Method for producing vinyl ether polymer having hydroxyl group on side chain and temperature-responsive polymer mixture

Patent metadata

Field	Value
Publication number	US-10711079-B2
Application number	US-201615780843-A
Country	US
Kind code	B2
Filing date	Dec 14, 2016
Priority date	Dec 21, 2015
Publication date	Jul 14, 2020
Grant date	Jul 14, 2020

Abstract

[Means for solving problem] The present invention relates to a method for producing a vinyl ether polymer having a hydroxyl group on the side chain, characterized in that vinyl ether comprising a hydroxyl group is subjected to radical polymerization by using an oil-soluble azo polymerization initiator, in the presence of a mixed solvent comprising water and an organic solvent selected from alcohol or cyclic ether radical polymerization.

First claim

The invention claimed is:

1. A method for producing a vinyl ether polymer having a hydroxyl group on a side chain, comprising a step of
subjecting a vinyl ether comprising a hydroxyl group to radical polymerization by using an oil-soluble azo polymerization initiator, in the presence of a mixed solvent comprising water and an organic solvent selected from alcohol or cyclic ether, and wherein a monomer conversion rate is 95% or more.

2. The method for producing a vinyl ether polymer according to claim 1 , wherein
the vinyl ether comprising a hydroxyl group is one or two or more kinds of vinyl ether represented by the following formula (1):
H 2 C═CH—O—(R 1 O) n —H  (1)

wherein R 1 represents an aliphatic hydrocarbon group having 1 to 10 carbons or a group removed of n+1 hydrogen atoms from straight-chain, branched-chain or cyclic ether having 3 to 7 carbons, wherein n is 1 to 5.

3. The method for producing a vinyl ether polymer according to claim 1 , wherein
the vinyl ether comprising a hydroxyl group is one or two or more kinds of vinyl ether selected from the group consisting of 2-hydroxyl ethyl vinyl ether, 3-hydroxyl propyl vinyl ether, 4-hydroxyl butyl vinyl ether, and diethylene glycol vinyl ether.

4. The method for producing a vinyl ether polymer according to claim 1 , wherein
the organic solvent is primary alcohol or secondary alcohol having 2 to 12 carbons, or tetrahydrofuran.

5. The method for producing a vinyl ether polymer according to claim 1 , wherein
the oil-soluble azo polymerization initiator is an azo ester compound.

6. The method for producing a vinyl ether polymer according to claim 1 , wherein
the vinyl ether polymer has a number average molecular weight (Mn) within a range from 500 to 10,000.

7. The method for producing a vinyl ether polymer according to claim 1 , wherein
the vinyl ether polymer has a viscosity within a range from 500 to 10,000 mPa·s when measured as 80% by mass polymer solution at 25° C.

8. A temperature-responsive polymer mixture comprising a vinyl ether polymer, the vinyl ether polymer being a polymer of vinyl ether comprising a hydroxyl group, wherein
the temperature-responsive polymer mixture comprises:
(1) a vinyl ether polymer having an oxygen-containing group derived from an organic solvent selected from alcohol or cyclic ether on the polymer chain terminal; and
(2) a vinyl ether polymer having a terminal structure derived from an oil-soluble azo polymerization initiator on the polymer chain terminal.

9. The temperature-responsive polymer mixture according to claim 8 , wherein
the oxygen-containing group derived from an organic solvent is an alcoholic hydroxyl group or cyclic ether, and the terminal structure derived from an oil-soluble azo polymerization initiator is ester.

10. The temperature-responsive polymer mixture according to claim 8 , wherein
the vinyl ether is one or two or more kinds of vinyl ether represented by the following formula (1):
H 2 C═CH—O—(R 1 O) n —H  (1)

wherein R 1 represents an aliphatic hydrocarbon group having 1 to 10 carbons or a group removed of n+1 hydrogen atoms from straight-chain, branched-chain or cyclic ether having 3 to 7 carbons, wherein n is 1 to 5.

11. The temperature-responsive polymer mixture according to claim 8 , wherein
the vinyl ether comprising a hydroxyl group is one or two or more kinds of vinyl ether selected from the group consisting of 2-hydroxyl ethyl vinyl ether, 3-hydroxyl propyl vinyl ether, 4-hydroxyl butyl vinyl ether, and diethylene glycol vinyl ether.

12. The temperature-responsive polymer mixture according to claim 8 , wherein
the organic solvent is primary alcohol or secondary alcohol having 2 to 12 carbons, or tetrahydrofuran.

13. The temperature-responsive polymer mixture according to claim 8 , wherein
the oil-soluble azo polymerization initiator is an azo ester compound.

14. The temperature-responsive polymer mixture according to claim 8 , wherein
a number average molecular weight (Mn) is within a range from 500 to 10,000.

15. The temperature-responsive polymer mixture according to claim 8 , wherein
a viscosity is within the range from 500 to 10,000 mPa·s when measured as 80% by mass polymer solution at 25° C.

16. The temperature-responsive polymer mixture according to claim 10 , wherein
the vinyl ether is one kind of vinyl ether represented by said formula (1), and the difference between the temperature when transmission against light having a wave length of 750 nm reaches 95% and the temperature when said transmission reaches 50% when 1% by mass polymer aqueous solution is heated (ΔT) is less than 7° C.

17. The temperature-responsive polymer mixture according to claim 10 , wherein
the vinyl ether is two or more kinds of vinyl ether represented by said formula (1), and the difference between the temperature when transmission against light having a wave length of 750 nm reaches 95% and the temperature when said transmission reaches 50% when 1% by mass polymer aqueous solution is heated (ΔT) is less than 12° C.

Assignees

• Maruzen Petrochem Co Ltd

Inventors

• Yoshida Norihiro
• Sugihara Shinji

Classifications

• C08F116/12 Primary

  by an ether radical · CPC title

• C08F216/1416 Primary

  Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether · CPC title

• C08F16/26

  Monomers containing oxygen atoms in addition to the ether oxygen · CPC title

• C08L29/10

  Homopolymers or copolymers of unsaturated ethers (C08L35/08 takes precedence) · CPC title

• C08F4/04

  Azo-compounds · CPC title