Compositions comprising rigid-rod polymers and carbon nanotubes and process for making the same

• US 6,900,264 B2
• Filed: 08/27/2002
• Issued: 05/31/2005
• Est. Priority Date: 08/29/2001
• Status: Expired due to Fees

• Current Assignee: Georgia Tech Research Corporation (University System of Georgia)
• Original Assignee: Georgia Tech Research Corporation (University System of Georgia)
• Inventors: Dang, Thuy D., Kumar, Satish, Arnold, Fred E.
• Primary Examiner(s): WYROZEBSKI LEE, KATARZYNA I
• Application Number:
  US10/228,483
• Publication Number:
  US 20030083421A1
• Time in Patent Office: 1,008 Days
• Field of Search: 524/495, 524/496
• US Class Current: 524/495
• CPC Class Codes: A61K 9/70 Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug hollow drug-filled fibres A61K9/0092
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08F 14/12 1,2- Dichloroethene
• CPC Class Codes: C08F 14/28 Hexafluoropropene
• CPC Class Codes: C08K 3/041 Carbon nanotubes
• CPC Class Codes: C08K 7/24 inorganic
• CPC Class Codes: C08L 79/04 Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: D01F 1/10 Other agents for modifying properties
• CPC Class Codes: D01F 6/74 from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
• CPC Class Codes: F41H 5/0471 Layered armour containing fibre- or fabric-reinforced layers in combination with ceramic layers F41H5/0428, with metal layers F41H5/0457
• CPC Class Codes: F41H 5/0478 Fibre- or fabric-reinforced layers in combination with plastics layers
• CPC Class Codes: Y10S 977/753 with polymeric or organic binder

Abstract

The present invention relates to compositions comprising rigid-rod polymers and carbon nanotubes. The compositions comprise dispersed carbon nanotubes aligned with rigid-rod polymers. The alignment of the nanotubes and polymers can be liquid crystalline. The rigid-rod polymers of this invention include, but are not limited to, polymers and copolymers comprising benzobisazole, pyridobisimidazole and benzamidazobenzo-phenanthroline repeat units. Dispersion of carbon nanotubes is achieved by in-situ polymerization in the presence of the carbon nanotubes, which may be either single-wall or multi-wall or a combination of both. The polymer compositions comprising carbon nanotubes may be spun into fibers or formed into films. The strength of the resulting fibers of the present invention is significantly greater than that of fibers without carbon nanotubes.

Claims

1. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

2. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

3. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

4. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

5. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

6. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

7. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

wherein R is —

CH₃ and R′

is —

CH₃ or R is —

CH₃ and R′

is —

H.

8. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

9. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

10. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

11. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

12. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

13. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

wherein R is —

CH₃ and R′

is —

CH₃ or R is —

CH₃ and R′

is —

H.

14. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

15. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

16. A composition comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

17. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

79. An article comprising the fiber of claim 17.

80. The article of claim 79 wherein the article is selected from the group consisting of vehicle armor, bullet-proof vests, body armor and armor for a structure.

81. The article of claim 79 wherein the article is an element of a ballistic protection system.

18. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

19. A fiber comprisinn a rigid-rod polymer and carbon nanotube,s wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

20. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

21. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

22. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

wherein R is —

CH₃ and R′

is —

CH₃ or R is —

CH₃ and R′

is —

H.

23. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

24. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

25. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

26. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

27. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

28. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

wherein R is —

CH₃ and R′

is —

CH₃ or R is —

CH₃ and R′

is —

H.

29. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

30. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

31. A fiber comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprises a repeat group of the formula

32. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer comprises a benzobisazole polymer comprising a repeat group of the formula

wherein Y is —

O—

, —

S—

or —

NR′

, wherein R′

is selected from the group consisting of —

H, alkyl having 1 to 4 carbon atoms, and an aromatic group having 1 or 2 aromatic rings.

33. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer comprises a para-ordered heterocyclic polymer comprising a repeat group of the formula

wherein Y is —

S—

, —

O—

, or —

NR′

, and wherein R′

is —

H, an alkyl group having 1 to 4 carbon atoms or an aromatic group having 1 or 2 aromatic rings.

34. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer comprises a para-ordered heterocyclic polymer comprising a repeat group of the formula

wherein Y is —

S—

, —

O—

, —

NR′

, n is 1 or 2, R is a hydroxyl group, a sulfo group or an alkyl group having 1 to 4 carbon atoms and R′

is —

H, an alkyl group having 1 to 4 carbon atoms or an aromatic group having 1 or 2 aromatic rings.

35. The film of claim 34 wherein n is 1.

36. The film of claim 35 wherein R is —

HSO₃.

37. The film of claim 35 wherein R is —

CH₃.

38. The film of claim 34 wherein n is 2.

39. The film of claim 38 wherein R is —

CH₃.

40. The film of claim 38 wherein R is —

OH.

41. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

42. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

43. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

44. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

45. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

46. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

47. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

wherein R is —

CH₃ and R′

is —

CH₃ or R is —

CH₃ and R′

is —

H.

48. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

49. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

50. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

51. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

wherein R is —

CH₃ and R′

is —

CH₃ or R is —

CH₃ and R′

is —

H.

52. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

53. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

54. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

55. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

wherein R is —

CH₃ and R′

is —

CH₃ or R is —

CH₃ and R′

is —

H.

56. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

57. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

58. A film comprising a rigid-rod polymer and carbon nanotubes, wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

59. The method for preparing a composite comprising a rigid-rod polymer and a carbon nanotube, comprising polymerizing a rigid-rod polymer in the presence of carbon nanotubes.

60. The method of claim 59 wherein the polymer is a liquid crystalline polymer.

61. The method of claim 59 wherein the polymerizing is by polycondensation.

62. The method of claim 59 wherein the carbon nanotubes are selected from the group consisting of single-wall carbon nanotubes, multi-wall carbon nanotubes and a combination thereof.

63. The method of claim 59 wherein the rigid-rod polymer comprises a benzobisazole polymer comprising a repeat group of the formula

wherein Y is —

O—

, —

S—

or —

NR′

, wherein R′

is selected from the group consisting of —

H, alkyl having 1 to 4 carbon atoms, and an aromatic group having 1 or 2 aromatic rings.

64. The method of claim 59 wherein the rigid-rod polymer comprises a para-ordered heterocyclic polymer comprising a repeat group of the formula

wherein Y is —

S—

, —

O—

, or —

NR′

, and wherein R′

is —

H, an alkyl group having 1 to 4 carbon atoms or an aromatic group having 1 or 2 aromatic rings.

65. The method of claim 59 wherein the rigid-rod polymer comprises a para-ordered heterocyclic polymer comprising a repeat groups of the formula

wherein Y is —

S—

, —

O—

, —

NR′

, n is 1 or 2, R is a hydroxyl group, a sulfo group or an alkyl group having 1 to 4 carbon atoms and R′

is —

H, an alkyl group having 1 to 4 carbon atoms or an aromatic group having 1 or 2 aromatic rings.

66. The method of claim 65 wherein n is 1.

67. The method of claim 66 wherein the R is —

HSO₃.

68. The method of claim 66 wherein R is —

CH₃.

69. The method of claim 65 wherein n is 2.

70. The method of claim 69 wherein R is —

CH₃.

71. The method of claim 69 wherein R is —

OH.

72. The method of claim 59 wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

73. The method of claim 59 wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

74. The method of claim 59 wherein the rigid-rod polymer is a polymer comprising a repeat group of the formula

75. The method of claim 59 further comprising spinning the composite into a fiber.

76. The method of claim 75 wherein the fiber is spun by the dry-jet wet technique.

77. The method of claim 75 further comprising washing and drying the fiber.

78. The method of claim 75 further comprising heat treating the fiber.

82. An article comprising a film, wherein the film comprises a rigid-rod polymer and carbon nanotubes, wherein the article is selected from the group consisting of vehicle armor, bullet-proof vests, body armor and armor for a structure.

83. An article comprising a film, wherein the film comprises a rigid-rod polymer and carbon nanotubes, wherein the article is an element of a ballistic protection system.