Azo Polymerization Initiators Comprehensive Catalog

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180401 K2 SI 01 Introduction/What is Radical Polymerization? What is Azo Polymerization Initiator? Radical Formation Mechanism 01 INDEX 01 Introduction/What is Radical Polymerization? P1 07 Detailed Explanations 1. Azo Nitrile P11-14 What are Azo Polymerization Initiator? What are Azo Polymerization Initiator? Radical Formation Mechanism P2 2. Azo Ester P15-16 An azo polymerization initiator is a compound having an azo group (R-N=N-R’), which decomposes with heat 3. Azo Amide P17-18 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides P3 02 4. Azo Imidazoline P19-20 and/or light, and forms carbon radical. The formed carbon radical is excellent in reactivity, and progresses polym- Examples of radical reactions using Azo Polymerization Initiators P4 5. Azo Amidine P21-22 erization and halogenation reactions of different types of vinyl monomers. 03 Selection Guide P5-6 6. Macro Azo Initiator P23-26 04 Decomposition Products P7-8 08 Product List P27-28 Radical Formation Mechanism of Azo Polymerization Initiators (Thermal Decomposition) 05 Solubility at a Glance P9 09 List of Related Items P29-32 06 [Reference] Photocharacterization P10 10 List of Applicable Laws P33-34 H2C=CH Carbon radical – N 2 Y CH3 CH3 CH 3 CH3

Monomer – – – Introduction – R – C – N=N – C – R 2 R – C R – C C – CH2 – – H2

or – – We develop a large variety of products taking advantage of our original – hv X Y organic synthesis technology, production technology, and refining technology X X X (1) Formation (2) Initiation reaction/ Polymer accumulated in our long experience in the manufacturing of reagents. of radical Propagation reaction Azo polymerization initiators are used as reaction initiators in the synthesis of polymers. They are used mainly as radical polymerization initiators in a wide (3)Recombination (4) Disproportionation range of industries, such as acryl resins for paints, water absorbent resins, polymer coagulants, adhesives, and paper finishing agents. R R CH3 CH2 = – – – We have approximately 20 types of azo polymerization initiators of 3 3 H C – C – C – CH R – C – H + R – C Formation by side reaction – – – organic-solvent soluble type and water-soluble type. – X X X X P7 Decomposition product What is Radical Polymerization? Radical polymerization is initiated by the formation of free radicals. Free radicals are formed by thermac energy, light, or (1) Formation of radical: Azo polymerization initiators decompose with heat or light, and form nitrogen gas and radioactivity. Radical polymerization is mainly used for the polymerization of vinyl monomers. In addition to radical carbon radicals. polymerization, cationic polymerization and anionic polymerization are common polymerization methods. In the case of *The decomposition rate (in solution) follows first-order reaction rate kinetics and aries due to structure differences. radical polymerization, initiators are generally used. The typical initiators are azo polymerization initiators and peroxides. (2) Initiation reaction/Propagation reaction: Azo polymerization initiator addition-polymerizes with vinyl monomers and forms a polymer. Characteristics of Radical Polymerization Initiators *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) ■ Radical polymerization initiator shows an effect even in a small amount. recombination or (4) disproportionation ■ It is not polar-sensitive, and a large number of solvent is available, a wide range of monomers can be polymerized. (3) Recombination: The carbon radicals which did not engage in polymerization recombine. ■ Polymerization at a low to high temperature ranges is possible. (4) Disproportionation: The carbon radicals which did not engage in polymerization abstracts hydrogen of other ■ Reaction with simple facility and equipment is possible. carbon radicals.

Active Species Typical Reaction Addition Amount Type of Solvent Reference! Radical Formation Mechanism of Peroxides Usable in many X X Small amount Radical solvents CO 2R CO 2R CO 2R CO 2R ¡ R – C – O – O – C – R 2 R – C – O = = ¡ = O O O

R – C – O R + CO 2 + O = XH O O O O Cationic HO O r × O

Where R is an alkyl. R-CO2· decomposes (decarboxylation) immediately, and R· starts polymerization. Base O O R – Si(OMe 3) + H2O R Si O Si R O O Where R is an aryl, r Anionic × R-CO2· is hard to decompose (decarboxylation), so decarboxylation and addition reaction

Base OH OH 2 O to monomers are competitive reactions. Therefore, R· or R-CO are the radical active species. HS SH + S S

1 Azo Polymerization Initiators Azo Polymerization Initiators 2 01 Introduction/What is Radical Polymerization? What is Azo Polymerization Initiator? Radical Formation Mechanism 01 INDEX 01 Introduction/What is Radical Polymerization? P1 07 Detailed Explanations 1. Azo Nitrile P11-14 What are Azo Polymerization Initiator? What are Azo Polymerization Initiator? Radical Formation Mechanism P2 2. Azo Ester P15-16 An azo polymerization initiator is a compound having an azo group (R-N=N-R’), which decomposes with heat 3. Azo Amide P17-18 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides P3 02 4. Azo Imidazoline P19-20 and/or light, and forms carbon radical. The formed carbon radical is excellent in reactivity, and progresses polym- Examples of radical reactions using Azo Polymerization Initiators P4 5. Azo Amidine P21-22 erization and halogenation reactions of different types of vinyl monomers. 03 Selection Guide P5-6 6. Macro Azo Initiator P23-26 04 Decomposition Products P7-8 08 Product List P27-28 Radical Formation Mechanism of Azo Polymerization Initiators (Thermal Decomposition) 05 Solubility at a Glance P9 09 List of Related Items P29-32 06 [Reference] Photocharacterization P10 10 List of Applicable Laws P33-34 H2C=CH Carbon radical – N 2 Y CH3 CH3 CH 3 CH3

Monomer – – – Introduction – R – C – N=N – C – R 2 R – C R – C C – CH2 – – H2

R – C – O R + CO 2 + O = XH O O O O Cationic HO O r × O

Base OH OH 2 O to monomers are competitive reactions. Therefore, R· or R-CO are the radical active species. HS SH + S S

1 Azo Polymerization Initiators Azo Polymerization Initiators 2 02 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides Examples of radical reactions using Azo Polymerization Initiators 02 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides Examples of radical reactions using Azo Polymerization Initiators Peroxides are used as an initiator for radical polymerization, in addition to azo polymerization initiators. Azo polymerization initiators are used as catalyst and foaming agent in organic synthesis, in addition to in polymer synthesis.

N2 CH3 CH3 CH3 − − Characteristics of Azo Polymerization Initiators − R−C−N=N− C −R 2 R−C ● − ■ Azo polymerization initiators can be used safely as they do not decompose by induction and there is no risk of explosion. − or hv − X X X ■ 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, Carbon radical but forms linear polymers.

Comparison with Peroxides Polymer Synthesis Radical polymerization of styrene Item Azo Polymerization Initiator Peroxide

R R R Reversibility of decomposition Irreversible reaction Reversible reaction Radical active species Efficiency of initiator 0.5 to 0.7 0.9 to 1 Radical polymerization of acrylic ester

R R R R Decomposition rate First-order reaction rate equation shall apply. Depends on additives and solvents. R R R R R CO R CO R 2 CO 2R CO 2R CO2R 2 CO 2R Solvent effect*1 Small Large Copolymerization of styrene and acrylic ester R R Reactive R Induced decomposition Not reactive R R R (Pay attention to contact with metal.) R R

Decomposability m n CO 2R CO 2R

Reactive Redox*2 decomposition Not reactive (Forms redox system with Catalyst for Organic Synthesis a reducing substance) Addition reaction to olefins Br Azo polymerization initiator can be used for addition reactions of HBr, H2S, etc. to olefins. Especially, when Azo polymerization initiator Formed radical RC ● RO ● + HBr using styrenes, bromine or mercapto groups may be Δ or hv selectively introduced to the β position. Hydrogen abstractability Small Large Mitsunobu reaction *3 OH Nu Azo compounds*4 can be used as reagents for *4 + NuH + Azo compound + Ph3 P=O R R' R R' Graft/crosslinking polymer Hard to occur Easy to form. Mitsunobu reaction.

Formed polymer Forms linear polymers. Forms branched polymers. Reactivity of Formed Radicals Reactivity Formed of Foaming Agent

Azo polymerization initiators are used as foaming agents for vinyl chloride or other plastics, Gas generation Reactive Not reactive taking advantage of the property of generating nitrogen gas.

Others Oxdizability Not reactive Reactive *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. *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.

