Applications: Free Radical Initiators

Photoinitiators: Classification
A photoinitiator is a compound especially added to a formulation to convert absorbed light energy, UV or visible light, into chemical energy in the form of initiating species, viz., free radicals or cations. Based on the mechanism by which initiating radicals are formed, photoinitiators are generally divided into two classes:

Type II photoinitiators undergo a bimolecular reaction where the excited state of the photoinitiator interacts with a second molecule (a coinitiator) to generate free radicals.

Type I photoinitiators undergo a unimolecular bond cleavage upon irradiation to yield free radicals.

UV photoinitiators of both Type I and Type II are available. However, visible light photoinitiators belong almost exclusively to the Type II class of photoinitiators. Table I summarizes the various classes of available Type I and Type II photoinitiators and their common applications.

Table I: Common Applications for Different Classes of Photoinitiators

UV-Photoinitiators Type I Photoinitiators Photoinitiator Class Application Wood coatings (polyester) Paper coatings Clear coatings (on metal, wood, plastic) Printing plates Offset inks Screen inks Pigmented coatings White lacquers Photo resists X X Benzoin ethers X Benzil ketals X a-Dialkoxy- a-Hydroxy- a-Amino Acylacetoalkylalkylphosphine phenones phenones phenones oxides X X X X2 X X Type II Visible Photoinitiators

BenzoThiophenones/ xanthones/ Titanocenes amines amines

X X1

X X X3 X X4 X3

X X X X X X X X

(1) In combination with benzophenone. (2) Only systems of high reactivity. (3) Partially in combination with thioxanthones. (4) Thin layers only.

This chart is reprinted with permission from SITA Technology Ltd.

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Photoinitiators: UV Absorption Spectra
For photoinitiation to proceed efficiently, the absorption bands of the photoinitiator must overlap with the emission spectrum of the source and there must be minimal competing absorption by the components of the formulation at the wavelengths corresponding to photoinitiator excitation. For the initial selection of a photoinitiator in your application, viz., one with excitation wavelengths that lie in the emission spectrum of your UV source, as well as in the absorption window of your formulation, information about the photoinitiator absorption spectrum is essential. To aid in this initial selection, UV absorption spectra of 47 commonly used radical and cationic photoinitiators (see Table I) are displayed in this section. Approximately 100
Table I:

additional substituted acetophenones and benzophenones that are potential photoinitiators are available from Aldrich; search our product database at www.sigma-aldrich.com. Spectra were recorded on a Perkin Elmer UV/Vis Lambda 2 spectrophotometer using Perkin Elmer Computerized Spectroscopy Software 4.01. Concentrations are expressed as % weight of solute in volume of solvent. The solvent used was A.C.S. spectrophotometric grade methyl alcohol. For comparison purposes, the emission spectrum of a medium pressure mercury lamp, the most widely used energy source, is shown as the last figure.

Commonly Used Radical and Cationic Photoinitiators whose UV Absorption Spectra are Displayed in this Section. (Click on the photoinitiator name coded red to view the UV spectrum. Click on the product number coded blue to link to the product document sheet on the Sigma-Aldrich Web site.)

Cat. No. Photoinitiator A1,070-1 A8,840-9 A9,000-4 12,324-2 11,931-8 B515-1 39,939-6 17,200-6 19,578-2 B870-3 B930-0 40,562-0 26,246-3 B1,260-1 40,564-7 16,032-6 14,783-4 12,489-3 C7,240-4 40,807-7 D3,173-7 22,710-2 D11,050-7 Acetophenone, 99% Anisoin, 95% Anthraquinone, 97% Anthraquinone-2-sulfonic acid, sodium salt monohydrate, 97% (Benzene) tricarbonylchromium, 98% Benzil, 98% Benzoin, sublimed, 99.5+% Benzoin ethyl ether, 99% Benzoin isobutyl ether, tech., 90% Benzoin methyl ether, 96% Benzophenone, 99% Benzophenone/1-Hydroxycyclohexyl phenyl ketone, 50/50 blend 3,3',4,4'-Benzophenonetetracarboxylic dianhydride, sublimed, 98% 4-Benzoylbiphenyl, 99% 2-Benzyl-2-(dimethylamino)-4'morpholinobutyrophenone, 97% 4,4'-Bis(diethylamino)benzophenone, 99+% 4,4'-Bis(dimethylamino)benzophenone, 98% Camphorquinone, 98% 2-Chlorothioxanthen-9-one, 98% (Cumene)cyclopentadienyliron(II) hexafluorophosphate, 98% Dibenzosuberenone, 97% 2,2-Diethoxyacetophenone, 95% 4,4'-Dihydroxybenzophenone, 99%

Cat. No. 19,611-8 14,934-9 14,670-6 D14,966-7 D14,967-5 40,566-3 27,571-9 E1,220-6 F40-8 32,810-3 27,856-4 22,043-4 H2,020-2 40,561-2 40,565-5 15,753-8 19,805-6 M3,050-7 40563-9 15,650-7 29,074-2 T3,400-2 40,722-4 40,721-6

