Synthesis of Main Chain Polymeric Benzophenone Photoinitiator via

Thiol-ene Click Chemistry and Its Use in Free Radical Polymerization

GOKHAN TEMEL,1,2 NURCAN KARACA,2 NERGIS ARSU2

1
Department of Polymer Engineering, Faculty of Engineering, Yalova University, Yalova 77100, Turkey
2
Department of Chemistry, Yildiz Technical University, 34210 Davutpasa, Istanbul, Turkey

Received 10 August 2010; accepted 19 August 2010

DOI: 10.1002/pola.24330
Published online 13 October 2010 in Wiley Online Library (wileyonlinelibrary.com).

ABSTRACT: Main chain polymeric benzophenone photoinitiator PBP was found as 250 ns. The photoinitiation efficiency of PBP
(PBP) was synthesized by using ‘‘Thiol-ene Click Chemistry’’ was determined for the polymerization of Hexanedioldiacrylate
and characterized with 1H NMR, FTIR, UV, and phosphores- (HDDA) with PBP and BP in the presence of a coinitiator
cence spectroscopies. PBP as a polymeric photoinitiator pre- namely, N-methyldiethanolamine (MDEA) by Photo-DSC. The
sented excellent absorption properties (e294 ¼ 28,300 mol
1 L
1 initiation efficiency of PBP for polymerization of HDDA is much
cm
1) compared to the molecular initiator BP (e252 ¼ 16,600 higher than for the formulation consisting of BP. V C 2010 Wiley

mol
1 L
1 cm
1). The triplet energy of PBP was obtained from Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5306–
the phosphorescence measurement in 2-methyl tetrahydrofur- 5312, 2010
ane at 77 K as 298.3 kJ/mol and according to phosphorescence
lifetime, the lowest triplet state of PBP has an n-p* nature. Tri- KEYWORDS: benzophenone; click chemistry; photopolymeriza-
plet–triplet absorption spectrum of PBP at 550 nm following tion; photochemistry; polymeric photoinitiator; radical poly-
laser excitation (355 nm) were recorded and triplet lifetime of merization; thiol-ene

INTRODUCTION Photopolymerization processes receive con- meric photoinitiators and of photoproducts means that cured
tinuous interest because of their wide application in UV-cur- coatings are less prone to yellowing.12,13
able coatings, printing inks, photoresist, and microelec- In our previous studies, to overcome some of the problems,
tronics. Free radical photoinitiators can be classed as a- we successfully synthesized novel side chain thioxanthone
cleavage (Type I) and H-abstraction (Type II) initiators. Free and benzophenone containing polystyrene based polymeric
radical generation process is H-abstraction reaction of tri- photoinitiators and they were used as polymeric photoinitia-
plet photoinitiator from hydrogen donors such as amines tors in free radical polymerization.5,6,10,14–16
and alcohols. The radical derived from the donor can initiate
the polymerization while ketyl radicals stemming from aro- Over the last decade, efficient and versatile cross reactions such
as radical coupling reactions,14,17,18 click chemistry,5,16,19–32
matic carbonyl compound are usually not reactive toward
diels alder reactions,5,33,34 thio-bromo click reaction,35–37 etc.,
vinyl monomers due to bulkiness and/or the delocalization
have been used to obtain functional polymers in quantitative
of the unpaired electrons. The overall process is depicted on
yield. Cu (I) catalyzed 1,3-Huisgen dipolar cycloaddition is the
the example of benzophenone in Scheme 1.
most widely used reaction to synthesize telechelic poly-
There have been many new developments in synthesis and mers,26,27 functional dendrimers,23,38,39 hyperbranched poly-
photochemical studies of novel polymeric photoinitiators. mers,40 biopolymers,41 polymeric photoinitiators5,16 and so on.
Polymeric photoinitiators have attracted much attention in High temperature conditions or the requirement of metal cata-
recent years for they combine the properties of polymers lysts, which generally need to be removed by various purifica-
with those of low molecular weight photoinitiators.1–11 Solu- tion methods after the reaction, are the only deterrents of the
bility and miscibility problems, often observed with coatings click method. Recently, thiol-ene chemistry has appeared as a
containing low molecular weight photoinitiators, do not new type of click chemistry method in the absence of a toxic
occur with the polymeric ones since polymers are easily mis- metal catalyst.20,42 Thiol-ene click chemistry has been success-
cible with the resin to be cured as well as with the final fully employed to synthesize biomaterials,43,44 star polymers,45
cured film. Moreover, odor and toxicity problems do not crosslinked materials,42,46,47 and UV-curable coatings.42,48,49
occur with macrophotoinitiators owing to the low volatility However, thiol-ene reactions can be initiated photochemically
of the large molecules. The low migration tendency of poly- or thermally in the presence of a photo or thermal initiator.20,42

