Porous composite membrane and process

• US 5,629,084 A
• Filed: 10/19/1995
• Issued: 05/13/1997
• Est. Priority Date: 07/28/1994
• Status: Expired due to Term

• Current Assignee: EMD Millipore Corporation (Merck & Co., Inc.)
• Original Assignee: Millipore Investment Holdings, Ltd. (Merck & Co., Inc.)
• Inventors: Moya, Wilson
• Primary Examiner(s): McCamish, Marion E.
• Assistant Examiner(s): Cole, Elizabeth M.
• Application Number:
  US08/545,230
• Time in Patent Office: 572 Days
• Field of Search: 428/308.4, 428/315.5, 428/315.7, 428/316.6, 428/315.9
• US Class Current: 428/315.7
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: Y10T 428/249958 Void-containing component is synthetic resin or natural rubbers
• CPC Class Codes: Y10T 428/249978 Voids specified as micro
• CPC Class Codes: Y10T 428/249979 Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
• CPC Class Codes: Y10T 428/24998 Composite has more than two layers
• CPC Class Codes: Y10T 428/249981 Plural void-containing components

Abstract

A composite porous membrane is provided which comprises a porous membrane substrate having an average pore size between 0.01 and 10 microns formed of a first polymer which is coated over its entire surface with a crosslinked second polymer. The second polymer is dissolved in a solvent with a free radical polymerization initiator in the absence of a crosslinking agent. The second polymer is crosslinked in situ and rendered insoluble by mild heating and/or exposure to ultraviolet light.

Claims

1. A composite porous membrane which comprises a porous membrane substrate having an average pore size of between about 0.01 and 10 microns formed of a first polymer, said substrate having directly deposited over its entire surface a self-crosslinked second polymer free of a crosslinking agent and being formed from at least one uncrosslinked, self-crosslinkable polymer and a free radical initiator free of a crosslinking agent, said composite porous membrane having essentially the same porous configuration as said porous membrane substrate.

2. The composite porous membrane of claim 1 wherein said self crosslinked second polymer is derived from a hydrophilic polymer deposited on said substrate from an aqueous solution.

3. The composite porous membrane of any one of claims 1 or 2 wherein said substrate has an average pore size between about 0.05 and 5 microns.

4. The composite porous membrane of any one of claims 1 or 2 wherein said substrate has an average pore size between 0.1 and 1.0 microns.

5. The composite porous membrane of claim 1 in the form of a flat sheet.

6. The composite porous membrane of claim 2 in the form of a flat sheet.

7. The composite porous membrane of claim 1 in the form of a hollow fiber.

8. The composite porous membrane of claim 2 in the form of a hollow fiber.

9. The composite porous membrane of any one of claims 1, 2, 3, 4, 5, 6, 7 or 8 wherein said self crosslinked second polymer is a crosslinked polymer containing hydroxyl groups.

10. The composite porous membrane of claim 9 wherein said self crosslinked second polymer is a crosslinked polyvinyl alcohol.

11. The composite porous membrane of any one of claims 1, 2, 3, 4, 5, 6, 7 or 8 wherein said self crosslinked second polymer is a crosslinked polymer containing nitrogen.

12. The composite porous membrane of claim 11 wherein said self crosslinked second polymer is a crosslinked polyvinylpyrrolidone.

13. The composite porous membrane of claim 11 wherein said self crosslinked second polymer is a crosslinked polyacrylamide.

14. The composite porous membrane of claim 11 wherein said self crosslinked second polymer is a crosslinked polyvinyl amine.

15. The composite porous membrane of any one of claims 1, 2, 3, 4, 5, 6, 7 or 8 wherein said self crosslinked second polymer is a crosslinked polymer containing carboxyl groups.

16. The composite porous membrane of claim 15 wherein said self crosslinked second polymer is a crosslinked polyacrylic acid.

17. The composite porous membrane of claim 15 wherein said self crosslinked second polymer is a crosslinked polymethacrylic acid.

18. The composite porous membrane of any one of claims 1, 2, 3, 4, 5, 6, 7 or 8 wherein said self crosslinked second polymer comprises a crosslinked polymer containing sulfonic acid groups and/or phosphonic acid groups.

19. The composite porous composition of any one of claims 1, 2, 3, 4, 5, 6, 7 or 8 wherein said self crosslinked second polymer includes at least one additional polymerized monomer.

20. The composite porous membrane of claim 19 wherein said monomer comprises a sulfonic acid or a phosphonic acid.

21. The composite porous membrane of claim 19 wherein said monomer is diallyldimethylammonium chloride.

22. The composite porous membrane of claim 19 wherein said monomer is acrylic acid.

23. The composite porous membrane of claim 19 wherein said monomer is methacrylic acid.

24. The composite porous membrane of any of the claims 1, 2, 5, 6, 7, or 8 wherein said first polymer is a halogenated hydrocarbon polymer.

25. The composite porous membrane of claim 24 wherein said first polymer is a fluorinated hydrocarbon polymer.

26. The composite porous membrane of claim 25 wherein said first polymer is a polyvinylidene fluoride polymer.

27. The composite porous membrane of claim 25 wherein said first polymer is a polytetrafluoroethylene polymer.

28. The composite porous membrane of any one of claims 1, 2, 3, 4, 5, 6, 7, or 8 wherein said first polymer is a perfluoroalkoxy resin.

29. The composite porous membrane of claim 24 wherein said first polymer is polyvinyl chloride.

30. The composite porous membrane of any one of claims 1, 2, 5, 6, 7, or 8 wherein said first polymer is a nitrogen containing polymer.

31. The composite porous membrane of claim 30 wherein said first polymer is a polyamide.

32. The composite porous membrane of any of the claims 1, 2, 5, 6, 7 or 8 wherein said first polymer is an olefin polymer.

33. The composite porous membrane of claim 32 wherein said first polymer is polyethylene.

34. The composite porous membrane of claim 32 wherein said first polymer is polypropylene.

35. The composite porous membrane of any of the claims 1, 2, 5, 6, 7 or 8 wherein said first polymer is a polysulfone polymer.

36. The composite porous membrane of claim 35 wherein said first polymer is polyethersulfone.

37. The composition of any one of claims 1, 2, 5, 6, 7 or 8 wherein said polymerization initiator comprises a persulfate.