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WO1990013601A1 - Melanges de polymeres conducteurs-polyamides et leur procede de production - Google Patents

Melanges de polymeres conducteurs-polyamides et leur procede de production Download PDF

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Publication number
WO1990013601A1
WO1990013601A1 PCT/US1990/001844 US9001844W WO9013601A1 WO 1990013601 A1 WO1990013601 A1 WO 1990013601A1 US 9001844 W US9001844 W US 9001844W WO 9013601 A1 WO9013601 A1 WO 9013601A1
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WO
WIPO (PCT)
Prior art keywords
conductive polymer
polyaniline
polymer
polyamide
conductive
Prior art date
Application number
PCT/US1990/001844
Other languages
English (en)
Inventor
Randy Edwin Cameron
Original Assignee
Lockheed Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lockheed Corporation filed Critical Lockheed Corporation
Publication of WO1990013601A1 publication Critical patent/WO1990013601A1/fr

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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
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • n is between 0 and 1.
  • the oxidation state of polyaniline referred to as "e eraldine” is believed to have a value of n of about 0.5.
  • This free-base form of polyaniline is an electrical insulator. Reaction of emeraldine free-base with protonic acids of the form HX, where X is, for example, Cl, causes the polymer to undergo an insulator to conductor transition, as disclosed in A. G. MacDiar id, et al., Mol. Cryst. Liq. Cry ⁇ t. 121, 173 (1985) . Conductive polyaniline of this type has been employed in batteries as disclosed, for example, in French Patent No. 1,519,729.
  • a base-type non-conductive polymer such as polyaniline
  • a base-type non-conductive polymer such as polyaniline
  • methyl iodide emeraldine free-base
  • reagents of the form RS0 2 C1 e.g., tosyl chloride
  • conductive multisulfonic acid derivatives of polyaniline which are highly thermally stable.
  • the conductive polymers of the above applications tend to be brittle, and there is a lack of flexibility and elongation ability in such conductive materials, resulting in inferior mechanical properties.
  • the proportion of conductive polymer to non-conductive polymer in the blend must be relatively high (e.g., greater than 50%) in order for charge to be transferred effectively between polymer chains.
  • the blend materials tend to phase separate, that is, the polyaniline aggregates into clumps within the non-conductive polymer matrix. These clumps are separated by the matrix material, and the blend thus is an insulator. Further, the mechanical properties of the material suffer upon phase separation. It would be desirable to form blends where the polyaniline is dispersed evenly on a molecular level at all loadings, to thus form a conductive polymer blend.
  • a conductive polymer blend formed by first reacting a base-type non-conductive polymer containing carbon- nitrogen linkages, such as polyaniline, with a carbonyl anhydride, such as 3,3', 4,4 '-benzophenone tetracarboxylic dianhydride, to form a conductive polymer containing polyimide-like groups covalently linked to nitrogen atoms of the base-type polymer, mixing such conductive polymer with non-conductive polyimide in a suitable solvent, removing the solvent, and forming a conductive continuous phase blend of the polyimide and the conductive polymer.
  • a base-type non-conductive polymer containing carbon- nitrogen linkages such as polyaniline
  • a carbonyl anhydride such as 3,3', 4,4 '-benzophenone tetracarboxylic dianhydride
  • Patent No. 4,025,463 to Trevoy discloses amine salts of linear polyaniline compounds as semiconductors alone or in combination with a co-dissolvable binder material.
  • binders listed in the patent are polyamides. These compounds are stated to be useful in the formation of semiconductor compositions including self-supporting films and fibers.
  • An electrically conductive thermoplastic resin composition comprising (1) at least one thermoplastic resin, such as polyamide resin, (2) at least one metallic powder, such as nickel, copper, iron or aluminum, and (3) a diphosphonic acid derivative.
  • An object of the present invention is the provision of improved electrically conductive polymer materials of the class of conductive polyaniline blended with a polyamide. Another object is to provide conductive polymer materials having improved elongation and flexibility, mechanical properties, including toughness, and thermal stability, in the
  • a still further object is to render polyamides conductive by doping with a conductive polymer, particularly an improved relatively highly conductive form of polyaniline, to produce an easily processable, conductive polymer blend.
