Polymer International 45 (1998) 133È141

Special Review
The Use of UV Irradiation in
Polymerization

Christian Decker

Laboratoire de Photochimie Generale (URAÈCNRS No. 431), Ecole Nationale Superieure de Chimie de Mulhouse, Universite de
Haute Alsace, 3, rue A. Werner, Mulhouse, F-68200, France

(Received 28 November 1997 ; accepted 9 December 1997)

Abstract : Photoinitiation is one of the most efficient methods for achieving

quasi-instantaneous polymerization, transforming a liquid molecule into a
solid polymer material within less than 1 s. The kinetics of such ultrafast reaction
can be advantageously followed by real-time infrared spectroscopy, a technique
which records directly conversion versus time curves and allows evaluation of the
important kinetic parameters of cross-linking polymerization. Photoinitiation
has proved to be well suited to inducing frontal polymerization and achieving a
deep-through cure of thick specimens. UV technology is also capable of causing
fast polymerization in solid media, despite severe mobility restrictions, because of
the high initiation rate provided by intense illumination. This review presents
some recent advances in the UV-curing technology, special emphasis being
given to the kinetic aspect of ultrafast polymerization reactions induced by light.
( 1998 SCI.

Polym. Int. 45, 133È141 (1998)

Key words : polymerization ; cross-linking ; acrylates ; epoxides ; kinetics ; UV