Photoinitiator 2,2-Dimethoxy-2-phenylacetophenone, 99% 4-(Dimethylamino)benzophenone, 98% 4,4'-Dimethylbenzil, 97% 2,5-Dimethylbenzophenone, tech., 95% 3,4-Dimethylbenzophenone, 99% Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide/ 2-Hydroxy-2-methylpropiophenone, 50/50 blend 4'-Ethoxyacetophenone, 98% 2-Ethylanthraquinone, 97+% Ferrocene, 98% 3'-Hydroxyacetophenone, 99+% 4'-Hydroxyacetophenone, 99% 3-Hydroxybenzophenone, 99% 4-Hydroxybenzophenone, 98% 1-Hydroxycyclohexyl phenyl ketone, 99% 2-Hydroxy-2-methylpropiophenone, 97% 2-Methylbenzophenone, 98% 3-Methylbenzophenone, 99% Methybenzoylformate, 98% 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone, 98% Phenanthrenequinone, 99+% 4'-Phenoxyacetophenone, 98% Thioxanthen-9-one, 98% Triarylsulfonium hexafluoroantimonate salts, mixed, 50% in propylene carbonate Triarylsulfonium hexafluorophosphate salts, mixed, 50% in propylene carbonate

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
A1,070-1 Acetophenone, 99% A8,840-9 Anisoin, 95%

O C CH 3
CH O 3 O CH C OH OCH 3

0.0224 % 0.0011 %

0.0040 % 0.0014 %

A9,000-4 Anthraquinone, 97%

12,324-2 Anthraquinone-2-sulfonic acid, sodium salt monohydrate, 97%

O S ONa O H O 2

0.0010% 0.0004 %

0.0033 % 0.0006 %

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Photoinitiators: UV Absorption Spectra (continued)
11,931-8 (Benzene) tricarbonylchromium , 98% B515-1
1

Benzil, 98%

O O
.8

C C

OC

Cr CO

CO

.8

.6

0.0023 %
Absorbance

.6
Absorbance

0.0029 % 0.0011 %

0.0012 %

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

39,939-6 Benzoin, sublimed, 99.5+%

17,200-6 Benzoin ethyl ether, 99%

O
.8

O
.8

CH OH

CH C OCH CH 2 3

.6

0.0056 % 0.0017 %
Absorbance

.6

0.0027 % 0.0019 %

Absorbance

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
19,578-2 Benzoin isobutyl ether, tech., 90% B870-3 Benzoin methyl ether, 96%

O
.8

O CH C
.8

CH C O CH CHCH 2 3 CH 3

OCH

.6

0.0110 %
Absorbance

.6

0.0043 % 0.0020 %

0.0069 %

.4

Absorbance
.4 .2 0 220

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

240

260

280

300

320 340 360 Nanometers

380

400

420

440

B930-0

Benzophenone, 99%

40,562-0 Benzophenone/1-Hydroxycyclohexyl phenyl ketone, 50/50 blend

O
.8

O
.8

O C OH
.6

0.0030 % 0.0012 %
Absorbance

.6

0.0150 % 0.0015 %

Absorbance
.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

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Photoinitiators: UV Absorption Spectra (continued)
26,246-3 3,3',4,4'-Benzophenonetetracarboxylic dianhydride, sublimed, 98% B1,260-1 4-Benzoylbiphenyl, 99%

O
.8

O O C O O

O C

O O

.6

0.0030 %
Absorbance

0.0031 % 0.0004 %

0.0010 %

.4

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

40,564-7 2-Benzyl-2-(dimethylamino)-4'morpholinobutyrophenone, 97%

16,032-6 4,4'-Bis(diethylamino)benzophenone, 99+%

CH C

2 N(CH ) 32

.8

.8

CH CH 2 3

.6

0.0035 % 0.0020 %
Absorbance

.6

0.0020 % 0.0008 %

Absorbance
.4

.4

.2

.2
CH CH 3 2 CH CH N 3 2 O C CH CH 2 3 NCH CH 2 3

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

10

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
14,783-4 4,4'-Bis(dimethylamino)benzophenone, 98% 12,489-3 Camphorquinone, 98%

CH
.8
.8

CH 3

3 R

R = CH R= H

R = H R = CH 3

or

.6
Absorbance

0.0031% 0.0008 %
Absorbance

.6

0.0271 % 0.0071 %

.4

.4

.2

.2

CH

3 N 3

O C N

CH CH

3 3

CH

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

C7,240-4 2-Chlorothioxanthen-9-one, 98%

40,807-7 (Cumene)cyclopentadienyliron(II) hexafluorophosphate, 98%

O Cl

Fe
S
.8
.8

CH 3 CH CH 3

PF

.6

0.0024 % 0.0007 %
Absorbance

.6

0.0055 % 0.0027 %

Absorbance

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
D3,173-7 Dibenzosuberenone, 97% 22,710-2 2,2-Diethoxyacetophenone, 95%