  • a still further object is to provide novel procedure for blending polyaniline in the solution phase with a polyamide, whereby on removal of the solvent, the resulting polymer blend can be processed to yield conductive fibers, films or bulk materials.
  • a conductive polymer blend is produced according to the invention by solution blending in a suitable solvent a mixture of (a) an electrically conductive polymer containing carbon-nitrogen linkages and having an organic or inorganic group covalently linked to nitrogen atoms of the polymer, particularly a conductive polyaniline or a polyaniline derivative, and (b) a polyamide, removing the solvent and forming a continuous phase blend of the conductive polymer and the polyamide.
  • the invention is carried out by first reacting a base- type non-conductive polymer containing carbon-nitrogen linkages, particularly from the family of the polyanilines, with a cation donor compound capable of covalently binding to the nitrogens of the polymer, such as a carbonyl or sulfonyl anhydride, to thereby form an electrically conductive polymer, e.g., a derivatized polyaniline having an organic or inorganic group covalently linked to nitrogen atoms of the base-type polymer, e.g., as described in the above U.S. Application Serial No. 158,477 of S. I. Yaniger, et al.
  • the conductive polymer so formed is mixed with a polyamide, such as nylon, e.g. , in certain ranges of proportions as described hereinafter, in a suitable solvent, such as N-methyl pyrrolidone (NMP) , to form a completely miscible blend of the two components in the solution phase.
  • NMP N-methyl pyrrolidone
  • the blend is solution processable and upon removal of the solvent, the mixture forms a continuous phase blend, the blended materials resulting in an electrically conductive resin which is strong and can be formed into very flexible, stretchable conductive materials, such as fibers and films.
  • Another advantage of these blends is improved morphology of cast films. For example, emeraldine free-base has a large optical non-linearity in the near infrered (about 1 micron wavelength) . It cannot at present be used in non-linear optical devices because, cast films of the polymer are
  • Suitable polymer blends form a continuous phase, with no fibrillar structure. It is again necessary to achieve a high loading of the polyaniline into the optically inactive polyamide so that the large optical activity of the emeraldine is not diluted. This cannot be achieved by prior art technology, as mentioned above.
  • Another advantage of this invention is that the polyamide matrix serves as a physical barrier against environmental degradation or hydrolysis, since such polyamides are extremely hydrophobic.
  • the electrically conductive polymer e.g., conductive polyaniline
  • the electrically conductive polymer can be formed in situ, during solution blending with the polyamide component, by incorporating in the solvent solution the non- conductive polymer, e.g., polyaniline, and the cation donor compound for reaction with such non-conductive polymer, to form the resulting conductive polymer, in solution with the polyamide component.
  • the present invention discloses a technique for increasing the electrical conductivity of a polyamide, without materially adversely affecting, or without decreasing, the mechanical properties thereof.
  • a base-type non-conductive polymer containing carbon-nitrogen linkages is first reacted with a cation donor compound to form a polymer salt in which a covalent bond is formed between the nitrogens of the polymer and such donor cation.
  • a preferred form of non-conductive polymer can be represented as follows:
  • A is a carbon-containing group, such as aryl, particularly the benzene ring, as in polyaniline, and including naphthyl and biphenyl, and substituted benzene, naphthyl or biphenyl groups, such as the alkyl substituted derivatives, e.g., 2-methyl biphenyl, butyl naphthalene, 2- methyl aniline, and aryl substituted derivatives, e.g., beta phenyl naphthalene and beta tolyl naphthalene; and y is an integer ranging from about 1 to about 1,000, e.g., about 10 to about 100.
  • non-conductive polyaniline family of polymers can be further characterized as consisting of polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl .substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives.
  • the preferred non-conductive polymer containing carbon- nitrogen linkages is the basic polymeric starting material, polyaniline emeraldine free-base (PFB) .
