NLi+] in the THF, where these salts were about 5–20
wt% of the polymer full mass. The solution contained 0.8 g salt in the 2
mL THF (Scheme 13.4).
Siloxane Matrix with Methylpropionate Side Groups 299

Me Me

Me3SiO Si O Si O SiMe3

C2H4Si(OEt)3
C2H 4COOCH 3
3 x
SCHEME 13.4  Experimental Solution Used.

The solution of polymer in the THF was prepared in the cylindrical


form (diameter 4 cm) vessel made from Teflon. After the salt solution
in the THF and 1–2 drops of 0.1 N alcohol solutions were added to the
initial mixture. Mixing elapsed for 30 min. The mixture was allowed to
stay in the inert atmosphere and then out-gassed; hence, the transpar-
ent yellow films were formed. The sol gel process was conducted by
adding the hydrochloric acid alcohol solution, which is accompanied
by cross-link reactions shown in Scheme 13.5.

Me Me
Me Me
H+
Si O Si O Si O Si O
-C2H5OH
R' R' C2H4
C2H4
Si
O O
Si(OC2H5)3 O

SCHEME 13.5  The Sol-Gel Cross-Linking Reaction of the Polymer.

The investigation of the electric-physical properties of synthesized


polyelectrolytes was conducted. The conductivity and its dependence
on the temperature were measured. We prepared the solid polymer
electrolyte membranes with 5, 15, and 20 wt% of lithium salts. The de-
pendence of the specific volumetric electric conductivity of the mem-
branes on temperature was studied. The curves on Figure 13.8 show
that their characters correspond to analogical dependences for poly-
electrolytes based on silicon-organic polymers and some lithium salts
and are well described by so-called “Vogel-Taman-Fulcher” formula:8,9
300 Additives in Polymers: Analysis and Applications

C ( T ) = a / T exp(-E / kT),

where a is the pre-exponential factor, E is the activation energy of charge
transfer, and k is Boltzmann constant.
It is worth mentioning that based on preliminary measures of the
membranes described above, the low conductivity of membrane con-
taining 5 wt% salt (~10-9 S/cm) is reported..
Dependence of conductivity of membranes based on polymer II with
15 (1) and 20 (2) wt% contents of lithium salt triflate on the temperature is
presented in Figure 13.8.
The character of voltammograms obtained for membranes based on
polymer II and 15 and 20 wt% of triflate salt is in full accordance with the
values of their conductivity (Fig. 13.9).

FIGURE 13.8  Dependence of Conductivity of Membranes Based on Polymer II with 15


(1) and 20 (2) wt% of Lithium Salt Triflate on the Temperature.
Siloxane Matrix with Methylpropionate Side Groups 301

FIGURE 13.9  Voltammograms of Membranes Based on the Polymer II and 15 (1) and
20 wt% (2) of Lithium Triflate.

Thus, on the basis of the temperature dependences and correspond-


ing voltammograms for the membranes based on polymer II and lithium
triflate salt, it can be said that the ionic conducting character essentially
is due to both structure of electrolytes polymer matrix and its behavior
under conditions of the change of external temperature. First of all, it is
expressed in the essential difference between initial and end values of the
conductivity at increasing temperature. It may be proposed that micro-
structure of this type of membrane is highly permeable for the ions while
heating, which is due to increase in the concentration of micro-empties in
the polymer matrix because of high level of heterogeneity of the macro-
molecules with different side groups.

CONCLUSION

Hydrosilylation reaction of tetrahydrotetramethylcyclotetrasiloxane with


methyl acrylate and vinyltriethoxysilane at 1:3:1 ratio of initial com-
302 Additives in Polymers: Analysis and Applications

pounds, in the presence of Karstedt’s catalyst, has been studied and cor-
responding additional product have been obtained. Through co-polymer-
ization reaction of organocyclotetrasiloxane and hexamethyldisiloxane as
a terminating agent, corresponding comb-type polymers have been ob-
tained. Through sol-gel processes doped with lithium trifluoromethane-
sulfonate (triflate) or lithium bis(trifluoromethanesulfonyl)imide oligomer
systems, solid polymer electrolyte membranes have been obtained. The
dependence of ionic conductivity as a function of temperature and salt
concentration was investigated. The electric conductivity of investigated
polymer electrolyte membranes at room temperature changes in the range
of 3 × 10-9–2 × 10-8 S/cm.

KEYWORDS

•• Polymer electrolytes
•• transport mechanism
•• polysiloxane-based polymer
•• sodium and potassium salts
•• simulations
•• transports of ions

REFERENCES

1. Wright, P. V. Electrical conductivity in ionic complexes of poly(ethylene oxide). Br.


Polym. J. 1975, 7, 319–327.
2. Armand, M. B.; Chabagno, J. M.; Duclot, M. J. Polyethers as solid electrolytes, Sec-
ond International Meeting on Solid Electrolytes, St. Andrews, Scotland, 1–4, 1978.
3. Ratner, M. A.; Shriver, D. F. Ion transport in solvent-free polymers. Chem. Rev. 1988,
88, 109–124.
4. Nagaoka, K.; Naruse, H.; Shinohara, I.; Watanabe, M. High ionic conductivity in
poly(dimethyl siloxane-co-ethylene oxide) dissolving lithium perchlorate. J. Polym.
Sci., Polym. Lett. Ed. 1984, 22, 659–665.
5. Albinsson, I.; Mellander, B. E.; Stevens, J. R. Ionic conductivity in poly(ethylene ox-
ide) modified poly(dimethylsiloxane) complexed with lithium salts. Polymer. 1991,
32, 2712–2715.
Siloxane Matrix with Methylpropionate Side Groups 303

