CATALYSTS AND METHODS FOR POLYESTER PRODUCTION

• US 20150368394A1
• Filed: 06/27/2013
• Published: 12/24/2015
• Est. Priority Date: 06/27/2012
• Status: Abandoned Application

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Allen, Scott D.
• Application Number:
  US14/410,763
• Publication Number:
  US 20150368394A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08G 63/00 Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule polyester-amides C08G69/44; polyester-imides C08G73/16
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 63/82 characterised by the catalyst used
• CPC Class Codes: C08G 63/823 for the preparation of polylactones or polylactides
• CPC Class Codes: C08G 63/826 Metals not provided for in groups C08G63/83 - C08G63/86 C08G63/823 takes precedence

Abstract

Disclosed are polymerization systems and methods for the formation of polyesters from epoxides and carbon monoxide. The inventive polymerization systems feature the combination of metal carbonyl compounds and polymerization initiators and are characterized in that the molar ratios of metal carbonyl compound, polymerization initiators and provided epoxides are present in certain ratios.

Claims

1. A method for the copolymerization of an epoxide and carbon monoxide comprising the steps of:

a) providing an epoxide;

b) contacting the epoxide with carbon monoxide in the presence of a metal carbonyl compound and a polymerization initiator wherein the epoxide is provided in a molar excess relative to the polymerization initiator, and the polymerization initiator is provided in a molar excess relative to the metal carbonyl compound; and

c) producing a polyester product comprising a polymer of formula

2. The method of claim 1, wherein the metal carbonyl compound comprises a hydrido metal carbonyl.

3. The method of claim 2, wherein the hydrido metal carbonyl comprises HCo(CO)₄.

4. The method of claim 1, wherein the polymerization initiator comprises an alcohol.

5. The method of claim 1, wherein the polymerization initiator comprises a carboxylate anion.

6. The method of claim 1, wherein the epoxide comprises ethylene oxide.

7. The method of claim 1, wherein the molar ratio of epoxide to polymerization initiator is greater than 5:

1;

or

wherein the molar ratio of epoxide to polymerization initiator is greater than 10;

1;

or

wherein the molar ratio of epoxide to polymerization initiator is greater than 20;

1;

or

wherein the molar ratio of epoxide to polymerization initiator is greater than 50;

1.

8. The method of claim 1, wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 5:

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 10;

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 20;

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 50;

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 100;

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 200;

1.

9. The method of claim 1, wherein the epoxide is ethylene oxide, the metal carbonyl compound is a cobalt carbonyl compound, the polymerization initiator is selected from the group consisting of:

alcohols, carboxylic acids, carboxylate salts, and a combination of any two or more of these, and

wherein the molar ratio of the epoxide to the polymerization is greater than 10;

1 and the molar ratio of polymerization initiator to cobalt carbonyl compound is greater than 5;

1.

10. The method of claim 1, wherein a yield of polyester product (based on epoxide consumed) is at least 10%;

at least 20%;

at least 30%;

at least 50%, at least 75%, or at least 90%.

11. The method of claim 1, further comprising converting the polyester product to a small molecule product.

12. The method of claim 11, wherein the small molecule product comprises acrylic acid, a substituted alpha beta unsaturated carboxylic acid, an acrylate ester, an acrylamide, or an ester or amide of an alpha beta unsaturated acid.

13. The method of claim 1, further comprising converting the polyester product to a consumer packaging item, a film, a molded plastic article, a plastic component of a consumer product, a fiber or a fabric.

14. A polymerization system for the copolymerization of epoxides and carbon monoxide, the system comprising:

an epoxide, a metal carbonyl compound, and a polymerization initiator, characterized in that the epoxide is present in a molar excess relative to the polymerization initiator and the polymerization initiator is present in a molar excess relative to the metal carbonyl compound.

15. The polymerization system of claim 14, wherein the metal carbonyl compound comprises a hydrido metal carbonyl.

16. The polymerization system of claim 15, wherein the hydrido metal carbonyl comprises HCo(CO)₄.

17. The polymerization system of claim 14, wherein the polymerization initiator comprises an alcohol.

18. The polymerization system of claim 17, wherein the alcohol comprises a diol.

19. The polymerization system of claim 14, wherein the polymerization initiator comprises a carboxylate anion.

20. The polymerization system of claim 14, wherein the epoxide comprises ethylene oxide.

21. The polymerization system of claim 14, wherein the molar ratio of epoxide to polymerization initiator is greater than 5:

1;

or

wherein the molar ratio of epoxide to polymerization initiator is greater than 10;

1;

or

wherein the molar ratio of epoxide to polymerization initiator is greater than 20;

1;

or

wherein the molar ratio of epoxide to polymerization initiator is greater than 50;

1.

22. The polymerization system of claim 14, wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 5:

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 10;

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 20;

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 50;

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 100;

1;

or

wherein the molar ratio of polymerization initiator to metal carbonyl compound is greater than 200;

1.