polymers

Article
Structural Insights of Humins/Epoxidized Linseed
Oil/ Hardener Terpolymerization
Erol Licsandru, Marc Gaysinski and Alice Mija *
Institut de Chimie de Nice, Université Côte d’Azur, UMR CNRS 7272, Cedex 02, 06108 Nice, France;
[email protected] (E.L.); [email protected] (M.G.)
* Correspondence: [email protected]




Received: 22 June 2020; Accepted: 13 July 2020; Published: 16 July 2020


Abstract: Bio-based thermosetting resins were synthesized from a ternary composition: humins;
epoxidized linseed oil (ELO); and an industrial hardener, Capcure3-800 (CAP). Humins are in
a focused attention in the last years, as biorefinery by-product, therefore its valorization through
materials design is very important. Here we present a structural study of terpolymerization of humins/
ELO/CAP. The reactivity of these systems was highlighted by in situ FT-IR and 1 H and 13 C NMR.
The integration of humins in thermosetting resins gives alternatives to new feedstocks for future
bio-based materials.

Keywords: renewable resources; biorefinery by-products; humins; copolymerization; epoxidized

vegetal oils; reaction mechanism; 1 H; 13 C NMR

1. Introduction
The variance in oil prices and the inherent instability of oil producing zones lead to an increased
pressure in the development of alternative materials’ feedstock. Bio-refineries are a promising step
towards the future [1–3] by conversion of bio-polymers such as cellulose and hemicellulose to simple
monomeric building blocks such as hydroxymethylfurfural (HMF), methoxymethylfurfural (MMF),
and levulinic acid (LA). The process requires the catalytical conversion of simple carbohydrates towards
the aforementioned monomers [4]. These bio-monomers can be used in the synthesis of bio-plastics.
In this work, we focus on the synthesis of thermosetting resins starting from renewable products
for the eco-design of a novel family of materials. The design of the bio-based thermosets has been done
by choosing three main components: the humins (HU), a by-product from bio-refineries; the epoxidized
linseed oil (ELO), an epoxy derivative of natural poly unsaturated oils; and Capcure 3-800 (CAP),
an industrial hardener for epoxy resins. The ternary polymerization strategy was applied with the aim to
combine two biobased and antagonist (macro)monomers: the humins and ELO. In this way, the humins
contribute the polyfuranic branched chains, giving rigidity to the network while the aliphatic chains of
ELO give elasticity and a ductile character. Due to their low miscibility and reactivity, the Capcure was
used both as hardener and as compatibilizer. The rationale of this work was the valorization of humins,
as biorefinery by-product. For this reason, the design of formulations, of reactivity, etc., were realized
considering the humins as the main component, with a proposed structure presented in Figure 1 [5].

Polymers 2020, 12, 1583; doi:10.3390/polym12071583 www.mdpi.com/journal/polymers

Polymers 2020, 12,2020,
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Figure 1. Proposed fragment of a humins [5]. Polyfuranic moieties observed. Multiple types of reactive
Figure oxygen
1. Proposed fragment
atoms are of aalcohol,
present (acids, humins [5]. etc.).
ketones, Polyfuranic moieties observed. Multiple types of
reactive oxygen atoms are present (acids, alcohol, ketones, etc.).
Humins are materials with complex composition and behaviour, depending on biorefinery process.
The elemental composition was determined by Mulder in 1840 [6] as constituted by ~64–65% C, ~5% H,
Humins are materials with complex composition and behaviour, depending on biorefinery
and ~31–32% O. Other studies have placed the composition between 58–65.5% C and 4.5% H,
process.depending
The elemental composition
on the starting feedstockwas[7,8].
determined
Humins are by mixtures
Mulder ofinmacromolecules
1840 [6] as constituted
containing by ~ 64–
65% C, ~fused
5% H, andand ~ 31–32%
condensed O. Other
cycles, generallystudies
derivedhave
from placed
furan the(60%)composition
and aliphaticbetween 58–65.5%
linkers (20%) [9]. C and
Given their limited solubility, alternative strategies have been
4.5% H, depending on the starting feedstock [7,8]. Humins are mixtures of macromoleculesdevised in order to characterize these
structures. 13 C NMR
containing fusedTitirici and Baccile [10,11]
and condensed
13
cycles, investigated
generallythederived
structures generated
from furanby(60%)solid state
and aliphatic linkers
as well as through C labelling, based on reaction conditions and feedstock. Electron microscopy
(20%) [9]. Given their limited solubility, alternative strategies have been devised in order to
studies, SEM and TEM, have revealed structures made up of spheres with diameters between 0.5
characterize
and 5 these structures.
µm [12–15]. Titiricistudies
The Raman and Baccile [10,11] investigated
[14] confirmed the presence ofthe structures
reactive oxygengenerated
atoms in by solid
state Cthe
13 NMR
humins as macrostructure.
well as through 13 C labelling,
The presence basedoxygen
of reactive on reaction
species conditions
is a structuraland key feedstock.
allowing to Electron
transform the humins into thermosetting resins. Through
microscopy studies, SEM and TEM, have revealed structures made up of spheres specific derivatization with a fluorinated
with diameters
hydrazine derivative ((trifluoromethyl)phenylhydrazine), the total
between 0.5 and 5 μm [12–15]. The Raman studies [14] confirmed the presence of reactive oxygen amount of carbonyl functions
present in industrial humins was evaluated by Constant et al. using fluorine NMR to 6.6 wt % [16].
atoms in the humins macrostructure. The presence of reactive oxygen species is a structural key
Fluorine NMR presents the advantage of providing a distinct response since the proton and carbon
allowing to transform
spectra would be too the humins
complex into thermosetting
for quantitative resins.
and qualitative Through
analyses. The assayspecific
provided derivatization
quantitative with a
fluorinated
data onhydrazine
the reactivederivative
oxygen species((trifluoromethyl)phenylhydrazine),
found in humins, also revealing a richness theoftotal amount
ketones compared of carbonyl
functionsto alcohol
presentand inacid functions.
industrial This information
humins is particularly
was evaluated useful inetdetermining
by Constant the chemical
al. using fluorine NMR to 6.6
wt % [16]. Fluorine NMR presents the advantage of providing a distinct response since IR
reactivity of the humins. Recently, another study concerning humins solubility correlated with the proton
characterization has been published [17]. Successive attempts of solubilizing/extracting of various
and carbon spectra would be too complex for quantitative and qualitative analyses. The assay
fractions from the raw humins were partially successful. Indeed, some smaller and more soluble
provided quantitative
molecules data onfrom
were isolated the the
reactive
mixture;oxygen
however,species
the IRfound
spectra insuffered
humins, alsomodifications.
small revealing a richness
of ketones comparedprovides
This publication to alcohola veryandastuteacid functions.
understanding overThis information
the general spectral is particularly
imprint of humins.useful in
determining
The study thealso
chemical
revealed reactivity
that contraryof the humins.
to previous proposalsRecently, another
the molecular weight study
of the concerning
components humins
might be significantly lower, and the oligomers might be the most prevalent
solubility correlated with IR characterization has been published [17]. Successive attempts of species.
Bio-sourced oils are a renewable feedstock with multiple applications as bio-diesel and in last
solubilizing/extracting of various fractions from the raw humins were partially successful. Indeed,
decades as precursors of polymers [18–21]. In this case, the polyunsaturated triglycerides allow a
some smaller and more
facile transition soluble
towards molecules
epoxidized were
oils, via isolated
direct oxidationfrom thedouble
of the mixture;
bondshowever, the IR spectra
or by enzymatic
sufferedroute
small modifications.
[22,23]. The epoxidized Thisoilspublication
can then be provides a very astute
used in various understanding
formulations of lubricantsover the general
[24,25]
spectral imprint of humins. The study also revealed that contrary to previous proposals the molecular
polyurethanes, [18,26,27] and thermosetting polymers [28–31]. To develop thermosetting resins,
weight theof most commonly usedmight
the components oils are be
the significantly
epoxidized soybean lower, oil (ESO)
and the and the epoxidized
oligomers linseedbe
might oilthe most
(ELO) with 3.5 and 5.5 oxirane rings respectively per triglyceride. Both in the case of ESO [24,32–35]
prevalent species.
and ELO [29,36–39], numerous applications were reported. In this study, we used the epoxidized
Bio-sourced oils are
linseed oil (ELO) withatherenewable feedstock
structure given in Figurewith
2. multiple applications as bio-diesel and in last
decades as precursors of polymers [18–21]. In this case, the polyunsaturated triglycerides allow a
facile transition towards epoxidized oils, via direct oxidation of the double bonds or by enzymatic
route [22,23]. The epoxidized oils can then be used in various formulations of lubricants [24,25]
polyurethanes, [18,26,27] and thermosetting polymers [28–31]. To develop thermosetting resins, the
most commonly used oils are the epoxidized soybean oil (ESO) and the epoxidized linseed oil (ELO)
 Polymers
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Figure 2. Epoxidized linseed oil (ELO). The triglyceride presents a mixture of oleic, linoleic, and linolenic
Figure 2.Figure
acid
2. Epoxidized
Epoxidized linseed
linseed
residues. Average oil oil
number
(ELO).The
(ELO).
of oxirane
Thetriglyceride
triglyceride presents
presents
cycles per triglyceride
a mixture of oleic, linoleic, and
= 5.5. a mixture of oleic, linoleic, and
linolenic acid residues. Average number of oxirane cycles per triglyceride = 5.5.
linolenic acid residues. Average number of oxirane cycles per triglyceride = 5.5.
To promote the crosslinking reaction the Capcure 3-800 (CAP) was used. Its backbone contains
To promote the crosslinking reaction the Capcure 3-800 (CAP) was used. Its backbone contains
polypropoxy segments that improve the compatibility between the polar structure of humins
To promote
polypropoxythesegments
crosslinking reaction
that improve the Capcurebetween
the compatibility 3-800 the
(CAP)
polarwas used.ofIts
structure backbone
humins and thecontains
and the nonpolar structure of ELO. The ends of the CAP backbone have both thiol and hydroxyl
polypropoxy segments
nonpolar
moieties, opening that improve
structure of ELO.
several possiblethe compatibility
The ends of between
the CAP backbone
reactions with ELO and
have the
bothpolar
HU components structure
thiol and
3). of humins and the
hydroxyl
(Figure
moieties,
opening several possible reactions with ELO and HU components (Figure 3).
nonpolar structure of ELO. The ends of the CAP backbone have both thiol and hydroxyl moieties,
opening several possible reactions with ELO and HU components (Figure 3).