3 Azo Polymerization Initiators Azo Polymerization Initiators 4 02 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides Examples of radical reactions using Azo Polymerization Initiators 02 Characteristics of Azo Polymerization Initiators and Comparison with Peroxides Examples of radical reactions using Azo Polymerization Initiators Peroxides are used as an initiator for radical polymerization, in addition to azo polymerization initiators. Azo polymerization initiators are used as catalyst and foaming agent in organic synthesis, in addition to in polymer synthesis.

Comparison with Peroxides Polymer Synthesis Radical polymerization of styrene Item Azo Polymerization Initiator Peroxide

R R R Reversibility of decomposition Irreversible reaction Reversible reaction Radical active species Efficiency of initiator 0.5 to 0.7 0.9 to 1 Radical polymerization of acrylic ester

Decomposability m n CO 2R CO 2R

Formed polymer Forms linear polymers. Forms branched polymers. Reactivity of Formed Radicals Reactivity Formed of Foaming Agent

Azo polymerization initiators are used as foaming agents for vinyl chloride or other plastics, Gas generation Reactive Not reactive taking advantage of the property of generating nitrogen gas.

3 Azo Polymerization Initiators Azo Polymerization Initiators 4 03 Selection Guide Selection Guide 03 Selection Guide

Selection of Polymerization Process

Step 1 Is polymerization process a radical reaction? Step 2 Is the solvent an organic solvent or water? Step 3 Polymerization Method Step 4 Polymerization Temperature

A polymerization method to heat the Suspension polymerization oil-soluble monomers in a dispersed condition 88 ºC V-40 in water (The initiator solves in monomers.) 66 ºC V-601 Organic solvent Solution polymerization A polymerization method under which the initiator, 51 ºC V-65 Radical polymerization monomers and formed polymers are all dissolved status. etc initiator A polymerization method under which liquid monomers Water Bulk polymerization are polymerized by itself or with adding the initiator. 86 ºC VA-086 A polymerization method under which oil-soluble 56 ºC V-50 Emulsion polymerization monomer is dispersed in water with emulsifying 44 ºC VA-044 agent. (The initiator dissolves in water.) etc 10-hour Half-life Temperature by Structure

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

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

P17 VAm-110 (110 ºC) P17 VA-086 (86 ºC)

O CH CH O O CH CH O 110 ºC 3 3 3 3 C C N N C C C C N N C C CH CH HOCH2CH2NH CH3 CH3 NHCH2CH2OH P13 V-40 (88 ºC) CH3 CH2 CH2 CH2NH 3 3 NHCH2 CH2 CH2 CH3 80 ºC

N N NC CN 80 ºC P12 V-59 (67 ºC) 70 ºC

CH3 CH3 − − P13 V-501 (69 ºC)

CH3CH2−C−N=N−C−CH 2CH3 CH3 CH3 − − − −

HOOCH2CH2C−C−N=N−C−CH 2CH2COOH CN CN − − P19 VA-061 (61 ºC) 70 ºC CN CN 60 ºC N CH3 CH3 N P12 AIBN (65 ºC) P15 V-601 (66 ºC) C C N N C C * Metal-content-control-grade N CH CH N products are also available. * Metal-content-control-grade P21 VA-057 (57 ºC) H 3 3 H products are also available. CH CH CH3 CH3 HN 3 3 NH − − 3 3 CH CH ●4H2O − − C C N N C C 3 3 HOOCH 2CH2CHN NHCH 2CH2COOH H C−C−N=N−C−CH CH − − H3C−C−N=N−C−CH 3 3 CH3 − − CN CN 60 ºC COOCH3 COOCH3 P21 V-50 (56 ºC) P11 V-65 (51 ºC) NH CH3 CH3 NH * Metal-content-control-grade products are also available. 50 ºC C C N N C C ●2HCl CH3 CH3 CH3 CH3 NH2 CH3 CH3 NH2 50 ºC CH CH2 C N N C CH2 CH CH3 CN CN CH3

P11 V-70 (30 ºC) P19 VA-044 (44 ºC)

OCH3 CH3 CH3 OCH3 N CH3 CH3 N 30 ºC 30 ºC C C N N C C ●2HCl H3C C CH2 C N N C CH2 C CH3 N N CH3 CH3 CH3 CN CN CH3 H H

5 Azo Polymerization Initiators Azo Polymerization Initiators 6 03 Selection Guide Selection Guide 03 Selection Guide

Selection of Polymerization Process

Step 1 Is polymerization process a radical reaction? Step 2 Is the solvent an organic solvent or water? Step 3 Polymerization Method Step 4 Polymerization Temperature

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

P17 VAm-110 (110 ºC) P17 VA-086 (86 ºC)

O CH CH O O CH CH O 110 ºC 3 3 3 3 C C N N C C C C N N C C CH CH HOCH2CH2NH CH3 CH3 NHCH2CH2OH P13 V-40 (88 ºC) CH3 CH2 CH2 CH2NH 3 3 NHCH2 CH2 CH2 CH3 80 ºC

N N NC CN 80 ºC P12 V-59 (67 ºC) 70 ºC

CH3 CH3 − − P13 V-501 (69 ºC)

CH3CH2−C−N=N−C−CH 2CH3 CH3 CH3 − − − −

P11 V-70 (30 ºC) P19 VA-044 (44 ºC)

OCH3 CH3 CH3 OCH3 N CH3 CH3 N 30 ºC 30 ºC C C N N C C ●2HCl H3C C CH2 C N N C CH2 C CH3 N N CH3 CH3 CH3 CN CN CH3 H H

5 Azo Polymerization Initiators Azo Polymerization Initiators 6 04 Decomposition Products Decomposition Products 04 Decomposition Product of Azo Polymerization Initiators 3. Volatility of Decomposition Products The decomposition product of V-601 is characterized by a higher volatility than that of AIBN. Also, the decomposition 1. Formed Amount of each Decomposition Product of Azo Nitrile product of V-601 is azeotropic with water, therefore, thus can be easily removed from the post-reaction system.

CH3 CH3 ● Boiling point of decomposition product of V-601: 85-90 ºC (5 mmHg) – – ● Azeotropic point of decomposition product of V-601 with water: 90 ºC R – C – N=N – C – R On the other hand, the decomposition product of V-40 is hardly volatile, therefore, applications such as paint are expected. – – CN CN Ratio of decomposition product in the case of thermal decomposition with GC (%) Evaporation Rate of Decomposition Products Disproportionation Recombination 50 R R Compound R R Polymer – – R – Name – Unknown H3C – C – CN H3C – C – C – CH3 V-601 H2C=C – CN – H – (AIBN) CN CN 40 V-59 *5 AIBN CH3 4 4 92 Trace V-65 )

*6 2 V-59 C2H5 6 Trace 86 8 V-40 *5 V-65 (CH3)2CHCH2 7 7 85 Trace 30 *5 V-70 CH3OC(CH 3)2CH2 8 8 78 8 (mg/h r • cm

*5 V-40 c-C6H10 9 9 82 1 *5 In-house Data *6 Polymer journal 9275 (1977) 20 7

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

*7 H.TANAKA, T.KAGAWA, T.SATO, T.OTA, Macromolecules, 19(3), 934(1986) N2 CH3 CH3 CH3 – – – 10 CH3 – C – N=N – C – CH3 2 CH3 – C ● – – or hv – COOCH3 COOCH3 COOCH3 (I)

CH3 CH3 – Recombination – 0 CH3 – C – C – CH3 (I) 0 20 40 60 80 100 120 140 – – COOCH3 COOCH3 (IV) Temperature (ºC)

Disproportionation CH3 – + CH3

CH3 – CH –

2 CH =C – – COOCH3 (II) COOCH3 (III)

CH3 CH3 – – (I) + (III) CH3 – C – CH2 – C ● – – COOCH3 COOCH3 (V)

CH3 CH3 CH3 (I) – – – (V) CH3 – C – CH2 – C – C – CH3 – – – COOCH3 COOCH3COOCH3 (VI)

CH3

Disproportionation – CH3 – C – CH2 – C=CH2 – – COOCH3 COOCH3 (VII) Ratio of decomposition product in the toluene solution (%) Photodecomposition (25 ºC) Decomposition Product Thermal Decomposition (80 ºC) (100 W HP Hg lamp) IV 42.1 42.7 II 36.4 38.5 VI 13.8 13.8

7 Azo Polymerization Initiators Azo Polymerization Initiators 8 04 Decomposition Products Decomposition Products 04 Decomposition Product of Azo Polymerization Initiators 3. Volatility of Decomposition Products The decomposition product of V-601 is characterized by a higher volatility than that of AIBN. Also, the decomposition 1. Formed Amount of each Decomposition Product of Azo Nitrile product of V-601 is azeotropic with water, therefore, thus can be easily removed from the post-reaction system.