Correspondence to: G. Temel (E-mail: [email protected]) or N. Arsu (E-mail: [email protected])

Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 48, 5306–5312 (2010) V
C 2010 Wiley Periodicals, Inc.

5306 WILEYONLINELIBRARY.COM/JOURNAL/JPOLA
 ARTICLE

the basic alumina just before use. All other reagents were pur-
chased from Aldrich and Merck and used as received.

Synthesis of Diallyl Benzophenone (BP-Al)

A solution of 4,40 -dihydroxybenzophenone (1 g, 4.67 mmol)
and anhydrous potassium carbonate (1.6 g, 12 mmol) in 30
mL of acetone was stirred for 6 h. After that, allyl bromide
(1.32 g, 11 mmol) was added and the mixture was refluxed
for 24 h. Acetone was removed on the rotary evaporator, and
the residue was diluted with dichloromethane and washed
with water. Then, it was dried over Na2SO4. The crude prod-
uct was recrystallized from ethanol (yield 75%).
GC-MS (70 eV) m/e: 294 (Mþ). ELEM. ANAL. for C19H18O3
(294.13 g mol
1): Calc., C, 77.53%; H, 6.16%; Found, C,
77.49%; H, 6.09%. IR (ATR): m (cm
1) 3069 (CAH, aro-
SCHEME 1 Photoinduced radical polymerization mechanism of ¼O, ketone), 1599
matic), 2930 (CAH, aliphatic), 1636 (C¼
benzophenone in the presence of a coinitiator. ¼C, aromatic) cm
1.
(C¼
1
H NMR (CDCl3 250 MHz): d ¼ 7.78-7.75 (d, 4H, aromatic),
In this study, we used the thiol-ene click chemistry method 7.24-6.97 (d, 4H, aromatic), 6.13-5.98 (m, 2H, CH), 5.46-5.29
to synthesize benzophenone based macromolecular photoini- (m, 4H, CH2), 4.61-4.59 (d, 4H, CH2).
tiator and it was used in photoinduced free radical polymer-
ization as the photoinitiator in the presence of a coinitiator Synthesis of Polymeric Photoinitiator with Thiol-ene
namely N-methyldiethanolamine. The main chain polymeric Click Chemistry (PBP)
photoinitiator was characterized by GPC, 1H NMR, UV, and BP-Al (0.5 g, 1.7 mmol) and a catalytic amount of AIBN (1–2%
phosphorescence spectroscopy and the monomer conver- w/w) were dissolved in 3 mL of DMF in a Schlenk tube and
sions and rate of polymerization of diacrylate monomer the solution was bubbled with argon for 15 min. 1, 2-ethanedi-
were also determined by Photo-DSC experiments in air and thiol (1.7 mmol, 143 lL) was added to this solution and the
nitrogen atmospheres. solution was bubbled for another 5 min with argon. After that
tube was kept under argon and stirred at 85  C for 24 h. At
the end of the period, polymeric photoinitiator was isolated by
EXPERIMENTAL
two times of precipitation in excess methanol. The white prod-
Materials uct was filtered and dried in vacuo at room temperature.
2,20 -Azobis(isobutyronitrile) (AIBN, 98%, Aldrich) and Benzo- (Yield: 60%, Mn,GPC ¼ 2300 g mol
1, Mw/Mn¼ 1.28).
phenone (99%, Aldrich) were recrystallized from ethanol. 4,40 -
IR (ATR): m (cm
1) 3068 (C¼ ¼C, aromatic), 2926 (CAH, ali-
Dihydroxybenzophenone (97%, Aldrich), allyl bromide (97%,
¼C, aromatic) cm
1.
¼O ketone), 1599 (C¼
phatic), 1637 (C¼
Aldrich), 1, 2-ethanedithiol (>90%, Aldrich), and N-methyldie-
thanolamine (MDEA, 99%, Aldrich) were used as received. 1
H NMR (CDCl3 250 MHz): d ¼ 7.76-6.91 (m, 8H, aromatic),
Hexandioldiacrylate (HDDA, 93%, ABCR) was passed through 6.10-6.00 (m, 2H, CH), 5.46-5.29 (m, 4H, CH2), 4.61-4.59

SCHEME 2 Synthesis of bisallyl-

benzophenone (BP-Al) and poly-
meric photoinitiator (PBP) via
Thiol-ene click polymerization.