  • polymeric starting materials can include other non- conductive base-type polymers containing carbon atoms linked to nitrogen, such as cyanogen polymer containing the recurring unit:
  • the starting materials of the invention can also include non-conductive mixtures and blends of the above polymers, and copolymers of the above polymers and other polymers, such as a blend of polyaniline and polymethylmethacrylate, and polymer alloys, such as polybenzimidazole-polyimide alloys, containing carbon-nitrogen groups.
  • non-conductive polymer as employed herein is intended to denote any of the above homopolymer or copolymer materials.
  • the invention will be described hereinafter, however mostly in terms of the use of the preferred non-conductive free-base polyaniline as polymeric starting material. This is a high polymer having a molecular weight of the order of 50,000 to 80,000.
  • Lower molecular weight forms of polyaniline can also be employed, such as an oligomer of polyaniline containing 8 sub-units and having a molecular weight of about 800 to 900.
  • the preferred conductive polymers according to the invention are those prepared by reacting the non-conductive polymer containing carbon-nitrogen linkages, such as polyaniline, with a cation donor compound capable of covalently binding to the nitrogens of such polymer to form an electrically conductive polymer.
  • the resulting conductive polymer containing carbon-nitrogen linkages has an organic or inorganic group covalently linked to nitrogen atoms of the polymer, and an anion associated with such nitrogen atoms to form a polymer salt.
  • R + donor compound such as RX, R 3 OX, R 2 S0 4 , R'S0 2 C1 or R j SiQ, where R, R'S0 2 or R j Si is group which readily forms a covalent bond with nitrogen
  • R, R 1 and R" each can be alkyl containing from 1 to 20 carbon atoms, e.g., methyl, ethyl and the like, and aryl, e.g., p-toluene sulfonyl (tosyl) , benzyl, tolyl, xylyl, and other aromatic moieties
  • X is an anion such as halogen, e.g., Cl ⁇ , I ⁇ or Br "" ; PF 6 " SbCl 6 ⁇
  • the above reaction forms a conductive polymer salt having a group as defined above covalently linked to the nitrogen atoms.
  • the reactant which forms a covalent chemical bond with the nitrogen of the polyaniline free-base or equivalent polymer noted above can be, for example, one of the above R + donor compounds, such as an alkyl halide, wherein the alkyl group can contain from 1 to 20 carbon atoms, such as methyl iodide, or dimethylsulfate.
  • base-type non-conductive polymers containing carbon-nitrogen linkages can be converted to conductive polymers by reacting the non-conductive polymer with an anhydride, such as R-S0 2 -0-S0 2 R' , R-CO-O-CO-R 1 , or R- CO-0-S0 2 R', or mixtures thereof, where R and R' are alkyl or aryl, e.g., tosylic anhydride, benzophenone tetracarboxylic dianhydride, or o-sulfobenzoic anhydride, according to the general reaction shown above, and forming an electrically conductive polymer in which the S0 2 R and COR groups are covalently linked to the nitrogen atoms of the conductive polymer and the anion of the conductive polymer is the
  • base- type non-conductive polymers containing carbon-nitrogen linkages are converted to conductive polymers of high thermal stability, by reacting the non-conductive polymer with a multiprotic acid in the form of an aromatic multisulfonic acid, e.g., having the formula R(S0 3 H) n , where R is aryl, such as benzene or naphthalene, or their substituted derivatives, and n is an integer of at least 2, preferably 2 to 4, such as m-benzene disulfonic acid, or mixtures thereof, to form a polymer salt in which the -S0 3 H groups are covalently linked to the nitrogens of the polymer through the hydrogen bond.
  • a multiprotic acid in the form of an aromatic multisulfonic acid, e.g., having the formula R(S0 3 H) n , where R is aryl, such as benzene or naphthalene, or their substituted derivatives, and n is an integer of at least 2,
  • the molar proportions of cation donor compound to non- conductive, e.g., nitrogen-containing polymer free-base can be varied but is sufficient to increase the electrical conductivity of the polymer.
  • the molar proportions of donor compound to nitrogen-containing polymer can range from about 0.01 to
  • SUBSTITUTE SHEET about 2 cation groups, e.g., S0 2 R + or C0R + groups in the case of the anhydride, per nitrogen, and in the case of polyaniline, such molar proportions can range from about 0.01 to about 8, per polymer repeat unit.