radiation ; IR spectroscopy

INTRODUCTION By exposing a monomer for a brief time to intense

UV-radiation curing has become a well-accepted tech-
nology which has found a large variety of industrial
applications because of its distinct advantages.1 Light-
induced polymerization of multifunctional monomers is
indeed a powerful method to achieve, selectively in the
illuminated areas, a quasi-instantaneous transformation
of a liquid resin into a solid polymer. UV radiation is
best known for its deleterious e†ects on organic com-
pounds, particularly upon prolonged sunlight exposure.
By breaking chemical bonds, UV radiation causes
severe changes in the mechanical and optical properties
of polymer materials, thereby reducing their service life
in outdoor applications.2 However, UV radiation can
also have a beneÐcial e†ect and be used to initiate
desired chemical reactions, like polymerization.
( 1998 SCI. Polymer International 0959È8103/98/$17.50
UV radiation, in the presence of a photoinitiator, large
amounts of free radicals are generated at once. Under
such high initiation rate conditions, one would expect
the polymerization to proceed with short kinetic chains,
because of enhanced bimolecular termination, thus
leading to low molecular weight waxy polymers.
Actually, this prediction proved to be wrong for multi-
functional monomers, such as di- or tri-acrylates which
were found to polymerize extensively within a fraction
of a second upon UV or laser irradiation to form
strongly cross-linked polymer networks.3,4 The steady
development of the UV-curing technology in the past 20
years is a direct consequence of this unexpected behav-
iour ; it has opened the way to an ever-increasing
number of end-uses. The most important ones are to be
found in the coating industry for the surface protection
133
Printed in Great Britain
134
of all kinds of materials (metals, plastics, glass, paper,
wood, etc.) by fast-drying varnishes, paints, or printing
inks. In photolithography, light-induced insolubilization
of photoresists is being used to produce the high-
deÐnition images needed for the manufacture of print-
ing plates, optical disks and microcircuits. Besides its
great speed and spatial resolution, light-induced poly-
merization presents a number of other advantages, such
as solvent-free formulation, low energy consumption,
ambient temperature operations and tailor-made
properties of the UV-cured polymers.
During the last decade, a considerable amount of
work has been devoted to UV-radiation curing, most of
the research e†orts being focused both on the kinetics
and mechanism of such ultrafast cross-linking poly-
merization reactions, and on the design of new photo-
initiators, monomers and telechelic oligomers, best
suited to producing high-performance polymer networks.
The subject has been extensively covered in several
textbooks and comprehensive review articles.1,5h14
GENERAL FEATURES OF PHOTOINITIATED
POLYMERIZATION
One of the basic laws in photochemistry states that a
photochemical reaction can only occur if light has been
absorbed by the medium. As most monomers are essen-
tially transparent to the radiations emitted by conven-
tional UV sources, usually mercury lamps, they do not
produce initiating species with sufficiently high yields.
Therefore, it is necessary to introduce in the UV-curable
formulation a photoinitiator which will e†ectively
absorb the incident light and generate reactive free rad-
icals or ions by cleavage of the electronically excited
states. The photoinitiator plays a key role in that it
governs both the rate of initiation and the depth of cure
through its absorbance. The rate of initiation (r ) is
i
directly related to the incident light intensity (I ), the
0
sample thickness (l), the absorptivity (e) and concentra-
tion of the photoinitiator ([PI]), and the quantum yield
of initiation (' ) (number of initiating species produced
i
per photon absorbed) :
r \ ' I [1 [ exp([el[PI])
i i 0
Once polymerization is started, by reaction of the initi-
ating species with the monomer functional groups, the
chain reaction proceeds very much as in a conventional
thermal polymerization, except for the much larger rate
of initiation that can be reached by intense illumination
and for the lower temperature. With multifunctional
monomers and telechelic oligomers, the polymerization
will develop in three dimensions to yield strongly cross-
linked polymer networks.
There are two major classes of UV-curable resins,
which di†er basically by their polymerization mechan-
ism : (i) photoinitiated radical polymerization of multi-
C. Decker
functional acrylates and (ii) photoinitiated cationic
polymerization of multifunctional epoxides and vinyl
ethers.
Acrylates are by far the most widely used resins in
UV-curing applications because of their high reactivity,
together with the large choice of acrylate functionalized
oligomers (polyesters, polyethers, polyurethanes, poly-
siloxanes,. . .). Low-modulus elastomers are generally
obtained with aliphatic compounds, whereas hard and
glassy materials are formed if the cross-link segments
contain aromatic structures. A typical UV-curable for-
mulation is made of three basic components : a photo-
initiator, usually an aromatic ketone, a telechelic
oligomer, and a monomer acting as a reactive diluent.
An increase of the monomer functionality was shown to
speed up the reaction, but at the expense of the Ðnal
conversion, because of premature mobility restrictions
caused by gelation and vitriÐcation.13 The increased
cross-link density makes the UV-cured polymer harder,
more solvent resistant, but also more brittle.
Monomers which are inactive towards free radicals,
such as epoxides, or vinyl ethers, undergo rapid poly-
merization upon UV irradiation in the presence of aryl
sulfonium or iodonium salts (' S`PF~ , ' I`SbF~).
3 6 2 6
These compounds were shown to generate protonic
acids upon their photolysis in the presence of a hydro-
gen donor molecule.12 The ring-opening polymerization
of epoxides proceeds through the oxonium ion, with
formation of a polyether chain.9 Vinyl ethers poly-
merize much faster than epoxides because of the elec-
tron rich CxC bond and the stabilization by resonance
of the carbocation. Three-dimensional polymer net-
works with tailor-made properties have been obtained
by UV irradiation of vinyl ether telechelic oligomers
containing ether, ester, urethane or siloxane struc-
tures.15 One of the distinct advantages of cationic poly-
merization is its lack of sensitivity toward atmospheric
oxygen, thus providing a rapid surface cure of protec-
tive coatings.
By mixing monomers that polymerize by di†erent
mechanisms, e.g. vinyl ethers and acrylates,16 or
epoxides and acrylates,17 two interpenetrating polymer
networks can be produced within a few seconds by UV
irradiation in the presence of both radical and cationic
photoinitiators. The main advantage of such hybrid
systems is to allow one to control precisely the Ðnal
properties of the cured polymer by a proper selection of
the two components, and by adjusting their proportions
as well.
KINETICS OF ULTRAFAST
PHOTOPOLYMERIZATION
The bulk polymerization of multifunctional monomers
is a complex process which exhibits a number of anom-
alous behaviours with respect to the reaction kinetics
POLYMER INTERNATIONAL VOL. 45, NO. 2, 1998
T he use of UV irradiation in polymerization 135