6. Fish, D.; Khan, I. M.; Smid, J. Conductivity of solid complexes of lithium perchlorate
with poly{[w-methoxyhexa(oxyethylene)ethoxy]methylsiloxane}. Macromol. Chem.
Rapid Commun. 1986, 7, 115–120.
7. Doyle, M.; Fuller, T. F.; Newman, J. The importance of the lithium ion transference
number in lithium/polymer cells. Electrochim. Acta. 1994, 39, 2073–2081.
8. Karatas, Yu; Kaskhedikar, N.; Wiemhofer, H. D. Synthesis of cross-linked comb
polysiloxane for polymer electrolyte membranes. Macromol. Chem. Phys. 2006, 207,
419–425.
9. Zhang, Zh; Lyons, L. J.; Jin, J. J.; Amine, Kh; West, R. Synthesis and ionic conductiv-
ity of cyclosiloxanes with ethyleneoxy-containing substituent’s. Chem. Mater. 2005,
17, 5646–5650.
10. Snyder, J. F.; Ratner, M. A.; Shriver, D. F. Polymer electrolytes and polyelectrolytes:
Monte Carlo simulations of thermal effects on conduction. Solid State Ionics. 2002,
147, 249–257.
11. Mukbaniani, O.; Koynov, K.; Aneli, J.; Tatrishvili, T.; Markarashvili, E.; Chigvinadze,
M. Solid polymer electrolyte membranes based on siliconorganic backbone. Macro-
mol. Symp. 2013, 328(1), 38–44.
12. Mukbaniani, O.; Aneli, J.; Esartia, I.; Tatrishvili, T.; Markarashvili, E.; Jalagonia, N.
Siloxane oligomers with epoxy pendant group. Macromol. Symp. 2013, 328(1), 25–37.
13. Iwahara, T.; Kusakabe, M.; Chiba, M.; Yonezawa, K. Synthesis of novel organic oligo-
mers containing Si-H bonds. J. Polym. Sci., A. 1993, 31, 2617–2631.
14. Mukbaniani, O.; Tatrishvili, T.; Markarashvili, E.; Esartia, E. Hydrosilylation reaction
of tetramethylcyclotetrasiloxane with allyl butyrate and vinyltriethoxysilane. Geor-
gian Chem. J. 2011, 2(11), 153–155.
15. Uhlig, F.; Marsmann, H. Chr.29Si NMR Some Practical Aspects; Springer: Heidelberg,
2008.
16. Khan, I. M.; Yuan, Y.; Fish, D.; Wu, E.; Smid, J. Comblike polysiloxanes with
oligo(oxyethylene) side chains. Synth. Prop. Macromol. 1988, 21, 2684–2689.
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M. J. M. Synthesis of cross-linked comb-type polysiloxane for polymer electrolyte
membranes. E-Polym. 2012, 089, 1–14.
CHAPTER 14

COMPOSITES ON THE BASIS OF


GLYCIDOXYGROUP CONTAINING
PHENYLSILSESQUIOXANES
MARINA ISKAKOVA1, ELIZA MARKARASHVILI2,3,
JIMSHER ANELI3, and OMAR MUKBANIANI2,3
1
Аk. Tsereteli Kutaisi state University, Department of Chemical Technology,
I. Chavchavadze Ave. 1, 0179 Tbilisi, Georgia
2
Iv. Javakhishvili Tbilisi State University, Department of Chemistry,
I. Chavchavadze Ave. 1, 0179 Tbilisi, Georgia
3
Institute of Macromolecular Chemistry and Polymeric Materials, Iv. Javakhishvili
Tbilisi State University, I. Chavchavadze Ave. 13, 0179 Tbilisi, Georgia
E-mail: [email protected]

CONTENTS

Introduction........................................................................................................ 306
Experimental Part............................................................................................... 306
Results and Discussion...................................................................................... 308
Conclusion......................................................................................................... 320
Keywords........................................................................................................... 321
References.......................................................................................................... 321
306 Additives in Polymers: Analysis and Applications

INTRODUCTION

Recently, intense interest has been shown in the development of silses-


quioxane-based materials because of their three-dimensional (3D) nature,
ability to offer a very high degree of functionalization, ease of synthe-
sis, and typically high thermal stability. This is evidenced by the fact that
at present, there are approximately three reviews on silsesquioxanes and
the related silicates.1–3 These references describe their potential applica-
tion in a broad range of areas from biomedical to organic light-emitting
diodes, to nanocomposites, and so on. In the literature data, there is a lot
of information about the dependence of the properties of the substance
on the polyorganosiloxane organic framing at the silicon atom. For ex-
ample, polyorganosiloxanes containing aromatic radicals different from
polydimethylsiloxanes are characterized by high thermostability and di-
electric characteristics.4
For improving the dielectric properties of the modified filler com-
pounds, the oligotetraepoxysiloxane oligomers with organosilsesquioxane
fragments in the chain have been synthesized. As initial components for
the synthesis of tetraepoxyphenylsilsesquioxane during condensation re-
action of epichlorohydrin, the cis–2.4.6.8-tetrahydroxy-2.4.6.8-tetraphe-
nylcyclotetrasiloxane and tetrahydroxyphenyl oligomer (n = 2¸10) with
sodium hydroxide have been used, and phenylethoxysilsesquioxanes
PhES-80 (n-1) and PhES-50 (n = 2) in the presence of catalysts iron chlo-
ride (III) 0.01% by weight have been investigated.

EXPERIMENTAL PART

MATERIALS AND TECHNIQUES

Initially, cis–2.4.6.8-tetrahydroxy-2.4.6.8-tetraphenylcyclotetrasiloxane
and tetrahydroxyphenylsilsesquioxane were synthesized as given in the
literature.5,6
FTIR spectra were recorded on a Varian 660/670/680-IR series spec-
trometer. Chromatographic analysis of the purity of the starting reactants
and the reaction was carried out using a chromatograph grade LKhM-80,
Model 2 (column 3000 chromatografic-4 mm) Media-Chromosorb W or
Chromaton. For the analysis, the following phases were used: Silicone
Composites on The Basis of Glycidoxygroup 307

SE-30 resin, REOPLEX-400, and carrier gas-helium. Match of the applied


phase separating substances possessed the ability to OV-17 supported on
Chromaton-NAW. For better separation of different monomers, the tem-
perature was selected in the range 130–200°C.

