IP Library Granted Patent US 10,186,344
Granted Patent B2
US 10,186,344 · App. 15/000,554 · Granted Jan 22, 2019

Conductive polymer composite

Inventors: Rachel Prestayko (Hamilton, CA); Sarah J. Vella (Milton, CA); Carolyn Moorlag (Mississauga, CA); Barkev Keoshkerian (Thornhill, CA)
Assignee: XEROX CORPORATION
H01B1/24B29C64/106B29C64/40B29K2067/04B29K2105/167B29K2507/04B29K2995/0005B33Y10/00B33Y70/00
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Quick Facts
Patent No.
US 10,186,344
App. No.
15/000,554
Filed
Jan 19, 2016
Granted
Jan 22, 2019
Kind
B2
Art Unit
1768
USPC
524/424
Abstract

A conductive polymer composite is disclosed. The composite comprises a thermoplastic polymer; carbon nanotubes; at least one electron donor molecule and at least one electron acceptor molecule. A method of three-dimensional printing using the conductive polymer composite and a conductive polymer composite filament are also disclosed.

Claims (30)

1. A conductive polymer composite, comprising:

a thermoplastic polymer;

carbon nanotubes;

at least one electron donor molecule selected from the group consisting of benzidine, conjugated derivatives of benzidine, N,N′-diphenyl-N,N′-bis(alkylphenyl)-1,1-biphenyl-4,4′-diamine and N,N′-bis(4-methylphenyl) -N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′dimethyl)biphenyl]4,4′-diamine; and

at least one electron acceptor molecule.

2. The composite of claim 1 , wherein the thermoplastic polymer comprises at least one repeating unit selected from the group consisting of acrylate units, carboxylic acid ester units, amide units, lactic acid units, benzimidazole units, carbonate ester units, ether units, sulfone units, arylketone units, arylether units, arylalkyl units, etherimide units, ethylene units, phenylene oxide units, propylene units, styrene units, vinyl halide units and carbamate units.

3. The composite of claim 2 , wherein the thermoplastic polymer is a copolymer of two or more of the repeating units.

4. The composite of claim 3 , wherein the copolymer comprises one or more acrylate units.

5. The composite of claim 1 , wherein the thermoplastic polymer comprises at least one polymer selected from the group consisting of polyacrylates, polybenzimidazoles, polycarbonates, polyether sulfones, polyaryl ether ketones, polyethylenes, polyphenylene oxides, polypropylenes, polystyrenes, polyesters, polyurethanes, polyamides, Poly(vinylidene fluoride) (PVDF) and polyvinyl chlorides, polyether ether ketone, poly(ethylene-co-vinylacetate), polyetherimide, polypropylene, Poly(vinylidene fluoride-co-hexafluoropropylene), poly(styrene isoprene styrene), acrylonitrile butadiene styrene (ABS), poly(Styrene Ethylene Butylene Styrene) (SEBS), polyethylene terephthalate, polylactic acid (PLA), polycaprolactone and nylon.

6. The composite of claim 1 , wherein the thermoplastic polymer is in an amount ranging from about 10% to about 90% by weight, relative to the total weight of the conductive polymer composite.

7. The composite of claim 1 , wherein the carbon nanotubes are multi-walled carbon nanotubes.

8. The composite of claim 1 , wherein the carbon nanotubes are in an amount ranging from about 1% to about 40% by weight, relative to the total weight of the conductive polymer composite.

9. The composite of claim 1 , wherein the at least one electron donor molecule is selected from the group consisting of N,N′-diphenyl-N,N′-bis(alkylphenyl)-1,1-biphenyl-4,4′-diamine and N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]4,4′-diamine.

10. The composite of claim 1 , wherein the at least one electron donor molecule is in an amount ranging from about 0.5% to about 50% by weight, relative to the total weight of the conductive polymer composite.

11. The composite of claim 1 , wherein the at least one electron acceptor molecule is selected from the group consisting of tetracyanoquinodimethane (TCNQ) and conjugated derivatives thereof, tetracyanoethylene (TCNE) and conjugated derivatives thereof, quinones and conjugated derivatives thereof.

12. The composite of claim 1 , wherein the at least one electron acceptor molecule is tetracyanoquinodimethane.

13. The composite of claim 1 , wherein the electron acceptor molecule is in an amount ranging from about 0.1% to about 10% by weight, relative to the total weight of the conductive polymer composite.

