Overcoming the Oxygen Inhibition in the Photopolymerization of
Acrylates: A Study of the Beneficial Effect of Triphenylphosphine
C. BELON, X. ALLONAS, C. CROUTXE-BARGHORN, J. LALEVEE
Departement de Photochimie Generale, UMR 7525 CNRS, Ecole Nationale Superieure de Chimie de Mulhouse,
Universite de Haute-Alsace, 3 rue Alfred Werner, 68093 Mulhouse, France
Received 17 August 2009; accepted 9 March 2010
DOI: 10.1002/pola.24017
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Triphenylphosphine (TPP) was used in free-radical
UV-curable resins to reduce oxygen inhibition effect. The
relative influence of concentration, monomer viscosity, light
intensity and sample thickness on TPP efficiency was investi-
gated by real time infrared spectroscopy. It is shown that TPP
is an effective oxygen scavenger. The mechanism was investi-
INTRODUCTION The inhibition effect of molecular oxygen in
free-radical photopolymerization reactions has always been a
key issue.15 Indeed, the radicals formed during the initiation
of the reaction are scavenged by oxygen leading to peroxy
radicals that can hardly initiate or contribute to the polymer-
ization reaction. Moreover, oxygen is also capable to quench
the photoinitiator excited states. Consequently, detrimental
effects are observed such as the presence of an inhibition
time and the decrease in both polymerization rate and final
conversion ratio, resulting in tacky surfaces. These features
were nicely confirmed recently by modeling the effect of oxy-
gen inhibition on the photopolymerization kinetics, providing
a good description of the different mechanisms involved.6
Physical and chemical methods that may be used to over-
come oxygen inhibition have been recently reviewed.5
Increasing light intensity or photoinitiator concentration is a
possible way to achieve this goal. Thereby, a large concentra-
tion of radicals is generated upon irradiation, consuming the
dissolved oxygen during the light curing process. Use of
high-viscosity monomers or increase in sample thickness is
also an alternative way to limit the oxygen diffusion from
the surrounding atmosphere to the bulk. Another effective
method is to purge the sample with an inert gas (nitrogen
or carbon dioxide) before the polymerization process,7,8 the
drawback being the important additional costs. The addition
of compounds containing easily abstractable hydrogen atoms
such as amines or thiols is a different way to limit the oxy-
gen inhibition effect: the peroxy radicals formed from the
reaction of the initiating radicals or the growing chain with
oxygen react with a hydrogen donor and create a new ini-
tiating radical and a hydroperoxide. The latter can lead to
Correspondence to: X. Allonas (E-mail: xavier.allonas@uha.fr)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 48, 24622469 (2010) V
2462
gated by means of Laser Flash Photolysis. V
C 2010 Wiley Peri-
odicals, Inc. J Polym Sci Part A: Polym Chem 48: 24622469,
2010
KEYWORDS: laser-induced polymers; photopolymerization; radi-
cal polymerization
further photodecomposition.911 Similarly, use of monomer
containing some abstractable hydrogen (i.e., N-vinylamides,
acrylate containing ether groups) has been shown to be ben-
eficial.12 Besides these different ways, photochemical meth-
ods may also be used to consume dissolved oxygen before
polymerization. One method is based on light-absorbing spe-
cies that sensitize singlet oxygen from dissolved molecular
oxygen. Once it is produced, singlet oxygen can react with a
scavenger such as benzofuran derivatives to form hydroper-
oxides or endoperoxides; these compounds are subject to
further decomposition upon irradiation, thereby, removing
the molecular oxygen from the system.13
Finally, phosphorus compounds, whose antioxidant effects
have been described over the past, could be an attractive
photochemical route.14 Indeed, trivalent phosphorus com-
pounds have been reported to act as reductants of peroxy
radicals.15 Therefore, beneficial effects of trivalent phosphites
and phosphines can be expected. These effects have been
scarcely reported in terms of increase in polymerization rate
of acrylate formulations and investigated by photo-gel time
measurements, DSC, photo-DSC techniques or measurement
of the depletion of dissolved oxygen during the polymeriza-
tion.1619 However, to the best of our knowledge, no detailed
study was specifically devoted to this topic. Continuing our
work on inhibition effect of oxygen toward free-radical poly-
merization,2023 we found interesting to investigate the abil-
ity of triphenylphosphine (TPP) to overcome oxygen inhibi-
tion in free-radical photopolymerization. This article focuses
on a study of acrylate systems by real-time Fourier
transform infrared spectroscopy (RT-FTIR) and laser flash
photolysis (LFP), thus providing information on both
C 2010 Wiley Periodicals, Inc.
INTERSCIENCE.WILEY.COM/JOURNAL/JPOLA

