Microporous products

• US 4,519,909 A
• Filed: 11/23/1979
• Issued: 05/28/1985
• Est. Priority Date: 07/11/1977
• Status: Expired due to Term

• Current Assignee: Akzona Incorporated
• Original Assignee: Akzona Incorporated
• Inventors: Castro, Anthony J.
• Primary Examiner(s): Spear, Frank
• Application Number:
  US06/097,474
• Time in Patent Office: 2,013 Days
• Field of Search: 210/500 M, 210/490, 210/491, 210/500.2, 521/64, 264/41, 264/48, 264/331, 264/319, 264/178 R, 264/28, 264/178 F, 204/180 P, 204/296, 204/301, 429/249, 429/250
• US Class Current: 210/500.27
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: B41N 7/00 Shells for rollers of printing machines
• CPC Class Codes: C08J 2201/052 Inducing phase separation by thermal treatment, e.g. cooling a solution
• CPC Class Codes: C08J 2201/0543 the non-solvent being organic
• CPC Class Codes: C08J 2201/0546 the non-solvent being organic
• CPC Class Codes: C08J 9/28 by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
• CPC Class Codes: C09K 3/149 Antislip compositions

Abstract

Novel microporous polymers in forms ranging from films to blocks and intricate shapes from synthetic thermoplastic polymers, such as, olefinic, condensation, and oxidation polymers, are disclosed. In one embodiment the microporous polymers are characterized by a relatively homogeneous, three-dimensional cellular structure having cells connected by pores of smaller dimension. Also disclosed are microporous polymer products which contain relatively large amounts of functionally useful liquids and behave as solids.

Claims

1. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said pores and said cells being void and said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxidation polymers and blends thereof.

2. The polymer structure of claim 1 wherein said polymer is an olefinic polymer.

3. The polymer structure of claim 2 wherein the ratio of the average cell diameter to the average pore diameter is from about 5:

1 to about 40;

1.

4. The polymer structure of claim 3 wherein the average cell diameter is from about 1 to about 20 microns and the average pore diameter is from about 0.05 to about 10 microns.

5. The polymer structure of claim 4 wherein the average pore size is from about 0.1 to about 1.0 micron.

6. The polymer structure of claim 5 wherein the polymer is a non-acrylic polyoefin.

7. The polymer structure of claim 6 wherein the polymer is selected from the group consisting of low density polyethylene, high density polyethylene, polypropylene, polystyrene, polyvinylchloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers, styrene butadiene copolymers, poly(4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol.

8. The polymer structure of claim 5 wherein the polymer is an acrylic polyolefin.

9. The polymer structure of claim 8 wherein the polymer is selected from the group consisting of polymethyl-methacrylate, polymethyl-acrylate, ethylene-acrylic acid copolymers, and ethylene-acrylic acid metal salt copolymers.

10. The polymer structure of claim 1 wherein the polymer is an oxidation polymer.

11. The polymer structure of claim 10 wherein the ratio of the average cell diameter to the average pore diameter is from about 5:

1 to about 40;

1.

12. The polymer structure of claim 11 wherein the average cell diameter is from about 1 to about 20 microns and the average pore diameter is from about 0.05 to about 10 microns.

13. The polymer structure of claim 12 wherein the average pore diameter is from about 0.1 to about 1.0 micron.

14. The polymer structure of claim 13 wherein the polymer is polyphenylene oxide.

15. The polymer structure of claim 1 wherein said polymer is a condensation polymer.

16. The polymer structure of claim 15 wherein the ratio of the average cell diameter to the average pore diameter is from about 5:

1 to about 40;

1.

17. The polymer structure of claim 16 wherein the average cell diameter is from about 1 to about 20 microns and the average pore diameter is from about 0.05 to about 10 microns.

18. The polymer structure of claim 17 wherein the average pore diameter is from about 0.1 to about 1.0 microns.

19. The polymer structure of claim 18 wherein the polymer is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, Nylon 6, Nylon 11, Nylon 13, Nylon 66, polycarbonates and polysulfone.

20. The polymer structure of claim 1 wherein the polymer is a non-acrylic polyolefin.

21. The polymer structure of claim 1 wherein the polymer is selected from the group consisting of low density polyethylene, high density polyethylene, polypropylene, polystyrene, polyvinylchloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers, styrene butadiene copolymers, poly(4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol.

22. The polymer structure of claim 1 wherein the polymer is an acrylic polyolefin.

23. The polymer structure of claim 1 wherein the polymer is selected from the group consisting of polymethyl-methacrylate, polymethyl-acrylate, ethylene-acrylic acid copolymers, and ethylene-acrylic acid metal salt copolymers.

24. The polymer structure of claim 1 wherein the polymer is polyphenylene oxide.

25. The polymer structure of claim 1 wherein the polymer is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, Nylon 6, Nylon 11, Nylon 13, Nylon 66, polycarbonates and polysulfone.

