Halogen containing-polymer nanocomposite compositions, methods, and products employing such compositions

• US 20020161101A1
• Filed: 03/21/2002
• Published: 10/31/2002
• Est. Priority Date: 03/22/2001
• Status: Active Grant

• Current Assignee: Clemson University
• Original Assignee: Clemson University
• Inventors: Carroll, David, Ballato, John, Czerw, Richard, Foulger, Stephen, Wagener, Earl, Shah, Hiren, Smith, Dennis
• Granted Patent: US 7,265,174 B2
• Time in Patent Office: Days
• US Class Current: 524/495
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C04B 14/022 Carbon
• CPC Class Codes: C04B 14/026 of particular shape, e.g. nanotubes
• CPC Class Codes: C04B 14/04 Silica-rich materials; Silicates
• CPC Class Codes: C04B 14/10 Clay sepiolite C04B14/042; grog C04B18/025
• CPC Class Codes: C04B 20/0008 Materials specified by a shape not covered by C04B20/0016 - C04B20/0056, e.g. nanotubes
• CPC Class Codes: C04B 20/008 Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder colloidal silica C04B14/062 ; silica fume C04B18/146
• CPC Class Codes: C04B 2103/0046 added as monomers or as oligomers
• CPC Class Codes: C04B 26/08 containing halogen
• CPC Class Codes: C08J 2327/00 Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; 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 7/24 inorganic
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

The disclosure provides compositions prepared by combining nanomaterials with a halide-containing polymer, thereby forming a combined polymer matrix having dispersed nanomaterials within the matrix. The nanomaterials may be carbon-based nanotubes, in some applications. A halide-containing monomer is combined with nanotubes, and then polymerized in some compositions. In other applications, a halide-containing polymer is solution processed with nanotubes to form useful compositions in the invention. Also disclosed are probes for near field detection of radiation.

Claims

1. A composition prepared by combining

(a) nanomaterials, and

(b) a halogen-containing monomer.

2. The composition of claim 1 in which the nanomaterials comprise carbon-based nanotubes.

3. The composition of claim 2 in which the nanotubes are dispersed within a polymeric matrix, said polymeric matrix being formed by polymerization of said halogen-containing monomer.

4. The composition of claim 2 wherein the halogen-containing monomer comprises a monomer selected from the group consisting of:

bromine, chlorine, fluorine, and iodine.

5. The composition of claim 2 in which the halogen of the halogen-containing monomer comprises fluorine, and further wherein said monomer is capable of polymerizing to form a fluoropolymer.

17. The composition of claim 1 in which the nanomaterials are homogenously dispersed.

20. The composition of claim 2 in which the composition exhibits an optical transmission of greater than 80% at a nanomaterial loading levels from about 0.01 to about 80 weight %.

6. A polymeric composition prepared by combining

(a) nanomaterials, and

(b) a halogen-containing polymer.

7. The composition of claim 6 in which the nanomaterials consist essentially of carbon-based nanotubes.

8. The composition of claim 7 in which the nanotubes are spatially and orientationally randomly dispersed.

9. The composition of claim 7 in which the nanotubes are non-randomly dispersed.

10. The composition of claim 7 in which the halogen-containing polymer comprises a fluoropolymer.

11. The composition of claim 10 wherein the fluoropolymer comprises a trifluorovinylether.

12. The composition of claim 10 wherein the fluoropolymer comprises perfluorocyclobutane.

13. The composition of claim 6 in which the halogen-containing polymer comprises a chloropolymer.

14. The composition of claim 13 wherein the chloropolymer comprises a vinyl chloride.

15. The composition of claim 14 in which the chloropolymer comprises poly(vinylidene-dichloride).

16. The composition of claim 13 in which the chloropolymer comprises chlorotrifluoroethylene.

18. The composition of claim 7 in which the composition exhibits a thermal conductivity greater than 1.25 W/mK at a nanomaterial loading level from about 0.01 to about 10 weight %.

19. The composition of claim 7 in which the composition exhibits a volume resistivity of less than 10¹⁰ ohm cm at a nanomaterial loading level from about 0.01 to about 10 weight %.

21. The composition of claim 7 in which the composition exhibits an optical transmission of greater than 50% at a nanomaterial loading levels from about 0.01 to about 5 weight %.

22. The composition of claim 7 in which the composition exhibits an optical transmission of greater than 50%.

24. The composition of claim 23 in which the clay material is selected from the group of clay materials consisting of:

bentonite, kaolinite, montmorillonite, attapulgite, illite, halloysite, fullers earth, kaolin, mica, talc, silica nanoparticles and polyorganosilicate graft polymers.

25. The composition of claim 24 in which the clay material comprises bentonite.

26. The composition of claim 24 in which the clay material comprises kaolinite.

27. The composition of claim 24 in which the clay material comprises silica nanoparticles.

30. The composition of claim 29 in which the polymer comprises poly(vinylchloride).

31. The composition of claim 29 in which the polymer comprises poly(vinylidene-dichloride).

32. The composition of claim 29 in which the polymer comprises a vinyl chloride.

23. A composition prepared by combining

(a) a halogen-containing monomer, and

(b) a clay material, said clay material comprising nanomaterials.

28. A polymeric composition prepared by combining

(a) a halogen-containing polymer, and

(b) a clay material, said clay material comprising nanomaterials.

29. A composition comprising:

(a) carbon-based nanotubes, and

(b) a chloride-containing polymer.

33. A composition prepared by combining

(a) carbon-based nanotubes;

and

(b) a halogen-containing polymer, wherein the halogen-containing polymer includes at least one halogen selected from the group consisting of fluorine, chlorine, bromine, and iodine;

(c) thereby forming a combined polymer matrix having dispersed carbon nanotubes within the polymer matrix.

34. The composition of claim 33 in which the halogen-containing polymer comprises a fluoropolymer.

35. The composition of claim 33 in which the halogen-containing polymer is copolymerized using a monomer of triflurovinyl ether (TFVE).

36. The composition of claim 34 in which the fluoropolymer comprises a perfluorocyclobutane (PFCB) aromatic ether polymer.

38. The composition of claim 37 in which the copolymer is prepared from a trifluorovinyl aromatic ether.

37. A composition formed by combining:

(a) carbon nanotubes, and

(b) a copolymer comprising a poly-aryl ether with perfluoroocyclobutyl (PFCB) linkages.

39. A probe for microscopy, comprising:

a fiber with a frontal surface comprised of a polymeric matrix having dispersed carbon nanotubes within the polymeric matrix.

40. A composition prepared by combining

(a) carbon-based nanotubes,

(b) a halogen-containing monomer, and

(c) a naturally occurring material selected from the group of materials consisting of:

Group IIII elements and Group V dopants.

41. The composition of claim 40 in which the naturally occurring material is combined with a halogen-containing monomer.

42. The composition of claim 40 in which the naturally occurring material is combined with a halogen-containing polymer.

43. The composition of claim 40 in which the naturally occurring material is combined with a nanomaterials.