BETA-PROPIOLACTONE BASED COPOLYMERS CONTAINING BIOGENIC CARBON, METHODS FOR THEIR PRODUCTION AND USES THEREOF

• US 20190071538A1
• Filed: 11/01/2018
• Published: 03/07/2019
• Est. Priority Date: 12/05/2016
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Sookraj, Sadesh H.
• Granted Patent: US 10,669,373 B2
• Time in Patent Office: Days
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 63/664 derived from hydroxy carboxylic acids
• CPC Class Codes: C08G 63/6882 derived from hydroxy carboxylic acids

Abstract

Provided herein are methods and systems for producing biodegradable beta-propiolactone-based polyester polymers from renewable EO and CO on an industrial scale.

Claims

1. A copolymer comprising beta-propiolactone monomers and at least one co-monomer from the group consisting of other beta-lactones, anyhydrides, or alcohol having at least two hydroxyl groups and wherein the polypropiolactone monomer units are produced by the decyliztion of beta-propiolactone derived from the carbonylation of ethylene oxide with carbon monoxide using ethylene oxide having a bio-content greater than 10% and using carbon monoxide that optionally has a bio-content greater than 10%.

2. The copolymer of claim 1, wherein the ethylene oxide has a bio-content of at least 75% and preferably at least 95% and optionally the carbon monoxide has a bio-content of at least 75% and preferably at least 95%.

3. The copolymer of claim 1, wherein the comonomer has a bio-content.

4. The copolymer of claim 1, wherein the comonomer has a bio-content of at least 50%.

5. The copolymer of claim 1, wherein the copolymer has a bio-content of at least 50% and optionally at least 75%.

6. The copolymer of claim 1, wherein the copolymer is a linear polymer including an anionic nucleophile and cationic chain ends.

7. The copolymer of claim 6, wherein the anionic nucleophile is at least one compound with the formula R^xO⁻

, R^xC(═

O)O⁻

, R^xS⁻

, R^xO(C═

O)O⁻

, R^x(SO²) O⁻

and PR^x₃O⁻

, wherein each R^x is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

8. The copolymer of claim 6, wherein R^xO⁻

, R^x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.

9. The copolymer of claim 8, wherein the anionic nucleophile is a hydroxide, methoxide, and/or ethoxide.

10. The copolymer of claim 6, wherein the anionic nucleophile is a halide.

11. The polymer of claim 6, wherein the anionic nucleophile is at least one compound with the formula CH₂═

CHCO₂—

, CH₃CO₂⁻

, or CF₃CO₂⁻

.

12. The polymer of claim 6, wherein the cation is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Al³⁺ and Na⁺.

13. The copolymer of claim 6, wherein cation is an organic cation.

14. The copolymer of claim 13, wherein the organic cation is selected from the group consisting of quaternary ammonium, imidazolium, bis(triphenylphosphine)iminium and tetraalkyl ammonium.

15. The copolymer of claim 1, wherein the comonomer is derived from a beta lactone.

16. The copolymer of claim 1, wherein the copolymer it is forms at least part of a sanitary product.

17. The copolymer of claim 1, wherein the copolymer is formed into at least part of a structural product.

18. The copolymer of claim 1, wherein the copolymer is a linear polymer.

19. The copolymer of claim 15, wherein the higher beta-lactone are selected from the group consisting of beta-butyrolactone, beta-valerolactone, beta-heptanolactone, beta-tridecanolactone, cis-3,4-dimethyloxetan-2-one, 4-(but-3-en-1-yl)oxetan-2-one, 4-(butoxymethyl)-2-oxetanone, 4-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-2-oxetanone, 4-[(2-propen-1-yloxy)methyl]-2-oxetanone, 4-[(benzoyloxy)methyl]-2-Oxetanone.

20. The copolymer of claim 1, wherein the co-monomer is a cyclic anhydride.

21. The copolymer of claim 20, wherein cyclic anhydride comprises at least one of succinic anhydride and maleic anhydride.

22. The copolymer of claim 1, wherein the comonomer comprises a diol.

23. The copolymer of claim 22, wherein the diol is selected from the group comprising ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, bis(hydroxymethyl)octadecanol, 1,6-hexanediol and combination thereof.

24. A linear copolymer comprising chains of propiolactone monomer units and at least one co-monomer derived from at least one higher beta lactone moiety wherein the higher beta lactone moiety is derived from a beta lactone other than propiolactone and wherein the polypropiolactone monomer units are produced by the decyliztion of beta-propiolactone derived from the carbonylation of ethylene oxide with carbon monoxide using ethylene oxide that has a bio-content of at least 10% and using carbon monoxide that optionally has a bio-content greater than 10%.

25. The copolymer of claim 24, wherein the ethylene oxide has a bio-content of at least 75% and preferably at least 95% and optionally the carbon monoxide has a bio-content of at least 75% and preferably at least 95%.

26. The copolymer of claim 24, wherein the copolymer is formed into at least part of a sanitary product.

27. The copolymer of claim 24, wherein the copolymer is formed into a structural product.