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Azo Polymerization Initiators Comprehensive Catalog
180401 K2 SI
Specialty Chemicals Web Site
http://www.wako-chem.co.jp/kaseihin_en/
FUJIFILM Wako Chemicals Europe GmbHFuggerstrasse 12 D-41468 Neuss GERMANYTEL+49-2131-311-0Germany
Wako Chemicals (Shanghai) Co., Ltd.C1-C2, 26F, Junyao International Plaza,789 Zhaojiabang Road,Shanghai 200032, ChinaTEL+86-21-6407-0511
China
FUJIFILM Wako Pure Chemical Corporation4-1 Nihonbashi Honcho 2-Chome,Chuo-Ku, Tokyo 103-0023, JapanTEL+81-3-3244-0305
Japan
FUJIFILM Wako Chemicals U.S.A. Corporation1600 Bellwood Road Richmond,VA 23237, U.S.A.TEL+1-804-271-7677
USA
01 01Introduction/What is Radical Polymerization?
Radical polymerization is initiated by the formation of free radicals. Free radicals are formed by thermac energy, light, or radioactivity. Radical polymerization is mainly used for the polymerization of vinyl monomers. In addition to radical 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.
Introduction
What are Azo Polymerization Initiator?
(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.
What is Radical Polymerization?
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)
■ Radical polymerization initiator shows an effect even in a small amount.■ It is not polar-sensitive, and a large number of solvent is available, a wide range of monomers can be polymerized.■ Polymerization at a low to high temperature ranges is possible.■ Reaction with simple facility and equipment is possible.
Radical
Cationic
Anionic
Small amount¡
r
×
Usable in many solvents¡
×
r
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.
1 2
What is Azo Polymerization Initiator? Radical Formation Mechanism
Azo Polymerization Initiators Azo Polymerization Initiators
We develop a large variety of products taking advantage of our original organic synthesis technology, production technology, and refining technology accumulated in our long experience in the manufacturing of reagents.Azo polymerization initiators are used as reaction initiators in the synthesis of polymers. They are used mainly as radical polymerization initiators in a wide range of industries, such as acryl resins for paints, water absorbent resins, polymer coagulants, adhesives, and paper finishing agents.We have approximately 20 types of azo polymerization initiators of organic-solvent soluble type and water-soluble type.
Characteristics of Radical Polymerization Initiators
Active Species Typical Reaction Addition Amount Type of Solvent Reference! Radical Formation Mechanism of PeroxidesX X
CO 2R CO 2R CO 2R CO 2R
XH OHO
OO
OO
RO
O
O
O
BaseO
Base
SOH
SOH
R – Si(OMe 3) H2O+
HS SH +
O Si RSi
R – C – O – O – C – R
O
=
O
=
2 R – C – O
O
=
R – C – O
O
=
R CO 2+
Carbon radical
R – C – N=N – C – R
CH3
X
–
–
CH 3
X
–
–
N 2
R – C
CH3
X
–
– 2
Introduction/What is Radical Polymerization?What are Azo Polymerization Initiator? Radical Formation Mechanism
Characteristics of Azo Polymerization Initiators and Comparison with PeroxidesExamples of radical reactions using Azo Polymerization Initiators
Selection Guide
Decomposition Products
Solubility at a Glance
[Reference] Photocharacterization
IND
EX
01
02
03040506
P1P2
P3P4
P5-6
P7-8
P9
P10
Detailed Explanations 1. Azo Nitrile 2. Azo Ester 3. Azo Amide 4. Azo Imidazoline 5. Azo Amidine 6. Macro Azo Initiator
Product List
List of Related Items
List of Applicable Laws
07
080910
P11-14P15-16P17-18P19-20P21-22P23-26
P27-28
P29-32
P33-34
hvor
Polymer(1)Formation of radical
(2) Initiation reaction/Propagation reaction
R – C
CH3
X
–
– 2
YH2 –
Monomer
H2C=CH
Y
–
(3)Recombination (4)Disproportionation
H3C – C – C – CH3
R
X
–
–
R
X
–
– R – C – H
CH3
X
–
– R – C
CH2
X
=
– +
Decomposition productFormation by side reaction
P7
+O
C – CH
01 01Introduction/What is Radical Polymerization?
Radical polymerization is initiated by the formation of free radicals. Free radicals are formed by thermac energy, light, or radioactivity. Radical polymerization is mainly used for the polymerization of vinyl monomers. In addition to radical 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.
Introduction
What are Azo Polymerization Initiator?
(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.
What is Radical Polymerization?
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)
■ Radical polymerization initiator shows an effect even in a small amount.■ It is not polar-sensitive, and a large number of solvent is available, a wide range of monomers can be polymerized.■ Polymerization at a low to high temperature ranges is possible.■ Reaction with simple facility and equipment is possible.
Radical
Cationic
Anionic
Small amount¡
r
×
Usable in many solvents¡
×
r
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.
1 2
What is Azo Polymerization Initiator? Radical Formation Mechanism
Azo Polymerization Initiators Azo Polymerization Initiators
We develop a large variety of products taking advantage of our original organic synthesis technology, production technology, and refining technology accumulated in our long experience in the manufacturing of reagents.Azo polymerization initiators are used as reaction initiators in the synthesis of polymers. They are used mainly as radical polymerization initiators in a wide range of industries, such as acryl resins for paints, water absorbent resins, polymer coagulants, adhesives, and paper finishing agents.We have approximately 20 types of azo polymerization initiators of organic-solvent soluble type and water-soluble type.
Characteristics of Radical Polymerization Initiators
Active Species Typical Reaction Addition Amount Type of Solvent Reference! Radical Formation Mechanism of PeroxidesX X
CO 2R CO 2R CO 2R CO 2R
XH OHO
OO
OO
RO
O
O
O
BaseO
Base
SOH
SOH
R – Si(OMe 3) H2O+
HS SH +
O Si RSi
R – C – O – O – C – R
O
=
O
=
2 R – C – O
O
=
R – C – O
O
=
R CO 2+
Carbon radical
R – C – N=N – C – R
CH3
X
–
–
CH 3
X
–
–
N 2
R – C
CH3
X –
– 2
Introduction/What is Radical Polymerization?What are Azo Polymerization Initiator? Radical Formation Mechanism
Characteristics of Azo Polymerization Initiators and Comparison with PeroxidesExamples of radical reactions using Azo Polymerization Initiators
Selection Guide
Decomposition Products
Solubility at a Glance
[Reference] Photocharacterization
IND
EX
01
02
03040506
P1P2
P3P4
P5-6
P7-8
P9
P10
Detailed Explanations 1. Azo Nitrile 2. Azo Ester 3. Azo Amide 4. Azo Imidazoline 5. Azo Amidine 6. Macro Azo Initiator
Product List
List of Related Items
List of Applicable Laws
07
080910
P11-14P15-16P17-18P19-20P21-22P23-26
P27-28
P29-32
P33-34
hvor
Polymer(1)Formation of radical
(2) Initiation reaction/Propagation reaction
R – C
CH3
X
–
– 2
YH2 –
Monomer
H2C=CH
Y
–
(3)Recombination (4)Disproportionation
H3C – C – C – CH3
R
X
–
–
R
X
–
– R – C – H
CH3
X
–
– R – C
CH2
X=
– +
Decomposition productFormation by side reaction
P7
+O
C – CH
02 02Characteristics of Azo Polymerization Initiators and Comparison with Peroxides
Peroxides are used as an initiator for radical polymerization, in addition to azo polymerization initiators.
Examples of radical reactions using Azo Polymerization InitiatorsCharacteristics of Azo Polymerization Initiators and Comparison with PeroxidesAzo polymerization initiators are used as catalyst and foaming agent in organic synthesis, in addition to in polymer synthesis.
■ 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.
3 4
Examples of radical reactions using Azo Polymerization Initiators
Azo Polymerization Initiators Azo Polymerization Initiators
Characteristics of Azo Polymerization Initiators
Item Azo Polymerization Initiator Peroxide
Reversibility of decomposition
Efficiency of initiator
Decomposition rate
Solvent effect*1
Induced decomposition
Redox*2 decomposition
Formed radical
Hydrogen abstractability
Graft/crosslinking polymer
Formed polymer
Gas generation
Oxdizability
Irreversible reaction
0.5 to 0.7
First-order reaction rate equation shall apply.
Small
Not reactive
Not reactive
RC ●
Small
Hard to occur
Forms linear polymers.
Reactive
Not reactive
Reversible reaction
0.9 to 1
Depends on additives and solvents.
Large
Reactive(Pay attention to contact with metal.)
Reactive(Forms redox system with a reducing substance)
RO ●
Large
Easy to form.
Forms branched polymers.
Not reactive
Reactive
R−C−N=N− −R
CH3
−
−
X
CH3
X
−
C
−
2 R−C●CH3
X
−
−
N2
Carbon radical
Comparison with Peroxides
Dec
ompo
sabi
lity
Reac
tivity
of F
orm
ed R
adic
alsO
ther
s
*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.
Polymer Synthesis
Catalyst for Organic Synthesis
Foaming Agent
Azo polymerization initiator can be used for addition reactions of HBr, H2S, etc. to olefins. Especially, when using styrenes, bromine or mercapto groups may be selectively introduced to the β position.
Azo compounds*4 can be used as reagents for Mitsunobu reaction.
Azo compoundR R'
OH+ NuH + + Ph3P=O
R R'
Nu
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.
Radical polymerization of styrene
Addition reaction to olefins
Mitsunobu reaction
Radical polymerization of acrylic ester
Copolymerization of styrene and acrylic ester
*4
*3
RCO2R
R
CO2RR
R
CO2R
R
CO2RR
CO2R CO2R
R R R
R R R
RR R
R
CO2R
R
Radical active species
R
R2CO
R R
m n
+ HBr
Br
Azo polymerization initiator
hvor
Δ hvor
02 02Characteristics of Azo Polymerization Initiators and Comparison with Peroxides
Peroxides are used as an initiator for radical polymerization, in addition to azo polymerization initiators.
Examples of radical reactions using Azo Polymerization InitiatorsCharacteristics of Azo Polymerization Initiators and Comparison with PeroxidesAzo polymerization initiators are used as catalyst and foaming agent in organic synthesis, in addition to in polymer synthesis.
■ 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.
3 4
Examples of radical reactions using Azo Polymerization Initiators
Azo Polymerization Initiators Azo Polymerization Initiators
Characteristics of Azo Polymerization Initiators
Item Azo Polymerization Initiator Peroxide
Reversibility of decomposition
Efficiency of initiator
Decomposition rate
Solvent effect*1
Induced decomposition
Redox*2 decomposition
Formed radical
Hydrogen abstractability
Graft/crosslinking polymer
Formed polymer
Gas generation
Oxdizability
Irreversible reaction
0.5 to 0.7
First-order reaction rate equation shall apply.
Small
Not reactive
Not reactive
RC ●
Small
Hard to occur
Forms linear polymers.
Reactive
Not reactive
Reversible reaction
0.9 to 1
Depends on additives and solvents.
Large
Reactive(Pay attention to contact with metal.)
Reactive(Forms redox system with a reducing substance)
RO ●
Large
Easy to form.
Forms branched polymers.
Not reactive
Reactive
R−C−N=N− −R
CH3
−
−
X
CH3
X
−
C
−
2 R−C●CH3
X
−
−
N2
Carbon radical
Comparison with Peroxides
Dec
ompo
sabi
lity
Reac
tivity
of F
orm
ed R
adic
alsO
ther
s
*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.
Polymer Synthesis
Catalyst for Organic Synthesis
Foaming Agent
Azo polymerization initiator can be used for addition reactions of HBr, H2S, etc. to olefins. Especially, when using styrenes, bromine or mercapto groups may be selectively introduced to the β position.
Azo compounds*4 can be used as reagents for Mitsunobu reaction.
Azo compoundR R'
OH+ NuH + + Ph3P=O
R R'
Nu
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.