*6 2 V-59 C2H5 6 Trace 86 8 V-40 *5 V-65 (CH3)2CHCH2 7 7 85 Trace 30 *5 V-70 CH3OC(CH 3)2CH2 8 8 78 8 (mg/h r • cm

*5 V-40 c-C6H10 9 9 82 1 *5 In-house Data *6 Polymer journal 9275 (1977) 20 7

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

*7 H.TANAKA, T.KAGAWA, T.SATO, T.OTA, Macromolecules, 19(3), 934(1986) N2 CH3 CH3 CH3 – – – 10 CH3 – C – N=N – C – CH3 2 CH3 – C ● – – or hv – COOCH3 COOCH3 COOCH3 (I)

CH3 CH3 – Recombination – 0 CH3 – C – C – CH3 (I) 0 20 40 60 80 100 120 140 – – COOCH3 COOCH3 (IV) Temperature (ºC)

Disproportionation CH3 – + CH3

CH3 – CH –

2 CH =C – – COOCH3 (II) COOCH3 (III)

CH3 CH3 – – (I) + (III) CH3 – C – CH2 – C ● – – COOCH3 COOCH3 (V)

CH3 CH3 CH3 (I) – – – (V) CH3 – C – CH2 – C – C – CH3 – – – COOCH3 COOCH3COOCH3 (VI)

CH3

7 Azo Polymerization Initiators Azo Polymerization Initiators 8 05 Solubility [Reference] Photocharacterization 06 Solubility Reference! Photocharacterization Oil-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature) R1 R1 These products are decomposed by exiting of Azo (N=N) group by light irradiation. R2 N=N R2 V-70 V-65 AIBN V-601 V-59 V-40 VAm-110 They are able to be used also as photo radical initiators. Water 0.1 <0.1 <0.1 0.3 <0.1 0.1 <0.1 X X Absorbs around 360 nm. Methanol 1 28 7.5 >50 >50 4.4 >50 Acetone 3.3 >50 29 >50 >50 30 >50 Chloroform 20 >50 25 >50 >50 >50 >50 Ethyl Acetate 2.0 >50 14 >50 >50 15 >50 Photo Polymerization by Oil-Soluble Azo Polymerization Initiators Toluene 3.0 >50 7.0 >50 >50 27 >50 Photodecomposition Reaction Rate Constant Example of Photo Polymerization (Bulk Polymerization)

Solvent: Toluene 30 Water-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature) Light source: 100 W high-pressure mercury lamp 25 20

15 VA-044 V-50 VA-057 VA-086 4 Azo Molar Absorbance Coefficient kd×10 MW λmax (nm) 10 Water 34.7 23.2 14.0 4.5 Compound ε (L/mol·cm) (sec-1) Polymerization ratio (%) Methanol 1.7 2.1 28.8 7.4 V-59 192.26 348 16 3.76 5 Acetone Not soluble Not soluble Not soluble Not soluble 0 AIBN 164.21 347 13 3.97 0 50 100 150 Ethyl Acetate Not soluble Not soluble Not soluble Not soluble V-40 244.34 350 17 4.13 time/min Toluene Not soluble Not soluble Not soluble Not soluble V-601 230.26 368 14 4.43 Monomer Methyl methacrylate N,N-Dimetylformamide Not soluble Not soluble Not soluble 4.4 V-65 248.37 350 22 4.86 Initiator 0.01 mol/l (ratio to monomer) VAm-110 312.45 376 30 8.01 Light Source 100 W high-pressure mercury lamp

Photo Polymerization of Water-Soluble Azo Polymerization Initiators Photodecomposition Reaction Rate Constant Example of Photo Polymerization (Solution Polymerization)

Solvent: Water 100 Light source: 100 W high-pressure mercury lamp 90 80 70 4 Azo Molar Absorbance Coefficient d 60 MW λmax (nm) k ×10 Compound ε (L/mol·cm) (sec-1) 50 40 V-50 271.19 367 22 5.37 30 Polymerization ratio (%) VA-057 414.46 371 26 7.23 20 10 VA-044 323.33 363 23 7.53 0 0 10 20 30 40 VA-086 288.35 375 30 7.72 time/min Monomer Acrylamide 10 w/wt% Initiator 0.01 mol/l (ratio to monomer) Light Source 100 W high-pressure mercury lamp

*Since photodecomposition reaction rate constant depends on the strength of light source, the above photodecomposition reaction rate constant is not an absolute value. However, since these are data measures with a same light source, these data can be used for relative comparison. 9 Azo Polymerization Initiators Azo Polymerization Initiators 10 05 Solubility [Reference] Photocharacterization 06 Solubility Reference! Photocharacterization Oil-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature) R1 R1 These products are decomposed by exiting of Azo (N=N) group by light irradiation. R2 N=N R2 V-70 V-65 AIBN V-601 V-59 V-40 VAm-110 They are able to be used also as photo radical initiators. Water 0.1 <0.1 <0.1 0.3 <0.1 0.1 <0.1 X X Absorbs around 360 nm. Methanol 1 28 7.5 >50 >50 4.4 >50 Acetone 3.3 >50 29 >50 >50 30 >50 Chloroform 20 >50 25 >50 >50 >50 >50 Ethyl Acetate 2.0 >50 14 >50 >50 15 >50 Photo Polymerization by Oil-Soluble Azo Polymerization Initiators Toluene 3.0 >50 7.0 >50 >50 27 >50 Photodecomposition Reaction Rate Constant Example of Photo Polymerization (Bulk Polymerization)

Solvent: Toluene 30 Water-soluble Azo Polymerization Initiators (g/100 g solvent, ambient temperature) Light source: 100 W high-pressure mercury lamp 25 20

Photo Polymerization of Water-Soluble Azo Polymerization Initiators Photodecomposition Reaction Rate Constant Example of Photo Polymerization (Solution Polymerization)

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

OCH3 CH3 CH3 OCH3 CH3 CH3 Characteristics − − Characteristics: H3C C CH2 C N N C CH2 C CH3 V-70 is an oil-soluble azo polymerization initiator of which 10-hour half-life temperature is 30 ºC. H3C−C−N=N−C−CH 3 AIBN is the most common oil-soluble azo polymerization initiator, and is used for − − V-70 can be used as a polymerization initiator for different types of vinyl monomers and a polymerization of versatile polymers. CH3 CN CN CH3 catalyst for organic radical reactions at a low temperature. CN CN Properties Applicable Laws and Regulations Properties Applicable Laws and Regulations Low-temperature type Oil-soluble type Item Item Oil-soluble type Item Item

Molecular formula C16H28N4O2 TSCA Listed Molecular formula C8H12N4 TSCA Listed Molecular weight 308.43 EINECS Listed Molecular weight 164.21 EINECS Listed CAS No. 15545-97-8 CAS No. 78-67-1 nearly white, crystalline powder Form white, crystalline powder Form *Contains water. Melting point 100-103(dec.) °C Packaging and Storage Requirements Melting point 50-96(dec.) °C Packaging and Storage Requirements 10-hour half life temperature 65 ºC (Toluene) Item 10-hour half life temperature 30 ºC (Toluene) water : very slightly soluble. Item acetone : free soluble. methanol, water : practically insoluble. Packaging 20 kg Solubilities toluene : soluble. dichloromethane : freely soluble. Packaging 100 g Ethanol : sparingly soluble. Storage requirement Please keep at 20 ºC or less. Solubilities acetonitrile, N,N-Dimethylformamide : 25 kg soluble. methanol, acetone, toluene : slightly soluble. Storage requirement Please keep at -10 ºC or less.