FIGURE 1 Photopolymerization profiles obtained for TPGDA.
(a) under air without TPP, (b) under air with 1 wt % TPP, (c)
laminated without TPP, and (d) laminated with 1 wt % TPP.
Photoinitiator: 4 wt % TPO, light intensity: 21 mW/cm2.
polymerization parameters and mechanism involved. To
afford relevant information, diphenyl-(2,4,6-trimethylben-
zoyl)-phosphine oxide (TPO) was used as photoinitiator for
two reasons: (i) it is known to be sensitive to oxygen inhibi-
tion, (ii) the formation and decay of the initiating phosphi-
noyl radicals generated after TPO photolysis can be easily
detected by laser flash photolysis in solution.24
EXPERIMENTAL
Materials
Difunctional monomers having different viscosities g were
used: hexanediol diacrylate (HDDA from CYTEC, g 10 mPa
s); tripropylene glycol diacrylate (TPGDA from CYTEC, g
15 mPa s); silicone diacrylate (Ebecryl 350, Eb350 from
CYTEC, g 300 mPa s); ethoxylated bisphenol A diacrylate
(Sartomer 349, SR349 from Sartomer, g 1500 mPa s). The
polymerizations were performed with diphenyl-(2,4,6-trime-
thylbenzoyl)-phosphine oxide (TPO, Ciba Specialty Chemi-
cals) as photoinitiator introduced at 4 wt % in the formula-
tion. The triphenylphosphine (TPP, Aldrich) was used as
oxygen scavenger with a concentration ranging from 0 to 4
wt %.
Methods
The curing profiles (final conversion, polymerization rate,
and inhibition time) were determined by RT-FTIR measure-
ments: the sample was exposed simultaneously to the UV
irradiation and to the IR analytical beam.25 Thereby, the
decay of the vibration band at 1410 cm
1 was monitored as
a function of photocuring time. A spectrophotometer (Vertex
70, Bruker) equipped with a MCT detector was used for
these FTIR experiments with a spectral resolution of 4 cm
1.
The error was about 1015% on the rates of photopolymeri-
zation and about 5% on the final conversions. The curing
lamp was a Hamamatsu L8252 Hg-Xe equipped with a filter
at 366 nm. Its intensity ranged from 0 to 21 mW/cm2. For
the IR measurements, the formulation was applied onto a
BaF2 ship using a calibrated bar to obtain a 10.5-lm-thick
layer (initial IR absorbance of 1.2 at 1410 cm
1). In some
BENEFICIAL EFFECT OF TRIPHENYLPHOSPHINE, BELON ET AL.
ARTICLE
cases, a thin film of polypropylene was used to cover the
sample, thereby, preventing the sample from the diffusion of
oxygen.
Laser flash photolysis was used to evaluate the effect of TPP
on oxygen inhibition. A nanosecond Nd:YAG laser beam at
355 nm was used to excite the photoinitiator that generates
the transient species.26 The formation and the decay of these
radicals are followed by UVvisible absorption spectroscopy.
The transient absorption analyzing system (LP900, Edin-
burgh Instruments) used a 450 W pulsed xenon arc lamp, a
Czerny-Turner monochromator, a fast photomultiplier, and a
transient digitizer (TDS 340, Tektronix). For this experiment,
the photoinitiator was dissolved in acetonitrile and its
optical density was adjusted at about 0.5 at 355 nm. The
experiments could be performed under air, argon, or O2
atmosphere.
RESULTS AND DISCUSSION
Polymerization Kinetics
Effect of TPP on Acrylate Polymerization
To evaluate the oxygen scavenging effect of TPP on acrylate
curing, the photopolymerization of TPGDA in the absence or
the presence of various amount of TPP was followed using a
photoinitiator content of 4 wt %. The polymerization profiles
obtained for samples cured under air or sealed conditions
are shown in Figure 1, and the data are reported in Table 1.
Under air and in the absence of TPP, the rate of polymeriza-
tion is very low and the final conversion hardly reaches
30%. The consumption of TPO seems to follow the same
kinetics as the photopolymerization one: indeed, from Figure
2, 85% of TPO was consumed after 50s in the film, in agree-
ment with the corresponding conversion profile (Fig. 1,
curve a) showing that the conversion reaches 88% of its
maximum at the same time. Consequently, the photopolyme-
rization under air is merely limited by the full consumption
of the photoinitiator. Moreover, in that case, the polymeriza-
tion starts after an inhibition period of 2.3 s, which corre-
sponds to the time required by the initiating radicals to con-
sume the oxygen dissolved in the sample.
The effect of TPP is significant when the sample is cured
under air (Fig. 1, curve b): the polymerization rate is
increased by a factor of 10 and the final conversion by a fac-
tor of 2. The inhibition time is completely suppressed, show-
ing that the use of TPP in a radical formulation leads to the
rapid consumption of dissolved oxygen during the early