Radical polymerization of styrene
Addition reaction to olefins
Mitsunobu reaction
Radical polymerization of acrylic ester
Copolymerization of styrene and acrylic ester
*4
*3
RCO2R
R
CO2RR
R
CO2R
R
CO2RR
CO2R CO2R
R R R
R R R
RR R
R
CO2R
R
Radical active species
R
R2CO
R R
m n
+ HBr
Br
Azo polymerization initiator
hvor
Δ hvor
03 03Selection Guide
Selection Guide
Selection of Polymerization Process
6
Selection Guide
Azo Polymerization Initiators Azo Polymerization Initiators
10-hour Half-life Temperature by StructureWe 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) Water-soluble type (water solubility)10-hour Half-life
Temperature Azo nitrile Azo Ester Azo Amide
110 ºC
80 ºC
70 ºC
60 ºC
50 ºC
30 ºC
10-hour Half-lifeTemperature Azo nitrile Azo Amidine Azo ImidazolineAzo Amide
80 ºC
70 ºC
60 ºC
50 ºC
30 ºC
HOOCH2CH2C−C−N=N−C−CH2CH2COOH
CH3CH3
−
−
CNCN
−
−
N NC CCH3
CCH3
CCH3
CH3
NHCH2CH2OH
O
NH
O
CH2CH2HO
C C N
CH3
CH3
N C C
CH3
CH3
NHHN
HOOCH 2CH2CHN NHCH2CH2COOH
●4H2O
5
VAm-110 (110 ºC)P17
V-501 (69 ºC)P13
VA-086 (86 ºC)P17
VA-057 (57 ºC)P21
V-50 (56 ºC)P21
VA-061 (61 ºC)P19
VA-044 (44 ºC)P19
NH
CN
CCH3
NCH3
N CCH3
CCH3
NH
N
* Metal-content-control-grade products are also available.
N N
CNNC
CH3CH2−C−N=N−C−CH2CH3
CH3
−
−
CN
CH3
CN
−
−
H3C−C−N=N−C−CH3
CH3
−
−
CN
CH3
CN
−
−
N NC CCN
CH2
CH3
CH2
CN
CH3
CHCH3
CH3
CHCH3
CH3
H3C C
OCH3
CH3
H2C C N
CH3
CN
N C H2C C CH3
CH3
CN CH3
OCH3
V-601 (66 ºC)P15
H3C−C−N=N−C−CH3
CH3
COOCH3
−
−
CH3
COOCH3
−
−
V-40 (88 ºC)P13
V-59 (67 ºC)P12
AIBN (65 ºC)P12
V-65 (51 ºC)P11
V-70 (30 ºC)P11
N NC CCH3
CCH3
CCH3
CH3
NHCH2 CH2 CH2 CH3
O
NH
O
CH2CH2CH2CH3
N NC CCH3
CCH3
CCH3
CH3
NH2
NH●2HCl
NH2
NH
NH
CN
CCH3
NCH3
N CCH3
CCH3
NH
N●2HCl
* Metal-content-control-grade products are also available.
* Metal-content-control-grade products are also available.
Radical polymerizationinitiator
Organic solvent
Water
Suspension polymerization A polymerization method to heat the oil-soluble monomers in a dispersed condition in water (The initiator solves in monomers.)
Solution polymerization A polymerization method under which the initiator, monomers and formed polymers are all dissolved status.
Bulk polymerization A polymerization method under which liquid monomers are polymerized by itself or with adding the initiator.
Emulsion polymerization A polymerization method under which oil-soluble monomer is dispersed in water with emulsifying agent. (The initiator dissolves in water.)
88 ºC V-4066 ºC V-60151 ºC V-65
86 ºC VA-08656 ºC V-50 44 ºC VA-044
etc
etc
Step 3 Polymerization Method Step 4 Polymerization TemperatureStep 1 Is polymerization process a radical reaction? Step 2 Is the solvent an organic solvent or water?
03 03Selection Guide
Selection Guide
Selection of Polymerization Process
6
Selection Guide
Azo Polymerization Initiators Azo Polymerization Initiators
10-hour Half-life Temperature by StructureWe 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) Water-soluble type (water solubility)10-hour Half-life
Temperature Azo nitrile Azo Ester Azo Amide
110 ºC
80 ºC
70 ºC
60 ºC
50 ºC
30 ºC
10-hour Half-lifeTemperature Azo nitrile Azo Amidine Azo ImidazolineAzo Amide
80 ºC
70 ºC
60 ºC
50 ºC
30 ºC
HOOCH2CH2C−C−N=N−C−CH2CH2COOH
CH3CH3
−
−
CNCN
−
−
N NC CCH3
CCH3
CCH3
CH3
NHCH2CH2OH
O
NH
O
CH2CH2HO
C C N
CH3
CH3
N C C
CH3
CH3
NHHN
HOOCH 2CH2CHN NHCH2CH2COOH
●4H2O
5
VAm-110 (110 ºC)P17
V-501 (69 ºC)P13
VA-086 (86 ºC)P17
VA-057 (57 ºC)P21
V-50 (56 ºC)P21
VA-061 (61 ºC)P19
VA-044 (44 ºC)P19
NH
CN
CCH3
NCH3
N CCH3
CCH3
NH
N
* Metal-content-control-grade products are also available.
N N
CNNC
CH3CH2−C−N=N−C−CH2CH3
CH3
−
−
CN
CH3
CN
−
−
H3C−C−N=N−C−CH3
CH3
−
−
CN
CH3
CN
−
−
N NC CCN
CH2
CH3
CH2
CN
CH3
CHCH3
CH3
CHCH3
CH3
H3C C
OCH3
CH3
H2C C N
CH3
CN
N C H2C C CH3
CH3
CN CH3
OCH3
V-601 (66 ºC)P15
H3C−C−N=N−C−CH3
CH3
COOCH3
−
−
CH3
COOCH3
−
−
V-40 (88 ºC)P13
V-59 (67 ºC)P12
AIBN (65 ºC)P12
V-65 (51 ºC)P11
V-70 (30 ºC)P11
N NC CCH3
CCH3
CCH3
CH3
NHCH2 CH2 CH2 CH3
O
NH
O
CH2CH2CH2CH3
N NC CCH3
CCH3
CCH3
CH3
NH2
NH●2HCl
NH2
NH
NH
CN
CCH3
NCH3
N CCH3
CCH3
NH
N●2HCl
* Metal-content-control-grade products are also available.
* Metal-content-control-grade products are also available.
Radical polymerizationinitiator
Organic solvent
Water
Suspension polymerization A polymerization method to heat the oil-soluble monomers in a dispersed condition in water (The initiator solves in monomers.)
Solution polymerization A polymerization method under which the initiator, monomers and formed polymers are all dissolved status.
Bulk polymerization A polymerization method under which liquid monomers are polymerized by itself or with adding the initiator.
Emulsion polymerization A polymerization method under which oil-soluble monomer is dispersed in water with emulsifying agent. (The initiator dissolves in water.)
88 ºC V-4066 ºC V-60151 ºC V-65
86 ºC VA-08656 ºC V-50 44 ºC VA-044
etc
etc
Step 3 Polymerization Method Step 4 Polymerization TemperatureStep 1 Is polymerization process a radical reaction? Step 2 Is the solvent an organic solvent or water?
04 04Decomposition Products
7 8
Decomposition Products
Azo Polymerization Initiators Azo Polymerization Initiators
CH3 – C – N=N – C – CH3
CH3
COOCH3
–
–
CH3
COOCH3
–
–
CH3 – C – C – CH3
CH3
COOCH3
–
–
CH3
COOCH3
–
–
CH3 – C – CH2 – C – C – CH3
CH3
COOCH3
–
–
CH3
COOCH3
–
–
CH3
COOCH3
–
–
CH3 – C – CH2 – C=CH2
CH3
COOCH3
–
–
COOCH3
–
CH3 – CH
COOCH3
CH3
–
– CH2=C
COOCH
CH3
3
– –
2 CH3 – C ●
CH3
COOCH3
–
–
CH3 – C – CH2 – C ●
CH3
COOCH3
–
–
CH3
COOCH3
–
–
Decomposition Product Thermal Decomposition (80 ºC) Photodecomposition (25 ºC)(100 W HP Hg lamp)
IV
II
VI
42.1
36.4
13.8
42.7
38.5
13.8
(I)
(II)
+
(III)
(IV)
(I)
(V)
(VI)
(VII)
(V)
(I) + (III)
(I)
N2
1. Formed Amount of each Decomposition Product of Azo Nitrile
R – C – N=N – C – R
CH3
CN
–
–
CH3
CN
–
–
CH3
C2H5
(CH3)2CHCH2
CH3OC(CH 3)2CH2
c-C6H10
4
6
7
8
9
AIBN
V-59
V-65
V-70
V-40
4
Trace
7
8
9
92
86
85
78
82
Trace
8
Trace
8
1*5 In-house Data *6 Polymer journal 9275 (1977)
RCompound
Name
Disproportionation Recombination
PolymerUnknownH3C – C – CN
R
–
HH3C – C – C – CH3
R
–
–
R
–
–
CN CNH2C=C – CN
R
–
Ratio of decomposition product in the case of thermal decomposition with GC (%)
Ratio of decomposition product in the toluene solution (%)
*5
*5
*5
*5
*6
Decomposition Product of Azo Polymerization InitiatorsThe 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 ºCOn the other hand, the decomposition product of V-40 is hardly volatile, therefore, applications such as paint are expected.
Evaporation Rate of Decomposition Products
Eva
pora
tion
Rat
e (m
g/hr
• cm
2 )
Temperature (ºC)
0
0
10
20
30
40
50
20 40 60 80 100 120 140
V-601(AIBN)
V-59
V-40
V-65
3. Volatility of Decomposition Products
*7 H.TANAKA, T.KAGAWA, T.SATO, T.OTA, Macromolecules, 19(3), 934(1986)
2. Decomposition Product of V-601 (Special Case)*7
hvor
Recombination
Disproportionation
Disproportionation
04 04Decomposition Products
7 8
Decomposition Products
Azo Polymerization Initiators Azo Polymerization Initiators
CH3 – C – N=N – C – CH3
CH3
COOCH3
–
–
CH3
COOCH3
–
–
CH3 – C – C – CH3
CH3
COOCH3
–
–
CH3
COOCH3
–
–
CH3 – C – CH2 – C – C – CH3
CH3
COOCH3
–
–
CH3
COOCH3
–
–
CH3
COOCH3
–
–
CH3 – C – CH2 – C=CH2
CH3
COOCH3
–
–
COOCH3
–
CH3 – CH
COOCH3
CH3
–
– CH2=C
COOCH
CH3
3
– –
2 CH3 – C ●
CH3
COOCH3
–
–
CH3 – C – CH2 – C ●
CH3
COOCH3
–
–
CH3
COOCH3
–
–
Decomposition Product Thermal Decomposition (80 ºC) Photodecomposition (25 ºC)(100 W HP Hg lamp)
IV
II
VI
42.1
36.4
13.8
42.7
38.5
13.8
(I)
(II)
+
(III)
(IV)
(I)
(V)
(VI)
(VII)
(V)
(I) + (III)
(I)
N2
1. Formed Amount of each Decomposition Product of Azo Nitrile
R – C – N=N – C – R
CH3
CN
–
–
CH3
CN
–
–
CH3
C2H5
(CH3)2CHCH2
CH3OC(CH 3)2CH2
c-C6H10
4
6
7
8
9
AIBN
V-59
V-65
V-70
V-40
4
Trace
7
8
9
92
86
85
78
82
Trace
8
Trace
8
1*5 In-house Data *6 Polymer journal 9275 (1977)
RCompound
Name
Disproportionation Recombination
PolymerUnknownH3C – C – CN
R
–
HH3C – C – C – CH3
R
–
–
R
–
–
CN CNH2C=C – CN
R
–
Ratio of decomposition product in the case of thermal decomposition with GC (%)
Ratio of decomposition product in the toluene solution (%)
*5
*5
*5
*5
*6
Decomposition Product of Azo Polymerization InitiatorsThe 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 ºCOn the other hand, the decomposition product of V-40 is hardly volatile, therefore, applications such as paint are expected.
