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European Polymer Journal xxx (2014) xxx–xxx
EPJ 6350 No. of Pages 1, Model 3G
4 February 2014
al 2014, &, &&&
Contents lists available at ScienceDirect
European Polymer Journal
journal homepage: www.elsevier .com/locate /europol j
Graphical abstract
European Polymer JournPerylene derivatives as photoinitiators in blue light sensitive cationic orradical curable films and panchromatic thiol-ene polymerizable films
erner,
can ibased
Pu Xiao a, Frédéric Dumur b,c,d, Michel Frigoli e,Bernadette Graff a, Fabrice Morlet-Savary a,Guillaume Wantz c,d, Harald Bock f, Jean PierreFouassier g, Didier Gigmes b, *, Jacques Lalevée a, *
a Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15,rue Jean Starcky, 68057 Mulhouse Cedex, Franceb Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273,F-13397 Marseille Cedex 20, Francec Univ. Bordeaux, IMS, UMR 5218, F-33400 Talence, Franced CNRS, IMS, UMR 5218, F-33400 Talence, Francee Institut Lavoisier de Versailles, UMR CNRS 8180, UVSQ, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, Francef Centre de Recherche Paul Pascal, CNRS & Université de Bordeaux, 115 Avenue Schweitzer, 33600 Pessac, France
g Formerly, ENSCMu-UHA, 3 rue Alfred W� The perylene derivative based PISsefficient than the camphorquinonecombination of 3 perylenes.
68093 Mulhouse Cedex, France
Highlights
nitiate various polymerizations under blue lights. � The PTCTE based PISs are morePISs. � A panchromatic thiol-ene polymerizable film can be prepared using the
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European Polymer Journal xxx (2014) xxx–xxx
lable
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EPJ 6350 No. of Pages 9, Model 3G
4 February 2014
erylene derivatives as photoinitiatoationic or radical curable films andolymerizable films
u Xiao a, Frédéric Dumur b,c,d, Michel Frigoli e,uillaume Wantz c,d, Harald Bock f, Jean Pierre
Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 1Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, F-1Univ. Bordeaux, IMS, UMR 5218, F-33400 Talence, FranceCNRS, IMS, UMR 5218, F-33400 Talence, FranceInstitut Lavoisier de Versailles, UMR CNRS 8180, UVSQ, 45 Avenue des Etats-UCentre de Recherche Paul Pascal, CNRS & Université de Bordeaux, 115 Avenue
Contents lists avai
European Po
journal homepage: www.e
Formerly, ENSCMu-UHA, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France
36ives (37lly an38ion (C39ymeri40e. ver41ight e42the43TCTE44an i45lm (446, yel47tolysi48nce sp49
50
61p62p63n64l
r t i c l e i n f o
rticle history:eceived 21 December 2013eceived in revised form 14 January 2014ccepted 21 January 2014vailable online xxxx
eywords:hotoinitiatorerylene derivativelue lightationic photopolymerizationadical photopolymerizationhiol-ene photopolymerization
a b s t r a c t
The perylene derivatamine (and optionacationic polymerizator the thiol-ene polirradiation sources i.light). Upon a blue lFRP and better thanthe combination of Pylene derivatives andene polymerizable fitions (i.e. blue, greenby steady state phoelectron spin resona
. Introduction
Dyes with interesting long wavelength light absorptionroperties and high molar extinction coefficients find
arvelous applications in photoinitiating systems (PISs)or various photopolymerization reactions: through inter-ctions with suitable additives under specific light irradia-ions, different initiating species can be generated i.e.adicals for free radical polymerization (FRP) or thiol-eneolymerization (TEP), cations or radical cations for cationic
tnopl[Btp
014-3057/$ - see front matter � 2014 Published by Elsevier Ltd.ttp://dx.doi.org/10.1016/j.eurpolymj.2014.01.024
⇑ Corresponding authors.E-mail addresses: [email protected] (D. Gigmes), jacques.
[email protected] (J. Lalevée).
