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WO1990002763A1 - Dispersions de polymeres electroconducteurs - Google Patents

Dispersions de polymeres electroconducteurs Download PDF

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Publication number
WO1990002763A1
WO1990002763A1 PCT/US1989/003767 US8903767W WO9002763A1 WO 1990002763 A1 WO1990002763 A1 WO 1990002763A1 US 8903767 W US8903767 W US 8903767W WO 9002763 A1 WO9002763 A1 WO 9002763A1
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particles
polymer
stabilizing
stabilizing polymer
conducting
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PCT/US1989/003767
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English (en)
Inventor
Brian Vincent
Timothy M. Obey
Nicolas S. Cawdery
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BIOSYN-R Corp
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BIOSYN-R Corp
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Definitions

  • This application is in the field of polymer chemistry, and is in particular a method of forming dispersions of electrically conducting latex particles.
  • Colloidal particles having a high electrical conductivity have mainly been metal particles, perhaps the most famous being Faraday's gold sol preserved in The Royal Institution in London.
  • metal sols have now been produced, particularly for use in heterogeneous catalysis.
  • organic polymers which show high electrical conductivities comparable to the electrical conductivities of metals.
  • the most studied conducting polymer system is polyacetylene.
  • pristine polyacetylene is a semiconductor
  • MacDiarmid et al. M. M. Maricq, J. S. augh, A. G. MacDiarmid, H. Shirakawa, and A. J. Heeger, J. A er. Che . Soc. 100, 7729 (1978)
  • doping the bulk or surface polymerized material with a suitable oxiding agent e.g., I2, AsF 5 , FeCl 3
  • reducing agent e.g., Na, n-BuLi
  • Dispersion polymerization involves the polymerization of a monomer dissolved in a liquid which is a solvent for the monomer and initiator but a nonsolvent for the polymer, where a dispersant is added to prevent gross flocculation of the polymer and to control particle size. The dispersant also prevents aggregation of polymer particles caused by high salt content in the solvent.
  • Water soluble dispersants are generally organic polymers such as gelatin, methyl cellulose, poly(vinyl alcohol) and alkali salts of poly(methacrylic acid) . See generally, G. Odian, Principles of Polymerization. (2nd Ed. 1981) , . E. J.
  • Bjorklund and Lundstrom prepared polypyrrole/cellulose composites by an aqueous dispersion technique.
  • the composites have a conductivity of 2 ohm ""1 cm “"1 f when measured in a dilute HC1 solution of FeCl 3 -6H2 ⁇ , as reported by R. B. Bjorklund and I. Lundstrom, J. Electron. Mater. 13, 211 (1984) .
  • Bjorkland and Liedberg later reported that the resulting polymeric composition had essentially no Fe +3 ion present while the Cl- anion was neutralizing the charge on the polymer.
  • the composite was used to prepare thin films displaying a maximum conductivity of 0.2 ohm" 1 cm “1 , as described by R. Bjorkland and B. Liedberg, in "Electrically Conducting Composites of Collodial Polypyrrole and Methyl Cellulose", J. Chem. Soc. Che . Common, 1293 (1986) .
  • the emeraldine salt form of polyaniline is prepared by adding aniline to an aqueous solution of (NH4)2 2 ⁇ s-
  • the polymer has a symmetric conjugated structure with extensive charge delocalization and a high conductivity resulting from proton addition to the polymer. This is in contrast to partial oxidation of the polymer i ⁇ system, as in the p-doping of other conducting polymers, W. Huang, B. Humphrey, and H. MacDiarmid, "Polyaniline, a Novel Conducting Polymer", J. Chem. Soc. Farady Trans. 1. 82, 2385 (1986) .
  • Another problem that results from the adsorption of polymeric dispersant by the growing conducting polymer is the decrease in conductivity with increasing mass ratio of dispersant to monomer in the particle. This is a direct effect of incorporation of nonconducting dispersant into the conducting, pellet.
  • the dispersant cannot be eliminated from the method of preparation of the latex particles, however, because it is needed in the dispersion polymerization reaction to prevent aggregation of the polymer particles as a result of high salt content.
