Azo Polymerization Initiators

Comprehensive Catalog

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 10
01 Introduction/What
List of ApplicableisLaws
Radical Polymerization?

List01ofIntroduction/What
Applicable is RadicalLaw
Polymerization? P1 Detailed Explanations 1. Azo Nitrile P11-14
INDEX

07
What are Azo Polymerization Initiator? Radical Formation Mechanism P2 2. Azo Ester P15-16
3. Azo Amide P17-18
02 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides P3
4. Azo Imidazoline P19-20
Azo Compounds
Examples of radical reactions using Azo PolymerizationCAS
Initiators No.
P4 TSCA 5. Azo AmidineEINECS P21-22
03 Selection Guide P5-6 6. Macro Azo Initiator P23-26

08 Product List
04 V-70 Products
Decomposition 15545-97-8
P7-8 Listed Listed
P27-28

05 Solubility at a Glance P9 09 List of Related Items P29-32

10 List of Applicable Laws

06 V-65Photocharacterization
[Reference] 4419-11-8
P10 Listed Listed
P33-34

Introduction
AIBN 78-67-1 Listed Listed
Azo Nitriles

We develop a large variety of products taking advantage of our original

organic synthesis technology, production technology, and refining technology
V-59 13472-08-7
accumulated in our long experience in the manufacturing of reagents.
Listed Listed
Azo polymerization initiators are used as reaction initiators in the synthesis of
polymers. They are used mainly as radical polymerization initiators in a wide
V-40 2094-98-6
range of industries, such as acryl resins for paints, water absorbent resins,
Listed Listed
polymer coagulants, adhesives, and paper finishing agents.
We have approximately 20 types of azo polymerization initiators of
V-501 2638-94-0 Listed Listed
organic-solvent soluble type and water-soluble type.
Azo Esters

V-601
What is Radical 2589-57-3
Polymerization? Listed* Listed
Radical polymerization is initiated by the formation of free radicals. Free radicals are formed by thermac energy, light, or
radioactivity. Radical polymerization is mainly61551-69-7
VA-086 used for the polymerization of vinyl monomers. In addition Listed
Listed to radical
Azo Amides

polymerization, cationic polymerization and anionic polymerization are common polymerization methods. In the case of
radical polymerization, initiators are generally used. The typical initiators are azo polymerization initiators and peroxides.

VAm-110
Characteristics 195520-32-2
of Radical Polymerization Initiators Not Listed Not Listed
■ Radical polymerization initiator shows an effect even in a small amount.
Azo Imidazolines

VA-044 and a large number

■ It is not polar-sensitive, 27776-21-2 Listed
of solvent is available, a wide range Listed
of monomers can be polymerized.
■ Polymerization at a low to high temperature ranges is possible.
■ Reaction with simple facility and equipment is possible.
VA-061 20858-12-2 Listed Listed

Active Species Typical Reaction Addition Amount Type of Solvent

Azo Amidines

V-50 2997-92-4 Listed Listed

Usable in many
Radical X X Small amount
CO 2 R 1041483-94-6
CO R CO R CO 2 R
¡
solvents
VA-057 Not Listed Not Listed
2 2

¡
n-hydrate

VPS-1001 XH O 158947-07-0 Not Listed Not Listed

Macro Azo Initiators

+ O
O O
Cationic O
HO O r ×

VPS-1001N 158947-07-0 Not Listed Not Listed

Base O O
R – Si(OMe 3 ) + H2 O R Si O Si R

AnionicVPE-0201 105744-24-9 O O
Not Listed
× Not Listed
r
Base OH OH
O
HS SH + S S
*Listed under 5e Consent Order
133 Azo
AzoPolymerization
PolymerizationInitiators
Initiators

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 What is Azo Polymerization Initiator? Radical Formation Mechanism

01
What are Azo Polymerization Initiator?
An azo polymerization initiator is a compound having an azo group (R-N=N-R’), which decomposes with heat
and/or light, and forms carbon radical. The formed carbon radical is excellent in reactivity, and progresses polym-
erization and halogenation reactions of different types of vinyl monomers.

Radical Formation Mechanism of Azo Polymerization Initiators (Thermal Decomposition)

H2 C=CH
Carbon radical

–
N2 Y
CH 3 CH 3 CH 3 CH3
Monomer

–
–
–

R – C – N=N – C – R 2 R–C R–C C – CH2

hv H2

–
or
–
–

X X (1) X X Y
Formation (2) Initiation reaction/ Polymer
of radical Propagation reaction

(3) Recombination (4) Disproportionation

R R CH 3 CH 2
–
–

=
H3 C – C – C – CH3 R–C–H + R–C
Formation by side reaction
–
–

X X X –X
P7 Decomposition product

(1) Formation of radical: Azo polymerization initiators decompose with heat or light, and form nitrogen gas and
carbon radicals.
*The decomposition rate (in solution) follows first-order reaction rate kinetics and aries due to structure differences.
(2) Initiation reaction/Propagation reaction: Azo polymerization initiator addition-polymerizes with vinyl monomers
and forms a polymer.
*Since a section of the azo polymerization initiator is introduced at the end of polymer, the effect of end group is expected.
The efficiency of common azo polymerization initiators is approximately 0.5-0.7, and the remaining results in (3)
recombination or (4) disproportionation
(3) Recombination: The carbon radicals which did not engage in polymerization recombine.
(4) Disproportionation: The carbon radicals which did not engage in polymerization abstracts hydrogen of other
carbon radicals.

!
Reference Radical Formation Mechanism of Peroxides
R–C–O–O–C–R 2R–C–O
=

O O O

R–C–O R + CO 2
=

Where R is an alkyl.
R-CO2· decomposes (decarboxylation) immediately, and R· starts polymerization.

Where R is an aryl,
R-CO2· is hard to decompose (decarboxylation), so decarboxylation and addition reaction
to monomers are competitive reactions. Therefore, R· or R-CO2 are the radical active species.

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 02 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides

Characteristics of Azo Polymerization Initiators and Comparison with Peroxides

Peroxides are used as an initiator for radical polymerization, in addition to azo polymerization initiators.

Characteristics of Azo Polymerization Initiators

■ Azo polymerization initiators can be used safely as they do not decompose by induction and there is no risk of explosion.
■ They decompose at a constant rate regardless of the solvent used, so they can be used with different solvents.
■ Unlike the case of peroxides, the resulting carbon radical does not cause a hydrogen abstraction reaction,
but forms linear polymers.

Comparison with Peroxides

Item Azo Polymerization Initiator Peroxide

Reversibility of decomposition Irreversible reaction Reversible reaction

Efficiency of initiator 0.5 to 0.7 0.9 to 1

Decomposition rate First-order reaction rate equation shall apply. Depends on additives and solvents.
Decomposability

Solvent effect*1 Small Large

Reactive
Induced decomposition Not reactive
(Pay attention to contact with metal.)

Reactive
Redox decomposition
*2 Not reactive (Forms redox system with
a reducing substance)

RC ● RO ●
Reactivity of Formed Radicals

Formed radical

Hydrogen abstractability Small Large

Graft/crosslinking polymer Hard to occur Easy to form.

Formed polymer Forms linear polymers. Forms branched polymers.

Gas generation Reactive Not reactive

Others

Oxdizability Not reactive Reactive

*1 Solvent effect: This means that the system is affected by polarization of hydrogen bonding, etc. depending on the types of solvent.
*2 Redox: Redox reaction is a chemical reaction that electrons are given and received between atoms, ions, or compounds in the process of formation of products from reactants.

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 Examples of radical reactions using Azo Polymerization Initiators

02
Examples of radical reactions using Azo Polymerization Initiators
Azo polymerization initiators are used as catalyst and foaming agent in organic synthesis, in addition to in polymer synthesis.

N2
CH3 CH3 CH3
− − −
R−C−N=N− C −R 2 R−C●
− − or hv −
X X X

Carbon radical

Polymer Synthesis

Radical polymerization of styrene

R R R
Radical
active species

Radical polymerization of acrylic ester

R R R R
R R R R
R
CO 2 R CO 2 R CO 2 R CO2 R
CO 2 R CO 2 R

Copolymerization of styrene and acrylic ester

R R
R
R R R R
R
m n
CO 2 R
CO 2 R

Catalyst for Organic Synthesis

Addition reaction to olefins Br

Azo polymerization initiator can be used for addition

reactions of HBr, H2S, etc. to olefins. Especially, when Azo polymerization initiator
+ HBr
using styrenes, bromine or mercapto groups may be Δ or hv
selectively introduced to the β position.

