Polymers for enhanced solubility of nanomaterials, compositions and methods therefor

• US 20060041104A1
• Filed: 08/18/2004
• Published: 02/23/2006
• Est. Priority Date: 08/18/2004
• Status: Active Grant

• Current Assignee: Evermore Applied Materials Corp.
• Original Assignee: Zyvex Corporation
• Inventors: Rutkofsky, Marni Loriel, Ait-Haddou, Hassan
• Granted Patent: US 7,296,576 B2
• Time in Patent Office: Days
• US Class Current: 528/397
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08G 61/02 Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• CPC Class Codes: C08J 2365/00 Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08J2307/00 - C08J2357/00, C08J2361/00 take precedence; Derivatives of such polymers
• CPC Class Codes: C08J 5/005 Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: C08K 3/041 Carbon nanotubes
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 65/00 Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08L7/00 - C08L57/00, C08L61/00 take precedence; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers

Abstract

Poly(aryleneethynylene) polymers, poly(ferrocenylaryleneethynylene) polymers and poly(ferrocenylethynylene) polymers having properties particularly useful for solubilizing nanomaterials and for effecting subsequent re-solubilization of a solid polymer-solubilized nanomaterial, and compositions and methods thereto are provided.

Claims

1. A method of making a rigid poly(aryleneethynylene) polymer, the polymer having at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2, the method comprising:

coupling a para-diethynyl-(R₁-R_x)arylene and an (R₁-R_y)-para-dihaloarylene in the presence of a first polymerization-terminating haloaryl agent,

wherein each R of (R₁-R_x) and (R₁-R_y) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R₁-R_x) and (R₁-R_y) is a functional group for solubilizing nanomaterial, and

wherein x of (R₁-R_x) is the maximum number of substituents on the para-diethynyl-(R₁-R_x)arylene, and y of (R₁-R_y) is the maximum number of substituents on the (R₁-R_y)-para-dihaloarylene,

under conditions and for a period of time to produce fluorescence; and

terminating the coupling by addition of a second polymerization-terminating haloaryl agent, the second haloaryl agent having equal or greater activity for coupling as the (R₁-R_y)-para-dihaloarylene.

2. The method of claim 1 wherein the arylene of the para-diethynyl-(R₁-R_x)arylene and the arylene of the (R₁-R_y)-para-dihaloarylene are the same arylene structure.

5. The method of claim 1 wherein the coupling is carried out at a first temperature for a period of time followed by a second temperature for a period of time, wherein the second temperature is greater than the first temperature.

6. The method of claim 5 wherein the first temperature is about room temperature.

7. The method of claim 6 wherein the coupling at about room temperature is for about 10 min to 1 hour.

8. The method of claim 5 wherein the second temperature is less than about 80°

C.

9. The method of claim 8 wherein the coupling at 80°

C. is for about 24 hours.

10. The method of claim 1 wherein the poly(aryleneethynylene) rigid polymer comprises a poly(phenyleneethynylene) polymer, the para-diethynyl-(R₁-R_x)arylene comprises a para-diethynyl-(R₁-R_x)benzene, and the (R₁-R_y)-para-dihaloarylene comprises a (R₁-R_y)-para-dihalobenzene.

11. The method of claim 1 wherein the first or second polymerization-terminating haloaryl agent comprises an iodoalkyloxybenzene or a bromoalkyloxybenzene, or a combination thereof.

12. The method of claim 1 wherein the iodoalkyloxybenzene comprises iodoanisole, iodoethoxybenzene, or iodopropoxybenzene, or a combination thereof.

13. The method of claim 1 wherein the bromoalkyloxybenzene comprises bromoanisole, bromoethoxybenzene, or bromopropoxybenzene, or a combination thereof.

14. The method of claim 1 wherein the polydispersity of the polymer is about 1.2 to about 1.8.

15. The method of claim 1 wherein the polydispersity of the polymer is about 1.4 to about 1.6.

16. The method of claim 1 wherein at least one R of (R₁-R_x) or (R₁-R_y) is alkoxy or alkyl.

17. The method of claim 10 wherein x is 4, y is 4, one set of para R'"'"'s of (R₁-R_x) is H and a corresponding set of para R'"'"'s of (R₁-R_y) is H.