  • the present invention is a method of preparation of "bare" dispersions of electrically conducting polymers, and products thereof.
  • the invention provides a method to prepare charge stabilized, collodial dispersions of electrically conducting polymer particles which do not contain significant quantities of water soluble sterically stabilizing polymers, and the product thereof.
  • charge- stabilized "bare" conducting polymeric particulate dispersions are produced by polymerizing an electrically conducting polymer in an aqueous solution containing a water soluble stabilizing/dispersant polymer (referred to hereafter as stabilizing polymer) , then stripping the particles of the stabilizing polymer.
  • stabilizing polymer a water soluble stabilizing/dispersant polymer
  • a sterically stabilized conducting polymeric latex can be polymerized from an aqueous solution of monomer, initiator and stabilizing polymer, followed by removal of the stabilizing polymer by repeated washing with a solvent for the stabilizing polymer, chemical or biological degradation of the stabilizing polymer sheath, or by manipulation of the solution pH, promoting repulsion between the conducting polymer and the stabilizing polymer.
  • the bare particles may be freeze dried or redispersed in solution after stripping the conducting particles of their dispersant-stabilizing polymer sheath.
  • a dispersant-stabilizing polymer is added to the solvent.
  • One advantage of the present invention is that the bare particles can be resuspended in a non-aqueous solvent and coated with block or graft copolymers which are not soluble in aqueous solutions.
  • the bare or recoated particles can also be incorporated onto or within non-conducting polymeric particles or latices.
  • This method produces polymer particles having approximate diameters of 40 to 500 nm which have conductivities in the range of approximately one to ten ⁇ "1 cm -1 .
  • the "bare” electrically conducting polymers obtained are useful for a variety of applications, including incorporation into electrically conducting composites, chromatographic materials, adsorbents, high surface area electrodes, and electrophoresis materials.
  • the present invention is a method of producing "bare" electrically conducting polymeric particles and dispersions, and the products thereof.
  • the method includes preparation of charge-stabilized colloidal dispersions of electrically conducting polymer particles which do not have adsorbed to them water soluble dispersant, stabilizing polymers such as poly(ethylene oxide), poly[vinyl alcohol-co-acetate], poly(vinyl pyrrolidone), carboxymethylcellulose, carboxymethacrylate (CMA) , poly(methacrylic acid) , and copolymers thereof.
  • stabilizing polymers such as poly(ethylene oxide), poly[vinyl alcohol-co-acetate], poly(vinyl pyrrolidone), carboxymethylcellulose, carboxymethacrylate (CMA) , poly(methacrylic acid) , and copolymers thereof.
  • CMA carboxymethacrylate
  • copolymers thereof copolymers thereof.
  • These particles can be dispersed in non-aqueous ssolutions and used in a
  • the method of the present invention to make charge-stabilized, or "bare", conducting polymeric particles is summarized as follows.
  • An electrically conducting polymer is polymerized in an aqueous solution of a water soluble dispersant or stabilizing polymer, thereby forming polymeric particles stabilized within a latex.
  • the stabilizing polymers are defined as those which have properties similar to those of poly(ethylene oxide and poly[vinyl alcohol-co-acetate] with respect to their solvent miscibility and their interaction with the electrically conducting polymers such as polyaniline and polypyrrole. j ' , - ⁇
  • the stabilizing polymer is then removed from the particles.
  • Several methods can be used. The three preferred methods at this time are by repeated washing of the sterically stabilized conducting polymeric latex with a good solvent for the stabilizing polymer, by chemical or biological degradation of the polymeric sheath, and by manipulation of the solution pH, to promote repulsion between the conducting polymer and the stabilizing polymer.
  • the bare particles can be freeze dried or redispersed in the same or a different solution.
  • the particles can be directly suspended in solvents of high dielectric constant such as water or methanol or mixtures thereof.
  • the conducting particles can be dispersed in solvents of low dielectric constant or high ionic strength if a dispersant-stabilizing polymer is added to the solvent. Since the bare particles can be dispersed in non-polar solvents, non-water soluble stabilizing polymers can be added as the dispersants.
