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WO2008038609A1 - Procédé de production d'un composite conducteur de polyaniline - Google Patents

Procédé de production d'un composite conducteur de polyaniline Download PDF

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Publication number
WO2008038609A1
WO2008038609A1 PCT/JP2007/068498 JP2007068498W WO2008038609A1 WO 2008038609 A1 WO2008038609 A1 WO 2008038609A1 JP 2007068498 W JP2007068498 W JP 2007068498W WO 2008038609 A1 WO2008038609 A1 WO 2008038609A1
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Prior art keywords
polyaniline
group
surfactant
polyaniline complex
compound
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English (en)
Japanese (ja)
Inventor
Ichiro Nasuno
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for producing a polyaniline complex that is soluble in an organic solvent and exhibits high conductivity, and a polyaniline composition.
  • Polyaniline is known as a conductive material that is thermally stable and stable even in the air, and is expected to be applied to capacitors, batteries, sensors, electoluminescence materials, antistatic materials, and the like.
  • polyaniline In the state of emeraldine salt showing conductivity, polyaniline has a problem that workability in forming a film or sheet or forming a conductive film is extremely low in solubility in a solvent. Yes. Therefore, a method for producing a polyaniline excellent in conductivity and solubility stably and powerfully has been sought.
  • Non-Patent Document 1 discloses that dodecylbenzenesulfonic acid and dibutylnaphthalenesulfonic acid are present in water / acetone mixed solvent, Has been described to obtain polyaniline which is soluble in chloroform, tetrahydrofuran and m-taresole. However, the conductivity of the obtained polyaniline was as low as 1.8 S / cm. Further, there is no disclosure or suggestion about a combination of a surfactant having a sulfone group and another surfactant.
  • Non-Patent Document 2 discloses that poly (ethylene darrigol) block poly (propylene glycol) block (as a nonionic surfactant in aniline dissolved in black mouth form without using a protic acid (A method is described in which an aqueous solution containing an aqueous solution containing a polyethylene glycol copolymer is added to make an emulsion, and an aqueous ammonium persulfate solution is dropped to obtain a polymer.
  • the obtained polyaniline was insoluble in the polymerization solvent, and the conductivity was as low as about 1. ox io — 2 s / cm.
  • a compound having a sulfone group is added to the polymerization reaction system. There is no disclosure about.
  • Patent Document 1 discloses a complex (emeraldine salt) soluble in an organic solvent by adding a protonic acid having a sulfonic group when polymerizing aniline in a two-layer system of an organic layer and an aqueous layer. And a polyaniline composition exhibiting high conductivity and excellent solubility by adding a compound having a phenolic hydroxyl group.
  • Patent Document 2 discloses polyaniline exhibiting high conductivity. However, in order to obtain a polyaniline exhibiting high conductivity, the polymerized polyaniline must be dedoped and then mixed with the acid again, and the production method was not simple. Also in this document, there is no disclosure or suggestion of a method for polymerizing aniline using a protonic acid having a sulfone group and a surfactant in combination.
  • Patent Document 1 International Publication No. 2005/052058 Pamphlet
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-272840
  • Non-Patent Document 1 European Polymer Journal 36 (2000) 2201
  • Non-Patent Document 2 Journal oi Macromolecular Science, Part A: Pure and Applied Chemistry, 42: 891 (2005)
  • an object of the present invention is to provide a method for producing a polyaniline complex having high conductivity in a short reaction time.
  • a two-phase polymerization solvent consisting of an organic solvent that is substantially immiscible with water and water or an aqueous solution.
  • a method for producing a polyaniline complex in which aniline or an aniline derivative is polymerized in the presence of the following components ⁇ and (b):
  • a polyaniline complex obtained by the production method according to any one of 1 to 4 above and containing (b) a surfactant.
  • a polyaniline composition comprising the polyaniline complex according to 5 above and a compound having a phenolic hydroxyl group.
  • the polymerization solvent is a two-phase system composed of an organic solvent substantially immiscible with water and water or an aqueous solution, and is a monomer among them.
  • An aniline or an aniline derivative is polymerized in the presence of the following components ⁇ and (b).
  • the reaction system forms a stable emulsion state, and the reaction rate is improved.
  • the sulfone group-containing compound has a function as a dopant in the polyaniline complex.
  • Sulfone group-containing compounds reduce the size of droplets (organic layers) during polymerization Working force S, this compound alone cannot make the droplet size small enough. Therefore, as a result, in order to obtain a polyaniline complex having a high conductivity, it is necessary to lengthen the polymerization time.
  • the droplets are sufficiently small, and even if the polymerization time is shortened, a polyaniline complex having a high conductivity can be obtained.