Please cite this article in press as: Xiao P et al. Perylene derivatives as phoand panchromatic thiol-ene polymerizable films. Eur Polym J (2014), htt
n blue light sensitivechromatic thiol-ene
nadette Graff a, Fabrice Morlet-Savary a,assier g, Didier Gigmes b,⇑, Jacques Lalevée a,⇑Jean Starcky, 68057 Mulhouse Cedex, Francearseille Cedex 20, France
8035 Versailles Cedex, Franceeitzer, 33600 Pessac, France
PTCTE, BPTI and DPPDI) combined with an iodonium salt or anadditive) are used as photoinitiating systems to initiate the
P) of epoxides, the free radical polymerization (FRP) of acrylates,zation (TEP) of a Trithiol/divinylether mixture under differenty soft halogen lamp or laser diodes at 473 nm or 457 nm (bluexposure, the PTCTE based systems are very efficient for CP andcamphorquinone (CQ) based reference systems. Interestingly,with previously studied green light and red light sensitive per-
odonium salt ensures the manufacture of a panchromatic thiol-00–650 nm) usable under various household LED bulbs irradia-low or red lights). The photochemical mechanisms are studieds, fluorescence, cyclic voltammetry, laser flash photolysis andin-trapping techniques.
� 2014 Published by Elsevier Ltd.
olymerization (CP) or free radical promoted cationicolymerization (FRPCP). It is of great interest to developovel high performance dyes sensitive to different wave-
engths for photopolymerization reactions usable in radia-
at ScienceDirect
er Journal
ier .com/locate /europol j
65ion curing, material elaboration, microelectronics,66anotechnology, medicine, or imaging and optics technol-67gies [1–5]. Camphorquinone (CQ) is well known as a68hotoinitiator for polymerization reactions with blue69ights [1]. We have e [6], naphthalimide [7], indanedione708,9], and thiophene derivatives [10], indoline dye [11],71ODIPY [12], chromone [13], barbituric and acid deriva-72ives [14], Michler’s ketone [15], pyrene derivatives [16],73yrromethene dyes [17], anthracene derivatives [18],
toinitiators in blue light sensitive cationic or radical curable filmsp://dx.doi.org/10.1016/j.eurpolymj.2014.01.024
74 etc.) sensitive to wavelengths up to 500 nm. One fascinat-75 ing challenge remains on the design of more efficient76 derivatives within a given scaffold.77 In our recent research, perylene derivatives have been78 proposed and used in PISs under green light [19] or red79 light [20] irradiations. Perylene has also been found as a80 photosensitizer for the photolysis of sulfonium salts81 [21,22], N-ethoxy-2-methylpyridinium hexafluorophos-82 phate [23], phenacylanilinium salt [24], or iodonium salts83 [25], at long-wavelength UV light irradiations and thus ini-84 tiate the photopolymerization. Herein, we use novel blue85 light sensitive perylene derivatives Pers (Scheme 1; two86 previously studied compounds D_1 and Per1 will also be87 considered, and their chemical structures are given in the88 Scheme S1 in the Supporting information SI) as photoiniti-89 ators incorporable in PISs with other additives. The photo-90
91
92
93
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95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119monomers to characterize the photopolymerization effi-120ciency of the photoinitiating systems.
1212.2. Computational procedure
122Molecular orbital calculations were carried out with the123Gaussian 03 package. The electronic absorption spectra of124the different Pers were calculated with the time-depen-125dent density functional theory at B3LYP/6-31G� level on126the relaxed geometries calculated at UB3LYP/6-31G� level;127the molecular orbitals involved in these transition can be128extracted [28,29]. The geometries were frequency checked.
1292.3. Irradiation sources
130Different irradiation sources were used for the photopoly-131
132
2 P. Xiao et al. / European Polymer Journal xxx (2014) xxx–xxx
EPJ 6350 No. of Pages 9, Model 3G
4 February 2014
initiating abilities of these PISs towards different types ofpolymerization reactions as well as irradiation sources(blue lights for CP and FRP, blue to red lights for TEP) are
studied. The photochemical mechanisms involved in the133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
initiation species formation are investigated by steadystate photolysis, fluorescence, cyclic voltammetry, laserflash photolysis and electron spin resonance spin trappingtechniques.
