Polymerization Kinetics of Photocurable Acrylic Resins

EWA ANDRZEJEWSKA, MACIEJ ANDRZEJEWSKI

Poznan University of Technology, Institute of Chemical Technology and Engineering, Pl. Sklodowskiej-Curie 2,
60-965 Poznan, Poland

Received 25 March 1997; accepted 25 August 1997

ABSTRACT: The polymerization kinetics of photocurable compositions based on an ep-

oxyacrylate oligomer and three analogous diacrylate monomers were investigated. The
effects of the oligomer-to-monomer ratio, curing conditions, and monomer structure
were considered. The polymerization is characterized by a synergistic effect observed
in a wide temperature range and occurring for the polymerization rate both in air and
Ar and for final conversions in air. The final conversion in Ar is determined by viscosity
of a formulation. The presence of a heteroatom (S or O) in the ester group of the
reactive diluent is beneficial for the polymerization course, especially in air atmosphere.
The best results were obtained for the sulfur-containing monomer. q 1998 John Wiley &
Sons, Inc. J Polym Sci A: Polym Chem 36: 665673, 1998
Keywords: epoxyacrylate; diacrylates; photopolymerization; kinetics; synergistic ef-
fect; temperature effect; heteroatom effect

INTRODUCTION While final film properties result from the

Photosensitive resins that polymerize readily un-
der intense UV radiation are being increasingly
used in various sectors of applications, mainly in
the coating industry, the graphic arts, and micro-
electronics. UV curing technology allows the pro-
duction of high resolution relief images that are
required for the manufacture of integrated cir-
cuits or printing plates, as well as to achieve fast
hardening of clear or pigmented coatings, adhe-
sives, and composites.1 3 Photocurable composi-
tions are used for the surface protection of all kind
of materials (metals, plastics, glass, paper, wood,
fabrics, etc.) by fast-drying varnishes, paints, or
printing inks as well as in dentistry.1,2,4 Most of-
ten these photosensitive resins consist of multi-
functional oligomers and monomers that polymer-
ize to form highly crosslinked polymer network,
additives of various types, and a photoinitiator
that yields reactive initiating species upon UV ex-
posure.
Correspondence to: E. Andrzejewska
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 36, 665673 (1998)
q 1998 John Wiley & Sons, Inc. CCC 0887-624X/98/040665-09
blend of ingredients, each compound lends its spe-
cial character to the coating. The oligomers, gen-
erally acrylate functional, impart properties asso-
ciated with their basic structure. Typical commer-
cial oligomers are acrylated urethane, polyesters,
silicones, and epoxides. Acrylated epoxides, for in-
stance, impart chemical resistance, hardness, and
adhesive strength. The monomers, also typically
acrylate functional, provide viscosity control, as
well as impart properties based on their structure.
Highly functional monomers (containing at least
two double bonds) increase crosslink density of
the polymer, increasing in this way hardness of
the coating. Alkoxylated monomers can reduce
surface tension, enhance the wetting and adhe-
sive character, but can also reduce water resis-
tance and toughness.2,5 Recently studied sulfur-
containing monomers improve thermo-oxidative
stability 6 reduce solvent swellability and mois-
ture absorption 7 as well as increase refractive in-
dex 8 of the coating.
However, the nature of the resultant polymer
may depend not only on the properties of the reac-
tive components but also on cure kinetics. Gener-
ally, the rate of polymerization depends first of
665