  • an aromatic multisulfonic acid is employed as cation donor compound, a range of proportions of about 1/16 to about 2 moles of multisulfonic acid per nitrogen of each polymer unit is employed and, in the case of polyaniline, from about 1/8 to about 2 moles of multisulfonic acid, for every 2 aniline units in the polyaniline chain.
  • the reaction can be carried out as a heterogeneous reaction wherein the polymer starting material is not dissolved but is reacted directly with the cation donor compound, e.g., anhydride, or the polymer starting material, such as polyaniline non-conductive free-base, can be dissolved in a suitable solvent which does not react irreversibly with such donor compound, e.g., N-methyl pyrrolidone, dimethylsulfoxide (DMSO) , dimethylformamide (DMF) , formic acid, dimethylacetamide (DMAC) , acetonitrile, tetrahydrofuran (THF) , and pyridine.
  • a suitable solvent which does not react irreversibly with such donor compound, e.g., N-methyl pyrrolidone, dimethylsulfoxide (DMSO) , dimethylformamide (DMF) , formic acid, dimethylacetamide (DMAC) , acetonitrile, tetrahydrofuran
  • the rate of reaction can range widely, depending on the particular cation donor compound reactant employed. Thus, the reaction rate can range from almost instantaneous to several hours or longer.
  • the conductivity of the resulting conductive polymers e.g., conductive polyaniline, can be varied by reducing or increasing the number of covalently linked side chains on the nitrogen atoms, as by controlling the degree of completeness of the reaction and/or by varying the types of cation donor compound employed in producing such side chains on the polymer.
  • the polyamide component which is blended with the above conductive polymer can be any suitable polyamide which can be mutually dissolved with the conductive polyaniline component in a suitable solvent to form a blend.
  • suitable polyamides are nylon, such as Nylon 8 having the recurring unit:
  • Nylon 6/6 having the recurring unit:
  • Nylon 6 having the recurring unit:
  • Nylon 6/12 having the recurring unit:
  • polyamides which can be employed according to the invention have a molecular weight ranging from about 10,000 to about 500,000 gm/mol.
  • the conductive polymer can be blended in a wide range of proportions with non-conductive polyamide component, generally ranging from about 1 to about 99% conductive polymer to 1 to about 99% non-conductive polyamide component, by weight of the mixture. Particularly to obtain higher conductivity, it is preferred to employ about 50 to about 99% conductive polymer and about 1 to about 50% non-conductive polyamide component, by weight.
  • Such blending can be carried out by mixing the conductive polymer with non-conductive polyamide component in a suitable solvent, such as N-methyl pyrrolidone or formic acid. Other solvents which can be employed are noted above.
  • the reaction of the non-conductive base-type polymer, such as polyaniline, with the appropriate cation donor compound, e.g., anhydride or multisulfonic acid can be carried out in a suitable solvent, such as N-methyl pyrrolidone, and the polyamide component can then-be added to the resulting reaction mixture containing the resulting conductive base-type polymer.
  • a suitable solvent such as N-methyl pyrrolidone
  • the non- conductive polyaniline can be mixed with cation donor compound, e.g., an anhydride or multisulfonic acid, in solvent solution with polyamide component, and the reaction to form the conductive polymer, e.g., conductive polyaniline, takes place in situ during blending thereof with the polyamide component.
  • cation donor compound e.g., an anhydride or multisulfonic acid
  • the reaction to form the conductive polymer e.g., conductive polyaniline
  • the resulting blend in which the conductive polymer and polyamide components are completely soluble is applied to any suitable substrate, either conductive or non-conductive, such as glass, quartz, metal or plastic, and the solvent is evaporated.
  • the solvent is evaporated, a tough, flexible film in the form of a continuous phase blend of the conductive polymer and the polyamide component is obtained, which has high electrical conductivity.
  • SUB S TITUTESHEET polyamide component in the continuous phase blend forming the conductive film is the same as that noted above in preparing the solutions of the blends.
  • the films of the blend of polyaniline and polyamide can have a conductivity, e.g. of 10 "2 S/cm. This conductivity can be altered by changing the weight fraction of polyaniline in the blend.