Mitsunobu reaction *3
OH Nu
Azo compounds*4 can be used as reagents for *4
+ NuH + Azo compound + Ph3 P=O
Mitsunobu reaction. R R' R R'

Foaming Agent
Azo polymerization initiators are used as foaming agents for vinyl chloride or other plastics,
taking advantage of the property of generating nitrogen gas.

*3 Mitsunobu reaction: Sn2 (reaction) that activates hydroxyl group of alcohol with azo carboxylic acid ester and triphenylphosphine.
*4 Azo compounds: Bis (2-methoxyethl) azodicarboxylate, etc.

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 03 Selection Guide

Selection Guide

Selection of Polymerization Process

Step 1 Is polymerization process a radical reaction? Step 2 Is the solvent an organic solvent or water?

Organic solvent
Radical polymerization
initiator
Water

10-hour Half-life Temperature by Structure

We have azo polymerization initiators fit for a large extent of 10-hour half life temperature (*). You can select an initiator fit for your purpose.
(*10-hour half-life temperature: A temperature at which the concentration (amount) of azo group becomes a half in 10 hours in the solvent.)

Organic solvent soluble type (oil-solubility)

10-hour Half-life
Temperature Azo nitrile Azo Ester Azo Amide

P17 VAm-110 (110 ºC)

110 ºC O CH3 CH3 O
C C N N C C
P13 V-40 (88 ºC) CH3 CH2 CH2 CH2 NH CH3 CH3 NHCH2 CH2 CH2 CH3

N N
NC CN
80 ºC
P12 V-59 (67 ºC)
CH3 CH3
− −
CH3CH2−C−N=N−C−CH2CH3
− −

70 ºC CN CN

P12 AIBN (65 ºC) P15 V-601 (66 ºC)

* Metal-content-control-grade
products are also available. * Metal-content-control-grade
products are also available.
CH3 CH3
− − CH3 CH3
− −
H3C−C−N=N−C−CH3
− − H3C−C−N=N−C−CH3
− −
60 ºC CN CN
COOCH3 COOCH3

P11 V-65 (51 ºC)

* Metal-content-control-grade
products are also available.
CH3 CH3 CH3 CH3
50 ºC CH CH2 C N N C CH2 CH
CH3 CN CN CH3

P11 V-70 (30 ºC)

OCH3 CH3 CH3 OCH3
30 ºC H 3C C CH2 C N N C CH2 C CH3
CH3 CN CN CH3

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 Selection Guide

03
Step 3 Polymerization Method Step 4 Polymerization Temperature

Suspension polymerization
A polymerization method to heat the
oil-soluble monomers in a dispersed condition
88 ºC V-40
in water (The initiator solves in monomers.) 66 ºC V-601
Solution polymerization A polymerization method under which the initiator, 51 ºC V-65
monomers and formed polymers are all dissolved status. etc
A polymerization method under which liquid monomers
Bulk polymerization are polymerized by itself or with adding the initiator. 86 ºC VA-086
A polymerization method under which oil-soluble
56 ºC V-50
Emulsion polymerization monomer is dispersed in water with emulsifying 44 ºC VA-044
agent. (The initiator dissolves in water.) etc

Water-soluble type (water solubility)

10-hour Half-life
Temperature Azo nitrile Azo Amide Azo Amidine Azo Imidazoline

P17 VA-086 (86 ºC)

O CH3 CH3 O
C C N N C C
HOCH2CH2 NH CH3 CH3 NHCH2CH2OH

80 ºC

70 ºC
P13 V-501 (69 ºC)
CH3 CH3
− −
HOOCH2CH2C−C−N=N−C−CH2CH2COOH
− − P19 VA-061 (61 ºC)
CN CN

60 ºC N CH3 CH3 N
C C N N C C
P21 VA-057 (57 ºC) N
H
CH3 CH3 N
H
CH3 CH3
HN NH
●4H2O
C C N N C C
HOOCH 2CH2CHN NHCH 2CH2COOH
CH3 CH3

P21 V-50 (56 ºC)

NH CH3 CH3 NH
50 ºC C C N N C C ●2HCl
NH2 CH3 CH3 NH2

P19 VA-044 (44 ºC)

CH3 CH3 N
30 ºC N
C C N N C C ●2HCl
N CH3 CH3 N
H H

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 04 Decomposition Products

Decomposition Product of Azo Polymerization Initiators

1. Formed Amount of each Decomposition Product of Azo Nitrile
CH 3 CH 3
–

–
R – C – N=N – C – R
–

CN CN Ratio of decomposition product in the case of thermal decomposition with GC (%)

Disproportionation Recombination
R R R
Compound R Polymer

–
–
R

–
Name Unknown

–
H3 C – C – CN H3 C – C – C – CH3
H2 C=C – CN
H

–
–
CN CN
AIBN CH 3 *5 4 4 92 Trace
V-59 C 2 H5 *6
6 Trace 86 8
V-65 (CH 3 ) 2 CHCH 2 *5
7 7 85 Trace
V-70 CH 3 OC(CH 3 ) 2 CH 2 *5 8 8 78 8
V-40 c-C 6 H10 *5
9 9 82 1
*5 In-house Data *6 Polymer journal 9275 (1977)

2. Decomposition Product of V-601 (Special Case)*7

N2 *7 [Link], [Link], [Link], [Link], Macromolecules, 19(3), 934(1986)

CH3 CH3 CH3

–

CH 3 – C – N=N – C – CH 3 2 CH3 – C ●
or hv
–

COOCH3 COOCH3 COOCH3 (I)

CH3 CH3
–

Recombination CH 3 – C – C – CH3
(I)
–

COOCH3 COOCH3 (IV)

Disproportionation CH3
+ CH 3
–

CH 3 – CH
– –

CH 2 =C
–

COOCH 3 (II) COOCH 3 (III)

CH3 CH3
–

(I) + (III) CH 3 – C – CH2 – C ●

–

COOCH3 COOCH3 (V)

CH3 CH3 CH3
(I)
–

(V) CH 3 – C – CH2 – C – C – CH 3
–

COOCH3 COOCH3 COOCH3 (VI)

CH3
Disproportionation
–

CH 3 – C – CH2 – C=CH2
–

COOCH3 COOCH3 (VII)

Ratio of decomposition product in the toluene solution (%)

Decomposition Product Thermal Decomposition (80 ºC) Photodecomposition

(100 W HP Hg lamp)
(25 ºC)

IV 42.1 42.7
II 36.4 38.5
VI 13.8 13.8

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 Decomposition Products

04
3. Volatility of Decomposition Products
The decomposition product of V-601 is characterized by a higher volatility than that of AIBN. Also, the decomposition
product of V-601 is azeotropic with water, therefore, thus can be easily removed from the post-reaction system.
● Boiling point of decomposition product of V-601: 85-90 ºC (5 mmHg)
● Azeotropic point of decomposition product of V-601 with water: 90 ºC
On the other hand, the decomposition product of V-40 is hardly volatile, therefore, applications such as paint are expected.

Evaporation Rate of Decomposition Products

50

V-601
(AIBN)
40
V-59
V-65
Evaporation Rate (mg/hr • cm2)

V-40

30

20

10

0
0 20 40 60 80 100 120 140

Temperature (ºC)

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 05 Solubility

Solubility
Oil-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature)

V-70 V-65 AIBN V-601 V-59 V-40 VAm-110

Water 0.1 <0.1 <0.1 0.3 <0.1 0.1 <0.1
Methanol 1 28 7.5 >50 >50 4.4 >50
Acetone 3.3 >50 29 >50 >50 30 >50
Chloroform 20 >50 25 >50 >50 >50 >50
Ethyl Acetate 2.0 >50 14 >50 >50 15 >50
Toluene 3.0 >50 7.0 >50 >50 27 >50

Water-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature)

VA-044 V-50 VA-057 VA-086

Water 34.7 23.2 14.0 4.5
Methanol 1.7 2.1 28.8 7.4
Acetone Not soluble Not soluble Not soluble Not soluble
Ethyl Acetate Not soluble Not soluble Not soluble Not soluble
Toluene Not soluble Not soluble Not soluble Not soluble
N,N-Dimetylformamide Not soluble Not soluble Not soluble 4.4

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 [Reference] Photocharacterization

06
! Photocharacterization
Reference
R1 R1
These products are decomposed by exiting of Azo (N=N) group by light irradiation.
R2 N=N R2
They are able to be used also as photo radical initiators.
X X
Absorbs around 360 nm.