/ 8G66$$050T 01-05-98 14:31:52 polca W: Poly Chem

97050T
666 ANDRZEJEWSKA AND ANDRZEJEWSKI

all on the reactivity of the functional groups, on (b) curing conditions (temperature and atmo-
their concentration and on the viscosity of the sphere), and
resin, whereas the chemical structure and func- (c) monomer structure (the presence and type
tionality of both the monomer and the oligomer of the heteroatom in the ester group).
determine the final degree of polymerization.9 For
a given formulation, the polymerization kinetics
depend on reaction conditions, i.e., atmosphere, EXPERIMENTAL
temperature, light intensity, photoinitiator con-
centration, etc.2,10,11 Thus, to obtain the best phys-
Synthesis and characteristics of the monomers
ical and mechanical properties of the polymeriza-
are described elsewhere.7 Chemical formulae of
tion product one must not only consider the mate-
the acrylates used are given in the following:
rials used, but also the conditions under which the
polymer was formed. These reaction conditions,
along with the type of reactant system chosen,
will completely control the polymerization rate
and conversion of double bond in the system. The
conversion, in turn, will determine the mechani-
cal, physical, and wear properties of the material where: n 0.1514
formed.
The polymerization of multifunctional mono-
mers shows a complex behavior.2,4,10,11 One of the
most characteristic features is autoacceleration,
i.e., the increase in rate of polymerization despite
the consumption of monomer, which occurs due
to extremely restricted diffusion of radicals in the
highly crosslinked polymer. Another process, au-
todeceleration occurs because the propagation
eventually becomes diffusion controlled along
with the termination. Both these processes lead
to the appearance of a maximum polymerization
rate. Polymerization is continued until it stops X|S: TEDA
from vitrification. Depending on the monomer sys- X|O: OEDA
tem and the reaction conditions by which the sys-
tem was polymerized, the polymerization typi- X|CH2 : PDA
cally ceases before complete conversion of the
functional groups.4 The polymerization kinetics were monitored by
The aim of this work was to investigate the a differential scanning calorimeter (DSC 605 M,
polymerization kinetics of photocurable composi- UNIPAN-TERMAL, Warsaw, Poland) equipped
tions based on an epoxyacrylate oligomer (EPA) with a lid especially designed for photochemical
and three analogous diacrylate monomers: 2.2 *- measurements and computer-aided data analysis
thiobisethanol diacrylate (TEDA), 2,2 *-oxybis- software. The initiator, 2,2-dimethoxy-2-phenyl-
ethanol diacrylate (OEDA), and pentane-1,5-diol acetophenone (Irgacure 651t from CibaGeigy,
diacrylate (PDA). Due to a variety of technologi- Basel) was applied in concentration 0.01 mol/kg.
cal curing conditions (air atmosphere or an inert Accurately weighed ( 10 mg) samples of the pho-
gas blanketing, often elevated temperatures due tocurable composition were polymerized in 6.8
to large amounts of heat emitted by UV lamps), mm diameter open aluminum DSC pans. When
the polymerization kinetics were followed in the polymerization was carried out in an inert atmo-
presence and in the absence of atmospheric oxy- sphere, the sample was allowed to equilibrate in
gen and at a wide temperature range. the apparatus under argon (0.0005% O2 ) for 10
The results obtained in this work are discussed min at the chosen polymerization temperature. A
in terms of the effects of the following factors on medium-pressure mercury lamp equipped with a
the polymerization kinetics: glass filter was used for the irradiation. The trans-
mitted light was in the range of 310400 nm with
(a) oligomer to monomer ratio; lmax at 366 nm. The incident light intensity at the

