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ABSTRACT: Triphenylphosphine (TPP) was used in free-radical gated by means of Laser Flash Photolysis. V
C 2010 Wiley Peri-
UV-curable resins to reduce oxygen inhibition effect. The odicals, Inc. J Polym Sci Part A: Polym Chem 48: 24622469,
relative influence of concentration, monomer viscosity, light 2010
intensity and sample thickness on TPP efficiency was investi-
gated by real time infrared spectroscopy. It is shown that TPP KEYWORDS: laser-induced polymers; photopolymerization; radi-
is an effective oxygen scavenger. The mechanism was investi- cal polymerization
INTRODUCTION The inhibition effect of molecular oxygen in further photodecomposition.911 Similarly, use of monomer
free-radical photopolymerization reactions has always been a containing some abstractable hydrogen (i.e., N-vinylamides,
key issue.15 Indeed, the radicals formed during the initiation acrylate containing ether groups) has been shown to be ben-
of the reaction are scavenged by oxygen leading to peroxy eficial.12 Besides these different ways, photochemical meth-
radicals that can hardly initiate or contribute to the polymer- ods may also be used to consume dissolved oxygen before
ization reaction. Moreover, oxygen is also capable to quench polymerization. One method is based on light-absorbing spe-
the photoinitiator excited states. Consequently, detrimental cies that sensitize singlet oxygen from dissolved molecular
effects are observed such as the presence of an inhibition oxygen. Once it is produced, singlet oxygen can react with a
time and the decrease in both polymerization rate and final scavenger such as benzofuran derivatives to form hydroper-
conversion ratio, resulting in tacky surfaces. These features oxides or endoperoxides; these compounds are subject to
were nicely confirmed recently by modeling the effect of oxy- further decomposition upon irradiation, thereby, removing
gen inhibition on the photopolymerization kinetics, providing the molecular oxygen from the system.13
a good description of the different mechanisms involved.6
Finally, phosphorus compounds, whose antioxidant effects
Physical and chemical methods that may be used to over- have been described over the past, could be an attractive
come oxygen inhibition have been recently reviewed.5 photochemical route.14 Indeed, trivalent phosphorus com-
Increasing light intensity or photoinitiator concentration is a pounds have been reported to act as reductants of peroxy
possible way to achieve this goal. Thereby, a large concentra- radicals.15 Therefore, beneficial effects of trivalent phosphites
tion of radicals is generated upon irradiation, consuming the and phosphines can be expected. These effects have been
dissolved oxygen during the light curing process. Use of scarcely reported in terms of increase in polymerization rate
high-viscosity monomers or increase in sample thickness is of acrylate formulations and investigated by photo-gel time
also an alternative way to limit the oxygen diffusion from measurements, DSC, photo-DSC techniques or measurement
the surrounding atmosphere to the bulk. Another effective of the depletion of dissolved oxygen during the polymeriza-
method is to purge the sample with an inert gas (nitrogen tion.1619 However, to the best of our knowledge, no detailed
or carbon dioxide) before the polymerization process,7,8 the study was specifically devoted to this topic. Continuing our
drawback being the important additional costs. The addition work on inhibition effect of oxygen toward free-radical poly-
of compounds containing easily abstractable hydrogen atoms merization,2023 we found interesting to investigate the abil-
such as amines or thiols is a different way to limit the oxy- ity of triphenylphosphine (TPP) to overcome oxygen inhibi-
gen inhibition effect: the peroxy radicals formed from the tion in free-radical photopolymerization. This article focuses
reaction of the initiating radicals or the growing chain with on a study of acrylate systems by real-time Fourier
oxygen react with a hydrogen donor and create a new ini- transform infrared spectroscopy (RT-FTIR) and laser flash
tiating radical and a hydroperoxide. The latter can lead to photolysis (LFP), thus providing information on both
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TPP
Concentration Final Rp/[M]0 Induction
(wt %) Conversion (%) (s1) Time (s)
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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 (%) (s1) 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 (%) (s1) 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)
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) (%) (s1) 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 M1 s1, and the rate constant of reaction with oxygen (DOD 0.005) which corresponds to the photolysis product
is 4.2 109 M1 s1 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 M1 s1, and the rate constant of reaction with oxygen
is 3 109 M1 s1 in acetonitrile.3,33 From these data, it
turns out that the benzoyl radical is not the most efficient
initiating radical. (2)
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ARTICLE
FIGURE 6 Transient absorption kinetics of acetonitrile solutions FIGURE 7 Transient absorption kinetics of oxygen saturated
of TPO monitored at 340 nm and in the absence of TPP under acetonitrile solutions of TPO monitored at 340 nm. (a) 0 M,
(a) nitrogen (black), (b) air ([O2] 0.0019 M, red), (c) oxygen (b) 4.1 104 M, (c) 8.2 104 M, (d) 1.23 103 M, (e) 2.46
([O2] 0.0091 M, blue). 103 M of TPP.
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ARTICLE
detection of a transient which increases when the concentra- 16 Hoyle, C. E. In Technical Conference ProceedingsUV & EB
tion of TPP increases. During this process, TPP is consumed Technology Expo & Conference, Charlotte, NC, United States,
and turns into phosphine oxide (Scheme 1). 2004; pp 892899.
17 Zadok, E.; Eitan, A.; Tamir, I. Thermochim Acta 1989, 148,
387393.
CONCLUSIONS 18 Kuang, W.; Hoyle, C.; Vishwanathan, K.; Jonsson, S. In
In this article, the effect of TPP as oxygen scavenger in free- Technical Conference ProceedingsRadTech 2002: The Pre-
mier UV/EB Conference & Exhibition, Indianapolis, IN, United
radical photopolymerization of acrylates was cleared up. It
States, 2002; pp 292299.
was found that the effect of oxygen inhibition decreases in
the presence of TPP. Different factors such as monomer vis- 19 Morgan, C. R.; Kyle, D. R. J Rad Curing 1983, 10, 47.
cosity, light intensity, and sample thickness were investigated 20 Lalevee, J.; Dirani, A.; El Roz, M.; Allonas, X.; Fouassier, J.
by real-time FTIR spectroscopy. Their relative influence with P. Macromolecules 2008, 41, 20032010.
respect to the oxygen inhibition and the efficiency of TPP
21 Lalevee, J.; Allonas, X.; Fouassier, J. P. Chem Phys Lett
was evidenced. Laser flash photolysis was used to propose a
2009, 469, 298303.
mechanism for the beneficial reaction of TPP in agreement
with the literature. Therefore, the use of TPP in free-radical 22 Lalevee, J.; Blanchard, N.; Graff, B.; Allonas, X.; Fouassier,
polymerization appears to be very useful for low-viscosity J. P. J Organomet Chem 2008, 693, 36433649.
samples, thin formulations or reduced light intensities. 23 Versace, D. L.; Soppera, O.; Lalevee, J.; Croutxe-Barghorn,
C. New J Chem 2008, 32, 22702278.
24 Sumiyoshi, T.; Schnabel, W.; Henne, A.; Lechkten, P. Poly-
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