  • organic solvents include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, cumene, dichloromethane, chloroform, carbon tetrachloride, 1, 2 -Halogen solvents such as dichloroethane, trichloroethane, tetrachloroethane, and ester solvents such as ethyl acetate.
  • hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, cumene, dichloromethane, chloroform, carbon tetrachloride, 1, 2 -Halogen solvents such as dichloroethane, trichloroethane, tetrachloroethane, and ester solvents such as ethyl acetate.
  • Toluene, xylene, and black mouth form are preferred from the viewpoint of excellent solubility of the produced polyani
  • an acidic aqueous solution can be used, and examples thereof include a dilute hydrochloric acid aqueous solution of about 1 N.
  • the volume ratio of the polymerization solvent in the reaction system is preferably such that the amount of water or aqueous solution is larger than that of the organic solvent. This facilitates the removal of the polymerization reaction heat and reduces side reactions.
  • aniline or aniline derivative that is a monomer an aniline derivative that is unsubstituted or substituted with a methyl group, an ethyl group, a hexyl group, a methoxy group, an ethoxy group, a hexyloxy group, or the like can be used. Unsubstituted aniline is preferred because it is readily available.
  • Examples of the compound (a) having a sulfone group include alkylbenzene sulfonic acid, polyoxyethylene alkyl ether sulfate, naphthalene sulfonate formalin condensate, alkyl sulfosuccinate and the like. Alkylsulfosuccinate is preferable.
  • Preferable sulfone group-containing compounds include organic protonic acids represented by the following formula (I) or salts thereof (hereinafter referred to as organic protonic acid (I) or salts thereof! /).
  • This compound is preferable because of its high acidity and easy doping. This improves the conductivity and solubility of the protonated polyaniline.
  • M is a hydrogen atom or an organic or inorganic free radical.
  • organic free radical include a pyridinium group, an imidazolium group, an anilinium group, and the like.
  • free radical include sodium, lithium, potassium, cerium, ammonium and the like.
  • Y is a so-group.
  • A is a hydrocarbon group which may contain a substituent, for example, a straight chain or branched alkyl or alkenyl group having carbon atoms;! To 24, cyclopentyl, cyclohexyl, cycloheptyl, Cycloalkyl group which may contain a substituent such as cyclooctyl and menthyl, dicycloalkyl group which may be condensed such as bicyclohexyl, norbornyl and adamantyl or polycycloalkyl group, phenyl, tosyl, thiophenyl, Aryl groups containing an aromatic ring which may contain a substituent such as linyl, pyridinyl, furanyl, naphthyl, anthracenyl, fluorenyl, 1,2,3,4 tetrahydronaphthyl, indanyl, quinolinyl, indonyl, etc. Examples thereof may include a
  • Each R is independently -R 1 , -COOR 1 , -CO (COR 1 ),
  • R 1 is a hydrocarbon group, silyl group, alkylsilyl group, or — (R 2 O) x—R 3 group, — (OSiR 3 ) x-OR, which may contain a substituent having 4 or more carbon atoms.
  • R 2 is an alkylene group
  • R 3 may be the same or different from each other! / May be a hydrocarbon group
  • X is an integer of 1 or more.
  • R 1 is a hydrocarbon group
  • examples of when R 1 is a hydrocarbon group include linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, eicosanyl. Groups and the like.
  • n is an integer greater than or equal to 2
  • m is the valence of M.
  • dialkylbenzenesulfonic acid dialkylnaphthalene sulfonic acid, sulfophthalic acid ester, and a compound represented by the following formula (II) are preferably used from the viewpoint of easy doping. it can.
  • M is a hydrogen atom or an organic or inorganic free radical as in the case of the formula (I).
  • the organic free radical include a pyridinium group, an imidazolium group, and an anilium group
  • examples of the inorganic free radical include sodium, lithium, potassium, cerium, and ammonium.
  • Y is a SO— group.
  • R 4 and R 5 are each independently a hydrogen atom, a hydrocarbon group or an R 8 Si group (where R 8
  • hydrocarbon group when R 4 and R 5 are hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, aryl groups containing aromatic rings, and alkyl aryl groups.
  • the hydrocarbon group when R 8 is a hydrocarbon group is the same as in the case of R 4 and R 5 .
  • R 6 and R 7 are each independently a hydrocarbon group or — (R 9 O) — R 1 () group [where R 9 is a hydrocarbon group or a silylene group, and R 1Q is hydrogen Atom, hydrocarbon group or R 11 Si— (R 11
  • hydrocarbon group 3 is a hydrocarbon group, three R 11 may be the same or different), and q is an integer of 1 or more.
