Silicon compound and method for producing same, and use thereof

Patent metadata

Field	Value
Publication number	US-9434794-B2
Application number	US-201314384012-A
Country	US
Kind code	B2
Filing date	Mar 28, 2013
Priority date	Apr 2, 2012
Publication date	Sep 6, 2016
Grant date	Sep 6, 2016

Abstract

A novel silicon compound capable of initiating radical polymerization is provided. The silicon compound is represented by the following general formula (1)

A-Z 1 —S—Z 2 —Si(OR 1 ) n (R 2 ) 3-n   (1)

wherein A is a group capable of initiating radical polymerization, Z 1 and Z 2 are each independently a bivalent group that has at least a carbon atom, R 1 and R 2 are each independently an alkyl group having from 1 to 3 carbon atoms, and n is an integer of 1 to 3. A radical polymerization initiator comprising the silicon compound, and a polymer obtained by radical polymerization of a monomer with the radical polymerization initiator are also provided. Also provided is a complex having a polymer graft chain formed on a solid substance surface with the use of the silicon compound.

First claim

The invention claimed is:

1. A silicon compound represented by the following general formula (1)
A-Z 1 —S—Z 2 —Si(OR 1 ) n (R 2 ) 3-n   (1)

wherein A is represented by the general formula (2)

wherein R 3 , R 4 , and R 5 are each independently a hydrogen atom, a hydrocarbon group, or a halogen atom, and at least one selected from the group consisting of R 3 , R 4 , and R 5 is halogen,
Z 1 and Z 2 are each independently a bivalent group that has at least a carbon atom, R 1 and R 2 are each independently an alkyl group having from 1 to 3 carbon atoms, and n is an integer of 1 to 3.

2. The silicon compound according to claim 1 , wherein A is represented by the following formula (4-1), Z 1 is represented by the following formula (4-2), and Z 2 is represented by the following formula (4-3)

wherein X is halogen, R 7 and R 8 are each independently hydrogen, or an alkyl group having from 1 to 3 carbon atoms, and are not hydrogen at the same time, and wherein a is an integer of 3 to 11, and m is an integer of 1 to 3.

3. A method for producing a silicon compound represented by the following general formula (5),
the method comprising reacting a compound represented by the following general formula (6) with a compound represented by the following general formula (7)

wherein R 1 and R 2 are each independently an alkyl group having from 1 to 3 carbon atoms, R 3 , R 4 , and R 5 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom, and at least one selected from the group consisting of R 3 , R 4 , and R 5 is halogen, and wherein Z 1 , Z 2 , and Z 3 are each independently a bivalent group that has at least a carbon atom, and n is an integer of 1 to 3.

4. The method according to claim 3 ,
wherein the compound represented by the general formula (6) is represented by the following general formula (8), the compound represented by the general formula (7) is represented by the following general formula (9), and the silicon compound represented by the general formula (5) is represented by the following general formula (4)

wherein X is halogen, R 1 and R 2 are each independently an alkyl group having from 1 to 3 carbon atoms, R 7 and R 8 are each independently hydrogen, or an alkyl group having from 1 to 3 carbon atoms, and are not hydrogen at the same time, and wherein a is an integer of 3 to 11, m is an integer of 1 to 3, and n is an integer of 1 to 3.

5. The method according to claim 3 , wherein the compound represented by the general formula (6) and the compound represented by the general formula (7) are reacted with each other by using a radical generating agent as a reaction catalyst.

6. A radical polymerization initiator that comprises the silicon compound of claim 1 .

7. A method for producing a polymer, the method comprising subjecting a monomer to radical polymerization or living radical polymerization with the radical polymerization initiator of claim 6 .

8. A polymer having a terminal alkoxysilyl group and obtained by using the method of claim 7 .

9. The polymer according to claim 8 , wherein the polymer has a polymer chain resulting from living radical polymerization of the monomer, and a structure of the following formula (1-1) at one end of the polymer chain

wherein R 1 and R 2 are each independently an alkyl group having from 1 to 3 carbon atoms, R 4 and R 5 are each independently a hydrogen atom, a hydrocarbon group, or a halogen atom, Z 1 and Z 2 are each independently a bivalent group that has at least a carbon atom, and n is an integer of 1 to 3.

10. A rubber composition comprising the polymer of claim 8 in 0.1 to 100 parts by mass with respect to 100 parts by mass of a rubber component.

11. A method for producing a complex, the method comprising fixing the silicon compound of claim 1 to a surface of a solid substance, and polymerizing a monomer from the fixed silicon compound through living radical polymerization to form a polymer graft chain.

12. The method for producing a complex according to claim 11 , wherein the solid substance is at least one selected from the group consisting of a silica fine particle, a zinc oxide fine particle, a titanium oxide fine particle, and a barium titanate fine particle.

13. The method for producing a complex according to claim 11 , wherein the monomer is at least one selected from the group consisting of a vinyl monomer and a diene monomer.

14. The method for producing a complex according to claim 11 , wherein the amount of the polymer graft chain formed by living radical polymerization of the monomer is 5 to 1,000 parts by mass with respect to 100 parts by mass of the solid substance.

15. A complex obtained by using the method of claim 11 .

16. A molded article that comprises the complex of claim 15 .

17. A method for producing a rubber or plastic reinforcing agent, the method comprising fixing the silicon compound of claim 1 to a surface of a solid substance, and polymerizing a radically polymerizable monomer through living radical polymerization started from the fixed silicon compound at the group capable of initiating radical polymerization.

18. A rubber or plastic reinforcing agent obtained by using the method of claim 17 , wherein the amount of the polymer graft chain on the solid substance surface is 5 to 1,000 parts by mass with respect to 100 parts by mass of the solid substance.

19. The rubber or plastic reinforcing agent according to claim 18 , wherein the solid substance is at least one selected from the group consisting of a silica fine particle, a zinc oxide fine particle, a titanium oxide fine particle, and a barium titanate fine particle.

20. A rubber composition that comprises the reinforcing agent of claim 18 in 1 to 200 parts by mass with respect to 100 parts by mass of a rubber component.

21. A plastic composition that comprises the reinforcing agent of claim 18 in 1 to 200 parts by mass with respect to 100 parts by mass of a plastic component.

Assignees

• Toyo Tire & Rubber Co

Inventors

• Hishikawa Yasuhiro
• Kojima Masaaki
• Morinaga Takashi
• Sato Takaya

Classifications

• C07F7/1892

  by reactions not provided for in C07F7/1876 - C07F7/1888 · CPC title

• C09C1/36

  Compounds of titanium {(C09C1/0009, C09C1/0015, C09C1/0078 take precedence)} · CPC title

• C08L51/04

  grafted on to rubbers · CPC title

• C08L51/10

  grafted on to inorganic materials · CPC title

• C08F4/00

  Polymerisation catalysts · CPC title