Photo Polymerization by Oil-Soluble Azo Polymerization Initiators

Photodecomposition Reaction Rate Constant Example of Photo Polymerization (Bulk Polymerization)

Solvent: Toluene 30

Light source: 100 W high-pressure mercury lamp 25

Polymerization ratio (%)

20

15
Azo Molar Absorbance Coefficient kd×104
MW λmax (nm) 10
Compound ε (L/mol·cm) (sec-1)
5
V-59 192.26 348 16 3.76
AIBN 164.21 347 13 3.97 0
0 50 100 150
time/min
V-40 244.34 350 17 4.13
V-601 230.26 368 14 4.43 Monomer Methyl methacrylate
V-65 248.37 350 22 4.86 Initiator 0.01 mol/l (ratio to monomer)
VAm-110 312.45 376 30 8.01 Light Source 100 W high-pressure mercury lamp

Photo Polymerization of Water-Soluble Azo Polymerization Initiators

Photodecomposition Reaction Rate Constant Example of Photo Polymerization (Solution Polymerization)

Solvent: Water 100

Light source: 100 W high-pressure mercury lamp 90

80
Polymerization ratio (%)

70
Azo Molar Absorbance Coefficient kd×104 60
MW λmax (nm)
Compound ε (L/mol·cm) (sec-1) 50
40
V-50 271.19 367 22 5.37 30

VA-057 414.46 371 26 7.23 20

10

VA-044 323.33 363 23 7.53 0

0 10 20 30 40
VA-086 288.35 375 30 7.72 time/min

Monomer Acrylamide 10 w/wt%

Initiator 0.01 mol/l (ratio to monomer)
Light Source 100 W high-pressure mercury lamp

*Since photodecomposition reaction rate constant depends on the strength of light source, the above photodecomposition reaction rate constant is not an absolute value.
However, since these are data measures with a same light source, these data can be used for relative comparison.

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 07 Detailed Explanations 1. Azo Nitrile

Detailed Explanations
1. Azo Nitrile

V-70 2,2’-Azobis(4-methoxy-2,4-dimethylvaleronitrile)

OCH3 CH3 CH3 OCH3

Characteristics
H 3C C CH 2 C N N C CH 2 C CH3 V-70 is an oil-soluble azo polymerization initiator of which 10-hour half-life temperature is 30 ºC.
V-70 can be used as a polymerization initiator for different types of vinyl monomers and a
CH3 CN CN CH3 catalyst for organic radical reactions at a low temperature.
Properties Applicable Laws and Regulations
Low-temperature type Oil-soluble type Item Item
Molecular formula C16H28N4O2 TSCA Listed
Molecular weight 308.43 EINECS Listed
CAS No. 15545-97-8
nearly white, crystalline powder
Form
*Contains water.
Melting point 50-96(dec.) °C Packaging and Storage Requirements
10-hour half life temperature 30 ºC (Toluene)
Item
water : practically insoluble.
dichloromethane : freely soluble. Packaging 100 g
Solubilities acetonitrile, N,N-Dimethylformamide : 25 kg
soluble. methanol, acetone,
toluene : slightly soluble. Storage requirement Please keep at -10 ºC or less.

V-65 2,2’-Azobis(2,4-dimethylvaleronitrile)

CH3 CH3 CH3 CH3 Characteristics:

CH CH2 C N N C CH2 CH When compared with AIBN, the 10-hour half-life temperature of this oil-soluble azo polymerization initiator is
CH3 CN CN CH3 10 ºC or lower than AIBN.
This product can be used for a wide range of applications, from versatile polymers to cosmetics-related use.
Properties Applicable Laws and Regulations
Low-temperature type Oil-soluble type Item Item
Molecular formula C14H24N4 TSCA Listed
Molecular weight 248.37 EINECS Listed
CAS No. 4419-11-8
Form white, crystalline powder
Melting point 45-70(dec) °C
Packaging and Storage Requirements
10-hour half life temperature 51 ºC (Toluene) Item
water : insoluble. benzene, Packaging 500 g
acetone, ether, 25 kg
Solubilities N,N-Dimethylformamide, toluene,
methanol : soluble. Storage requirement Please keep at 10 ºC or less.

V-65HP (Metal-content-control-grade products)

Semiconductors LCD
Packaging and Storage Requirements Metal Content
Item Metal Specification value
Packaging 500 g Na 500 ppb or less
10 kg Li,Mg,Al
Storage requirement Please keep at 10 ºC or less. K,Ca,Cr
Mn,Fe,Ni 300 ppb or less
Cu,Zn,Zr
Pb,Sn

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 Detailed Explanations 1. Azo Nitrile
07
AIBN 2,2’-Azobis(isobutyronitrile)

CH3 CH3
− − Characteristics:
H3C−C−N=N−C−CH3 AIBN is the most common oil-soluble azo polymerization initiator, and is used for
− −
polymerization of versatile polymers.
CN CN
Properties Applicable Laws and Regulations
Oil-soluble type Item Item
Molecular formula C8H12N4 TSCA Listed
Molecular weight 164.21 EINECS Listed
CAS No. 78-67-1
Form white, crystalline powder
Melting point 100-103(dec.) °C
10-hour half life temperature 65 ºC (Toluene)
Packaging
Item
and Storage Requirements
water : very slightly soluble.
acetone : free soluble. methanol, Packaging 20 kg
Solubilities toluene : soluble.
Ethanol : sparingly soluble. Storage requirement Please keep at 20 ºC or less.

AIBN-HP (Metal-content-control-grade products)

Semiconductors LCD
Packaging and Storage Requirements Metal Content
Item Metal Specification value
Packaging 500 g Li,Na,Mg
10 kg Al,K,Ca
Storage requirement Please keep at 20 ºC or less. Cr,Mn,Fe 500 ppb or less
Ni,Cu,Zn
Zr,Pb,Sn

V-59 2,2’-Azobis (2-methylbutyronitrile)

CH3 CH3
− − Characteristics:
CH3CH2−C−N=N−C−CH2CH3 V-59 is an oil-soluble azo polymerization initiator which shows almost a similar
− −
10-hour half-life temperature to that of AIBN and has excellent solubility to many
CN CN
different solutions.
Applicable Laws and Regulations
Oil-soluble type
Properties Item
Item TSCA Listed
Molecular formula C10H16N4 EINECS Listed
Molecular weight 192.26
CAS No. 13472-08-7 Packaging and Storage Requirements
Form white, powder Item
Melting point 48 - 52 ºC Packaging 500 g
10-hour half life temperature 67 ºC (Toluene) 10 kg
water : very slightly soluble. 25 kg
Solubilities dimethyl sulfoxide : free soluble.
toluene, methanol : Very soluble. Storage requirement Please keep at 10 ºC or less.

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 07 Detailed Explanations 1. Azo Nitrile

V-40 1,1’-Azobis(cyclohexane-1-carbonitrile)

Characteristics:
N N Since the 10-hour half-life temperature is as high as 88 ºC, V-40 can be used to decrease residual
NC CN monomer concentration when used with other initiators, such as V-65. This is an oil-soluble azo
polymerization initiator which has a high solubility in various organic solvents. The decomposition product of
V-40 has a unique characteristic of low volatility, therefore it could be useful for cow-voc paint applications.

Properties Applicable Laws and Regulations

High-Temperature Type Oil-soluble type Item Item
Molecular formula C14H20N4 TSCA Listed
Molecular weight 244.34 EINECS Listed
CAS No. 2094-98-6
Form white, crystals
Packaging and Storage Requirements
Melting point 110-120 ºC
10-hour half life temperature 88 ºC (Toluene) Item
Water : practically insoluble. Packaging 500 g
acetone, chloroform, 20 kg
Solubilities benzene : freely soluble. Ethanol : soluble.
petroleum ether : practically insoluble Storage requirement Please keep at 20 ºC or less.

