Synthesis of free radical polymerizable ethylenically unsaturated poloxamers and poloxamines

Patent metadata

Field	Value
Publication number	US-9309357-B2
Application number	US-201414308229-A
Country	US
Kind code	B2
Filing date	Jun 18, 2014
Priority date	Jun 18, 2013
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

A new synthetic method of forming free radical polymerizable end terminal functionalized poloxamers and poloxamines in commercial scale batches which uses a binary system of inhibitors to eliminate the formation of high molecular weight impurities. It has also been surprisingly discovered that the inorganic impurities formed during the commercial scale synthetic process are removed by the use of resin materials.

First claim

What is claimed is:

1. A method comprising reacting a poloxamer or poloxamine compound with a first methacrylating agent in the presence of a solvent stabilized with a first free radical inhibitor to form a first reaction product, and further reacting the first reaction product with an organic base and a second methacrylating agent stabilized with a second free radical inhibitor to form a second reaction product, wherein the second free radical inhibitor is hydroquinone monomethyl ether (MEHQ), and wherein the first free radical inhibitor is a different compound than the second free radical inhibitor.

2. The method of claim 1 wherein the first and second methacrylating agents are the same.

3. The method of claim 2 wherein the methacrylating agent is methacryloyl chloride.

4. The method of claim 3 wherein the first free radical inhibitor is 2,6 di tert-butyl-4-methyl phenol (BHT).

5. The method of claim 4 wherein the organic base is triethylamine (TEA).

6. The method of claim 1 wherein the first free radical inhibitor is 2,6 ditert-butyl-4-methyl phenol (BHT).

7. The method of claim 1 wherein the organic base is triethylamine (TEA).

8. The method of claim 1 wherein the poloxamer or poloxamine compound is a poloxamer compound, wherein the first reaction product is a monomethacrylated poloxamer compound and wherein the second reaction product is a dimethacrylated poloxamer compound.

9. The method of claim 5 wherein the poloxamer or poloxamine compound is reacted with the first methacrylating agent in the presence of the organic base.

10. The method of claim 1 wherein the poloxamer or poloxamine compound is a poloxamine compound, wherein the first reaction product is a monomethacrylated poloxamine compound and wherein the second reaction product is a polymethacrylated poloxamine compound.

11. The method of claim 10 wherein the first and second methacrylating agents are methacryloyl chloride, and the first free radical inhibitor is 2,6 di tert-butyl-4-methyl phenol (BHT).

12. The method of claim 11 wherein the organic base is triethylamine (TEA).

13. The method of claim 12 wherein the poloxamine compound is reacted with the first methacrylating agent in the presence of the organic base.

14. The method of claim 1 wherein the poloxamer or poloxamine compound is reacted with the first methacrylating agent in the presence of the organic base.

15. A method comprising reacting a monomethacrylated poloxamer or monomethacrylated poloxamine compound with an organic base and a methacrylating agent stabilized with a hydroquinone monomethyl ether (MEHQ) free radical inhibitor to form a dimethacrylated poloxamer compound or a polymethacrylated poloxamine compound.

16. The method of claim 15 , wherein the monomethacrylated poloxamer compound is reacted with an organic base and a methacrylating agent stabilized with a hydroquinone monomethyl ether (MEHQ) free radical inhibitor to form a dimethacrylated poloxamer compound.

17. The method of claim 15 , wherein the monomethacrylated poloxamine compound is reacted with an organic base and a methacrylating agent stabilized with a hydroquinone monomethyl ether (MEHQ) free radical inhibitor to form a polymethacrylated poloxamine compound.

18. A reaction mixture comprising a monomethacrylated poloxamer or monomethacrylated poloxamine compound, an organic base, a methacrylating agent, and a hydroquinone monomethyl ether (MEHQ) free radical inhibitor.

19. The reaction mixture of claim 18 , wherein the monomethacrylated poloxamer or monomethacrylated poloxamine compound comprises a monomethacrylated poloxamer compound.

20. The reaction mixture of claim 18 , wherein the monomethacrylated poloxamer or monomethacrylated poloxamine compound comprises a monomethacrylated poloxamine compound.

Assignees

• Bausch & Lomb

Inventors

• Awasthi Alok Kumar
• Kunzler Jay F
• Satyanarayana Ganugapati
• Rai Nooji Satheesha

Classifications

• C08G65/3322

  acyclic · CPC title

• C08G65/337

  containing other elements (organic compounds containing halogens only as halides of a carboxyl group C08G65/332) · CPC title

• C08G65/48 Primary

  Polymers modified by chemical after-treatment · CPC title

• C08F290/062 Primary

  Polyethers · CPC title

• C08F222/1006

  of polyhydric alcohols or polyhydric phenols · CPC title