/ 8G66$$050T 01-05-98 14:31:52 polca W: Poly Chem

97050T

Table I. The Concentration of Double Bonds in the
Compositions and in the Components
Concentration of Double Bonds
(mol/kg)
In
Compositions
EPA to
Monomer Molar
Ratio
Components In Components 1 : 2.5 1:1
TEDA 8.70 6.35 5.28
OEDA 9.35 6.59 5.40
PDA 9.43 6.62 5.41
EPA 3.80
sample pan position was measured to be 1.8 mW/
cm2 (by the carbon black method).
For calculations, a value for the heat of poly-
merization DH0 86 kJ/mol 7 (per one double
bond) was taken. Conversion at the time at which
the polymerization rate decreased to 0 (ca. 20
min.) was taken as the final conversion. The DSC
data obtained were analyzed for the corrected
base line.
RESULTS
The most often used in practical applications
oligomer-to-monomer ratio varies between 50 : 50
to 70 : 30 by weight. Both these ratios were chosen
to formulate the oligomer and monomer mixtures
used in this work for the investigation of the cure
kinetics. Thus, the compositions contained: (a)
oligomer and monomer in weight ratio 50 : 50,
which corresponds to molar ratio 1 : 2.5; and (b)
oligomer and monomer in weight ratio 70 : 30,
which corresponds to molar ratio 1 : 1.
The concentration of double bonds in the com-
positions and in the components are given in Ta-
ble I. The polymerization was carried out isother-
mally in the temperature range from 30 to 1007C
in the presence or absence of atmospheric oxygen.
The most important parameters characterizing
the cure kinetics of multifunctional monomers
are: the rate at peak maximum (maximum poly-
merization rate R pmax ) and final degree of double
bond conversion (p f ). The discussion of the re-
sults in this work is based mainly on the values
/ 8G66$$050T 01-05-98 14:31:52
PHOTOCURABLE ACRYLIC RESINS 667
of these parameters obtained for the polymeriza-
tion of individual formulations.
The exemplary comparison of the polymeriza-
tion courses of OEDA, EPA, and their mixtures
at 507C in Ar is given in Figure 1(a) and (b). As
can be seen, the formulations containing mixtures
of the oligomer and the monomer polymerize
much faster (higher R pmax and shorter time needed
to reach R pmax ) than individual components. The
lowest reactivity of the oligomer results from its
high viscosity (as high as 10 5 of that of mono-
mers), which restricts diffusional mobility of EPA
molecules. Such dependence is typical for lower
and medium polymerization temperatures and for
all the monomers, both in Ar and air. At higher
temperatures, about 807C, this dependence is of-
ten disturbed by an increase in rates of processes
parallel to propagation (e.g., degradation, chain
transfer, oxidation, etc.). The plots of p f and
R pmax vs. polymerization temperature obtained for
Ar and air atmospheres for the monomers, oligo-
mers, and their compositions are presented in Fig-
ures 25. The values of p f and R pmax for polymer-
ization carried out in air are lower than those
for polymerization in Ar due to the well-known
inhibitory effect of atmospheric oxygen. However,
it is worthy to note that detrimental effect of oxy-
gen is much less pronounced in the polymeriza-
tion of the oligomer, which is associated with re-
duced oxygen diffusion to the highly viscous me-
dium.
Registered by DSC, overall heat effect results
from several various processes, besides the most
importantpropagation, also from those men-
tioned above, like degradation, depolymerization
or oxidation (H-abstraction is a zero-enthalpy pro-
cess 2 ). The contribution of these processes to the
overall heat flow (and heat evolved) depends to a
high degree on the state of the polymerizing sys-
tem, mainly on the conversion degree of double
bonds. For this reason the discussion of the re-
sults also includes the temperature dependence of
the polymerization rate during an early reaction
stageat 3% of double bond conversion ( R 3p , Figs.
6 and 7). The lack of some points related to bound-
ary temperatures on these plots result from the
fact that corresponding R pmax values were reached
at conversions lower than 3%.
Another factor that influences the results ob-
tained at the highest temperatures is possible evap-
oration of the monomers during the polymerization.
For instance, whereas volatility of PDA at 807C is
negligible, at 1007C the weight loss after about 20
min can reach several percent. This may somewhat
polca W: Poly Chem
97050T
668 ANDRZEJEWSKA AND ANDRZEJEWSKI

Figure 1. Polymerization of EPA, OEDM, and their mixtures in 1 : 1 and 1 : 2.5

oligomer to monomer molar ratios in Ar at 507C: (a) reaction rate profiles; (b) double
bond conversion profiles.

lower the parameters obtained, especially p f values.
On the other hand, EPA is completely nonvolatile
in the temperature range studied.
DISCUSSION
The Influence of the Oligomer-to-Monomer Ratio
As was mentioned above, the formulations based
on mixtures of EPA and the monomers show an
increased reactivity, which is manifested by a sub-
stantial increase in the polymerization rates, both
in air and Ar, in comparing to Rp values of the
individual components. The enhanced reactivity
of such compositions is reflected also by the in-
creased final conversions achieved in air atmo-
sphere (not in Ar). The best results were obtained
for equimolar mixtures of EPA and reactive dilu-
ents. When the registered effect of a mixture of
two or more components is not additive but
greater than would be expected from the additiv-
ity law, synergism between the components of the
mixture is said to occur.12 This synergistic effect
is illustrated by Figure 8, which shows the de-
pendencies of R pmax and p f at 707C on the composi-

