Durable high strength polymer composites suitable for implant and articles produced therefrom

• US 9,554,900 B2
• Filed: 03/13/2013
• Issued: 01/31/2017
• Est. Priority Date: 04/01/2011
• Status: Active Grant

• Current Assignee: W. L. Gore & Associates (W.L. Gore & Associates)
• Original Assignee: W. L. Gore & Associates (W.L. Gore & Associates)
• Inventors: Bruchman, William C., Gassler, Paul D., Hartman, Cody L., Walsh, Peter J., White, Charles F.
• Primary Examiner(s): Gherbi, Suzette J
• Application Number:
  US13/798,595
• Publication Number:
  US 20130325117A1
• Time in Patent Office: 1,420 Days
• Field of Search: 623 21- 219
• US Class Current: 1/1
• CPC Class Codes: A61F 2/2412 with soft flexible valve members, e.g. tissue valves shaped like natural valves check valves with flexible valve members in general F16K15/14
• CPC Class Codes: A61F 2/2415 Manufacturing methods
• CPC Class Codes: A61F 2/2418 Scaffolds therefor, e.g. support stents
• CPC Class Codes: A61F 2/2472 Devices for testing
• CPC Class Codes: A61F 2220/0075 sutured, ligatured or stitched, retained or tied with a rope, string, thread, wire or cable
• CPC Class Codes: A61F 2230/0054 V-shaped
• CPC Class Codes: A61L 2430/20 for reconstruction of the heart, e.g. heart valves
• CPC Class Codes: A61L 27/26 Mixtures of macromolecular compounds
• CPC Class Codes: A61L 27/48 with macromolecular fillers
• CPC Class Codes: A61L 27/507 for artificial blood vessels apparatus for applying cells on a blood vessel prosthesis A61F2/062
• CPC Class Codes: A61L 27/56 Porous materials, e.g. foams or sponges
• CPC Class Codes: C08L 27/12 containing fluorine atoms
• CPC Class Codes: Y10T 156/10 Methods of surface bonding and/or assembly therefor

Abstract

Thin, biocompatible, high-strength, composite materials are disclosed that are suitable for use in a valve for regulating blood flow direction. In one aspect, the composite material maintains flexibility in high-cycle flexural applications, making it particularly applicable to high-flex implants such as a prosthetic heart valve leaflet. The composite material includes a porous polymer membrane and an elastomer, wherein the elastomer fills substantially all of the pores of the porous polymer membrane.

Claims

1. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, wherein a diameter of a majority of the fibers is less than about 1 μ

m, the space between the fibers defining pores, the elastomer being disposed in substantially all of the pores, wherein the elastomer is a TFE/PMVE copolymer.

2. The valve of claim 1, wherein the composite material further includes a layer of the elastomer.

3. The valve of claim 1, wherein the at least one synthetic polymer membrane is fluoropolymer membrane.

4. The valve of claim 1, wherein the at least one synthetic polymer membrane is porous polyethylene membrane.

5. The valve of claim 4, wherein the porous polyethylene membrane has a matrix tensile strength in at least one direction greater than about 150 MPa.

6. The valve of claim 1, wherein the TFE/PMVE copolymer comprises essentially of between about 40 and 80 weight percent perfluoromethyl vinyl ether and complementally 60 and 20 weight percent tetrafluoroethylene.

7. The valve of claim 1, wherein the leaflet has a thickness of less than about 350 μ

m.

8. The valve of claim 1, wherein the composite material comprises at least one layer of the synthetic polymer membrane.

9. The valve of claim 1, wherein the composite material comprises more than two layers of the synthetic polymer membrane.

10. The valve of claim 9, wherein the leaflet comprises wrapped layers of the composite material, wherein a number of layers of the synthetic polymer membrane is defined by a number of times the composite material is overwrapped.

11. The valve of claim 10, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

12. The valve of claim 10, wherein the leaflet has at least 10 layers and the composite material comprising less than about 50% synthetic polyethylene membrane by weight.