  • hydrocarbon group when R 6 and R 7 are hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, aryl groups containing an aromatic ring, alkyl aryl groups, and the like. Among these, those having 4 or more carbon atoms are preferred from the viewpoint of being easily soluble in an organic solvent immiscible with water! / And obtaining a polyaniline complex! /.
  • Specific examples of the hydrocarbon group when R 6 and R 7 are hydrocarbon groups include, for example, linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group and the like.
  • R 6 and R 7 when R 9 is a hydrocarbon group, the hydrocarbon group includes a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, and an alkyl arylene. Group, arylene alkylene group and the like.
  • the hydrocarbon group in R 6 and R 7 when R 10 and R 11 are hydrocarbon groups is the same as in R 4 and, and q is preferably! -10. .
  • R 6 and R 7 are — (R 9 0) —R 1 () groups include groups represented by the following formulas.
  • p is the valence of M.
  • the organic protonic acid ( ⁇ ) or a salt thereof is a sulfosuccinic acid derivative represented by the following formula (III) (hereinafter referred to as a sulfosuccinic acid derivative (III)) from the viewpoint of conductivity and solubility. More preferred.
  • R 12 and R 13 are each independently a hydrocarbon group or — (R 14 ⁇ ) — R 15 group [wherein R 14 is a hydrocarbon group or a silylene group, R 15 is a hydrogen atom, Hydrocarbon group or R 16 Si group (
  • R 16 is a hydrocarbon group, three R 16 may be the same or different), and r is an integer of 1 or more.
  • R 12 and R 13 the hydrocarbon group in the case where R 14 is a hydrocarbon group includes the above R
  • R 12 and R 13 the hydrocarbon group when R 15 and R 16 are hydrocarbon groups is the same as R 4 and R 5 described above.
  • r is preferably 1 to 10; [0033] Specific examples in the case where R 12 and R 13 are one (R 14 0 —R 15 group are the same as those of — (R 9 0) —R 1 () in R 6 and R 7 .
  • R 12 and R 13 are hydrocarbon groups
  • the hydrocarbon group is the same as R 6 and R 7 and is immiscible with water! /
  • the organic protonic acid or a salt thereof has a function of protonating polyaniline and exists as a dopant (counter anion) in the polyaniline complex.
  • surfactants include anions such as fatty acids, disproportionated rosin soaps, higher alcohol esters, polyoxyethylene alkyl ether phosphates, alkenyl succinic acids, sarcosinates, and salts thereof.
  • Nonionic surfactants such as surfactants, polyoxyethylene alkyl etherol, polypropylene glycolenopolyethylene glycolenoateolene, polyoxyethylene glycerol porate fatty acid esters, alkyldimethylbenzyl ammonium salts, alkyltrimethyl ammonium salts, etc.
  • Examples include cationic surfactants, alkylbetaine types, alkylamide betaine types, amino acid types, and amine amine types.
  • the surfactant a general surfactant made of a compound having a sulfone group as described above may be used.
  • the production method of the present invention uses two or more “compounds containing a sulfone group”.
  • Preferable examples include anionic surfactants and nonionic (nonionic) surfactants.
  • anionic surfactants those based on phosphoric acid are preferred.
  • the surfactants may be used alone or in combination of two or more.
  • oxidizing agent examples include persulfuric acid or a salt thereof, chromic acid or a salt thereof, perchloric acid or a salt thereof, iodic acid, permanganic acid or a salt thereof, and the like.
  • persulfates such as ammonium persulfate are preferred.
  • the monomer charge concentration is usually 1 to; lOOg / l, preferably 5 to 50 g / l.
  • the addition amount of the sulfone group-containing compound ( a ) is 0. 0.5 equivalent (molar ratio) is preferred, and about 0.2-2 to 0.4 equivalent (molar ratio) is particularly preferred.
  • the addition amount of the surfactant (b) is preferably about 0.05 to 0.2 equivalent (molar ratio) of the sulfone group-containing compound (a).
  • the reaction can be carried out in the range from -20 ° C to around room temperature. Preferably it is 5 ° C or less. In addition, when the polymerization is carried out at a temperature near room temperature, for example, a temperature exceeding 30 ° C., the side reaction proceeds, which is preferable!
  • the polymerization time is about 2 to 20 hours, but it can be completed in a short time of about 2 to 10 hours.
  • reaction system is milky white.
  • the stirring time at this time is about 5 minutes to 8 hours, preferably about 30 minutes to 2 hours.
  • This polyaniline complex has high conductivity.
  • the production method of the present invention can stably produce a polyaniline complex having a high conductivity even if a polyaniline complex is repeatedly produced with reproducibility.
  • the polyaniline composition of the present invention includes a polyaniline complex produced by the above-described method of the present invention and a compound having a phenolic hydroxyl group.
  • the compound having a phenolic hydroxyl group functions as a dopant.
