Chloroprene polymer and production method therefor

Patent metadata

Field	Value
Publication number	US-11254807-B2
Application number	US-201816631594-A
Country	US
Kind code	B2
Filing date	Jul 20, 2018
Priority date	Jul 21, 2017
Publication date	Feb 22, 2022
Grant date	Feb 22, 2022

Abstract

Provided is a chloroprene-based polymer having an industrially applicable sufficient molecular weight and capable of obtaining a vulcanized rubber excellent in durability and fatigue endurance and an adhesive excellent in layer separation resistance. A chloroprene-based polymer having a number average molecular weight Mn of 150000 to 300000 and comprising a functional group of a structure represented by the general formula (1) or (2) below:(wherein in the general formula (1), R1 shows hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group.)

First claim

The invention claimed is:

1. A chloroprene-based polymer having a number average molecular weight Mn of 150000 to 300000, wherein the chloroprene-based polymer is a homopolymer of a chloroprene monomer and further comprises a functional group of a structure represented by the general formula (1) or (2) below:

wherein in the general formula (1), R 1 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group,
wherein the chloroprene-based polymer has a molecular weight distribution Mw/Mn, as a ratio of a weight average molecular weight Mw to the number average molecular weight Mn, of 1.5 to 5.0.

2. The chloroprene-based polymer according to claim 1 , comprising a functional group of a structure represented by the above general formula (1).

3. A method for producing the chloroprene-based polymer according to claim 1 , wherein
a solution (A) in which a chain transfer agent represented by the general formula (3) or (4) below is added to 100 parts by mass of a total monomer to achieve a ratio of an amount of substance of the total monomer to that of the chain transfer agent [M] 0 /[CTA] at a start of polymerization of 5/1 to 500/1 and 500 to 5000 parts by mass of an aqueous solution (B) of 0.1 to 10% by mass of an emulsifier are mixed and emulsified, then, radical polymerization is performed, and 100 to 5000 parts by mass of a chloroprene monomer singly is additionally added when a polymerization ratio reaches 20 to 50%:

wherein in the general formula (3), R 2 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group; and in the general formulas (3) and (4), R 3 —R 5 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted and saturated or unsaturated aromatic carbocycle, a substituted or unsubstituted and saturated or unsaturated aromatic heterocycle, an organometallic species, or any polymer chain.

4. The method for producing the chloroprene-based polymer according to claim 3 , wherein the chain transfer agent represented by the above general formula (3) is added.

5. A composition comprising the chloroprene-based polymer according to claim 1 .

6. An adhesive composition comprising the composition according to claim 5 .

7. A vulcanized rubber comprising the composition according to claim 5 .

8. The vulcanized rubber according to claim 7 , wherein there is no cracking when Demattia flex fatigue test has been run one million times.

9. An antivibration rubber, a belt, a component for an overhead vehicle, an antiseismic rubber, a hose, a wiper, an immersion product, a seal component, boots, a rubberized cloth, a rubber roll, or a sponge product, wherein the vulcanized rubber according to claim 7 is utilized.

10. A latex comprising the chloroprene-based polymer according to claim 1 .

11. A chloroprene-based polymer having a number average molecular weight Mn of 150000 to 300000, wherein the chloroprene-based polymer is a statistical copolymer consisting of a chloroprene monomer and a monomer copolymerizable with the chloroprene monomer and further comprises a functional group of a structure represented by the general formula (1) or (2) below:

wherein in the general formula (1), R 1 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group.

12. The chloroprene-based polymer according to claim 11 , comprising a functional group of a structure represented by the above general formula (1).

13. The chloroprene-based polymer according to claim 11 , wherein a molecular weight distribution Mw/Mn, as a ratio of a weight average molecular weight Mw to the number average molecular weight Mn, is 1.5 to 5.0.

14. The chloroprene-based polymer according to claim 11 , wherein the monomer copolymerizable with the chloroprene monomer is at least one selected from the group consisting of 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, acrylic acid, an acrylate, methacrylic acid, a methacrylate, acrylamide, an unsaturated nitrile, and an aromatic vinyl compound.

15. A method for producing the chloroprene-based polymer according to claim 11 , wherein
a solution (A) in which a chain transfer agent represented by the general formula (3) or (4) below is added to 100 parts by mass of a total monomer to achieve a ratio of an amount of substance of the total monomer to that of the chain transfer agent [M] 0 /[CTA] at a start of polymerization of 5/1 to 500/1 and 500 to 5000 parts by mass of an aqueous solution (B) of 0.1 to 10% by mass of an emulsifier are mixed and emulsified, then, radical polymerization is performed, and 100 to 5000 parts by mass or of a chloroprene monomer and a monomer copolymerizable with the chloroprene monomer are additionally added when a polymerization ratio reaches 20 to 50%:

wherein in the general formula (3), R 2 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group; and in the general formulas (3) and (4), R 3 —R 5 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted and saturated or unsaturated aromatic carbocycle, a substituted or unsubstituted and saturated or unsaturated aromatic heterocycle, an organometallic species, or any polymer chain.

16. The method for producing the chloroprene-based polymer according to claim 15 , wherein the chain transfer agent represented by the above general formula (3) is added.

17. A composition comprising the chloroprene-based polymer according to claim 11 .

18. An adhesive composition comprising the composition according to claim 17 .

19. A vulcanized rubber comprising the composition according to claim 17 .

20. The vulcanized rubber according to claim 19 , wherein there is no cracking when Demattia flex fatigue test has been run one million times.

21. An antivibration rubber, a belt, a component for an overhead vehicle, an antiseismic rubber, a hose, a wiper, an immersion product, a seal component, boots, a rubberized cloth, a rubber roll, or a sponge product, wherein the vulcanized rubber according to claim 19 is used.

22. A latex comprising the chloroprene-based polymer according to claim 11 .

Assignees

• Denka Company Ltd

Inventors

• Ishigaki Yuhei
• Hagiwara Shogo
• Yamagishi Uichiro
• Onuki Suguru
• Fujimoto Kosuke
• NISHINO Wataru

Classifications

• C09J111/02

  Latex · CPC title

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C09J111/00

  Adhesives based on homopolymers or copolymers of chloroprene · CPC title

• C08F36/18 Primary

  containing chlorine · CPC title