CONDENSATION REACTION OF EPICHLOROHYDRIN


WITH CIS–2.4.6.8-TETRAHYDROXY-2.4.6.8-
TETRAPHENYLCYCLOTETRASILOXANE

In a four-necked flask equipped with a thermometer, mechanical stirrer, re-


flux condenser, and dropping funnel, 5.52 g (0.01 mol) of tetrahydroxytet-
raphenylcyclotetrasiloxane and 30 mL of diethyl ether were taken. While
stirring at 40°C, 7.52 g (0.08 mol) of epichlorohydrin (100% excess) was
added, and then distilled ether was added slowly and gradually. The reac-
tion temperature was increased to 60–70°C and then the reaction mixture
was stirred again and heated for 1 h. After carrying out these steps, 0.4 mol
(16 g NaOH, 48 g H2O) of 25% sodium hydroxide solution was added in
three portions. After addition of the last portion of the alkaline solution
mixture, the mixture was stirred for another 1 hour at a temperature of
70°C. Then 9.3 g of epichlorohydrin was added, and the reaction mixture
was diluted with 100 mL of ether. Ether was removed by suction. Unre-
acted part of epichlorohydrin was evacuated at 30°C for 3 h at a residual
pressure of 1 mm Hg. As a result, approximately 6.8 g of slow-moving vis-
cous mass (compound I) with a yellowish color at 96% yield was obtained.

CONDENSATION REACTION OF EPICHLOROHYDRIN WITH


OLIGOPHENYLSILSESQUIOXANE (N»3)

Compounds (II) were prepared as given in Scheme 14.2. In the flask,


15.84 g (0.01 mol) of tetrahydroxypolyphenyloligotetrole in 60 mL of
dry toluene and 7.52 g (0.08 mole) epichlorohydrin (100% excess) were
taken. The 16.74 g (96%) tetraepoxypolyphenylsilsesquioxane (II) was
obtained. Condensation reaction of epichlorohydrin with oligotetrapheny-
silsesquioxane (n≈10) was carried out in the same manner as explained in
the section Condensation Reaction of Epichlorohydrin with cis–2.4.6.8-
tetrahydroxy-2.4.6.8-Tetraphenylcyclotetrasiloxane.
308 Additives in Polymers: Analysis and Applications

CONDENSATION REACTION OF EPICHLOROHYDRIN WITH


TETRAETHOXYTETRAPHENYLCYCLOTETRASILOXANE (PHES-80)

The reaction between an industrial product tetraethoxytetraphenylcyclo-


tetrasiloxane PhES-50 (n = 1) and PhES-80 (n = 2) with epichlorohydrin
was conducted in a four-necked flask equipped with a dropping funnel, a
reflux condenser, a mechanical stirrer, and a thermometer. In this flask,
118 g (0.1 mol) of PhES-80 (phenethylsilsesquioxane-80), 2.4 g of iron
chloride (III) 0.01% by weight of the reaction mixture, and 75.2 g (0.8
mol) epichlorohydrin (100% excess) were added. The reaction mixture
was heated up to 80–85°C. The reaction was carried out for 5–6 h, and low
molecular byproduct C2H5Cl was collected in a flask. The resulting mass
was centrifuged to precipitate the catalyst. After evacuating the unreacted
products, the 112.5 g of a dark brown color gummy product I’ was ob-
tained with a 95% yield.
Similarly, the condensation reaction of epichlorohydrin with PhES-50 (n
= 1) in the presence of catalysts, iron (I’), and aluminum chloride (IV’) have
been carried out and dark brown color gummy products have been obtained.

RESULTS AND DISCUSSION

There are certain methods of synthesis of epoxyorganosiloxanes. From


these methods, it is significant to denote oxidative epoxidation of unsatu-
rated bond containing organosilanes and siloxanes,7,8 hydrosilylation re-
actions of ≡Si–H bond containing silanes and siloxanes to allyl glycidyl
ether in the presence of catalysts,9,10 and the reactions of oganosilanoles or
organosiloxanoles with epichlorohydrin.11,12
The condensation reaction of epichlorohydrin with Cis–2.4.6.8-tetra-
hydroxy-2.4.6.8-tetraphenylcyclotetrasiloxane with the excess epichloro-
hydrin in the presence of 25% sodium hydroxide solution was performed.
The reaction was carried out as given in Scheme 14.1.
Ph Ph Ph Ph
HO Si O Si OH
H2C CH H2C O Si O Si O CH2 HC CH2
4NaOH
O O + 4 Cl CH2 HC CH2 O O
-4NaCI O O
HO Si O Si OH O
H2C CH H2C O Si O Si O CH2 HC CH2
Ph Ph O O
Ph Ph I

SCHEME 14.1  The Condensation Reaction of Epichlorohydrin with cis–2.4.6.8-


Tetrahydroxy- 2.4.6.8-Tetraphenylcyclotetrasiloxane.
Composites on The Basis of Glycidoxygroup 309

A transparent yellow viscous compound I well soluble in organic sol-


vents was obtained. The composition and structure of the obtained com-
pound I was studied on the basis of elemental analysis, definition of num-
ber of epoxy groups, determination of molecular masses, and FTIR spectra
data. Some physicochemical data of the synthesized compounds are pre-
sented in Table 14.1.

TABLE 14.1  Some Physicochemical Data of the Synthesized Compounds


Yield, Amount of Epoxideb Elemental Analysisb,%
# n Мamass
% Groups,% C H Si
24.16 712 60.67 5.62 15.73
I 1 96
24.05 709 60.40 5.60 15.66
9.86 1744 57.80 4.59 19.27
II 3 95
10.00 1769 58.63 4.66 19.55
3.23 5324 56.80 4.13 21.04
III 10 96
3.18 5242 55.92 4.07 20.72
Notes: aMolecular masses have been determined via ebulliometric method; bValues above
the line are calculated values and those below the line are found values.

In the FTIR spectra of obtained compounds in the range of asymmetric


and symmetric valence oscillations ºSi–O–Siº bond, the bifurcation of the
strips with maximums nas -1045 and 1145 сm-1, and nas –455 and 480 сm-1
were observed. In the case of phenylcyclotetrasiloxane, ring condensation
in the presence of nucleophilic sodium may occur with the opening of
cyclotetrasiloxane ring, which leads to the formation of the structure dif-
ferent from cis–configuration (see Figs. 14.1 and 14.2). This opinion is in
accordance with the known data.13,14
310 Additives in Polymers: Analysis and Applications

FIGURE 14.1  The FTIR spectra of initial cis–2.4.6.8-tetrahydroxy-2.4.6.8-


tetraphenylcyclotetrasiloxane.