Evaporation Rate of Decomposition Products
Eva
pora
tion
Rat
e (m
g/hr
• cm
2 )
Temperature (ºC)
0
0
10
20
30
40
50
20 40 60 80 100 120 140
V-601(AIBN)
V-59
V-40
V-65
3. Volatility of Decomposition Products
*7 H.TANAKA, T.KAGAWA, T.SATO, T.OTA, Macromolecules, 19(3), 934(1986)
2. Decomposition Product of V-601 (Special Case)*7
hvor
Recombination
Disproportionation
Disproportionation
Reference! Photocharacterization
These products are decomposed by exiting of Azo (N=N) group by light irradiation. They are able to be used also as photo radical initiators.
Absorbs around 360 nm.
N=NR2 R2
R1
X
R1
X
05 06Solubility
9 10
[Reference] Photocharacterization
Azo Polymerization Initiators Azo Polymerization Initiators
Water
Methanol
Acetone
Ethyl Acetate
Toluene
VA-04434.7
1.7
Not soluble
Not soluble
Not soluble
Not soluble
V-5023.2
2.1
Not soluble
Not soluble
Not soluble
Not soluble
VA-05714.0
28.8
Not soluble
Not soluble
Not soluble
Not soluble
VA-0864.5
7.4
Not soluble
Not soluble
Not soluble
4.4N,N-Dimetylformamide
Photo Polymerization by Oil-Soluble Azo Polymerization InitiatorsPhotodecomposition Reaction Rate Constant Example of Photo Polymerization (Bulk Polymerization)
Pol
ymer
izat
ion
ratio
(%)
time/min0
0
30
150
25
20
15
10
5
50 100
Monomer Methyl methacrylate
Initiator 0.01 mol/l (ratio to monomer)
Light Source 100 W high-pressure mercury lamp
AzoCompound MW λmax (nm) Molar Absorbance Coefficient
ε (L/mol·cm) kd×104
V-59 192.26 348 16 3.76
AIBN 164.21 347 13 3.97
V-40 244.34 350 17 4.13
V-601 230.26 368 14 4.43
V-65 248.37 350 22 4.86
VAm-110 312.45 376 30 8.01
(sec-1)
Photo Polymerization of Water-Soluble Azo Polymerization InitiatorsPhotodecomposition Reaction Rate Constant Example of Photo Polymerization (Solution Polymerization)
Monomer Acrylamide 10 w/wt%
Initiator 0.01 mol/l (ratio to monomer)
Light Source 100 W high-pressure mercury lamp
AzoCompound MW λmax (nm) Molar Absorbance Coefficient
ε (L/mol·cm) kd×104
V-50 271.19 367 22 5.37
VA-057 414.46 371 26 7.23
VA-044 323.33 363 23 7.53
VA-086 288.35 375 30 7.72
(sec-1)
Acetone
Ethyl Acetate
Methanol
Chloroform
Toluene
Water
3.3
2.0
1
20
3.0
0.1V-70
>50
>50
28
>50
>50
<0.1V-65
29
14
7.5
25
7.0
<0.1AIBN
>50
>50
>50
>50
>50
0.3V-601
>50
>50
>50
>50
>50
<0.1V-59 V-40
30
15
4.4
>50
27
0.1VAm-110
>50
>50
>50
>50
>50
<0.1
Pol
ymer
izat
ion
ratio
(%)
time/min0
0
100
40
90
80
70
60
50
40
30
20
10
2010 30
Solvent: WaterLight source: 100 W high-pressure mercury lamp
Solvent: TolueneLight 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.
Solubility
Oil-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature)
Water-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature)
Reference! Photocharacterization
These products are decomposed by exiting of Azo (N=N) group by light irradiation. They are able to be used also as photo radical initiators.
Absorbs around 360 nm.
N=NR2 R2
R1
X
R1
X
05 06Solubility
9 10
[Reference] Photocharacterization
Azo Polymerization Initiators Azo Polymerization Initiators
Water
Methanol
Acetone
Ethyl Acetate
Toluene
VA-04434.7
1.7
Not soluble
Not soluble
Not soluble
Not soluble
V-5023.2
2.1
Not soluble
Not soluble
Not soluble
Not soluble
VA-05714.0
28.8
Not soluble
Not soluble
Not soluble
Not soluble
VA-0864.5
7.4
Not soluble
Not soluble
Not soluble
4.4N,N-Dimetylformamide
Photo Polymerization by Oil-Soluble Azo Polymerization InitiatorsPhotodecomposition Reaction Rate Constant Example of Photo Polymerization (Bulk Polymerization)
Pol
ymer
izat
ion
ratio
(%)
time/min0
0
30
150
25
20
15
10
5
50 100
Monomer Methyl methacrylate
Initiator 0.01 mol/l (ratio to monomer)
Light Source 100 W high-pressure mercury lamp
AzoCompound MW λmax (nm) Molar Absorbance Coefficient
ε (L/mol·cm) kd×104
V-59 192.26 348 16 3.76
AIBN 164.21 347 13 3.97
V-40 244.34 350 17 4.13
V-601 230.26 368 14 4.43
V-65 248.37 350 22 4.86
VAm-110 312.45 376 30 8.01
(sec-1)
Photo Polymerization of Water-Soluble Azo Polymerization InitiatorsPhotodecomposition Reaction Rate Constant Example of Photo Polymerization (Solution Polymerization)
Monomer Acrylamide 10 w/wt%
Initiator 0.01 mol/l (ratio to monomer)
Light Source 100 W high-pressure mercury lamp
AzoCompound MW λmax (nm) Molar Absorbance Coefficient
ε (L/mol·cm) kd×104
V-50 271.19 367 22 5.37
VA-057 414.46 371 26 7.23
VA-044 323.33 363 23 7.53
VA-086 288.35 375 30 7.72
(sec-1)
Acetone
Ethyl Acetate
Methanol
Chloroform
Toluene
Water
3.3
2.0
1
20
3.0
0.1V-70
>50
>50
28
>50
>50
<0.1V-65
29
14
7.5
25
7.0
<0.1AIBN
>50
>50
>50
>50
>50
0.3V-601
>50
>50
>50
>50
>50
<0.1V-59 V-40
30
15
4.4
>50
27
0.1VAm-110
>50
>50
>50
>50
>50
<0.1
Pol
ymer
izat
ion
ratio
(%)
time/min0
0
100
40
90
80
70
60
50
40
30
20
10
2010 30
Solvent: WaterLight source: 100 W high-pressure mercury lamp
Solvent: TolueneLight 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.
Solubility
Oil-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature)
Water-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature)
07Detailed Explanations 1. Azo Nitrile Detailed Explanations 1. Azo Nitrile07
11 12Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations
V-70 2,2’-Azobis(4-methoxy-2,4-dimethylvaleronitrile)
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 catalyst for organic radical reactions at a low temperature.
Characteristics
ItemApplicable Laws and Regulations
Oil-soluble typeLow-temperature type Item
Properties
N NC CCN
CH2
CH3
CH2
CN
CH3
CHCH3
CH3
CHCH3
CH3
H3C C
OCH3
CH3
CH2 C N
CH3
CN
N C CH2 C CH3
CH3
CN CH3
OCH3
Semiconductors LCD
H3C−C−N=N−C−CH3
CH3CH3
−
−
CNCN
−
−
CH3CH2−C−N=N−C−CH2CH3
CH3CH3
−
−
CNCN
−
−
1. Azo Nitrile
TSCAEINECS
ListedListed
Item
Packaging and Storage Requirements
Packaging
Storage requirement
100 g25 kgPlease keep at -10 ºC or less.
Molecular formulaMolecular weightCAS No.
Form
Melting point10-hour half life temperature
Solubilities
C16H28N4O2
308.4315545-97-8nearly white, crystalline powder*Contains water.50-96(dec.) °C30 ºC (Toluene)water : practically insoluble. dichloromethane : freely soluble.acetonitrile, N,N-Dimethylformamide : soluble. methanol, acetone, toluene : slightly soluble.
V-65 2,2’-Azobis(2,4-dimethylvaleronitrile)
When compared with AIBN, the 10-hour half-life temperature of this oil-soluble azo polymerization initiator is 10 ºC or lower than AIBN.This product can be used for a wide range of applications, from versatile polymers to cosmetics-related use.
Characteristics:
ItemApplicable Laws and Regulations
Oil-soluble typeLow-temperature type Item
Properties
TSCAEINECS
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g25 kgPlease keep at 10 ºC or less.
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C14H24N4
248.374419-11-8white, crystalline powder45-70(dec) °C51 ºC (Toluene)water : insoluble. benzene, acetone, ether,N,N-Dimethylformamide, toluene, methanol : soluble.
ListedListed
Metal Specification valueMetal Content
NaLi,Mg,AlK,Ca,CrMn,Fe,NiCu,Zn,ZrPb,Sn
500 ppb or less
300 ppb or less
V-65HP (Metal-content-control-grade products)
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g10 kgPlease keep at 10 ºC or less.
Semiconductors LCD
AIBN 2,2’-Azobis(isobutyronitrile)
AIBN is the most common oil-soluble azo polymerization initiator, and is used for polymerization of versatile polymers.
Characteristics:
ItemApplicable Laws and Regulations
Item
Oil-soluble type Item
Properties
TSCAEINECS
Packaging and Storage Requirements
PackagingStorage requirement
20 kgPlease keep at 20 ºC or less.
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C8H12N4
164.2178-67-1white, crystalline powder100-103(dec.) °C65 ºC (Toluene)water : very slightly soluble. acetone : free soluble. methanol,toluene : soluble. Ethanol : sparingly soluble.
ListedListed
V-59 2,2’-Azobis (2-methylbutyronitrile)
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 different solutions.
Characteristics:
ItemApplicable Laws and Regulations
Oil-soluble typeItem
PropertiesTSCAEINECS
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g10 kg25 kgPlease keep at 10 ºC or less.
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C10H16N4
192.2613472-08-7white, powder48 - 52 ºC67 ºC (Toluene)water : very slightly soluble. dimethyl sulfoxide : free soluble.toluene, methanol : Very soluble.
ListedListed
Metal Specification valueMetal Content
Li,Na,MgAl,K,CaCr,Mn,FeNi,Cu,ZnZr,Pb,Sn
500 ppb or less
ItemPackaging and Storage Requirements
AIBN-HP (Metal-content-control-grade products)
Packaging
Storage requirement
500 g10 kgPlease keep at 20 ºC or less.
07Detailed Explanations 1. Azo Nitrile Detailed Explanations 1. Azo Nitrile07
11 12Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations
V-70 2,2’-Azobis(4-methoxy-2,4-dimethylvaleronitrile)
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 catalyst for organic radical reactions at a low temperature.
Characteristics
ItemApplicable Laws and Regulations
Oil-soluble typeLow-temperature type Item
Properties
N NC CCN
CH2
CH3
CH2
CN
CH3
CHCH3
CH3
CHCH3
CH3
H3C C
OCH3
CH3
CH2 C N
CH3
CN
N C CH2 C CH3
CH3
CN CH3
OCH3
Semiconductors LCD
H3C−C−N=N−C−CH3
CH3CH3
−
−
CNCN
−
−
CH3CH2−C−N=N−C−CH2CH3
CH3CH3
−
−
CNCN
−
−
1. Azo Nitrile
TSCAEINECS
ListedListed
Item
Packaging and Storage Requirements
Packaging
Storage requirement
100 g25 kgPlease keep at -10 ºC or less.
Molecular formulaMolecular weightCAS No.
Form
Melting point10-hour half life temperature
Solubilities
C16H28N4O2
308.4315545-97-8nearly white, crystalline powder*Contains water.50-96(dec.) °C30 ºC (Toluene)water : practically insoluble. dichloromethane : freely soluble.acetonitrile, N,N-Dimethylformamide : soluble. methanol, acetone, toluene : slightly soluble.
V-65 2,2’-Azobis(2,4-dimethylvaleronitrile)
When compared with AIBN, the 10-hour half-life temperature of this oil-soluble azo polymerization initiator is 10 ºC or lower than AIBN.This product can be used for a wide range of applications, from versatile polymers to cosmetics-related use.
Characteristics:
ItemApplicable Laws and Regulations
Oil-soluble typeLow-temperature type Item
Properties
TSCAEINECS
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g25 kgPlease keep at 10 ºC or less.