14. The composite of claim 1 , wherein the composite has a bulk conductivity greater than 0.7 S/cm, where the conductivity is calculated using the formula σ=L/(R*A), based on the measured resistance (R) of an extruded filament made from the composite and having silver painted tips, the filament having a length (L) of 10 cm and a diameter of 1.75 mm.

15. A method of three dimensional printing, the method comprising:

providing a composite to a three-dimensional printer, the composite comprising a thermoplastic polymer, carbon nanotubes, at least one electron donor molecule and at least one electron acceptor molecule, the at least one electron donor molecule being selected from the group consisting of benzidine, conjugated derivatives of benzidine, N,N′-diphenyl-N,N′-bis(alkylphenyl)-1,1-biphenyl-4,4′-diamine and N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]4,4′-diamine;

heating the composite; and

extruding the heated composite onto a build platform to form a three dimensional object.

16. The method of claim 15 , wherein the heated composite is in the form of a filament.

17. A conductive polymer composite filament, comprising:

a thermoplastic polymer;

carbon nanotubes;

at least one electron donor molecule selected from the group consisting of benzidine, conjugated derivatives of benzidine, N,N′-diphenyl-N,N′-bis(alkylphenyl)-1,1-biphenyl-4,4′-diamine and N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]4,4′-diamine; and

at least one electron acceptor molecule.

18. The conductive polymer composite filament of claim 17 , wherein the thermoplastic polymer comprises at least one polymer selected from the group consisting of polyacrylates, polybenzimidazoles, polycarbonates, polyether sulfones, polyaryl ether ketones, polyethylenes, polyphenylene oxides, polypropylenes, polystyrenes, polyesters, polyurethanes, polyamides, Poly(vinylidene fluoride) (PVDF) and polyvinyl chlorides, polyether ether ketone, poly(ethylene-co-vinylacetate), polyetherimide, polypropylene, Poly(vinylidene fluoride-co-hexafluoropropylene), poly(styrene isoprene styrene), acrylonitrile butadiene styrene (ABS), poly(Styrene Ethylene Butylene Styrene) (SEBS), polyethylene terephthalate, polylactic acid (PLA), polycaprolactone and nylon.

19. The conductive polymer composite filament of claim 17 , wherein the at least one electron acceptor molecule is selected from the group consisting of tetracyanoquinodimethane (TCNQ) and conjugated derivatives thereof, tetracyanoethylene (TCNE) and conjugated derivatives thereof, quinones and conjugated derivatives thereof.

Assignments (10)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 14, 2025
From: XEROX CORPORATION
To: GENESEE VALLEY INNOVATIONS, LLC
Reel/Frame 073562/0677 →
SECOND LIEN NOTES PATENT SECURITY AGREEMENT Recorded Jul 2, 2025
From: XEROX CORPORATION
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 071785/0550 →
FIRST LIEN NOTES PATENT SECURITY AGREEMENT Recorded Apr 11, 2025
From: XEROX CORPORATION
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 070824/0001 →
SECURITY INTEREST Recorded Feb 13, 2024
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 066741/0001 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENTS RECORDED AT RF 064760/0389 Recorded Feb 13, 2024
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: XEROX CORPORATION
Reel/Frame 068261/0001 →
SECURITY INTEREST Recorded Nov 20, 2023
From: XEROX CORPORATION
To: JEFFERIES FINANCE LLC, AS COLLATERAL AGENT
Reel/Frame 065628/0019 →
SECURITY INTEREST Recorded Jun 22, 2023
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 064760/0389 →
RELEASE OF SECURITY INTEREST IN PATENTS AT R/F 062740/0214 Recorded May 18, 2023
From: CITIBANK, N.A., AS AGENT
To: XEROX CORPORATION
Reel/Frame 063694/0122 →
SECURITY INTEREST Recorded Nov 10, 2022
From: XEROX CORPORATION
To: CITIBANK, N.A., AS AGENT
Reel/Frame 062740/0214 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 19, 2016
From: PRESTAYKO, RACHEL; VELLA, SARAH J.; MOORLAG, CAROLYN; KEOSHKERIAN, BARKEV
To: XEROX CORPORATION
Reel/Frame 037522/0941 →
Continuity (1)
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