Highly branched block copolymers

• US 6,172,180 B1
• Filed: 08/25/1998
• Issued: 01/09/2001
• Est. Priority Date: 08/25/1998
• Status: Expired due to Term

• Current Assignee: CB Biomedical, Inc. (Arbios Systems, Inc.)
• Original Assignee: CB Biomedical, Inc. (Arbios Systems, Inc.)
• Inventors: Hancock, Lawrence F., Fagan, Stephen M., Mullon, Claudy J.-P.
• Primary Examiner(s): Moore, Margaret G.
• Application Number:
  US09/140,284
• Time in Patent Office: 868 Days
• Field of Search: 528/391, 528/335, 528/360, 528/310, 528/370, 528/220, 528/421, 528/403, 528/392, 528/393, 528/396, 528/397, 528/373, 528/398, 528/345, 528/328, 526/345, 526/344, 526/341, 526/342, 526/317.1, 526/318.6, 526/310, 526/348, 526/307, 526/307.8, 526/255, 526/250, 526/277, 526/278, 526/287, 526/286, 526/303.1, 525/56, 525/57, 525/58, 525/59, 525/90, 525/92.A, 525/92.B, 525/92.E, 525/92.H, 525/92.J, 525/92.M, 525/88, 525/93, 525/94
• US Class Current: 528/391
• CPC Class Codes: C08G 75/23 Polyethersulfones
• CPC Class Codes: C08G 81/00 Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers involving only carbon-to-carbon unsaturated bond reactions C08F299/00 ; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42
• CPC Class Codes: C08G 83/002 Dendritic macromolecules
• CPC Class Codes: C08G 83/005 Hyperbranched macromolecules
• CPC Class Codes: C08L 71/00 Compositions of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 71/02 Polyalkylene oxides

Abstract

The present invention relates to a block copolymer containing 1-50 first polymer segments and 1-50 second polymer segments. Each first polymer segment has an average mole fraction of monomers possessing a branch point of 0.0001 to 1, whereas each second polymer segment has an average mole fraction of monomers possessing a branch point of 0 to 0.5. The average molecular weights range from 5-2,000 kDa for the first polymer segments, which constitute 5-95% by weight of the block copolymer. The average molecular weights also range from 5-2,000 kDa for the second polymer segments, which constitute 5-95% by weight of the block copolymer. The ratio of the average mole fraction of monomers possessing a branch point of the second polymer segments to that of the first polymer segments is 0 to 0.5. An example of such a copolymer has ethylene oxide or ethylene oxide/propylene oxide as the first polymer segment and polysulfone as the second polymer segment. This block copolymer can further be blended with a bulk polymer.

Claims

1. A block copolymer comprising

1 to 50 first polymer segments, each first polymer segment having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 2,000 kDa;

and

1 to 50 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 to 0.5 and an average molecular weight range of 5 to 2,000 kDa, wherein the first polymer segments are 5 to 95% by weight of the block copolymer, the second polymer segments are 5 to 95% by weight of the block copolymer, the ratio of the average mole fraction of monomers possessing a branch point of the second polymer segments to that of the first polymer segments is 0 to 0.5, and the first polymer segments are more hydrophilic than the second polymer segments;

wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), ethylene oxide/propylene oxide copolymer, poly(acrylic acid), poly(methacrylic acid), poly(acryl amide), poly(vinyl alcohol), poly(vinyl sulfonic acid), poly(styrene sulfonate), poly(vinyl phosphoric acid), poly(ethylene imine), poly(amino acid), or a mixture thereof.

2. The block copolymer of claim 1 comprising 1 to 10 first polymer segments.

3. The block copolymer of claim 1 comprising 1 to 5 first polymer segments.

4. The block copolymer of claim 1 comprising 1 to 2 first polymer segments.

5. The block copolymer of claim 4 wherein at least one of the first polymer segments is terminally located.

6. The block copolymer of claim 1 comprising 1 to 10 second polymer segments.

7. The block copolymer of claim 1 comprising 1 to 5 second polymer segments.

8. The block copolymer of claim 1 comprising 1 to 2 second polymer segments.

9. The block copolymer of claim 8 wherein at least one of the second polymer segments is terminally located.

10. The block copolymer of claim 4 comprising 1 to 2 second polymer segments.

11. The block copolymer of claim 1 which has a molecular weight of 10 to 2,000 kDa.

12. The block copolymer of claim 1 wherein the first polymer segment is an ethylene oxide/propylene oxide copolymer or poly(ethylene oxide) and the second polymer segment is polysulfone.

13. The block copolymer of claim 12 comprising 1-3 first polymer segment, each first polymer segment having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 200 kDa, and

1-3 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 and an average molecular weight range of 20 to 200 kDa, wherein the first polymer segments are 20 to 60% by weight of the block copolymer, the second polymer segments are 40 to 80% by weight of the block copolymer.

