Preparation of poly(phenylene oxide) asymmetric gas separation membranes

• US 4,944,775 A
• Filed: 07/11/1989
• Issued: 07/31/1990
• Est. Priority Date: 07/11/1989
• Status: Expired due to Term

• Current Assignee: L'Air Liquide SA
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Hayes, Richard A.
• Primary Examiner(s): Spitzer, Robert
• Application Number:
  US07/378,097
• Time in Patent Office: 385 Days
• Field of Search: 55/16, 55/68, 55/158, 55/70, 55/73, 264/176.1, 264/178 F, 264/211.14
• US Class Current: 95/51
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 2323/40 in-situ membrane formation
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 67/0016 Coagulation
• CPC Class Codes: B01D 67/00165 Composition of the coagulation baths
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/5223 Polyphenylene oxide, phenyl ether polymers or polyphenylethers

Abstract

A process for producing integrally-skinned asymmetric poly(phenylene oxide) gas separation membranes is disclosed. The process involves forming a solution of the poly(phenylene oxide) in an aprotic solvent at an elevated temperature, forming a nascent membrane from the solution, partially drying the nascent membrane, followed by coagulating the partially dried nascent membrane in a coagulation bath formed from a non-solvent for the poly(phenylene oxide) which non-solvent is miscible with the aprotic solvent.

Claims

1. A process for preparing an integrally-skinned asymmetric poly(phenylene oxide) gas separation membrane comprising, forming a solution of from 5 to 50 weight percent of film forming molecular weight poly(2,6-dimethylphenylene-1,4-oxide) in a solvent mixture comprising a main constituent of an aprotic solvent at from 50°

C. to 200°

C.,

forming said solution into a nascent membrane,

partially drying said nascent membrane for 0.005 to 10 minutes at 20°

C. to 200°

C., and

precipitating said nascent membrane in a coagulation bath at 0°

C. to 80°

C., said coagulation bath being a non-solvent for the poly(phenylene oxide) while being miscible with the main constituent of the solvent mixture.

2. The process of claim 1 wherein the nascent membrane is dried at from 70°

C. to 125°

C.

3. The process of claim 2 wherein the poly(2,6-dimethylphenylene-1,4 oxide) is dissolved in the aprotic solvent at 70°

C. to 125°

C.

4. The process of claim 3 wherein the aprotic solvent is N-methylpyrrolidone, N,N-dimethylacetamide or mixtures thereof.

5. The process of claim 4 wherein the nascent membrane is dried from 0.05 to 5.0 minutes.

6. The process of claim 5 wherein the coagulation bath consists essentially of a lower alcohol containing from 1 to 10 carbon atoms, a lower ketone containing from 1 to 10 carbon atoms, water or mixtures thereof.

7. The process of claim 6 wherein the coagulation bath consists essentially of water.

8. The process of claim 3 wherein the aprotic solvent is a mixture of an aprotic solvent and an aromatic cosolvent.

9. The process of claim 8 wherein the aprotic solvent component is N-methylpyrrolidone, N,N-dimethylacetamide or mixtures thereof.

10. The process of claim 9 wherein the nascent membrane is dried from 0.05 to 5.0 minutes.

11. The process of claim 10 wherein the coagulation bath consists essentially of a lower alcohol containing from 1 to 10 carbon atoms, a lower ketone containing from 1 to 10 carbon atoms, water or mixtures thereof.

12. The process of claim 11 wherein the coagulation bath consists essentially of water.

13. The process of claim 8 wherein the aromatic cosolvent is toluene, xylene, or mixtures thereof.

14. The process of claim 13 wherein the nascent membrane is dried from 0.05 to 5.0 minutes.

15. The process of claim 14 wherein the coagulation bath consists essentially of a lower alcohol containing from 1 to 10 carbon atoms, a lower ketone containing from 1 to 10 carbon atoms, water or mixtures thereof.

16. The process of claim 15 wherein the coagulation bath consists essentially of water.

17. The process of claim 3 wherein the aprotic solvent is a mixture of an aprotic solvent and a nonsolvent.

18. The process of claim 17 wherein the aprotic solvent component is N-methylpyrrolidone, N,N-dimethylacetamide or mixtures thereof.

19. The process of claim 17 wherein the nonsolvent component is dipropylene glycol.

20. The process of claim 19 wherein the nascent membrane is dried from 0.05 to 5.0 minutes.

21. The process of claim 20 wherein the coagulation bath consists essentially of a lower alcohol containing from 1 to 10 carbon atoms, a lower ketone containing from 1 to 10 carbon atoms, water or mixtures thereof.

22. The process of claim 21 wherein the coagulation bath consists essentially of water.

23. The process of claim 1 wherein the nascent membrane is dried from 0.05 to 5.0 minutes.

24. The process of claim 23 wherein the coagulation bath consists essentially of a lower alcohol containing from 1 to 10 carbon atoms, a lower ketone containing from 1 to 10 carbon atoms, water or mixtures thereof.

25. The process of claim 24 wherein the coagulation bath consists essentially of water.

26. A gas separation membrane prepared by the process of claim 1.

27. A process for separating at least one gas from a gaseous mixture comprising bringing said gaseous mixture into contact with the gas separation membrane of claim 26 under conditions whereby one gas of said gaseous mixture permeates said membrane preferentially to at least one other gas of said mixture.