P h o t o p o l y m e r i z a t i o n

R e a c t i o n s

J. P. Fouassier Laboratoire de Photochimie Generale, Mulhouse, Cedex, France

A. Introduction 11-169 B. Tables 11-170 Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in Radical Photoinitiators 11-170 Annex to Table 1. Photoinitiator Compound Chemistries 11-173 Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with Various Monomers in Cyclohexane at Room Temperature 11-176 Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with Various Olefinic Monomers at Room Temperature 11-176 Table 4. Bimolecular Rate Constants for the Reaction of Ph 2 P=O and Ph2P = S with Various Monomers 11-176 Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts 11-176 Table 6. Electron Transfer Rate Constants (ke) Between Photosensitizers and Cationic Photoinitiators and Quenching Rate Constants (fcq) for Cyclohexene Oxide in Methanol (M) and Acetonitrile (AN) 11-177 Table 7. Excitation Transfer Rate Constants (kj) for Thioxanthones and Photoinitiators 11-178 Annex to Table 7. Compound Chemistries 11-178 Table 8. Triplet State Lifetimes (rT) of the Sensitizer (TXI) in Different Media, and Rate Constant (A:T) of the Interaction between TXI and TPMK 11-179 Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and Monomers 11-179 Table 10. Values of r f , rT, and k% in Solution 11-179 Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution 11-179 Annex to Table 11 11-179 C. References 11-180

A.

INTRODUCTION

UV curing technologies use light beams to start photochemical and chemical reactions in organic materials (monomers, oligomers, prepolymers, polymers), mostly through a Photo-Induced Polymerization (PIP) reaction. This leads to the formation of a new polymeric material whose applications lie in various industrial sectors, such as coatings, graphic arts, imaging, microelectronics, etc. Specific advantages of these technologies over the usual thermal operations are rapid through-cure, solvent-free formulation, room temperature treatment and low energy requirements. This PIP process is concerned with the creation of a polymer P through a chain radical or cationic reaction initiated by light in the presence of a photoinitiator (PI) and a coupled Pl/photosensitizer (PS):
light

light

add species :X

light

excited PS excited PI

R* or acid species

The reactivities of PI and PS govern, for a large part, the practical efficiency of the PIP reaction. The present chapter reports typical data obtained (through time-resolved laser spectroscopy experiments) on the excited state processes in PI and PS occurring after the absorption of the photon. Rate constants reported in the following tables correspond to the following processes:
1. PI (ground singlet state)
light
1 PI* first excited singlet state 3 Pi* triplet state

cleavage H abstraction monomer quenching electron transfer

2. R' (or A# or S*...) + M ^ 3. 3 P F + light stabilizer (LS)

3
k

RM'

(b) Energy and electron transfer can also occur in the first excited singlet state 1 PS*. Detailed data are available, especially in several chapters of two edited books (1) and in a recent monograph (2). Few data are known on the photopolymerization itself and largely depend on the practical formulation used as well as the experimental conditions. Typically, one photon absorbed can lead to ~10000 polymerized double bonds (3). Rate constants of propagation kp and termination fct for a polyurethane acrylate resin containing an acrylate monomer (weight ratio, 1:1) as reactive diluent are ~10 4 1/mol/s and 3 x 10 4 l/mol/s respectively (when half of the double bonds have been polymerized) (3).

4. PS* + PI - excitation transfer 5. Tj'. Triplet state lifetime under the given conditions (equal to the reciprocal value of the sum of the first-order rate constants of the different processes) Tj: Triplet state lifetime in the presence of a given additive
6 3

- PS* + cationic photoinitiator C+ - PS" + C* (a) Energy transfer can sometimes occur: 3 PS*+ C+ - PS+ C+*

B. TABLES TABLE 1. RATE CONSTANTS OF CLEAVAGE, ELECTRON TRANSFER AND MONOMER QUENCHING IN RADICAL PHOTOINITIATORS0
Compound Ha Hb Hc lid lie Hf Hg Hh Hi Ha 10 "8Jk0 (s"1) 10~9A:e (1/mol/s) 1.3 2.0 1.2 1.2 0.2 0.07 1.5 0.6 0.27 10~6A:q (1/mol/s) 66 150 2.5 2 1 13 180 8 0.05 3200 360 5.4 34 Monomers famines 7 solventsd Mi, AHi, Si Refs. 4

Ha Ha

0.003e 0.001^ 7 2 1.9 2 0.56 10 0.5 0.9 0.0064* 0.0025e 0.0056e 0.0043*

M2, M5, M3, M4,

S2 S2 S2 S2

21 21 21 21 22 26

Hj Ilk 111 Hm Hn Up Hq Hr Hs Ilr Hs Hr Hs Hr Ils Ilr Hs I2a I2b I2c I2d I2e I2f I2g I2h I2i

