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 I photoinitiators undergo a unimolecular bond cleav-
age upon irradiation to yield free radicals.
• 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.
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 Visible
Type I Photoinitiators Type II Photoinitiators
Photoinitiator a-Dialkoxy- a-Hydroxy- a-Amino Acyl- Benzo- Thio-
Class Benzoin Benzil
aceto- alkyl- alkyl- phosphine phenones/ xanthones/ Titanocenes
Application ethers ketals phenones phenones phenones oxides amines amines

Wood coatings
X X X X
(polyester)

Paper coatings X X
Clear coatings
(on metal, X X X X2
wood, plastic)

Printing plates X X X X

Offset inks X1 X X X

Screen inks X3 X X

Pigmented
X X
coatings

White lacquers X4 X

Photo resists X3 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.

a The Link to All Your Polymer Needs _ 5

 Applications:
Applications: Free Radical Initiators
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
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.

Table I: 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 Cat. No. Photoinitiator

A1,070-1 Acetophenone, 99% 19,611-8 2,2-Dimethoxy-2-phenylacetophenone, 99%

A8,840-9 Anisoin, 95% 14,934-9 4-(Dimethylamino)benzophenone, 98%
A9,000-4 Anthraquinone, 97% 14,670-6 4,4'-Dimethylbenzil, 97%
12,324-2 Anthraquinone-2-sulfonic acid, sodium salt D14,966-7 2,5-Dimethylbenzophenone, tech., 95%
monohydrate, 97% D14,967-5 3,4-Dimethylbenzophenone, 99%
11,931-8 (Benzene) tricarbonylchromium, 98% 40,566-3 Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide/
B515-1 Benzil, 98% 2-Hydroxy-2-methylpropiophenone, 50/50 blend
39,939-6 Benzoin, sublimed, 99.5+% 27,571-9 4'-Ethoxyacetophenone, 98%
17,200-6 Benzoin ethyl ether, 99% E1,220-6 2-Ethylanthraquinone, 97+%
19,578-2 Benzoin isobutyl ether, tech., 90% F40-8 Ferrocene, 98%
B870-3 Benzoin methyl ether, 96% 32,810-3 3'-Hydroxyacetophenone, 99+%
B930-0 Benzophenone, 99% 27,856-4 4'-Hydroxyacetophenone, 99%
40,562-0 Benzophenone/1-Hydroxycyclohexyl phenyl 22,043-4 3-Hydroxybenzophenone, 99%
ketone, 50/50 blend H2,020-2 4-Hydroxybenzophenone, 98%
26,246-3 3,3',4,4'-Benzophenonetetracarboxylic 40,561-2 1-Hydroxycyclohexyl phenyl ketone, 99%
dianhydride, sublimed, 98% 40,565-5 2-Hydroxy-2-methylpropiophenone, 97%
B1,260-1 4-Benzoylbiphenyl, 99% 15,753-8 2-Methylbenzophenone, 98%
40,564-7 2-Benzyl-2-(dimethylamino)-4'- 19,805-6 3-Methylbenzophenone, 99%
morpholinobutyrophenone, 97% M3,050-7 Methybenzoylformate, 98%
16,032-6 4,4'-Bis(diethylamino)benzophenone, 99+% 40563-9 2-Methyl-4'-(methylthio)-2-morpholinopropio-
14,783-4 4,4'-Bis(dimethylamino)benzophenone, 98% phenone, 98%
12,489-3 Camphorquinone, 98% 15,650-7 Phenanthrenequinone, 99+%
C7,240-4 2-Chlorothioxanthen-9-one, 98% 29,074-2 4'-Phenoxyacetophenone, 98%
40,807-7 (Cumene)cyclopentadienyliron(II) T3,400-2 Thioxanthen-9-one, 98%
hexafluorophosphate, 98% 40,722-4 Triarylsulfonium hexafluoroantimonate salts,
D3,173-7 Dibenzosuberenone, 97% mixed, 50% in propylene carbonate
22,710-2 2,2-Diethoxyacetophenone, 95% 40,721-6 Triarylsulfonium hexafluorophosphate salts,
D11,050-7 4,4'-Dihydroxybenzophenone, 99% mixed, 50% in propylene carbonate