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

2,2’-Azobis(2,4-dimethylvaleronitrile) Packaging and Storage Requirements Metal Content V-65 Semiconductors LCD Item Metal Specification value Packaging 500 g Li,Na,Mg CH3 CH3 CH3 CH3 Characteristics: 10 kg Al,K,Ca CH CH2 C N N C CH2 CH When compared with AIBN, the 10-hour half-life temperature of this oil-soluble azo polymerization initiator is Storage requirement Please keep at 20 ºC or less. Cr,Mn,Fe 500 ppb or less 10 ºC or lower than AIBN. CH3 CN CN CH3 Ni,Cu,Zn This product can be used for a wide range of applications, from versatile polymers to cosmetics-related use. Zr,Pb,Sn Properties Applicable Laws and Regulations Low-temperature type Oil-soluble type Item Item

Molecular formula C14H24N4 TSCA Listed Molecular weight 248.37 EINECS Listed CAS No. 4419-11-8 Form white, crystalline powder Packaging and Storage Requirements 2,2’-Azobis (2-methylbutyronitrile) Melting point 45-70(dec) °C V-59 10-hour half life temperature 51 ºC (Toluene) Item water : insoluble. benzene, Packaging 500 g CH3 CH3 − − Characteristics: Solubilities acetone, ether, 25 kg N,N-Dimethylformamide, toluene, CH3CH2−C−N=N−C−CH 2CH3 V-59 is an oil-soluble azo polymerization initiator which shows almost a similar methanol : soluble. Storage requirement Please keep at 10 ºC or less. − − 10-hour half-life temperature to that of AIBN and has excellent solubility to many CN CN different solutions. Applicable Laws and Regulations Oil-soluble type Properties Item V-65HP (Metal-content-control-grade products) Item TSCA Listed

Molecular formula C10H16N4 EINECS Listed

Semiconductors LCD Packaging and Storage Requirements Metal Content Molecular weight 192.26 Item Metal Specification value CAS No. 13472-08-7 Packaging and Storage Requirements Packaging 500 g Na 500 ppb or less Form white, powder Item 10 kg Li,Mg,Al Melting point 48 - 52 ºC Packaging 500 g Storage requirement Please keep at 10 ºC or less. K,Ca,Cr 10-hour half life temperature 67 ºC (Toluene) 10 kg Mn,Fe,Ni 300 ppb or less water : very slightly soluble. 25 kg Solubilities dimethyl sulfoxide : free soluble. Cu,Zn,Zr toluene, methanol : Very soluble. Storage requirement Please keep at 10 ºC or less. Pb,Sn

11 Azo Polymerization Initiators Azo Polymerization Initiators 12 07 Detailed Explanations 1. Azo Nitrile Detailed Explanations 1. Azo Nitrile 07 Detailed Explanations 1. Azo Nitrile

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

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

Molecular formula C10H16N4 EINECS Listed

11 Azo Polymerization Initiators Azo Polymerization Initiators 12 07 Detailed Explanations 1. Azo Nitrile Detailed Explanations 1. Azo Nitrile 07 V-40 1,1’-Azobis(cyclohexane-1-carbonitrile) Half-life of Azo Nitriles in Solution

Characteristics: N N Since the 10-hour half-life temperature is as high as 88 ºC, V-40 can be used to decrease residual NC CN monomer concentration when used with other initiators, such as V-65. This is an oil-soluble azo polymerization initiator which has a high solubility in various organic solvents. The decomposition product of (2) (3)(4)(6) (5) V-40 has a unique characteristic of low volatility, therefore it could be useful for cow-voc paint applications. 10000

Properties Applicable Laws and Regulations

High-Temperature Type Oil-soluble type Item Item Molecular formula C14H20N4 TSCA Listed Molecular weight 244.34 EINECS Listed CAS No. 2094-98-6 Form white, crystals Packaging and Storage Requirements Melting point 110-120 ºC 10-hour half life temperature 88 ºC (Toluene) Item Packaging 500 g Water : practically insoluble. 1000 acetone, chloroform, 20 kg Solubilities benzene : freely soluble. Ethanol : soluble. petroleum ether : practically insoluble Storage requirement Please keep at 20 ºC or less. 600 (1)

Example of Polymerization Block Polymerization of Styrene Suspension Polymerization of MMA by co-using with V-40 and V-65.

% % (Relationship between the addition amount of initiator and residual monomers) 100 100 Initiator concentration 7.0×10−3 mol/ℓ Initiator concentration 7.0×10−3 mol/ℓ Polymerization temperature 90 ºC Polymerization temperature 120 ºC 4 Temperature Time 80 80 V-40 Polymerization conditions: 80 ºC 1 Hr 100 95 ºC 2 Hrs V-40 3

60 60 Half-life (minutes) AIBN 2

40 40 V-65 Co-using with V-65 0.1 % 1 Residual monomers (%) Polymerization Ratio (%) Co-using with V-65 0.15 % 20 20 0 Without adding initiator 0 0.01 0.02 0.03 0.04 0.05 Addition Amount of V-40 (Ratio to Monomer %) 0 0 0 1 5 10 0 1 2 3 Polymerization time (h) Polymerization time (h) 10

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

CH3 CH3 − − Characteristics:

HOOCH2CH2C−C−N=N−C−CH 2CH2COOH V-501 is a nitrile-based water-soluble azo polymerization initiator, having a carboxyl group at the end. By − − introducing carboxyl group at polymer, post-polymerization mddification can be achieved. CN CN Properties Applicable Laws and Regulations 1 Water-soluble type Non-halogen Item Item 3.3 3.2 3.1 3 2.9 2.8 2.7 2.6 Molecular formula C12H16N4O4 TSCA Listed -1 3 F Cl Molecular weight 280.28 EINECS Listed (K ×10 ) Br I CAS No. 2638-94-0 white, powder Form *Containing water 30 40 50 60 70 80 90 100 110 Melting point 120-123(dec.) °C Packaging and Storage Requirements 10-hour half life temperature 69 ºC (In water, as sodium salt) Item Temperature (ºC) water : practically insoluble. Packaging 500 g Ethanol, ether, formamide : freely 10 kg Solubilities soluble methanol : soluble. toluene : insoluble. Storage requirement Please keep at 20 ºC or less. (1)● V-70 (2) V-65 (3) AIBN (4) V-59 (5) V-40 (6) V-501

13 Azo Polymerization Initiators Azo Polymerization Initiators 14 07 Detailed Explanations 1. Azo Nitrile Detailed Explanations 1. Azo Nitrile 07 V-40 1,1’-Azobis(cyclohexane-1-carbonitrile) Half-life of Azo Nitriles in Solution

Properties Applicable Laws and Regulations

Example of Polymerization Block Polymerization of Styrene Suspension Polymerization of MMA by co-using with V-40 and V-65.

60 60 Half-life (minutes) AIBN 2

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

CH3 CH3 − − Characteristics:

13 Azo Polymerization Initiators Azo Polymerization Initiators 14 07 Detailed Explanations 2. Azo Ester Detailed Explanations 2. Azo Ester 07 2. Azo Ester Half-life of Azo Esters in Solution

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

CH3 CH3 − − Characteristics: H3C−C−N=N−C−CH 3 V-601 is a nitrile-free oil-soluble azo polymerization initiator which has similar level of polymerization (1) − − activity as AIBN. A safer developed as alternative to AIBN, V-601 decomposition results in much less 100000 COOCH3 COOCH3 toxic byproducts. As a nitrile-free azo initiator, V-601 displays excellent solubility characteristics in organic solvents. Since the volatility of the decomposition product is higher than that of others, such a product can be removed in the process of polymer manufacturing. Being of non-nitrile type, the polymerized polymers are highly transparent, therefore, semiconductors and LCDs applications are expected.

Properties Applicable Laws and Regulations Non-nitrile Oil-soluble type Item Item 10000 Molecular formula C10H18N2O2 TSCA Listed (Listed under 5e Consent Order) CN Molecular weight 230.26 EINECS Listed CAS No. 2589-57-3 Form slight yellow or pale yellow, crystals or oily Packaging and Storage Requirements Melting point 22-28 °C 10-hour half life temperature 66 ºC (Toluene) Item water : insoluble. benzene, Ethanol, Packaging 500 g N,N-Dimethylformamide, 10 kg Solubilities dioxane, DMSO : freely soluble. methanol, 1000 toluene, chloroform, hexane : soluble. Storage requirement Please keep at 10 ºC or less. 600

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

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

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

30 40 50 60 70 80 90 100 110 120 Temperature (ºC)

(1) V-601

15 Azo Polymerization Initiators Azo Polymerization Initiators 16 07 Detailed Explanations 2. Azo Ester Detailed Explanations 2. Azo Ester 07 2. Azo Ester Half-life of Azo Esters in Solution

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

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

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

30 40 50 60 70 80 90 100 110 120 Temperature (ºC)

(1) V-601

15 Azo Polymerization Initiators Azo Polymerization Initiators 16 07 Detailed Explanations 3. Azo amide Detailed Explanations 3. Azo amide 07 3. Azo amide Half-Life of Azo Amides in Solution

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

CH3 CH3 O= − − O= Characteristics: C−C−N=N−C−C VA-086 is a non-ionic and non nitrile water-soluble azo polymerization − − (1) (2) − − 10000 HOCH2CH2NH NHCH2CH2OH initiator having a hydroxyl group at the end. The 10-hour half-life CH3 CH3 temperature is as high as 86 ºC, therefore, reduction of residual monomer can be expected by co-using it with another initiator. Properties Applicable Laws and Regulations

Non-nitrile Non-halogen Item Item F Cl Molecular formula C12H24N4O4 TSCA Listed CN Molecular weight 288.35 EINECS Not Listed Br I CAS No. 61551-69-7 Form white - slightly yellow, crystalline powder Packaging and Storage Requirements 1000 Water-soluble type Melting point 138-145(dec.) °C Item 10-hour half life temperature 86 ºC (Water) Packaging 500 g 600 water, methanol : soluble. 5 kg Solubilities chloroform : slightly soluble Storage requirement Please keep at 25 ºC or less.