  • Both the conductive polymer, particularly conductive polyaniline, and the polyamide are quite thermostable, and the resulting blend of the two polymers is a continuous single phase having high thermostability.
  • the blended polymer also has the good mechanical properties of the polyamide component while having the good electrical conductivity properties of the conductive base-type polymer, such as conductive polyaniline.
  • the continuous single-phase blends of the conductive polymer and non-conductive polyamide component produced according to the invention do not separate out upon forming a film from the blend.
  • the conductive polymer and polyamide component blend can be processed to form fibers. This can be achieved, e.g., by pultruding the blend while some solvent is still present in the material.
  • Example 1 5 grams of PA (polyaniline) free-base and 5 grams of Nylon 8 are dissolved in 100 ml of formic acid. To this solution is added 2.5 grams o-sulfobenzoic anhydride. This solution contains about 60% of conductive PA and about 40% of Nylon 8 (polyamide) . The solution is cast on a glass sub- strate to form a film. The resulting film is heated at 40 6 C. under air flow for 2 hours. The cured film is electrically
  • Example 2 The solution of Example 1 is subjected to a pultrusion process to pull fibers from the solution, which are conductive, stretchable and strong.
  • Example 3 The procedure of Example 1 is repeated except employing 0.5 gram m-benzene disulfonic acid or 0.5 gram tosylic anhydride in place of the o-sulfobenzoic anhydride. Similar results to Example 1, are obtained, except conductivity is 0.5 S/cm.
  • Example 4 The procedure of Example 1 is followed except using 150 ml N-methyl pyrrolidone (NMP) in place of formic acid. Results similar to Example 1 are obtained.
  • NMP N-methyl pyrrolidone
  • Example 5 The procedure of Example 4 is followed, except p- toluenesulfonic anhydride is used in place of o-sulfobenzoic anhydride, and in the same amount. Results obtained are similar to Example 4, except conductivity is 0.06 S/cm.
  • Example 6 The procedure of Example 4 is followed, except methyl p- toluenesulfonic acid is used in place of o-sulfobenzoic anhydride, and in the same amount. Results similar to Example 4 are obtained, except conductivity is 0.03 S/cm.
  • Example 7 The procedure of Example 1 is followed except using Nylon 6/6 in place of Nylon 8 and in the same amount. Results similar to Example 1 are obtained.
  • Example 8 The procedure of Example 1 is followed except employing Nylon 6 or Nylon 6/12 in place of Nylon 8 and in the same amount. Results similar to Example 1 are obtained.
  • Example 9 The procedure of Example 1 is followed except employing Nomex in place of Nylon 8 and in the same amount. Results similar to Example 1 are obtained.
  • the electrically conductive polymer blends of the invention have utility in the production of conductive composites, electronic components, electrical conductors, electrodes, batteries, switches, electrical shielding material, resistors, capacitors, and the like.
  • the invention provides a novel class of conductive polymer materials which can be readily cast into tough, flexible conductive films, or formed into fibers or bulk materials " , by solution blending conductive, preferably nitrogen-containing, polymers, such as conductive polyaniline, as described above, with a polyamide component.
  • conductive, preferably nitrogen-containing, polymers such as conductive polyaniline, as described above
  • the resulting resin blend increases the electrical conductivity of the polyamide component without decreasing its mechanical integrity.
  • the result is a conductive resin of superior strength, toughness, flexibility and processibility.

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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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne le mélange en solution de (a) un polymère conducteur contenant des liaisons carbone-azote, tel que la polyaniline comportant un groupe organique ou un groupe inorganique, par exemple, dérivé d'un anhydride ou d'un acide aromatique multisulfonique, lié de manière covalente à des atomes d'azote dudit polymère, et (b) un polyamide, par exemple, le nylon, dans un solvant adapté. Lors de l'élimination du solvant, un mélange en phase continue dudit polymère conducteur et dudit polyamide est formé, lequel présente une bonne conductivité électrique et une bonne résistance. On peut transformer le mélange en solution en films ou en fibres conducteurs résistants, présentant une bonne flexibilité.