18. The method of claim 10 wherein x is 4, y is 4, one set of para R'"'"'s of (R₁-R_x) is alkoxy and a corresponding set of para R'"'"'s of (R₁-R_y) is alkoxy.

19. The method of claim 10 wherein x is 4, y is 4, one set of para R'"'"'s of (R₁-R_x) is alkyl and a corresponding set of para R'"'"'s of (R₁-R_y) is alkyl.

20. The method of claim 10 wherein x is 4, y is 4, and each set of para R'"'"'s of (R₁-R_x) is identical to a corresponding set of para R'"'"'s of (R₁-R_y).

21. The method of claim 1 wherein the length of the polymer is about 25 nm to about 55 nm.

49. A rigid poly(aryleneethynylene) polymer made by the method of claim 1.

52. A rigid poly(phenyleneethynylene) polymer made by the method of claim 10.

3. A method of making a rigid poly(ferrocenylaryleneethynylene) polymer, the polymer having at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2, the method comprising:

coupling a 1,1′

-diethynyl-(R₁-R₈)ferrocene and an (R₁-R_z)-para-dihaloarylene, or coupling a 1,1′

-dihalo-(R₁-R₈)ferrocene and a para-diethynyl-(R₁-R_z)arylene, in the presence of a first polymerization-terminating haloaryl agent,

wherein each R of (R₁-R₈) and (R₁-R_z) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R₁-R₈) and (R₁-R_z) is a functional group for solubilizing nanomaterial, and

wherein z of (R₁-R_z) is the maximum number of substituents on the (R₁-R_z)-para-dihaloarylene,

under conditions for a period of time to produce fluorescence; and

terminating the coupling by addition of a second polymerization-terminating haloaryl agent, the second haloaryl agent having equal or greater activity for coupling as the (R₁-R_z)-para-dihaloarylene or the 1,1′

-dihalo-(R₁-R₈)ferrocene.

50. A rigid poly(ferrocenylaryleneethynylene) polymer made by the method of claim 3.

4. A method of making a rigid poly(ferrocenylethynylene) polymer, the polymer having at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2, the method comprising:

coupling a 1,1′

-diethynyl-(R₁-R₈)ferrocene and an (R₁-R₈)-1,1′

-dihaloferrocene in the presence of a first polymerization-terminating haloaryl agent,

wherein each R of (R₁-R₈) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R₁-R₈) is a functional group for solubilizing nanomaterial,

wherein corresponding R groups of the 1,1′

-diethynyl-(R₁-R₈)ferrocene and the (R₁-R₈)-1,1′

-dihaloferrocene are identical;

under conditions for a period of time to produce fluorescence; and

terminating the coupling by addition of a second polymerization-terminating haloaryl agent, the second haloaryl agent having equal or greater activity for coupling as the (R₁-R₈)-1,1′

-dihaloferrocene.

51. A rigid poly(ferrocenylethynylene) polymer made by the method of claim 4.

22. A method of processing nanomaterial comprising:

forming a solution of nanomaterial by mixing nanomaterial, a solubilization solvent, and a rigid polymer selected from the group consisting of poly(aryleneethynylene) polymers, poly(ferrocenylaryleneethynylene) polymers, and poly(ferrocenylethynylene) polymers, wherein the selected rigid polymer has at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2.

23. The method of claim 22 wherein the rigid polymer is a poly(aryleneethynylene) polymer comprising a poly(phenyleneethynylene) polymer, the para-diethynyl-(R₁-R_x)arylene comprises a para-diethynyl-(R₁-R_x)benzene, and the (R₁-R_y)-para-dihaloarylene comprises a (R₁-R_y)-para-dihalobenzene.

26. The method of claim 22 wherein the nanomaterial comprises a multi-wall carbon nanotube, double-wall carbon nanotube, single-wall carbon nanotube, carbon nanoparticle, carbon rope, carbon ribbon, carbon fibril, or a carbon needle.

27. The method of claim 22 wherein the nanomaterial comprises a multi-wall boron nitride nanotube, single-wall boron nitride nanotube, boron nitride nanoparticle, boron nitride fiber, boron nitride rope, boron nitride ribbon, boron nitride fibril, or a boron nitride needle.