1500 1550

S 2 , AH3 S 2 , AH4 S 2 , AH2 S 2 , AH5 S 2 , AH6 S3 M 7 , AH2, S 4 S2

23 25 26

7.14 0.87 0.003 0.00025 0.83 0.003 0.67 1.18 0.80

0.26 < 0.001 0.08 0.20 0.08 0.17 0.15 0.05

56 110 5500 7400 5100 6500 49 140 9.4 50 250 20 4.5 8 22 10 29 20 21

S 6 , Mi S6, M2 S6, M5 S6, M3 S6, M4 Mi, AHi, Si

26 26 26 26 26 5

TABLE 1. cont'd
Compound Ba I3b 13c I3d I3e I3f I3g I3h I4a I4b I4c I4d I4e I4f I4g I4h I4i I4e I4f I4g I4h I4i I4f I4g I4h I4i I4f I4g I4h I4i I5a I6a I7a I7b I8a I9a HOa Ilia IHb IHc Hid I12a I12b I12c I12d I12e I12a I12b I12c I12d I12e I12b I12c I12d I12e I12b I12c I12d I12e I13a I14a I14b I14c I14d I15a I15b I15c 10 8A: c (s"1) 10 1 25 0.005 10 0.006 0.007 0.13 >100 >100 > 100 >100 W~9ke (1/mol/s) 10 6 A: q (I/moI/s) >200 2 <10~ 4 10 ~4 <10~ 4 <10~ 4 Si 7 Monomers famines 7 solvents^ Mi5AHi5S1 Refs. 6

8100 4800 6500 1500 190 480 800 1000 200 13 60 17 <1 5.7 1300 700 380 180 > 10 7 xlO-3 0.7 6 XlO" 5 0.85 2.5 > 10 0.8 >1 0.12 0.01 0.7 0.05 440 0.35 11

M2, S2

Mi, S 2

M3, S2

M4, S2

Mj5S1 Mi, AHi, Si Mi7AHi9S1 Mi5AH19Si Mi, AHi, Si

8 9 9 9 9 10 10

0.9 0.4

700 1200 480 800 1000 200 13 8100 4800 6500 1500 190 6 17 <10 5.7 1300 700 380 180 11000 2900 15 1200

M15S2

11

M25S2

11

M3, S2

11

M4, S2

11

1.4

1.6 6.5 6.0 3.5

AH 2 , S 2 M19AH15S1

12 13

>5 4 >5

S2

14

References page 11-180

TABLE 1. cont'd
Compound I15d I16a I16b I17a I18a I19a I20a I21a I22a I22b I22c I22d I23a I23b I23c I23d I23e I23f I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23a I23b I23b I23g I23h 124 125 126 127 128 129
a 1}

10*kc (s1) 3.3

10~9ke (1/mol/s) 1.5

10~6kq (1/mol/s) 180 300

Monomers famines 7 solvents^ AH 1 9 S 1 S1 S1 S1 S2 S2 S3

Refs. 15 16 17 18 18 18 19

>3 0.05 0.16 0.3 29 60 -10 -5 0.02 0.014

0.7

100

6 5 4 4 0.01 0.017 2.5

93 2.3 2.0 15 2 3 3 3000 6000 6000 6000 0.2 0.02 0.03 0.04 4 0.4 1 1 40 30 5 6 1 1 0.3 0.3

M 1 , AH3, S 2

20

AH2, S 5 M 2 , S 2 , AH2

24 20

M3, S2

20

M4, S2

20

M5, S2

20

M6, S2

20

8 6 6 6 26 23 8 0.85 <10~5 <10~5 65 37 0.016 0.006 0.007

S 2 , AH4

26

S1, M8 S19M9 S 2 , AH7 S 2 , AH8 M7, S 4 S 2 , Mi S2, M10 S2, M10 S2 S 7 , AH 9

13 13 26 26 25 37 37 37 39 41

4.4-f 0.3 0.015

Compound chemistries given in Annex to Table 1. Monomers: Mi - methyl methacrylate; M2 - styrene; M3 - vinyl acetate; M4 - acrylonitrile; M5 - vinyl pyrrolidone; M6 - butylvinylether; M 7 - acrylamide; Mg PETA; M 9 - TMPTA; M10 - butylmethacrylate. c Amines: AHi - methyl diethanolamine; AH 2 - triethylamine; AH 3 - ethyl-4-(dimethylamino)-benzoate; AH 4 - bis-(2-hydroxy ethyl)-methylamine; AH 5 - methyl-4amino benzoate; AH 6 - 1,4-diazabicyclo [2.2.2] octane (DABCO); AH 7 - dimethylamine; AHg - 2-(dimethyl aminoethyl)-benzoate; AH 9 - diethylaniline. d Solvents: Si - toluene; S 2 - benzene; S 3 - acetonitrile; S 4 - water; S5 - 2-propanol; S 6 - acetone; S 7 - ethanol. e Rate constant of H abstraction by THF. ^Rate constant of H abstraction by isopropanol.