2. Experimental
2.1. Materials
The Chemical structures of the studied perylene deriva-tives Pers i.e. perylene-3,4,9,10-tetracarboxylic tetraethylester (PTCTE), benzo[ghi]perylene-1,2,4,5,10,11-hexacarb-oxylic tris(2-ethylhexyl) imide (BPTI) and 1,7-dipiperidi-nyl-perylene-3,4,9,10-tetracarboxylic dioctyl imide(DPPDI), and other studied compounds are shown inSchemes 1 and 2. PTCTE and BPTI were prepared accordingto published procedures [26,27]. DPPDI was preparedaccording to a procedure described in detail in the SI.
Diphenyliodonium hexafluorophosphate (Iod), N-
vinylcarbazole (NVK), methyl diethanolamine (MDEA),151
152
153ter. The interaction rate constant kq between Pers and Iod154was extracted by classical Stern–Volmer treatments [32]155(I0/I = 1 + kqs0[Iod], where I0 and I stand for the fluorescent156intensity of Pers in the absence and the presence of the Iod157quencher, respectively, and s0 stands for the lifetime of Pers158excited singlet state in the absence of Iod). The fluorescence
2,4,6-tris(trichloromethyl)-1,3,5-triazine (R’-Cl), tri(ethyl-ene glycol) divinyl ether (DVE-3), trimethylolpropanetris(3-mercaptopropionate) (Trithiol), and the other re-agents and solvents were purchased from Sigma-Aldrichor Alfa Aesar and used as received without further purifica-tion. (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexyl-carboxylate (EPOX) and trimethylolpropane triacrylate(TMPTA) were obtained from Cytec and used as benchmark
O
N
O
O
HexylEt
Et
I
N N
O
O O
ON
N
DPPDI
CH2H2C 88HH
ctures of PTCTE, BPTI and DPPDI.
NO
N
O
O
Et
Hexyl
Hexyl
EtO2C
EtO2C
CO2Et
CO2Et
BPTPTCTE
Scheme 1. Chemical stru
Please cite this article in press as: Xiao P et al. Perylene derivatives as pand panchromatic thiol-ene polymerizable films. Eur Polym J (2014),
merization experiments: polychromatic light from a halogenlamp (Fiber-Lite, DC-950; incident light intensity: I0 �12 mW cm�2 in the 370–800 nm range); laser diodes at457 nm (100 mW cm�2), 473 nm (100 mW cm�2) or635 nm (100 mW cm�2) and household blue LED bulb at462 nm (�10 mW cm�2), green LED bulb at 514 nm(�10 mW cm�2), yellow LED bulb at 591 nm(�10 mW cm�2) or red LED bulb at 630 nm (�10 mW cm�2).
2.4. Photopolymerization experiments
The experimental conditions of the photopolymeriza-tion reactions are given in the figure captions. The photo-sensitive formulations were deposited on a BaF2 pelletunder air or in laminate (25 lm thick) for irradiation withdifferent lights. The evolution of the epoxy group contentof EPOX, the double bond content of TMPTA, the doublebond content of DVE-3 and the thiol (S–H) content of Trith-iol were continuously followed by real time FTIR spectros-copy (JASCO FTIR 4100) [30,31] at about 790 cm�1,1630 cm�1, 1620 cm�1 and 2580 cm�1, respectively.
2.5. Fluorescence measurements
The fluorescence properties of the studied perylenederivatives were studied using a JASCO FP-750 spectrome-
hotoinitiators in blue light sensitive cationic or radical curable filmshttp://dx.doi.org/10.1016/j.eurpolymj.2014.01.024
159 quantum yields of the studied Pers were determined using160 anthracene as a reference.