28. The method of claim 22 wherein the nanomaterial comprises a carbon nanomaterial.

29. The method of claim 22 wherein the solubilization solvent comprises water, acetic acid, acetone, acetonitrile, aniline, benzene, benzonitrile, benzyl alcohol, bromobenzene, bromoform, 1-butanol, 2-butanol, carbon disulfide, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, cyclohexanol, decalin, dibromethane, diethylene glycol, diethylene glycol ethers, diethyl ether, diglyme, dimethoxymethane, N,N-dimethylformamide, ethanol, ethylamine, ethylbenzene, ethylene glycol ethers, ethylene glycol, ethylene oxide, formaldehyde, formic acid, glycerol, heptane, hexane, iodobenzene, mesitylene, methanol, methoxybenzene, methylamine, methylene bromide, methylene chloride, methylpyridine, morpholine, naphthalene, nitrobenzene, nitromethane, octane, pentane, pentyl alcohol, phenol, 1-propanol, 2-propanol, pyridine, pyrrole, pyrrolidine, quinoline, 1,1,2,2-tetrachloroethane, tetrachloroethylene, tetrahydrofuran, tetrahydropyran, tetralin, tetramethylethylenediamine, thiophene, toluene, 1,2,4-trichlorobenzene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, triethylamine, triethylene glycol dimethyl ether, 1,3,5-trimethylbenzene, m-xylene, o-xylene, p-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dichloroethane, methyl ethyl ketone, dioxane, or dimethyl sulfoxide.

30. The method of claim 22 wherein the solubilization solvent comprises a halogenated organic solvent.

31. The method of claim 22 wherein the solubilization solvent comprises chlorobenzene.

32. The method of claim 22 further comprising:

removing the solubilization solvent from the solution to form solid processed nanomaterial.

36. The method of claim 32 further comprising:

re-solubilizing the solid processed nanomaterial by mixing the solid processed nanomaterial with a re-solubilization solvent to produce re-solubilized processed nanomaterial.

40. The method of claim 36 wherein the re-solubilization solvent comprises water, acetic acid, acetone, acetonitrile, aniline, benzene, benzonitrile, benzyl alcohol, bromobenzene, bromoform, 1-butanol, 2-butanol, carbon disulfide, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, cyclohexanol, decalin, dibromethane, diethylene glycol, diethylene glycol ethers, diethyl ether, diglyme, dimethoxymethane, N,N-dimethylformamide, ethanol, ethylamine, ethylbenzene, ethylene glycol ethers, ethylene glycol, ethylene oxide, formaldehyde, formic acid, glycerol, heptane, hexane, iodobenzene, mesitylene, methanol, methoxybenzene, methylamine, methylene bromide, methylene chloride, methylpyridine, morpholine, naphthalene, nitrobenzene, nitromethane, octane, pentane, pentyl alcohol, phenol, 1-propanol, 2-propanol, pyridine, pyrrole, pyrrolidine, quinoline, 1,1,2,2-tetrachloroethane, tetrachloroethylene, tetrahydrofuran, tetrahydropyran, tetralin, tetramethylethylenediamine, thiophene, toluene, 1,2,4-trichlorobenzene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, triethylamine, triethylene glycol dimethyl ether, 1,3,5-trimethylbenzene, m-xylene, o-xylene, p-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dichloroethane, methyl ethyl ketone, dioxane, or dimethyl sulfoxide.

41. The method of claim 36 wherein the re-solubilization solvent comprises a halogenated organic solvent.

42. The method of claim 36 wherein the re-solubilization solvent comprises 1,1,2,2-tetrachloroethane, chlorobenzene, chloroform, methylene chloride, or 1,2-dichloroethane.

43. The method of claim 36 further comprising:

heating the re-solubilized processed nanomaterial to produce insoluble processed nanomaterial.

47. The method of claim 36 wherein the mixing of the solid processed nanomaterial with a re-solubilization solvent produces a solution having a concentration of nanomaterial greater than about 0.2 mg/ml.

48. The method of claim 36 wherein the mixing of the solid processed nanomaterial with a re-solubilization solvent produces a solution having a concentration of nanomaterial greater than or equal to about 1.0 mg/ml.