Example of Polymerization Block Polymerization of Styrene Suspension Polymerization of MMA by co-using with V-40 and V-65.
% % (Relationship between the addition amount of initiator and residual monomers)
100 100
Initiator concentration 7.0×10 mol/ℓ Initiator concentration 7.0×10 mol/ℓ
−3 −3

Polymerization temperature 90 ºC Polymerization temperature 120 ºC 4

Temperature Time
80 80
V-40 Polymerization conditions: 80 ºC 1 Hr
95 ºC 2 Hrs
Residual monomers (%)
Polymerization Ratio (%)

V-40 3
60 60
AIBN
2

40 40 Co-using with V-65 0.1 %

V-65
1
Co-using with V-65 0.15 %
20 20
0
Without adding initiator 0 0.01 0.02 0.03 0.04 0.05
Addition Amount of V-40 (Ratio to Monomer %)
0 0
0 1 5 10 0 1 2 3
Polymerization time (h) Polymerization time (h)

V-501 4,4’–Azobis(4–cyanovaleric acid)

CH3 CH3 Characteristics:

− −
HOOCH2CH2C−C−N=N−C−CH2CH2COOH V-501 is a nitrile-based water-soluble azo polymerization initiator, having a carboxyl group at the end. By
− −
introducing carboxyl group at polymer, post-polymerization mddification can be achieved.
CN CN
Properties Applicable Laws and Regulations
Water-soluble type Non-halogen Item Item

F Cl Molecular formula
Molecular weight
C12H16N4O4
280.28
TSCA
EINECS
Listed
Listed
Br I CAS No. 2638-94-0
white, powder
Form
*Containing water
Melting point 120-123(dec.) °C
Packaging and Storage Requirements
10-hour half life temperature 69 ºC (In water, as sodium salt) Item
water : practically insoluble. Packaging 500 g
Ethanol, ether, formamide : freely 10 kg
Solubilities soluble methanol : soluble.
toluene : insoluble. Storage requirement Please keep at 20 ºC or less.

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 Half-life of Azo Nitriles in Solution
Detailed Explanations 1. Azo Nitrile
07
(2) (3)(4)(6) (5)
10000

1000

600
(1)
Half-life (minutes)

100

10

1
3.3 3.2 3.1 3 2.9 2.8 2.7 2.6
(K-1×103)

30 40 50 60 70 80 90 100 110

Temperature (ºC)

(1)
● V-70 (2) V-65 (3) AIBN (4) V-59 (5) V-40 (6) V-501

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 07 Detailed Explanations 2. Azo Ester

2. Azo Ester

V-601 Dimethyl 2,2’-azobis(2-methylpropionate)

CH3 CH3
− − Characteristics:
H3C−C−N=N−C−CH3 V-601 is a nitrile-free oil-soluble azo polymerization initiator which has similar level of polymerization
− −
activity as AIBN. A safer developed as alternative to AIBN, V-601 decomposition results in much less
COOCH3 COOCH3
toxic byproducts. As a nitrile-free azo initiator, V-601 displays excellent solubility characteristics in organic
solvents. Since the volatility of the decomposition product is higher than that of others, such a product
can be removed in the process of polymer manufacturing. Being of non-nitrile type, the polymerized
polymers are highly transparent, therefore, semiconductors and LCDs applications are expected.

Properties Applicable Laws and Regulations

Non-nitrile Oil-soluble type Item Item
Molecular formula C10H18N2O2 TSCA Listed (Listed under 5e Consent Order)
CN Molecular weight 230.26 EINECS Listed
CAS No. 2589-57-3
Form slight yellow or pale yellow, crystals or oily
Packaging and Storage Requirements
Melting point 22-28 °C
10-hour half life temperature 66 ºC (Toluene) Item
water : insoluble. benzene, Ethanol, Packaging 500 g
N,N-Dimethylformamide, 10 kg
Solubilities dioxane, DMSO : freely soluble. methanol,
toluene, chloroform, hexane : soluble. Storage requirement Please keep at 10 ºC or less.

V-601HP (Metal-content-control-grade products)

Semiconductors LCD
Packaging and Storage Requirements Metal Content
Item
Packaging 500 g Na 200 ppb or less
10 kg Li,Mg,Al
Storage requirement Please keep at 10 ºC or less. K,Ca,Cr
Mn,Fe,Ni 100 ppb or less
Cu,Zn,Zr
Pb,Sn

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 Half-life of Azo Esters in Solution
Detailed Explanations 2. Azo Ester
07
(1)
100000

10000

1000
Half-life (minutes)

600

100

10

1
3.3 3.2 3.1 3 2.9 2.8 2.7 2.6 2.5
(K-1×103)

30 40 50 60 70 80 90 100 110 120

Temperature (ºC)

(1) V-601

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 07 Detailed Explanations 3. Azo amide

3. Azo amide

VA-086 2,2’-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide]

CH3 CH3
O − − O Characteristics:
=

=
C−C−N=N−C−C VA-086 is a non-ionic and non nitrile water-soluble azo polymerization
− −
initiator having a hydroxyl group at the end. The 10-hour half-life
−

HOCH2CH2NH −
CH3 CH3 NHCH2CH2OH
temperature is as high as 86 ºC, therefore, reduction of residual monomer
can be expected by co-using it with another initiator.

Properties Applicable Laws and Regulations

Non-nitrile Non-halogen Item Item

CN F Cl Molecular formula
Molecular weight
C12H24N4O4
288.35
TSCA
EINECS
Listed
Not Listed
Br I CAS No. 61551-69-7
Form white - slightly yellow, crystalline powder Packaging and Storage Requirements
Water-soluble type Melting point 138-145(dec.) °C Item
10-hour half life temperature 86 ºC (Water) Packaging 500 g
water, methanol : soluble. 5 kg
Solubilities chloroform : slightly soluble Storage requirement Please keep at 25 ºC or less.

VAm-110 2,2’-Azobis (N-butyl-2-methylpropionamide)

CH3 CH3 Characteristics:

O − − O
=

C−C−N=N−C−C VAm-110 is an oil-soluble azo polymerization initiator which is active in high

− −
temperatures, the 10-hour half-life temperature is as high as 110 ºC. This product
−

CH3CH2CH2CH2NH CH3 CH3 NHCH2CH2CH2CH3

has characteristics which show high solubility to different organic solvents.

Properties Applicable Laws and Regulations

Non-nitrile High-Temperature Type Item Item
Molecular formula C16H32N4O2 TSCA Not Listed
CN Molecular weight 312.46 EINECS Not Listed
CAS No. 195520-32-2
Form slight yellow powder Packaging and Storage Requirements
Oil-soluble type Melting point 65 °C Item
10-hour half life temperature 110 ºC (Ethylbenzene) Packaging 500 g
Water : insoluble. methanol, 5 kg
Solubilities ethyl acetate, toluene, methyl
ethyl ketone : freely soluble. Storage requirement Please keep at 25 ºC or less.