161 2
162
163 s164 t165 (166 T167 e168 w169 t170 p171 c172 w173 (174 p175 s176 i177 c178
D180180
181 2
182
183 w184 l185 1186 c187 f188 L
189 2
190
191 s192 e193 s194 (195 i196 w
1973. Results and discussion
1983.1. 1/Light absorption properties
199UV-visible absorption spectra of PTCTE, BPTI and DPPDI200in acetonitrile/toluene (50%/50%, V/V) are given in Fig. 1.201The absorption maxima of PTCTE, BPTI and DPPDI are202located at 469 nm (molar extinction coefficient
DVE-3O O
3
I PF6N
Iod NVK
O
O
OOO
OOO
O
OEPOX TMPTA
HO N OH
MDEA R'-Cl
O
O
O SHHS
HS
O
O
O
Trithiol
N
N
N
Cl Cl
Cl
ClCl Cl
Cl
Cl
Cl
Scheme 2. Chemical structures of the additives and the monomers.
Q2
P. Xiao et al. / European Polymer Journal xxx (2014) xxx–xxx 3
EPJ 6350 No. of Pages 9, Model 3G
4 February 2014
.6. Redox potentials
The oxidation potentials (Eox vs SCE) of Pers were mea-ured in acetonitrile/toluene (50%/50%, V/V) by cyclic vol-
ammetry with tetrabutylammonium hexafluorophosphate203e � 39,800 M�1cm�1), 466 nm (e � 44,500 M�1cm�1) and204673 nm (e � 18,800 M�1cm�1), respectively. They exhibit205a good overlapping with the emission spectra of the206halogen lamp, the blue laser diodes at 473 nm207(�36,700 M�1cm�1 and �29,300 M�1cm�1 for PTCTE and208BPTI, respectively) and 457 nm (�28,400 M�1cm�1 and209�28,800 M�1cm�1 for PTCTE and BPTI, respectively), and210the LED bulb at 462 nm (�34,200 M�1cm�1 and211�40,200 M�1cm�1 for PTCTE and BPTI, respectively). The212absorption of DPPDI presents a red-shifted wavelength213maximum due to the alkylamino substituents of the pery-214lene moiety [20] and matches quite well the emission215spectra of the halogen lamp and the laser diode at216635 nm (�16,000 M�1cm�1).217The molecular orbitals involved in the lowest energy218transition (HOMO ? LUMO) are depicted in Fig. 2 for219PTCTE and BPTI (these two Pers correspond to reactive220dyes in the proposed photoinitiating systems – see below).
0.1 M) as a supporting electrolyte (Voltalab 6 Radiometer).he working electrode was a platinum disk and the referencelectrode was a saturated calomel electrode (SCE). Ferroceneas used as a standard, and the potentials determined from
he half peak potential were referred to the reversible formalotential of this compound (+0.44 V/SCE). The free energyhange DG for an electron transfer between Pers and Iodas calculated from the classical Rehm–Weller equation
Eq. (1), where Eox, Ered, ES (or ET), and C are the oxidationotential of Pers, the reduction potential of Iod, the excitedinglet (or triplet) state energy of Pers, and the electrostaticnteraction energy for the initially formed ion pair, generallyonsidered as negligible in polar solvents) [33]:
G ¼ Eox � Ered � ESðorETÞ þ C ð1Þ
.7. Laser flash photolysis
Nanosecond laser flash photolysis (LFP) experimentsere carried out using a Q-switched nanosecond Nd/YAG
aser (kexc = 355 nm, 9 ns pulses; energy reduced down to0 mJ) from Continuum (Minilite) and an analyzing systemonsisted of a ceramic xenon lamp, a monochromator, aast photomultiplier and a transient digitizer (LuzchemFP 212) [34].
.8. ESR spin trapping (ESR-ST) experiment
ESR-ST experiment was carried out using an X-Bandpectrometer (MS 400 Magnettech). The radicals were gen-
rated at room temperature upon the halogen lamp expo-Ft
ure under N2 and trapped by phenyl-N-tert-butylnitronePBN) according to a procedure [35] described elsewheren detail. The ESR spectra simulations were carried out
ith the WINSIM software.
Please cite this article in press as: Xiao P et al. Perylene derivatives as phoand panchromatic thiol-ene polymerizable films. Eur Polym J (2014), htt
ig. 1. UV–vis absorption spectra of PTCTE, BPTI and DPPDI in acetoni-rile/toluene (50%/50%, V/V).
toinitiators in blue light sensitive cationic or radical curable filmsp://dx.doi.org/10.1016/j.eurpolymj.2014.01.024
221 Interestingly, they exhibit very similar HOMO and LUMO in222 full agreement with their very similar light absorption223 properties (see their respective UV–vis absorption spectra224 in Fig. 1).