53. Processed nanomaterial made by the method of claim 22.

57. Solid processed nanomaterial made by the method of claim 32.

61. A re-solubilized processed nanomaterial made by the method of claim 36.

65. An insoluble processed nanomaterial made by the method of claim 43.

24-25. -25. (canceled)

33-35. -35. (canceled)

37-39. -39. (canceled)

44-46. -46. (canceled)

54-56. -56. (canceled)

58-60. -60. (canceled)

62-64. -64. (canceled)

66-68. -68. (canceled)

69. A rigid polymer comprising a poly(aryleneethynylene) polymer, a poly(ferrocenylaryleneethynylene) polymer or a poly(ferrocenylethynylene) polymer, the polymer comprising at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2.

70. The rigid polymer of claim 69 wherein the polymer is a poly(aryleneethynylene) polymer.

71. The rigid polymer of claim 70 wherein the poly(aryleneethynylene) polymer is a poly(phenyleneethynylene) polymer.

72. The polymer of claim 69 wherein the polymer has a terminal aryl group.

73. The polymer of claim 69 wherein the polymer has a terminal alkoxyaryl group.

74. The polymer of claim 69 wherein the polymer has a terminal alkylaryl group.

75. The polymer of claim 69 wherein the polydispersity of the polymer is about 1.2 to about 1.8.

76. The polymer of claim 69 wherein the polydispersity of the polymer is about 1.4 to about 1.6.

77. The polymer of claim 69 wherein the at least one functional group is alkoxy.

78. The polymer of claim 69 wherein the at least one functional group is alkyl.

79. The polymer of claim 69 wherein the polymer has a length of about 25 nm to about 75 nm.

80. The polymer of claim 69 wherein the polymer has a length of about 25 nm to about 55 nm.

100. An article of manufacture comprising the polymer of claim 69.

101. An article of manufacture comprising the polymer of claim 70.

81. A composition comprising:

processed nanomaterial, and

a rigid polymer comprising a poly(aryleneethynylene) polymer, a poly(ferrocenylaryleneethynylene) polymer or a rigid poly(ferrocenylethynylene) polymer, the polymer comprising at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2.

82. The composition of claim 81 wherein the polymer is a poly(aryleneethynylene) polymer, and the poly(aryleneethynylene) polymer is a poly(phenyleneethynylene) polymer.

83. The composition of claim 81 wherein the nanomaterial comprises a multi-wall carbon nanotube, double-wall carbon nanotube, single-wall carbon nanotube, carbon nanoparticle, carbon rope, carbon ribbon, carbon fibril, or a carbon needle.

84. The composition claim 81 wherein the nanomaterial comprises a multi-wall boron nitride nanotube, single-wall boron nitride nanotube, boron nitride nanoparticle, boron nitride fiber, boron nitride rope, boron nitride ribbon, boron nitride fibril, or a boron nitride needle.

85. The composition of claim 81 wherein the nanomaterial comprises a carbon nanotube.

86. The composition of claim 81 further comprising water, acetic acid, acetone, acetonitrile, aniline, benzene, benzonitrile, benzyl alcohol, bromobenzene, bromoform, 1-butanol, 2-butanol, carbon disulfide, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, cyclohexanol, decalin, dibromethane, diethylene glycol, diethylene glycol ethers, diethyl ether, diglyme, dimethoxymethane, N,N-dimethylformamide, ethanol, ethylamine, ethylbenzene, ethylene glycol ethers, ethylene glycol, ethylene oxide, formaldehyde, formic acid, glycerol, heptane, hexane, iodobenzene, mesitylene, methanol, methoxybenzene, methylamine, methylene bromide, methylene chloride, methylpyridine, morpholine, naphthalene, nitrobenzene, nitromethane, octane, pentane, pentyl alcohol, phenol, 1-propanol, 2-propanol, pyridine, pyrrole, pyrrolidine, quinoline, 1,1,2,2-tetrachloroethane, tetrachloroethylene, tetrahydrofuran, tetrahydropyran, tetralin, tetramethylethylenediamine, thiophene, toluene, 1,2,4-trichlorobenzene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, triethylamine, triethylene glycol dimethyl ether, 1,3,5-trimethylbenzene, m-xylene, o-xylene, p-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dichloroethane, methyl ethyl ketone, dioxane, or dimethyl sulfoxide.