Examples of polymerization Bulk Polymerization of Styrene Solution Polymerization of n-Butyl methacrylate

100 100

75 75
Polymerization Ratio (%)

Polymerization Ratio (%)

50 50

Polymerization conditions (Sealed tube polymerization) Polymerization conditions

Concentration of initiator 0.4 mmol/l Monomer concentration 20 wt%
Polymerization temperature 110 ºC 25 Initiator concentration 0.19 mol%/monomer 25
Polymerization temperature 120 ºC
VAm-110 Polymerization solvent Diisobutyl Ketone

Thermal polymerization VAm-110

0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Polymerization Time (h) Polymerization Time (h)

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 Half-Life of Azo Amides in Solution
Detailed Explanations 3. Azo amide
07
(1) (2)
10000

1000

600
Half-life (minutes)

100

10

3.1 3 2.9 2.8 2.7 2.6 2.5 2.4 2.3

(K-1×103)

50 60 70 80 90 100 110 120 130 140 150

Temperature (ºC)

(1) VA-086 (2) VAm-110

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 07 Detailed Explanations 4. Azo Imidazolin

4. Azo Imidazolin

VA-044 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride

CH 3 CH 3
N N Characteristics: VA-044 is a non-nitrile, cationic water-soluble azo polymerization initiator. It is highly
C C N N C C ●2HCl effective for the polymerization of water-soluble vinyl monomer. The 10-hour half-life
N N
H
CH 3 CH 3
H temperature is as low as 44 ºC, and the product is active at low temperatures.
Properties Applicable Laws and Regulations
Non-nitrile Low-temperature type Item Item
Molecular formula C12H24Cl2N2 TSCA Listed
CN Molecular weight 323.27 EINECS Listed
CAS No. 27776-21-2
white - light yellow
Water-soluble type
Form
crystals or crystalline powder
Packaging and Storage Requirements
Melting point 188-193(dec.) °C
10-hour half life temperature 44 ºC (Water) Item
water : free soluble. Packaging 500 g
methanol : sparingly 20 kg
Solubilities soluble. Ethanol : very slightly soluble.
acetone, toluene : insoluble. Storage requirement Please keep at 40 ºC or less.

VA-061 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]

CH3 CH3
N N
Characteristics: VA-061 is the free base of VA-044 and VA-046B, which are water-soluble azo polymerization initiators. By forming salts with different
C C N N C C
organic acids, the product dissolves in water, creating a highly effective initiator for polymerization of water-soluble vinyl monomers.
N CH3 CH3 N
H H Properties Applicable Laws and Regulations
Non-nitrile Non-halogen Item Item

CN F Cl Molecular formula
Molecular weight
C12H22N6
250.35
TSCA
EINECS
Listed
Listed
Br I CAS No. 20858-12-2
Form slightly yellowish white, crystalline powder
Water-soluble type Melting point 115-125(dec.) °C Packaging and Storage Requirements
10-hour half life temperature 61 ºC (Methanol)
Item
water : practically insoluble.
methanol : soluble. Ethanol, Packaging 500 g
Solubilities chloroform : slightly soluble.
5 kg
toluene : insoluble.
*Acid: Soluble Storage requirement Please keep at 10 ºC or less.

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 Detailed Explanations 4. Azo Imidazoline

Half-Life of Azo Imidazolines in Solution

07
100000

(2)

10000
Half-life (minutes)

(1)

1000

600

100
3.2 3.1 3 2.9

(K-1×103)

40 50 60 70

Temperature (ºC)

(1) VA-044 (2) VA-061

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 07 Detailed Explanations 5. Azo Amidine

5. Azo Amidine

V-50 2,2’-Azobis(2-methylpropionamidine)dihydrochloride

NH CH3 CH3 NH
Characteristics:
C C N N C C 2HCl
V-50 is a highly active water-soluble azo polymerization initiator. A variety of polymerization
NH 2 CH3 CH3 NH 2
applications can be expected. This product is uniquely characterized by the amidine group which is
cationic. Cationic emulsions, latex, etc. can be synthesized easily and in a stable manner, therefore
an excellent effect can be expected for emulsion polymerization of synthetic rubber, adhesives, etc.

Applicable Laws and Regulations

Non-nitrile Water-soluble type
Properties Item
Item TSCA Listed
CN Molecular formula C8H20Cl2N6 EINECS Listed
Molecular weight 271.19
CAS No. 2997-92-4
Form nearly white, Granular
Packaging and Storage Requirements
Melting point 160-169(dec.) °C Item
10-hour half life temperature 56 ºC (Water) Packaging 500 g
water : freely soluble. 5 kg
methanol, Ethanol, acetone, 20 kg
Solubilities N,N-Dimethylformamide,
dioxane : practically insoluble. Storage requirement Please keep at 40 ºC or less.

VA-057 2,2’-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate

NH CH3 CH3 NH
4H2O
Characteristics:
C C N N C C
VA-057 is a water-soluble azo polymerization initiator which has a zwitterinoic structure. The 10-hour half-life tempera-
HOOC CH2 CH2 NH CH3 CH3 NHCH 2 CH2 COOH
ture is 57 ºC, which allows a polymerization under a mild condition. As a non-halogenated initiator, VA-057
is uniquely characterized by not causing any concerns about coloring of polymer or corrosion of polymerization facilities
with halogen. Since the product has a zwitterionic structure, formation of both cationic and anionic latex is expected.

Properties Applicable Laws and Regulations

Non-nitrile Non-halogen Item Item

CN F Cl Molecular formula
Molecular weight
C14H34N6O8
414.46
TSCA
EINECS
Not Listed
Not Listed
Br I CAS No. 1041483-94-6 (n-hydrate)
white - pale yellow
Form
Water-soluble type powder - crystalline powder Packaging and Storage Requirements
Melting point 97(dec.) °C Item
10-hour half life temperature 57 ºC (Water) Packaging 500 g
water, methanol : free soluble. 5 kg
Solubilities Ethanol, isopropanol, acetone,
toluene : very slightly soluble. Storage requirement Please keep at 10 ºC or less.

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 Detailed Explanations 5. Azo Amidine

Half-Life of Azo Amidines in Solution

07
(1) (2)
10000

1000

600
Half-life (minutes)

100

10

1
3.3 3.2 3.1 3 2.9 2.8 2.7 2.6
(K-1×103)

30 40 50 60 70 80 90 100 110

Temperature (ºC)

(1) V-50 (2) VA-057

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 07 Detailed Explanations 6. Macro Azo Initiator

What is a Macro Azo Initiator?

Macro Azo Initiator (MAI) is a unique azo compound which gives block polymer easily through a polymerization with different vinyl
monomers. MAI has a structure in which polymer segment and azo group are repeatedly bonded, and there are several radical
forming points in a molecule. Therefore, when monomers are polymerized, polymers with high blocking efficiency can be designed.
Since this product is soluble in different solvents, various polymerization methods (solution polymerization, suspension polymeriza-
tion and emulsion polymerization) can be adopted. This product offers a wide range of options of monomers for co-polymerization,
and allows molecule design and structure control of block polymers fit for the purpose.

VPS-1001 Methyl methacrylate (MMA)

VPS-1001
Methyl methacrylate (MMA)
Toluene

Polymerization in N2 gas flow

Formation Process of Block Polymer

Azo group
N=N

N=N
N=N
N=N

N=N

MMA monomer Polydimethylsiloxane chain

The process from the start of polymerization with azo groups in polymers to the growing of block polymers is shown in a schematic drawing.

A-B type

ABA type

(AB) n type n

Conceptual Drawing
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 Detailed Explanations 6. Macro Azo Initiator
07
6. Macro Azo Initiator (MAI : Macro Azo Initiator)
4,4-Azobis(4-cyanovaleric acid),polymer with alpha,
VPS-1001 VPS-1001N omega-bis(3-aminopropyl)polydimethylsiloxane

CH3 CH3 CH3 CH3

OCH2CH2C N N CH2CH2CONHCH2CH2CH2Si OSi CH2CH2CH2NH
m
CN CN CH3 CH3 n

Characteristics:
In the block polymer obtained by this product, polydimethylsiloxane and vinyl polymer are chemically bonded. Therefore, the product is completely new co-polymer
having the characteristics of the two materials. This product has fundamentally different characteristics from a polymer alloy, which is formed only by blending. The
largest advantage of this product is its ability to combine polydimethylsiloxane with a polymer material which hardly has a compatibility, therefore the properties of
polydimethylsiloxane (heat resistance, cold resistance, weathering resistance, abrasion resistance, water repellency, electric insulation, bio-affinity, gas permeabil-
ity, lubricity, surface gloss, etc.) are possibly reflected to the material.
Applicable Laws and Regulations
Item
Emulsion Suspension Solution TSCA Not Listed
polymerization polymerization polymerization EINECS Not Listed

Forms and molecular weight of different types Packaging and Storage Requirements
VPS-1001N Item VPS-1001 VPS-1001N
Item VPS-1001 (solvent contained) 500 g Net 5 kg
Packaging
Molecular formula [C20H34N6O2Si(C2H6Si)m]n 5 kg
CAS No. 158947-07-0 Storage requirement Please keep at 10 ºC or less.
Form clear gum white

Molecular weight of macro initiator (Mn) Approximately 80,000 to 120, 000

Molecular weight of polydimethylsiloxane Approximately 10,000
Approximately 0.1 mmol/g
Molecular number of azo group per 1 g of VPS
(1/60 of AIBN)
10-hour half life temperature 65 - 70 ºC
*Compared with mol number of azo group per 1 g of AIBN (M.W.: 164.21) = 6 mmol/g.