Figure 3. Capcure 3-800 structure.

Figure 3. Capcure 3-800 structure.
In a previous study, we proved for the first time that we can prepare bioresins by incorporating
In a previous study, we proved for the first time that we can prepare bioresins by incorporating
up to 60% weight of humins in formulations with ELO and CAP leading to resins with a bio-sourced
up to 60% weight of humins in formulations with ELO and CAP leading to resins with a bio-sourced
content up to 70% [40]. Four formulations
Figure 3. were prepared
Capcure 3-800and tested in this study, containing from 30%
structure.
content up to 70% [40]. Four formulations were prepared and tested in this study, containing from
to 60% HU, and the thermomechanical properties of obtained resins characterized, showing tan δ values
30% to 60% HU, and the thermomechanical properties of obtained resins characterized, showing tan
~10 to 60 ◦ C and Td5% values from 250 to 300 ◦ C. The hardness of the resulted materials varied
In aδfrom
previous
values from study,
~ 10 towe proved
60 °C and Td5% for the first
values from time
250 tothat weThe
300 °C. canhardness
prepare of bioresins
the resultedby incorporating
materials
between 64A and 49D, characteristic of elastomers to rigid thermosets. Starting from these preliminary
up to 60% weight
varied of humins
between 64A andin49D, formulations
characteristicwith ELO andtoCAP
of elastomers rigidleading
thermosets.to resins
results on formulation design and on thermomechanical properties of produced thermosets, the aim
Startingwith
fromathese
bio-sourced
preliminary
content up to 70% results on formulation design and on thermomechanical properties of produced
of this study[40]. Fourknowledge
is to gain formulations were mechanism
on chemical prepared and andstructural
tested inaspects
this study, containing from
of HU/ELO/CAP
thermosets,
30% to 60% the aim
HU, and the The of this study
thermomechanical is to gain knowledge
properties on chemical
of obtained mechanism and structural aspects
terpolymerization. formulation with 50% HU was selected for thisresins
study, characterized,
with the aim to keep showing
a tan
of HU/ELO/CAP terpolymerization. The formulation with 50% HU was selected for this study, with
maximal
δ values the
from humins ratio and also
~ 10 to 60 °C and Td5% values a representative proportion between the three comonomers.
from 250 to 300 °C. The hardness of the resulted materials To go
aim to keep a maximal humins ratio and also a representative proportion between the three
further within the terpolymerization mechanism, we studied in a first stage the HU/ELO, HU/CAP,
varied between
comonomers. 64AToand 49D, characteristic
go further of elastomers
within the terpolymerization to rigidwe
mechanism, thermosets.
studied in a Starting from these
first stage the
and ELO/CAP binary copolymerization by in situ FTIR spectroscopy and by reacting the formulations
preliminary
duringresults
HU/ELO,
selected on
HU/CAP,formulation
and ELO/CAP design
time and analyzing them andNMR.on Thereafter,
thermomechanical
binary copolymerization
by liquid properties
by in situ FTIR spectroscopy
the terpolymerization of by
and
formulation produced
reacting aim
thermosets, the formulations during toselected time and analyzing them by liquid NMR.and Thereafter, the aspects
was the
investigatedof this study
by rheometry is and gain
by theknowledge on of
same protocols chemical
FTIR andmechanism
NMR analyses. structural
terpolymerization formulation was investigated by rheometry and by the same protocols of FTIR and
of HU/ELO/CAP terpolymerization. The formulation with 50% HU was selected for this study, with
NMR analyses.
2. Materials and Methods
the aim to keep a maximal humins ratio and also a representative proportion between the three
comonomers.
2.1.
2. To goand
Materials
Materials further
Methodswithin the terpolymerization mechanism, we studied in a first stage the
HU/ELO, HU/CAP, and ELO/CAP
The epoxidized binary
linseed oil (ELO) wascopolymerization
obtained from Valtris byLtd.
in situ FTIR spectroscopy
as a viscous-liquid at room and by
2.1. Materials
reacting temperature,
the formulations
having aduring
viscosityselected time
of about 1200 and ELO
mPa·s. analyzing them by
has a molecular liquid
weight NMR.
of about g·mol−1
980 Thereafter, the
and The epoxidized
contains about linseed
5.5 epoxy oil (ELO)
groups, onwas obtained
average, per from Valtris
triglyceride. Ltd. as a viscous-liquid
terpolymerization formulation was investigated by rheometry and by the same protocols of FTIR and at room
temperature,
Humins having a viscosity
(HU) were provided of about 1200 mPa∙s.
by Avantium ELO has
Chemicals a molecular
as produced at weight of about
the Avantium 980plant
pilot g∙molin
−1
NMR analyses.
and contains
Geleen about 5.5 These
(Netherlands). epoxyhumins
groups,oligomers
on average, permolecular
have triglyceride.
masses that generally range from 270
to 650 g·mol−1(HU)
Humins [41]. were provided by Avantium Chemicals as produced at the Avantium pilot plant
2. Materials and (Netherlands).
in Geleen Methods These humins oligomers have molecular masses that generally range from
270 to 650 g∙mol−1[41].
2.1. Materials
The epoxidized linseed oil (ELO) was obtained from Valtris Ltd. as a viscous-liquid at room
temperature, having a viscosity of about 1200 mPa∙s. ELO has a molecular weight of about 980 g∙mol−1
Polymers 2020, 12, 1583 4 of 17