Figure 2. Temperature dependence of final conver-

sions for polymerization in Ar. ( h) TEDA, ( s) OEDA,
(n) PDA, ( L) EPA. Open symbols and dashed lines
denote monomer and oligomer polymerizations; filled
symbols denote polymerization of compositions con-
taining corresponding monomer; solid lines denote po-
lymerization of compositions with 1 : 2.5 oligomer-to-
monomer molar ratio, and dotted lines denote polymer-
ization of compositions with 1 : 1 oligomer-to-monomer Figure 3. Temperature dependence of final conve-
molar ratio. sions for polymerization in air. Symbols as in Figure 2.

/ 8G66$$050T 01-05-98 14:31:52 polca W: Poly Chem

97050T

Figure 4. Temperature dependence of maximum po-
lymerization rates in Ar. Symbols as in Figure 2.
tion of EPA / monomer mixtures. The appearance
of a synergistic effect was also shortly mentioned
by other authors for the polymerization rate of
mixtures of an epoxyacrylate oligomer and mo-
noacrylates containing heterocyclic structures in
their ester groups.13
Synergistic effect does not occur in the case of
final conversion for the polymerization carried out
in Ar. That means that in the inert atmosphere,
the oligomer-to-monomer ratio determines the po-
lymerization rate, whereas the final conversion is
determined by viscosity of a formulation: the
lower viscosity, the higher conversion. The mobil-
ity of the polymer network plays a dominant role
in determining the value of p f . Although it de-
Figure 5. Temperature dependence of maximum po-
lymerization rates in air. Symbols as in Figure 2.
/ 8G66$$050T 01-05-98 14:31:52
PHOTOCURABLE ACRYLIC RESINS 669
Figure 6. Temperature dependence of the polymer-
ization rates at 3% of double bond conversion in Ar.
Symbols as in Figure 2.
pends on the crosslink density (the lower initial
double bond concentration, the higher network
mobility), nevertheless, the diffusional limita-
tions caused by high initial viscosity of the formu-
lation are the crucial factors in this case.
Synergistic effect is observed also for the poly-
merization rate at low degrees of conversion ( R 3p
Figs. 6 and 7). In Ar it exists only to about 607C
due to fast increase in R 3p of EPA with tempera-
ture that results from very strong temperature
dependence of the oligomer viscosity (high activa-
tion energy of viscosity equal to 129 kJ/mol 14 ). At
907C, R 3p value of EPA reaches the R 3p value ob-
Figure 7. Temperature dependence of the polymer-
ization rates at 3% of double bond conversion in air.
Symbols as in Figure 2.
polca W: Poly Chem
97050T
670 ANDRZEJEWSKA AND ANDRZEJEWSKI
Figure 8. Synergistic effect in the polymerization of EPA and monomer mixtures at
707C in Ar and air: (a) maximum polymerization rate; (b) final conversion. (j) TEDA,
(l) OEDA, ( m) PDA.
tained for equimolar mixture of the reactants, in-
dicating, that under conditions where diffusion of
reactants is not strongly restricted (low conver-
sion, reduced viscosity) the polymerization rate
tends to increase with the oligomer content in the
composition.
As the reaction proceeds, the network density
and viscosity of the polymerizing system increase
and near R pmax the propagation and termination
become diffusion and reaction diffusion con-
trolled, 15,16 respectively. Because the strongest
diffusional limitations occur for EPA homopoly-
merization, its R pmax values are the lowest in the
whole temperature range (Fig. 4). Very high vis-
cosity of EPA results from hydrogen bonding due
to the presence of hydroxy group.14 The enhanced
reactivity of the oligomer / monomer mixture
needs a good compatibility between the reactants,
for example, solubility, which is usually facili-
tated by intermolecular interactions. One may ex-
pect that a type of intermolecular interactions
may exist also between oligomer and monomer
molecules (C|O and OH groups), especially at
equimolar oligomer-to-monomer ratio. This, to-
gether with the reduced viscosity of the formula-
tion, would favor an increase in the polymeriza-
tion rate. It was found, that biunsaturated acrylic
monomers are able to form associates and that
their polymerization rate is sensitive to intermo-
lecular interactions.17 Further increase in the
monomer content continues to decrease diffu-
/ 8G66$$050T 01-05-98 14:31:52
sional limitations, but simultaneously reduces
possible interactions between EPA and monomer
molecules.
The existence of an association may explain the
occurrence of the synergistic effect in the case of
final conversions in air. The close neighborhood
of the interacting comonomers causes substantial
reduction of the inhibitory effect of atmospheric
oxygen due to lowering of oxygen diffusion, which,
in turn, enables the polymerization to proceed to
higher conversions. This effect, observed to about
907C, may find practical importance in production
of protective coatings cured in air atmosphere.
Thus, the 1 : 1 composition gives the optimum
effect of increasing the polymerization rate at low
and medium polymerization temperatures and re-
duction of oxygen diffusion in air.
The Influence of Temperature
As can be seen in Figures 2 and 4, the values of
R pmax and p f for the polymerization in Ar increase
with temperature up to about 60807C, de-
pending on formulation, but further grow with
temperature is hampered, and even a declining
tendency is observed in some cases.
Although evaporative loss of the monomers
may complicate the interpretation of the results
obtained at the highest temperatures (from about
907C), the main reason of such polymerization
behaviors must be chemical in nature, most prob-
polca W: Poly Chem
97050T