FIGURE 14.2  FTIR spectrum of 2.4.6.8-glycidoxy-2.4.6.8-tetraphenylcyclotetrasiloxane


(I).
Composites on The Basis of Glycidoxygroup 311

However, the realization of the cis–isotactic structure is associated


with several steric hindrances and characterized by a short length of the
molecules. During the tetrole polycondensation without initiator of the ba-
sis type, which allows the obtaining of the polymer without breaking the
siloxane bond in the organocyclosiloxane, the conditions of synthesis en-
sures the perfect cyclolinear ladder structure and the macromolecules with
the Kuhn segment with length about 50 Å are formed.
From the spectroscopic investigations14 the structure of macromole-
cules of PPSSO, obtained by condensation of tetrole Т4, differs from the
structure obtained from phenyltrichlorosilane and anion polymerization.
The conducted experimental investigations suggest that the macromol-
ecules with Kuhn segment that is approximately 50 Å have the structure
somewhat similar to cis–anti-cis–tactic one:13,14

HO O OH

O cis-anti-cis-tactic
OH O conf iguration
HO O
O O
cis-T4-bath O
O

cis-isotactic conf iguration


SCHEME 14.2  Cis–anti-cis–Tactic and cis–Isotactic Configuration of PPSSO.

Due to the combination of the Т4 fragments with transdisplacement


of the functional groups, the cis–syndiotactic structure of chain may be
formed with cis–syndiotactic configuration (Scheme 14.3).

O OH
OH
O OH O
O
OH
cis-syndiotactic
trans-T4-coach conf iguration
SCHEME 14.3  Cis–Syndiotactic Configuration of PPSSO.
312 Additives in Polymers: Analysis and Applications

Such structure of the chain is satirically more profitable and is char-


acterized by high rigidity of the chain. Therefore, the dual structure of
the molecules of ladder fragments lay under hydrolytic condensation or-
ganotriclorosilane and products of its partial hydrolysis and condensation.
So, it was established that in the presence of sodium hydroxide, the re-
arrangement of polyphenylsilsesquioxane skeleton takes place and cis–an-
ti-cis structure of silsesquixane structure turn to cis–syndiotactic structure,
which indicates the doublet character of absorption bands of ≡Si–O–Si≡
bonds.
With the aim of defining the effect of the fragment length of organocy-
closiloxane in the tetraepoxy compounds based on the properties of com-
posite materials, we investigated analogically the condensation reactions
of tetrahydroxyoligoorganosilsesquioxanes with bifurcated epichlorohy-
drin in the presence of 25% solution of sodium hydroxide at room tem-
perature.
The initial tetrahydroxyphenylsilsesquioxanes (n»3, 10) with cis–anti-
cis–tactic structure as initial compounds obtained by thermal condensation
of cis-2.4.6.8-tetrahydroxy-2.4.6.8-tetraphenylcyclotetrasiloxane were
used.5,6 Due to the interaction of the fragments of Т4 with cis–location of
functional groups, polyphenylsilsesquioxanes with cis-isotactic configu-
ration may be formed if the atoms of silicon in the tetrole molecules are
in one and same plane and in cis–anti-cis–tactic configuration, if the Т4
cycles are in the parallel planes (Scheme 14.2).
However, the realization of cis-isotactic structure is associated with
several steric hindrances and characterized by the short length of the mol-
ecules. During the tetrole polycondensation without initiator of the basis
type, which allows the obtaining of the polymer without breaking of silox-
ane bond in the organocyclosiloxane, the conditions of synthesis ensures
the perfect cyclolinear ladder structure and the macromolecules with the
Kuhn segment with length about 50 Å are formed (Scheme 14.2).
Performing spectroscopic research13 gives grounds to assume that the
structure of macromolecules polyphenylsilsesquioxane obtained by the
thermal condensation of tetrol T4 toluene solution is different from the
structure of the macromolecules polyphenylsilsesquioxane obtained from
products phenyltrichlorsilane anionic polymerization initiator in the pres-
ence of the basic type. The experimental studies have assumed that the
macromolecule with Kuhn segment with length of ~50 Å have a structure
close to the cis–anti-cis–tactic configuration.14
Composites on The Basis of Glycidoxygroup 313

So the condensation reaction of tetrahydroxyoligoorganosilsesquiox-


anes with epichlorohydrin was carried out according to Scheme 14.4.

Ph Ph
Ph Ph
HO Si O Si O H
H2C CH H2C O Si O Si O CH2 HC CH2
4NaOH
O O + 4 Cl CH2 HC CH2 O O
O O
-4NaCI
O
HO Si O Si O H H2C CH H2C O Si O Si O CH2 HC CH2
Ph Ph O Ph Ph n O
n

SCHEME 14.4  Condensation of Tetraethoxypolyphenylsilsesquioxane (n = 3, 10) with


Epichlorohydrin in the Presence of Sodium Hydroxide.

Where n = 3 (II) and 10 (III).


The obtained compounds II and III were amber-colored viscous prod-
ucts well soluble in the acetone, methylethylketone, and ethyl acetate. The
yield, number of epoxy groups, molecular masses, and elemental analysis
of the obtained silicon-organic oligomers are presented in Table 14.1.
For obtained epoxy-phenylsilsesquioxsane, the reaction between an
industrial product tetraethoxyphenylsilsesquioxanes PhES-50 (n = 1) and
PhES-80 (n = 2) with epichlorohydrin were investigated. The reaction was
carried out at a temperature of 80–100°C in an inert gas atmosphere in the
presence of a catalytic amount of iron chloride (III) or aluminum chloride,
as shown in Scheme 14.5:

Ph Ph Ph Ph
C2H5O Si O Si O C2H5 H2C HC H2C O Si O Si O CH2 CH CH2
Cat O O
O O + 4 Cl CH2 CH CH2 O O
O -4C2H5Cl
C2H5O Si O Si O C2H5 H2C HC H2C O Si O Si O CH2 CH CH2
Ph Ph O Ph Ph n O
n

SCHEME 14.5  Condensation of Tetraethoxypolyphenylsilsesquioxane (PhES-50 and


PhES- 80) with Epichlorohydrin in the Presence of Catalyst.

Where Cat-FeCl3: n = 1 – I’, 2 (IV); Cat – AlCl3, n = 2 – IV’.