Capcure® 3-800 (CAP) is a mercaptan-terminated product used as a liquid curing agent with
unique rapid-cure characteristics for epoxy resins at ambient temperatures provided by Gabriel
Performance Products.

2.2. Samples Preparation

To prepare a resin with the maximum amount of humins we used in this study a ratio HU/
ELO/CAP of 50/37.5/12.5 (wt %). The general protocol for the preparation of resins containing humins,
Capcure, and ELO is as follows. ELO and CAP were mixed together at room temperature in the desired
proportion. Then, the mixture containing ELO and CAP was mixed with the humins preheated at 80 ◦ C.
The formulation was thoroughly mixed until a homogeneous phase was obtained. Then, the resin
mixture was poured into molds at 80 ◦ C. The curing process takes 4 h followed by post-curing 130 ◦ C
for another 3 h.
The samples for rheometry were prepared as follows. The reaction mixture was made following
the presented protocol and placed in the rheometer at 30 ◦ C. This mixture was heated from 50 to 200 ◦ C
at 0.2 ◦ C·min−1 .
The IR formulations were prepared in the above stated fashion. Then, the reactions were conducted
directly on the heating plate of the instrument, at 80 ◦ C for 4 h then at 130 ◦ C for 4 h (post curing).
In the case of the NMR samples this protocol was adapted as follows. An amount of humins was
introduced in the tube. The corresponding amounts of CAP and ELO were calculated and premixed.
The humins were then dissolved in deuterated DMSO. The sample was well homogenized prior to
add the other components. After, the sample was again homogenized using a vortex and ultrasounds.
All samples were made using a proportion of 10% (w/w) resin precursors to the DMSO. All samples
were kept, during the lengthy experiment, in an oven at a constant temperature of 80 ◦ C, in order
to respect the standard reaction conditions. They were removed only during the NMR experiments
and the time was calculated accordingly.

2.3. Experimental Techniques

Rheometry measurements were performed using an Anton Paar MCR–302 rheometer using
disposable plate–plate geometries (25 mm diameter and 1 mm gap). The measurements were carried
out at a scan rate of 0.2 ◦ C·min−1 over a temperature range 50 ◦ C to 200 ◦ C. Complex viscosity, storage
modulus (G’) and loss modulus (G”) were measured by oscillatory shear experiments with an angular
frequency of 10 rad·s−1 and a deformation of 0.2%. The temperature of crossover of the values of
storage (G’) and loss (G”) moduli was considered as the temperature of gelation (Tgel ).
FT-IR spectroscopy was used to investigate the structural changes occurred during the curing.
A Thermo Scientific Nicolet iS50 FT-IR spectrophotometer was employed in attenuated total reflectance
(ATR) mode with a PIKE GladiATR diamond crystal. The spectrum of air was recorded as background,
all the measurements being provided at 32 scans with a resolution of 4 cm−1 . The starting components
HU, ELO, CAP, the HU/ELO/CAP mixtures and thermoset material obtained following the protocol
given in Section 2.2 (curing at 80 ◦ C during 4 h and post curing at 130 ◦ C during 3 h) have been
analyzed and compared.
High resolution NMR spectra were recorded in DMSO d6, at 25 ◦ C (temperature control BCU 6.0,
BVT 3000), on a Bruker Avance DRX 500 spectrometer operating at 500.13 MHz for 1 H and 125.76 MHz
for 13 C. 1D and 2D NMR spectra were run with a direct probe head: 5 mm PADUL 13 C-1 H Z-GRD.
Spectrum calibration was performed by using DMSO d6 signal as internal reference (2.5 ppm for
1 H NMR, 39.5 ppm for 13 C NMR). Chemical shifts (δ) are expressed in parts per million (ppm)

and coupling constants (J) in Hertz. All NMR experiments were carried out using pulse sequences
supplied by the spectrometer manufacturer (Bruker–TOPSPIN 2.1).
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3. Results and Interpretations
3. Results and Interpretations
3.1. Hypothesis on HU/ELO/CAP Copolymerization Mechanism
3.1. Hypothesis on HU/ELO/CAP Copolymerization Mechanism
As humins are complex chemical compounds, the approach considered in this study is
As humins
contrary are complex
to the standard chemical
chemical compounds,
approach. the approach
Instead considered
of targeting specific in this study
reaction is contrary
by interaction
to the
of standard
specific chemical
species approach.
or function, we Instead
proposeofhere targeting
the usespecific reaction by
of unselective interaction
pathways of specific
reactions, by
species or function, we propose here the use of unselective pathways reactions,
multiple chemical connectivity implying multiple moieties. As previously mentioned, the humins by multiple chemical
connectivity
present implying nature,
a polydisperse multiple moieties.
containing As previously
reactive mentioned,alcohols,
functions comprising the humins present a
acids, aldehydes,
polydisperse nature, containing reactive functions comprising alcohols, acids,
and ketones [5]. From the standpoint of an epoxide, such as ELO, of interest are the alcohol and acid aldehydes, and
ketones [5]. From
functionalities. the standpoint
Given the fact thatofboth
an epoxide,
alcohols such as ELO,
and acids are of interest
weak are the alcohol
nucleophiles the firstand acid
step of
functionalities.
the reaction is the Given the factofthat
protonation theboth alcohols
oxirane ring toand
the acids
oxoniumare ion.
weakAnucleophiles the first
nucleophilic attack step of the
is performed
reaction
by is the protonation
both alcohol of the oxirane on
and acid functionalities ring to carbon
the the oxonium
of the ion. A nucleophilic
oxonium attack
ion. In this step,isthe
performed
oxygen
by bothbond
carbon alcohol and acid
is broken andfunctionalities on theThe
the ring is opened. carbon of the an
products, oxonium
ether inion.
the In this
case ofstep, the oxygen
alcohols and an
carbon
ester in bond
the caseis broken
of acidsand
arethe ring is
formed byopened. The products,
the elimination an ether
of a proton. Thisin mechanism
the case of alcohols and an
is presented in
ester in
Scheme 1. the case of acids are formed by the elimination of a proton. This mechanism is presented in
Scheme 1.

Scheme 1.
Scheme 1: Proposed reaction mechanism for the
the interaction
interaction between
between humins
humins and
and epoxides
epoxides function
function
from ELO.
from ELO.