ably chaintransfer reaction and thermal degra-
dation or depolymerization, 7,14 16,18 which rates
increase with temperature. The existence of a pla-
teau region on the final conversiontemperature
plots suggests a topologically controlled conver-
sion limit.15 At temperatures higher than 807C
the conversion appears to decrease, suggesting in
turn, the occurrence of degradation/depolymer-
ization processes. On the other hand, the chain
transfer reaction, i.e., the abstraction of mobile
hydrogens from initial components or polymer by
the growing macroradical can increase the rate of
bimolecular termination and decrease in this way
the polymerization rate. Activation energy of
chaintransfer reaction is higher by about 2040
kJ/mol from activation energy of propagation, 19
so, its contribution increases with polymerization
temperature. This reaction is probably responsi-
ble for the drop in the polymerization rate with
temperature rise above 907C for EPA polymeriza-
tion in Ar at the early polymerization stages
(R 3p , Fig. 6) due to the presence of readily ab-
u conditions of fast initiation the temperature de-
stractable hydrogens H{C(OH) . For formula-
v should resemble those in Ar.
tions based only on monomers or containing EPA
and monomers in the molar ratio 1 : 2.5, R 3p in-
creases monotonically with temperature, indicat-
ing that the possible degradation/depolymeriza-
tion processes are slow at very low polymer con-
centrations (and at low concentration of trapped
and mobile radicals) and that the chaintransfer
reaction for the oligomeric component of the
formulation is of little importance. The increase
of EPA content in the formulation ( 1 : 1 ratio )
stops further increase of R 3p with temperature
above 807C.
As the polymerization proceeds, the degrada-
tion/depolymerization and chaintransfer pro-
cesses intensify, due to an increase in polymer
(and radical) concentration and resulting in-
crease in concentration of tertiary hydrogen
atoms in the polymer backbone. This is mani-
fested by the appearance of a plateau on the plots
of R pmax vs. temperature and a declining tendency
of R pmax and p f at the highest temperatures (Figs.
2 and 4).
Somewhat different temperature dependencies
are observed for polymerization in air (Figs. 3, 5,
and 7). The values of p f , R pmax , and R 3p for the
monomers and oligomer increase monotonically
with temperature, whereas p f , R pmax and R 3p val-
ues of the mixtures of monomers and oligomer
pass through a plateau at about 50807C.
/ 8G66$$050T 01-05-98 14:31:52
PHOTOCURABLE ACRYLIC RESINS 671
The difference between the strong growing
temperature tendency of R pmax of monomers and
EPA in air and its tendency to reach a plateau
in Ar in the polymerization above 807C may be
explained, assuming that the increase in the poly-
merization rate with temperature rise in the pres-
ence of oxygen is faster than the increase in rates
of decelerating processes like degradation/depoly-
merization or chain transfer at low conversion de-
grees reached in air. The exothermic effects of oxi-
dation processes may contribute to a degree to the
observed heat flow. The fast increase in R pmax of
OEDA and PDA with temperature in air is proba-
bly associated with acceleration of initiation by
peroxides formed.7,20 At low initiation rates (as in
the present work), this effect may significantly
affect the temperature dependence of the poly-
merization rate. However, at higher initiation
rates (higher light intensity and/or initiator con-
centration), the effect of oxygen will be less pro-
nounced because the contribution of peroxides to
the initiation process will be reduced. Thus, under
pendencies of polymerization parameters in air
The lack of the maximum on the plots R pmax
and R 3p vs. temperature for EPA polymerization
in air may result in part from earlier increase in
chaintransfer effects due to oxygen assistance
in this reaction.2 The reason of the rapid drop of
R pmax , R 3p , and p f values for monomer / oligomer
compositions above 807C in air is still uncer-
tain.
The Influence of the Heteroatom
From the plots presented in Figures 27 it is
clearly seen that the presence of the heteroatom