TABLE 1 Effect of TPP (1 wt %) on TPGDA
Photopolymerization: Final Conversions, Polymerization
Rates, and Induction Times
Final Induction
Conversion (%) Rp/[M]0 (s
1) Time (s)
Under air 55.6 (33.7) 1.02 (0.008) 0.03 (2.3)
Laminated 100 (95.9) 1.63 (1.52) 0.1 (0.1)
In bracket: without TPP.
2463
JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
FIGURE 2 Photoinitiator photobleaching in TPGDA under air
and without TPP. Photoinitiator: 4 wt % TPO, light intensity:
21 mW/cm2.
stage of the photopolymerization, an effect that was already
reported. Consequently, one can assume that the concentra-
tion of initiating radicals available to initiate the reaction is
increased leading to a higher polymerization rate.
When the sample is laminated, the effect of TPP is obviously
less important: the conversion profiles obtained for the sam-
ples with and without TPP are similar. In this case, the addi-
tion of TPP is relevant as far as the inhibition period is con-
cerned, the latter being attributed to the time required for
the consumption of the oxygen initially dissolved in the for-
mulation (which is typically at concentration about 2  10
3
mol/dm3 in organic media27).
All these experiments clearly show that TPP is particularly
effective to reduce the inhibitory effect of the diffusion of O2
during the curing under atmospheric conditions.
Influence of TPP Concentration
The photopolymerization of TPGDA under air was evaluated
using different concentrations of TPP up to 6 wt %. The cor-
responding polymerization kinetics are shown in Figure 3,
and the relevant data are collected in Table 2. An increase in
FIGURE 3 Photopolymerization kinetics of TPGDA under air
using different concentrations of TPP. (a) 0 wt %, (b) 1 wt %,
(c) 4 wt % and (d) 6 wt %. Photoinitiator: 4 wt % TPO, light
intensity: 21 mW/cm2.
2464
TABLE 2 Effect of TPP Concentration on TPGDA
Polymerization: Final Conversions, Polymerization Rates, and
Induction Times
TPP
Concentration Final Rp/[M]0 Induction
(wt %) Conversion (%) (s
1) Time (s)
0 33.7 0.008 2.3
1 55.6 1.02 0.03
4 74.3 0.69 0.03
6 90.5 0.91 0.03
TPP concentration results in an improvement of the poly-
merization efficiency as already reported.1619 As stated
above, the inhibition time is completely suppressed by add-
ing only 1 wt % of TPP (Table 2). The highest polymeriza-
tion rate is obtained using this concentration, although the
error on Rp prevents further analysis at higher concentra-
tions. Considering these results, the TPP concentration was
set at 1 wt % for the following experiments.
Influence of the Monomer Viscosity
The effect of oxygen inhibition on the photopolymerization
reaction is dependent on the viscosity.7 During the earliest
stage of the photopolymerization, the dissolved oxygen tends
to be consumed. The equilibrium between dissolved and
atmospheric oxygen is then displaced and a diffusion process
from the atmosphere to the bulk takes place tending to an
equilibrated concentration of O2 in the bulk. One can antici-
pate that in highly viscous formulations, oxygen will diffuse
much slowly from the atmosphere to the film and the inhibi-
tion effect will be limited.
Therefore, it is quite interesting to quantify the effect of TPP
on the polymerization of difunctional monomers having dif-
ferent viscosities. The polymerization profiles of the resins in
the presence or in the absence of TPP are reported Figure 4.
As shown in Table 3, the effect of TPP is obvious for low-vis-
cosity monomers: indeed, in the case of both HDDA and
TPGDA, the polymerization hardly proceeds under air due to
an important effect of oxygen inhibition. When TPP is added,
final conversions and polymerization rates increase and the
inhibition time is suppressed proving that TPP consumes the
oxygen which diffuses in the sample.
Concerning the monomers with higher viscosities (Eb350
and SR349), the addition of TPP in the formulation does not
significantly change the polymerization profile, albeit a clear
decrease of the inhibition time can be noted.
Influence of the Light Intensity
The kinetics of acrylate photopolymerization reactions are
strongly affected by light intensity. At high irradiance, an im-
portant concentration of initiating radical is immediately
produced. Consequently, the oxygen inhibition is reduced.
The effect of TPP on the polymerization of Sartomer 349
was studied at different light intensities, and the correspond-
ing data are reported in Table 4. This monomer was of par-
ticular interest as it still led to measurable final conversion
INTERSCIENCE.WILEY.COM/JOURNAL/JPOLA
 ARTICLE