225 3.2. 2/Photoinitiating abilities
226 3.2.1. 2-a/Cationic polymerization of epoxide227 The photopolymerization of EPOX under air in the pres-228 ence of Pers/Iod or Pers/Iod/NVK PISs were carried out229 using several different visible irradiation sources. In the230 absence of Pers, no polymerization occurred in the pres-231 ence of Iod or Iod/NVK as Iod works only below 300 nm232 [32,36,37]. Camphorquinone (CQ) is a well known visible233
234
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256
257
HOMO
LUMO
PTCTE BPTI
Fig. 2. Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) of PTCTE and BPTI at UB3LYP/6-31G� level; for BPTI,the alkyl chains have been replaced by methyl groups to reduce the computational cost.
4 P. Xiao et al. / European Polymer Journal xxx (2014) xxx–xxx
EPJ 6350 No. of Pages 9, Model 3G
4 February 2014
light photoinitiator [1], but the CQ/Iod (0.5%/2%) systemis not efficient under the conditions employed here (e.g.
halogen lamp). Typical conversion-time profiles are given in Fig. 3 and the conversions after 800 s of light irradiationare summarized in Table 1. Upon the halogen lamp expo-sure, the PTCTE/Iod combination initiates CP with a lowconversion (18% after 800 s) while the BPTI/Iod or DPPDI/Iod PISs are not efficient. Upon addition of NVK (a known suitable additive [38]), the EPOX polymerization profilewas enhanced with a higher conversion of 60% withPTCTE/Iod/NVK in the same irradiation condition (Fig. 3,curve 1; tack free coatings). The PTCTE/Iod/NVK combina-tion also works under the laser diode at 473 nm (conver-sion = 48%; Fig. 3, curve 3) with a higher polymerizationrate than that obtained with the halogen lamp. Under the457 nm light, lower polymerization rate and conversionwere obtained (conversion = 41%; Fig. 3, curve 2) probablydue to the lower molar extinction coefficient of PTCTE at457 nm (see Fig. 1). As to BPTI (or DPPDI)/Iod/NVK, theirefficiencies for the polymerization of EPOX were relativelylow (conversions < 35%; Table 1).3.2.2. 2-b/Free radical polymerization of acrylateThe PTCTE/Iod or PTCTE/MDEA PISs can initiate the FRP
of TMPTA in laminate under the halogen lamp irradiationbut the final conversions were very low (Fig. 4 and
Please cite this article in press as: Xiao P et al. Perylene derivatives as pand panchromatic thiol-ene polymerizable films. Eur Polym J (2014),
0 200 400 600 8000
10
20
30
40
50
60
42
Con
vers
ion
(%)
Time (s)
1
3
Fig. 3. Photopolymerization profiles of EPOX under air in the presence ofPTCTE/Iod/NVK (0.5%/2%/3%, w/w/w) upon the halogen lamp (curve 1),laser diode at 457 nm (curve 2) or 473 nm (curve 3) exposure; BPTI/Iod/NVK (0.5%/2%/3%, w/w/w) upon the laser diode at 473 nm (curve 4)exposure.
Table 1EPOX conversions obtained under air upon exposure to different visiblelight sources for 800 s in the presence of Pers/Iod (0.5%/2%, w/w) or Pers/
258Table 2). Remarkably, with the addition of NVK or R0-Cl,259much higher polymerization rates and conversions are ob-260tained especially at 473 nm (see Fig. 4, curve 3 and curve 7261for PTCTE/Iod/NVK and PTCTE/MDEA/R0-Cl, respectively).262In any case, these three-component PISs under the halo-263gen lamp or the laser diode at 473 nm irradiation are
Iod/NVK (0.5%/2%/3%, w/w/w).