PCT/US1990/001844 1989-05-12 1990-04-10 Melanges de polymeres conducteurs-polyamides et leur procede de production WO1990013601A1 (fr)

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US350,806 1989-05-12

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Cited By (10)

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EP0545729A1 (fr) * 1991-12-05 1993-06-09 Neste Oy Matériau polymère conducteur et procédé pour produire celui-ci
EP0588906A1 (fr) * 1991-06-12 1994-03-30 Uniax Corporation Formes de polyaniline electriquement conductrices pouvant etre traitees et produits conducteurs constitues de cette matiere
US5340499A (en) * 1992-08-11 1994-08-23 Neste Oy Electrically conductive compositions and methods for their preparation
EP0627746A1 (fr) * 1993-06-04 1994-12-07 Neste Oy Méthode de préparation d'un matériau polymère conducteur façonnable
US5520852A (en) * 1994-06-08 1996-05-28 Neste Oy Processible electrically conducting polyaniline compositions
US5585038A (en) * 1993-06-04 1996-12-17 Neste Oy Conductive plastics material and a method for its preparation
US5783111A (en) * 1993-09-03 1998-07-21 Uniax Corporation Electrically conducting compositions
GB2360524A (en) * 2000-03-24 2001-09-26 Council Scient Ind Res Melt or solution processable highly conducting polyaniline and blends therof with thermoplastics and elastomers
US6552107B1 (en) 2000-03-24 2003-04-22 Council Of Scientific And Industrial Research Melt or solution processable highly conducting polyaniline and process for preparation thereof, and blends thereof with PVC and EVA
CN113355107A (zh) * 2021-07-05 2021-09-07 合肥中聚合臣电子材料有限公司 一种液晶取向剂

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0588906A1 (fr) * 1991-06-12 1994-03-30 Uniax Corporation Formes de polyaniline electriquement conductrices pouvant etre traitees et produits conducteurs constitues de cette matiere
EP0588906B1 (fr) * 1991-06-12 2000-08-02 Uniax Corporation Formes de polyaniline electriquement conductrices pouvant etre traitees et produits conducteurs constitues de cette matiere
US5928565A (en) * 1991-12-05 1999-07-27 Neste Oy Conducting polymer material and method for its production
EP0545729A1 (fr) * 1991-12-05 1993-06-09 Neste Oy Matériau polymère conducteur et procédé pour produire celui-ci
US5340499A (en) * 1992-08-11 1994-08-23 Neste Oy Electrically conductive compositions and methods for their preparation
US5531932A (en) * 1992-08-11 1996-07-02 Neste Oy Metal compound/protonic acid containing electrically conductive compositions and methods for their preparation
EP0627746A1 (fr) * 1993-06-04 1994-12-07 Neste Oy Méthode de préparation d'un matériau polymère conducteur façonnable
US5585038A (en) * 1993-06-04 1996-12-17 Neste Oy Conductive plastics material and a method for its preparation
US5585040A (en) * 1993-06-04 1996-12-17 Neste Oy Conductive plastics material and a method for its preparation
US5783111A (en) * 1993-09-03 1998-07-21 Uniax Corporation Electrically conducting compositions
US5520852A (en) * 1994-06-08 1996-05-28 Neste Oy Processible electrically conducting polyaniline compositions
US5866043A (en) * 1994-06-08 1999-02-02 Neste Oy Processible electrically conducting polyaniline compositions and processes for the preparation thereof
GB2360524A (en) * 2000-03-24 2001-09-26 Council Scient Ind Res Melt or solution processable highly conducting polyaniline and blends therof with thermoplastics and elastomers
US6552107B1 (en) 2000-03-24 2003-04-22 Council Of Scientific And Industrial Research Melt or solution processable highly conducting polyaniline and process for preparation thereof, and blends thereof with PVC and EVA
GB2360524B (en) * 2000-03-24 2004-02-11 Council Scient Ind Res Melt or solution processable doped polyaniline
CN113355107A (zh) * 2021-07-05 2021-09-07 合肥中聚合臣电子材料有限公司 一种液晶取向剂

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