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C14H24N4
248.374419-11-8white, crystalline powder45-70(dec) °C51 ºC (Toluene)water : insoluble. benzene, acetone, ether,N,N-Dimethylformamide, toluene, methanol : soluble.
ListedListed
Metal Specification valueMetal Content
NaLi,Mg,AlK,Ca,CrMn,Fe,NiCu,Zn,ZrPb,Sn
500 ppb or less
300 ppb or less
V-65HP (Metal-content-control-grade products)
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g10 kgPlease keep at 10 ºC or less.
Semiconductors LCD
AIBN 2,2’-Azobis(isobutyronitrile)
AIBN is the most common oil-soluble azo polymerization initiator, and is used for polymerization of versatile polymers.
Characteristics:
ItemApplicable Laws and Regulations
Item
Oil-soluble type Item
Properties
TSCAEINECS
Packaging and Storage Requirements
PackagingStorage requirement
20 kgPlease keep at 20 ºC or less.
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C8H12N4
164.2178-67-1white, crystalline powder100-103(dec.) °C65 ºC (Toluene)water : very slightly soluble. acetone : free soluble. methanol,toluene : soluble. Ethanol : sparingly soluble.
ListedListed
V-59 2,2’-Azobis (2-methylbutyronitrile)
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 different solutions.
Characteristics:
ItemApplicable Laws and Regulations
Oil-soluble typeItem
PropertiesTSCAEINECS
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g10 kg25 kgPlease keep at 10 ºC or less.
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C10H16N4
192.2613472-08-7white, powder48 - 52 ºC67 ºC (Toluene)water : very slightly soluble. dimethyl sulfoxide : free soluble.toluene, methanol : Very soluble.
ListedListed
Metal Specification valueMetal Content
Li,Na,MgAl,K,CaCr,Mn,FeNi,Cu,ZnZr,Pb,Sn
500 ppb or less
ItemPackaging and Storage Requirements
AIBN-HP (Metal-content-control-grade products)
Packaging
Storage requirement
500 g10 kgPlease keep at 20 ºC or less.
07
13 14Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 1. Azo Nitrile Detailed Explanations 1. Azo Nitrile
V-501 4,4’–Azobis(4–cyanovaleric acid)
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.
Characteristics:
ItemApplicable Laws and Regulations
Item
Properties
TSCAEINECS
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g10 kgPlease keep at 20 ºC or less.
Molecular formulaMolecular weightCAS No.
Form
Melting point10-hour half life temperature
Solubilities
C12H16N4O4
280.282638-94-0white, powder*Containing water120-123(dec.) °C69 ºC (In water, as sodium salt) water : practically insoluble. Ethanol, ether, formamide : freelysoluble methanol : soluble. toluene : insoluble.
ListedListed
07V-40 1,1’-Azobis(cyclohexane-1-carbonitrile)
Since the 10-hour half-life temperature is as high as 88 ºC, V-40 can be used to decrease residual 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.
Characteristics:
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g20 kgPlease keep at 20 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
ListedListed
N N
CNNC
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C14H20N4
244.342094-98-6white, crystals110-120 ºC88 ºC (Toluene)Water : practically insoluble. acetone, chloroform, benzene : freely soluble. Ethanol : soluble. petroleum ether : practically insoluble
Oil-soluble typeHigh-Temperature Type
Water-soluble type
Example of Polymerization
Half-life of Azo Nitriles in Solution
10000
1000
600
●(1) V-70 (2) V-65 (3) AIBN (4) V-59 (5) V-40 (6) V-501
(2) (3)(4) (5)
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
100
10
13.3
30 40
3.2 3.1 3 2.9 2.8 2.7 2.6
50 60 70 80 90 100 110
HOOCH2CH2C−C−N=N−C−CH2CH2COOH
CH3CH3
−
−
CNCN
−
−
100%
80
60
40
20
00 1 2 3
V-40
Without adding initiator
Polymerization time (h)
Initiator concentration 7.0×10−3 mol/ℓPolymerization temperature 120 ºC
Pol
ymer
izat
ion
Rat
io (%
)
100%
80
60
40
20
00 1 5 10
V-40
AIBN
V-65
Polymerization time (h)
Initiator concentration 7.0×10−3 mol/ℓPolymerization temperature 90 ºC
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)
Polymerization conditions:
00 0.01 0.02 0.03 0.04 0.05
1
2
3
4
Co-using with V-65 0.1 %
Co-using with V-65 0.15 %
Addition Amount of V-40 (Ratio to Monomer %)
Res
idua
l mon
omer
s (%
)
Temperature80 ºC95 ºC
1 Hr2 Hrs
Time
(6)
(1)
Non-halogen
F ClBr I
07
13 14Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 1. Azo Nitrile Detailed Explanations 1. Azo Nitrile
V-501 4,4’–Azobis(4–cyanovaleric acid)
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.
Characteristics:
ItemApplicable Laws and Regulations
Item
Properties
TSCAEINECS
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g10 kgPlease keep at 20 ºC or less.
Molecular formulaMolecular weightCAS No.
Form
Melting point10-hour half life temperature
Solubilities
C12H16N4O4
280.282638-94-0white, powder*Containing water120-123(dec.) °C69 ºC (In water, as sodium salt) water : practically insoluble. Ethanol, ether, formamide : freelysoluble methanol : soluble. toluene : insoluble.
ListedListed
07V-40 1,1’-Azobis(cyclohexane-1-carbonitrile)
Since the 10-hour half-life temperature is as high as 88 ºC, V-40 can be used to decrease residual 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.
Characteristics:
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g20 kgPlease keep at 20 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
ListedListed
N N
CNNC
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C14H20N4
244.342094-98-6white, crystals110-120 ºC88 ºC (Toluene)Water : practically insoluble. acetone, chloroform, benzene : freely soluble. Ethanol : soluble. petroleum ether : practically insoluble
Oil-soluble typeHigh-Temperature Type
Water-soluble type
Example of Polymerization
Half-life of Azo Nitriles in Solution
10000
1000
600
●(1) V-70 (2) V-65 (3) AIBN (4) V-59 (5) V-40 (6) V-501
(2) (3)(4) (5)
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
100
10
13.3
30 40
3.2 3.1 3 2.9 2.8 2.7 2.6
50 60 70 80 90 100 110
HOOCH2CH2C−C−N=N−C−CH2CH2COOH
CH3CH3
−
−
CNCN
−
−
100%
80
60
40
20
00 1 2 3
V-40
Without adding initiator
Polymerization time (h)
Initiator concentration 7.0×10−3 mol/ℓPolymerization temperature 120 ºC
Pol
ymer
izat
ion
Rat
io (%
)
100%
80
60
40
20
00 1 5 10
V-40
AIBN
V-65
Polymerization time (h)
Initiator concentration 7.0×10−3 mol/ℓPolymerization temperature 90 ºC
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)
Polymerization conditions:
00 0.01 0.02 0.03 0.04 0.05
1
2
3
4
Co-using with V-65 0.1 %
Co-using with V-65 0.15 %
Addition Amount of V-40 (Ratio to Monomer %)
Res
idua
l mon
omer
s (%
)
Temperature80 ºC95 ºC
1 Hr2 Hrs
Time
(6)
(1)
Non-halogen
F ClBr I
07
15 16Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 2. Azo Ester Detailed Explanations 2. Azo Ester07Half-life of Azo Esters in Solution
100000
10000
(1)
(1) V-601
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
1000
600
10
100
13.3
30 40
3.2 3.1 3 2.9 2.8 2.7 2.52.6
50 60 70 80 90 100 110 120
V-601 Dimethyl 2,2’-azobis(2-methylpropionate)
Characteristics:
Oil-soluble type
2. Azo Ester
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g10 kgPlease keep at 10 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
Listed (Listed under 5e Consent Order)Listed
H3C−C−N=N−C−CH3
CH3
COOCH3
−
−
CH3
COOCH3
−
−
Non-nitrile
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 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.
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C10H18N2O2
230.262589-57-3slight yellow or pale yellow, crystals or oily22-28 °C66 ºC (Toluene)water : insoluble. benzene, Ethanol, N,N-Dimethylformamide,dioxane, DMSO : freely soluble. methanol, toluene, chloroform, hexane : soluble.
Semiconductors LCDMetal Content
200 ppb or less
100 ppb or less
V-601HP (Metal-content-control-grade products)
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g10 kgPlease keep at 10 ºC or less.
NaLi,Mg,AlK,Ca,CrMn,Fe,NiCu,Zn,ZrPb,Sn
CN
07
15 16Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 2. Azo Ester Detailed Explanations 2. Azo Ester07Half-life of Azo Esters in Solution
100000
10000
(1)
(1) V-601
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
1000
600
10
100
13.3
30 40
3.2 3.1 3 2.9 2.8 2.7 2.52.6
50 60 70 80 90 100 110 120
V-601 Dimethyl 2,2’-azobis(2-methylpropionate)
Characteristics:
Oil-soluble type
2. Azo Ester
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g10 kgPlease keep at 10 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
Listed (Listed under 5e Consent Order)Listed
H3C−C−N=N−C−CH3
CH3
COOCH3
−
−
CH3
COOCH3
−
−
Non-nitrile
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 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.
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C10H18N2O2
230.262589-57-3slight yellow or pale yellow, crystals or oily22-28 °C66 ºC (Toluene)water : insoluble. benzene, Ethanol, N,N-Dimethylformamide,dioxane, DMSO : freely soluble. methanol, toluene, chloroform, hexane : soluble.
Semiconductors LCDMetal Content
200 ppb or less
100 ppb or less
V-601HP (Metal-content-control-grade products)
ItemPackaging and Storage Requirements
Packaging
Storage requirement
500 g10 kgPlease keep at 10 ºC or less.
NaLi,Mg,AlK,Ca,CrMn,Fe,NiCu,Zn,ZrPb,Sn
CN
07
17 18Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 3. Azo amide Detailed Explanations 3. Azo amide07Half-Life of Azo Amides in Solution
VA-086 2,2’-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide]
Characteristics:
3. Azo amide
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 25 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
ListedNot Listed
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 temperature is as high as 86 ºC, therefore, reduction of residual monomer can be expected by co-using it with another initiator.
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C12H24N4O4
288.3561551-69-7white - slightly yellow, crystalline powder138-145(dec.) °C86 ºC (Water)water, methanol : soluble. chloroform : slightly soluble
Water-soluble type
Oil-soluble type
High-Temperature Type
VAm-110 2,2’-Azobis (N-butyl-2-methylpropionamide)
Characteristics:
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 25 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
Not ListedNot Listed
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 has characteristics which show high solubility to different organic solvents.
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C16H32N4O2
312.46195520-32-2slight yellow powder65 °C110 ºC (Ethylbenzene)Water : insoluble. methanol, ethyl acetate, toluene, methylethyl ketone : freely soluble.
C−C−N=N−C−C=
CH3CH3
−
−
CH3CH3CH3CH2CH2CH2NH NHCH2CH2CH2CH3
O O−
−
=
−−
C−C−N=N−C−C
CH3CH3
−
−
CH3CH3NHCH2CH2OH
−
−
O=
−−
=O
HOCH2CH2NH
Examples of polymerization
Pol
ymer
izat
ion
Rat
io (%
)
100
75
50
25
00 1
Polymerization Time (h)2 3 4 5 6
Bulk Polymerization of Styrene
Polymerization conditions (Sealed tube polymerization)Concentration of initiator 0.4 mmol/lPolymerization temperature 110 ºC
VAm-110
Thermal polymerization
Pol
ymer
izat
ion
Rat
io (%
)
100
75
50
25
00 1
Polymerization Time (h)2 3 4 5 6
Solution Polymerization of n-Butyl methacrylate
Polymerization conditionsMonomer concentration 20 wt%Initiator concentration 0.19 mol%/monomerPolymerization temperature 120 ºCPolymerization solvent Diisobutyl Ketone
VAm-110
10000
1000
600
(1) VA-086 (2) VAm-110
(2)(1)
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
100
10
1
3.1
50 60 70 80 90 100 110 120 130 140 150
3 2.9 2.8 2.7 2.6 2.5 2.4 2.3
Non-nitrile
Non-nitrile
Non-halogen
F ClBr ICN
CN
07
17 18Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 3. Azo amide Detailed Explanations 3. Azo amide07Half-Life of Azo Amides in Solution
VA-086 2,2’-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide]
Characteristics:
3. Azo amide
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 25 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
ListedNot Listed
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 temperature is as high as 86 ºC, therefore, reduction of residual monomer can be expected by co-using it with another initiator.