It is interesting to note that because of iron (III) chloride, the reaction
mix appeared in dark brown color. Decolorizing of an obtained product
was not possible either by centrifugation or by the adsorption of a solu-
tion of siliconorganic oligomers on the activated coal. Therefore, further
researches were carried out in the presence of catalyst aluminum chloride.
The structure and composition of the synthesized oligomers were de-
termined by means of elementary and functional analyzes by calculating
314 Additives in Polymers: Analysis and Applications

molecular masses and FTIR and 1H NMR spectra data. In the FTIR spectra
of compounds I’ and IV, the absorption bands for nas asymmetric and for
symmetric valence oscillation of ≡Si–O–Si≡ bonds were kept in the field
of absorption at 1060–1010 cm-1, and also, new absorption bands at 820–
840 and 917 cm-1 characteristic for epoxy rings were formed. The spec-
tra did not observe the absorption bands characteristic of ethoxy groups
proving that the epoxy groups have replaced the ethoxy groups. In the1H
NMR spectra of synthesized oligomers, one can observe multiplet signals
characteristic for methylene protons in the -CH2O- group in the center of
chemical shift d = 3.3 ppm, multiplet signals characteristic for methine
group of oxirane cycle in the center of chemical shift d = 3.01 ppm, and
also multiplet signals characteristic for methylene group of oxirane cy-
cle in the center of chemical shift d = 2.5 ppm. Yields, amount of epoxy
groups, molecular masses`Mn,`Mw,`Mz, and polydispersity of synthesized
epoxy group containing siliconorganic oligomers I”, IV, and IV’ are pre-
sented in Table 14.2.

TABLE 14.2  Yields, Amount of Epoxy Groups, and Molecular Masses of Synthesized
tetraepoxypolyphenylsilsesquioxanes (I–II)

№ Yield,% Epoxy Group,% Мa `Mn `Mw `Mz `Mw/`Mn


I’ 94 4.74 3626 - - - -
4.80 3672
IV 93 13.52 1272 1260 2460 6250 1.95
13.58 1277
IV’ 95 13.52 1272 1200 2080 4100 1.83
13.48 1268
Notes: aThe calculated values are presented in the numerator, and experimental values are
presented in the denominator; Molecular masses were calculated from the values of epoxy
groups.

No change in the characteristic properties of the synthesized tetrae-


poxypolyphenylsilsesquioxanes I’ and IV for three months was observed,
which implies their long viability (Table 14.3).
Composites on The Basis of Glycidoxygroup 315

TABLE 14.3  Change of Specific Viscosity, Amount of Epoxy Groups for Oligomers I’
and IV Depending on Duration of their Storage

hsp 50% Benzene Solution at 20°C Amount of Epoxy Groups,%

№ After After After After


After 1 After 2 After 3 After 1 After 2 After 3
Reac- 10 Reac- 10
Month Months Months Month Months Months
tion Days tion Days
XVI 2.6 2.8 2.8 2.8 2.9 24.30 24.29 24.28 24.28 24.28

XVII 5.2 5.2 5.3 5.5 5.5 7.19 7.18 7.17 7.17 7.17

EPOXY GROUP FUNCTIONALIZED


POLYPHENYLSILSESQUIOXANE

For obtaining epoxyorganosilicon, the compounds I–III were used as


modifiers for epoxy-dian resin ED-22. The compounds were prepared on
the basis of ED-22 with 20–24% epoxy groups (100 mass parts) at differ-
ent ratio of modifier and hardener: D-1, methylphenyldiamine (MPDA);
D-2, 4,4′-diaminodiphenylsulfone (4,4′-DADPS); D-3, 4,4′-diaminodi-
phenylmethane (4,4’-DADPM); D-4, 4,4′-diaminotriphenyloxide (4,4’-
DATPO), and D-5, metatetrahydrophtalanhydride (МТHFА). The hard-
ening of composites was conducted both at room and high temperatures.
Composition and the hardening regime of obtained composites were also
conducted both at room and high temperatures. The composition and
hardening regime of obtained compounds are presented in Table 14.4 and
physical-mechanical and electric properties are presented in Table 14.5.
The obtained compounds have the high dielectric, mechanic characteris-
tics and thermal-oxidative stability. The results of investigation of depen-
dence of physical-mechanical and dielectric properties on the number of
the introduced modifier are presented in Table 14.6. The study of change
of viscosity of the compounds in the process of hardening on temperature
shows that compound differ from analogous by high viability in the range
80–90°С; however, at temperatures in the range of 150–160°С, its viability
sharply decrease, which is connected with quick destruction of the func-
tional groups and its consequent hardening.
316 Additives in Polymers: Analysis and Applications

TABLE 14.4  Composition and Hardening Regime of the Composites Based On


Tetraepoxypolyphenylsilsesquioxanes and Epoxy Resin Ed-22
Composite

Hardening
Mass Composite Hardening
Composite Content temperature,
Part Color time, h
TC°

Epoxy pitch ED-22 100


Light yellow
G-1 Oligomer I 40–45 160 4
viscous mass
Binder D-1 13
Epoxy pitch ED-22 100
Light yellow,
G-2 Oligomer III 40–45 155 4
transparent Mass
Binder D-2 13
Epoxy pitch ED-22 100
Dark-yellow 5
G-3 Oligomer IV 40–45 155
viscous mass
Binder D-4 10–15

TABLE 14.5  Mechanical and Electric Properties of Compounds Based on


Tetraepoxypolyphenylsilsesquioxanes and Epoxy Resin Ed-22
Compound
№ Characteristic Unit
G-1 G-2 G-3

1 Electrical strength 24.5 22 23.8 кВ/mm

Specific surface electrical re-


2 1 × 106 1.2 × 106 0.6 × 1017 Оm
sistivity at 20°C
Specific volumetric electric re-
3 1.5 × 1013 2 × 1014 5 × 1013 Оm/сm
sistivity at 20°С
4 Strength at bending 111.0 113.5 120.0 МPА
Heat resistance according to
5 77.8 77.5 87.5 С
°
Martens