and mechanism :10,18 initial auto-acceleration followed

by auto-deceleration due to gelation, radical trapping,
formation of structural heterogeneities and microgels,
termination process controlled by reaction di†usion.
While cross-linking polymerization proceeds, the phys-
ical state of the medium changes from a viscous liquid
to a viscoelastic rubber and, in some cases, Ðnally to a
glass. This causes drastic variations of the reactive
species mobility and will ultimately lead to a premature
ending of the chain reaction. A most remarkable feature
of ultrafast photopolymerization processes is that
higher Ðnal degrees of conversion are usually reached
than in thermal curing. This is because volume shrink-
age occurs over a much longer timescale than the
chemical reaction thus, generating a temporary excess Fig. 1. Polymerization proÐles of di†erent types of UV-
of free volume.10 In addition, the heat instantly evolved curable systems : 1, acrylate ; 2, vinyl ether ; 3, cycloepoxide ; 4,
by the exothermic reaction and the resulting increase methacrylate ; and 5, glycidyl ether.
of the sample temperature also contribute to a more
complete polymerization.
From the recorded proÐle one can also evaluate the
Real -time infrared spectroscopy Ðnal degree of conversion, i.e. the amount of unreacted
functional groups that remains in the UV-cured
For the polymer chemist who wants to study the polymer, a quantity likely to a†ect the long-term
kinetics of photopolymerization, it is a tough challenge properties of the Ðnal product.
to follow quantitatively, and in real time, reactions that
take place typically in less than 1 s. Di†erential scanning Kinetic chain length
calorimetry (DSC), which monitors the heat Ñow, is by
far the most widely used technique in photocuring RTIR spectroscopy is particularly well suited to study-
kinetic studies.10,18h22 Its main limitation lies in its ing the dark polymerization that occurs just after the
relatively long response time (D2 s), which makes it UV light has been switched o†. Figure 2 shows the
impossible to monitor accurately polymerization re- polymerization proÐle recorded after a 100 ms UV
actions occurring within less than 10 s, thus requiring exposure of an amino-polyester acrylate Ðlm. It can be
operation with low intensity UV radiation. seen that the dark polymerization proceeds extensively
Real-time infrared (RTIR) spectroscopy, with its during the Ðrst second, just after the 100 ms exposure,
milliseconds time resolution, does not su†er from this thus showing that a large number of initiating radicals
limitation ; it was successfully used to monitor photo- has been created during the short irradiation. It should
polymerizations occurring within a fraction of a second be noticed that, in photoinitiated cationic poly-
under intense UV23 or laser24 irradiation (up to merization, the dark reaction proceeds for a longer
500 mW cm~2). Conversion (x) versus time curves are period of time (up to a few hours) because, by contrast
directly recorded by following in situ the disappearance
upon UV exposure of the IR peak characteristic of the
reactive group, e.g. at 812 cm~1 for the acrylate double
bond (CH xCH twisting). Figure 1 shows some typical
2
polymerization proÐles recorded by RTIR spectroscopy
for various photocurable systems exposed to intense
UV light. As expected, the fastest polymerization is
observed with acrylates and vinyl ethers, whereas gly-
cidyl ethers are the least reactive of these monomers.
The actual rate of polymerization (R ) can be easily
p
determined at any stage of the reaction from the slope
of the RTIR curve (dx/dt) and the initial concentration
of reactive group ([M ]) :
0
R \ [M ] É (dx/dt)
p 0 Fig. 2. Polymerization proÐles of a polyurethane-acrylate
Its maximum value, usually reached between 10 and upon continuous (- - - -) or 100 ms (ÈÈÈ) UV exposure.
30% conversion, is one of the most reliable parameters Decay proÐle of the acrylphosphine oxide photoinitiator
for comparing the reactivity of di†erent formulations. (ÉÉÉÉÉÉÉÉÉ). I \ 80 mW cm~2.
0

POLYMER INTERNATIONAL VOL. 45, NO. 2, 1998

136 C. Decker

with free radicals, the propagating polymer cations are

not reacting among themselves.
The average kinetic chain length (kcl) of the cross-
linking polymerization can be directly determined from
the ratio of the total number of acrylate functions
polymerized during and after the UV exposure
([M ] É x ) to the number of initiating radicals gener-
0 f
ated during the irradiation : ' I [1 [ exp([el[PI])] É t.
i 0
In O -free samples, kcl values of the order of
2
3 ] 10~4 mol radical~1 were obtained,24 thus showing
how e†ectively the chain reaction can propagate in
these acrylate systems undergoing cross-linking
polymerization, even at the large initiation rate used
(r \ 10~3 radical l~1 s~1). This is mainly due to a rather
i
inefficient termination process (see next section), Fig. 3. Conversion dependence of the rate constant of
together with an efficient chain-transfer reaction involv- propagation (k ) and termination (k ) for a UV-curable
ing the labile hydrogens of the telechelic oligomers.14 p t
polyurethane-acrylate.