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C12H24N4O4
288.3561551-69-7white - slightly yellow, crystalline powder138-145(dec.) °C86 ºC (Water)water, methanol : soluble. chloroform : slightly soluble
Water-soluble type
Oil-soluble type
High-Temperature Type
VAm-110 2,2’-Azobis (N-butyl-2-methylpropionamide)
Characteristics:
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 25 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
Not ListedNot Listed
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 has characteristics which show high solubility to different organic solvents.
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C16H32N4O2
312.46195520-32-2slight yellow powder65 °C110 ºC (Ethylbenzene)Water : insoluble. methanol, ethyl acetate, toluene, methylethyl ketone : freely soluble.
C−C−N=N−C−C=
CH3CH3
−
−
CH3CH3CH3CH2CH2CH2NH NHCH2CH2CH2CH3
O O−
−
=
−−
C−C−N=N−C−C
CH3CH3
−
−
CH3CH3NHCH2CH2OH
−
−
O=
−−
=O
HOCH2CH2NH
Examples of polymerization
Pol
ymer
izat
ion
Rat
io (%
)
100
75
50
25
00 1
Polymerization Time (h)2 3 4 5 6
Bulk Polymerization of Styrene
Polymerization conditions (Sealed tube polymerization)Concentration of initiator 0.4 mmol/lPolymerization temperature 110 ºC
VAm-110
Thermal polymerization
Pol
ymer
izat
ion
Rat
io (%
)
100
75
50
25
00 1
Polymerization Time (h)2 3 4 5 6
Solution Polymerization of n-Butyl methacrylate
Polymerization conditionsMonomer concentration 20 wt%Initiator concentration 0.19 mol%/monomerPolymerization temperature 120 ºCPolymerization solvent Diisobutyl Ketone
VAm-110
10000
1000
600
(1) VA-086 (2) VAm-110
(2)(1)
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
100
10
1
3.1
50 60 70 80 90 100 110 120 130 140 150
3 2.9 2.8 2.7 2.6 2.5 2.4 2.3
Non-nitrile
Non-nitrile
Non-halogen
F ClBr ICN
CN
07
19 20Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 4. Azo Imidazolin Detailed Explanations 4. Azo Imidazoline07Half-Life of Azo Imidazolines in Solution
VA-044 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride
Characteristics:
4. Azo Imidazolin
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g20 kgPlease keep at 40 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
ListedListed
VA-044 is a non-nitrile, cationic water-soluble azo polymerization initiator. It is highly effective for the polymerization of water-soluble vinyl monomer. The 10-hour half-life temperature is as low as 44 ºC, and the product is active at low temperatures.
Item
Properties
Molecular formulaMolecular weightCAS No.
Form
Melting point10-hour half life temperature
Solubilities
C12H24Cl2N2
323.2727776-21-2white - light yellowcrystals or crystalline powder188-193(dec.) °C44 ºC (Water)water : free soluble. methanol : sparinglysoluble. Ethanol : very slightly soluble. acetone, toluene : insoluble.
Low-temperature type
Water-soluble type
VA-061 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]
VA-061 is the free base of VA-044 and VA-046B, which are water-soluble azo polymerization initiators. By forming salts with different organic acids, the product dissolves in water, creating a highly effective initiator for polymerization of water-soluble vinyl monomers.
Water-soluble type
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 10 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
ListedListed
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C12H22N6
250.3520858-12-2slightly yellowish white, crystalline powder115-125(dec.) °C61 ºC (Methanol)water : practically insoluble. methanol : soluble. Ethanol, chloroform : slightly soluble. toluene : insoluble.*Acid: Soluble
100000
10000
(1)
(1) VA-044 (2) VA-061
(2)
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
1000
600
100
40
3.2 3.1 3 2.9
50 60 70
NH
CN
C
CH 3
N
CH 3
N C
CH 3
C
CH 3
NH
N
NH
CN
C
CH3
N
CH3
N C
CH3
C
CH3
NH
N
●2HCl
Characteristics:
Non-nitrile Non-halogen
F ClBr I
Non-nitrile
CN
CN
07
19 20Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 4. Azo Imidazolin Detailed Explanations 4. Azo Imidazoline07Half-Life of Azo Imidazolines in Solution
VA-044 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride
Characteristics:
4. Azo Imidazolin
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g20 kgPlease keep at 40 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
ListedListed
VA-044 is a non-nitrile, cationic water-soluble azo polymerization initiator. It is highly effective for the polymerization of water-soluble vinyl monomer. The 10-hour half-life temperature is as low as 44 ºC, and the product is active at low temperatures.
Item
Properties
Molecular formulaMolecular weightCAS No.
Form
Melting point10-hour half life temperature
Solubilities
C12H24Cl2N2
323.2727776-21-2white - light yellowcrystals or crystalline powder188-193(dec.) °C44 ºC (Water)water : free soluble. methanol : sparinglysoluble. Ethanol : very slightly soluble. acetone, toluene : insoluble.
Low-temperature type
Water-soluble type
VA-061 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]
VA-061 is the free base of VA-044 and VA-046B, which are water-soluble azo polymerization initiators. By forming salts with different organic acids, the product dissolves in water, creating a highly effective initiator for polymerization of water-soluble vinyl monomers.
Water-soluble type
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 10 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
ListedListed
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C12H22N6
250.3520858-12-2slightly yellowish white, crystalline powder115-125(dec.) °C61 ºC (Methanol)water : practically insoluble. methanol : soluble. Ethanol, chloroform : slightly soluble. toluene : insoluble.*Acid: Soluble
100000
10000
(1)
(1) VA-044 (2) VA-061
(2)
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
1000
600
100
40
3.2 3.1 3 2.9
50 60 70
NH
CN
C
CH 3
N
CH 3
N C
CH 3
C
CH 3
NH
N
NH
CN
C
CH3
N
CH3
N C
CH3
C
CH3
NH
N
●2HCl
Characteristics:
Non-nitrile Non-halogen
F ClBr I
Non-nitrile
CN
CN
07
21 22Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 5. Azo Amidine Detailed Explanations 5. Azo Amidine07Half-Life of Azo Amidines in Solution
Water-soluble type
V-50 2,2’-Azobis(2-methylpropionamidine)dihydrochloride
Characteristics:
5. Azo Amidine
ItemApplicable Laws and Regulations
TSCAEINECS
ListedListed
V-50 is a highly active water-soluble azo polymerization initiator. A variety of polymerization 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.
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C8H20Cl2N6
271.192997-92-4nearly white, Granular160-169(dec.) °C56 ºC (Water)water : freely soluble. methanol, Ethanol, acetone, N,N-Dimethylformamide, dioxane : practically insoluble.
Water-soluble type
4H2O
VA-057 2,2’-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate
Characteristics:
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 10 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
Not ListedNot Listed
VA-057 is a water-soluble azo polymerization initiator which has a zwitterinoic structure. The 10-hour half-life tempera-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.
Item
Properties
Molecular formulaMolecular weightCAS No.
Form
Melting point10-hour half life temperature
Solubilities
C14H34N6O8
414.461041483-94-6 (n-hydrate)white - pale yellowpowder - crystalline powder97(dec.) °C57 ºC (Water)water, methanol : free soluble. Ethanol, isopropanol, acetone,toluene : very slightly soluble.
10000
1000
600
(1)
(1) V-50 (2) VA-057
(2)
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
10
100
1
4030
3.23.3 3.1 3 2.72.82.9 2.6
50 60 908070 110100
2HClN NC CCH3
CCH3
CCH3
CH3
NH2
NH
NH2
NH
N NC C
CH3
C
CH3
C
CH3
CH3
NHCH 2CH2COOH
NH
NH
NH
CH2CH2HOOC
Non-nitrile Non-halogen
F ClBr I
Non-nitrile
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g 5 kg20 kgPlease keep at 40 ºC or less.
CN
CN
07
21 22Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 5. Azo Amidine Detailed Explanations 5. Azo Amidine07Half-Life of Azo Amidines in Solution
Water-soluble type
V-50 2,2’-Azobis(2-methylpropionamidine)dihydrochloride
Characteristics:
5. Azo Amidine
ItemApplicable Laws and Regulations
TSCAEINECS
ListedListed
V-50 is a highly active water-soluble azo polymerization initiator. A variety of polymerization 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.
Item
Properties
Molecular formulaMolecular weightCAS No.FormMelting point10-hour half life temperature
Solubilities
C8H20Cl2N6
271.192997-92-4nearly white, Granular160-169(dec.) °C56 ºC (Water)water : freely soluble. methanol, Ethanol, acetone, N,N-Dimethylformamide, dioxane : practically insoluble.
Water-soluble type
4H2O
VA-057 2,2’-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate
Characteristics:
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 10 ºC or less.
ItemApplicable Laws and Regulations
TSCAEINECS
Not ListedNot Listed
VA-057 is a water-soluble azo polymerization initiator which has a zwitterinoic structure. The 10-hour half-life tempera-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.
Item
Properties
Molecular formulaMolecular weightCAS No.
Form
Melting point10-hour half life temperature
Solubilities
C14H34N6O8
414.461041483-94-6 (n-hydrate)white - pale yellowpowder - crystalline powder97(dec.) °C57 ºC (Water)water, methanol : free soluble. Ethanol, isopropanol, acetone,toluene : very slightly soluble.
10000
1000
600
(1)
(1) V-50 (2) VA-057
(2)
Hal
f-life
(min
utes
)
(K-1×103)
Temperature (ºC)
10
100
1
4030
3.23.3 3.1 3 2.72.82.9 2.6
50 60 908070 110100
2HClN NC CCH3
CCH3
CCH3
CH3
NH2
NH
NH2
NH
N NC C
CH3
C
CH3
C
CH3
CH3
NHCH 2CH2COOH
NH
NH
NH
CH2CH2HOOC
Non-nitrile Non-halogen
F ClBr I
Non-nitrile
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g 5 kg20 kgPlease keep at 40 ºC or less.
CN
CN
07
23 24Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 6. Macro Azo Initiator Detailed Explanations 6. Macro Azo Initiator07VPS-1001 VPS-1001N 4,4-Azobis(4-cyanovaleric acid),polymer with alpha,
omega-bis(3-aminopropyl)polydimethylsiloxane
6. Macro Azo Initiator (MAI : Macro Azo Initiator)
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.
NCH3
CNN
CH3
CNCH2CH2CONHCH2CH2CH2SiOCH2CH2C CH2CH2CH2NHOSi
CH3
CH3
CH3
CH3 nm
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.
What is a Macro Azo Initiator?
Azo group
Formation Process of Block Polymer
Conceptual Drawing
The process from the start of polymerization with azo groups in polymers to the growing of block polymers is shown in a schematic drawing.
N=N
N=N
N=N
N=N
N=N
Polydimethylsiloxane chainMMA monomer
n
A-B type
ABA type
(AB) n type
VPS-1001Methyl methacrylate (MMA)Toluene
Polymerization in N2 gas flow
VPS-1001 Methyl methacrylate (MMA)
ItemApplicable Laws and Regulations
TSCAEINECS
Not ListedNot Listed
Emulsion polymerization
Suspension polymerization
Solution polymerization
Item VPS-1001 VPS-1001N
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 10 ºC or less.
Net 5 kgItem VPS-1001 VPS-1001N
(solvent contained)
Forms and molecular weight of different types
Molecular formulaCAS No.
Form
Molecular weight of macro initiator (Mn)Molecular weight of polydimethylsiloxane
Molecular number of azo group per 1 g of VPS
10-hour half life temperature
[C20H34N6O2Si(C2H6Si)m]n158947-07-0
Approximately 80,000 to 120, 000Approximately 10,000
Approximately 0.1 mmol/g(1/60 of AIBN)
65 - 70 ºC
clear gum white
*Compared with mol number of azo group per 1 g of AIBN (M.W.: 164.21) = 6 mmol/g.