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

CH3 CH3

− − 100 O= O= Characteristics: C−C−N=N−C−C VAm-110 is an oil-soluble azo polymerization initiator which is active in high − − − − CH3CH2CH2CH2NH NHCH2CH2CH2CH3 temperatures, the 10-hour half-life temperature is as high as 110 ºC. This product CH3 CH3 Half-life (minutes) has characteristics which show high solubility to different organic solvents. Properties Applicable Laws and Regulations

Non-nitrile High-Temperature Type Item Item

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

Examples of polymerization Bulk Polymerization of Styrene Solution Polymerization of n-Butyl methacrylate 1 100 100 3.1 3 2.9 2.8 2.7 2.6 2.5 2.4 2.3

75 75 (K-1×103)

50 50 50 60 70 80 90 100 110 120 130 140 150

Polymerization conditions (Sealed tube polymerization) Polymerization conditions Concentration of initiator 0.4 mmol/l Monomer concentration 20 wt% Polymerization Ratio (%) Polymerization Ratio (%) Polymerization temperature 110 ºC 25 Initiator concentration 0.19 mol%/monomer 25 Polymerization temperature 120 ºC Temperature (ºC) VAm-110 Polymerization solvent Diisobutyl Ketone

Thermal polymerization VAm-110 0 0 0 1 2 3 4 5 6 0 1 2 3 4 5 6 (1) VA-086 (2) VAm-110 Polymerization Time (h) Polymerization Time (h)

17 Azo Polymerization Initiators Azo Polymerization Initiators 18 07 Detailed Explanations 3. Azo amide Detailed Explanations 3. Azo amide 07 3. Azo amide Half-Life of Azo Amides in Solution

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

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

CH3 CH3

Non-nitrile High-Temperature Type Item Item

Examples of polymerization Bulk Polymerization of Styrene Solution Polymerization of n-Butyl methacrylate 1 100 100 3.1 3 2.9 2.8 2.7 2.6 2.5 2.4 2.3

75 75 (K-1×103)

50 50 50 60 70 80 90 100 110 120 130 140 150

Thermal polymerization VAm-110 0 0 0 1 2 3 4 5 6 0 1 2 3 4 5 6 (1) VA-086 (2) VAm-110 Polymerization Time (h) Polymerization Time (h)

17 Azo Polymerization Initiators Azo Polymerization Initiators 18 07 Detailed Explanations 4. Azo Imidazolin Detailed Explanations 4. Azo Imidazoline 07 4. Azo Imidazolin Half-Life of Azo Imidazolines in Solution

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

N CH 3 CH 3 N Characteristics: VA-044 is a non-nitrile, cationic water-soluble azo polymerization initiator. It is highly 100000 C C N N C C ●2HCl effective for the polymerization of water-soluble vinyl monomer. The 10-hour half-life N CH CH N H 3 3 H temperature is as low as 44 ºC, and the product is active at low temperatures. Properties Applicable Laws and Regulations Non-nitrile Low-temperature type Item Item

Molecular formula C12H24Cl2N2 TSCA Listed CN Molecular weight 323.27 EINECS Listed CAS No. 27776-21-2 white - light yellow Form Water-soluble type crystals or crystalline powder (2) Packaging and Storage Requirements Melting point 188-193(dec.) °C 10-hour half life temperature 44 ºC (Water) Item water : free soluble. Packaging 500 g methanol : sparingly 20 kg Solubilities soluble. Ethanol : very slightly soluble. acetone, toluene : insoluble. Storage requirement Please keep at 40 ºC or less. 10000

VA-061 2,2’-Azobis[2-(2-imidazolin-2-yl)propane] CH CH N 3 3 N Characteristics: VA-061 is the free base of VA-044 and VA-046B, which are water-soluble azo polymerization initiators. By forming salts with different C C N N C C organic acids, the product dissolves in water, creating a highly effective initiator for polymerization of water-soluble vinyl monomers. N CH CH N Half-life (minutes) (1) H 3 3 H Properties Applicable Laws and Regulations

Non-nitrile Non-halogen Item Item F Cl Molecular formula C12H22N6 TSCA Listed CN Molecular weight 250.35 EINECS Listed Br I CAS No. 20858-12-2 1000 Form slightly yellowish white, crystalline powder Water-soluble type Melting point 115-125(dec.) °C Packaging and Storage Requirements 10-hour half life temperature 61 ºC (Methanol) Item 600 water : practically insoluble. methanol : soluble. Ethanol, Packaging 500 g Solubilities chloroform : slightly soluble. toluene : insoluble. 5 kg *Acid: Soluble Storage requirement Please keep at 10 ºC or less.

100 3.2 3.1 3 2.9

(K-1×103)

40 50 60 70

Temperature (ºC)

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

19 Azo Polymerization Initiators Azo Polymerization Initiators 20 07 Detailed Explanations 4. Azo Imidazolin Detailed Explanations 4. Azo Imidazoline 07 4. Azo Imidazolin Half-Life of Azo Imidazolines in Solution

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

100 3.2 3.1 3 2.9

(K-1×103)

40 50 60 70

Temperature (ºC)

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

19 Azo Polymerization Initiators Azo Polymerization Initiators 20 07 Detailed Explanations 5. Azo Amidine Detailed Explanations 5. Azo Amidine 07 5. Azo Amidine Half-Life of Azo Amidines in Solution

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

NH CH CH3 NH 3 Characteristics: C C N N C C 2HCl V-50 is a highly active water-soluble azo polymerization initiator. A variety of polymerization (1)(2) NH CH CH NH 2 3 3 2 applications can be expected. This product is uniquely characterized by the amidine group which is 10000 cationic. Cationic emulsions, latex, etc. can be synthesized easily and in a stable manner, therefore an excellent effect can be expected for emulsion polymerization of synthetic rubber, adhesives, etc.

Applicable Laws and Regulations

Non-nitrile Water-soluble type Properties Item Item TSCA Listed CN Molecular formula C8H20Cl2N6 EINECS Listed Molecular weight 271.19 CAS No. 2997-92-4 Form nearly white, Granular Packaging and Storage Requirements 1000 Melting point 160-169(dec.) °C Item 10-hour half life temperature 56 ºC (Water) Packaging 500 g 600 water : freely soluble. 5 kg methanol, Ethanol, acetone, 20 kg Solubilities N,N-Dimethylformamide, dioxane : practically insoluble. Storage requirement Please keep at 40 ºC or less.

VA-057 2,2’-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate 100

NH CH3 CH3 NH 4H2O Characteristics: C C N N C C Half-life (minutes) VA-057 is a water-soluble azo polymerization initiator which has a zwitterinoic structure. The 10-hour half-life tempera- HOOC CH2 CH2NH CH3 CH3 NHCH 2 CH2 COOH ture is 57 ºC, which allows a polymerization under a mild condition. As a non-halogenated initiator, VA-057 is uniquely characterized by not causing any concerns about coloring of polymer or corrosion of polymerization facilities with halogen. Since the product has a zwitterionic structure, formation of both cationic and anionic latex is expected.

