Electroconductive curable resins

• US 8,114,314 B2
• Filed: 07/20/2006
• Issued: 02/14/2012
• Est. Priority Date: 07/20/2005
• Status: Active Grant

• Current Assignee: Agency For Science Technology and Research
• Original Assignee: Agency For Science Technology and Research
• Inventors: Kotaki, Masaya, Wang, Ke, He, Chaobin
• Primary Examiner(s): Kopec, Mark
• Assistant Examiner(s): THOMAS, JAISON P
• Application Number:
  US11/996,067
• Publication Number:
  US 20090127516A1
• Time in Patent Office: 2,035 Days
• Field of Search: 252/510, 252/511, 252/500, 252/512
• US Class Current: 252/500
• CPC Class Codes: C08G 59/50 Amines
• CPC Class Codes: C08K 2201/011 Nanostructured additives
• CPC Class Codes: C08K 3/346 Clay
• CPC Class Codes: C08K 7/06 Elements
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 27/16 Homopolymers or copolymers or vinylidene fluoride
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Abstract

An electroconductive polymer composition comprises a curable liquid thermosetting resin matrix; conductive nano-fibers such as carbon nano-tubes, carbon nano-fibers, metallic nano-fibers or non-conductive nano-fibers with an electrically conductive coating; and a particulate non-conductive phase discontinuously dispersed throughout the thermosetting matrix. The conductive nano-particles are dispersed throughout the matrix whereby when the thermosetting resin is cured, a percolation threshold is established within the thermoset matrix. The particulate non-conductive phase is selected from thermoplastic resin powders or exfoliated particles of nano-clay intercalated with the liquid thermosetting resin.

Claims

1. An electroconductive polymer composition comprising:

a curable liquid resin matrix;

conductive nano-fibres; and

,

a particulate non-conductive phase selected from the group consisting of a particulate nano-clay containing from about 0.05 to 15 wt % organic modifier and a particulate thermoplastic polymer, said particulate non-conductive phase discontinuously dispersed throughout said matrix, said composition characterized in that said conductive nano-fibres are dispersed throughout said matrix to establish a percolation threshold therein when said matrix is cured.

2. A composition according to claim 1 wherein said electroconductive polymer composition comprises a fluid in an uncured state.

3. A composition according to claim 1 wherein said curable liquid resin matrix is selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a vinyl ester resin and a phenolic resin.

4. A composition according to claim 1 wherein said conductive nano-fibres are selected from the group consisting of carbon nano-tubes, carbon nano-fibres, metallic nano-fibres and non-conductive nano-fibres with an electrically conductive coating.

5. A composition according to claim 4 wherein said conductive nano-fibres are vapour grown carbon fibre (VGCF).

6. A composition according to claim 5 wherein said conductive nano-fibres have a diameter in the range of from 0.05 to 10 μ

m and a length in the range of from 1 to 500 μ

m.

7. A composition according to claim 6 wherein said conductive nano-fibres are present in said electroconductive polymer composition in the range of from 1 to 30 wt %.

8. A composition according to claim 1 wherein said particles of nano-clay are intercalated with said curable liquid resin matrix.

9. A composition according to claim 1 wherein said particles of nano-clay are present in said electroconductive polymer composition in the range of from 1 to 20 wt %.

10. A composition according to claim 1 wherein said particulate thermoplastic polymer has a mean particle diameter in the range of from 0.1 to 100 μ

m.

11. A composition according to claim 1 wherein said particulate thermoplastic polymer is selected from the group consisting of crystalline polar thermoplastic polymers, crystalline non-polar thermoplastic polymers, non-crystalline non-polar thermoplastic polymers, non-crystalline polar thermoplastic polymers and copolymers thereof.

12. A composition according to claim 1 wherein said particulate thermoplastic polymer is present in said electroconductive polymer composition in the range of from 1 to 70 wt %.

13. A method for the manufacture of an electroconductive polymer composition according to claim 1 wherein conductive nano-fibres and a particulate non-conductive phase are intensively mixed with a liquid curable resin, which polymer composition, when cured, forms a discontinuous non-conductive phase dispersed throughout a conductive phase in which a percolation threshold is established by distribution of conductive nano-fibres therethrough.

14. A method according to claim 13 wherein said conductive nano-fibres and said liquid curable resin are mixed prior to the addition of said particulate non-conductive phase.

15. A method according to claim 13 wherein said particulate non-conductive phase comprises a thermoplastics resin added in dry powder form.

16. A method according to claim 15 wherein said particulate non-conductive phase comprising exfoliated nano-clay particles intercalated with liquid curable resin is added to a mixture of said liquid curable resin and said conductive nano-fibres.

17. A method according to claim 15 wherein said liquid curable resin is formed as a dispersion of exfoliated nano-clay intercalated with said liquid curable resin prior to addition of said conductive nano-fibres.

18. A method as claimed in claim 17 wherein said dispersion is formed by treatment of pristine clay with water to swell said clay, exchanging said water with an organic solvent while maintaining said clay in a swollen state in a slurry with said organic solvent, treating said solvent exchanged swollen clay slurry with a modifier selected from a surfactant, a coupling agent, a compatibilizer or any combination thereof and subsequently mixing said slurry with a liquid curable resin and thereafter removing said solvent from said dispersion.

19. A method according to claim 13 wherein said particulate non-conductive phase comprises a thermoplastics resin added in dry powder form.