Example of polymerizationIn 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)]
Mn Mw Mw/Mn
Formed Block Polymer – Molecular Weight Data
Content of polydimethylsiloxane segment in BP80,700 149,000 1.85 31 %
Methyl polymethacrylate segment
C CH2CCH3
CNCCH3
CN
CH3
CH3
CH3
CH3
CH3
COOCH3
CH2CH2CONHCH2CH2CH2Si CH2CH2CH2NHOCCH2CH2
IOSi mn
Polydimethylsiloxane segment
07
23 24Azo Polymerization Initiators Azo Polymerization Initiators
Detailed Explanations 6. Macro Azo Initiator Detailed Explanations 6. Macro Azo Initiator07VPS-1001 VPS-1001N 4,4-Azobis(4-cyanovaleric acid),polymer with alpha,
omega-bis(3-aminopropyl)polydimethylsiloxane
6. Macro Azo Initiator (MAI : Macro Azo Initiator)
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.
NCH3
CNN
CH3
CNCH2CH2CONHCH2CH2CH2SiOCH2CH2C CH2CH2CH2NHOSi
CH3
CH3
CH3
CH3 nm
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.
What is a Macro Azo Initiator?
Azo group
Formation Process of Block Polymer
Conceptual Drawing
The process from the start of polymerization with azo groups in polymers to the growing of block polymers is shown in a schematic drawing.
N=N
N=N
N=N
N=N
N=N
Polydimethylsiloxane chainMMA monomer
n
A-B type
ABA type
(AB) n type
VPS-1001Methyl methacrylate (MMA)Toluene
Polymerization in N2 gas flow
VPS-1001 Methyl methacrylate (MMA)
ItemApplicable Laws and Regulations
TSCAEINECS
Not ListedNot Listed
Emulsion polymerization
Suspension polymerization
Solution polymerization
Item VPS-1001 VPS-1001N
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease keep at 10 ºC or less.
Net 5 kgItem VPS-1001 VPS-1001N
(solvent contained)
Forms and molecular weight of different types
Molecular formulaCAS No.
Form
Molecular weight of macro initiator (Mn)Molecular weight of polydimethylsiloxane
Molecular number of azo group per 1 g of VPS
10-hour half life temperature
[C20H34N6O2Si(C2H6Si)m]n158947-07-0
Approximately 80,000 to 120, 000Approximately 10,000
Approximately 0.1 mmol/g(1/60 of AIBN)
65 - 70 ºC
clear gum white
*Compared with mol number of azo group per 1 g of AIBN (M.W.: 164.21) = 6 mmol/g.
Example of polymerizationIn 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)]
Mn Mw Mw/Mn
Formed Block Polymer – Molecular Weight Data
Content of polydimethylsiloxane segment in BP80,700 149,000 1.85 31 %
Methyl polymethacrylate segment
C CH2CCH3
CNCCH3
CN
CH3
CH3
CH3
CH3
CH3
COOCH3
CH2CH2CONHCH2CH2CH2Si CH2CH2CH2NHOCCH2CH2
IOSi mn
Polydimethylsiloxane segment
07
25 26Azo Polymerization Initiators Azo Polymerization Initiators
07 Detailed Explanations 6. Macro Azo Initiator Detailed Explanations 6. Macro Azo Initiator
VPE-0201 4,4’-Azobis(4-cyanopentanoicacid)·Polyethyleneglycolpolymer
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.
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
Methyl polymethacrylate segment Polyethylene oxide segment
C CH2CCH3
CNCCH3
CN
CH3
COOCH3
CH2CH2COO CH2CH2O mOCCH2CH2
I
■ Reference Data on Polymerization
Change of Polymerization Ratio in Solution Polymerization
100
102030405060708090
100
2 3 4 5 6 7 8Polymerization time (h)
●VPE-0201+MMA
Figure 2: Change of Polymerization Ratio in Solution Polymerization
Pol
ymer
izat
ion
ratio
(%) [Polymerization conditions]
VPE-0201 : 12.5 gMMA : 100 gToluene : 260 gPolymerization temperature : 70 ºC
Control of Polydimethylsiloxane Amount Introduced to Block Polymer
10 20 30 40 50 60 7000
10
20
30
40
50
60
70
Charged ratio of VPS-1001 (%)
Con
tent
of p
olyd
imet
hyls
iloxa
ne (%
) [Polymerization conditions]Initiator : VPS-1001Monomer : MMASolvent : Toluene
Charged ratio : (Initiator + Monomer)/Solvent = 1/2Polymerization temperature : 70 ºCPolymerization time : 8 hoursPurification by crystallization with methanol
*Cautions at the time of Block Polymer Structure DesignMacro 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).
NCH3
CNN
CH3
CNCH2CH2COOOCH2CH2C
nmCH2CH2O
ItemApplicable Laws and Regulations
TSCAEINECS
Not ListedNot Listed
Emulsion polymerization
Suspension polymerization
Solution polymerization
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease 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.
Forms and molecular weight of different types
Molecular formulaCAS No.FormMolecular weight of macro initiator (Mn)Molecular weight of polyethylene oxide
Molecular number of azo group per 1 g of VPE
10-hour half life temperature
[C12H14N4O3(C2H4O)m]n105744-24-9white, powderApproximately 15,000 to 30, 000Approximately 2,000Approximately 0.45 mmol/g(1/14 of AIBN)65 - 70 ºC
Item
Formed Block Polymer – Molecular Weight Data
Monomer Mn Mw/Mn Content of polyethylene oxide segment in BP
MMA 53,200 1.46 21 %
Styrene 61,200 2.62
Mw
77,800
160,200 21 %
n
07
25 26Azo Polymerization Initiators Azo Polymerization Initiators
07 Detailed Explanations 6. Macro Azo Initiator Detailed Explanations 6. Macro Azo Initiator
VPE-0201 4,4’-Azobis(4-cyanopentanoicacid)·Polyethyleneglycolpolymer
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.
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
Methyl polymethacrylate segment Polyethylene oxide segment
C CH2CCH3
CNCCH3
CN
CH3
COOCH3
CH2CH2COO CH2CH2O mOCCH2CH2
I
■ Reference Data on Polymerization
Change of Polymerization Ratio in Solution Polymerization
100
102030405060708090
100
2 3 4 5 6 7 8Polymerization time (h)
●VPE-0201+MMA
Figure 2: Change of Polymerization Ratio in Solution Polymerization
Pol
ymer
izat
ion
ratio
(%) [Polymerization conditions]
VPE-0201 : 12.5 gMMA : 100 gToluene : 260 gPolymerization temperature : 70 ºC
Control of Polydimethylsiloxane Amount Introduced to Block Polymer
10 20 30 40 50 60 7000
10
20
30
40
50
60
70
Charged ratio of VPS-1001 (%)
Con
tent
of p
olyd
imet
hyls
iloxa
ne (%
) [Polymerization conditions]Initiator : VPS-1001Monomer : MMASolvent : Toluene
Charged ratio : (Initiator + Monomer)/Solvent = 1/2Polymerization temperature : 70 ºCPolymerization time : 8 hoursPurification by crystallization with methanol
*Cautions at the time of Block Polymer Structure DesignMacro 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).
NCH3
CNN
CH3
CNCH2CH2COOOCH2CH2C
nmCH2CH2O
ItemApplicable Laws and Regulations
TSCAEINECS
Not ListedNot Listed
Emulsion polymerization
Suspension polymerization
Solution polymerization
Item
Packaging and Storage Requirements
Packaging
Storage requirement
500 g5 kgPlease 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.
Forms and molecular weight of different types
Molecular formulaCAS No.FormMolecular weight of macro initiator (Mn)Molecular weight of polyethylene oxide
Molecular number of azo group per 1 g of VPE
10-hour half life temperature
[C12H14N4O3(C2H4O)m]n105744-24-9white, powderApproximately 15,000 to 30, 000Approximately 2,000Approximately 0.45 mmol/g(1/14 of AIBN)65 - 70 ºC
Item
Formed Block Polymer – Molecular Weight Data
Monomer Mn Mw/Mn Content of polyethylene oxide segment in BP
MMA 53,200 1.46 21 %
Styrene 61,200 2.62
Mw
77,800
160,200 21 %
n
08 08Product List
27 28
Product List
Azo Polymerization Initiators Azo Polymerization Initiators
Product List Product List
■Azo Polymerization Initiators
CAS No. 15545-97-8
2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile)V-70
N NC CCN
CH2
CH3
CH2
CN
CH3
CCH3
OCH3
CH3CCH3
CH3
OCH3100 g25 kg
Oil-soluble typeAzo Nitriles
CAS No. 13472-08-7
2,2'-Azobis(2-methylbutyronitrile)V-59500 g10 kg25 kg
N NC CCN
CH2CH3
CH3
CH3CH2
CN
CH3
CAS No. 2094-98-6
1,1'-Azobis(cyclohexane-1-carbonitrile)V-40500 g20 kg
N N
CAS No. 2638-94-0
4,4'-Azobis(4-cyanovaleric acid)V-501500 g10 kg HOOCH2CH2C C N
CH3
CN
N C CH2CH2COOH
CH3
CN
Water-soluble type
CAS No. 195520-32-2
2,2'-Azobis(N -butyl-2-methylpropionamide)VAm-110500 g5 kg N NC C
CH3
CCH3
CCH3
CH3
NHCH2CH2CH2CH3
O
NH
O
CH2CH2CH2CH3
Oil-soluble typeAzo Amides
CAS No. 61551-69-7
2,2'-Azobis[2-methyl-N -(2-hydroxyethyl)propionamide]VA-086500 g5 kg N NC C
CH3
CCH3
CCH3
CH3
NHCH2CH2OH
O
NH
O
CH2CH2HO
Water-soluble type
CAS No. 27776-21-2
2,2’-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochlorideVA-044500 g20 kg(4×5 kg) N
H
CN
CCH3
NCH3
N CCH3
CCH3
NH
N• 2HCl
Water-soluble typeAzo Imidazolines
CAS No. 4419-11-8
2,2'-Azobis(2,4-dimethylvaleronitrile)V-65500 g25 kg
N NC CCN
CH2
CH3
CH2
CN
CH3
CHCH3
CH3
CH
CH3
CH3500 g10 kg
V-65HP (Metal-content-control-grade products)
CAS No. 78-67-1
2,2'-Azobis(isobutyronitrile)AIBN20 kg
N NC CCN
CH3
CH3
CH3
CN
CH3AIBN-HP (Metal-content-control-grade products)
CAS No. 2589-57-3
Dimethyl 2,2'-azobis(2-methylpropionate)V-601500 g10 kg
500 g10 kg
Oil-soluble typeAzo Esters
V-601HP (Metal-content-control-grade products)
CAS No. 1041483-94-6 (n-hydrate)
2,2'-Azobis[N -(2-carboxyethyl)-2-methylpropionamidine]tetrahydrateVA-057500 g5 kg
CAS No. 2997-92-4
2,2'-Azobis(2-methylpropionamidine)dihydrochlorideV-50500 g5 kg20 kg(4×5 kg)
N NC CCH3
CCH3
CCH3
CH3
NHCH2CH2COOH
NH
NH
NH • 4H 2O
CH2CH2HOOC
N NC CCH3
CCH3
CCH3
CH3
NH2
NH• 2HCl
NH2
NH