By studying the thermal oxidation destruction of obtained composites,


it was established that in comparison with initial epoxy resin, the polymers
are of high thermal proof systems.
Figure 14.3 shows that increasing the ladder fragment length of a chain
increases mainly the relative stability of the composites. The same case is
true while studying the stability of the composites with different hardeners
as in preliminary case in accordance with the Figure 14.3.
Composites on The Basis of Glycidoxygroup 317

All composites G–D based on epoxy resin ED-22 modified by syn-


thetic tetraepoxypolyphenylsilsesquioxanes and hardened by amine type
hardeners are divided into two stages. In the first stage, destruction of
composites is followed by high loss of the mass. This process occurs at
temperatures from 180 to 420°С. Probably, on this stage, the compounds’
organic groups burn out (Fig. 14.4).
In the study of polymers with different properties along with the re-
search of new methods for the synthesis of oligomers and polymers, com-
posites modified in optimal curing condition have gained a special atten-
tion. In this regard, elaboration of rational designs temperature of curing
of composites has gained particular attention. We have studied the harden-
ing of composite G–D with different amine hardener D-1, D-2, D-3, D-4,
and D-5 at different temperatures from 80°C to 160–180oC.

TABLE 14.6  Physical-Mechanical Properties of Epoxy Resin ED-22, Modified by


Epoxyorganosilicon Oligomer XII with Hardener MTGPA (D-5)
Containing of modifier, Mass Parts (at

Tangent of Dielectric Losses Angle at

Specific volumetric Electric Resistance,


Destruction Stress at Stretching, MPa

Relative Elongation at Rupture,%

Dielectric Penetration at 103Gz


100 Mass Parts of the Resin)

Electric Durability, kV/mm


Hardness by Brinnel, MPa

×1013 Ohm × cm
103Gz

1 10 7.15 10 1.0 61 0.022 5.92 4.3


2 15 8.1 12 1.0 68 0.029 6.06 4.3
3 20 6.8 10 1.2 52 0.018 5.85 4.3
4 25 5.2 9 1.4 46 0.011 5.02 4.2
5 35 5.01 8 1.5 44 0.011 5.02 4.2
6 45 5.01 7 1.7 42 0.010 5.02 4.1
7 0 3.5 0.8 1.0 20-25 0.0045 3.90 -
318 Additives in Polymers: Analysis and Applications

FIGURE 14.3  Thermogravimetric Curves for the Compounds G-1(1), G-2 (2), and G-3
(3) Hardened by Hardener D-1.

FIGURE 14.4  Thermogravimetric Curves of Thermal Oxidative Destruction for the


Compound G-2 Hardened by Hardeners D-1 (1), D-2 (2), D-3 (3), and D-4 (4).

While synthesizing superposed composites of epoxyorganosilicon


oligomers (I and III) and epoxy-dian resin ED-22, the chemical interac-
tion between them and decreasing of the functional epoxy groups were not
observed. However, during hardening, the result was different. Due to the
presence of functional groups with high reaction ability, the presence of
even the amine-type hardeners leads to chemical interaction, resulting in
the step by step disappearance of the functional groups.
Composites on The Basis of Glycidoxygroup 319

From Table 14.7, it can be seen that full curing of the composite G–1
with binder D-2 at a temperature of 150°C has been reached within 4–5 h.

TABLE 14.7  Yields of Gel-fraction of the Composite K-1 with Hardener D-1 in
Dependence of Hardening Temperature

Hardening Time, Hardening Temperature, Yield of Gel-fraction,



min °
С %
1 20 18 0
2 60 45 0.1
3 120 60 0.2
4 160 80 2.8
5 180 110 10.0
6 240 120 40.0
7 270 130 60.0
8 300 140 80.0
9 360 150 100.0

The monomers containing organosilicon fragments and epoxy groups


in the molecule are cured in the presence of amine curing agents that re-
sults in a three-dimensional cross-linked polymers, while the deformation
heat resistance should be kept in the range 250–300°С. Combinations of
different types behave differently when cured. During curing of com-
posites by hardeners of cold cure, for example, polyethylene polyamine
(PEPA), increasing of the hardening time till 3 days was observed.
The hardening kinetics for composites G–D and for pure ED-22 were
studied using hardeners PEPA and MTGPA. It was shown that hardening
rate for ED-22 was essentially higher compared with that of the other com-
pounds. While heating of these composites, the fullness of hardening in-
creases; however, the hardening rate for epoxy resin is higher than that of
all organosilicon composites. This fact once more proves that the modified
composites are characterized with lower reaction ability and high viability
than that of epoxy resin. Therefore, these composites are more suitable for
embedding materials.
Thus from all the analyses, it may be concluded that hardening of the
epoxy resin modified by organosilicon oligomers (I–III) may be divided
320 Additives in Polymers: Analysis and Applications

into two stages. In the first stage, the process of the slow formation of
the linear polymers takes place and then increasing of the polymer grid
because of the interaction between functional groups and hardener occurs,
the consumption on which reaches about 30%. The temperature of reac-
tion mass on the first stage of hardening must not exceed 60°С. This proves
the application of MTGPA instead of PEPA.
In the second stage of the process, heating of the composition up to
120–150°C for 3 h takes place. Under such conditions, insoluble and in-
fusible polymers are obtained by the interaction of the functional groups
and the formation of new cross-links due to the reaction of the secondary
hydroxyl groups.
In the threefold system (ED-22 + epoxyorganosilicon oligomer + hard-
ener), interaction of hardener occurs with ED-22 and with epoxyorgano-
silicon modifier. And the second reaction is intense during heat treatment.
The hardened material presents relatively rare grid of epoxy polymer filled
with thermoplastic product epoxyorganosilicon modifier + hardener and
therefore has high strengthening and thermal stability than pure epoxy
polymer.
Increasing the amount of hardener in the threefold system leads to the
synthesis of the polymer with high density of the grid. Such polymer is
characterized by more stress structure, which leads to the decreasing of its
mechanical strength because of which the polymer becomes fragile. For
hardening of composites of the threefold system, the optimal amount of
hardener is 10–15 mass part (20–25 wt%). For the samples hardened for
5 h at 150°С, decreasing of softening temperature and increasing of high
elastic deformation were observed. This fact can be explained by the com-
pletion of the chemical processes of hardening of thermal-treated samples.
So, it appears that polymer materials based on epoxy-dian resin ED-
22 modified by epoxyorganosilicon oligomers possess the complex of
the valuable exploitation properties: high thermal stability and improved
dielectrical, physical, and mechanical properties. The complex of these
properties corresponds to modern technical demands and is perspective.