From
From the standpoint of Capcure and ELO the reaction follows a standard initiation/propagation
polymerization
polymerization mechanism.
mechanism. Generally, thiol-based
thiol-based epoxy curing agents react react under basic conditions
and require
require the
the presence
presence of
of aa tertiary
tertiary amine
amine as initiator.
initiator. The tertiary amine removes the proton from
the thiol and
and the
the resulting
resultingsulfur
sulfuranion
anionattacks
attacksthetheoxirane
oxirane moiety
moiety through
through nucleophilic
nucleophilic addition.
addition. In
In
thethe particular
particular case
case of Capcure,
of Capcure, thethe amine
amine initiator
initiator is not
is not required,
required, thethe hydroxyl
hydroxyl moiety
moiety bonded
bonded to
to the
the α-carbon
α-carbon atom
atom from
from thethe thiol
thiol carbon
carbon atom
atom actsasasthe
acts theinitiator.
initiator.The
Thehydroxyl
hydroxyl function
function performs a
nucleophilic
nucleophilicattack
attackononthe
theepoxy
epoxy ring. The
ring. oxygen
The oxygen from thethe
from oxirane moiety
oxirane removes
moiety then then
removes the proton from
the proton
the
fromthiol,
the thus
thiol,ending the initiation
thus ending phase. phase.
the initiation The resulting thiol anion
The resulting thiolisanion
a strong
is a nucleophile and readily
strong nucleophile and
readily attacks the epoxy moieties. Just like in the case of the amine-initiated process, the propagation
is achieved through the removal of protons from thiol containing molecules by the resulting
negatively charged oxygen atom (Scheme 2).
Polymers 2020, 12, 1583 6 of 17

attacks the epoxy moieties. Just like in the case of the amine-initiated process, the propagation is
achieved through the removal of protons from thiol containing molecules by the resulting negatively
charged
Polymers oxygen
2020, 12, xatom (Scheme
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Polymers 2020, 12, x FOR PEER REVIEW 6 of 17

Scheme2.2:Capcure–ELO
Scheme Capcure–ELOnucleophilic
nucleophilic addition
addition to
to oxirane
oxirane ring.
ring.
Scheme 2: Capcure–ELO nucleophilic addition to oxirane ring.
OurOurexperiments
experimentsshowed showedthat thatinin
thethe specified
specified conditions
conditions nono measurable
measurable chemical
chemical reaction
reaction cancan
be
perceived Ourbetween
be perceived experiments
between
Capcure showedand that
Capcure andin humins.
humins. theHowever,
specified conditions
However,
this does no
thisnot
does measurable
not exclude
exclude chemical reaction
the possibility
the possibility can
of reactionsof
be perceived
reactions
between between between
intermediaries ofCapcure
intermediaries and
of the
the Capcure-ELO humins. However,
Capcure-ELO
reaction this does
reaction
and humins. not
andpoor
The exclude
humins. Thethe
miscibility possibility
poor
betweenmiscibility
huminsof
andreactions
between between
ELO ishumins
solved and intermediaries
by the ELO is solved
Capcure of the Capcure-ELO
by thealso
playing Capcure playing
the role reaction and humins.
also the roleagent.
of compatibilizer The
of compatibilizer poor miscibility
agent. The
The polypropoxylated
between
chains huminstoand
polypropoxylated
belonging chainsELObelonging
Capcure is
actsolved by
to the
as a phase Capcure
Capcure playing
actagent,
transition as a phasealsotransition
while the role ofagent,
presenting compatibilizer
a goodwhile agent.
presenting
reactivity The
towards a
polypropoxylated
good reactivity chains
towards belonging
ELO. The to Capcure
intermediary act as
opened a phase
ring transition
epoxide
ELO. The intermediary opened ring epoxide may readily react with the alcohol and acid moieties from may agent, while
readily presenting
react with the a
good
alcohol reactivity
and
humins’ structure. acid towards
moieties ELO.
from The intermediary
humins’ structure. opened ring epoxide may readily react with the
alcohol and acid moieties from humins’ structure.
3.2.Study
3.2. StudyofofHU/ELO/CAP
HU/ELO/CAPReactivity Reactivityand andGelation
Gelationby byRheometry
Rheometry
3.2. Study of HU/ELO/CAP Reactivity and Gelation by Rheometry
As Aswe wecan canobserve
observe in in Figure
Figure 4 by the the results
resultsofofthe
therheometry
rheometryanalysis
analysis thethereaction
reactionmixture
mixture is
As we can
ischaracterized
characterized observe
bybyhigh
high in Figure
values
valuesof G’ 4 by
of and
G’ themoduli,
G”
and G”results of the
and
moduli, also
and rheometry
by by aanalysis
a high
also value
high of the viscosity
value reaction mixture
at around
of the viscosity is
at
characterized
750
around Pa∙s.
750 by high
Increasing
Pa·s. thevalues
Increasing of G’temperature,
temperature,
the and theG” moduli,
viscosity and
thedrops also bydrops
a highwith
drastically,
viscosity value of the
three
drastically, viscosity
decades,
with atdecades,
reaching
three around
the
reaching the value of ~1.4 Pa·s at temperature above 100 C. The mixture starts to react, when heatedthe
750
value Pa∙s.
of ~Increasing
1.4 Pa∙s at the temperature,
temperature above the viscosity
100 °C. The drops
mixture
◦ drastically,
starts to with
react, three
when decades,
heated atreaching
0.2 °C/min −
at
1value of ~ 1.4 Pa∙s at temperature above 100 °C. The mixture starts to react, when heated at 0.2 °C/min −
0.2, atC/min
◦ around, 110
−1 °C. The110
at around hardening
◦ C. The of resin, given
hardening by thegiven
of resin, gel point
by theof gel
the point
system, of occurs at around
the system, occurs 125at
1, at around 110 °C. The hardening of resin, given by the gel point of the system, occurs at around 125
°C, being
around 125 taken as crossover
◦ C, being between G’
taken as crossover and G’’.
between G’WeandcanG”.observe
We can by the shape
observe by the ofshape
the curves
of theand by
curves
and by the fast increase of the viscosity that the reaction occurs fast, being completed at around 180 ◦by
°C,
the being
fast taken
increase as
of crossover
the viscositybetween
that theG’ and G’’.
reaction We
occurscan observe
fast, being by the shape
completed at of the
around curves
180 and
°C. C.
the fast increase of the viscosity that the reaction occurs fast, being completed at around 180 °C.
G'
G''
105 G'
Viscosity 105
5
G''
10 Viscosity 105
4
10 104
4
10 104
s) s)
(Pa·

3
103
G'' (Pa)

10
(Pa·

3
103
G', (Pa)

10
Viscosity

2
10 102
Viscosity
G', G''

2
10 102
1
10 101
1
10 101
0
10 100
0
10 100
-1
10 10-1
-1 40 60 80 100 120 140 160 180 200
10 10-1
40 60 80 Temperature
100 120 (°C)140 160 180 200
Temperature (°C)
Figure 4. Rheometry study of HU/ELO/CAP during copolymerization. Evolution of moduli and
Figure 4. Rheometry study of HU/ELO/CAP during copolymerization. Evolution of moduli and viscosity.
Figure 4. Rheometry study of HU/ELO/CAP during copolymerization. Evolution of moduli and
viscosity.
viscosity.
3.3. Infrared Spectroscopies Study on HU/ELO/CAP Copolymerization System
3.3. Infrared Spectroscopies Study on HU/ELO/CAP Copolymerization System
In order to validate the hypothesis presented for the copolymerization mechanism, infrared
In orderwas
spectroscopy to validate
employed theunder
hypothesis presented
the exact for the copolymerization
copolymerization mechanism,
conditions. The spectra of the infrared
starting
spectroscopy was employed under the exact copolymerization
materials, humins, Capcure, and ELO are presented in Figure 5. conditions. The spectra of the starting
 Polymers 2020, 12, 1583 7 of 17

3.3. Infrared Spectroscopies Study on HU/ELO/CAP Copolymerization System

In order to validate the hypothesis presented for the copolymerization mechanism, infrared
spectroscopy was employed under the exact copolymerization conditions. The spectra of the starting
Polymers 2020, 12, x FOR PEER REVIEW 7 of 17
materials, humins, Capcure, and ELO are presented in Figure 5.