SYNTHESIS OF MAIN CHAIN POLYMERIC BENZOPHENONE PHOTOINITIATOR, TEMEL, KARACA, AND ARSU 5307
JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA

FIGURE 1 1H NMR spectra of BP-Al and PBP in CDCl3.

(d, 4H, CH2), 4.12 (t, 4H, CH2), 2.86-2.75 (m, 8H), 2.1-2.0 were taken on a Varian UV-Visible Carry 50 Spectrophotome-
(m, 4H). ter. Gel permeation chromatography (GPC) analyses of the
polymers were performed with a set-up consisting of a
Instrumentation pump (Waters) and four ultrastyragel columns of different
1
H NMR measurements were recorded in CDCl3 with Si porosities. Tetrahydrofuran (THF) was used as the eluent
(CH3)4 as internal standard, using a Bruker AC250 (250.133 (flow rate 0.3 mL min
1), and detection was carried out
MHz) instrument. FTIR spectra were recorded on a Perkin– with the aid of a differential refractometer. The number-aver-
Elmer FTIR Spectrum One-B spectrometer. UV-Vis spectra age molecular weights were determined using polystyrene

SCHEME 3 Photoinitiated radical

polymerization mechanism of
PBP in the presence of MDEA as
a coinitiator.

5308 WILEYONLINELIBRARY.COM/JOURNAL/JPOLA
 ARTICLE

FIGURE 2 UV absorption spectra of BP [9  10
5] M and PBP

[6  10
5] in CHCl3.
FIGURE 4 Transient optical absorption spectrum recorded at
280 and 480 ns following laser excitation (355 nm, 5 ns) in ar-
standards. Gas chromatography-mass spectroscopy (GC-MS) gon saturated chloroform solution of PBP. Inset: Triplet decay
was performed using an Agilent 6890/ 5973 inert gas chro- at 550 nm.
matograph/mass selective detector system in electrospray
ionization mode (70 eV), through an HP-5MS capillary col-
and the measurements were carried out in isothermal mode
umn using helium as the carrier gas at a flow rate of 1.6
at room temperature under a nitrogen atmosphere (nitrogen
mL/min. Laser flash photolysis experiments employed the
or air flow: 50 mL min
1). The samples were irradiated for
pulses from an Applied Photophysics with YAG laser
4 min. at room temperature. The heat flow as a function of
(355 nm, pulse, 5 ns) and a computer controlled system. A
reaction time was monitored using Photo-DSC under isother-
chloroform solution of polymeric benzophenone photoinitia-
mal conditions, and both the rate of polymerization and con-
tor (PBP) was prepared with a concentration of BP such
version were then calculated as a function of time. The heat
that the absorbance was 0.5 at the excitation wavelength
of reaction value DHtheor
p ¼ 86 kJ/mol was used as the theo-
(355 nm).
retical heat evolved for acrylate double bonds.50 Rates of po-
lymerization were calculated according to the following
Photo Differential Scanning Calorimetry (Photo-DSC) equation; Rp ¼ (Q/s)M/n DHpm where Q/s is heat flow per
The photoinitiated polymerization of HDDA was carried out second, M the molar mass of the monomer, n the number of
by TA-DSCQ100 equipped with a medium pressure mercury double bonds per monomer molecule and m the mass of
arc lamp. This unit emits radiation predominantly in the monomer in the sample.
220–400 nm range, and provides light intensity of 50 mW
cm
2 as measured by a UV radiometer capable of broad UV
range coverage. The mass of the samples was 2 6 0.1 mg RESULTS AND DISCUSSION