Water-soluble typeAzo Amidines
CAS No. 20858-12-2
2,2’-Azobis[2-(2-imidazolin-2-yl)propane]VA-061500 g5 kg
NH
CN
CCH3
NCH3
N CCH3
CCH3
NH
N
CAS No. 158947-07-0
4,4-Azobis(4-cyanovalericacid),polymer withalpha,omegabis(3-aminopropyl)polydimethylsiloxaneVPS-1001500 g5 kg
CAS No. 105744-24-9
4,4’-Azobis(4-cyanopentanoicacid) • PolyethyleneglycolpolymerVPE-0201500 g5 kg
Net5 kg
N NC CCN
CH3
OCCH2CH2
CN
CH3
CH2CH2CONHCH2CH2CH2Si(OSi) CH2CH2CH2NHm
nCH3
CH3
CH3
CH3
N NC CCN
CH3
OCCH2CH2
CN
CH3
CH2CH2COO(CH2CH2O)mn
Oil-soluble type
Water-soluble type
Macro Azo Initiators
VPS-1001N
CNNC
H3C C N N C CH3
CH3
COOCH3
CH3
COOCH3
500 g10 kg
08 08Product List
27 28
Product List
Azo Polymerization Initiators Azo Polymerization Initiators
Product List Product List
■Azo Polymerization Initiators
CAS No. 15545-97-8
2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile)V-70
N NC CCN
CH2
CH3
CH2
CN
CH3
CCH3
OCH3
CH3CCH3
CH3
OCH3100 g25 kg
Oil-soluble typeAzo Nitriles
CAS No. 13472-08-7
2,2'-Azobis(2-methylbutyronitrile)V-59500 g10 kg25 kg
N NC CCN
CH2CH3
CH3
CH3CH2
CN
CH3
CAS No. 2094-98-6
1,1'-Azobis(cyclohexane-1-carbonitrile)V-40500 g20 kg
N N
CAS No. 2638-94-0
4,4'-Azobis(4-cyanovaleric acid)V-501500 g10 kg HOOCH2CH2C C N
CH3
CN
N C CH2CH2COOH
CH3
CN
Water-soluble type
CAS No. 195520-32-2
2,2'-Azobis(N -butyl-2-methylpropionamide)VAm-110500 g5 kg N NC C
CH3
CCH3
CCH3
CH3
NHCH2CH2CH2CH3
O
NH
O
CH2CH2CH2CH3
Oil-soluble typeAzo Amides
CAS No. 61551-69-7
2,2'-Azobis[2-methyl-N -(2-hydroxyethyl)propionamide]VA-086500 g5 kg N NC C
CH3
CCH3
CCH3
CH3
NHCH2CH2OH
O
NH
O
CH2CH2HO
Water-soluble type
CAS No. 27776-21-2
2,2’-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochlorideVA-044500 g20 kg(4×5 kg) N
H
CN
CCH3
NCH3
N CCH3
CCH3
NH
N• 2HCl
Water-soluble typeAzo Imidazolines
CAS No. 4419-11-8
2,2'-Azobis(2,4-dimethylvaleronitrile)V-65500 g25 kg
N NC CCN
CH2
CH3
CH2
CN
CH3
CHCH3
CH3
CH
CH3
CH3500 g10 kg
V-65HP (Metal-content-control-grade products)
CAS No. 78-67-1
2,2'-Azobis(isobutyronitrile)AIBN20 kg
N NC CCN
CH3
CH3
CH3
CN
CH3AIBN-HP (Metal-content-control-grade products)
CAS No. 2589-57-3
Dimethyl 2,2'-azobis(2-methylpropionate)V-601500 g10 kg
500 g10 kg
Oil-soluble typeAzo Esters
V-601HP (Metal-content-control-grade products)
CAS No. 1041483-94-6 (n-hydrate)
2,2'-Azobis[N -(2-carboxyethyl)-2-methylpropionamidine]tetrahydrateVA-057500 g5 kg
CAS No. 2997-92-4
2,2'-Azobis(2-methylpropionamidine)dihydrochlorideV-50500 g5 kg20 kg(4×5 kg)
N NC CCH3
CCH3
CCH3
CH3
NHCH2CH2COOH
NH
NH
NH • 4H 2O
CH2CH2HOOC
N NC CCH3
CCH3
CCH3
CH3
NH2
NH• 2HCl
NH2
NH
Water-soluble typeAzo Amidines
CAS No. 20858-12-2
2,2’-Azobis[2-(2-imidazolin-2-yl)propane]VA-061500 g5 kg
NH
CN
CCH3
NCH3
N CCH3
CCH3
NH
N
CAS No. 158947-07-0
4,4-Azobis(4-cyanovalericacid),polymer withalpha,omegabis(3-aminopropyl)polydimethylsiloxaneVPS-1001500 g5 kg
CAS No. 105744-24-9
4,4’-Azobis(4-cyanopentanoicacid) • PolyethyleneglycolpolymerVPE-0201500 g5 kg
Net5 kg
N NC CCN
CH3
OCCH2CH2
CN
CH3
CH2CH2CONHCH2CH2CH2Si(OSi) CH2CH2CH2NHm
nCH3
CH3
CH3
CH3
N NC CCN
CH3
OCCH2CH2
CN
CH3
CH2CH2COO(CH2CH2O)mn
Oil-soluble type
Water-soluble type
Macro Azo Initiators
VPS-1001N
CNNC
H3C C N N C CH3
CH3
COOCH3
CH3
COOCH3
500 g10 kg
O N
O
O
O
NEt2
O NH
O
O N
O
O NH
OO
O
CH3
O N
OO
O
CH3
O N
OO
O
CH3
N
H2n+1
PF6
Cn H2n+1
10 to 13n =
Cn
H2n+1
SbF6
Cn H2n+1
n 10 to 13=
Cn
C4F9SO2
C4F9SO2
N
PF6
CnH2n+1Cn
B
F F
F
F 4F
H2n+1
n 10 to 13=
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N ,N -Bis(2-hydroxypropyl)-p-toluidineAccelerator A
OH
CH2CH CH2
OC2H4OCH2CH
C2H4OCH2CH
CH2
CH2
NHCOCH CH2CH2CHCONHCH2
Cl
Cl
Cl
Cl
COOCH2CH
COOCH2CH
CH2
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ClCl
COOCH2CHCOOCH2CH
COOCH2CH
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CH2
CH2
COOCH2CH
COOCH2CH
CH2
CHCH2OOC
CHCH2OOC
CH2
CH2
CH2
N(CH2CHCH3CH3 )2
OH
HCH2C C
O HN C
CH2
CH2
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O
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(CH2)3
(CH2)3
HN C
HC CH2
O (CH2)3
O
HN C
O HC CH2
HN C
O HC CH2
NNO
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9-Anthrylmethyl N,N-dicyclohexylcarbamateWPBG-172
CAS No. 1418139-51-1
1-(Anthraquinon-2-yl)ethyl imidazole-1-carboxylateWPBG-140
■Photo Cationic Initiators (WPI Series)
■Photo Base Generators (WPBG Series)
932-11706 100g
930-12606 10g
865-26310 100g
934-12506 10g 932-12507 100g
353-33651 1g reagent product359-33653 5g reagent product
351-33691 1g reagent product357-33693 5g reagent product
354-33681 1g reagent product350-33683 5g reagent product
359-33631 1g reagent product355-33633 5g reagent product
356-33641 1g reagent product352-33643 5g reagent product
350-33661 1g reagent product356-33663 5g reagent product
357-33671 1g reagent product353-33673 5g reagent product
032-04902 25g reagent product872-40408 500g874-40402 5kg
143-04562 25g reagent product872-40501 1kg870-40502 5kg
027-07212 25g reagent product021-07215 500g reagent product905-41706 15kg
171-00242 25g reagent product175-00245 500g reagent product
085-01212 25g reagent product089-01215 500g reagent product
084-01282 25g reagent product088-01285 500g reagent product
904-41411 1kg902-41412 5kg
909-40246 500g903-40244 20kg
863-43710 500g868-43726 3kg
741-10436 100g
902-11600 500g
904-40534 20kg
201-20051 5g reagent product209-20052 25g reagent product
715-10333 10kg
937-40809 5g
O N
O
O
O
NEt2
O NH
O
O N
O
O NH
OO
O
CH3
O N
OO
O
CH3
O N
OO
O
CH3
N
H2n+1
PF6
Cn H2n+1
10 to 13n =
Cn
H2n+1
SbF6
Cn H2n+1
n 10 to 13=
Cn
C4F9SO2
C4F9SO2
N
PF6
CnH2n+1Cn
B
F F
F
F 4F
H2n+1
n 10 to 13=
09 09List of Related Items
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CAS No. 135-20-6
Ammonium N -nitrosophenylhydroxylamineQ-1300
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N -Nitrosophenylhydroxylamine aluminium saltQ-1301
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2-tert-ButylhydroquinoneTBHQ
CAS No. 106-51-4
p-Benzoquinone
CAS No. 123-31-9
Hydroquinone
CAS No. 150-76-5
p-Methoxyphenol
CAS No. 110-26-9
N ,N ' -Methylenebis(acrylamide)TRIAM -507
CAS No. 2694-54-4
Triallyl trimellitateTRIAM -705
CAS No. 13360-98-0
Tetraallyl pyromellitateTRIAM -805
CAS No. 13677-69-5
4-Ally-2,6-di-tert-butylphenolTRIAM -100
CAS No. 57947-82-7
Diethyleneglycol diallyl etherTRIAM -501
CAS No. 3232-62-0
Diallyl chlorendateTRIAM -605
CAS No. 1393329-90-2
N-[Tris(3-acrylamidopropoxymethyl)methyl]acrylamide
CAS No. 38668-48-3
N ,N -Bis(2-hydroxypropyl)-p-toluidineAccelerator A
OH
CH2CH CH2
OC2H4OCH2CH
C2H4OCH2CH
CH2
CH2
NHCOCH CH2CH2CHCONHCH2
Cl
Cl
Cl
Cl
COOCH2CH
COOCH2CH
CH2
CH2
ClCl
COOCH2CHCOOCH2CH
COOCH2CH
CH2
CH2
CH2
COOCH2CH
COOCH2CH
CH2
CHCH2OOC
CHCH2OOC
CH2
CH2
CH2
N(CH2CHCH3CH3 )2
OH
HCH2C C
O HN C
CH2
CH2
CH2
O
O
(CH2)3
(CH2)3
HN C
HC CH2
O (CH2)3
O
HN C
O HC CH2
HN C
O HC CH2
NNO
ONH4
NNO
OAl
3
OH
OH
O
O
OH
HO
OH
H3CO
■Polymerization Inhibitors
■Resin Modifiers
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CAS No. 477602-76-9
WPI-113 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium hexafluorophosphate
CAS No. 71786-70-4
WPI-116 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium hexafluoroantimonate
CAS No. 524067-97-8
WPI-169 Bis (4-tert-butylphenyl) iodonium bis (perfluorobutansulfonyl) imide
CAS No. 61358-25-6
WPI-170 Bis (4-tert-butylphenyl) iodonium hexafluorophosphate
CAS No. 210290-42-9
WPI-124 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium tetrakispentafluorophenylborate
CAS No. 501003-75-4
9-Anthrylmethyl N-cyclohexylcarbamateWPBG-041
CAS No. 1421440-15-4
1-(Anthraquinon-2-yl)ethyl N-cyclohexylcarbamateWPBG-174
CAS No. 1421440-01-8
1-(Anthraquinon-2-yl)ethyl N,N-dicyclohexylcarbamateWPBG-166
CAS No. 1228312-02-4
9-Anthrylmethyl Piperidine-1-carboxylateWPBG-015
CAS No. 1228312-05-7
9-Anthrylmethyl N,N-diethylcarbamateWPBG-018
CAS No. 1421440-13-2
9-Anthrylmethyl N,N-dicyclohexylcarbamateWPBG-172
CAS No. 1418139-51-1
1-(Anthraquinon-2-yl)ethyl imidazole-1-carboxylateWPBG-140
■Photo Cationic Initiators (WPI Series)
■Photo Base Generators (WPBG Series)
932-11706 100g
930-12606 10g
865-26310 100g
934-12506 10g 932-12507 100g
353-33651 1g reagent product359-33653 5g reagent product
351-33691 1g reagent product357-33693 5g reagent product
354-33681 1g reagent product350-33683 5g reagent product
359-33631 1g reagent product355-33633 5g reagent product
356-33641 1g reagent product352-33643 5g reagent product
350-33661 1g reagent product356-33663 5g reagent product
357-33671 1g reagent product353-33673 5g reagent product
032-04902 25g reagent product872-40408 500g874-40402 5kg
143-04562 25g reagent product872-40501 1kg870-40502 5kg
027-07212 25g reagent product021-07215 500g reagent product905-41706 15kg
171-00242 25g reagent product175-00245 500g reagent product
085-01212 25g reagent product089-01215 500g reagent product
084-01282 25g reagent product088-01285 500g reagent product
904-41411 1kg902-41412 5kg
