Impregnation of a non-conductive material with an intrinsically conductive polymer through in-situ polymerization
View Patent ↗Composite materials are made by impregnating a non-conductive material with a conducting monomer to form a monomer-impregnated non-conductive material, and polymerizing the monomer-impregnated non-conductive material to form the composite material. The composite materials are used in medical devices and implants.
1. A method of making a composite material comprising a non-conductive substrate enclosed within a non-conducting polymer and a conducting polymer blend, the method comprising the steps of:
mixing a non-conductive polymer and a conducting monomer to form a non-conductive polymer blend;
enclosing a non-conductive substrate in the non-conductive polymer blend;
drying the non-conductive polymer blend to form a monomer-containing composite; and
polymerizing the monomer-containing composite to form the composite material.
2. The method of claim 1 , wherein the polymerizing step comprises oxidizing the monomer-containing composite with an oxidizer to form the composite material.
3. The method of claim 2 , wherein the oxidizing step comprises soaking the monomer-containing composite in an oxidation medium comprising the oxidizer and an optional solvent such that the conducting monomer and the oxidizer react to form the composite material.
4. The method of claim 3 , wherein the oxidizer comprises benzoyl peroxide, hydrogen peroxide, iron(III) para-toluenesulfonate, iron(III) chloride, gold (III) chloride, iodine or bromine; the solvent comprises dichloromethane, acetonitrile, dimethylsulfoxide, N,N-dimethylformamide, chloroform, tetrahydrofuran, isopropanol, methanol, ethanol, n-butanol, acetone, methyl ethyl ketone, benzonitrile, toluene, propylene carbonate, or water; or the solvent comprises a counterion comprising a negatively charged functional group comprising a phosphate group, a phosphonate group, a sulfamate group, a carboxylate group, a sulfate group, a sulfonate group, or a combination thereof.
5. The method of claim 4 , wherein the solvent comprises the counterion, and either:
the counterion comprises polyvinyl sulfonate, polystyrene sulfonate, polyallyl sulfonate, polyethyl acrylate sulfonate, polybutyl acrylate sulfonate, polyacryl sulfonate, polymethacryl sulfonate, poly-2-acrylamide-2-methylpropane sulfonate, polyisoprene sulfonate, polyvinyl carboxylate, polystyrene carboxylate, polyallyl carboxylate, polyacryl carboxylate, polymethacryl carboxylate, poly-2-acrylamide-2-methylpropane carboxylate, polyisoprene carboxylate, a polyacrylate, a polyamino acid, polydopamine, sulfonated poly ether ether ketone (S-PEEK), a sulfonated polyurethane, vinyl sulfonate, styrene sulfonate, allyl sulfonate, ethyl acrylate sulfonate, butyl acrylate sulfonate, acryl sulfonate, methacryl sulfonate, 2-acrylamide-2-methylpropane sulfonate, isoprene sulfonate, vinyl carboxylate, styrene carboxylate, allyl carboxylate, acryl carboxylate, methacryl carboxylate, 2-acrylamide-2-methylpropane carboxylate, isoprene carboxylate, an acrylate, an amino acid, dopamine, sulfonated ether ether ketone (S-PEEK), a sulfonated urethane, or a mixture thereof; or
the counterion comprises sulfonic acid, fluorosulfonate, toluene sulfonate, taurine, anthraquinone sulfonate, vinyl sulfonate, 2-acrylamido-2-methyl-1-propanesulfonic acid, polystyrene sulfonate, polyvinyl sulfonate, sulfonated polytetrafluoroethylene, polyanetholesulfonic acid, a salt or functionalized derivative thereof, or a mixture thereof; the counterion comprises para-toluenesulfonate (tosylate), trifluoromethanesulfonate (triflate), naphthalene sulfonate, camphor sulfonate, benzene sulfonate, perchlorate, tetrafluoroborate, hexafluorophosphate, dodecylbenzene sulfonic acid, fluoride, chloride, bromide, or iodide or a salt or mixture thereof; or
the counterion is of a salt comprising a lithium (Li+), sodium (Na+), potassium (K+), hydrogen (H+), hydronium, ammonium, tetraethylammonium, tetrapropylammonium, or tetrabutylammonium cation.
6. The method of claim 3 , wherein the oxidation medium further comprises a surfactant.
7. The method of claim 3 , wherein the oxidation medium comprises from about 0.01 to about 20% w/v oxidizer and from about 80 to about 99.99% w/v organic solvent.
8. The method of claim 2 , wherein the oxidizing step occurs for about 12 hours to about 36 hours at 25 to 37° C.
9. The method of claim 1 , wherein the substrate comprises a tube, scaffold, rod, fiber, mesh, ring, patch, sheet, sponge, gel, foam, bag, balloon, particle, powder, pellet, hook and loop fastener, film, needle, braid, weaved material, knitted material, extruded material, or injection-molded material.