Figure 5. FTIR spectra of the starting materials.

Figure 5. FTIR spectra of the starting materials.
The reaction was studied in situ at a temperature program mirroring the experimental conditions
as described
The in Section
reaction 2.2. Spectra
was studied inwere
situcollected at fixed intervals
at a temperature of time tomirroring
program monitor thethe
modifications
experimental
in the signal. These results are presented in Figure 6a and summarized in Table S1.
conditions as described in Section 2.2. Spectra were collected at fixed intervals of time to monitor the
By analyzing the IR spectra three conclusions can be drawn. Firstly, the copolymerization took
modifications in the signal. These results are presented in Figure 6a and summarized in Table S1.
place, fact sustained by the multiple modifications in the spectra. Secondly, the chemical structures of
the starting materials present multiple bands representing the same type of chemical bonds with a
large amount of overlap between the bands, with many of them being present in the starting materials,
in the intermediaries, and in the final product. Therefore, one can draw only qualitative information
from the FTIR experiment. Thirdly, the most relevant modifications in the IR spectra are found in
the carbonyl area, between 1720 and 1660 cm−1 . While the attribution of individual bands is impossible
due to the multitude of carbonyl moieties, found particularly in the humins, a trend is displayed.
In the initial spectra, an envelope of all carbonyl moieties is observed (Figure 6b), representing an
average of all the bands. However, as the chemical reaction takes place, several smaller signals become
more and more apparent. These bands correspond to specific aldehyde, ester, and α, β- unsaturated
ketones. This segregation of signals is a strong indicator of the passage from the structure specific to
humins, towards a more organized structure of a resin. The limits of the sensibility of this method being
clear, a more sensitive method—NMR—was employed to provide supplementary structural data.
 Figure 5. FTIR spectra of the starting materials.

The reaction was studied in situ at a temperature program mirroring the experimental
Polymers 2020, 12, 1583 8 of 17
conditions as described in Section 2.2. Spectra were collected at fixed intervals of time to monitor the
modifications in the signal. These results are presented in Figure 6a and summarized in Table S1.

Figure 6. (a)
Figure and
6. (a) (b):(b):
and FTIR spectra
FTIR spectrapresenting thethe
presenting evolution of of
evolution thethe
HU/ELO/CAP copolymerization
HU/ELO/CAP copolymerization
reaction over time (a) and detail of the carbonyl area (b).
reaction over time (a) and detail of the carbonyl area (b).
3.4. NMR Spectroscopy Studies

3.4.1. Characterization of the Components of Copolymerization System ELO

At 25 ◦ C, 1D and 2D NMR analyses allowed us to identify the structure of ELO (Figure S1a–f).
The obtained results are summarized in Table 1 and are in good agreement with previous reported
data [42].

Table 1. 1 H and 13 C NMR (DMSO d6) Assignments of ELO.

13 C 1H
Signal Structure
δ ppm δ ppm
aE 13.75–13.93 0.81–0.88 CH3 –(CH2 )3 -
bE 10.23–10.55 0.93–0.99 CH3 –CH2 -epoxide
21.94–22.17
cE 28.14–29.15 1.18–1.33 (CH2 ) β group (epoxide, carbonyl)
31–31.4
20.51–20.74
dE 25.51–26.15 1.34–1.47 (CH2 ) α group (epoxide, carbonyl)
27–27.43
eE 24.23–24.51 1.47–1.55 (CH2 ) β group (carbonyl)
fE 33.20–33.50 2.21–2.31 –CH2 –C=O
gE 57.22–53.15 2.84–3.12 CH epoxide
hE 26.26–26.63 1.56–1.88 (CH2 ) α, α’ epoxide
iE 172.01–172.57 / C=O
jE 61.75 4.29–4.77 –CH2 –O
kE 68.73 5.14–5.21 O–CH–(CH2 –O)2
Polymers 2020, 12, 1583 9 of 17

Briefly, the resonance frequency of CH2 –eE were attributed by corroborating the presence of
correlation in COSY experiment between CH2 –fE (δH = 2.21–2.31 ppm) and CH2 –eE (δH = 1.47–1.55 ppm).
CH2 - hE are more deshielded due to the presence of two epoxides groups in α and α’ positions.
This fact is confirmed in COSY and TOCSY experiments by the presence of correlations between
methylene proton hE (δH between 1.56 ppm and 1.88 ppm) and CH–gE proton (δH between 2.84 ppm
and 3.12 ppm). 2D NMR also allow us to detect the presence of methyne resonance peak (δH = 5.54 ppm,
δC = 126.57 ppm) indicating the presence of some residual double bonds in ELO sample [43].

3.4.2. Capcure
Capcure is a reaction product of pentaerythritol, propoxylated, and 1-chloro-2,3-epoxypropane
with hydrogen sulphide. At 25◦ C, 1D and 2D NMR experiments (Figure S2a–f) permitted us to
identify the different elements of this compound and in particular his reactive part: 3-mercapto-2
propanoyl residue. The results are presented in Table 2. Briefly, we can see in TOCSY experiment a
correlation between the thiol proton SH-1c (δH = 2.08 ppm) and the methylene proton 2c in α position
(δH = 2.47 ppm, δH = 2.61 ppm), the CH-3c proton in β position (δH = 3.60 ppm), the hydroxyl proton
4c (δH = 4.91 ppm) and the methylene proton 5c in γ position (δH = 3.58 ppm). NMR experiments
also show the presence of other resonance frequencies together with those of the main product.
Different conformers of the main product in solution, non-functionalized compounds, by-product,
or rearrangement product are hard to distinguish. In order to know how many reactive groups are
per molecule we integrated the signals of hydrogen sulphur (δH = 2.09 ppm – triplet) and all the 1 H
signals corresponding to methyl proton (δH = 1.042 ppm – m). The ratio gives a result between 1/5 (big
doublet centered at 1.04 ppm) and 1/7 (all the 1 H signal corresponding to methyl proton). Normally,
if the entire site is functionalized, we should have a ratio of 4/15. This result indicates that we have
approximatively a functionalization ranging between 53% and 75% that means around 2 and 3 reactive
groups (3-mercapto-2 propanoyl residue) per molecule.

Table 2. 1 H and 13 C NMR (DMSO d6) assignments of Capcure; R1 = CH2 –O–CH2 –CH(CH3 )
–O–CH2 –CH(OH)–CH2 –SH.