Rate constants of propagation (k ) and

p
termination (k )
t
Photoinitiation is a useful process for determining
kinetic rate constants in free-radical poly-
merization.18,25,26 By monitoring the rate of poly-
merization during UV-exposure and afterwards in the
dark, one can evaluate the rate constants k and k
p t
which are directly controlling the polymerization
process. The ratio k /k0Õ5 is calculated from rate meas-
p t
urements under steady-state irradiation conditions
using the following equation :
R \ (k /k0Õ5)M' I [1 [ exp([el[PI])]N0Õ5[M]
p p t i 0
Under the non-steady conditions prevailing during the
dark polymerization, when initiating radicals are no
longer produced, the rate equation becomes :27
[M] [M] k A simple way to evaluate the actual rate at which the
t[ i\ t ]t
(R ) (R ) k
pt pi p merization proÐle after a very short and intense UV
where i and t refer to the monomer concentration and
the rate of polymerization at the onset of the dark reac-
tion and after a given time, respectively. The linear time
dependence of the left-hand term allows one to evaluate
the ratio k /k and, together with the k /k0Õ5 ratio, to
t p p t
determine individual values of k and k .
p t
Figure 3 shows the variation of k and k with the
p t
degree of conversion for a UV-curable polyurethane-
acrylate resin. In the initial stage of the polymerization,
the propagation is reaction controlled and k remains
p
relatively constant, of the order of 104 l mol~1 s~1. It
starts to decrease above 20% conversion when propaga-
tion becomes controlled by di†usion, due to increasing
mobility restrictions. By contrast, the bimolecular ter-
mination process is already controlled by radical di†u-
sion at the very beginning of the polymerization, the k
t
value dropping rapidly as the polymer network is build-
ing up. At conversions beyond 10%, k was found to be
t
proportional to the product k É [M], which indicates
p
that reaction di†usion dominates the termination step.
At that stage, polymer radicals are essentially moving
by propagating through unreacted double bonds. The
fact that reaction di†usion controls the termination
kinetics from low double conversion in photo-
polymerization of multifunctional monomers was dis-
covered recently by Anseth and Bowman, and discussed
thoroughly in several outstanding papers.18,20,28 It
must be emphasized that the resulting low value of k is
t
one of the main reasons why polymerization of multi-
functional monomers proceeds so e†ectively at high ini-
tiation rates, thus accounting for the present
development of the UV-curing technology.
Growth rate of polymer chains
polymer chains are growing is by recording the poly-
exposure, e.g. from a pulsed laser.13 The rate of the
polymerization which proceeds in the dark depends
primarily on the propagation rate constant, the number
of initiating radicals generated by the laser Ñash (R~)
and the monomer concentration : R \ k [R~][M]. By
p p
taking the ratio R /[R~], we evaluated the growth rate
p
of the polymer chains in a UV-curable urethane-
acrylate resin to be initially of the order of
5 ] 104 mol radical~1 s~1. From this value, the average
time for the addition of one monomer unit to the
growing polymer chain was calculated to be 20 ls. As
polymerization proceeds to above 20% conversion, R
p
starts to drop due to growing mobility restrictions and
consumption of the monomer, thus leading to a con-
comitant increase of the addition time value.
It should be remembered that, in most UV-curing
applications, the sample is exposed brieÑy to intense
radiation by passing rapidly under a powerful UV lamp
(typically for 0É1 s at 800 mW cm~2). This means that
POLYMER INTERNATIONAL VOL. 45, NO. 2, 1998
T he use of UV irradiation in polymerization
most of the polymerization reaction is actually pro-
ceeding in the dark, just after the UV exposure. The
polymerization proÐle should therefore be quite similar
to that recorded upon exposure to a laser Ñash.
Influence of the light intensity
One of the unique advantages of photoinduced reactions
is to a†ord a precise control of the initiation step with
respect to both the onset and the end of the period of
initiation, as well as to its magnitude, by acting on the
light intensity. If desired, the initiation rate can even be
varied in the course of the reaction through an intensity
modulator. Numerous studies10,19,29h31 on the e†ect of
the light intensity (I ) on the polymerization kinetics of
0
UV-curable resins have shown that an increase of I
0
leads not only to faster polymerization but also to a
more extensive cure, so that the Ðnal product contains a
lower amount of unreacted functional groups. In a UV-
cured polyurethane-acrylate for example,31 the Ðnal
degree of conversion was found to rise from 80 to 95%