13. The valve of claim 10, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

14. The valve of claim 1, wherein the support structure is selectively diametrically adjustable for endovascular delivery and deployment at a treatment site, wherein the valve is operable to be a prosthetic heart valve.

15. The valve of claim 1, wherein the pores have a pore size that is less than about 5 μ

m.

16. The valve of claim 1, wherein the pores have a pore size that is less than about 1 μ

m.

17. The valve of claim 1, wherein the pores have a pore size that is less than about 0.1 μ

m.

18. The valve of claim 1, wherein the diameter of a majority of the fibers is less than about 0.1 μ

m.

19. The valve of claim 1, wherein the at least one synthetic polymer membrane comprises substantially only of fibers.

20. The valve of claim 1, wherein the composite material comprises elastomer by weight in a range from about 10% to about 90%.

21. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, wherein a diameter of a majority of the fibers is less than about 1 μ

m, the space between the fibers defining pores, the elastomer being disposed in substantially all of the pores,

a cushion member located between at least a portion of the support structure and at least a portion of the leaflet, wherein the cushion member comprises a second composite material with at least one synthetic polymer membrane having a plurality of pores and an elastomer present in substantially all of the pores.

22. The valve of claim 21, wherein the cushion member includes porous polyethylene membrane.

23. The valve of claim 21, wherein the cushion member at least partially covers the at least a portion of the support structure to provide a cushion between the at least a portion of the support structure and the leaflet.

24. The valve of claim 21, wherein the cushion member is wrapped about the at least a portion of the support structure to provide a cushion between the at least a portion of the support structure and the leaflet.

25. The valve of claim 21, wherein the support structure includes a first end and a second end opposite the first end, the second end comprising a plurality of posts extending longitudinally therefrom, wherein the cushion member is wrapped about each post to provide a cushion between the post and a portion of the leaflet coupled to at least a portion of the post.

26. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, wherein a diameter of a majority of the fibers is less than about 1 μ

m, the space between the fibers defining pores, the elastomer being disposed in substantially all of the pores, wherein the composite material comprises at least one layer of the synthetic polymer membrane, wherein the at least one synthetic polymer membrane is expanded fluoropolymer membrane, wherein the elastomer is a TFE/PMVE copolymer, and wherein the valve is operable to be a prosthetic heart valve.

27. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane having a plurality of pores and an elastomer present in substantially all of the pores, the composite material comprising elastomer by weight in a range from about 10% to about 90%.

28. The valve of claim 27, wherein the composite material comprises less than about 70% synthetic polymer membrane by weight.

29. The valve of claim 27, wherein the composite material comprises less than about 60% synthetic polymer membrane by weight.

30. The valve of claim 27, wherein the composite material comprises less than about 50% synthetic polymer membrane by weight.

31. The valve of claim 27, wherein the composite material further includes a layer of an elastomer.

32. The valve of claim 27, wherein the at least one synthetic polymer membrane is fluoropolymer membrane.

33. The valve of claim 27, wherein the synthetic polymer membrane is porous polyethylene membrane.

34. The valve of claim 33, wherein the elastomer is silicone.

35. The valve of claim 33, wherein the porous polyethylene membrane has a matrix tensile strength in at least one direction greater than about 150 MPa.

36. The valve of claim 33, wherein the leaflet has at least 10 layers of porous polyethylene membrane and the composite material comprising less than about 50% synthetic polyethylene membrane by weight.

37. The valve of claim 33, wherein the pores are defined by a fibrous structure comprising fibers that have an average fiber diameter of less than about 1 μ

m.

38. The valve of claim 33, wherein the pores are defined by a fibrous structure comprising fibers that have an average fiber diameter of less than about 0.1 μ

m.

39. The valve of claim 27, wherein the elastomer is a fluoroelastomer.

40. The valve of claim 27, wherein the elastomer is a urethane.

41. The valve of claim 39, wherein the elastomer is a TFE/PMVE copolymer.

42. The valve of claim 41, wherein the TFE/PMVE copolymer consists essentially of between about 40 and 80 weight percent perfluoromethyl vinyl ether and complementally 60 and 20 weight percent tetrafluoroethylene.