O C
.8

OCH CH 2 3 CH OCH CH 2 3

.8

.6

0.0016 % 0.0005 %
Absorbance

.6

0.0100 % 0.0014 %

Absorbance

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

D11,050-7 4,4'-Dihydroxybenzophenone, 99%

19,611-8 2,2-Dimethoxy-2-phenylacetophenone, 99%

1

O HO C OH

O OCH3 C C OCH 3

.8

.8

.6

0.0036 % 0.0009 %
Absorbance

.6

0.0020 % 0.0011 %

Absorbance
.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

12

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
14,934-9 4-(Dimethylamino)benzophenone, 98% 14,670-6 4,4'-Dimethylbenzil, 97%
1

O O
.8

CH
.8

C C

CH 3

.6

0.0043 %
.6

0.0030 %
Absorbance

Absorbance

0.0009 %

0.0010 %

.4

.4

.2
CH 3 N CH 3 O C

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

D14,966-7 2,5-Dimethylbenzophenone, tech., 95%

D14,967-5 3,4-Dimethylbenzophenone, 99%

O

CH
.8

CH
3 O C CH 3
.8

3 3

CH

.6

.6

0.0296 %
Absorbance

0.0039 %
Absorbance

0.0015 %

0.0013 %

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
40,566-3 Diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide 2-Hydroxy-2-methylpropiophenone 50/50 blend
CH 3O O
.8

27,571-9

4'-Ethoxyacetophenone, 98%

CH 3

C CH 3

P
.8

O C CH 3

O OH
.6

OCH CH 2 3

CH 3

CH 3

0.0223 %
Absorbance

.6

0.0044 % 0.0009 %

0.0019 %

.4

Absorbance
.4 .2 0 220

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

240

260

280

300

320 340 360 Nanometers

380

400

420

440

E1,220-6 Ethylanthraquinone, 97+%

1

F40-8

Ferrocene, 98%

O CH CH 2 3
.8
.8

Fe

.6

0.0018 % 0.0005 %
Absorbance

.6

0.0065 % 0.0028 %

Absorbance

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

14

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
32,810-3
1

3'-Hydroxyacetophenone, 99+%

27,856-4

4'-Hydroxyacetophenone, 99%

O C CH 3

O C CH 3
.8

.8

OH

OH

.6

0.0026 %
Absorbance

.6

0.0048 % 0.0009 %

Absorbance

0.0007 %

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

22,043-4
1

3-Hydroxybenzophenone, 99%

H2,020-2

4-Hydroxybenzophenone, 98%

O C HO
.8 .8

O HO C

0.0030 %
.6

.6

0.0051 % 0.0013 %

Absorbance

0.0011 %

Absorbance
.4 .2 0 220

.4

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

240

260

280

300

320 340 360 Nanometers

380

400

420

440

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
40,561-2 1-Hydroxycyclohexyl phenyl ketone, 99% 40,565-5
1

2-Hydroxy-2-methylpropiophenone, 97%

O C OH
.8

O C
.8

OH C CH CH 3 3

.6

0.0047 %
Absorbance

.6

0.0053 % 0.0008 %

Absorbance

0.0019 %

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

15,753-8 H2,020-2

2-Methylbenzophenone, 98% 4-Hydroxybenzophenone, 98%

19,805-6

3-Methylbenzophenone, 99%

O
O C

C CH 3

.8

CH

.8

.6

0.0122 % 0.0013 %
Absorbance

.6

0.0071 % 0.0012 %

Absorbance
.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

16

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
M3,050-7 Methybenzoylformate, 98% 40,563-9 2-Methyl-4'-(methylthio)-2morpholinopropiophenone, 98%

O O C
.8

.8

O CH S 3 C

CH C CH

3 N 3

OCH 3

.6 .6

0.0625 % 0.0025%
Absorbance

0.0052 % 0.0014 %

Absorbance

.4

.4

.2 .2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

15,650-7
1

Phenanthrenequinone, 99+%

29,074-2

4'-Phenoxyacetophenone, 98%

O
O O
.8

C CH 3

.8

.6

0.0049 % 0.0028 %
Absorbance

.6

0.0032 % 0.0008 %

Absorbance

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

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Applications: Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
T3,400-2
1

Thioxanthen-9-one, 98%

40,722-4

Triarylsulfonium hexafluoroantimonate salts, mixed, 50% in propylene carbonate

S
.8

.8

SbF 6

.6

0.0016 %
Absorbance

.6

0.0108 % 0.0048 %

Absorbance

0.0005 %

.4

.4

.2

.2

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

40,721-6

Triarylsulfonium hexafluorophosphate salts, mixed, 50% in propylene carbonate

.8

PF

.6

0.0223 % 0.0039 %

Absorbance
.4 .2 0 220

240

260

280

300

320 340 360 Nanometers

380

400

420

440

18

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Applications: Free Radical Initiators

Photoinitiators: UV Absorption Spectra (continued)
Emission spectrum of a medium pressure mercury arc lamp

SPECTROPHOTOMETRIC GRADE SOLVENTS

Excellent for applications requiring -High purity -UV transparecy -Low residue on evaporation Rigorously analyzed during and after production, and during packaging to ensure high purity Once packaged, leakage and breathing problems are eliminated because we use the Sealed for Quality system 4-Liter sizes come in standard amber glass bottles. These bottles have a PVC shrink band around the neck to provide additional closure integrity and tamper evidence.

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