Polyglycolic acid and copolymers thereof from C1 feedstocks

Patent metadata

Field	Value
Publication number	US-9303118-B2
Application number	US-201314383681-A
Country	US
Kind code	B2
Filing date	Mar 8, 2013
Priority date	Mar 8, 2012
Publication date	Apr 5, 2016
Grant date	Apr 5, 2016

Abstract

A method of preparing a poly(glycolic acid) (PGA) from the C1 feedstocks carbon monoxide and formaldehyde or its equivalent. By controlling the comonomer feed ratios and the polymerization temperatures, high quality PGA can be prepared. The method is extended to copolymers of PGA where alkylene oxides or cyclic ether comonomers are included into the polymerization mixture with the C1 monomers to yield polyester-ether thermoplastics.

First claim

We claim:

1. A method of preparing a biorenewable polyglycolic acid (PGA) comprising:
providing a pressure of carbon monoxide (CO);
providing a solution of formaldehyde or a formaldehyde equivalent;
mixing the solution with a strong Brønsted acid; and
copolymerizing the CO and the formaldehyde or formaldehyde equivalent at a temperature in excess of 170° C., wherein the Brønsted acid has a pK a of less than −1, wherein the PGA has no readily observable acetal units.

2. The method of claim 1 , wherein the formaldehyde equivalent is paraformaldehyde or trioxane.

3. The method of claim 1 , wherein copolymerizing occurs at a pressure of 800 psi or greater.

4. The method of claim 1 , wherein the strong Brønsted acid is trifluoromethane sulfonic acid (triflic acid) (TfOH).

5. The method of claim 1 , wherein the solvent for the solution is methylene chloride.

6. A method of preparing a biorenewable copolymer of PGA comprising:
providing a pressure of carbon monoxide (CO);
providing a solution of formaldehyde or a formaldehyde equivalent and a cyclic ether;
mixing the solution with a strong Brønsted acid or a Lewis acid; and
polymerizing the formaldehyde or formaldehyde equivalent and the cyclic ether with the CO at a temperature equal to or greater than 100° C., wherein the Brønsted acid has a pK a of less than −1, to form a copolyester-ether.

7. The method of claim 6 , wherein the cyclic ether is an alkylene oxide.

8. The method of claim 7 , wherein the alkylene oxide is ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-octylene oxide, cyclohexene oxide, or 1,2-hexene oxide.

9. A copolymer of PGA, comprising: a copolyester-ether having a plurality of a first repeating unit that are glycolic acid residues; and a plurality of a second repeating unit derived from a cyclic ether randomly incorporated into the copolyester-ether, wherein the first repeating unit comprises at least 95% of the repeating units.

10. The copolymer of claim 9 , wherein the cyclic ether is dioxolane, 1,4-dioxane, or tetrahydrofuran.

11. A method of preparing a biorenewable polyglycolic acid (PGA) comprising:
providing a pressure of carbon monoxide (CO);
providing a solution of formaldehyde or a formaldehyde equivalent in methylene chloride, dichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, or heptane;
mixing the solution with a strong Brøonsted acid; and
copolymerizing the CO and the formaldehyde or formaldehyde equivalent at a temperature in excess of 100° C., wherein the Brønsted acid has a pK a of less than −1, wherein the PGA has no readily observable acetal units.

12. The method of claim 11 , wherein the formaldehyde equivalent is paraformaldehyde or trioxane.

13. The method of claim 11 , wherein copolymerizing occurs at a pressure of 800 psi or greater.

14. The method of claim 11 , wherein the strong Brønsted acid is trifluoromethane sulfonic acid (triflic acid) (TfOH).

15. The method of claim 6 , wherein the cyclic ether is 1,3-dioxolane, 1,4-dioxane, or tetrahydrofuran.

Assignees

• Univ Florida

Inventors

• Gokturk Ersen
• Pemba Alexander G
• Miller Stephen A

Classifications

• C08G63/06 Primary

  derived from hydroxycarboxylic acids · CPC title

• C08G63/87 Primary

  Non-metals or inter-compounds thereof (boron C08G63/84) · CPC title

• C08G63/66

  Polyesters containing oxygen in the form of ether groups (C08G63/42, C08G63/58 take precedence) · CPC title

• C08G67/02

  Copolymers of carbon monoxide and aliphatic unsaturated compounds · CPC title

• C08G63/78

  Preparation processes · CPC title