43. The valve of claim 27, wherein the leaflet has a thickness of less than about 350 μ

m.

44. The valve of claim 27, wherein the composite material comprises at least one layer of the synthetic polymer membrane.

45. The valve of claim 44, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

46. The valve of claim 27, wherein the composite material comprises more than two layers of the synthetic polymer membrane.

47. The valve of claim 46, wherein the leaflet comprises wrapped layers of the composite material, wherein a number of layers of the synthetic polymer membrane is defined by a number of times the composite material is overwrapped.

48. The valve of claim 27, wherein the pores have a pore size that is less than about 5 μ

m.

49. The valve of claim 27, wherein the pores have a pore size that is less than about 1 μ

m.

50. The valve of claim 27, wherein the pores have a pore size that is less than about 0.10 μ

m.

51. The valve of claim 27, further comprising:

a cushion member located between at least a portion of the support structure and at least a portion of the leaflet, wherein the cushion member comprises a second composite material with at least one synthetic polymer membrane having a plurality of pores and an elastomer present in substantially all of the pores.

52. The valve of claim 51, wherein the cushion member includes porous polyethylene membrane.

53. The valve of claim 52, wherein the cushion member is wrapped generally helically about the at least a portion of the support structure to provide a cushion between the at least a portion of the support structure and the leaflet.

54. The valve of claim 51, wherein the cushion member at least partially covers the at least a portion of the support structure to provide a cushion between the at least a portion of the support structure and the leaflet.

55. The valve of claim 51, wherein the support structure includes a first end and a second end opposite the first end, the second end comprising a plurality of posts extending longitudinally therefrom, wherein the cushion member is wrapped about each post to provide a cushion between the post and a portion of the leaflet coupled to at least a portion of the post.

56. The valve of claim 27, wherein the support structure is selectively diametrically adjustable for endovascular delivery and deployment at a treatment site.

57. The valve of claim 27, wherein the composite material comprises at least one layer of the synthetic polymer membrane, wherein the at least one synthetic polymer membrane is expanded fluoropolymer membrane, and wherein the elastomer is a TFE/PMVE copolymer.

58. The valve of claim 27, wherein the composite material comprises at least one layer of the synthetic polymer membrane, wherein the at least one synthetic polymer membrane is porous polyethylene membrane, and wherein the elastomer is a silicone.

59. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, the space between the fibers defining pores that have a pore size that is less than about 5 μ

m, the elastomer being disposed in substantially all of the pores, wherein the elastomer is a TFE/PMVE copolymer.

60. The valve of claim 59, wherein the composite material further includes a layer of an elastomer.

61. The valve of claim 59, wherein the at least one synthetic polymer membrane is fluoropolymer membrane.

62. The valve of claim 59, wherein the at least one synthetic polymer membrane is porous polyethylene membrane.

63. The valve of claim 62, wherein the porous polyethylene membrane has a matrix tensile strength in at least one direction greater than about 150 MPa.

64. The valve of claim 62, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

65. The valve of claim 59, wherein the TFE/PMVE copolymer comprises essentially of between about 40 and 80 weight percent perfluoromethyl vinyl ether and complementally 60 and 20 weight percent tetrafluoroethylene.

66. The valve of claim 59, wherein the leaflet has a thickness of less than about 350 μ

m.

67. The valve of claim 59, wherein the composite material comprises at least one layer of the synthetic polymer membrane.

68. The valve of claim 67, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

69. The valve of claim 59, wherein the composite material comprises more than two layers of the synthetic polymer membrane.

70. The valve of claim 69, wherein the leaflet comprises wrapped layers of the composite material, wherein a number of layers of the synthetic polymer membrane is defined by a number of times of the composite material is overwrapped.

71. The valve of claim 59, wherein the support structure is selectively diametrically adjustable for endovascular delivery and deployment at a treatment site, wherein the valve is operable to be a prosthetic heart valve.

72. The valve of claim 59, wherein a diameter of a majority of the fibers is less than about 1 μ

m.