FIGURE 4 Photopolymerization profiles obtained for diacrylates with different viscosities. 1/HDDA, 2/TPGDA, 3/Eb350 and 4/SR349
with (a) 1 wt % TPP and (b) without TPP. Photoinitiator: 4 wt % TPO, light intensity: 21 mW/cm2, curing under air.

ratios even at low intensity when the polymerization was decreases when the light intensity increases: as the oxygen
performed without TPP. The effect of light intensity on the inhibition vanishes, the difference between the samples con-
polymerization is clearly evidenced when comparing the taining or not TPP is less significant. It is interesting to note
data of the four samples which do not contain TPP. An that the beneficial effect of TPP is found for low light
increase in intensity leads to a higher final conversion, a intensity.
higher polymerization rate, and a decrease of the inhibition
Influence of the Sample Thickness
time.
Table 5 reports the effect of TPP for samples based on
In all cases, the polymerization kinetics are improved by the TPGDA with different thicknesses. The photoinitiator absorb-
addition of TPP in the samples. Nevertheless, this effect ance being lower than 0.48 at the irradiation wavelength
(366 nm) in the thicker film, no significant internal filter
TABLE 3 Effect of the Monomer Viscosity on Final effect is expected to influence the photopolymerization
Conversions, Polymerization Rates, and Induction Times with
1 wt % of TPP TABLE 4 Effect of the Light Intensity on Sartomer 349
Polymerization: Final Conversions, Polymerization Rates,
Final and Induction Times with 1 wt % of TPP
Conversion Rp/[M]0 Induction
Monomer (%) (s
1) Time (s) Final
Light Conversion Rp/[M]0 Induction
HDDA (10 mPa s) 62.7 (32.1) 0.019 (0.009) 0 (0.4)
Intensity (%) (s
1) Time (s)
TPGDA (15 mPa s) 55.6 (33.7) 1.02 (0.008) 0.03 (2.3)
Ebecryl 350 55.4 (53.9) 0.38 (0.31) 0.1 (0.238) 2 mW/cm2 57.3 (51.9) 0.51 (0.06) 0.1 (0.94)
(300 mPa s) 7 mW/cm2 64.8 (61.9) 0.93 (0.54) 0.03 (0.24)
Sartomer 349 70.2 (67) 1.81 (1.43) 0.03 (0.1) 11 mW/cm2 67.1 (64.1) 1.18 (0.85) 0.03 (0.14)
(1500 mPa s) 21 mW/cm2 70.2 (67) 1.81 (1.43) 0.03 (0.1)

In bracket: without TPP. In bracket: without TPP.