when I was increased from 10 to 80 mW cm~2 reaching
0
nearly 100% at 600 mW cm~2. This trend was explained
by two factors : (i) an increase in the sample temperature
at high I , which provides more molecular mobility and
0
leads to higher ultimate conversion, and (ii) a longer
time lag between conversion and shrinkage, which gen-
erates a greater excess of free volume and thus increases
the molecular mobility.
To evaluate the contribution of the Ðrst of these two
factors, temperature proÐles of samples undergoing
photopolymerization were recorded by RTIR spectros-
copy. The IR peak at 843 cm~1 for the polypropylene
Ðlm used as support was taken as the temperature
probe, as its intensity was found to vary linearly with
temperature in the 20 to 100¡C range.31 Figure 4 shows
the temperature proÐles, together with the conversion
proÐles, recorded for a polyurethane-acrylate sample
exposed to UV radiation at two di†erent light inten-
sities (10 and 80 mW cm~2). It can be seen that the tem-
Fig. 4. InÑuence of the light intensity on the polymerization
(É É É É É É É) and temperature (ÈÈÈ) proÐles of a polyurethane-
acrylate exposed to UV light.
POLYMER INTERNATIONAL VOL. 45, NO. 2, 1998
137
perature starts to rise as soon as polymerization begins
and that it reaches its maximum value once the reaction
slows down because of gelation. The temperature later
decreases slowly as air cooling becomes predominant
over the small amount of heat evolved at that stage.
Figure 4 shows clearly that the rise in temperature is
faster and more important for the sample irradiated at
high light intensity, reaching a maximum value of 90¡C
at 80 mW cm~2, compared to 40¡C at 10 mW cm~2. By
acting on the cure extent through the sample tem-
perature, the light intensity will a†ect the physical
properties of UV-cured polymers, in particular the
elastic modulus and T which will both increase as I is
g 0
being increased.
FRONTAL POLYMERIZATION
Photochemical reactions may proceed as typical frontal
processes if three conditions are fulÐlled : high light
absorbance, photoinduced bleaching and restricted
mass transfer.32 In the case of photoinitiated poly-
merization, this type of process would be highly beneÐ-
cial to cure thick specimens. Today, UV irradiation is
mostly used to polymerize thin samples, typically
between 5 and 200 lm, because of the limited penetra-
tion of UV light (inner Ðlter e†ect).
In highly absorbing UV-curable systems, the initi-
ating radicals are mainly generated in the top layer
exposed to light, which leads to a sharp depth of cure
proÐle within the sample undergoing polymerization.
As the absorbing photoinitiator is being destroyed upon
UV exposure, the incident radiation will be able to pen-
etrate deeper into the sample, thus allowing the poly-
merization front to move progressively towards the
deep-lying layers. Such frontal polymerization has been
achieved by UV-irradiation of a polyurethane-acrylate
resin containing 5% by weight of a triarylacylphosphine
oxide, a strongly absorbing photoinitiator which is
rapidly destroyed upon UV-exposure (Fig. 1), with
formation of transparent photoproducts. From the poly-
merization proÐles recorded from Ðlms of increasing
thickness, we have been able to determine the shape of
the front and see how fast it propagates into the bulk of
the sample (Fig. 5). The velocity of the front, calculated
to be 2 mm min~1, can be easily increased by acting on
the light intensity. Up to 2 cm thick specimens, and as
large as 5 cm in diameter, have been cured within a few
minutes by photoinitiated frontal polymerization of this
acrylate formulation. Light-induced frontal poly-
merization was also achieved in photoinitiator-free
systems where one of the monomers, N-substituted
maleimide, is undergoing photobleaching upon poly-
merization.33
UV-radiation curing has been successfully used to
produce interpenetrating polymer networks (IPN) by
photopolymerization of a blend of difunctional acrylate
138
Fig. 5. Frontal polymerization proÐles of a polyurethane-
acrylate resin exposed to UV radiation for various durations.
and epoxy monomers, known to polymerize by di†erent
mechanisms. In this system, the front velocity of each
polymerization process is directly controlled by the
photolysis rate of the corresponding photoinitiator. A
most remarkable feature in dual frontal photo-
polymerization is that the two polymer networks can be
produced one after the other by changing the wave-
length of the UV radiation (Fig. 6). The IPNs obtained
by both the simultaneous or the step-wise frontal
photopolymerization are clear, which indicates that
phase separation of the acrylate and epoxy products has
not occurred.
Large dimension samples made from this hybrid
system were cured by simple exposure to sunlight for a