6 • Polymer Products from Aldrich a

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

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

0.0224 % 0.0040 %

0.0011 % 0.0014 %

12,324-2 Anthraquinone-2-sulfonic acid, sodium salt

A9,000-4 Anthraquinone, 97%
monohydrate, 97%

O O
O
S ONa
O H O
2
O
O

0.0010% 0.0033 %

0.0004 % 0.0006 %

a The Link to All Your Polymer Needs • 7

 Applications: Free Radical Initiators
Photoinitiators: UV Absorption Spectra (continued)

11,931-8 (Benzene) tricarbonylchromium , 98% B515-1 Benzil, 98%

1

O O

.8 C C
Cr
OC CO
CO
.8

.6
0.0023 % 0.0029 %
.6

Absorbance
Absorbance

0.0012 % 0.0011 %

.4
.4

.2
.2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

39,939-6 Benzoin, sublimed, 99.5+% 17,200-6 Benzoin ethyl ether, 99%

O O
CH C CH C
.8 .8
OH OCH CH
2 3

.6 0.0056 % .6 0.0027 %
Absorbance
Absorbance

0.0017 % 0.0019 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

8 • Polymer Products from Aldrich a

 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 O

.8 CH C CH C
OCH
O CH CHCH .8 3
2 3
CH
3

.6

0.0110 % .6 0.0043 %
Absorbance

Absorbance
0.0069 % 0.0020 %

.4
.4

.2
.2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

40,562-0 Benzophenone/1-Hydroxycyclohexyl
B930-0 Benzophenone, 99%
phenyl ketone, 50/50 blend

O O
.8 C C
.8

O
C
OH
.6 0.0030 % .6 0.0150 %
Absorbance

Absorbance

0.0012 % 0.0015 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

a The Link to All Your Polymer Needs • 9

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

O O O
.8 C
O O
O

O C O

.6
0.0030 % 0.0031 %
Absorbance

0.0010 % 0.0004 %

.4

.2

0
220 240 260 280 300 320 340 360 380 400 420 440
Nanometers

40,564-7 2-Benzyl-2-(dimethylamino)-4'- 16,032-6 4,4'-Bis(diethylamino)benzophenone, 99+%

morpholinobutyrophenone, 97%

CH
O 2
.8 O N C C N(CH ) .8
32
CH CH
2 3

.6 0.0035 % .6 0.0020 %
Absorbance

Absorbance

0.0020 % 0.0008 %

.4 .4

.2 .2

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

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

10 • Polymer Products from Aldrich a

 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 CH
3 3
R R = CH R = H or
.8 O 3
.8
R= H R = CH
3
R
O

.6 0.0031% .6 0.0271 %

Absorbance
Absorbance

0.0008 % 0.0071 %

.4 .4

.2 .2

CH O CH
3 3
N C N
CH CH
3 3

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

C7,240-4 2-Chlorothioxanthen-9-one, 98% 40,807-7 (Cumene)cyclopentadienyliron(II)

hexafluorophosphate, 98%

O
Cl

Fe
S CH PF
3 6
.8 .8
CH CH
3

.6 0.0024 % .6 0.0055 %
Absorbance
Absorbance

0.0007 % 0.0027 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

a The Link to All Your Polymer Needs • 11

 Applications:
Applications: Free Radical Initiators
Photoinitiators: UV Absorption Spectra (continued)

D3,173-7 Dibenzosuberenone, 97% 22,710-2 2,2-Diethoxyacetophenone, 95%

O OCH CH
2 3
C CH

.8 .8 OCH CH
O 2 3

.6 0.0016 % .6 0.0100 %

Absorbance
Absorbance

0.0005 % 0.0014 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

D11,050-7 4,4'-Dihydroxybenzophenone, 99% 19,611-8 2,2-Dimethoxy-2-phenylacetophenone, 99%

O O OCH3
HO C OH
C C
OCH
3
.8
.8

.6
0.0036 % 0.0020 %
.6
Absorbance

Absorbance

0.0009 % 0.0011 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

12 • Polymer Products from Aldrich a

 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
CH C C CH
.8 3 3
.8

.6 0.0043 % 0.0030 %
.6
Absorbance

Absorbance
0.0009 % 0.0010 %

.4
.4

.2 .2
CH O
3
N C
CH
3

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

D14,966-7 2,5-Dimethylbenzophenone, tech., 95% D14,967-5 3,4-Dimethylbenzophenone, 99%