CONCLUSION

The condensation reaction of tetraethoxyphenylsilsesquioxane with the


excess epichlorohydrin in the presence of catalysts has been investigated
Composites on The Basis of Glycidoxygroup 321

and corresponding tetraepoxy derivatives has been obtained. These com-


posite compounds may be used as a potting material.

KEYWORDS

•• Thermal stability
•• Biomedical
•• Degree of functionalization
•• Modified filler
•• Tetraphenylcyclotetrasiloxane
•• Phenylethoxysilsesquioxanes
•• Catalysts iron chloride

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ference, Organosilicon Compounds: Synthesis, Properties and Application, Moscow,
Russian Federation, 25-30 May, 3C12, 2005.
13. Volchek, B. Z.; Purkina, A. B. Macromolecules. 1976, 28А(6), 1203.
14. Tverdochlebova, I. I.; Mamaeva, I. I. Macromolecules. 1984, 26А(9), 1971.
CHAPTER 15

THE COMPARATIVE STUDY


OF THERMOSTABLE PROTEIN
MACROMOLECULAR COMPLEXES
(CELL PROTEOMICS) FROM
DIFFERENT ORGANISMS
D. DZIDZIGIRI, M. RUKHADZE, I. MODEBADZE,
N. GIORGOBIANI, L. RUSISHVILI, G. MOSIDZE, E. TAVDISHVILI,
and E. BAKURADZE
Department of Biology Faculty of Exact and Natural Sciences, Iv. Javakhishvili
Tbilisi State University, Tbilisi, Georgia
Email: [email protected]

CONTENTS

Introduction........................................................................................................ 324
Aim ................................................................................................................. 324
Experimental Part............................................................................................... 325
Results and Discussion...................................................................................... 326
Conclusions........................................................................................................ 328
Keywords........................................................................................................... 329
References.......................................................................................................... 329
INTRODUCTION

Identification of the functions of proteins and other polymeric complexes


or cell proteomes, in which the achievements of proteomics contributes
greatly, is the subject of intensive research.1 Modern technology now al-
lows us not only to investigate individual protein molecules in living cell,
but also to understand their interaction with other macromolecules and
reveal their previously unknown functions. Several facts are determined:
participation of polyfunctional macromolecular protein complexes in the
biosynthesis of fatty acids, involvement of erythrocyte membrane pro-
teins macromolecular complexes in exchange of CO2/O2, biological ef-
fects of some growth factors (polyfunctional proteins), which sometimes
is achieved by interactions of other protein complexes, and so on.2–4
Earlier, we have identified the protein complex with such properties in
various cells of adult white rats.5–7 The main feature of those complexes
is the thermostability of the containing components. With gel electropho-
reses and chromatography of hydrophobic interaction, it was determined
that components with high molecular weight (45–60 kD) are hydrophobic,
whereas components with low molecular weight (11–12 kD) are hydro-
philic according to the column retention time. Through the inhibition of
transcription, complex reduces the mitotic activity of homo- and hetero-
typic cells in growing animals.5,8 Components of complex are water sol-
uble and is not characterized by species specificity. Thus, we can assume
that they are maintained in cells of phylogenetic distance organisms, and
in case of confirmation of this fact, they may belong to the conservative
family of proteins. In order to determine general regularities of effects of
complex described by us, it is necessary to examine in detail the compo-
nents phylogenesis.

AIM

The aim of this study is the extraction and comparative characterization


of thermostable protein complexes (TSPCs) from phylogenetic distance
organisms.
The Comparative Study of Thermostable Protein 325

EXPERIMENTAL PART

MATERIAL AND METHODS

The thermostable protein complexes obtained by alcohol extraction from


normal cells of various organisms (bacteria, snail, lizard, guinea pig, rat,
and also human postsurgical material and cell culture) were used for re-
search.
Thermostable protein fractions were obtained by the method
of alcohol precipitation described by Balazs and Blazsek,9 with
modification. Animals were decapitated under diethyl ether. Or-
gans were removed quickly, separated from capsules of connec-
tive tissues and vessels, rinsed with the physiological solution, and
crushed. Aqueous homogenates were prepared in a tissue/distilled
water ratio of 1:8. The homogenates were saturated stepwise with
96% ethanol to obtain 81% ethanol fraction, which was heated in
a water bath (100°C) for 20 min, cooled, and centrifuged (600 g,
15 min). The supernatant was frozen in liquid nitrogen and dried
in an absorptive-condensate lyophilizer. As a result, a residue of a
thermostable protein complex (TSPC) was obtained, which is a light
gray powder soluble in water. Samples were kept at 4°C. Protein
concentration was determined by the method of Lowry et al.10
Hydrophobic interaction chromatography (HIC) was used for the
comparative analysis of TSPC.11 A hydrophilic polymeric sorbent,
HEMA BIO Phenyl-1000 (particle size 10 mm) modified by phenyl
groups, served as the stable phase. The mobile phase was phosphate
buffer (pH 7.4) with ammonium sulfate. Elution was performed with
the mobile phase in molar concentration range of 2.0 M–0.0 M (pure
buffer) with respect to (NH4)2SO4. For coelution of hydrophilic and
hydrophobic components of protein fractions, Brij-35 polyoxyeth-
ylene dodecyl ether with increasing concentration from 0 to 3% was
added to the mobile phase. UV detection was usually set at 230 nm.
326 Additives in Polymers: Analysis and Applications

RESULTS AND DISCUSSION

Dynamic interaction between the protein molecules (protein–protein)


determines vital activity of the cells. In the past few years, as a result
of intensive research in this field, some knowledge about formation and
function of protein complex has been accumulated. Dynamic interactions
of proteins are studied not only in individual species but also in different
types of cells and tissues. Therefore, in the first stage, the aim of the re-
search was to obtain and compare the TSPC from organisms of different
classes.

FIGURE 15.1  Chromatography of Protein Complex: (a) Protein Complex from


Phylogenetically Distance Animals; (b) Protein Complex from Various Tissues of White
Rat.