  • polymers which can be used in hydrocarbons include polyacrylate with polyhydroxysteric acid, polylaurylmethacrylate, and polytertiarybutylstyrene. Bare particles can be dispersed in a solvent to a concentration of between approximately 50 to 100 g/1. Coated particles can be dispersed in a solvent to a concentration of approximately 400 g/1.
  • Electrically conductive polymers which may be used according to the present invention include any polymer that conducts electricity, which can be dispersion polymerized and maintains its integrity when the dispersant-sheath is removed.
  • Examples of semiconducting organic polymers which can be used to make the polymeric particles of the present invention include polypyrrole (PPy) , polyacetylene, polyaniline, polythiophene, poly(p-phenylene) and substituted polymers thereof.
  • the monomers corresponding to these polymers are added to the solution in a concentration range of 0.5% to 5%, preferably 1%, by volume.
  • Initiators which can be used in the present invention include Lewis acids such as ferric chloride (FeCl 3 ), ferric bromide (FeBr 3 ) , Fe(N0 3 ) 3 , K 3 Fe(CN) 6 , CuCl , CuBr 2 , Cu(N0 3 ) 2 , A1C1 3 , BF 3 , SnCl , ZnCl 2 , TiCl , or PCI 5 , organometallic derviatives such as RA1C1 2 , R 2 AICI, R 3 A1 (where R is an organic ion), oxyhalides such as P0C1 3 , Cr0 Cl, S0C1 , V0C1 / acetyl perchlorate, and oxidizers such as potassium persulphate (K2S 2 O 3 ) and ammonium persulphate ( (NH4)2 S 2°8) • ⁇ ⁇ e selection of the initiator can be used to vary the particle size
  • the initiator is present in the solution in a range of between approximately 1% to 20% by mass, depending on the particular initiator and monomer being used.
  • Polymers suitable as dispersant-stabilizers in the present invention include poly(ethylene oxide) (PEO) (MW > 10 5 ) , poly[vinyl alcohol-co-acetate], pol (vinyl pyrrolidone) (PVP) , carboxymethylcellulose, carboxymethacrylate (CMA) , poly(methacrylic acid) , and copolymers thereof.
  • PEO poly(ethylene oxide)
  • PVP poly[vinyl alcohol-co-acetate], pol (vinyl pyrrolidone) (PVP)
  • carboxymethylcellulose carboxymethacrylate (CMA)
  • CMA carboxymethacrylate
  • poly(methacrylic acid) poly(methacrylic acid)
  • the stabilizing polymers are added to the solution in a concentration ranging from 0.3% to 3% by mass, preferably 1%.
  • the choice of stabilizing polymers can be used to modify the particle size.
  • the average diameter (3) of the particles made using PEO as the stabilizer is significantly greater than when either PVP or PVA is employed.
  • Polypyrrole particles made using PVP or PVA have diameters typically in the range 70-150 nm.
  • the "effective equilibrium adsorption isotherm" for the preparation of sterically-stabilized conducting polymers may be prepared by plotting the mass ratio of stabilizer to monomer versus the equilibrium concentration of the stabilizing polymer in the solution used to prepare the dispersion. A decrease in concentration of the dispersant stabilizer in the solution corresponds to an adsorption of the dispersant into the polymer particles. The isotherm curve rises to a certain height at which point the slope of the curve changes. This "knee” represents the optimum stabilizing polymer to monomer mass ratio.
  • Composites of the bare electrically conducting polymeric particles are prepared by suspending the particles in a solution of monomer and stabilizing polymer and polymerizing.
  • the particles can be bound to the surface of non-conducting polymeric supports or larger oxide or carbon particles using methods known to those skilled in the art. Similarly, the particles can be adsorbed onto non-conducting latices or particles using methods and materials known to those skilled in the art. These materials are particularly useful in absorbents, high surface area electrodes, electrophoresis and chromatographic reagents, and in other separation technologies.
  • Example 1 Modification of particle size by selection of stabilizing polymer.
  • Particles were prepared as summarized: 8.83 g of ferric chloride hexahydrate dissolved in 50 ml H 2 0 was added to a stirred solution of X g of polymer in 50 ml H2O. Freshly distilled pyrrole (1 ml) was added and stirring continued for 24 hrs at 25°C. The latex was then decanted into well-boiled "Visking" tubing and dialyzed against water (the dialysate being changed every 12 hrs for a period of one week) .