Properties Applicable Laws and Regulations Non-nitrile Non-halogen Item Item 10 F Cl Molecular formula C14H34N6O8 TSCA Not Listed CN Molecular weight 414.46 EINECS Not Listed Br I CAS No. 1041483-94-6 (n-hydrate) white - pale yellow Form Water-soluble type powder - crystalline powder Packaging and Storage Requirements Melting point 97(dec.) °C Item 10-hour half life temperature 57 ºC (Water) Packaging 500 g water, methanol : free soluble. 5 kg Solubilities Ethanol, isopropanol, acetone, toluene : very slightly soluble. Storage requirement Please keep at 10 ºC or less. 1 3.3 3.2 3.1 3 2.9 2.8 2.7 2.6 (K-1×103)

30 40 50 60 70 80 90 100 110 Temperature (ºC)

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

21 Azo Polymerization Initiators Azo Polymerization Initiators 22 07 Detailed Explanations 5. Azo Amidine Detailed Explanations 5. Azo Amidine 07 5. Azo Amidine Half-Life of Azo Amidines in Solution

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

Applicable Laws and Regulations

VA-057 2,2’-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate 100

30 40 50 60 70 80 90 100 110 Temperature (ºC)

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

21 Azo Polymerization Initiators Azo Polymerization Initiators 22 07 Detailed Explanations 6. Macro Azo Initiator Detailed Explanations 6. Macro Azo Initiator 07 What is a Macro Azo Initiator? 6. Macro Azo Initiator (MAI : Macro Azo Initiator) Macro Azo Initiator (MAI) is a unique azo compound which gives block polymer easily through a polymerization with different vinyl 4,4-Azobis(4-cyanovaleric acid),polymer with alpha, omega-bis(3-aminopropyl)polydimethylsiloxane monomers. MAI has a structure in which polymer segment and azo group are repeatedly bonded, and there are several radical VPS-1001 VPS-1001N forming points in a molecule. Therefore, when monomers are polymerized, polymers with high blocking efficiency can be designed.

CH3 CH3 Since this product is soluble in different solvents, various polymerization methods (solution polymerization, suspension polymeriza- CH3 CH3

OCH2CH2C N N CH2CH2CONHCH2CH2CH2Si OSi CH2CH2CH2NH tion and emulsion polymerization) can be adopted. This product offers a wide range of options of monomers for co-polymerization, m CN CN CH3 CH3 and allows molecule design and structure control of block polymers fit for the purpose. n Characteristics: VPS-1001 Methyl methacrylate (MMA) 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. VPS-1001 Applicable Laws and Regulations Methyl methacrylate (MMA) Item Emulsion Suspension Solution TSCA Not Listed Toluene polymerization polymerization polymerization EINECS Not Listed

Polymerization in N2 gas flow Forms and molecular weight of different types Packaging and Storage Requirements VPS-1001N Item VPS-1001 VPS-1001N Item VPS-1001 (solvent contained) 500 g Net 5 kg Packaging Molecular formula [C20H34N6O2Si(C2H6Si)m]n 5 kg Formation Process of Block Polymer CAS No. 158947-07-0 Storage requirement Please keep at 10 ºC or less. Form clear gum white Azo group Molecular weight of macro initiator (Mn) Approximately 80,000 to 120, 000 N=N Molecular weight of polydimethylsiloxane Approximately 10,000 Approximately 0.1 mmol/g Molecular number of azo group per 1 g of VPS (1/60 of AIBN) N=N 10-hour half life temperature 65 - 70 ºC N=N N=N *Compared with mol number of azo group per 1 g of AIBN (M.W.: 164.21) = 6 mmol/g.

N=N

Example of polymerization MMA monomer Polydimethylsiloxane chain In a four necked flask equipped with a thermometer, nitrogen gas induction tube, mixer, and reflux condenser, 25 g of VPS-1001, 100 g of methyl methacrylate (MMA) as monomer, and 260 g of toluene as solvent are The process from the start of polymerization with azo groups in polymers to the growing of block polymers is shown in a schematic drawing. charged and polymerized under the nitrogen gas flow at 70 ºC and for five hours.

[Formed Block Polymer (BP)]

CH3 CH3 CH3 CH3 CH3 OCCH2CH2 C CH2C n C CH2CH2CONHCH2CH2CH2Si OSi m CH2CH2CH2NH CN COOCH3 CN CH3 CH3 I A-B type

ABA type Methyl polymethacrylate segment Polydimethylsiloxane segment

(AB) n type n Formed Block Polymer – Molecular Weight Data Mn Mw Mw/Mn Content of polydimethylsiloxane segment in BP 80,700 149,000 1.85 31 % Conceptual Drawing

23 Azo Polymerization Initiators Azo Polymerization Initiators 24 07 Detailed Explanations 6. Macro Azo Initiator Detailed Explanations 6. Macro Azo Initiator 07 What is a Macro Azo Initiator? 6. Macro Azo Initiator (MAI : Macro Azo Initiator) Macro Azo Initiator (MAI) is a unique azo compound which gives block polymer easily through a polymerization with different vinyl 4,4-Azobis(4-cyanovaleric acid),polymer with alpha, omega-bis(3-aminopropyl)polydimethylsiloxane monomers. MAI has a structure in which polymer segment and azo group are repeatedly bonded, and there are several radical VPS-1001 VPS-1001N forming points in a molecule. Therefore, when monomers are polymerized, polymers with high blocking efficiency can be designed.

CH3 CH3 Since this product is soluble in different solvents, various polymerization methods (solution polymerization, suspension polymeriza- CH3 CH3

N=N

[Formed Block Polymer (BP)]

CH3 CH3 CH3 CH3 CH3 OCCH2CH2 C CH2C n C CH2CH2CONHCH2CH2CH2Si OSi m CH2CH2CH2NH CN COOCH3 CN CH3 CH3 I A-B type

ABA type Methyl polymethacrylate segment Polydimethylsiloxane segment

(AB) n type n Formed Block Polymer – Molecular Weight Data Mn Mw Mw/Mn Content of polydimethylsiloxane segment in BP 80,700 149,000 1.85 31 % Conceptual Drawing

23 Azo Polymerization Initiators Azo Polymerization Initiators 24 07 Detailed Explanations 6. Macro Azo Initiator Detailed Explanations 6. Macro Azo Initiator 07 ■ Reference Data on Polymerization

VPE-0201 4,4’-Azobis(4-cyanopentanoicacid)·Polyethyleneglycolpolymer Change of Polymerization Ratio in Solution Polymerization

CH3 CH3

OCH2CH2C N N CH2CH2COO CH2CH2O m 100 CN CN n 90 80 [Polymerization conditions] Characteristics: 70 VPE-0201 : 12.5 g 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 60 MMA : 100 g polyethylene oxide segments are combined by the intermediary of azo group. When used for polymerization of vinyl monomers, this product forms a block 50 polymer with a structure in which polyethylene oxide and vinyl polymers are chemically bonded, therefore the properties of polyethylene oxide (hydrophilicity 40 Toluene : 260 g of polymer, prevention of static charge, improvement of dispersity, addition of compatibility, prevention of dulling, etc.) are possibly reflected to the material. 30 Polymerization temperature : 70 ºC Polymerization ratio (%) 20 ●VPE-0201+MMA 10 Applicable Laws and Regulations 0 Emulsion Suspension Solution 0 1 2 3 4 5 6 7 8 Item Polymerization time (h) polymerization polymerization polymerization TSCA Not Listed EINECS Not Listed Figure 2: Change of Polymerization Ratio in Solution Polymerization

Forms and molecular weight of different types Item

Molecular formula [C12H14N4O3(C2H4O)m]n CAS No. 105744-24-9 Form white, powder Molecular weight of macro initiator (Mn) Approximately 15,000 to 30, 000 Packaging and Storage Requirements Control of Polydimethylsiloxane Amount Introduced to Block Polymer Molecular weight of polyethylene oxide Approximately 2,000 Item Approximately 0.45 mmol/g 500 g Molecular number of azo group per 1 g of VPE Packaging 70 (1/14 of AIBN) 5 kg [Polymerization conditions] 10-hour half life temperature 65 - 70 ºC Storage requirement Please keep at 10 ºC or less. 60 Initiator : VPS-1001 *Compared with mol number of azo group per 1 g of AIBN (M.W.: 164.21) = 6 mmol/g. 50 Monomer : MMA 40 Solvent : Toluene

30 Example of polymerization Charged ratio : (Initiator + Monomer)/Solvent = 1/2 20 Polymerization temperature : 70 ºC In a four necked flask equipped with a thermometer, nitrogen gas induction tube, mixer, and reflux condenser, 10 Polymerization time : 8 hours Content of polydimethylsiloxane (%) 20 g of VPE-0201, 80 g of methyl methacrylate (MMA) or styrene as monomer, and 300 g of toluene as solvent 0 Purification by crystallization with methanol are charged and polymerized under the nitrogen gas flow at 80 ºC and for eight hours. 0 10 20 30 40 50 60 70 Charged ratio of VPS-1001 (%)

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

CH3 CH3 CH3

OCCH2CH2 C CH2C C CH2CH2COO CH2CH2O n m CN COOCH3 CN I *Cautions at the time of Block Polymer Structure Design

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

Formed Block Polymer – Molecular Weight Data However, when compared with general low monocular azo polymerization initiator, the number of azo group per unit weight Monomer Mn Mw Mw/Mn Content of polyethylene oxide segment in BP 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 MMA 53,200 77,800 1.46 21 % of VPS-1001 is generally to be set to 10 to around 70 % of the block polymer ingredients (polymer azo initiator + monomer). Styrene 61,200 160,200 2.62 21 %

