Beta-propiolactone based copolymers containing biogenic carbon, methods for their production and uses thereof

• US 10,669,373 B2
• Filed: 11/01/2018
• Issued: 06/02/2020
• 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.
• Primary Examiner(s): Listvoyb, Gregory
• Application Number:
  US16/178,214
• Publication Number:
  US 20190071538A1
• Time in Patent Office: 579 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 comprising (i) anhydride or (ii) alcohol comprising at least two hydroxyl groups,

wherein the copolymer has a bio-content of at least 10%, and

wherein the copolymer is a linear polymer comprising an anionic nucleophile and cationic chain ends.

2. The copolymer of claim 1, wherein the at least one co-monomer has a bio-content.

3. The copolymer of claim 1, wherein the at least one co-monomer has a bio-content of at least 50%.

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

5. The copolymer of claim 1, wherein the anionic nucleophile comprises R^xO⁻

, R^xC(═

O)O⁻

, R^xS⁻

, R^xO(C═

O)O⁻

, R^x(SO₂)O⁻

or PR^x₃O⁻

, or any combination thereof, wherein each R^x is independently hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or and optionally substituted heteroaryl.

6. The copolymer of claim 1, wherein the anionic nucleophile comprises R^xO⁻

, wherein R^x is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and or optionally substituted heteroaryl.

7. The copolymer of claim 1, wherein the anionic nucleophile comprises a hydroxide, methoxide, or ethoxide.

8. The copolymer of claim 1, wherein the anionic nucleophile comprises a halide.

9. The copolymer of claim 1, wherein the anionic nucleophile is CH₂═

CHCO₂⁻

, CH₃CO₂⁻

, or CF₃CO₂.

10. The copolymer of claim 1, wherein the cationic chain ends comprise Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, or Al³⁺.

11. The copolymer of claim 1, wherein the cationic chain ends comprise an organic cation.

12. The copolymer of claim 11, wherein the organic cation comprises quaternary ammonium, imidazolium, bis(triphenylphosphine)iminium or tetraalkyl ammonium.

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

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

15. The copolymer of claim 1, wherein the anhydride is a cyclic anhydride.

16. The copolymer of claim 15, wherein the cyclic anhydride is succinic anhydride, or and maleic anhydride, or both.

17. The copolymer of claim 1, wherein the alcohol comprising at least two hydroxyl groups is a diol.

18. The copolymer of claim 17, wherein the diol is ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, or bis(hydroxymethyl)octadecanol,1,6-hexanediol, or any combination thereof.

19. The copolymer of claim 1, wherein the copolymer has a bio-content of at least 75%.

20. The copolymer of claim 1, wherein the copolymer has a bio-content of at least 95%.

21. The copolymer of claim 1, wherein the beta-propiolactone monomer units are derived from the carbonylation of ethylene oxide with carbon monoxide.

22. The copolymer of claim 21, wherein the ethylene oxide has a bio-content greater than 10%.

23. The copolymer of claim 21, wherein the carbon monoxide has a bio-content greater than 10%.