few minutes, with formation of a tack-free polymer,
because the dicycloepoxide polymerizes cationically
without interference of atmospheric oxygen. The same
technology proved also quite e†ective to stick together
two pieces of glass. As the cured polymer is perfectly
clear, this solar-assisted processing appears to be an
easy and economic way to produce large dimension
glass laminates,34 and glass composites as well. Ali-
phatic polyurethanes should be selected as telechelic oli-
gomers for the glass-laminate formulation to produce a
low-modulus elastomer showing strong adhesion and
TABLE 1. Physical properties of UV-cured polymers
Telechelic Aliphatic
oligomer urethane-acrylate
Glass transition É20 to ½20
temperature (¡C)
Tensile strength 5 20 to 40
(MPa)
Elongation at break ¿100
(%)
Pendulum 50 to 150
hardness (s)
Heat resistance 350
(¡C)
C. Decker
Fig. 6. Synthesis of interpenetrating polymer networks by a
two-step photopolymerization of a 1 :1 mixture of diacrylate
and dicycloepoxide monomers. Kinetic proÐles recorded by
RTIR spectroscopy.
impact resistance. By contrast, the glass-composite
formulation should be based on epoxy- or acrylate-
functionalized aromatic polyethers which give hard and
tough polymer materials upon UV-curing. Typical
values of the physical and viscoelastic properties of the
two types of photocured polymers are given in Table 1.
Another type of photoinitiated frontal polymerization
has been performed to estimate the spatial extent of the
propagation step. Here, the initiating radicals were not
produced by photocleavage of the photoinitiator excited
states, as they are in phosphine oxides, but by hydrogen
abstraction from a substrate, namely a polypropylene
(PP) Ðlm. A thin layer of benzophenone was deposited
at the surface of the PP Ðlm which was coated with an
acrylate monomer (hydroxypropylacrylate) and exposed
brieÑy to UV light. As the initiating radicals are only
formed at the polymer/monomer interface, the front of
Aromatic Aromatic
ether-acrylate ether-epoxide
50 to 100 80
30
5 to 10 5
250 to 350 300
400 400
POLYMER INTERNATIONAL VOL. 45, NO. 2, 1998
T he use of UV irradiation in polymerization
the polymerization will develop from the bottom
towards the surface over a certain distance. The thick-
ness of the grafted polymer layer obtained after solvent
development was found to be of the order of 2000 nm,
thus showing that the chain propagation can develop
over a relatively long distance.
This photografting technology proved to be quite
e†ective in modifying the surface properties of organic
materials, and in particular their wettability.35 In the
case of polyoleÐns, for instance, the contact angle of
water was found to drop from 90¡ for the untreated
sample to 35¡ for the acrylate grafted foil, thus making
the surface printable by aqueous-based inks. The
hydroxyl groups located on the grafted coating can be
used to promote some further chemical modiÐcations,
e.g. by reaction with isocyanate glycidyl ethers or carb-
oxylic acids. The same technology proved also quite
efficient to improve the adhesion of UV-cured coatings
onto polymer substrates by creating covalent bonds at
the interface.36
PHOTOINITIATED POLYMERIZATION IN THE
SOLID STATE
Besides transforming a liquid resin into a solid polymer,
UV irradiation can also be used to induce the poly-
merization of reactive groups present in a solid polymer
to achieve insolubilization and to modify its physical
properties. The functional groups can be located either
on an incorporated monomer or on the polymer chain
itself.
Polymerization of monomers in a polymer matrix
When multifunctional monomers or telechelic oligomers
are being polymerized in a polymer matrix, semi-
interpenetrating polymer networks are formed, but at a
slow pace because of severe molecular mobility
restrictions in such solid media. The great advantage of
the UV technology is to allow a fast cure to be achieved
because of the large initiation rate provided by the
intense illumination. Several reports have appeared
in recent years on the UV-curing of vinyl epoxy
and acrylic monomers dispersed in a polymer
matrix.29,37h39 The monomer/polymer compatibility
plays a key role as it a†ects both the reaction kinetics
and the optical and mechanical properties of the semi-
IPN formed. Clear coatings were obtained by photo-
polymerization of a triacrylate monomer dispersed in
poly(vinyl chloride), poly(methyl methacrylate) or ali-
phatic polyurethanes.39 The fact that the gel fraction
was substantially higher than the original monomer
content was taken as evidence of a grafting process,
probably through a chain-transfer reaction involving
the labile hydrogens of the polymer chain.
POLYMER INTERNATIONAL VOL. 45, NO. 2, 1998
139
Cross -linking polymerization of functionalized
polymers