PISs Halogenlamp
Laser diode457 nm
Laser diode473 nm
Laser diode635 nm
PTCTE/Iod 18% – – –PTCTE/Iod/NVK 60% 41% 48% –BPTI/Iod npa – – –BPTI/Iod/NVK 19% 22% 35% –DPPDI/Iod np – – –DPPDI/Iod/NVK 1% – – 4%
a np: no photopolymerization.
hotoinitiators in blue light sensitive cationic or radical curable filmshttp://dx.doi.org/10.1016/j.eurpolymj.2014.01.024
264 m265 r
266 3267 p268
269 P
F (a) PT( w/w)C a refe(4
TTlIRw
F0r
P. Xiao et al. / European Polymer Journal xxx (2014) xxx–xxx 5
EPJ 6350 No. of Pages 9, Model 3G
4 February 2014
0 100 200 300 4000
10
20
30
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60
CQ/Iod
(a)
4
2C
onve
rsio
n (%
)
Time (s)
1
3
ig. 4. Photopolymerization profiles of TMPTA in laminate in the presence ofcurve 2) upon the halogen lamp exposure; PTCTE/Iod/NVK (0.5%/2%/3%, w/Q/Iod (0.5%/2%, w/w) (curve CQ/Iod) upon the halogen lamp exposure as
uch more efficient than that of the CQ/Iod and CQ/MDEAeference systems under the halogen lamp irradiation.
.2.3. 2-c/Panchromatic thiol-ene polymerization usingerylene derivatives based multi-component PISs
Interestingly, the combination of the blue light sensitiveTCTE, the previously studied green light sensitive perylene
270d271t272f273t274h2753276t277t
dro
3
tdpa(to
0.5%/2%/3%, w/w/w) (curve 6) upon the halogen lamp exposure; PTCTE/MDEA/R57 nm (curve 8) exposure; CQ/MDEA (0.5%/2%, w/w) (curve CQ/MDEA) upon the
able 2MPTA conversions obtained in laminate upon exposure to different visible
ight sources for 400 s in the presence of PTCTE/Iod (0.5%/2%, w/w), PTCTE/od/NVK (0.5%/2%/3%, w/w/w), PTCTE/MDEA (0.5%/2%, w/w), PTCTE/MDEA/0-Cl (0.5%/2%/3%, w/w/w), CQ/Iod (0.5%/2%, w/w) or CQ/MDEA (0.5%/2%, w/).
Halogenlamp (%)
Laser diode(473 nm) (%)
Laser diode(457 nm) (%)
CQ/Iod 18PTCTE/Iod 27PTCTE/Iod/NVK 43 56 31CQ/MDEA 35PTCTE/MDEA 16PTCTE/MDEA/R’-Cl 43 51 28
0 30 60 90 120 150 1800
20
40
60
80
100 (a)
Con
vers
ion
(%)
Time (s)
DVE-3
Trithiol
ig. 5. Photopolymerization profiles of Trithiol/DVE-3 blend (40%/60%, n/n; 57%/4.2%/2%, w/w/w/w) upon exposure to the (a) blue LED bulb and (b) green LED bulbeader is referred to the web version of this article.)
Please cite this article in press as: Xiao P et al. Perylene derivatives as phoand panchromatic thiol-ene polymerizable films. Eur Polym J (2014), htt
erivative D_1 [19] and the red light sensitive Per1 [20] andhe iodonium salt in a single thiol-ene formulation, i.e. aour-component PIS (PTCTE/D_1/Per1/Iod), initiates thehiol-ene (Trithiol/DVE-3) polymerization under the house-old blue, green, yellow or red LED bulbs (Fig. 5 and Table). The vinyl double bond conversions (99% and 98% withhe blue LED and green LED, respectively) are higher thanhose of S–H (40% and 36%): as in Ref. [39], this reflects a
0 100 200 300 4000
10
20
30
40
50
60
CQ/MDEA
(b)
8
6
Con
vers
ion
(%)
Time (s)
5
7
CTE/Iod (0.5%/2%, w/w) (curve 1) or PTCTE/Iod/NVK (0.5%/2%/3%, w/w/w)upon the laser diode at 473 nm (curve 3) or 457 nm (curve 4) exposure;rence; (b) PTCTE/MDEA (0.5%/2%, w/w) (curve 5) or PTCTE/MDEA/R0-Cl0-Cl (0.5%/2%/3%, w/w/w) upon the laser diode at 473 nm (curve 7) orhalogen lamp exposure as a reference.