BENEFICIAL EFFECT OF TRIPHENYLPHOSPHINE, BELON ET AL. 2465

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA

TABLE 5 Effect of the Sample Thickness on TPGDA It should be noticed that even for high thickness, the addi-
Polymerization: Final Conversions, Polymerization Rates, tion of TPP has a beneficial effect on the inhibition by oxy-
and Induction Times with 1 wt % of TPP gen, although in limited extent. Concerning the thinner sam-
ple, better results are reached when TPP is used; however,
Sample Final the final conversion hardly reaches 30%. In this case, one
Thickness Conversion Rp/[M]0 Induction can suppose that the diffusion of oxygen is very important.
(lm) (%) (s
1) Time (s)
The competition between the peroxy radical formation and
17.5 72.7 (72.6) 1.25 (0.33) 0.03 (0.24) the scavenging effect by TPP clearly favors the inhibition
14 68.3 (42.3) 1.17 (0.01) 0.03 (1.63) reaction. By contrast, TPP was found to totally suppress the
detrimental effect of oxygen in 10-lm-thick samples, as can
10.5 55.6 (33.7) 1.02 (0.008) 0.03 (2.47)
be seen from the inhibition time. This clearly shows that
7.0 56 (24.2) 0.32 (0.006) 0.1 (2.88)
TPP is involved in competitive mechanism of reaction with
3.5 31.4 (10.8) 0.01 (0.004) 0.17 (4.28) O2 diffusion.
In bracket: without TPP.
Transient Absorption Spectroscopy
After excitation by light and intersystem crossing to the tri-
process. Under air and in the absence of TPP, the effect of
plet state, TPO leads to the formation of benzoyl (A) and
the thickness on the extent of oxygen inhibition is significant.
phosphinoyl (B) radicals (eq 1). This reaction occurs via the
For example, the final conversion varies from 11 to 73%
a-cleavage from a short-lived (0.080.1 ns) triplet excited
when the thickness increases by a factor of five. The inhibi-
state. The quantum yield of formation of radicals has been
tion time is also considerably reduced when increasing the
measured by steady-state photolysis between 0.4 and
thickness. Indeed, the greater the distance oxygen molecules
0.8.24,2830 A recent measurement yields a value of 0.7 for
have to diffuse into the film, the lower the inhibition effect
the dissociation quantum yield from the lowest triplet state
is.6
which proves the high efficiency of the reaction.38

(1)

Concerning the phosphinoyl radical, the rate constant of Figure 5 shows the formation and decay of the phosphinoyl
reaction with methylacrylate is reported to be about 23  radical B after laser flash. A residual absorption is observed
107 M
1 s
1, and the rate constant of reaction with oxygen (DOD  0.005) which corresponds to the photolysis product
is 4.2  109 M
1 s
1 in acetonitrile.24,31,32 These data high- C that was formed from the recombination of two phosphi-
light the fact that even if the reactivity of phosphinoyl radi- noyl radicals B (eq 2).
cals toward acrylates is very high, the initiating efficiency
will be affected by the competitive reaction with oxygen.
Concerning the benzoyl radical, the rate constant of reaction
with butylacrylate is reported at about 2.7  105 and 5 
105 M
1 s
1, and the rate constant of reaction with oxygen
is 3  109 M
1 s
1 in acetonitrile.3,33 From these data, it
turns out that the benzoyl radical is not the most efficient
initiating radical. (2)

The UV absorption spectra of both radicals are quite differ-

ent: the benzoyl radical exhibits a weak transient absorption
at 370 nm (extinction coefficient e 145 M
1 cm
1),34
whereas the phosphinoyl radical presents an absorption
maximum at 330 nm with a high extinction coefficient: e
1.6  104 M
1 cm
1.35 Therefore, even if both radicals are
formed, only the phosphinoyl radical B is observed at the
analyzing wavelength of 340 nm. Therefore, the following
discussion will focus on the reactivity of the phosphinoyl
radical with oxygen and in the presence of TPP.
Adding 2.5  10
3 mol/dm3 of TPP in the solution has no
effect on the decay curve of the phosphinoyl radical (Fig. 5).
This is in line with the RT-FTIR experiments showing that
TPP does not affect the polymerization when the sample is
cured in the absence of oxygen.
Focusing at short time allows the observation of O2 effect on
the phosphinoyl radical B (Fig. 6) in the absence of TPP. The
solution of TPO was first analyzed under air ([O2] 1.9 
10
3 mol/dm3 27) and then bubbled by oxygen before the

2466 INTERSCIENCE.WILEY.COM/JOURNAL/JPOLA

FIGURE 5 Transient absorption kinetics of argon saturated ace-
tonitrile solutions of TPO monitored at 340 nm without TPP
(black) and with 2.5  10
3 M of TPP (red).
measurements ([O2] 9.1  10
3 mol/dm3 27). The corre-
sponding transient absorption profiles of B at different con-
centrations of oxygen can be compared to the one obtained
under inert atmosphere (Fig. 6). The phosphinoyl radical
decays faster in the presence of oxygen: the lifetime falls
down to 145 ns under air and 15.1 ns in an oxygen satu-
rated atmosphere, showing the high quenching efficiency of
oxygen. From these results, the average value for the rate
constant kqO2 was determined to be 5.5  109 M
1 s
1, in
good agreement with the literature.32
(3)
FIGURE 6 Transient absorption kinetics of acetonitrile solutions
of TPO monitored at 340 nm and in the absence of TPP under
(a) nitrogen (black), (b) air ([O2] 0.0019 M, red), (c) oxygen
([O2] 0.0091 M, blue).
BENEFICIAL EFFECT OF TRIPHENYLPHOSPHINE, BELON ET AL.
ARTICLE
During this decay, the diphenylphosphinic peroxyl radical D
was formed (eq 3) which is not observed experimentally by
laser flash photolysis.32 However, the existence of such spe-
cies has been already proved by reaction of O