ANNEX TO TABLE 1. PHOTOINITIATOR COMPOUND CHEMISTRIES

Compound Ha lib lie Hd He iif Hg Hh R Ri R2 R3 R4

in
Hj

Ilk 111 Hm Hn Up Hq Hr

Hs

I2a I2b I2c I2d I2e I2f I2g I2h I2i Ba I3b 13c Dd I3e I3f Bg Dh I4a I4b I4c I4d I4e I4f I4g I4h I4i

References page 11-180

ANNEX TO TABLE 1. cont'd

Compound I5a R Ri R2 R3 R4

I6a

I7a I7b Fluorenone I8a I9a

H CH 2 SOjNa

I9b

HOa

C2H5

Ilia IHb IHc IHd I12a 112b I12c I12d I12e I13a CH 3 OH OCOCH3 H CH 3

H H CH 3 CH 3 O

H CH3 H H

I14a I14b I14c I14d

H /-C 3 H 7 OC 2 H 5 J-C 4 H 9

I15a

I15b I15c

H CH 3

I15d

I16a

ANNEX TO TABLE 1. cont'd Compound I16b I17a I18a I19a I20a I21a R Ri R2 R3 R4

I22a I22b I22c I22d I23a I23b I23c I23d I23e I23f I23g I23h H Cl CH 3 CH 3 (CH 3 ) 2 H H -OCH 2 COOH OCH 2 CH 2 CH 2 N(CH 3 ) 3 SO 3 Me-

124 Acridine Phenazine 125 126 127

128

129

References page 11-180

TABLE 2. BIMOLECULAR RATE CONSTANTS0 FOR THE REACTION OF PHOSPHONYL RADICALS WITH VARIOUS MONOMERS IN CYCLOHEXANE AT ROOM TEMPERATU RE *

Radical Monomer Methacrylonitrile Styrene Methylmethacrylate Acrylonitrile Methyl acrylate n-Butyl vinyl ether Vinyl acetate
a b

5.0 6.0 8.0 2.0 3.5 0.4 0.16

4.6 4.5 5.0 2.0 2.1 0.3 0.13

4.5 8.0 5.8 0.18 1.3 0.23 0.082

9.2 22 5.8 0.58 1.7 2.1 0.29

11 25 5.3 0.26 1.6 1.4 0.18

kRM in 10 7 l/mol/s. Ref. 26.

TABLE 3. BIMOLECULAR RATE C O N S T A N T S " FOR THE REACTION OF V A R I O U S RADICALS W I T H V A R I O U S OLEFINIC M O N O M E R S AT R O O M TEMPERATURE*

Radical

Monomer
3.5 x 10" 2 7 x 10~ 4 1.2 x 10 ~2

Styrene

Methylmethacrylate Acrylonitrile Methyl acrylate n-Butyl vinyl ether Vinyl acetate Af-Vinyrpyrrolidone
a fo c

9xlO~ 4 x 10 ~4 6 x 10 ~4

5.4xlO~ 1.6 x 10~2

4xlO"

0.9xl0~ 2 2 x 10 ~3 2 x 10 ~2

< 10 " 6 4xlO~

5

6 2 2 0.5 0.2

18C

10" 3t

IO"1*

kRU in 10 l/mol/s. Ref. 26. From Ref. 40. +From Ref. 16.

TABLE 4. BIMOLECULAR RATE C O N S T A N T S 0 FOR THE REACT I O N OF P h 2 R = O A N D Ph 2 P-=* W I T H V A R I O U S M O N O M E R S * 0

Radical Monomer Methacrylonitrile Styrene Methylmethacrylate Acrylonitrile Methyl acrylate rc-Butyl vinyl ether Vinyl acetate
a

Ph2P = O 1.9 4.6 4.1 1.3 1.7 5.0 1.4

Ph2P = S 0.9 0.4 0.19 0.52 0.62 0.15 0.042

TABLE 5. ELECTRON TRANSFER REACTION O F RADICALS W I T H D I P H E N Y L I O D O N I U M SALTS

Radicals

10"9Jt6 (1/mol/s)

Refs.

kRM in 10 7 l/mol/s *Ref. 27. c Experiments were carried out in CH 2 C^ solution at room temperature.