25 Azo Polymerization Initiators Azo Polymerization Initiators 26 07 Detailed Explanations 6. Macro Azo Initiator Detailed Explanations 6. Macro Azo Initiator 07 ■ Reference Data on Polymerization

VPE-0201 4,4’-Azobis(4-cyanopentanoicacid)·Polyethyleneglycolpolymer Change of Polymerization Ratio in Solution Polymerization

CH3 CH3

Forms and molecular weight of different types Item

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

CH3 CH3 CH3

OCCH2CH2 C CH2C C CH2CH2COO CH2CH2O n m CN COOCH3 CN I *Cautions at the time of Block Polymer Structure Design

25 Azo Polymerization Initiators Azo Polymerization Initiators 26 08 Product List Product List 08 Product List Product List

■Azo Polymerization Initiators Azo Nitriles Azo Amides Oil-soluble type Oil-soluble type V-70 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile) VAm-110 2,2'-Azobis(N -butyl-2-methylpropionamide) CAS No. 15545-97-8 100 g OCH3 CH3 CH3 OCH3 CAS No. 195520-32-2 500 g O CH3 CH3 O 25 kg CH3 C CH2 C N N C CH2 C CH3 5 kg C C N N C C

CH3 CN CN CH3 CH3CH2CH2CH2NH CH3 CH3 NHCH2CH2CH2CH3 Water-soluble type V-65 2,2'-Azobis(2,4-dimethylvaleronitrile) VA-086 2,2'-Azobis[2-methyl-N -(2-hydroxyethyl)propionamide] 500 g CAS No. 4419-11-8 CAS No. 61551-69-7 500 g O CH3 CH3 O 25 kg CH3 CH3 CH3 CH3 5 kg C C N N C C CH CH C N N C CH CH HOCH CH NH CH CH NHCH CH OH V-65HP (Metal-content-control-grade products) 2 2 2 2 3 3 2 2 500 g CH3 CN CN CH3 10 kg Azo Imidazolines Water-soluble type VA-044 2,2’-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride AIBN 2,2'-Azobis(isobutyronitrile) 500 g CAS No. 27776-21-2 N CH3 CH3 N CAS No. 78-67-1 20 kg 20 kg C C N N C C • 2HCl CH3 CH3 (4×5 kg) (Metal-content-control-grade products) N CH CH N AIBN-HP CH3 C N N C CH3 H 3 3 H 500 g CN CN 10 kg VA-061 2,2-Azobis[2-(2-imidazolin-2-yl)propane]’ CH CH V-59 2,2'-Azobis(2-methylbutyronitrile) CAS No. 20858-12-2 500 g N 3 3 N C C N N C C CH CH 5 kg CAS No. 13472-08-7 500 g 3 3 N N CH3 CH3 10 kg CH3CH2 C N N C CH2CH3 H H 25 kg CN CN Azo Amidines Water-soluble type V-40 1,1'-Azobis(cyclohexane-1-carbonitrile) VA-057 2,2'-Azobis[N -(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate CAS No. 2094-98-6 500 g CAS No. 1041483-94-6 500 g NH CH3 CH3 NH • 4H O 20 kg 2 (n-hydrate) 5 kg C C N N C C N N HOOCCH2CH2NH CH3 CH3 NHCH2CH2COOH NC CN Water-soluble type V-50 2,2'-Azobis(2-methylpropionamidine)dihydrochloride CAS No. 2997-92-4 500 g V-501 4,4'-Azobis(4-cyanovaleric acid) NH CH3 CH3 NH 5 kg CH3 CH3 C C N N C C • 2HCl CAS No. 2638-94-0 500 g 20 kg 10 kg HOOCH2CH2C C N N C CH2CH2COOH (4×5 kg) NH2 CH3 CH3 NH2 CN CN Macro Azo Initiators Azo Esters Oil-soluble type 4,4-Azobis(4-cyanovalericacid),polymer withalpha,omegabis(3-aminopropyl)polydimethylsiloxane Oil-soluble type VPS-1001 500 g V-601 Dimethyl 2,2'-azobis(2-methylpropionate) CAS No. 158947-07-0 CH3 CH3 CH3 CH3 5 kg OCCH2CH2 C N N C CH2CH2CONHCH2CH2CH2Si(OSi)m CH 2CH2CH2NH CAS No. 2589-57-3 500 g CH3 CH3 CN CN CH3 CH3 n 10 kg H3C C N N C CH3 VPS-1001N Net5 kg COOCH3 COOCH3 V-601HP (Metal-content-control-grade products) Water-soluble type 500 g VPE-0201 4,4’-Azobis(4-cyanopentanoicacid) • Polyethyleneglycolpolymer 10 kg CAS No. 105744-24-9 500 g CH3 CH3 5 kg OCCH CH C N N C CH CH COO(CH CH O) 2 2 2 2 2 2 m CN CN n

27 Azo Polymerization Initiators Azo Polymerization Initiators 28 08 Product List Product List 08 Product List Product List

27 Azo Polymerization Initiators Azo Polymerization Initiators 28 09 List of Related Items List of Related Items 09 List of Related Items List of Related Items

■Polymerization Inhibitors ■Photo Cationic Initiators (WPI Series) Q-1300 Ammonium N -nitrosophenylhydroxylamine WPI-113 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium hexafluorophosphate NO CAS No. 135-20-6 032-04902 25g reagent product CAS No. 477602-76-9 932-11706 100g H2n+1 Cn CnH2n+1 872-40408 500g N

874-40402 5kg ONH4 PF6 n =10 to 13 Q-1301 N -Nitrosophenylhydroxylamine aluminium salt WPI-116 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium hexafluoroantimonate 143-04562 25g reagent product 930-12606 10g CAS No. 15305-07-4 NO CAS No. 71786-70-4 H2n+1 Cn CnH2n+1 872-40501 1kg N Al

O = 870-40502 5kg 3 SbF6 n 10 to 13 TBHQ 2-tert-Butylhydroquinone WPI-169 Bis (4-tert-butylphenyl) iodonium bis (perfluorobutansulfonyl) imide OH CAS No. 1948-33-0 027-07212 25g reagent product CAS No. 524067-97-8 865-26310 100g

021-07215 500g reagent product SO2 C4F9 N

905-41706 15kg OH SO2 C4F9 p-Benzoquinone WPI-170 Bis (4-tert-butylphenyl) iodonium hexafluorophosphate O CAS No. 106-51-4 171-00242 25g reagent product CAS No. 61358-25-6 937-40809 5g 175-00245 500g reagent product O PF6 Hydroquinone WPI-124 (50 % Propylene carbonate solution) Bis[4-n-alkyl (C10 to 13) phenyl]iodonium tetrakispentafluorophenylborate CAS No. 123-31-9 085-01212 25g reagent product OH

H2n+1 Cn CnH2n+1 089-01215 500g reagent product HO CAS No. 210290-42-9 934-12506 10g n=10 to 13 932-12507 100g F F p-Methoxyphenol B F

F F 4 CAS No. 150-76-5 084-01282 25g reagent product OH 088-01285 500g reagent product H CO 3 ■Photo Base Generators (WPBG Series) Resin Modifiers WPBG-015 9-Anthrylmethyl Piperidine-1-carboxylate ■ O CAS No. 1228312-02-4 359-33631 1g reagent product TRIAM -100 4-Ally-2,6-di-tert-butylphenol O N OH 355-33633 5g reagent product CAS No. 13677-69-5 741-10436 100g WPBG-018 9-Anthrylmethyl N,N-diethylcarbamate CH2CH CH2 Diethyleneglycol diallyl ether O TRIAM -501 CAS No. 1228312-05-7 356-33641 1g reagent product O NEt C2H4OCH2CH CH2 2 CAS No. 57947-82-7 902-11600 500g O 352-33643 5g reagent product

