Method for producing dimethyl polyvinylphosphonate and polyvinylphosphonic acid

Patent metadata

Field	Value
Publication number	US-10087265-B2
Application number	US-201515315588-A
Country	US
Kind code	B2
Filing date	Jun 1, 2015
Priority date	Jun 3, 2014
Publication date	Oct 2, 2018
Grant date	Oct 2, 2018

Abstract

A method for producing poly(dimethyl vinylphosphonate) from a monomer component mainly containing dimethyl vinylphosphonate by anionic polymerization in the presence of an anionic polymerization initiator, the method being characterized in that an aliphatic ether is used as a polymerization solvent, and a method for producing poly(vinylphosphonic acid) characterized in that the poly(dimethyl vinylphosphonate) obtained by the former method is hydrolyzed in the presence of an acid are provided. The methods make it possible to easily produce a poly(dimethyl vinylphosphonate) which has a high molecular weight and in which the molecular weight is controlled, and make it possible to produce a poly(vinylphosphonic acid) which has a high molecular weight and in which the molecular weight is controlled corresponding to the poly(dimethyl vinylphosphonate).

First claim

The invention claimed is:

1. A method for producing poly(dimethyl vinylphosphonate) from a monomer component comprising dimethyl vinylphosphonate and dimethyl phosphite, the method comprising:
performing anionic polymerization of the dimethyl vinylphosphonate in the presence of an anionic polymerization initiator in a polymerization solvent, thereby producing poly(dimethyl vinyl phosphonate),
wherein the polymerization solvent is an aliphatic ether.

2. The method according to claim 1 , wherein the aliphatic ether has 2 to 10 carbon atoms.

3. The method according to claim 1 , wherein an amount of the dimethyl phosphite in the monomer component is in a range of 0.01 to 5% by mass.

4. A method for producing poly(vinylphosphonic acid), comprising: producing poly(dimethyl vinyl phosphonate) by the method claim 1
hydrolyzing the poly(dimethyl vinylphosphonate) in the presence of an acid.

5. The method according to claim 4 , further comprising, prior to the hydrolyzing:
contacting a polymerization liquid obtained by the anionic polymerization with water to extract the poly(dimethyl vinylphosphonate) into an aqueous phase comprising an aqueous solution,
wherein the aqueous solution is used to perform hydrolysis of the poly(dimethyl vinylphosphonate) in the hydrolyzing.

6. The method according to claim 1 , wherein the aliphatic ether comprises at least one selected from the group consisting of diethyl ether, dipropyl ether, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), dibutyl ether, diisoamyl ether, hexyl methyl ether, octyl methyl ether, cyclopenthyl methyl ether (CPME), and dicyclopentyl ether.

7. The method according to claim 1 , wherein the aliphatic ether comprises methyl tert-butyl ether (MTBE).

8. The method according to claim 1 , wherein the anionic polymerization initiator comprises an organic lithium compound, a basic organic metal compound, or both.

9. The method according to claim 1 , wherein the anionic polymerization initiator comprises at least one selected from the group consisting of methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, MeMgBr, EtMgBr, t-BuMgBr, t-BuMgCl, and PhMgBr.

10. The method according to claim 1 , wherein an amount of the dimethyl phosphite in the monomer component is in a range of 0.02 to 4.7% by mass.

11. A method for producing poly(vinylphosphonic acid), comprising: producing poly(diemethyl vinyl phosphonate) by the method of claim 2
hydrolyzing the poly(dimethyl vinylphosphonate) in the presence of an acid.

12. The method according to claim 11 , further comprising, prior to the hydrolyzing:
contacting a polymerization liquid obtained by the anionic polymerization with water to extract the poly(dimethyl vinylphosphonate) into an aqueous phase comprising an aqueous solution,
wherein the aqueous solution is used to perform hydrolysis of the poly(dimethyl vinylphosphonate) in the hydrolyzing.

13. The method according to claim 1 , wherein the anionic polymerization is performed for 0.5 to 24 hours.

14. The method according to claim 4 , wherein the acid comprises at least one selected from the group consisting of sulfuric acid, hydrochloric acid, and phosphoric acid.

15. The method according to claim 1 , wherein the poly(dimethyl vinylphosphonate) has a weight average molecular weight (Mw) of from 60,000 to 200,000.

16. The method according to claim 1 , wherein an amount of the dimethyl phosphite in the monomer component is in a range of 0.04 to 4.3% by mass.

17. A method for controlling a molecular weight of a produced poly(dimethyl vinylphosphonate), comprising:
adjusting an amount of dimethyl phosphite in a monomer component comprising dimethyl vinylphosphonate to a range of 0.01 to 5% by mass in anionic polymerization of the monomer component.

18. The method according to claim 7 , further comprising:
adjusting the temperature to be within a range of 0° C. to 50° C. such that the anionic polymerization is performed at the temperature in the range of 0° C. to 50° C.

19. The method according to claim 17 , wherein the anionic polymerization is performed for 0.5 to 24 hours.

20. The method according to claim 17 , wherein in the adjusting, the amount of the dimethyl phosphite in the monomer component is adjusted to a range of 0.02 to 4.7% by mass.

Assignees

• Maruzen Petrochem Co Ltd

Inventors

• Takahashi Takashi
• Matsushita Keisuke
• Sugiyama Masaki
• Yoshida Norihiro
• Ikawa Eiichi
• Mita Takahito
• Endo Masahiro

Classifications

• C08F8/12

  Hydrolysis · CPC title

• C08F130/02 Primary

  containing phosphorus · CPC title

• C08F2/06

  Organic solvent · CPC title

• C08F2/38

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