  • the particle size distributions were obtained from electron micrographs (Hitachi HA-11B electron microscope) with subsequent analysis using a Carl- Zeiss TGZ3 analyzer.
  • Conducting particles were prepared with diameters in the range of 80-440 nm. When PEO was used as the stabilizer, fairly large particles were obtained. Table 1 provides a representative list of particle sizes. Table 1: Conducting Polymer Particle Sizes
  • Example 2 Removal of stabilizing polymer from conducting polymer particles by washing with an appropriate solvent.
  • PEO was removed from PPy particles with repeated washing with a water/methanol mixture.
  • Other water soluble polymers such as PVA and PVP can be removed by washing with other suitable solvents or mixtures thereof.
  • bare PPy particles are produced from PPy/PEO composites after several, usually at least five, centrifugation/redispersals in water/methanol mixtures.
  • Other suitable solvents can be determined by testing the solubility of the dispersant-stabilizing polymer in the desired solvent system. The success of the removal step can be monitored spectrophotometrically with, for example, analysis of IR, NMR or UV, or, alternatively, by performing standard wet qualitative chemical analyses. Elemental analysis can also be used to confirm that the dispersant-stabilizing polymer has been removed.
  • Example 3 Demonstration of removal of the stabilizing polymer sheath from the electrically conducting polymer latex.
  • Table 3 demonstrates the mass ratio of adsorbed NaPSS 780K per meter 2 polypyrrole particle surface.
  • NaPSS is a negatively charged polyelectrolyte which is adsorbed onto a "bare" poly(pyrrole) surface which carries a positive charge, but will not be adsorbed onto a polymer particle which has a steric- stabilizer sheath.
  • pH 1.6 PPy/PEO particles that had been washed with water to remove PEO adsorbed approximately 3 mg/m 2 of NaPSS 780K.
  • the particles do not adsorb NaPSS, because the polymer is not protonated.
  • NaPSS adsorbed originally at pH 1.6 could be completely removed by raising the pH to 11.
  • the amount of NaPSS 780K that may be adsorbed onto water/ ethanol-washed latex is far greater than on untreated latex, indicative of a loss of the stabilizing sheath.
  • Example 4 Redispersion of bare conducting polymer particles.
  • PPy/PEO 300K, PPy/PVA 95K and PPY/PVP 44K were spun down using an MSE 'Hi-Spin 18' centrifuge at 15000 r.p.m. for 30 mins and redispersed in methanol (PPy/PEO 300K, PPy/PVA95K) or pyridine (PPy/PVP44K) using mechanical agitation and ultrasonics. Particles were redispersed six times, then the latices were redispersed in water.
  • PPy/PEO 30OK can also be dispersed in organic solvents (e.g. 1,4-dioxan) if dissolved polymer is present.
  • Example 5 Removal of stabilizing polymer by chemical or biological degradation.
  • a second method of removing the adsorbed dispersant-stabilizer sheath is by chemical or biological degradation of the sheath.
  • ether linkages can be cleaved by suitable acids such as an acetic acid/HBr mixture, HI, HBr, and HCl.
  • Glucoside linkages can be cleaved by mineral acids.
  • Enzymes known to cleave certain linkages in the stabilizing polymer can also be employed to remove the dispersant-stabilizer sheath.
  • cellulase is useful to remove carboxymethylcellulose from the conducting polymer.
  • an ether linkage can be cleaved with an acetic acid/HBr mixture.
  • PPy/PEO 30OK was treated with a 50/50 mixture of acetic acid/HBr at 60°C for 24 hrs.
  • glucoside links may be cleared by the action of mineral acids, using the method described in "Introduction to Carbohydrate Chemistry", R. D. Guthrie, Clarendon Press (1979), or with cellulases, as described in "Hydrolysis of Cellulose: Mechanisms of Enzymatic and Acid Hydrolysis” (R. R. Brown, Jr., L. and Juresek, wdx.) Adv. Chem. Ser. 101 (1980) .