Tridimensional polymer networks can be readily
obtained by photoinitiated polymerization of functional
groups located on the polymer chains. A typical
example is the photocross-linking of epoxidized
polybutadiene40,41 or polyisoprene42 which was per-
formed at ambient temperature by UV exposure of the
functionalized polymer in the presence of a sulfonium
salt. The ring-opening cationic polymerization of the
oxirane functions leads to the formation of ether cross-
links between the rubber chains, and to complete
insolubilization within a few seconds. The UV-cured
polymer proved to be both hard and Ñexible, for it
combines the elastomeric character of rubbers and the
toughness of epoxy-based polymers. When used as coat-
ings, these materials show excellent adhesion properties
to various substrates, in particular aluminium, steel and
glass.41
Similar results have been obtained by UV irradiation
of rubbers bearing pendent acrylate double bonds.43,44
In both types of functionalized polymers, intramolecu-
lar processes involving neighbouring reactive groups
were shown to become increasingly important as the
number of functional groups on the polymer chains was
being increased. This accounts for the unexpectedly fast
and extensive polymerization observed in these solid
media exposed to UV light (Fig. 7).
Polymerization of monomers in functionalized
polymers
The cure rate of solid functionalized polymers can be
substantially enhanced by the addition of a monomer
that will act as a reactive plasticizer. Copolymerization
Fig. 7. Polymerization proÐles of epoxidized polyisoprene
(EPI) and acrylated polyisoprene (API) Ðlms exposed to UV
radiation in the presence of a photoinitiator (2 wt%). (I \
0
600 mW cm~2).
140
Fig. 8. Insolubilization and hardness increase of an acrylated
polyisoprene containing 20 wt% of diacrylate upon UV expo-
sure (I \ 600 mW cm~2).
0 Another key issue concerns the through the matrix cure
will occur when the monomer and the polymer contain
the same functional group, e.g. an acrylate double bond
or an epoxy ring. The addition of a diacrylate (20%
by weight) to acrylated polyisoprene was found to
cause a faster and more complete polymerization
(Fig. 7). Within 0É2 s the low-modulus elastomer was
transformed into a high-modulus and insoluble
polymer (Fig. 8).
When the added multifunctional monomer poly-
merizes by a di†erent mechanism than the functional-
ized polymer, two IPNs will be formed simultaneously
upon UV-irradiation in the presence of both a cationic
and a radical photoinitiator. Di†erent types of IPN
have been generated by this UV technology :44,45 acryl-
ated polyisoprene plasticized by a vinyl ether or a
cycloepoxide monomer, and epoxidized polyisoprene
associated with a di- or triacrylate monomer. The UV-
cured polymers combine the properties of the elasto-
meric rubber network with those of the hard and glassy
acrylate or epoxy polymer network. They proved there-
fore to be very resistant to impact, scratching and abra-
sion, which makes these polymer materials particularly
well suited for coating applications.
OUTLOOK
The photoinitiated polymerization of multifunctional
monomers remains one of the fastest and most efficient
methods presently available to generate three-
dimensional polymer networks. In recent years, notable
progress has been made in the qualitative understand-
ing of the cross-linking mechanism, in particular that of
the widely used acrylate systems. The important kinetic
parameters have been determined in situ, under condi-
tions similar to those used in most industrial applica-
tions. Such evaluations, together with the mechanistic
studies, are necessary for a better control of the various
C. Decker
processes involved in ultrafast photocuring reactions.
SigniÐcant progress has also been achieved with the
development of very efficient photoinitiators, and highly
reactive monomers and telechelic oligomers capable of
generating polymer materials with speciÐc, tailor-made
properties upon curing. Because of its distinct advant-
ages regarding process facility and product quality, the
UV-curing technology has found major openings in the
coating industry and in photolithography.
Future research e†orts should be directed to areas
where improvement in some of the performances of
both the formulation and the cured product would be
highly desirable to overcome some of todayÏs lim-
itations of this technology. For example, various
methods have been proposed to reduce the strong in-
hibition e†ect of oxygen in UV-curable radical-type
systems, but so far none has proven really satisfactory.
of pigmented resins which is usually difficult to achieve
by UV light because of a strong screen e†ect. In these
systems, and in clear coats as well, adhesion to the sub-
strate appears as a crucial factor which will determine