73. The valve of claim 59, wherein a diameter of a majority of the fibers is less than about 0.1 μ

m.

74. The valve of claim 59, wherein the pores have a pore size that is less than about 1 μ

m.

75. The valve of claim 59, wherein the pores have a pore size that is less than about 0.10 μ

m.

76. The valve of claim 59, wherein the at least one synthetic polymer membrane comprises substantially only of fibers.

77. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, the space between the fibers defining pores that have a pore size that is less than about 5 μ

m, the elastomer being disposed in substantially all of the pores, wherein the composite material comprises elastomer by weight in a range from about 10% to about 90%.

78. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, the space between the fibers defining pores that have a pore size that is less than about 5 μ

m, the elastomer being disposed in substantially all of the pores, wherein the composite material comprises at least one layer of the synthetic polymer membrane, wherein the leaflet has at least 10 layers of porous polyethylene membrane and the composite material comprising less than about 50% synthetic polyethylene membrane by weight.

79. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, the space between the fibers defining pores that have a pore size that is less than about 5 μ

m, the elastomer being disposed in substantially all of the pores,

a cushion member located between at least a portion of the support structure and at least a portion of the leaflet, wherein the cushion member comprises a second composite material with at least one synthetic polymer membrane having a plurality of pores and an elastomer present in substantially all of the pores.

80. The valve of claim 79, wherein the cushion member includes porous polyethylene membrane.

81. The valve of claim 79, wherein the cushion member at least partially covers the at least a portion of the support structure to provide a cushion between the at least a portion of the support structure and the leaflet.

82. The valve of claim 79, wherein the cushion member is wrapped about the at least a portion of the support structure to provide a cushion between the at least a portion of the support structure and the leaflet.

83. The valve of claim 79, wherein the support structure includes a first end and a second end opposite the first end, the second end comprising a plurality of posts extending longitudinally therefrom, wherein the cushion member is wrapped about each post to provide a cushion between the post and a portion of the leaflet coupled to at least a portion of the post.

84. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, the space between the fibers defining pores that have a pore size that is less than about 5 μ

m, the elastomer being disposed in substantially all of the pores, wherein the composite material comprises at least one layer of the synthetic polymer membrane, wherein the at least one synthetic polymer membrane is expanded fluoropolymer membrane, wherein the elastomer is a TFE/PMVE copolymer, and wherein the valve is operable to be a prosthetic heart valve.

85. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, wherein a diameter of a majority of the fibers is less than about 1 μ

m, the space between the fibers defining pores, the elastomer being present in the pores, further comprising

a cushion member located between at least a portion of the support structure and at least a portion of the leaflet, wherein the cushion member comprises a second composite material with at least one synthetic polymer membrane having a plurality of pores and an elastomer present in the pores.

86. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane having a plurality of pores and an elastomer present in the pores, the composite material comprising elastomer by weight in a range from about 10% to about 90%.

87. The valve of claim 86, further comprising:

a cushion member located between at least a portion of the support structure and at least a portion of the leaflet, wherein the cushion member comprises a second composite material with at least one synthetic polymer membrane having a plurality of pores and an elastomer present in the pores.

88. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising more than two layers of a synthetic polymer membrane and an elastomer, the synthetic polymer membrane comprising fibers that define space therebetween, wherein a diameter of a majority of the fibers is less than about 1 μ

m, the space between the fibers defining pores, the elastomer being disposed in substantially all of the pores, wherein the leaflet comprises overlapping wrappings of the composite material, wherein the layers of the synthetic polymer membrane are defined by a number of overlapping wrappings of the composite material, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

89. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising more than two layers of a synthetic polymer membrane and an elastomer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, wherein a diameter of a majority of the fibers is less than about 1 μ

m, the space between the fibers defining pores, the elastomer being disposed in substantially all of the pores, wherein the leaflet comprises overlapping wrappings of the composite material, wherein the layers of the synthetic polymer membrane are defined by a number of overlapping wrappings of the composite material, wherein the leaflet has at least 10 layers and the composite material comprising less than about 50% synthetic polyethylene membrane by weight.