Example of polymerization
In a four necked flask equipped with a thermometer, nitrogen gas induction tube, mixer, and reflux condenser,
25 g of VPS-1001, 100 g of methyl methacrylate (MMA) as monomer, and 260 g of toluene as solvent are
charged and polymerized under the nitrogen gas flow at 70 ºC and for five hours.

[Formed Block Polymer (BP)]

CH3 CH3 CH3 CH3 CH3

OCCH2CH2 C CH2C n C CH2CH2CONHCH2CH2CH2Si OSi m CH2CH2CH2NH
CN COOCH3 CN CH3 CH3 I

Methyl polymethacrylate segment Polydimethylsiloxane segment

Formed Block Polymer – Molecular Weight Data

Mn Mw Mw/Mn Content of polydimethylsiloxane segment in BP

80,700 149,000 1.85 31 %

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 07 Detailed Explanations 6. Macro Azo Initiator

VPE-0201 4,4’-Azobis(4-cyanopentanoicacid)·Polyethyleneglycolpolymer

CH3 CH3
OCH2CH2C N N CH2CH2COO CH2CH2O
m
CN CN n

Characteristics:
This product is an amphipathic macro azo initiator which is soluble both in water-base and organic solvent-base solvents, having a structure in which several
polyethylene oxide segments are combined by the intermediary of azo group. When used for polymerization of vinyl monomers, this product forms a block
polymer with a structure in which polyethylene oxide and vinyl polymers are chemically bonded, therefore the properties of polyethylene oxide (hydrophilicity
of polymer, prevention of static charge, improvement of dispersity, addition of compatibility, prevention of dulling, etc.) are possibly reflected to the material.

Emulsion Suspension Solution Applicable Laws and Regulations

polymerization polymerization polymerization Item
TSCA Not Listed
EINECS Not Listed

Forms and molecular weight of different types

Item
Molecular formula [C12H14N4O3(C2H4O)m]n
CAS No. 105744-24-9
Form white, powder
Molecular weight of macro initiator (Mn) Approximately 15,000 to 30, 000 Packaging and Storage Requirements
Molecular weight of polyethylene oxide Approximately 2,000 Item
Approximately 0.45 mmol/g 500 g
Molecular number of azo group per 1 g of VPE Packaging
(1/14 of AIBN) 5 kg
10-hour half life temperature 65 - 70 ºC Storage requirement Please keep at 10 ºC or less.
*Compared with mol number of azo group per 1 g of AIBN (M.W.: 164.21) = 6 mmol/g.

Example of polymerization

In a four necked flask equipped with a thermometer, nitrogen gas induction tube, mixer, and reflux condenser,
20 g of VPE-0201, 80 g of methyl methacrylate (MMA) or styrene as monomer, and 300 g of toluene as solvent
are charged and polymerized under the nitrogen gas flow at 80 ºC and for eight hours.

[Formed Block Polymer (BP)] *When using methyl methacrylate (MMA) as monomer

CH3 CH3 CH3

OCCH2CH2 C CH2C n C CH2CH2COO CH2CH2O
m
CN COOCH3 CN I

Methyl polymethacrylate segment Polyethylene oxide segment

Formed Block Polymer – Molecular Weight Data

Monomer Mn Mw Mw/Mn Content of polyethylene oxide segment in BP

MMA 53,200 77,800 1.46 21 %
Styrene 61,200 160,200 2.62 21 %

25 Azo Polymerization Initiators

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 Detailed Explanations 6. Macro Azo Initiator
07
■ Reference Data on Polymerization

Change of Polymerization Ratio in Solution Polymerization

100
90
[Polymerization conditions]
Polymerization ratio (%)

80
70 VPE-0201 : 12.5 g
60 MMA : 100 g
50
40
Toluene : 260 g
30 Polymerization temperature : 70 ºC
20 ●VPE-0201+MMA
10
0
0 1 2 3 4 5 6 7 8
Polymerization time (h)

Figure 2: Change of Polymerization Ratio in Solution Polymerization

Control of Polydimethylsiloxane Amount Introduced to Block Polymer

70
[Polymerization conditions]
Content of polydimethylsiloxane (%)

60
Initiator : VPS-1001
50 Monomer : MMA
40 Solvent : Toluene
30
Charged ratio : (Initiator + Monomer)/Solvent = 1/2
20
Polymerization temperature : 70 ºC
10 Polymerization time : 8 hours
0 Purification by crystallization with methanol
0 10 20 30 40 50 60 70
Charged ratio of VPS-1001 (%)

*Cautions at the time of Block Polymer Structure Design

Macro Azo Initiator can quantitatively introduces its segment into the block polymer in accordance with the
charged amount of macro azo initiator under the selected polymerization conditions.

However, when compared with general low monocular azo polymerization initiator, the number of azo group per unit weight
is smaller. Therefore, the charge amount of macro azo initiator should be considered based on the concentration of the azo
group fit for polymerization. For example, when conducting a toluene solvent polymerization of VPS-1001, the charge ratio
of VPS-1001 is generally to be set to 10 to around 70 % of the block polymer ingredients (polymer azo initiator + monomer).

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 08 Product List

Product List

■Azo Polymerization Initiators

Azo Nitriles
Oil-soluble type
V-70 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile)

CAS No. 15545-97-8 100 g OCH3 CH3 CH3 OCH3

25 kg CH3 C CH2 C N N C CH2 C CH3
CH3 CN CN CH3

V-65 2,2'-Azobis(2,4-dimethylvaleronitrile)

CAS No. 4419-11-8 500 g

25 kg CH3 CH3 CH3 CH3

V-65HP (Metal-content-control-grade products) CH CH2 C N N C CH2 CH

500 g CH3 CN CN CH3
10 kg

AIBN 2,2'-Azobis(isobutyronitrile)

CAS No. 78-67-1 20 kg

CH3 CH3
AIBN-HP (Metal-content-control-grade products) CH3 C N N C CH3
500 g
CN CN
10 kg

V-59 2,2'-Azobis(2-methylbutyronitrile)

CAS No. 13472-08-7 500 g CH3 CH3

10 kg CH3CH2 C N N C CH2CH3
25 kg CN CN

V-40 1,1'-Azobis(cyclohexane-1-carbonitrile)

CAS No. 2094-98-6 500 g

20 kg
N N
NC CN
Water-soluble type
V-501 4,4'-Azobis(4-cyanovaleric acid)
500 g CH3 CH3
CAS No. 2638-94-0
10 kg HOOCH2CH2C C N N C CH2CH2COOH

CN CN

Azo Esters
Oil-soluble type
V-601 Dimethyl 2,2'-azobis(2-methylpropionate)

CAS No. 2589-57-3 500 g CH3 CH3

10 kg H 3C C N N C CH 3
COOCH3 COOCH3
V-601HP (Metal-content-control-grade products)
500 g
10 kg

27 Azo Polymerization Initiators

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 Product List

08
Product List

Azo Amides
Oil-soluble type
VAm-110 2,2'-Azobis(N -butyl-2-methylpropionamide)

CAS No. 195520-32-2 500 g O

CH3 CH3 O
5 kg C C N N C C
CH3CH2CH2CH2NH CH3 CH3 NHCH2CH2CH2CH3
Water-soluble type
VA-086 2,2'-Azobis[2-methyl-N -(2-hydroxyethyl)propionamide]

CAS No. 61551-69-7 500 g O CH3 CH3 O

5 kg C C N N C C
HOCH2CH2NH CH3 CH3 NHCH2CH2OH

Azo Imidazolines
Water-soluble type
VA-044 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride

CAS No. 27776-21-2 500 g CH3 CH3 N

N
20 kg C C N N C C • 2HCl
(4×5 kg)
N CH3 CH3 N
H H

VA-061 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]
500 g N CH3 CH3 N
CAS No. 20858-12-2
5 kg C C N N C C
N CH3 CH3 N
H H
Azo Amidines
Water-soluble type
VA-057 2,2'-Azobis[N -(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate

CAS No. 1041483-94-6 500 g NH

CH3 CH3 NH • 4H 2O
(n-hydrate) 5 kg C C N N C C
HOOC CH2CH2NH CH3 CH3 NHCH2CH2COOH

V-50 2,2'-Azobis(2-methylpropionamidine)dihydrochloride

CAS No. 2997-92-4 500 g NH CH3 CH3 NH

5 kg
C C N N C C • 2HCl
20 kg
(4×5 kg) NH2 CH3 CH3 NH2

Macro Azo Initiators

Oil-soluble type
VPS-1001 4,4-Azobis(4-cyanovalericacid),polymer withalpha,omegabis(3-aminopropyl)polydimethylsiloxane

CAS No. 158947-07-0 500 g CH3 CH3 CH3 CH3

5 kg OCCH 2CH2 C N N C CH2CH2CONHCH 2CH2CH2Si(OSi)m CH 2CH2CH2NH
CN CN CH3 CH3 n
VPS-1001N
Net5 kg
Water-soluble type
VPE-0201 4,4’-Azobis(4-cyanopentanoicacid) • Polyethyleneglycolpolymer

CAS No. 105744-24-9 500 g CH3 CH3

5 kg OCCH2CH2 C N N C CH2CH2COO(CH2CH2O)m
CN CN n

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 09 List of Related Items

List of Related Items

■Polymerization Inhibitors
Q-1300 Ammonium N -nitrosophenylhydroxylamine

CAS No. 135-20-6 032-04902 25g reageht product NO

872-40408 500g N
874-40402 5kg ONH4

Q-1301 N -Nitrosophenylhydroxylamine aluminium salt

CAS No. 15305-07-4 143-04562 25g reageht product NO

872-40501 1kg N Al

870-40502 5kg O
3

TBHQ 2-tert-Butylhydroquinone
027-07212 25g reageht product
OH
CAS No. 1948-33-0
021-07215 500g reageht product
905-41706 15kg OH

p-Benzoquinone
O
CAS No. 106-51-4 171-00242 25g reageht product
175-00245 500g reageht product O

Hydroquinone
CAS No. 123-31-9 085-01212 25g reageht product OH

089-01215 500g reageht product HO

p-Methoxyphenol
CAS No. 150-76-5 084-01282 25g reageht product OH

088-01285 500g reageht product

■Resin Modifiers
H3CO

TRIAM -100 4-Ally-2,6-di-tert-butylphenol

OH
CAS No. 13677-69-5 741-10436 100g

CH2CH CH2
TRIAM -501 Diethyleneglycol diallyl ether
C2H4OCH2CH CH2
CAS No. 57947-82-7 902-11600 500g O
C2H4OCH2CH CH2

TRIAM -507 N ,N ' -Methylenebis(acrylamide)

CAS No. 110-26-9 904-41411 1kg

CH2 CHCONH CH2 NHCOCH CH2
902-41412 5kg

TRIAM -605 Diallyl chlorendate

Cl
CAS No. 3232-62-0 904-40534 20kg Cl
Cl COOCH2CH CH2
Cl COOCH2CH CH2
Cl

TRIAM -705
Cl
Triallyl trimellitate
909-40246 500g
COOCH2CH CH2
CAS No. 2694-54-4 COOCH2CH CH2
903-40244 20kg
COOCH2CH CH2

TRIAM -805 Tetraallyl pyromellitate

863-43710 500g
CH2 CHCH2OOC COOCH2CH CH2
CAS No. 13360-98-0
868-43726 3kg CH2 CHCH2OOC COOCH2CH CH2

Accelerator A N ,N -Bis(2-hydroxypropyl)-p-toluidine
OH
CAS No. 38668-48-3 715-10333 10kg
CH 3 N(CH2CHCH3)2

N-[Tris(3-acrylamidopropoxymethyl)methyl]acrylamide
O

CAS No. 1393329-90-2 201-20051 5g reageht product O (CH2)3

H H
N C C CH2

209-20052 25g reageht product H O H CH2 O

H H
H2C C C N C CH2 O (CH2)3 N C C CH2
CH2 O
H H
O (CH2)3 N C C CH2

29 Azo Polymerization Initiators

和光純薬[Link] 29 2016/04/21 10:36

 List of Related Items

09
List of Related Items

■Photo Cationic Initiators (WPI Series)

WPI-113 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium hexafluorophosphate
CAS No. 477602-76-9 932-11706 100g H2n+1 Cn Cn H2n+1

PF6 n =10 to 13

WPI-116 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium hexafluoroantimonate
CAS No. 71786-70-4 930-12606 10g H2n+1 Cn Cn H2n+1

SbF6 n =10 to 13

WPI-169 Bis (4-tert-butylphenyl) iodonium bis (perfluorobutansulfonyl) imide

CAS No. 524067-97-8 865-26310 100g
SO2 C4F9
N
SO2 C4F9

WPI-170 Bis (4-tert-butylphenyl) iodonium hexafluorophosphate

CAS No. 61358-25-6 937-40809 5g

PF6

WPI-124 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium tetrakispentafluorophenylborate

CAS No. 210290-42-9 932-12507 100g H2n+1 Cn CnH2n+1

n =10 to 13

F F

B F

■Photo Base Generators (WPBG Series)

F F
4

WPBG-015 9-Anthrylmethyl Piperidine-1-carboxylate

359-33631 1g reageht product
O
CAS No. 1228312-02-4 O N
355-33633 5g reageht product

WPBG-018 9-Anthrylmethyl N,N-diethylcarbamate

CAS No. 1228312-05-7 356-33641 1g reageht product O

O NEt2
352-33643 5g reageht product

WPBG-041 9-Anthrylmethyl N-cyclohexylcarbamate

CAS No. 501003-75-4 353-33651 1g reageht product O

359-33653 5g reageht product

O N
H

WPBG-172 9-Anthrylmethyl N,N-dicyclohexylcarbamate

CAS No. 1421440-13-2 350-33661 1g reageht product O

O N
356-33663 5g reageht product

WPBG-174 1-(Anthraquinon-2-yl)ethyl N-cyclohexylcarbamate

351-33691 1g reageht product
O CH3 O
CAS No. 1421440-15-4 O N
357-33693 5g reageht product H

WPBG-166 1-(Anthraquinon-2-yl)ethyl N,N-dicyclohexylcarbamate

354-33681 1g reageht product
O CH3 O
CAS No. 1421440-01-8 O N
350-33683 5g reageht product
O

WPBG-140 1-(Anthraquinon-2-yl)ethyl imidazole-1-carboxylate

357-33671 1g reageht product
O CH3 O
CAS No. 1418139-51-1 O N
353-33673 5g reageht product N
O

Azo Polymerization Initiators 30

和光純薬[Link] 30 2016/04/21 10:36

 09 List of Related Items

List of Related Items

WPBG-158 (2-Nitrophenyl)methyl 4-hydroxypiperidine-1-carboxylate

O
CAS No. 1418139-52-2 358-33721 1g reageht product
354-33723 5g reageht product O N

NO2 OH

WPBG-165 (2-Nitrophenyl)methyl 4-(methacryloyloxy)piperidine-1-carboxylate

O
CAS No. 1292812-05-5 355-33731 1g reageht product
CH3
351-33733 5g reageht product O N

NO2 O O

WPBG-025 (E)-N-Cyclohexyl-3-(2-hydroxyphenyl)acrylamide
O
CAS No. 224432-97-7 354-33701 1g reageht product
350-33703 5g reageht product N
H
OH

WPBG-027 (E)-1-Piperidino-3-(2-hydroxyphenyl)-2-propen-1-one
O
CAS No. 1203424-93-4 351-33711 1g reageht product
357-33713 5g reageht product N

OH

WPBG-168 Cyclohexylammonium 2-(3-benzoylphenyl)propionate

O CH3
CAS No. 81928-83-8 359-33751 1g reageht product
355-33753 5g reageht product CO2
H3N