Signal δ ppm 1 H δ ppm 13 C Structure

1c 2.08 (t) / SH
2c 2.47 (m); 2.61 (m) 28.07 CH2 –SH
3c 3.85 (m) 70.9 CH–OH
4c 4.91 / OH
77.06–74.73 *
5c 3.58 (m) 73.7–69.92 * HO–CH–CH2 –O
69.88–69.38 *
6c 3.68 (m); 3.52(m) 64.96; 74.47 CH–CH3
7c 1.02 (m); 1.04 (m) 20.35; 17.24 CH3 –CH
77.06–73.73 *
8c 3.23; 3.33 73.7–69.92 * CH3 –CH–CH2 –O
69.88–69.38 *
77.06–74.73 *
9c 3.342 73.7–69.92 * (R1)3 –C–CH2 –O
69.88–69.38*
10c / 45.27 (R1)3 –C–R1

3.4.3. Humins
Humins are complex by product of biorefining process aimed at the valorization of lignocellulosic
biomass [44]. The 1 H and 13 C NMR spectra and the corresponding peaks and area assignments
are shown in Figure 7 and Figure S3a–f. As we can see in the NMR spectra, the humins cover a
wide range of frequency domain from 9.8 to 0.9 ppm for proton and from 210 to 10 ppm for carbon.
This result confirms the fact that humins are a mixture containing different molecular structures
Polymers 2020, 12, 1583 10 of 17

Polymers 2020, 12, x FOR PEER REVIEW 10 of 17

characterized by the presence of carbonyl like ketones (δC = 210 ppm), aldehydes (δC = 178.1 ppm,
δH = 9.5 ppm), acids or esters δC = 173.9 ppm). We can also notice the presence of alkenes δC from
ppm, δH = 9.5 ppm), acids or esters δC = 173.9 ppm). We can also notice the presence of alkenes δC
162.3 to 109.78 ppm and δH from 7.5 to 6.5 ppm). These functions can be part of a ring like furan or
from 162.3 to 109.78 ppm and δH from 7.5 to 6.5 ppm). These functions can be part of a ring like furan
of an alkene segment linking the furanic rings. The presence of a high field sp33 CH (between 104
or of an alkene segment linking the furanic rings. The presence of a high field sp CH (between 104
and 70 ppm) and CH (between 72 and 50 ppm) suggests the existence of strong electron withdrawing
and 70 ppm) and CH22 (between 72 and 50 ppm) suggests the existence of strong electron withdrawing
groups like oxygen in α and/or α’ positions (O–C–O or C–OH, C–O–C). This fact is not surprising if we
groups like oxygen in α and/or α’ positions (O–C–O or C–OH, C–O–C). This fact is not surprising if
consider the carbohydrate origin of humins.
we consider the carbohydrate origin of humins.

Figure
Figure 7. (A) 11H
7. (A) H NMR
NMR Spectrum
Spectrum of
of HU
HU (DMSO
(DMSO d6);
d6); (B) 13 C NMR Spectrum of HU (DMSO d6).
(B) 13 C NMR Spectrum of HU (DMSO d6).
3.4.4. Copolymerization Process
3.4.4. Copolymerization Process
To study the terpolymerization reaction of humins with Capcure and ELO, the three products
To study the terpolymerization reaction of humins with Capcure and ELO, the three products
were firstly individually solubilized in DMSO-d6 at room temperature and the resulting solution was
were firstly individually solubilized in DMSO-d6 at room temperature and the resulting solution was
heated at 80 ◦ C for 90 h (Figure S4a–b, Figure S5a–b and Figure S6a–b). Thereafter, samples collection
heated at 80 °C for 90 h (Figures S4a-b, Figures S5a-b, Figures S6a-b). Thereafter, samples collection
of the reaction mixtures prepared in the same conditions (80 ◦ C for 90 and supplementary 446 h)
of the reaction mixtures prepared in the same conditions (80 °C for 90 and supplementary 446 h) were
were analyzed by 1D and 2D NMR spectroscopies (Figure S10a–f, Figure S11a–f and Figure S12a–f).
analyzed by 1D and 2D NMR spectroscopies (Figures S10a-f, Figures S11a-f, Figures S12a-f). Until
Until 398 h, of reaction all the samples were liquid, and no precipitate appears upon cooling from
398◦h, of reaction all the samples were liquid, and no precipitate appears upon cooling from 80 °C to
80 C to room temperature. After 398 h, the samples become viscous at 25 ◦ C and no more liquid
room temperature. After 398 h, the samples become viscous at 25 °C and no more liquid high-
high-resolution NMR experiment could be done.
resolution NMR experiment could be done.
Considering the ELO structure, major changes arise in NMR spectra as the copolymerization
Considering the ELO structure, major changes arise in NMR spectra as the copolymerization
process occurs. As we can see in 1 H (Figure S11a) and in 13 C (Figure S11b) spectra, the resonance
process occurs. As we can see in 1H (Figures S11a) and in 13C (Figures S11b) spectra, the resonance
frequencies of signals corresponding to methyl bE , methylene dE , methylene hE , and methyne gE shifts,
frequencies of signals corresponding to methyl bE, methylene dE, methylene hE, and methyne gE shifts,
decrease in intensity, and/or become broader. We can also note that, the resonance peaks belonging to
decrease in intensity, and/or become broader. We can also note that, the resonance peaks belonging
methylene eE , fE , jE , methyne kE , and carbonyl iE remain and/or become broader. These results highlight
to methylene eE, fE, jE, methyne kE, and carbonyl iE remain and/or become broader. These results
the opening of epoxides groups during the copolymerization process and the fact that the glycerol part
highlight the opening of epoxides groups during the copolymerization process and the fact that the
of ELO is conserved. 2D HMBC experiment shown in Figure 8 indicates that the opening of epoxide
glycerol part of ELO is conserved. 2D HMBC experiment shown in Figure 8 indicates that the opening
ring leads to new correlation peak between proton hE , eE, dE cE, bE , and carbon resonance peaks (CH)
of epoxide ring leads to new correlation peak between proton hE, eE, dE cE, bE, and carbon resonance
ranging from 73.2 to 97.52 ppm.
peaks (CH) ranging from 73.2 to 97.52 ppm.
Polymers 2020, 12, 1583 11 of 17
Polymers 2020, 12, x FOR PEER REVIEW 11 of 17

Figure
Figure 8. 2D
8. 2D HMBC
HMBC NMRNMR experiments:
experiments: redred HU/ELO/CAP
HU/ELO/CAP = 0,
at t at t =black
0, black HU/ELO/CAP
HU/ELO/CAP after
after 398398
H atH at
◦
80 80C. °C.