in the ester group of the reactive diluent exerts a
deep influence on the polymerization kinetics. The
beneficial influence of the heteroatom is much
more pronounced in air atmosphere and is consid-
erably stronger for the sulfide than for the ether
group.7,21 Obviously, the effect of the heteroatom
is the strongest in the polymerization of the mono-
mers, but it is also kept in composition of the
monomers with EPA. The exemplary comparison
of the reaction rate profiles for the monomers,
EPA, and their mixtures in the 1 : 1 molar ratio
at 807C in air is given in Figure 9. The results of
TEDA, OEDA, and PDA polymerization are con-
sisted with those obtained previously.7
The differences in the polymerization kinetics
of the monomers studied result from the ability
polca W: Poly Chem
97050T
672 ANDRZEJEWSKA AND ANDRZEJEWSKI
Figure 9. Reaction rate profiles of the monomers,
EPA, and their mixtures in the 1 : 1 molar ratio at 807C
in air.
of the CH2 group attached to heteroatom to donate
hydrogen.7 In air, this reaction leads to significant
reduction of oxygen inhibition due to acceleration
of oxygen consumption in the peroxidation pro-
cess:
ROO 1CHX
ROOH 1CHX (1)
CHX 1 O CHX (2)
OO
where X 5 S or O.
This is the main reason of faster polymerization
rates and higher conversions of heteroatom-con-
taining monomers and their compositions in air.
Another possible reaction, hydrogen abstrac-
tion by growing macroradical both from the poly-
mer and monomer [reaction (3)], leads to en-
hanced network crosslink density due to grafting
and introduces some mobility to radical sites
attached to the network.
M 1 CHX
MH 1 CHX (3)
where ; M is macroradical.
This reaction affects the kinetics especially in
Ar and may be responsible in part for larger con-
versions of TEDA- and OEDA-based formula-
tions.
The hydrogen abstraction occurs easier in the
case of {CH2{S{ group 19,22 (the chaintrans-
fer constants for hydrogens in a CH2 group
/ 8G66$$050T 01-05-98 14:31:52
attached to sulfur atom are considerably higher
than those for hydrogens in a CH2 group attached
to oxygen atom and higher than for tertiary hy-
drogens 19 ). The importance of this reaction in the
polymerization of diacrylates was shown for the
formulations containing sulfide additives of vari-
ous structures.23 Thus, the TEDA-based formula-
tions are least sensitive to oxygen inhibition as
well as give the best results when polymerized
in Ar. These properties, together with improved
thermooxidative stability and reduced solvent
and moisture absorption 6,7 of the resulting poly-
mer, makes TEDA useful for potential applica-
tions as the reactive diluent in production of pro-
tective coatings.
CONCLUSIONS
The photoinitiated polymerization of acrylic res-
ins based on the epoxyacrylate oligomer and dia-
crylate monomers is characterized by the syner-
gistic effect occurring in a wide temperature
range. Synergism is observed for the maximum
polymerization rate both in air and in Ar and for
final conversions in air. The strongest effect oc-
curs for the equimolar oligomer-to-monomer ratio.
Such composition gives the optimum effect of in-
creasing the polymerization rate at early and me-
dium polymerization stages and low and medium
reaction temperatures as well as reduction of oxy-
gen diffusion in air. In Ar, the final conversions
increase with the decrease in viscosity of a formu-
lation. The presence of a heteroatom (S or O) in
the ester group of the reactive diluent is beneficial
for the polymerization course, especially in air at-
mosphere. The best results were obtained for the
sulfur-containing monomer.
The authors thank Dr. W. Charmas for synthesis of the
oligomer. This work was supported by grant of the Poznan
University of Technology number DS-32/282/97.
REFERENCES AND NOTES
1. S. P. Pappas, Ed., Radiation Curing Science and
Technology, Plenum Press, New York, 1992.
2. J. G. Kloosterboer, Adv. Polym. Sci., 84, 1 (1988).
3. Ullmanns Encyclopedia of Industrial Chemistry,
A14, VCH Verlagsgesellschaft mbH, D-6940 Wein-
heim, 1989, p. 171.
4. K. S. Anseth, S. M. Newman, and C. N. Bowman,
Adv. Polym. Sci., 122, 176 (1995).
polca W: Poly Chem
97050T