278ual CP/TEP polymerization of DVE-3. Upon the yellow or279ed LED bulb exposure, the thiol-ene polymerization is also280bserved (Table 3) but to a lesser extent.
281.3. 3/Photochemical mechanisms
282The steady state photolysis of PTCTE/Iod in acetonitrile/283oluene (50%/50%, V/V) (Fig. 6(a)) led to a dramatic and fast284ecrease of the 469 nm absorption band in line with the285hotoinitiating ability of this system. On the other hand,286very slow bleaching occurred in the BPTI/Iod system287Fig. 6(b)), which supports the much lower efficiency of288his system. For DPPDI/Iod where a clear bleaching was289bserved during the light irradiation, the low efficiency
0 200 400 600 8000
20
40
60
80
100 (b)
Con
vers
ion
(%)
Time (s)
DVE-3
Trithiol
3%, w/w) in laminate in the presence of PTCTE/D_1/Per1/Iod (0.2%/0.2%/. (For interpretation of the references to colour in this figure legend, the
toinitiators in blue light sensitive cationic or radical curable filmsp://dx.doi.org/10.1016/j.eurpolymj.2014.01.024
290 can be likely ascribed to a back electron transfer reaction291 that decreases the reactive species yield as observed for292 other systems in Ref. [20].293 Fluorescence quenching experiments led to a very high294 1PTCTE/Iod interaction rate constant (kq = �6.3 � 109 M�1
295 s�1; fluorescence quantum yield Ufluo: �0.65), which indi-296 cates an almost diffusion-controlled 1PTCTE/Iod interac-297 tion. The free energy change DG for the 1PTCTE/Iod298 electron transfer reaction was calculated to be �1.02 eV299 (oxidation potentials Eox of the PTCTE = 1.36 V, as mea-300 sured by cyclic voltammetry-this work; reduction poten-301 tial Ered of Iod = �0.2 V[1]; singlet state energy302 ES = 2.58 eV, extracted from the UV-vis absorption and303 fluorescence emission spectra as usually done [18]): the304 large negative DG value makes the process favorable. The305 PTCTE/Iod electron transfer quantum yield UeT in the sin-306 glet state, calculated according to UeT = kqs0 [Iod]/
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325326328328
329331331
332334334
Table 3
6 P. Xiao et al. / European Polymer Journal xxx (2014) xxx–xxx
EPJ 6350 No. of Pages 9, Model 3G
4 February 2014
DVE-3 and Trithiol (S–H) conversions of Trithiol/DVE-3 blend (40%/60%, n/n; 57%/43%, w/w) obtained in laminate upon exposure to blue LED for 180s; or green LED, yellow LED or red LED for 800 s in the presence of PTCTE/D_1/Per1/Iod (0.2%/0.2%/0.2%/2%, w/w/w/w).
DVE-3conversion (%)
Trithiolconversion (%)
335337337
338340340
0
6λ (nm
PPDI/
Blue LED @ 462 nm 99 40
300 400 500 600.0
0.2
0.4
0.6
0.8
1.0 (a)
O. D
.
λ (nm)
0 0.5 min 1 min 3 min
300 400 5000.0
0.2
0.4
0.6
0.8
1.0 (c)
O. D
.
Fig. 6. Steady state photolysis of (a) PTCTE/Iod, (b) BPTI/Iod and (c) D[Iod] = 38 mM. UV–vis spectra recorded at different irradiation times.
Green LED @ 514 nm 98 36Yellow LED @ 591 nm 22 6Red LED @ 630 nm 31 9
Please cite this article in press as: Xiao P et al. Perylene derivatives as pand panchromatic thiol-ene polymerizable films. Eur Polym J (2014),
(1 + kqs0 [Iod]), is 0.45 (for [Iod] = 4.7 � 10�2 M) andaround 7.5 times as that of BPTI/Iod (UeT = 0.059;Ufluo � 0.30): this is also in line with the higher efficiencyof PTCTE compared to BPTI. For DPPDI, the Ufluo was prettylow (�0.0014) and no fluorescence quenching was detect-able in the presence of Iod.