87. The composition of claim 81 further comprising a halogenated organic solvent.

88. The composition of claim 81 further comprising chlorobenzene.

89. The composition of claim 81 wherein the nanomaterial comprises solid processed nanomaterial.

93. The composition of claim 89 further comprising water, acetic acid, acetone, acetonitrile, aniline, benzene, benzonitrile, benzyl alcohol, bromobenzene, bromoform, 1-butanol, 2-butanol, carbon disulfide, carbon tetrachloride, chlorobenzene, chloroform, cyclohexane, cyclohexanol, decalin, dibromethane, diethylene glycol, diethylene glycol ethers, diethyl ether, diglyme, dimethoxymethane, N,N-dimethylformamide, ethanol, ethylamine, ethylbenzene, ethylene glycol ethers, ethylene glycol, ethylene oxide, formaldehyde, formic acid, glycerol, heptane, hexane, iodobenzene, mesitylene, methanol, methoxybenzene, methylamine, methylene bromide, methylene chloride, methylpyridine, morpholine, naphthalene, nitrobenzene, nitromethane, octane, pentane, pentyl alcohol, phenol, 1-propanol, 2-propanol, pyridine, pyrrole, pyrrolidine, quinoline, 1,1,2,2-tetrachloroethane, tetrachloroethylene, tetrahydrofuran, tetrahydropyran, tetralin, tetramethylethylenediamine, thiophene, toluene, 1,2,4-trichlorobenzene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, triethylamine, triethylene glycol dimethyl ether, 1,3,5-trimethylbenzene, m-xylene, o-xylene, p-xylene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dichloroethane, methyl ethyl ketone, dioxane, or dimethyl sulfoxide.

94. The composition of claim 89 further comprising a halogenated organic solvent.

95. The composition of claim 89 further comprising 1,1,2,2-tetrachloroethane, chlorobenzene, chloroform, methylene chloride, or 1,2-dichloroethane.

96. The composition of claim 89 wherein the nanomaterial comprises insoluble processed nanomaterial.

98. The composition of claim 89 further comprising a solvent in an amount sufficient to form a solution having a concentration of nanomaterial greater than about 0.2 mg/ml.

99. The composition of claim 89 further comprising a solvent in an amount sufficient to form a solution having a concentration of nanomaterial greater than or equal to about 1.0 mg/ml.

102. An article of manufacture comprising the composition of claim 89.

103. An article of manufacture comprising the composition of claim 86.

104. An article of manufacture comprising the composition of claim 81.

105. An article of manufacture comprising the composition of claim 87.

106. An article of manufacture comprising the composition of claim 96.

108. An article of manufacture comprising the composition of claim 95.

90-92. -92. (canceled)

97. (canceled)

107. (canceled)

109. (canceled)

110. A nanocomposite, comprising:

processed nanomaterial comprising nanomaterial solubilized with a polymer comprising a poly(aryleneethynylene) polymer, a poly(ferrocenylaryleneethynylene) polymer or a poly(ferrocenylethynylene) polymer, the polymer comprising at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2; and

at least one of a host matrix and a filler.

111. The nanocomposite of claim 110 wherein the polymer is a poly(aryleneethynylene) polymer, and the poly(aryleneethynylene) polymer is a poly(phenyleneethynylene) polymer.

112. The nanocomposite of claim 110 wherein the host matrix comprises polystyrene, polycarbonate, epoxy, or polyurethane, and the processed nanomaterial is dispersed within the host matrix.

113. The nanocomposite of claim 110 wherein the host matrix comprises polyester, polyamide, or polyimide, and the processed nanomaterial is dispersed within the host matrix.

114. The nanocomposite of claim 110 wherein the filler comprises a continuous fiber, a discontinuous fiber, a nanoparticle, a microparticle, a macroparticle, or a combination thereof.

115. The nanocomposite of claim 114 wherein the processed nanomaterial is a primary filler.

116. The nanocomposite of claim 114 wherein the filler is a primary filler.