It was established that all the protein complex samples contain qualita-
tively different two groups of proteins. I group is hydrophilic, and II group
is hydrophobic proteins with a column retention time of 5–6 min. and
20 min., respectively (Fig. 15.1a). The same subfractions were revealed in
case of protein complexes obtained from different tissues of white rat by
using this method (Fig. 15.1b).
It is known that dysfunctions of protein–protein interactions can lead
to the development of various diseases, including cancer, neurodegenera-
tion, autoimmune diseases, and so on. Therefore, the analysis of protein
The Comparative Study of Thermostable Protein 327

networks based on the protein–protein interaction may be used in develop-


ing various therapeutic approaches.12 On the next stage of the research, we
performed comparative analyses of protein complexes obtained from rat
kidney and normal and transformed renal tissue of human. The differences
between normal and transformed cells were revealed in this experiment. In
particular, the components with low molecular weight were not observed
in the protein complex obtained from human kidney cancer tissue, which
indicates the changes that occur in the composition and the function of
complexes during the development of the cancer (Fig. 15.2).

FIGURE 15.2  Chromatography of Protein Complexes Obtained from Rat Kidney and
Normal and Transformed Renal Tissue of Human.

The low-molecular-weight subfraction of protein complex has mito-


sis-inhibitory properties, reduces number of active and moderately active
nucleoli, and decreases the activation of RNA synthesis in nuclei of car-
diomyocytes of newborn rat.13 Usually, this subfraction is essential com-
ponent of any TSPC obtained from various organs of adult rat. It is always
seen as a major subfraction in native gel-electrophoresis (PAAG electro-
phoresis; Fig. 15.3).
328 Additives in Polymers: Analysis and Applications

FIGURE 15.3  Electropherogram of TPC from Different Organ of White Rat and Human
(Arrows Indicate Low-Molecular-Weight Subfraction of TPC).

Consequently, on the next stage of experiment, the low-molecular-


weight components of protein complexes obtained from intact (rat pan-
creas, kidney, and brain) and transformed cells (with different degrees;
human papillary carcinoma, CLL, and hemangioma) were examined.
As it is shown in Figure 15.3, component with low molecular weight
are well expressed in protein complexes from various organs (kidney, pan-
creas, and brain) of adult rat (Fig.15.3). Different picture is shown in com-
plexes from transforming cells. In particular, electropherograms shows
that protein components with low molecular weight are manifested in the
samples obtained from benign as well as malignant cells. However, inten-
sity of silver nitrate staining is much lower compared with the norm.

CONCLUSIONS

From these results, it can be concluded that pro- and eukaryotic cells con-
tain a TSPC that inhibits cell proliferation. Quantitative content of protein
components in the complex is changing with the growth of transformation
degree of cells. Currently, development of the relative proteomics allows
us to determine the identity of proteins within these complexes to reliably
identify the set of proteins that is responsible for and participates in the
regulation of proliferation are constantly presented in the cell. With the
help of comparative proteomics, it was identified that Nilaparvata lugens
proteins that are involved in the process of proliferation and their expres-
sion change in response to insecticide treatment.2
The Comparative Study of Thermostable Protein 329

KEYWORDS

•• Functions of proteins
•• macromolecules
•• biosynthesis
•• interactions
•• thermostability
•• hydrophobic interaction

REFERENCES

1. Amano, O.; Iseki, S. Expression and localization of cell growth factors in the salivary
gland. Kaibogaku Zasshi. 2001, 76(2), 201–212.
2. Balazs, A.; Blazsek, I. Control of Cell Proliferation by Endogenous Inhibitors; Aka-
demia Kiado: Budapest, 1979; p 302.
3. Dai, S.; Chen, T.; Chong, K.; Xue, Y.; Liu, S.; Wang, T. Proteomics identification of
differentially expressed proteins associated with pollen germination and tube growth
reveals characteristics of germinated, Oryza sativa. pollen. Mol Cell Proteomics.
2007, 6, 207–230.
4. Dijke, P. T.; Iwata, K. K. Growth factors for wound healing. BioTechnology. 1992,
7(8), 793–798.
5. Dzidziguri, D.; Iobadze, M.; Aslamazishvili, T.; Tumanishvili, G.; Bakhutashvili, V.;
Chigogidze, T.; Managadze, L. The influence kidney protein factors on the prolifera-
tive activity of MDSK cells. Tsitologiya. 2004, 46(10), 913–914.
6. Ge, L.-Q.; Cheng, Y.; Wu, J.-C.; Jahn, G. C. Proteomic analysis of insecticide triazo-
phos-induced mating-responsive proteins of Nilaparvata lugens Stal (Hemiptera: Del-
phacidae). J. Proteome Res. 2011, 10(10), 4597–4612.
7. Giorgobiani, N.; Dzidziguri, D.; Rukhadze, M.; Rusishvili, L.; Tumanishvili, G. Pos-
sible role of endogenous growth inhibitors in regeneration of organs: searching for
new approaches. Cell Biol. Int. 2005, 29, 1047–1049.
http://belki.com.ua/belki-struktura.html
8. Lowry, D. H.; Rosebrough, N. J.; Farr, A. L.; Randell, R. J. Protein measurement with
the folin phenol reagent. J. Biol. Chem. 1951, 193, 265–275.
9. Modebadze, I.; Rukhadze, M.; Bakuradze, E.; Dzidziguri, D. Pancreatic cell proteome
– qualitative characterization and function. Georgian Med. News. 2013, 7-8(220–221),
71–77.
10. Queiroz, J. A.; Tomaz, C. T.; Cabral, J. M. S. Hydrophobic interaction chromatogra-
phy of proteins. J. Chromatogr. 2001, 87, 143–159.
11. Rusishvili, L.; Giorgobiani, N.; Dzidziguri, D.; Tumanishvili, G. Comparative anal-
ysis of cardiomiocyte growth-ihibitory factor in animals of different classes. Proc.
Georgian Acad. Sci., Biol. Ser. B. 2003, 1(1–2), 42–45.
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12. Terentiev, A. A.; Moldogazieva, N. T.; Shaitan, K. V. The dynamic proteomics in the
modeling of living cell. Protein-protein interactions. Success of Biological Chemistry
(Adv. Biol. Chem.). 2009, 49, 429–480. (article in Russian).
Additives in Polymers
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