In LFP experiments (laser excitation at 355 nm), notriplet state absorption of PTCTE was observed in the400–700 nm range (same behavior in previously studiedperylenes [19,20]). This can be ascribed to the high Ufluo
and a low intersystem crossing pathway which preventsany significant triplet state population. As a consequence,the singlet route predominates in Pers/Iod interaction. Inline with the Pers/Iod interaction, phenyl radicals wereobserved in ESR spin trapping experiment on PTCTE/Iod(Fig. 7).
The overall mechanisms are easily explained on thebasis of the sets of reactions 1–4 already proposed in ourpreceding papers on perylene derivatives [19,20].
Pers! 1PersðhmÞ and 1Pers! 3Pers ð2Þ
1;3Persþ Ph2Iþ ! Pers�þ þ Ph2I� ð3aÞ
Pers�þ þ Ph2I� ! Pers�þ þ Ph� þ Ph-I ð3bÞ
Ph� þ NVK! Ph-NVK� ð4aÞ
Ph-NVK� þ Ph2Iþ ! Ph-NVKþ þ Ph� þ Ph-I ð4bÞ
300 400 500 6000.0
0.2
0.4
0.6
0.8
1.0 (b)
O. D
.
λ (nm)
0 1 min 5 min 10 min
00 700 800)
0 1 min 2 min 3 min
Iod in acetonitrile/toluene (50%/50%, V/V) upon halogen lamp exposure;
hotoinitiators in blue light sensitive cationic or radical curable filmshttp://dx.doi.org/10.1016/j.eurpolymj.2014.01.024
341P343343
344R346346
347R349349
350 4
351
352 i353 c354 m355 o356 C357 w358 p359 n360 d361 e362 h363 a364 w
365 A
366
367 fi
368 A
369
370 f371 j
372 R
373374375376377
378379380381382383384385386387388389390391392393394395396397398399[400401402403[404
FPPa
P. Xiao et al. / European Polymer Journal xxx (2014) xxx–xxx 7
EPJ 6350 No. of Pages 9, Model 3G
4 February 2014
h� þ RS-H! Ph-Hþ RS� ð5aÞ
3320 3330 3340 3350 3360
(b)
B (G)
(a)
ig. 7. ESR spectra of the radicals generated in PTCTE/Iod and trapped byBN in tert-butylbenzene: (a) experimental and (b) simulated spectra.BN/phenyl radical adducts obtained in P PTCTE/Iod: aN = 14.2 G,H = 2.2 G; reference values in Refs. [40,41].
S� þ R0—CH ¼ CH2 ! R0 � CH�—CH2SR ð5bÞ
0—CH�—CH2SR þ RSH! R0—CH2—CH2SR þ RS� ð5cÞ
. Conclusion
The perylene derivative PTCTE in combination with anodonium salt Iod and optionally N-vinylcarbazole NVKan be used as effective PISs to initiate the cationic poly-erization of EPOX and the free radical polymerization
f TMPTA under visible or blue lights. The Pers/MDEA/R0-l system initiates the radical polymerization of TMPTAith a better efficiency than that of the well known cam-
horquinone/amine combination. Remarkably, the combi-ation of PTCTE with previously studied peryleneerivatives and an iodonium salt could initiate the thiol-ne (Trithiol/DVE-3) polymerization under exposure toousehold blue, green, yellow or red LED bulbs therebyllowing the manufacture of panchromatic films. Otherorks are in progress.
cknowledgment
JL thanks the Institut Universitaire de France for thenancial support.
ppendix A. Supplementary material
Supplementary data associated with this article can beound, in the online version, at http://dx.doi.org/10.1016/.eurpolymj.2014.01.024.
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Please cite this article in press as: Xiao P et al. Perylene derivatives as photoinitiators in blue light sensitive cationic or radical curable filmsand panchromatic thiol-ene polymerizable films. Eur Polym J (2014), http://dx.doi.org/10.1016/j.eurpolymj.2014.01.024