In order to goto
In order deeper inside the
go deeper copolymerization
inside process, weprocess,
the copolymerization mixed 2we by 2mixed
the start
2 comonomers.
by 2 the start
Three reaction mixtures
comonomers. (ELO +
Three reaction HU, CAP
mixtures (ELO + +HU, CAP++ HU,
HU,ELO CAP)ELOwere solubilized
+ CAP) in DMSOind6DMSO
were solubilized in
thed6 same proportion as in initial terpolymerization mixture (ELO + CAP + HU) at
in the same proportion as in initial terpolymerization mixture (ELO + CAP + HU) at room room temperature
andtemperature
the resultingand solutions were solutions
the resulting 80 ◦ Cheated
heated at were duringat398 h. during
80 °C Sample398 collections
h. Sample were analyzed
collections were
through
analyzed1D and
through2D NMR1D and experiments at 298K (Figure
2D NMR experiments S7a–f,
at 298K Figure
(Figures S8a–f
S7a-f, and Figure
Figures S9a–f)All
S8a-f, Figures S9a-
thef)All
samples were liquid and no precipitate appears upon cooling to room temperature,
the samples were liquid and no precipitate appears upon cooling to room temperature, indicating in a
firstindicating
observationin athat noobservation
first copolymerization
that nooccurred in the analyzed
copolymerization bi-component
occurred mixtures.
in the analyzed bi-component
mixtures.
3.4.5. ELO Reactivity with the HU
3.4.5.
FigureELOS9a,b
Reactivity
represent the1HU
withthe H and 13 C NMR data obtained for the mixture of HU and ELO
at t = 0 Figure
and after S9a 90and at 80 ◦ C
h Figure S9bin represent
DMSO. We thecan firstly
1H and 13Cobserve
NMR data thatobtained
the glycerol part
for the of ELOofisHU
mixture
conserved.
and ELO at t = 0 and after 90 h at 80 °C in DMSO. We can firstly observe that the glycerol decrease
We can also detect that changes occurs in the ELO’s structure, particularly the part of ELO
in intensity and shift to height or lower field of the resonance peaks
is conserved. We can also detect that changes occurs in the ELO’s structure, particularly the of the epoxide ring (CHg E)
decrease
andinthose in α or β positions (CH 2 d E , CH 2 hE , CH 2 c E , and CH 3 b E ). These
intensity and shift to height or lower field of the resonance peaks of the epoxide ring (CHgE) and changes are also noted in
2D those
NMRinexperiments:
α or β positions in TOCSY
(CH2dE,(Figure
CH2hE, 9) CH we can observe new correlation spots between proton
2cE, and CH3bE). These changes are also noted in 2D NMR
in αor β positionin
experiments: ofTOCSY
epoxide(Figure
ring (CH 9)2wedE , CH hE , CH2 cnew
can2observe E , and CH3 bE ) and
correlation more
spots deshielded
between proton protons
in αor β
identified in HSQC (Figure 10) as methylene proton (δH = 2.49 ppm,
position of epoxide ring (CH2dE, CH2hE, CH2cE, and CH3bE) and more deshielded protons identified δ C = 37 ppm) and methyne
proton
in HSQC(δH =(Figure
3.20 ppm, = 57 ppm or/and
δCmethylene
10) as proton 71 δHppm),
= 2.49 (δ H =δ
ppm, 3.34 ppm, δ = 54 ppm or/and 72 ppm),
C = 37 ppm)Cand methyne proton δH = 3.20
= 3.87
(δHppm, δCppm, δC = or/and
= 57 ppm 76–77 ppm)).
71 ppm), In δ
HMBC (Figure 11), new correlations appear between CH3 bEδC =
H = 3.34 ppm, δC = 54 ppm or/and 72 ppm), (δH = 3.87 ppm,
and76CHppm – 77 ppm)). In HMBC (Figure 11), new ppm,
resonance peaks at 68.1–74.4–77.79–84.82 CH2 dEappear
correlations and CHbetween
resonance
CHpeaks at 76.28 ppm.
3bE and CH resonance
Also, HMBC
peaks let us
at 68.1 identify
– 74.4 the –formation
– 77.79 84.82 ppm, of carbonyl
CH2dE and function through the
CH resonance correlation
peaks at 76.28 between
ppm. Also, CHHMBC
3 bE,
CHlet
2 dEus
, CH 2 (δH = 2.48 ppm, δ C = 37.1 ppm—non identified), and 13 C resonance at 213.77 ppm.
identify the formation of carbonyl function through the correlation between CH3bE, CH2dE, CH2
(δH = 2.48 ppm, δC = 37.1 ppm – non identified), and 13C resonance at 213.77 ppm.
 Polymers 2020, 12, 1583 12 of 17
Polymers 2020, 12, x FOR PEER REVIEW 12 of 17

Polymers 2020, 12, x FOR PEER REVIEW 12 of 17

HU +++ELO atattt = ++ELO

9.9.2D TOCSY NMR experiments: ◦
Figure
Figure
Figure 9. 2D 2D TOCSY
TOCSY NMR
NMR experiments:red:
experiments: red: HU
red: HU ELOat
ELO 0,black
=0,
t =0,blackHU
blackHU
HU +ELO after9090hhatat8080°C.C.
after
ELO after 90 h at 80 °C.

Figure 10.
Figure 2D HSQC
10. 2D HSQC NMR
NMR experiments: HU ++ELO
experiments: HU ELOafter
after90
90 hh at
at 80 ◦ C; Arrows indicate the chemical
80 °C; Arrows indicate the chemical
shifts of
shifts of the
the carbon
carbon that
that we
we identified
identified by
by the
the new
new correlation
correlation in
in TOCSY.
TOCSY.

Figure 10. 2D HSQC NMR experiments: HU + ELO after 90 h at 80 °C; Arrows indicate the chemical
shifts of the carbon that we identified by the new correlation in TOCSY.
Polymers 2020, 12, 1583 13 of 17
Polymers 2020, 12, x FOR PEER REVIEW 13 of 17

Figure 11.
Figure experiments: red HU +
11. 2D HMBC NMR experiments: + ELO
ELO at t =0,0,black
at t= HU++ELO
blackHU ELOafter ◦ C.
after9090h hatat8080°C.

These results are

These areindicating
indicatingthe
thering opening
ring opening of epoxy
of epoxy groups occurs
groups whenwhen
occurs ELO is mixed
ELO and heated
is mixed and
◦
at 80 Catwith
heated 80 °Cthe humins
with sample.sample.
the humins In the literature, many nucleophilic
In the literature, groups groups
many nucleophilic [45] were used
[45] wereto used
open
the
to epoxide
open ring. Through
the epoxide 1D and
ring. Through 1D2DandNMR
2D NMR spectra the resulting
spectra products
the resulting productsareare
characterized
characterized by
the disappearance of the resonance peak of methyne belonging
by the disappearance of the resonance peak of methyne belonging to epoxide to epoxide ring and the appearance
the appearance
of new
of new resonance
resonance peaks,
peaks, more deshielded δ
more deshielded (δHH ==3.1
3.1ppm
ppm–– 4.6 ppm, δδCC ==70.5
4.6 ppm, 70.5ppm
ppm––84.4 84.4ppm),
ppm),
corresponding to secondary alcohol and methyne ether residue [42,46]. Zandvoort
corresponding to secondary alcohol and methyne ether residue [42,46]. Zandvoort et al. [5] indicate et al. [5] indicate
that humins
that huminsby-product
by-productareare polydisperse
polydispersesample composed
sample composedof soluble monomers
of soluble and/or low
monomers molecular
and/or low
weight macromonomers
molecular together with
weight macromonomers some with
together insoluble
somepolymers
insolublestructure.
polymersThe openingThe
structure. of the epoxide
opening of
seems to be due to functional groups present in HU: i.e., –OH, –C=O, CH=O,
the epoxide seems to be due to functional groups present in HU: i.e., –OH, –C=O, CH=O, –COOH. –COOH. This hypothesis
is confirmed by the new signals 1 H and 13 C NMR experiments.
This hypothesis is confirmed byobserved
the new in signals observed in 1H and 13C NMR The observed
experiments.carbonyl
The
belongs tocarbonyl
observed an ester-type
belongsmoiety
to anand could result
ester-type moietyfromandthecould
reaction of ELO
result fromwith –COOH moieties
the reaction of ELO with found–
in the humins.
COOH moieties found in the humins.