C2H4OCH2CH CH2 TRIAM -507 N ,N ' -Methylenebis(acrylamide) WPBG-041 9-Anthrylmethyl N-cyclohexylcarbamate CAS No. 501003-75-4 353-33651 1g reagent product O CAS No. 110-26-9 904-41411 1kg O N CH CHCONH CH NHCOCH CH H 902-41412 5kg 2 2 2 359-33653 5g reagent product Diallyl chlorendate TRIAM -605 9-Anthrylmethyl N,N-dicyclohexylcarbamate Cl WPBG-172 CAS No. 3232-62-0 904-40534 20kg Cl O Cl COOCH2CH CH2 350-33661 1g reagent product Cl CAS No. 1421440-13-2 COOCH2CH CH2 O N Cl 356-33663 5g reagent product Cl TRIAM -705 Triallyl trimellitate COOCH CH CH 909-40246 500g 2 2 WPBG-174 1-(Anthraquinon-2-yl)ethyl N-cyclohexylcarbamate CAS No. 2694-54-4 COOCH2CH CH2 903-40244 20kg O CH3 O CAS No. 1421440-15-4 351-33691 1g reagent product O N H COOCH2CH CH2 357-33693 5g reagent product O TRIAM -805 Tetraallyl pyromellitate CH CHCH OOC COOCH CH CH CAS No. 13360-98-0 863-43710 500g 2 2 2 2 WPBG-166 1-(Anthraquinon-2-yl)ethyl N,N-dicyclohexylcarbamate 868-43726 3kg CH2 CHCH2OOC COOCH2CH CH2 O CH O CAS No. 1421440-01-8 354-33681 1g reagent product 3 Accelerator A N ,N -Bis(2-hydroxypropyl)-p-toluidine O N 350-33683 5g reagent product OH CAS No. 38668-48-3 715-10333 10kg O CH3 N(CH2CHCH3)2 WPBG-140 1-(Anthraquinon-2-yl)ethyl imidazole-1-carboxylate N-[Tris(3-acrylamidopropoxymethyl)methyl]acrylamide O CH3 O CAS No. 1418139-51-1 357-33671 1g reagent product O O N H H N CAS No. 1393329-90-2 201-20051 5g reagent product O (CH2)3 N C C CH2 353-33673 5g reagent product O CH O O H H 2 H H 209-20052 25g reagent product H2C C C N C CH2 O (CH2)3 N C C CH2 CH O 2 H H O (CH2)3 N C C CH2 29 Azo Polymerization Initiators Azo Polymerization Initiators 30 09 List of Related Items List of Related Items 09 List of Related Items List of Related Items

021-07215 500g reagent product SO2 C4F9 N

H2n+1 Cn CnH2n+1 089-01215 500g reagent product HO CAS No. 210290-42-9 934-12506 10g n=10 to 13 932-12507 100g F F p-Methoxyphenol B F

■Photo Base Generators (WPBG Series)-related Reagents WPBG-158 (2-Nitrophenyl)methyl 4-hydroxypiperidine-1-carboxylate Silicic Acid Ester O CAS No. 1418139-52-2 358-33721 1g reagent product Tetraethyl Orthosilicate 354-33723 5g reagent product O N Si(OEt) CAS No. 78-10-4 053-03476 500㎖ reagent product 4 NO OH 2 Methyltrimethoxysilane WPBG-165 (2-Nitrophenyl)methyl 4-(methacryloyloxy)piperidine-1-carboxylate CAS No. 1185-55-3 305-60101 100g reagent product Me Si ( OMe)3 O CAS No. 1292812-05-5 355-33731 1g reagent product (3-Mercaptopropyl)trimethoxysilane CH 351-33733 5g reagent product O N 3 CAS No. 4420-74-0 505-62302 25g reagent product HS Si ( OMe)3 NO O O 2 3-Glycidoxypropyltrimethoxysilane

o Si ( OMe) WPBG-025 (E)-N-Cyclohexyl-3-(2-hydroxyphenyl)acrylamide CAS No. 2530-83-8 302-60432 25g reagent product o 3 O CAS No. 224432-97-7 354-33701 1g reagent product [2-(3,4-Epoxycyclohexyl)ethyl]trimethoxysilane 350-33703 5g reagent product N H CAS No. 3388-04-3 321-91252 25g reagent product o OH 329-91253 100g reagent product Si ( OMe)3

WPBG-027 (E)-1-Piperidino-3-(2-hydroxyphenyl)-2-propen-1-one 3-(Triethoxysilyl)propyl Isocyanate O 324-91242 25g reagent product OCN Si ( OEt)3 CAS No. 1203424-93-4 351-33711 1g reagent product CAS No. 24801-88-5 357-33713 5g reagent product N 322-91243 100g reagent product OH Crosslinking Agents 2,4,6-Tris(allyloxy)-1,3,5-triazine WPBG-168 Cyclohexylammonium 2-(3-benzoylphenyl)propionate CAS No. 101-37-1 201-02292 25g reagent product o 359-33751 1g reagent product O CH3 CAS No. 81928-83-8 205-02295 500g reagent product N N CO 355-33753 5g reagent product 2 o N o H3N Trimethylolpropane Tris(mercaptoacetate) HS o SH WPBG-167 Dicyclohexylammonium 2-(3-benzoylphenyl)propionate CAS No. 10193-96-1 327-21642 25g reagent product o o o O CH 321-21645 500g reagent product CAS No. 24021-57-6 356-33761 1g reagent product 3 o CH3 HS 352-33763 5g reagent product CO2 H2N o Pentaerythritol Tetrakis(mercaptoacetate) HS CAS No. 10193-99-4 326-21612 25g reagent product o SH o o WPBG-082 Guanidinium 2-(3-benzoylphenyl)propionate 320-21615 500g reagent product o o o O CH3 o CAS No. 1418139-48-6 352-33741 1g reagent product HS o SH NH2 358-33743 5g reagent product CO2 Pentaerythritol Tetrakis(3-mercaptopropionate) H2N NH2 HS CAS No. 7575-23-7 329-21722 25g reagent product HS o o 323-21725 500g reagent product o o 1,2-Diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propipnate WPBG-266 o o o SH O CH3 o CAS No. 1632211-89-2 932-12306 5g SH N 3,4-Epoxycyclohexylmethyl 3',4'-Epoxycyclohexanecarboxylate CO2 HN o N N NH CAS No. 2386-87-0 326-64072 25g reagent product o 320-64075 500g reagent product o o WPBG-300 1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate Methyl-5-norbornene-2,3-dicarboxylic Anhydride CAS No. 1801263-71-7 938-12406 5g CAS No. 25134-21-8 134-05951 200g reagent product o 136-05955 500g reagent product o N HN H3C o B N N NH Photosensitizers 2-Isopropylthioxanthone CAS No. 5495-84-1 352-28932 25g reagent product o CH3 WPBG-345 (Z)-{[Bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate 350-28933 100g reagent product CH3 F S Vitamin K1 H3C N HN 221-00371 1g reagent product o F H C CAS No. 84-80-0 3 CH3 B N N NH 227-00373 5g reagent product 3

F o Azo Polymerization Initiators Azo Polymerization Initiators 31 F 32 09 List of Related Items List of Related Items 09 List of Related Items List of Related Items

F o Azo Polymerization Initiators Azo Polymerization Initiators 31 F 32 10 List of Applicable Laws List of Applicable Laws 10 List of Applicable Law

Azo Compounds CAS No. TSCA EINECS

V-70 15545-97-8 Listed Listed

V-65 4419-11-8 Listed Listed

AIBN 78-67-1 Listed Listed

Azo Nitriles V-59 13472-08-7 Listed Listed

V-40 2094-98-6 Listed Listed

V-501 2638-94-0 Listed Listed

V-601 2589-57-3 Listed* Listed Azo Esters

VA-086 61551-69-7 Listed Listed

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

VA-044 27776-21-2 Listed Listed

VA-061 20858-12-2 Listed Listed Azo Imidazolines

V-50 2997-92-4 Listed Listed

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

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

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

Macro Azo Initiators VPE-0201 105744-24-9 Not Listed Not Listed

*Listed under 5e Consent Order

33 Azo Polymerization Initiators Azo Polymerization Initiators 34 10 List of Applicable Laws List of Applicable Laws 10 List of Applicable Law

Azo Compounds CAS No. TSCA EINECS

V-70 15545-97-8 Listed Listed

V-65 4419-11-8 Listed Listed

AIBN 78-67-1 Listed Listed

Azo Nitriles V-59 13472-08-7 Listed Listed

V-40 2094-98-6 Listed Listed

V-501 2638-94-0 Listed Listed

V-601 2589-57-3 Listed* Listed Azo Esters

VA-086 61551-69-7 Listed Listed

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

VA-044 27776-21-2 Listed Listed

VA-061 20858-12-2 Listed Listed Azo Imidazolines

V-50 2997-92-4 Listed Listed

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

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

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

Macro Azo Initiators VPE-0201 105744-24-9 Not Listed Not Listed

*Listed under 5e Consent Order

33 Azo Polymerization Initiators Azo Polymerization Initiators 34 Azo Polymerization Initiators Comprehensive Catalog

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180401 K2 SI