Polymer and method for using the polymer for noncovalently functionalizing nanotubes

• US 6,905,667 B1
• Filed: 12/13/2002
• Issued: 06/14/2005
• Est. Priority Date: 05/02/2002
• Status: Expired due to Term

• Current Assignee: Evermore Applied Materials Corp., University Of Pittsburgh (University of Pittsburgh of The Commonwealth System of Higher Education)
• Original Assignee: University Of Pittsburgh (University of Pittsburgh of The Commonwealth System of Higher Education), Zyvex Corporation
• Inventors: Chen, Jian, Liu, Haiying
• Primary Examiner(s): Lipman, Bernard
• Application Number:
  US10/318,730
• Time in Patent Office: 914 Days
• Field of Search: 428/367, 428/398, 428/408, 525/416, 423/445.B, 423/445.R, 423/460, 524/495, 524/496
• US Class Current: 423/447.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 2202/28 Solid content in solvents
• CPC Class Codes: C01B 32/174 Derivatisation; Solubilisation; Dispersion in solvents
• 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: C08G 61/122 derived from five- or six-membered heterocyclic compounds, other than imides
• CPC Class Codes: C08G 61/124 with a five-membered ring containing one nitrogen atom in the ring
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: D01F 11/14 with organic compounds, e.g. macromolecular compounds
• CPC Class Codes: Y10S 977/737 having a modified surface
• CPC Class Codes: Y10S 977/847 Surface modifications, e.g. functionalization, coating
• CPC Class Codes: Y10T 428/2918 including free carbon or carbide or therewith [not as steel]
• CPC Class Codes: Y10T 428/2975 Tubular or cellular
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

A new, non-wrapping approach to functionalizing nanotubes, such as carbon nanotubes, in organic and inorganic solvents is provided. In accordance with certain embodiments, carbon nanotube surfaces are functionalized in a non-wrapping fashion by functional conjugated polymers that include functional groups. Various embodiments provide polymers that noncovalently bond with carbon nanotubes in a non-wrapping fashion. For example, various embodiments of polymers are provided that comprise a relatively rigid backbone that is suitable for noncovalently bonding with a carbon nanotube substantially along the nanotube'"'"'s length, as opposed to about its diameter. In preferred polymers, the major interaction between the polymer backbone and the nanotube surface is parallel π-stacking. In certain implementations, the polymers further comprise at least one functional extension from the backbone that are any of various desired functional groups for functionalizing a carbon nanotube.

Claims

1. A method of functionalizing a nanotube, said method comprising:

noncovalently bonding a polymer comprising at least one functional group with a nanotube in a non-wrapping fashion.

2. The method of claim 1 further comprising mixing said polymer and said nanotube in a solvent under conditions whereby said polymer noncovalently bonds with said nanotube in said non-wrapping fashion.

3. The method of claim 2 wherein said solvent comprises an organic solvent.

4. The method of claim 2 wherein said solvent comprises an aqueous solvent.

5. The method of claim 2 wherein said solvent comprises one selected from the group consisting of:

chloroform, chlorobenzene, water, acetic acid, acetone, acetonitrile, aniline, benzene, benzonitrile, benzyl alcohol, bromobenzene, bromoform, 1-butanol, 2-butanol, carbon disulfide, carbon tetrachloride, 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, and 1,4-dichlorobenzene.

6. The method of claim 1 wherein said polymer comprises a backbone portion that noncovalently bonds with said nanotube in a non-wrapping fashion via π

-stacking.

7. The method of claim 1 wherein said nanotube is a carbon nanotube.

8. The method of claim 1 wherein said polymer comprises a poly(aryleneethynylene).

9. The method of claim 1 wherein said polymer comprises a poly(phenyleneethynylene).

10. The method of claim 1 wherein said polymer comprises poly(3-decylthiophene).

11. A product resulting from the process of claim 1.

12. A method of functionalizing carbon nanotubes, said method comprising:

interacting at least one polymer comprising at least one functional group with at least one carbon nanotube in a solvent, wherein said polymer interacts with said at least one carbon nanotube'"'"'s surface in a non-wrapping fashion via π

-stacking.

13. The method of claim 12 further comprising:

interacting said at least one polymer with said at least one carbon nanotube by mixing.

14. The method of claim 12 wherein said at least one polymer noncovalently bonds with said at least one carbon nanotube in a non-wrapping fashion.

15. The method of claim 12 wherein said at least one polymer comprises a poly(aryleneethynylene).

16. The method of claim 12 wherein said at least one polymer comprises a poly(phenyleneethynylene).

17. The method of claim 12 wherein said at least one polymer comprises poly(3-decylthiophene).

18. A product resulting from the process of claim 12.

19. A composition comprising:

a polymer associated with a nanotube, wherein said polymer comprises a backbone portion for noncovalently associating with said nanotube in a non-wrapping fashion.

20. The composition of claim 19 wherein said backbone portion associates with the nanotube by non-covalently bonding with the nanotube in said non-wrapping fashion.

21. The composition of claim 19 wherein said backbone portion comprises a portion selected from the group consisting of:

wherein M is

selected from the group consisting of Ni, Pd, and Pt,

wherein each of R₁-R₈ in the above-listed backbone portions a)-q) represents a functional group.

22. The composition of claim 19 wherein said polymer comprises a poly(aryleneethynylene).

23. The composition of claim 22 wherein said polymer further comprises at least 4 functional portions (R₁, R₂, R₃, and R₄), wherein said functional portions comprise functional portions selected from the group consisting of:

a) R₁═

R₄═

H and R₂═

R₃═

OC₁₀H₂₁,

b) R₁═

R₂═

R₃═

R₄═

F,

c) R₁═

R₄═

H and R₂═

R₃═

d) R₁═

R₄═

H and R₂═

R₃═

24. The composition of claim 19 wherein said polymer comprises at least one selected from the group consisting of:

poly(phenyleneethynylene) and poly(3-decylthiophene).

25. The composition of claim 19 wherein said nanotube is a carbon nanotube.

26. The composition of claim 19 wherein said backbone portion associates with said nanotube'"'"'s surface via π

-stacking interaction therewith.

27. The composition of claim 19 wherein said polymer further comprises:

at least one functional portion for functionalizing said nanotube.

28. The composition of claim 27 wherein said at least one functional portion comprises at least one selected from the group consisting of:

H, OC₁₀H₂₁, F,