Ph2PO Ph2COH (CHs)2COH

<10"3 0.03 0.06

42 43

TABLE 6. ELECTRON TRANSFER RATE CONSTANTS (ke) BETWEEN PHOTOSENSITIZERS AND CATIONIC PHOTOINITIATORS AND QUENCHING RATE CONSTANTS (kq) FOR CYCLOHEXENE OXIDE IN METHANOL (M) AND ACETONITRILE (AN)
Photosensitizer Chlorothioxanthone Cationic photoinitiator Anion AsF6" Cl" PF6BF4; AsF 6 AsF 6 Solvent M (1/mol/s) 24 24 26 24 290 400 36 Benzophenone AsF 6 Cl" BF4" BF 4 M 15 1 47 6.4 14 0.33 (1/mol/s) 0.3 Refs. 28

AN M

Chlorothioxanthone

Ketocoumarin Chlorothioxanthone

M M

0.04 29

PF 6

35

PF 6 SbF 6

28 4

AsF 6

BF 4 BF 4

570 110

PF 6

14

AsF 6 BF 4

100 38 15

References page 11-180

TABLE 6. cont'd
Photosensitizer Xanthone Michler's ketone Thioxanthone 10-Methylacridone Acridone Anthracene Chlorothioxanthone Pyrene Benzophenone Isopropylthioxanthone Cationic photoinitiator Anion Cl" Solvent M 10-7Are (1/mol/s) 140 0.7 200 350 740 M (NO2Cp)2I+ Cl" l 400 130 500 250 31 28 10~7A:q (1/mol/s) Refs. 30

TABLE 7. EXCITATION TRANSFER RATE CONSTANTS (kT) FOR THIOXANTHONES AND PHOTOINITIATORSa Thioxanthone TXI Initiator HMK OMK TPMK NMK ETX ITX "Ref. 32. TPMK TPMK Solvent Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol 10 " 6 ^ x (1/mol/s) 100 290 75 380 240 630 4700 7900 12 110 60 55

ANNEX TO TABLE 7. COMPOUND CHEMISTRIES Triplet state energy level (kcal/mol) 62 61 58,5 63

TX's

Ri H H CH 3 H

R2 Cl CH(CH 3 ) 2 H H H

R3 H H COOET

R4 H H H COOET

Abbrev. CTX ITX ETX TXI

Mok's H SCH 3 OCH 3 N(CH 3 ) 2 HMK TPMK OMK NMK 65 61 65 63

TABLE 8. TRIPLET STATE LIFETIMES (TT) OF THE SENSITIZER (TXI) IN DIFFERENT MEDIA*, AND RATE CONSTANT (kj) OF THE INTERACTION BETWEEN TXI AND TPMK*
XT tl Hr6Jkx

TABLE 11. RATE CONSTANT OF INTERACTION OF KETONES AND LIGHT STABILIZERS IN SOLUTION Photoinitiator Benzophenone Light stabilizer LSI LS2 LS3 LS4 LS5 SL6 LSI LS7 l<T6A:a (1/mol/s) 6500 8550 10300 15000 7050 5900 500 700 Refs. 34

Medium TMPTAC (100%) Acrylate (66/33) Toluene-Ep. acrylate (50/50) Toluene-TMPTA (25/75) Toluene-TMPTA (50/50) Toluene-TMPTA (75/25) HDDA^ (100%) HDDA-Ep. acrylate (50/50) Toluene-HDDA (50/50) Toluene-HDDA-Ep. acrylate (25/50/25) Toluene-PETAe (50/50) Toluene-PETA-Ep. acrylate (43/43/14) Toluene Methanol
a &

(ns) 650 2200 1500 270 200 280 650 2500 1000 850 220 360 50 140

(cp at 28 C) 40 185 9.5 5.8 1.7 0.9 5.2 58 1.2 5.8 3.1 6.9 0.53 0.52

(I/moI/s) 80 31 35 135 <40 150 95 22 140 68 40 69 240 630 Acetone

35 36

ANNEX TO TABLE 11. LSI:

Viscosity: 77. Ref. 33; for formula, see Annex to Table 7. Trimethylolpropane triacrylate. ^Hexanedioldiacrylate. Tentaerythritol triacrylate. TABLE 9. SOME VALUES OF THE TRIPLET STATE ENERGY LEVELS OF PHOTOINITIATORS AND MONOMERS

LS2:

Compound Ila I4a I7a I8a I9b M2 I14a 124

Triplet state energy (AE) (kcal/mol) 69 73 53 53 59 61 75 57 Cited in Ref. 13 LS3:

Cited in Ref. 38 LS4:

TABLE 10. VALUES OF T, T1, AND IrJt IN SOLUTION Photoinitiators t j (ns) Xj (ns) 10"6JkJ (1/mol/s) LS5:

4200

4000

0.85 LS6:

3300

2000

14

470

470

<5 LS7:

4000

1750

24

determined in bulk epoxyacrylate-HDDA (60:4OwAv); a in solution b in the presence of LSI (2%).; Ref. 34.

References page 11-180

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