  • PPy/CMCl was treated with cellulose trichoviride at 37°C and pH 4.2 for 24 hrs, and HCl solutions of varying concentration (10 ⁇ 2 - 5 mol dm "3 ) .
  • Acid hydrolysis of CMC stabilized PPy is not the preferred method for preparing electrostatistically- stabilized PPy, since very harsh conditions are needed to promote extensive degradation of the stabilizing sheath. At lower concentrations of acid, little of the coating is degraded. Enzyme hydrolysis produces particles that behave as if they are uncoated. If enzyme is adsorbed at the particle surface, it may be denatured using base.
  • Example 6 Removal of polymer using pH manipulation.
  • a third method of producing a bare latex conducting polymer particle is by manipulation of the pH of the solution of the coated polymer particle.
  • poly(pyrrole) has a positive charge and at high pH it has a negative charge. It is possible to desorb carboxymethylcellulose from the surface of the poly(pyrrole) by raising the pH of the system to promote repulsion between the polymer chain and the dispersant-stabilizer.
  • polyaniline is positively charged at low pH and negatively charged at high pH.
  • Suitable reagents to alter pH include HCl, acetic acid, HBr, and HI
  • Example 7 Measurement of electrophoretic mobility of bare polymers.
  • the electrophoretic mobility of both sterically and electrostatically-stabilized lattices was measured as a function of pH using a PenKem System 3000 instrument.
  • the background of electrolyte level was maintained at 10 ⁇ 2 mol dm "3 (NaCl) .
  • the electrophoretic mobility of the bare latex particles in aqueous 10 ⁇ 2 mol dm" 3 KC1 solution was measured as a function of pH. In general, bare particles have higher isoelectric points than do particles coated with stabilizing polymer.
  • Example 8 Measurement of conductivity of bare polymeric particles.
  • Particles were freeze dried to form pellets for conductivity measurements using a Research and Industrial Co. Model H301 pelletizing press at pressures of 250 atm.
  • the dc conductivities were obtained using the standard four point probe method, W. S. Huang, B. D. Humphrey, and A. G. MacDiarmid, J. Chem. Soc. Faraday Trans. 1 82, 2385 (1986).
  • Table 6 provides the results of the conductivity measurements.
  • “Bare” conducting polymer particles prepared as described are useful for a variety of applications.
  • such materials can be incorporated into conducting composites.
  • the organic conducting materials may be used in selective extractive technologies. Since conducting polymers may vary in charge as a function of applied current, they can be used in electrochromatography, electrophoresis, or any like technique that separates a mixture of compounds on the basis of charge. Water stable conducting polymers have a broad range of biological applications, as in the separation of proteins and other biological materials. A further application of these "bare" latex organic conducting polymers is for electrically conducting paint. Such a coating can change the radar profile of aircraft.
  • Example 9 Preparation of Polypyrrole Particles in the size range of 40 to 100 nm.
  • Particles of less than 100 nm diameter were prepared by making two microemulsions of water droplets in toluene, one containing pyrrole monomer and the other containing an initiator, ammonium persulfate, dissolved in the aqueous phase. Within an hour of mixing the two microemulsions, a clear blue- black "solution” had formed; after 24 hours, a dark green supernatant containing a black precipitate of flocculated polypyrrole (PPY) particles formed.
  • PPY flocculated polypyrrole

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Cette invention concerne un procédé de préparation de dispersions 'brutes' de polymères électroconducteurs, et de leurs produits. Notamment l'invention concerne un procédé de préparation de dispersions colloïdales stabilisées en charge, de particules polymères conductrices ne contenant pas de quantités importantes de polymères à stabilisation stérique, et de leurs produits. Ces particules présentent de nombreux avantages par rapport à l'art antérieur puisque l'on peut les utiliser pour réaliser des dispersions non aqueuses de particules électroconductrices, ou les incorporer dans des électrodes à aire de surface élevée et dans des matières chromatographiques et électrophorétiques.