WPBG-167 Dicyclohexylammonium 2-(3-benzoylphenyl)propionate

CAS No. 24021-57-6 356-33761 1g reageht product O CH3

352-33763 5g reageht product CO2 H2N

WPBG-082 Guanidinium 2-(3-benzoylphenyl)propionate

CAS No. 1418139-48-6 352-33741 1g reageht product O CH3

NH2
358-33743 5g reageht product CO2
H2 N NH2

WPBG-266 1,2-Diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propipnate

CH3
CAS No. 1632211-89-2 932-12306 5g O
N
CO2 HN

N N NH

WPBG-300 1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate

CAS No. 1801263-71-7 938-12406 5g

N HN

B N N NH

WPBG-345 (Z)-{[Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate

F
H3 C
N HN
F HC
3
B N N NH
F

31 Azo Polymerization Initiators

F

和光純薬[Link] 31 2016/04/21 10:36

 List of Related Items

09
List of Related Items

■Photo Base Generators (WPBG Series)-related Reagents

Silicic Acid Ester
Tetraethyl Orthosilicate
CAS No. 78-10-4 053-03476 500㎖ reageht product Si(OEt)4

Methyltrimethoxysilane
CAS No. 1185-55-3 305-60101 100g reageht product Me Si ( OMe) 3

(3-Mercaptopropyl)trimethoxysilane
CAS No. 4420-74-0 505-62302 25g reageht product HS Si ( OMe) 3

3-Glycidoxypropyltrimethoxysilane
CAS No. 2530-83-8 302-60432 25g reageht product o
o Si ( OMe)3

[2-(3,4-Epoxycyclohexyl)ethyl]trimethoxysilane
CAS No. 3388-04-3 321-91252 25g reageht product o
329-91253 100g reageht product Si ( OMe) 3

3-(Triethoxysilyl)propyl Isocyanate
CAS No. 24801-88-5 324-91242 25g reageht product OCN Si ( OEt) 3

322-91243 100g reageht product

Crosslinking Agents
2,4,6-Tris(allyloxy)-1,3,5-triazine
CAS No. 101-37-1 201-02292 25g reageht product o

205-02295 500g reageht product N N

o N o

Trimethylolpropane Tris(mercaptoacetate)
327-21642 25g reageht product
HS o SH
CAS No. 10193-96-1 o
o
321-21645 500g reageht product o
o
CH 3
HS o
Pentaerythritol Tetrakis(mercaptoacetate)
326-21612 25g reageht product
HS o SH
CAS No. 10193-99-4 o
o
320-21615 500g reageht product o
o o o
HS o SH
Pentaerythritol Tetrakis(3-mercaptopropionate)
329-21722 25g reageht product
HS
CAS No. 7575-23-7 HS o
o
323-21725 500g reageht product o o
o o o
o SH

3,4-Epoxycyclohexylmethyl 3',4'-Epoxycyclohexanecarboxylate SH

o
CAS No. 2386-87-0 326-64072 25g reageht product
320-64075 500g reageht product o
o
o

Methyl-5-norbornene-2,3-dicarboxylic Anhydride
CAS No. 25134-21-8 134-05951 200g reageht product o
136-05955 500g reageht product o
H 3C o

Photosensitizers
2-Isopropylthioxanthone
o
CAS No. 5495-84-1 352-28932 25g reageht product CH 3

350-28933 100g reageht product CH 3

S
Vitamin K1
o
CAS No. 84-80-0 221-00371 1g reageht product
227-00373 5g reageht product CH 3
3

Azo Polymerization Initiators 32

和光純薬[Link] 32 2016/04/21 10:36

 10 List of Applicable Laws

List of Applicable Law

Azo Compounds CAS No. TSCA EINECS

V-70 15545-97-8 Listed Listed

V-65 4419-11-8 Listed Listed

AIBN 78-67-1 Listed Listed

Azo Nitriles

V-59 13472-08-7 Listed Listed

V-40 2094-98-6 Listed Listed

V-501 2638-94-0 Listed Listed

Azo Esters

V-601 2589-57-3 Listed* Listed

VA-086 61551-69-7 Listed Listed

Azo Amides

VAm-110 195520-32-2 Not Listed Not Listed

Azo Imidazolines

VA-044 27776-21-2 Listed Listed

VA-061 20858-12-2 Listed Listed

Azo Amidines

V-50 2997-92-4 Listed Listed

1041483-94-6
VA-057 Not Listed Not Listed
n-hydrate

VPS-1001 158947-07-0 Not Listed Not Listed

Macro Azo Initiators

VPS-1001N 158947-07-0 Not Listed Not Listed

VPE-0201 105744-24-9 Not Listed Not Listed

*Listed under 5e Consent Order

33 Azo Polymerization Initiators

和光純薬[Link] 33 2016/04/21 10:36

 What is Azo Polymerization Initiator? Radical Formation
List of Applicable
Mechanism
Laws

01
10
What are Azo Polymerization Initiator?
An azo polymerization initiator is a compound having an azo group (R-N=N-R’), which decomposes with heat and
light, and forms carbon radical. The formed carbon radical is excellent in reactivity, and progresses polymerization
and halogenation reactions of different types of vinyl monomers.

Radical Formation Mechanism of Azo Polymerization Initiators (Thermal Decomposition)

H2 C=CH
Carbon radical

–
N2 Y
CH 3 CH 3 CH 3 CH3
Monomer

–
–
–

R – C – N=N – C – R 2 R–C R–C C – CH2

hv H2

–
or
–
–

X X (1) X X Y
Formation (2) Initiation reaction/ Polymer
of radical Propagation reaction

(3) Recombination (4) Disproportionation

R R CH 3 CH 2
–
–

=
H3 C – C – C – CH3 R–C–H + R–C
Formation by side reaction
–
–

–
X X X X
P7 Decomposition product

(1) Formation of radical: Azo polymerization initiators decompose with heat or light, and form nitrogen gas and
carbon radicals.
*The decomposition rate (in solution) follows the first-order reaction rate kinetics and aries due to structure differences.
(2) Initiation reaction/Propagation reaction: Azo polymerization initiator addition-polymerizes with vinyl monomers
and forms a polymer.
*Since a section of the azo polymerization initiator is introduced at the end of polymer, the effect of end group is expected.
The efficiency of common azo polymerization initiators is approximately 0.5-0.7, and the remaining results in (3)
recombination or (4) disproportionation
(3) Recombination: The carbon radicals which did not engage in polymerization recombine.
(4) Disproportionation: The carbon radicals which did not engage in polymerization abstracts hydrogen of other
carbon radicals.

Reference Radical Formation Mechanism of Peroxides

R–C–O–O–C–R 2R–C–O
=

O O O

R–C–O R + CO 2
=

Where R is an alkyl.
R-CO2· decomposes (decarboxylation) immediately, and R· starts polymerization.

Where R is an aryl,
R-CO2· is hard to decompose (decarboxylation), so decarboxylation and addition reaction
to monomers are competitive reactions. Therefore, R· or R-CO2 are the radical active species.

Azo
AzoPolymerization
PolymerizationInitiators
Initiators 234

和光純薬_H2-[Link] 3 2016/04/14 13:35

 Germany
Wako Chemicals GmbH
USA
Wako Chemicals USA, Inc.
Japan
Wako Pure Chemicals Industries, Ltd.
China
Wako Chemicals (Shanghai) Co., Ltd.

Wako Pure Chemicals Industries, Ltd.

4-1 Nihonbashi Honcho 2-Chome, Chuo-Ku, Tokyo 103-0023, Japan
Japan TEL+81-3-3244-0305 FAX+81-3-5255-6157
MAIL spec-chem@[Link]

Wako Chemicals USA, Inc.

1600 Bellwood Road Richmond, VA 23237, U.S.A.
USA TEL+1-804-271-7677 FAX+1-804-271-7791
MAIL info@[Link]

Wako Chemicals GmbH

Fuggerstrasse 12 D-41468 Neuss GERMANY
Germany TEL+49-2131-311-0 FAX+49-2131-311-100
MAIL spezchem@[Link]

Wako Chemicals (Shanghai) Co., Ltd.

Room 3611, The Center No989 Chang Le Road, Shanghai 200031, China
China TEL+86-21-6407-0511 FAX+86-21-6445-8610
MAIL info@[Link]

160420 K1 SI

和光純薬_H1-[Link] 1 2016/04/21 10:59