2 on diphenyl-
phosphoryl chloride.36
A growing residual absorption appeared within 3 ls which
is tentatively attributed to a recombination product E, a con-
ventional reaction for carbon based peroxy radicals (eq 4).15
(4)
The effect of TPP on peroxyl radicals was probed by adding
increasing concentrations of TPP in an oxygen saturated so-
lution of TPO. The corresponding transient absorption
kinetics are shown in Figure 7. In the presence of TPP, a
new transient appears in the microsecond time scale. Fitting
the rising signal with increasing concentration of TPP leads
to a reaction rate constant k  1.8  1010 M
1 s
1. This
transient exhibits a decay curve which depends on the TPP
concentration, and therefore, it can be clearly stated that this
transient arises from the reaction between TPP and the
diphenylphosphinic peroxyl radical D. Recently, the rate con-
stant of interaction between TPP and a carbon peroxyl radi-
cal formed by the addition of oxygen onto N,N-diethylami-
noethyl radical was measured to be 104 M
1 s
1 in non
polar solvent.37 It is anticipated that in polar solvent, the
reaction can be governed by electron transfer process, and
the rate constant is expected to increase. This could explain
the high rate constant of appearance for the transient
formed from the reaction between TPP and D in polar sol-
vent such as acetonitrile. To confirm this, the same reaction
FIGURE 7 Transient absorption kinetics of oxygen saturated
acetonitrile solutions of TPO monitored at 340 nm. (a) 0 M,
(b) 4.1  10
4 M, (c) 8.2  10
4 M, (d) 1.23  10
3 M, (e) 2.46 
10
3 M of TPP.
2467
JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
was performed in t-butylbenzene and the rising signal
observed in Figure 7 completely vanished, indicating that the
rate constant decreased. Unfortunately, the experimental set-
up does not allow the measurement of such low rate con-
stants. This reaction leads to the radical F (eq 5) which is
known to undergo a fast cleavage with the formation of an
diphenylphosphinic oxyl radical G and a phosphine oxide
(eq 6).
(5)
(6)
Further reaction of G with TPP leads to a phosphoranyl radi-
cal H (eq 7) which is known to absorb in the UV region:37
SCHEME 1 Mechanism of peroxyl radical scavenging by TPP.
2468
(7)
The attribution of the rising signal of Figure 7 to F, G, or H
is difficult on the sole basis of the described experiments.
However, this transient clearly shows that a reaction pro-
ceeds between TPP and the phosphinic peroxyl radical D.
This finding is in good agreement with the expected mecha-
nism of carbon peroxyl radical with TPP.15
Because of the high concentration of monomer in the photo-
polymerizable medium, G reacts predominantly with the
monomer leading to an increase of the rate of polymeriza-
tion and a higher final conversion.
From these experiments, the beneficial effect of TPP can be
summarized as follow. First of all, TPP does not affect the
initiation reaction, as no reaction was detected between TPP
and the phosphinoyl radical B. When oxygen reacts with an
initiating radical (or a growing chain), TPP scavenges the
peroxyl radical and leads to the formation of F. On the basis
of the known behavior of carbon based systems, F is
expected to cleave efficiently leading to the formation of a
diphenylphosphinic oxyl radical G that could initiate the
polymerization reaction. This hypothesis is supported by the
INTERSCIENCE.WILEY.COM/JOURNAL/JPOLA

detection of a transient which increases when the concentra-
tion of TPP increases. During this process, TPP is consumed
and turns into phosphine oxide (Scheme 1).
CONCLUSIONS
In this article, the effect of TPP as oxygen scavenger in free-
radical photopolymerization of acrylates was cleared up. It
was found that the effect of oxygen inhibition decreases in
the presence of TPP. Different factors such as monomer vis-
cosity, light intensity, and sample thickness were investigated
by real-time FTIR spectroscopy. Their relative influence with
respect to the oxygen inhibition and the efficiency of TPP
was evidenced. Laser flash photolysis was used to propose a
mechanism for the beneficial reaction of TPP in agreement
with the literature. Therefore, the use of TPP in free-radical
polymerization appears to be very useful for low-viscosity
samples, thin formulations or reduced light intensities.
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