any further growth of the “radcureÏ technology in coat-
ings and adhesives applications. For organic substrates,
adhesion can be greatly improved by promoting a
photografting reaction. Another area of potential
interest lies in the development of UV-cured coatings
showing enhanced resistance to natural weathering, and
likely to be used in outdoor applications, mainly in the
building and automotive industries.
The prospects of radiation curing look rather bright,
based on recent achievements and on expected progress
in the performance of these highly cross-linked poly-
mers. It is anticipated that UV irradiation will be
increasingly used in polymerization and will attract
attention in an ever growing number of industrial
sectors, due to the manifold advantages that are to be
gained by using this advanced technology.
ACKNOWLEDGEMENTS
The author wishes to thank his co-workers at the
Polymer Photochemistry Laboratory : Drs T. Bend-
aikha, D. Decker, B. Elzaouk, H. Le Xuan, F. Morel,
T. Nguyen Thi Viet and K. Zahouily.
REFERENCES
1 Oldring, P. K. T. (ed.), Chemistry and T echnology of UV and EB
Formulation for Coatings, Inks and Paints, SITA Techn., London,
1991, Vols 1È5.
2 Faucitano, A., Buttafava, A., Camino, G. & Greci, L., T rends
Polym. Sci. 4 (1996) 92.
3 Collins, G. L. & Costanza, J. R., J. Coat. T echn., 51(648) (1979) 57.
4 Decker, C., J. Polym. Sci., Polym. Chem. Ed., 21 (1983) 2451.
POLYMER INTERNATIONAL VOL. 45, NO. 2, 1998
T he use of UV irradiation in polymerization
5 Hoyle, C. E. & Kinstle, J. F. (ed.), Radiation Curing of Polymer
Materials, ACS Symp. Series 417, American Chemical Society,
Washington (1990).
6 Pappas, S. P. (ed.), Radiation Curing Science and T echnology,
Plenum Press, New York (1992).
7 Fouassier, J. P. & Rabek, J. F. (eds), Radiation Curing in Polymer
Science and T echnology, Chapman and Hall, London, 1992, Vols
1È5.
8 Fouassier, J. P., Photoinitiator, Photopolymerisation and Photo-
curing, Hanser, Munich (1995).
9 Crivello, J. V., Adv. Polym. Sci., 62 (1984) 2.
10 Kloosterboer, J. G., Adv. Polym. Sci., 84 (1988) 1.
11 Dietliker, K., in Ref. 1, Vol. 3 (1991) p. 59.
12 Crivello, J. V. & Dietliker, K., in Ref. 1, Vol. 3 (1991) p. 327.
13 Decker, C., Progr. Polym. Sci., 21 (1996) 593.
14 Decker, C., Materials Science and T echnology, VCH Verlag, Wein-
heim, 1997, Vol. 18, p. 615.
15 Lapin, S. C., in Ref. 6 (1992) p. 241.
16 Decker, C. & Decker, D., J. Macromol. Sci., Pure Appl. Chem., A34
(1997) 605.
17 Ravijst, J. P., Proc. RadT ech Conf., RadTech International,
Chicago, 1990, Vol. 1, p. 278.
18 Anseth, K. S., Wang, C. M. & Bowman, C. N., Polymer, 35 (1994)
3243.
19 Hoyle, C. E., in Ref. 6 (1992) p. 57.
20 Anseth, K. S., Wang, C. M. & Bowman, C. N., Macromolecules, 27
(1994) 650.
21 Andrzejewska, E. & Bogacki, M. B., Macromol. Chem. Phys., 198
(1997) 1649.
22 MuŽller, U., J. Macromol. Sci., Pure Appl. Chem., A31 (1994) 1905.
23 Decker, C. & Moussa, K., Makromol. Chem., 189 (1988) 2381.
24 Decker, C. & Moussa, K., Macromolecules, 22 (1989) 4455.
25 Olaj, O. F. & Bitai, I., Makromol. Chem., 186 (1985) 2569.
26 Buback, M., Huckenstein, B. & Russell, G. T., Macromol. Chem.
Phys., 195 (1994) 539.
POLYMER INTERNATIONAL VOL. 45, NO. 2, 1998
141
27 Tryson, G. R. & Shultz, A. R., J. Polym. Sci., Polym. Phys. Ed., 17
(1979) 2059.
28 Anseth, K. S., Kline, L. M., Walker, T. A., Anderson, K. J. &
Bowman, C. N., Macromolecules, 28 (1995) 2491.
29 Timpe, H. J. & Strehmel, B., Makromol. Chem., 192 (1991) 779.
30 Timpe, H. J. & Strehmel, B., Angew Makromol. Chem., 178 (1990)
131.
31 Decker, C., Elzaouk, B. & Decker, D., J. Macro. Sci. Pure Appl.
Chem., A33 (1996) 173.
32 Rytov, B. L., Ivanov, V. B. & Anisimov, V. M., Polymer, 37 (1996)
5695.
33 Decker, C., Morel, F., JoŽnsson, S., Clarck, S. C. & Hoyle, C. E.,
Polym. Mater. Sci. Eng., 75 (1996) 198.
34 Decker, C. & Moussa, K., J. Appl. Polym. Sci., 55 (1995) 359.
35 Decker, C. & Zahouily, K., Macromol. Chem. Symp. (in press).
36 Decker, C. & Zahouily, K., Proc. RadT ech Asia Conference (1997)
p. 518.
37 Krongauz, V. V. & Yohannan, R. M., Polymer, 31 (1990) 1130.
38 Fitzgerald, S. & Landry, J., J. Appl. Polym. Sci., 40 (1990) 1727.
39 Moussa, K. & Decker, C., J. Polym. Sci., Polym. Chem. Ed., 31
(1993) 2633.
40 Crivello, J. V. & Yang, B., J. Macromol. Sci., Chem. A31 (1994)
517.
41 Cazeaux, F., Coqueret, X., Lignot, B., Loucheux, C. & Rousseau,
R., J. Coat. T echn., 66(838) (1994) 27.
42 Decker, C., Le Xuan, H. & Nguyen Thi Viet, T., J. Polym. Sci.,
Polym. Chem. Ed., 33 (1994) 2759, and 34 (1995) 1771.
43 Le Xuan, H. & Decker, C., J. Polym. Sci., Polym. Chem. Ed., 31
(1993) 769.
44 Decker, C., Nguyen Thi Viet, T. & Le Xuan, H., Europ. Polym. J.,
32 (1996) 549 and 559.
45 Decker, C., Nguyen Thi Viet, T. & Le Xuan, H., Europ. Polym. J.,
32 (1996) 1319.