Etherification reaction of the allyl bromide with 4,40 -dihy-

droxybenzophenone photoinitiator was preferred because it
has a reactive click component, and it can be easily obtained
in high yield. In addition, allyl ethers are more reactive than
styrenes, acrylates, and methacrylates in thiol-ene reac-
tions.42 Therefore, the main chain PBP was synthesized with
‘‘Thiol-ene Click Polymerization’’ method with diallyl benzo-
phenone (BP-Al) and 1,2-ethanedithiol in the presence of cat-
alytic amounts of AIBN via thermal initiation (Scheme 2).
The resulting polymer was precipitated two times in metha-
nol to obtain a pure polymeric photoinitiator. According to
1
H NMR and FTIR studies, the desired polymeric structure
was entirely characterized. Allylic methine proton in 5.97–
6.13 and allylic methylene protons in 5.46–5.29 ppm showed
that a diallyl-end functional polymer was formed. Further-
more, a thiol signal could not be observed in either 1H NMR
or FTIR spectroscopic analyses (Fig. 1). According to 1H
FIGURE 3 Phosphorescence spectra of PBP in 2-methyl tetrahy- NMR spectrum, allylic protons at the end of the polymer and
drofurane at 77 K (kexc ¼ 300 nm). aromatic protons of the benzophenone in the main chain

SYNTHESIS OF MAIN CHAIN POLYMERIC BENZOPHENONE PHOTOINITIATOR, TEMEL, KARACA, AND ARSU 5309
JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA

were used to determine the molecular composition of the

polymeric photoinitiator. PBP has five repeating units and
possesses diallyl end groups according to calculations from
1
H NMR spectrum and these results were in strong agree-
ment with GPC results (Mn ¼ 2300 g mol
1).
The absorption behavior of the polymeric photoinitiator, PBP,
was compared with the low molecular weight analogue (BP)
which is used as a photoinitiator for many UV curing and
photopolymerization applications. As can be seen in Figure
2, the absorption of PBP shifted to the red region wave-
length (kmax ¼ 294 nm, e ¼ 28,300 mol L
1 cm
1) compared
to the low molecular weight analogue (kmax ¼ 252 nm, e ¼
16,600 mol L
1 cm
1).
To gain more insight into the photophysical properties, PBP
fluorescence emission could not be observed as usual for most
of the BP derivatives. Therefore, phosphorescence measure- FIGURE 6 Conversion versus time for the polymerization of
ments were performed at 77 K in 2-methyl tetrahydrofurane HDDA initiated by PBP/MDEA (0.1/1.0 w/w) and BP/MDEA (0.1/
to get information about the triplet configuration of the photo- 1.0 w/w) systems cured at 30  C by UV light with an intensity
initiator. PBP exhibited a phosphorescence emission spectrum of 50 mW cm
2 in the presence and absence of an air atmos-
similar to the parent benzophenone. The (0, 0) emission band phere. [Color figure can be viewed in the online issue, which is
occurred at 401 nm, corresponding to approximate triplet available at wileyonlinelibrary.com.]
energy of ca 298.3 kJ/mol (see Fig. 3). The phosphorescence
lifetime of PBP was calculated as 6.5 ms. Since the phosphores-
cence lifetime for n
p* triplets are significantly shorter (in the nm) observed in the case PBP indicates a fast quenching
order of several milliseconds) than p
p* triplets, we can com- process due to the polymeric effect of the photoinitiator.
ment that the lowest triplet state of PBP has an n
p* nature.
Photo-DSC is a unique method to obtain a fast and accurate
Laser flash photolysis studies were performed to investigate indication of the photoinitiator’s performance. It has been
the triplet state behavior of the PBP. Figure 4 exhibits the well established that Photo-DSC experiments are capable of
transient absorption spectra of degassed CHCl3 solution con- providing kinetics data in which the measured heat flow can
taining polymeric photoinitiator after irradiation with laser be converted directly to the ultimate percentage conversion
pulses of 355 nm. The maximum absorption is at 550 nm, and polymerization rate for a given amount of formulation.
which is similar to the triplet–triplet absorption of parent Photopolymerization of HDDA formulations containing pho-
BP.51,52 The transient was recorded at 250 ns, after the pulse toinitiators (BP and PBP) with amine (MDEA) either in air
for PBP. However, a short triplet lifetime (s ¼ 250 ns at 550 or nitrogen atmosphere was followed by Photo-DSC. To