14. A solution for preparing a polymer article, the solution comprising 0.5 to 80% by weight of the block copolymer of claim 1, and 20 to 99.5% by weight of a solvent;

wherein the block copolymer molecules are dissolved in the solvent.

15. The solution of claim 14 wherein the block copolymer has a molecular weight of 5 to 1,000 kDa.

16. The solution of claim 14 wherein the block copolymer has a molecular weight of 5 to 500 kDa.

17. The solution of claim 14 wherein the solution comprises 1 to 50% by weight of the block copolymer.

18. The solution of claim 14 wherein the solution comprises 1 to 30% by weight of the block copolymer.

19. The solution of claim 14 further comprising a bulk polymer wherein the second polymer segments are miscible with the bulk polymer.

20. The solution of claim 19 wherein the bulk polymer is polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinylchloride copolymer, poly(vinylidene fluoride), or fluoropolymer.

37. The block copolymer of claim 1 wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), or ethylene oxide/propylene oxide copolymer in which the monomers are linked together via a divalent sulfone group.

38. The block copolymer of claim 37 wherein the divalent sulfone group is a diaryl sulfone group.

39. The block copolymer of claim 38 wherein the second polymer segment is polysulfone or polyethersulfone.

40. The block copolymer of claim 12 wherein the monomers of the first polymer segment are linked together via a diaryl sulfone group.

41. The solution of claim 14 wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), or ethylene oxide/propylene oxide copolymer in which the monomers are linked together via a divalent sulfone group.

42. The solution of claim 41 wherein the divalent sulfone group is a diaryl sulfone group.

43. The article of claim 42 wherein the second polymer segment is polysulfone or polyethersulfone.

64. A solution for preparing a polymer article, the solution comprising 0.5 to 80% by weight of the block copolymer of claim 47, and 20 to 99.5% by weight of a solvent, wherein the block copolymer molecules are dissolved in the solvent.

65. The solution of claim 64 wherein the block copolymer has a molecular weight of 5 to 500 kDa.

66. The solution of claim 64 wherein the solution comprises 1 to 30% by weight of the block copolymer.

67. The solution of claim 64 further comprising a bulk polymer wherein the second polymer segments are miscible with the bulk polymer.

68. The solution of claim 67 wherein the bulk polymer is polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinylchloride copolymer, poly(vinylidene fluoride), or fluoropolymer.

69. The solution of claim 64 wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), or ethylene oxide/propylene oxide copolymer in which the monomers are linked together via a divalent sulfone group.

70. The solution of claim 69 wherein the divalent sulfone group is a diaryl sulfone group.

71. The solution of claim 70 wherein the second polymer segment is polysulfone.

21. An article comprising an aggregate of block copolymer molecules, each of the block copolymer molecules having

1 to 50 first polymer segments, each first polymer segment having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 2,000 kDa;

and

1 to 50 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 to 0.5 and an average molecular weight range of 5 to 2,000 kDa, wherein the first polymer segments are 5 to 95% by weight of the block copolymer, the second polymer segments are 5 to 95% by weight of the block copolymer, the ratio of the average mole fraction of monomers possessing a branch point of the second polymer segment to that of the first polymer segment is 0 to 0.5, and the first polymer segments are more hydrophilic than the second polymer segments;

wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), ethylene oxide/propylene oxide copolymer, poly(acrylic acid), poly(methacrylic acid), poly(acryl amide), poly(vinyl alcohol), poly(vinyl sulfonic acid), poly(styrene sulfonate), poly(vinyl phosphoric acid), poly(ethylene imine), poly(amino acid), or a mixture thereof.

22. The article of claim 21 further comprising a bulk polymer wherein the second polymer segments are miscible with the bulk polymer.

23. The article of claim 22 wherein the bulk polymer is polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinychloride copolymer, poly(vinylidene fluoride), or fluoropolymer.

24. The article of claim 23 wherein the bulk polymer is polysulfone or polyethersulfone and each of the second polymer segment is polysulfone or polyethersulfone.

44. The article of claim 21 wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), or ethylene oxide/propylene oxide copolymer in which the monomers are linked together via a divalent sulfone group.