PCT/US1989/003767 1988-09-02 1989-08-31 Dispersions de polymeres electroconducteurs Ceased WO1990002763A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888821631A GB8821631D0 (en) 1988-09-02 1988-09-02 Dispersions of electrically conducting polymers
GB8821631.2 1988-09-02

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WO1990002763A1 true WO1990002763A1 (fr) 1990-03-22

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993007243A1 (fr) * 1991-10-10 1993-04-15 The Lubrizol Corporation Fluides electrorheologiques renfermant des polymeres electroniquement conducteurs
WO2002000759A1 (fr) * 2000-06-26 2002-01-03 Agfa-Gevaert Latex redispersible a base de polyothiophene
WO2002014400A1 (fr) * 2000-08-14 2002-02-21 Pharmacia Corporation Preparation de polypyrrole hydrosoluble
US6605236B1 (en) * 1994-01-03 2003-08-12 Xerox Corporation Conductive polymeric composites, articles and processes for the preparation thereof
US6890584B2 (en) 2000-06-28 2005-05-10 Agfa-Gevaert Flexographic ink containing a polymer or copolymer of a 3,4-dialkoxythiophene
WO2009112382A1 (fr) * 2008-03-14 2009-09-17 Basf Se Particules fonctionnelles redispersibles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2181367A (en) * 1985-10-10 1987-04-23 Asea Ab A method of manufacturing an electrically conductive layer
US4665129A (en) * 1984-03-15 1987-05-12 Basf Aktiengesellschaft Electrically conductive thermoplastic mixtures of macromolecular compounds and finely divided pyrrole polymers
EP0229992A2 (fr) * 1985-12-20 1987-07-29 Polaroid Corporation Polymères conducteurs transformables
US4697000A (en) * 1984-09-04 1987-09-29 Rockwell International Corporation Process for producing polypyrrole powder and the material so produced

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4665129A (en) * 1984-03-15 1987-05-12 Basf Aktiengesellschaft Electrically conductive thermoplastic mixtures of macromolecular compounds and finely divided pyrrole polymers
US4697000A (en) * 1984-09-04 1987-09-29 Rockwell International Corporation Process for producing polypyrrole powder and the material so produced
GB2181367A (en) * 1985-10-10 1987-04-23 Asea Ab A method of manufacturing an electrically conductive layer
EP0229992A2 (fr) * 1985-12-20 1987-07-29 Polaroid Corporation Polymères conducteurs transformables

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF COLLOID AND INTERFACE SCIENCE, Volume 118, No. 2, issued August 1987, (Academic Press), by ARMES, MILLER and VINCENT: "Aqueous Dispersions of Electrically Conducting, Monodisperse Polypyrrole Particles". See the entire document. *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993007243A1 (fr) * 1991-10-10 1993-04-15 The Lubrizol Corporation Fluides electrorheologiques renfermant des polymeres electroniquement conducteurs
US5435932A (en) * 1991-10-10 1995-07-25 The Lubrizol Corporation Electrorheological fluids containing eletronically conductive polymers
US6605236B1 (en) * 1994-01-03 2003-08-12 Xerox Corporation Conductive polymeric composites, articles and processes for the preparation thereof
WO2002000759A1 (fr) * 2000-06-26 2002-01-03 Agfa-Gevaert Latex redispersible a base de polyothiophene
EP1780233A1 (fr) * 2000-06-26 2007-05-02 Agfa-Gevaert Latex rédispergeable comprenant un polythiophène
EP1801143A1 (fr) * 2000-06-26 2007-06-27 Agfa-Gevaert Solutions ou dispersions de revêtement, et encres d'impression comprenant un latex redispersable avec un polythiophène
KR100847904B1 (ko) * 2000-06-26 2008-07-23 아그파-게바에르트 폴리티오펜을 포함하는 재분산성 라텍스
US6890584B2 (en) 2000-06-28 2005-05-10 Agfa-Gevaert Flexographic ink containing a polymer or copolymer of a 3,4-dialkoxythiophene
WO2002014400A1 (fr) * 2000-08-14 2002-02-21 Pharmacia Corporation Preparation de polypyrrole hydrosoluble
WO2009112382A1 (fr) * 2008-03-14 2009-09-17 Basf Se Particules fonctionnelles redispersibles

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