10. The method of claim 1 , wherein the conducting monomer comprises acetylene, fluorene, para-phenylene, pyrene, pyrrole, carbazole, indole, phenyl azide, aniline, thiophene, pyridine, or a mixture or functionalized derivative thereof; the conducting monomer comprises 3,4-ethylenedioxythiophene (EDOT) or a functionalized derivative thereof; the conducting monomer comprises 3,4-ethylenedioxythiophene, hydroxymethyl-EDOT, EDOT-vinyl, EDOT-ether allyl, EDOT-COOH, EDOT-MeOH, EDOT-silane, EDOT-vinyl, EDOT-acrylate, EDOT-silane, EDOT-sulfonate, EDOT-amine, EDOT-amide, EDOT-thiol, ProDOT (3,4-Propylenedioxythiophene), 3,4-(2,2-Dimethylpropylenedioxy)thiophene, 3,4-(2′,2′-Diethylpropylene)dioxythiophene, or a dimerized or trimerized derivative of EDOT; or the conducting monomer comprises hydroxymethyl-EDOT, EDOT-vinyl, EDOT-ether allyl, or EDOT-acrylate.
11. A composite material comprising a substrate enclosed within a non-conducting polymer and a conducting polymer blend prepared by the method of claim 1 .
12. A method of making a composite material, the method comprising the steps of:
mixing a non-conductive polymer and a conducting monomer to form a non-conductive polymer blend;
enclosing a substrate in the non-conductive polymer blend or coating a surface of the substrate with the non-conductive polymer blend;
drying the non-conductive polymer blend to form a monomer-containing composite; and
polymerizing the monomer-containing composite to form the composite material,
wherein either:
the polymerizing step comprises electrochemically polymerizing the monomer within the monomer-containing composite by placing the monomer-containing composite in a deposition medium containing counter-ions and a solvent and applying a current; or
the polymerizing step comprises delivering a gas containing the oxidizer or a liquid containing the oxidizer into a sealed chamber containing the monomer-containing composite to form the composite material; or
the method further comprises electrochemically depositing a conductive polymer on a surface of the composite material; or
the monomer-containing composite is in the presence of a crosslinking agent during polymerization; or
the polymerizing step comprises oxidizing the monomer-containing composite with an oxidizer to form the composite material and the oxidation occurs in the presence of agitation; or
the substrate comprises a lumen through the material, and the method further comprises rinsing the lumen during the polymerizing step; or
the polymerizing step comprises oxidizing the monomer-containing composite with an oxidizer to form the composite material, the oxidizing step comprises soaking the monomer-containing composite in an oxidation medium comprising the oxidizer and an optional solvent such that the conducting monomer and the oxidizer react to form the composite material, the oxidizing step occurs for about 12 hours to about 36 hours at 25 to 37° C., and the oxidation medium further comprises a radioopacity additive which comprises tantalum, platinum, or iridium; or
the polymerizing step comprises oxidizing the monomer-containing composite with an oxidizer to form the composite material, the oxidizing step comprises soaking the monomer-containing composite in an oxidation medium comprising the oxidizer and an optional solvent such that the conducting monomer and the oxidizer react to form the composite material, the oxidizing step occurs for about 12 hours to about 36 hours at 25 to 37° C., and the oxidation medium further comprises a conductive additive which comprises carbon black, carbon fiber, a pre-polymerized conducting polymer, carbon nanotubes, graphite, graphene, metal particles, or a metal powder.
13. The method of claim 12 , wherein the polymerizing step comprises electrochemically polymerizing the monomer within the monomer-containing composite by placing the monomer-containing composite in a deposition medium containing counter-ions and a solvent and applying a current.
14. The method of claim 12 , wherein the polymerizing step comprises delivering a gas containing the oxidizer or a liquid containing the oxidizer into a sealed chamber containing the monomer-containing composite to form the composite material.
15. The method of claim 14 , wherein the chamber is at a pressure below atmospheric pressure to increase the porosity of the monomer-containing composite.
16. The method of claim 12 , wherein the method further comprises electrochemically depositing a conductive polymer on a surface of the composite material.
17. The method of claim 12 , wherein the monomer-containing composite is in the presence of a crosslinking agent during polymerization.
18. The method of claim 17 , wherein the crosslinking agent comprises a monomer functionalized with a silane, an acrylate, a methacrylate, epoxide, glycidyl ether, vinyl, allyl, azide, a derivative thereof, or a combination thereof.
19. The method of claim 12 , wherein the polymerizing step comprises oxidizing the monomer-containing composite with an oxidizer to form the composite material and the oxidation occurs in the presence of agitation.
20. The method of claim 12 , wherein the substrate comprises a lumen through the material, and the method further comprises rinsing the lumen during the polymerizing step.
21. The method of claim 12 , wherein the polymerizing step comprises oxidizing the monomer-containing composite with an oxidizer to form the composite material, the oxidizing step comprises soaking the monomer-containing composite in an oxidation medium comprising the oxidizer and an optional solvent such that the conducting monomer and the oxidizer react to form the composite material, the oxidizing step occurs for about 12 hours to about 36 hours at 25 to 37° C., and the oxidation medium further comprises a radioopacity additive which comprises tantalum, platinum, or iridium.
22. The method of claim 12 , wherein the polymerizing step comprises oxidizing the monomer-containing composite with an oxidizer to form the composite material, the oxidizing step comprises soaking the monomer-containing composite in an oxidation medium comprising the oxidizer and an optional solvent such that the conducting monomer and the oxidizer react to form the composite material, the oxidizing step occurs for about 12 hours to about 36 hours at 25 to 37° C., and the oxidation medium further comprises a conductive additive which comprises carbon black, carbon fiber, a pre-polymerized conducting polymer, carbon nanotubes, graphite, graphene, metal particles, or a metal powder.