O
CH C
CH 3
3 O
.8 CH
.8 C 3

CH
3

.6
.6
0.0296 % 0.0039 %
Absorbance
Absorbance

0.0015 % 0.0013 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

a The Link to All Your Polymer Needs • 13

 Applications:
Applications: Free Radical Initiators
Photoinitiators: UV Absorption Spectra (continued)
40,566-3 Diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide
27,571-9 4'-Ethoxyacetophenone, 98%
2-Hydroxy-2-methylpropiophenone 50/50 blend

CH
3O O

.8 CH C P O
3
C CH
CH 3
3 .8

OCH CH
O OH 2 3
C C CH
.6 3
CH
3
0.0223 % .6 0.0044 %
Absorbance

Absorbance
0.0019 % 0.0009 %

.4
.4

.2
.2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

E1,220-6 Ethylanthraquinone, 97+% F40-8 Ferrocene, 98%

O
Fe
CH CH
2 3

.8
.8 O

0.0018 % .6 0.0065 %
.6
Absorbance
Absorbance

0.0005 % 0.0028 %

.4
.4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

14 • Polymer Products from Aldrich a

 Applications:
Applications: Free Radical Initiators
Photoinitiators: UV Absorption Spectra (continued)

32,810-3 3'-Hydroxyacetophenone, 99+% 27,856-4 4'-Hydroxyacetophenone, 99%

1

O
C CH
3
O
C CH
3
OH .8
.8

OH

0.0026 % .6 0.0048 %
.6
Absorbance

Absorbance
0.0007 % 0.0009 %

.4
.4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

22,043-4 3-Hydroxybenzophenone, 99% H2,020-2 4-Hydroxybenzophenone, 98%

O O
C HO C

HO .8
.8

0.0030 % .6 0.0051 %
.6
Absorbance

Absorbance

0.0011 % 0.0013 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

a The Link to All Your Polymer Needs • 15

 Applications:
Applications: Free Radical Initiators
Photoinitiators: UV Absorption Spectra (continued)

40,561-2 1-Hydroxycyclohexyl phenyl ketone, 99% 40,565-5 2-Hydroxy-2-methylpropiophenone, 97%

O
O OH
C
OH C C CH
3
.8 CH
.8 3

.6 0.0047 % 0.0053 %
.6

Absorbance
Absorbance

0.0019 % 0.0008 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

15,753-8
H2,020-2 2-Methylbenzophenone,
4-Hydroxybenzophenone,98%
98% 19,805-6 3-Methylbenzophenone, 99%

O
O C
C
CH
3
.8 CH .8
3

.6
0.0122 % .6 0.0071 %
Absorbance

Absorbance

0.0013 % 0.0012 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

16 • Polymer Products from Aldrich a

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

.8 O CH
3
O O CH S C C N O
3
C C OCH CH
3 3
.8

.6

.6
0.0625 % 0.0052 %
Absorbance

Absorbance
0.0025% 0.0014 %

.4

.4

.2
.2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

15,650-7 Phenanthrenequinone, 99+% 29,074-2 4'-Phenoxyacetophenone, 98%

O O

O
O C CH
3
.8
.8

0.0049 % .6 0.0032 %
.6
Absorbance

Absorbance

0.0028 % 0.0008 %

.4 .4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

a The Link to All Your Polymer Needs • 17

 Applications:
Applications: Free Radical Initiators
Photoinitiators: UV Absorption Spectra (continued)

T3,400-2 Thioxanthen-9-one, 98% 40,722-4 Triarylsulfonium hexafluoroantimonate salts,

mixed, 50% in propylene carbonate
1

S S SbF
6
S .8
.8

0.0016 % .6 0.0108 %
.6

Absorbance
Absorbance

0.0005 % 0.0048 %

.4
.4

.2 .2

0 0
220 240 260 280 300 320 340 360 380 400 420 440 220 240 260 280 300 320 340 360 380 400 420 440
Nanometers Nanometers

40,721-6 Triarylsulfonium hexafluorophosphate salts,

mixed, 50% in propylene carbonate

S S PF
.8 6

.6 0.0223 %
Absorbance

0.0039 %

.4

.2

0
220 240 260 280 300 320 340 360 380 400 420 440
Nanometers

18 • Polymer Products from Aldrich a

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.

a The Link to All Your Polymer Needs _ 19