3.4.6.Capcure
3.4.6. CapcureReactivity
Reactivitywith
withthe
theHU
HU
Figure S8a
S8a,b display 1 and 13 C NMR data obtained for the mixture of humins and Capcure
Figure and Figurethe
S8bH display the 1H and 13C NMR data obtained for the mixture of humins
at t = 0 and after 90 h at 80 ◦ C in DMSO. No changes are observed indicating that in the conditions of
and Capcure at t= 0 and after 90 h at 80 °C in DMSO. No changes are observed indicating that in the
our experiment
conditions of ourthe Capcure did
experiment the not react with
Capcure thereact
did not humins
withsample.
the humins sample.
3.4.7. ELO Reactivity with the Capcure
3.4.7. ELO Reactivity with the Capcure
Figure S7a,b illustrate the 1 H and 13 C NMR spectra for the mixture of ELO and Capcure at t = 0
Figure S7a and◦ Figure S7b illustrate the 1H and 13C NMR spectra for the mixture of ELO and
and after 90 h at 80 C in DMSO. As shown in Figure S5a–b, we can notice that the glycerol part of ELO
Capcure at t= 0 and after 90 h at◦80 °C in DMSO. As shown in Figures S5a-b, we can notice that the
is conserved when heated at 80 C. We can also highlight that changes occurs for ELO in particularly
glycerol part of ELO is conserved when heated at 80 °C. We can also highlight that changes occurs
the resonance peaks of the epoxide ring (CHg ) and those in α or β positions (CH d , CH2 hE , CH2 cE ,
for ELO in particularly the resonance peaks ofE the epoxide ring (CHgE) and those2inEα or β positions
and CH3 bE ) that decrease in intensity and are shifted to higher or lower field. The HSQC and HMBC
(CH2dE, CH 2hE, CH2cE, and CH3bE) that decrease in intensity and are shifted to higher or lower field.
2D NMR experiments (Figures 12 and 13) permit us to identify new correlations between CH3 bE
The HSQC and HMBC 2D NMR experiments (Figure 12 and 13) permit us to identify new correlations
and CH resonance peaks at 73, 74.5, 75.6, and 83.95 ppm; the CH2 resonance at 75.52–77.39 ppm,
between CH3bE and CH resonance peaks at 73, 74.5, 75.6, and 83.95 ppm; the CH2 resonance at 75.52–
CH dE and CH2 resonance peaks at 70.58 ppm; CH resonance peaks at 84.11 ppm, CH2 hE and CH
77.392 ppm, CH2dE and CH2 resonance peaks at 70.58 ppm; CH resonance peaks at 84.11 ppm, CH2hE
resonance peaks at 70.99–82.25 ppm. These results are indicating the opening of the epoxide rings in
and CH resonance peaks at 70.99–82.25 ppm. These results are indicating the opening of the epoxide
presence of CAP at 80 ◦ C. Potentially the opening is possible through OH and/or SH reactive groups of
rings in presence of CAP at 80 °C. Potentially the opening is possible through OH and/or SH reactive
groups of CAP. In our case, we can observe the disappearance of the resonance of thiol proton. On
Polymers 2020, 12, 1583 14 of 17

Polymers 2020, 12, x FOR PEER REVIEW 14 of 17

CAP. In2020,
Polymers our case, we PEER
12, x FOR can observe
REVIEW the disappearance of the resonance of thiol proton. On the other14 hand,
of 17
we cannot see, qualitatively, changes in intensity of alcohol proton belonging to CAP. Together
the other hand, we cannot see, qualitatively, changes in intensity of alcohol proton belonging to CAP. with
the other
the hand, wethat
consideration cannot see, qualitatively,
the nucleophilicity changesisinhigher
intensity
thatofthe
alcohol proton belonging to CAP.
Together with the consideration that theofnucleophilicity
sulphur of sulphur oxygen one
is higher [46–48],
that these
the oxygen facts
one
Together
are in with
favor of the
the consideration
preferential that
opening the
of nucleophilicity
epoxide ring by of sulphur
thiol group. is higher that the oxygen one
[46,47,48], these facts are in favor of the preferential opening of epoxide ring by thiol group.
[46,47,48], these facts are in favor of the preferential opening of epoxide ring by thiol group.

Figure 12. 2D HSQC NMR experiments red: CAP+ ELO at t = 0, black CAP + ELO at t = 90 h at 80 ◦°C.
Figure
Figure 12. 2D HSQC
12. 2D HSQC NMR
NMR experiments
experimentsred:
red: CAP+
CAP+ ELO at tt == 0,
ELO at 0, black CAP +
black CAP at tt =
ELO at
+ ELO 90 h
= 90 h at
at 80
80 °C.
C.

Figure 13. 2D HMBC NMR experiments red CAP+ ELO at t = 0, black CAP + ELO at t = 90 h at 80 ◦ C.
Figure 13. 2D HMBC NMR experiments red CAP+ ELO at t = 0, black CAP + ELO at t = 90 h at 80 °C.
Figure 13. 2D HMBC NMR experiments red CAP+ ELO at t = 0, black CAP + ELO at t = 90 h at 80 °C.
Polymers 2020, 12, 1583 15 of 17

4. Conclusions
In this work, the pathways of terpolymerization between humins, Capcure, and ELO were
investigated. Our study showed that, in solution, ELO manifests reactivity towards humins. Moreover,
in a binary mixture, Capcure does not manifest reactivity towards the humins. NMR studies have
confirmed the reaction mechanisms proposed both in the case of humins/ELO mixtures as well
as in the case of Capcure/ELO. The entirety of the terpolymerization could not be completely
assessed. The complexity of the spectra did not allow for the assessment of the reactivity presented by
the intermediaries of the Capcure–ELO reaction towards humins. The same experiment was performed
via rheology and IR spectroscopy. The employment of these methods in real time through the course
of the polymerization provided supplementary information both about the chemical modifications
through the formation of the material, as well as about the physical parameters of the polymerization.
Since the use of technical grade starting materials (humins) raises new challenges in terms of
the characterization of the chemical copolymerization reaction, this study provides suggestions on
the strategy and approach for this type of materials synthesis, as well as for appropriate means of analysis.
As the push for eco-friendly materials becomes more urgent than ever, flexible reactions—applied to
by-products as starting materials—will become more enticing and pervasive.

Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4360/12/7/1583/s1,

Figure S1a–f: 1D and 2D NMR data for ELO; Figure S2a–f: 1D and 2D NMR data for Capcure; Figure S3a–f: 1D
and 2D NMR data for Humins; Figure S4a–b: 1D NMR data for Humins after 90 H at 353 K; Figure S5a–b: 1D NMR
data for ELO after 90 H at 353 K; Figure S6a–f: 1D NMR data for Capcure after 90 H at 353 K; Figure S7a–f: 1D NMR
data for Capcure + ELO after 90 H at 353 K; Figure S7a–f: 1D NMR data for Capcure + ELO after 90 H at 353 K;
Figure S8a–f: 1D NMR data for Capcure + Humins after 90 H at 353 K; Figure S9a–f: 1D NMR data for ELO + Humins
after 90 H at 353 K; Figure S10a–f: 1D NMR data for ELO + Humins + Capcure; Figure S11a–f: 1D NMR data for
ELO +Humins+ Capcure after 90 H at 353 K; Figure S12a–f: 1D NMR data for ELO + Humins + Capcure after
238 H at 353 K; Table S1: IR attributions of the signals found in the spectra.
Author Contributions: Conceptualization and Methodology, A.M.; The manuscript was written by E.L., M.G.
and A.M., M.G. did and analyzed the NMR experiments. E.L. performed and analyzed the FTIR and rheometry
experiments. The results were discussed by all the authors which have given approval to the publication of
the manuscript. A.M. corrected and worked the final version of the manuscript. All authors have read and agreed
to the published version of the manuscript.
Funding: This research was funded by Life program, grant number LIFE15 ENV/BE/000204, through
the “Recysite“ project.
Acknowledgments: The authors gratefully acknowledge the European commission for support through
the financial aid.
Conflicts of Interest: The authors declare no conflict of interest.

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