5. H. R. Ragin, in ref. 1, ch. 7.
6. A. Voelkel, E. Andrzejewska, R. Maga, and M. An-
drzejewski, Polymer, 37, 455 (1996).
7. E. Andrzejewska, Polymer, 37, 1039 (1996).
8. E. Andrzejewska and M. Andrzejewski, J. Polym.
Sci., Part A: Polym. Chem., 31, 2365 (1993).
9. C. Decker, Acta Polym., 45, 333 (1994).
10. C. E. Hoyle, in ref. 1, ch. 3.
11. E. Selli and I. R. Bellobono, in Radiation Curing
in Polymer Science and Technology, Vol. III, J. P.
Fouassier and J. F. Rabek, Eds., Elsevier Applied
Science, London, 1993.
12. J. F. Rabek, Mechanism of Photophysical Processes
and Photochemical Reactions in Polymers. Theory
and Applications, Wiley, Chichester, 1987, p. 574.
13. C. Decker, in ref. 11, ch. 2.
14. D. J. Broer, G. N. Mol, and G. Challa, Polymer, 32,
690 (1991).
/ 8G66$$050T 01-05-98 14:31:52
PHOTOCURABLE ACRYLIC RESINS 673
15. W. D. Cook, Polymer, 33, 2152 (1992).
16. W. D. Cook, J. Polym. Sci., Part A: Polym. Chem.,
31, 1053 (1993).
17. L. A. Sukhareva, Poliefirnye pokrytya, struktura i
svoistva, Khimiya, Moskva, 1987.
18. E. Andrzejewska, Polymer, 37, 1047 (1996).
19. G. Odian, Principles of Polymerization, 2nd ed., Wi-
ley, New York, 1981.
20. C. Decker and K. Moussa, J. Appl. Polym. Sci., 34,
1603 (1987).
21. E. Andrzejewska, Polym. Bull., 37, 199 (1996).
22. As showed semiempirical calculations (on the HF/
6-31G* level) the energy needed to break the C{H
bond in the {CH2{S{ group is by about 8.5 kJ/
mol lower than that needed to break the C{H
bond in the {CH2{O{ group. E. Andrzejewska
and M. Andrzejewski, unpublished work.
23. E. Andrzejewska, Polymer, 34, 3899 (1993).
polca W: Poly Chem
97050T