FIGURE 5 Rate of polymerization versus time for the polymer- FIGURE 7 Rate of polymerization versus time for the polymer-
ization of HDDA initiated by PBP/MDEA (0.1/1.0 w/w) and BP/ ization of HDDA initiated by PBP/MDEA (1.0/10.0 w/w) and BP/
MDEA (0.1/1.0 w/w) systems cured at 30  C by UV light with an MDEA (1.0/10.0 w/w) systems cured at 30  C by UV light with
intensity of 50 mW cm
2 in the presence and absence of an air an intensity of 50 mW cm
2 in the presence and absence of an
atmosphere. [Color figure can be viewed in the online issue, air atmosphere. [Color figure can be viewed in the online issue,
which is available at wileyonlinelibrary.com.] which is available at wileyonlinelibrary.com.]

5310 WILEYONLINELIBRARY.COM/JOURNAL/JPOLA
 ARTICLE

TABLE 1 Photo-DSC Results of BP and PBP in the Absence and

Presence of Air (Light Intensity 5 50 mW cm22)

Photoinitiator Rpmax Final

(wt %) N2 tmax (s) (s
1) Conv. (%)

BP (0.1)
4.05 0.006 12

BP (0.1) þ 3.05 0.013 38
BP (1.0)
4.90 0.020 35
BP (1.0) þ 1.25 0.052 59
PBP (0.1)
10.55 0.010 12
PBP (0.1) þ 7.85 0.045 52
PBP (1.0)
2.45 0.050 27
PBP (1.0) þ 2.25 0.153 65

MDEA reached 38% conversion in nitrogen atmosphere. The

effect of oxygen inhibition on the photopolymerization reaction
FIGURE 8 Conversion versus time for the polymerization of is dependent on various parameters, one of which is the type of
HDDA initiated by PBP/MDEA (1.0/10.0 w/w) and BP/MDEA (1.0/ initiator which was employed in the formulations. In our case
10.0 w/w) systems cured at 30  C by UV light with an intensity the molecular initiator BP and polymeric initiator PBP belong
of 50 mW cm
2 in the presence and absence of an air atmos- to the type II class and as clearly seen from Figures 5 and 6;
phere. [Color figure can be viewed in the online issue, which is the inhibition effect of oxygen is extremely detrimental.
available at wileyonlinelibrary.com.]
The influence of initiator concentration on the rate of poly-
merization was also determined and the results are given in
evaluate the initiation efficiency of photoinitiator PBP, two Figures 5 and 7. When the initiator concentration was
different concentrations of initiator were used and the poly- increased from 0.1 to 1.0 wt % (under nitrogen) the rate of
merization profiles obtained for the formulations cured in polymerization jumped from 0.045 to 0.153 s
1 for PBP.
air or nitrogen atmospheres are shown in Figures 5–9 and in Even in air atmosphere, the value of the rate of polymeriza-
Table 1. tion of formulations consisting of PBP (1.0 wt %) (0.050
Under air, for both of the initiators even with MDEA, the rate of s
1) was much higher than the formulation containing PBP
polymerization is very low and the final conversion reaches (0.1 wt %) (0.010 s
1). However, the effect of increasing the
12%. When air is omitted, under nitrogen atmosphere the poly- photoinitiator concentration for BP was not as effective as
merization rate is increased, especially for initiator PBP/MDEA PBP (Fig. 9). As stated above, the inhibition effect of oxygen
by a factor of 4. However, the formulations consisting of BP/ is suppressed by increasing the initiator concentration from
0.1 to 1.0% for PBP. The highest polymerization rate was
also obtained at high initiator concentrations for both initia-
tors and for both conditions (air and nitrogen).

CONCLUSIONS

The synthesis of PBP using thiol-ene click polymerization

was successfully achieved. Since PBP contains BP chromo-
phore groups, the initiation efficiency of PBP was compared
to low molecular weight analogue. Since the new polymeric
initiator PBP presents type II initiator characteristics (see
Scheme 3), it showed very good performance with N-methyl-
diethanolamine for the polymerization of HDDA possibly due
to the high molar absorptivity of PBP when compared to the
low molecular weight analogue BP.
The authors would like to thank to TUBITAK and Yildiz Techni-
cal University Research Fund for financial support.

FIGURE 9 Conversion versus time for the polymerization of

HDDA initiated by PBP/MDEA systems in different concentra- REFERENCES AND NOTES
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