909-40246 500g903-40244 20kg
863-43710 500g868-43726 3kg
741-10436 100g
902-11600 500g
904-40534 20kg
201-20051 5g reagent product209-20052 25g reagent product
715-10333 10kg
937-40809 5g
o
oo N
NN
3
o
HS
HS
SH
CH
oo
oo
o
HS
HS
SH
SH
ooo
oo
ooo
HSHS
SHSH
oo
ooo
o
o
o
o
ooH3C
o
oo o
o 3CH
3CH
SS
o
o
33CH
CAS No. 1632211-89-2
N
NN NH
HN
B
Silicic Acid Ester
Crosslinking Agents
Photosensitizers
CH3O
N N
N
NH
HNCO2
NO2
O N
O
OH
OH
NH
O
OH
N
O
O
CO2
CH3
H3N
O
CO2
CH3
H2N
O
CO2
CH3
NH2
NH2H2N
Si(OEt)4
Si ( OMe)Me 3
HS Si ( OMe)3
Sioo ( OMe)3
oSi ( OMe)3
Si ( OEt)3OCN
09 09List of Related Items
31 32
List of Related Items
Azo Polymerization Initiators Azo Polymerization Initiators
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CAS No. 1418139-52-2
(2-Nitrophenyl)methyl 4-hydroxypiperidine-1-carboxylateWPBG-158
CAS No. 1292812-05-5
(2-Nitrophenyl)methyl 4-(methacryloyloxy)piperidine-1-carboxylateWPBG-165
CAS No. 224432-97-7
(E)-N-Cyclohexyl-3-(2-hydroxyphenyl)acrylamideWPBG-025
CAS No. 1203424-93-4
(E)-1-Piperidino-3-(2-hydroxyphenyl)-2-propen-1-oneWPBG-027
CAS No. 81928-83-8
Cyclohexylammonium 2-(3-benzoylphenyl)propionateWPBG-168
CAS No. 24021-57-6
Dicyclohexylammonium 2-(3-benzoylphenyl)propionateWPBG-167
CAS No. 1418139-48-6
CAS No. 1801263-71-7
Guanidinium 2-(3-benzoylphenyl)propionateWPBG-082
1,2-Diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propipnate
1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborateWPBG-300
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CAS No. 78-10-4
Tetraethyl Orthosilicate
CAS No. 1185-55-3
Methyltrimethoxysilane
CAS No. 4420-74-0
(3-Mercaptopropyl)trimethoxysilane
CAS No. 2530-83-8
3-Glycidoxypropyltrimethoxysilane
CAS No. 3388-04-3
[2-(3,4-Epoxycyclohexyl)ethyl]trimethoxysilane
CAS No. 24801-88-5
3-(Triethoxysilyl)propyl Isocyanate
CAS No. 101-37-1
2,4,6-Tris(allyloxy)-1,3,5-triazine
CAS No. 10193-96-1
Trimethylolpropane Tris(mercaptoacetate)
CAS No. 10193-99-4
Pentaerythritol Tetrakis(mercaptoacetate)
CAS No. 7575-23-7
Pentaerythritol Tetrakis(3-mercaptopropionate)
CAS No. 2386-87-0
3,4-Epoxycyclohexylmethyl 3',4'-Epoxycyclohexanecarboxylate
CAS No. 25134-21-8
Methyl-5-norbornene-2,3-dicarboxylic Anhydride
CAS No. 5495-84-1
2-Isopropylthioxanthone
CAS No. 84-80-0
Vitamin K1
■Photo Base Generators (WPBG Series)-related Reagents
WPBG-266
O N
O
NO2 O O
CH3
358-33721 1g reagent product354-33723 5g reagent product
355-33731 1g reagent product351-33733 5g reagent product
354-33701 1g reagent product350-33703 5g reagent product
351-33711 1g reagent product357-33713 5g reagent product
359-33751 1g reagent product355-33753 5g reagent product
356-33761 1g reagent product352-33763 5g reagent product
352-33741 1g reagent product358-33743 5g reagent product
932-12306 5g
938-12406 5g
N
NN
F
F
F
FNH
HN
B
(Z)-{[Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borateWPBG-345
053-03476 500㎖ reagent product
305-60101 100g reagent product
505-62302 25g reagent product
302-60432 25g reagent product
321-91252 25g reagent product329-91253 100g reagent product
324-91242 25g reagent product322-91243 100g reagent product
201-02292 25g reagent product205-02295 500g reagent product
327-21642 25g reagent product321-21645 500g reagent product
326-21612 25g reagent product320-21615 500g reagent product
329-21722 25g reagent product323-21725 500g reagent product
326-64072 25g reagent product320-64075 500g reagent product
134-05951 200g reagent product136-05955 500g reagent product
352-28932 25g reagent product350-28933 100g reagent product
221-00371 1g reagent product227-00373 5g reagent product
H3C
H3C
o
oo N
NN
3
o
HS
HS
SH
CH
oo
oo
o
HS
HS
SH
SH
ooo
oo
ooo
HSHS
SHSH
oo
ooo
o
o
o
o
ooH3C
o
oo o
o 3CH
3CH
SS
o
o
33CH
CAS No. 1632211-89-2
N
NN NH
HN
B
Silicic Acid Ester
Crosslinking Agents
Photosensitizers
CH3O
N N
N
NH
HNCO2
NO2
O N
O
OH
OH
NH
O
OH
N
O
O
CO2
CH3
H3N
O
CO2
CH3
H2N
O
CO2
CH3
NH2
NH2H2N
Si(OEt)4
Si ( OMe)Me 3
HS Si ( OMe)3
Sioo ( OMe)3
oSi ( OMe)3
Si ( OEt)3OCN
09 09List of Related Items
31 32
List of Related Items
Azo Polymerization Initiators Azo Polymerization Initiators
List of Related Items
CAS No. 1418139-52-2
(2-Nitrophenyl)methyl 4-hydroxypiperidine-1-carboxylateWPBG-158
CAS No. 1292812-05-5
(2-Nitrophenyl)methyl 4-(methacryloyloxy)piperidine-1-carboxylateWPBG-165
CAS No. 224432-97-7
(E)-N-Cyclohexyl-3-(2-hydroxyphenyl)acrylamideWPBG-025
CAS No. 1203424-93-4
(E)-1-Piperidino-3-(2-hydroxyphenyl)-2-propen-1-oneWPBG-027
CAS No. 81928-83-8
Cyclohexylammonium 2-(3-benzoylphenyl)propionateWPBG-168
CAS No. 24021-57-6
Dicyclohexylammonium 2-(3-benzoylphenyl)propionateWPBG-167
CAS No. 1418139-48-6
CAS No. 1801263-71-7
Guanidinium 2-(3-benzoylphenyl)propionateWPBG-082
1,2-Diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propipnate
1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborateWPBG-300
List of Related Items
CAS No. 78-10-4
Tetraethyl Orthosilicate
CAS No. 1185-55-3
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CAS No. 4420-74-0
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CAS No. 2530-83-8
3-Glycidoxypropyltrimethoxysilane
CAS No. 3388-04-3
[2-(3,4-Epoxycyclohexyl)ethyl]trimethoxysilane
CAS No. 24801-88-5
3-(Triethoxysilyl)propyl Isocyanate
CAS No. 101-37-1
2,4,6-Tris(allyloxy)-1,3,5-triazine
CAS No. 10193-96-1
Trimethylolpropane Tris(mercaptoacetate)
CAS No. 10193-99-4
Pentaerythritol Tetrakis(mercaptoacetate)
CAS No. 7575-23-7
Pentaerythritol Tetrakis(3-mercaptopropionate)
CAS No. 2386-87-0
3,4-Epoxycyclohexylmethyl 3',4'-Epoxycyclohexanecarboxylate
CAS No. 25134-21-8
Methyl-5-norbornene-2,3-dicarboxylic Anhydride
CAS No. 5495-84-1
2-Isopropylthioxanthone
CAS No. 84-80-0
Vitamin K1
■Photo Base Generators (WPBG Series)-related Reagents
WPBG-266
O N
O
NO2 O O
CH3
358-33721 1g reagent product354-33723 5g reagent product
355-33731 1g reagent product351-33733 5g reagent product
354-33701 1g reagent product350-33703 5g reagent product
351-33711 1g reagent product357-33713 5g reagent product
359-33751 1g reagent product355-33753 5g reagent product
356-33761 1g reagent product352-33763 5g reagent product
352-33741 1g reagent product358-33743 5g reagent product
932-12306 5g
938-12406 5g
N
NN
F
F
F
FNH
HN
B
(Z)-{[Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borateWPBG-345
053-03476 500㎖ reagent product
305-60101 100g reagent product
505-62302 25g reagent product
302-60432 25g reagent product
321-91252 25g reagent product329-91253 100g reagent product
324-91242 25g reagent product322-91243 100g reagent product
201-02292 25g reagent product205-02295 500g reagent product
327-21642 25g reagent product321-21645 500g reagent product
326-21612 25g reagent product320-21615 500g reagent product
329-21722 25g reagent product323-21725 500g reagent product
326-64072 25g reagent product320-64075 500g reagent product
134-05951 200g reagent product136-05955 500g reagent product
352-28932 25g reagent product350-28933 100g reagent product
221-00371 1g reagent product227-00373 5g reagent product
H3C
H3C
10 List of Applicable Laws
33 34Azo Polymerization Initiators Azo Polymerization Initiators
Azo Compounds CAS No. TSCA EINECS
Azo
Nitr
iles
Azo E
sters
Azo
Am
idin
esM
acro
Azo
Initi
ator
sA
zo A
mid
esAz
o Im
idaz
olin
es
V-70 15545-97-8 Listed Listed
V-65 4419-11-8 Listed Listed
AIBN 78-67-1 Listed Listed
V-59 13472-08-7 Listed Listed
V-40 2094-98-6 Listed Listed
V-601 2589-57-3 Listed* Listed
VA-086 61551-69-7 Listed Listed
Not ListedVAm-110 195520-32-2 Not Listed
VA-044 27776-21-2 Listed Listed
V-50 2997-92-4 Listed Listed
Not ListedVA-057 1041483-94-6n-hydrate Not Listed
VA-061 20858-12-2 Listed Listed
Not Listed Not ListedVPS-1001 158947-07-0
Not Listed Not Listed
VPE-0201 105744-24-9 Not Listed Not Listed
VPS-1001N 158947-07-0
ListedV-501 2638-94-0 Listed
*Listed under 5e Consent Order
List of Applicable Law
10List of Applicable Laws
10 List of Applicable Laws
33 34Azo Polymerization Initiators Azo Polymerization Initiators
Azo Compounds CAS No. TSCA EINECS
Azo
Nitr
iles
Azo E
sters
Azo
Am
idin
esM
acro
Azo
Initi
ator
sA
zo A
mid
esAz
o Im
idaz
olin
es
V-70 15545-97-8 Listed Listed
V-65 4419-11-8 Listed Listed
AIBN 78-67-1 Listed Listed
V-59 13472-08-7 Listed Listed
V-40 2094-98-6 Listed Listed
V-601 2589-57-3 Listed* Listed
VA-086 61551-69-7 Listed Listed
Not ListedVAm-110 195520-32-2 Not Listed
VA-044 27776-21-2 Listed Listed
V-50 2997-92-4 Listed Listed
Not ListedVA-057 1041483-94-6n-hydrate Not Listed
VA-061 20858-12-2 Listed Listed
Not Listed Not ListedVPS-1001 158947-07-0
Not Listed Not Listed
VPE-0201 105744-24-9 Not Listed Not Listed
VPS-1001N 158947-07-0
ListedV-501 2638-94-0 Listed
*Listed under 5e Consent Order
List of Applicable Law
10List of Applicable Laws
Azo Polymerization Initiators Comprehensive Catalog
180401 K2 SI
Specialty Chemicals Web Site
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