26. The polymer structures of claim 1 wherein said structure is in the form of a block having a thickness up to about 21/2 inches.

27. The polymer structure of claim 1 wherein said structure has an essentially non-cellular skin.

28. The polymer structure of claim 27 wherein said skin is relatively impervious to the passage of liquid.

29. The polymer structure of claim 1 wherein said structure is in the form of a film.

30. A microporous cellular polymer structure comprising a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxidation polymers, and blends thereof characterized by a C/P ratio of from about 2 to about 200, an S value of from about 1 to about 30, and an average cell size from about 0.5 to about 100 microns.

31. The polymer structure of claim 30 wherein the polymer is selected from the group consisting of low density polyethylene, high density polyethylene, polypropylene, polystyrene, polyvinylchloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, poly(4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol.

32. The polymer structure of claim 30 wherein the polymer is selected from the group consisting of polymethyl-methacrylate, polymethyl-acrylate, ethylene-acrylic acid copolymers, and ethylene-acrylic acid metal salt copolymers.

33. The polymer of claim 30 wherein the polymer is polyphenylene oxide.

34. The polymer structure of claim 30 wherein the polymer is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, Nylon 6, Nylon 11, Nylon 13, Nylon 66, polycarbonates and polysulfone.

35. The polymer structure of claim 30 wherein the C/P ratio is from about 5 to about 40, the S value is from about 2 to about 10, and the average cell size is from about 1 to about 20 microns.

36. A microporous cellular structure comprising a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxidation polymers and blends thereof characterized by a log C/P value of from about 0.2 to about 2.4 and a log S/C value of from about -1.4 to about 1.0.

37. The polymer structure of claim 36 wherein the polymer is selected from the group consisting of low density polyethylene, polypropylene, polystyrene, polyvinylchloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers, styrene butadiene copolymers, poly(4-methyl-pentene-1), polybutylene, polyvinylidene chloride, polyvinyl butyral, chlorinated polyethylene, ethylene-vinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol.

38. The polymer structure of claim 36 wherein the polymer is selected from the group consisting of polymethyl-methacrylate, polymethyl-acrylate, ethylene-acrylic acid copolymers and ethylene-acrylic acid metal salt copolymers.

39. The polymer structure of claim 36 wherein the polymer is polyphenylene oxide.

40. The polymer structure of claim 36 wherein the polymer is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, Nylon 6, Nylon 11, Nylon 13, Nylon 66, polycarbonates and polysulfone.

41. The polymer structure of claim 36 wherein the log C/P value is from about 0.6 to about 2.2 and the log S/C value is from about -0.6 to about 0.4.

42. An isotropic microporous polymer structure comprising a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, oxidation polymers, and blends thereof characterized by an average pore diameter of from about 0.1 to about 5 microns and an S value of from about 1 to about 10.

43. The polymer structure of claim 42 wherein the polymer is selected from the group consisting of low density polyethylene, high density polyethylene, polypropylene, polystyrene, polyvinylchloride, acrylonitrile-butadiene-styrene terpolymers, styrene-acrylonitrile copolymers, styrene butadiene copolymers, poly(4-methyl-pentene-1), polybutylene, polyvinylidene chloride polyvinyl butyral, chlorinated polyethylene, ethylenevinyl acetate copolymers, polyvinyl acetate and polyvinyl alcohol.

44. The polymer structure of claim 42 wherein the polymer is selected from the group consisting of polymethyl-methacrylate, polymethyl-acrylate, ethylene-acrylic acid copolymers, and ethylene-acrylic acid metal salt copolymers.

45. The polymer structure of claim 42 wherein the polymer is polyphenylene oxide.

46. The polymer structure of claim 42 wherein the average pore diameter is from about 0.2 to about 1 micron and the S value is from about 5 to about 10.

47. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid lubricant.

48. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid surfactant.

49. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid slip agent.

50. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid moth repellant.

51. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid pesticide.

52. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid plasticizer.

53. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid medicinal.

54. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid fuel additive.

55. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid polishing agent.

56. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid insect repellant.

57. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid animal repellant.

58. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid fragrance.

59. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid flame retardant.

60. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid antioxidant.

61. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid odor masking agent.

62. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid antifogging agent.

63. A relatively homogeneous, three-dimensional, microporous cellular polymer structure comprising a plurality of substantially spherical cells having an average diameter from about 0.5 to about 100 microns, distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than said microcells, the ratio of the average cell diameter to the average pore diameter being from about 2:

1 to about 200;

1, said polymer being a synthetic thermoplastic polymer selected from the group consisting of olefinic polymers, condensation polymers, oxipolymers and blends thereof, and said cells and pores being at least partially filled with a liquid perfume.