45. The article of claim 44 wherein the divalent sulfone group is a diaryl sulfone group.

46. The article of claim 45 wherein the second polymer segment is polysulfone or polyethersulfone.

25. A casting solution for preparing a membrane, the casting solution comprising:

2 to 60% by weight of a bulk polymer having one or more polysulfone segments;

0.05 to 80% by weight of a block copolymer having a first polymer segment of poly(ethylene oxide) or ethylene oxide/propylene oxide copolymer having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 200 kDa, and a second polymer segment of polysulfone having an average mole fraction of monomers possessing a branch point of 0 and an average molecular weight range of 20 to 200 kDa; and

20 to 98% by weight of a solvent;

wherein the bulk polymer has a molecular weight of 10 to 2,000 kDa, the block copolymer has a molecular weight of 20 to 150 kDa and contains 0.01 to 95% by weight of the first polymer segment, the ratio of the average mole fraction of monomers possessing a branch point of the second polymer segment to that of the first polymer segment is 0 to 0.5, and the first polymer segments are more hydrophilic than the second polymer segments.

26. The casting solution of claim 25 wherein the bulk polymer is polysulfone.

27. The casting solution of claim 25 wherein the casting solution comprises 5 to 40% by weight of the bulk polymer.

28. The casting solution of claim 25 wherein the casting solution comprises 5 to 30% by weight of the bulk polymer.

29. The casting solution of claim 25 wherein the casting solution comprises 1 to 50% by weight of the block copolymer.

30. The casting solution of claim 25 wherein the casting solution comprises 1 to 30% by weight of the block copolymer.

31. The casting solution of claim 25 wherein the solvent is aprotic and water miscible.

32. The casting solution of claim 25 wherein the solvent is N-methylpyrrolidone, formamide, dimethylformamide, dimethylsulfoxide, dimethylacetylacetamide, or 4-butyrolactone.

33. The casting solution of claim 25 wherein the bulk polymer has a molecular weight of 15 to 1,000 kDa.

34. The casting solution of claim 33 wherein the bulk polymer has a molecular weight of 20 to 750 kDa.

35. The casting solution of claim 25 wherein the block copolymer contains 5 to 70% by weight of the first polymer segment.

36. The casting solution of claim 35 wherein the block copolymer contains 10 to 50% by weight of the first polymer segment.

47. A block copolymer comprising

1 to 50 first polymer segments, each first polymer segment having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 2,000 kDa;

and

1 to 50 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 to 0.5 and an average molecular weight range of 5 to 2.000 kDa, wherein the first polymer segments are 5 to 95% by weight of the block copolymer, the second polymer segments are 5 to 95% by weight of the block copolymer, the ratio of the average mole fraction of monomers possessing a branch point of the second polymer segments to that of the first polymer segments is 0 to 0.5, and the first polymer segments are more hydrophilic than the second polymer segments;

wherein the second polymer segment is polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinychloride copolymer, poly(vinylidene fluoride), fluoropolymer, or a mixture thereof.

48. The block copolymer of claim 47 comprising 1 to 2 first polymer segments.

49. The block copolymer of claim 48 wherein at least one of the first polymer segments is terminally located.

50. The block copolymer of claim 48 comprising 1 to 2 second polymer segments.

51. The block copolymer of claim 50 wherein at least one of the second polymer segments is terminally located.

52. The block copolymer of claim 50 comprising 1 to 2 second polymer segments.

53. The block copolymer of claim 47 which has a molecular weight of 10 to 2,000 kDa.

54. The block copolymer of claim 47 wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), or ethylene oxide/propylene oxide copolymer in which the monomers are linked together via a divalent sulfone group.

55. The block copolymer of claim 54 wherein the divalent sulfone group is a diaryl sulfone group.

56. The block copolymer of claim 55 wherein the second polymer segment is polysulfone.

57. An article comprising an aggregate of block copolymer molecules, each of the block copolymer molecules having

1 to 50 first polymer segments, each first polymer segment having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 2,000 kDa;

and

1 to 50 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 to 0.5 and an average molecular weight range of 5 to 2,000 kDa, wherein the first polymer segments are 5 to 95% by weight of the block copolymer, the second polymer segments are 5 to 95% by weight of the block copolymer, the ratio of the average mole fraction of monomers possessing a branch point of the second polymer segment to that of the first polymer segment is 0 to 0.5, and the first polymer segments are more hydrophilic than the second polymer segments;

wherein the second polymer segment is polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinychloride copolymer, poly(vinylidene fluoride), fluoropolymer, or a mixture thereof.

58. The article of claim 57 further comprising a bulk polymer wherein the second polymer segments are miscible with the bulk polymer.

59. The article of claim 58 wherein the bulk polymer is polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinychloride copolymer, poly(vinylidene fluoride), or fluoropolymer.

60. The article of claim 59 wherein the bulk polymer is polysulfone and each of the second polymer segment is polysulfone.

61. The article of claim 57 wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), or ethylene oxide/propylene oxide copolymer in which the monomers are linked together via a divalent sulfone group.

62. The article of claim 61 wherein the divalent sulfone group is a diaryl sulfone group.

63. The article of claim 62 wherein the second polymer segment is polysulfone.