  • the compounds having a phenolic hydroxyl group include phenol, o-, m-, p-creso-monore, o-, m-, p-ethenolevenore, o-, m-, p-pole pinolephenol. , O—, m— And substituted phenols such as p-chlorophenol, naphthols such as 1-naphthol and 2-naphthol, polyhydric phenols such as catechol and resorcinol, and polynuclear phenols such as biphenol and bisphenol A.
  • a composition can be prepared by referring to the method described in WO2005 / 052058.
  • a conductive polyaniline composition solution can be obtained by blending a phenolic compound into a solution in which the polyaniline complex is dissolved.
  • the ratio of the polyaniline complex in the organic solvent such as toluene depends on the type of the organic solvent.
  • the molar concentration of the phenolic compound in the entire polyaniline composition is 0. Olmol.
  • the range is preferably in the range of / L to 5 mol / L. In this range, particularly excellent conductivity can be obtained. In particular, the range is preferably 0.2 mol / L to 2 mol / L.
  • a conductive molded article is obtained by drying the polyaniline composition of the present invention and removing the organic solvent.
  • a conductive film can be produced by applying to a substrate such as glass, a resin film, or a sheet having a desired shape and removing the organic solvent.
  • Methods for applying the composition of the present invention to a substrate include known methods such as a casting method, a spray method, a dip coating method, a doctor blade method, a barcode method, a spin coating method, screen printing, and gravure printing.
  • the general method can be used.
  • the organic solvent should be volatilized by heating! /.
  • a method of volatilizing the water-immiscible organic solvent for example, it is heated at a temperature of 250 ° C or lower, preferably 50 to 200 ° C under an air stream, and further heated under reduced pressure as necessary. . still
  • the heating temperature and heating time are not particularly limited and may be appropriately selected depending on the material to be used.
  • the molded article of the present invention is a film or a film
  • the thickness thereof is usually 1 mm or less, preferably 101 111 to 50 111.
  • a film having a thickness in this range has advantages such as uniform electrical characteristics that are difficult to crack during film formation.
  • a molded body other than a film or a film a thread, a pellet, or the like can be given.
  • AOT Aralosol OT, sodium dioctylsulfosuccinate, manufactured by Wako Pure Chemical Industries
  • component (a) 1.8 g (4 mmol)
  • purified by distillation under reduced pressure and stored under nitrogen 50 ml of a toluene solution in which 1.8 g (20 mmol) of aniline was dissolved was added.
  • Surfmer FP-120 manufactured by Toho Chemical Industry Co., Ltd., phosphate anionic surfactant 0.33g (0.1 equivalent of AOT: molar ratio) was used as the component (b) surfactant. added.
  • 150 ml of 1N aqueous HC1 solution was poured, set in a constant temperature bath set at 5 ° C, and stirred for 30 minutes with a mechanical stirrer.
  • a solution obtained by adding 2.7 g (12 mmol) of ammonium persulfate (oxidizer) to 50 ml of 1N aqueous HC1 solution was added dropwise over 2 hours from the dropping funnel. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 8 hours (total reaction time 10 hours).
  • This solution was cast on a glass plate and dried at 80 ° C. for 30 minutes to form a film.
  • a self-supporting film having a thickness of 15 m was obtained.
  • the intrinsic conductivity of this film was measured by the four probe method (measuring instrument: Loresta GP, manufactured by Mitsubishi Chemical Corporation) and found to be 260 S / cm.
  • 0.05 ml of nitric acid and 0.5 ml of perchloric acid were added to 0.04 g of this membrane, it was diluted after being decomposed by a microwave pretreatment device, and phosphorus was quantified by inductively coupled plasma (ICP) emission spectrometry. It was found to contain 17%. Since no other compound containing phosphorus is added to the reaction system, this phosphorus is considered to be derived from component (b).
  • ICP inductively coupled plasma
  • a polyaniline complex was produced in the same manner as in Example 1 except that the surfactant as component (b) was not applied, and the polyaniline composition was formed into a film and evaluated.
  • the intrinsic conductivity of the obtained film was 62 S / cm, which was inferior to Example 1.
  • Example 2 After the stirring was stopped, the contents were transferred to a separatory funnel and treated in the same manner as in Example 1 to obtain a polyaniline complex solution. Thereafter, a polyaniline composition was produced in the same manner as in Example 1, and a film was formed. The conductivity of the obtained film was measured and found to be 218 S / cm.
  • the intrinsic conductivity of the obtained film was 193 S / cm.
  • a polyaniline composition can be obtained with 4 hours! It is.
  • a polyaniline complex was produced in the same manner as in Example 1 except that the reaction vessel volume was 1 L, and the amount of solvent and reagent were all doubled as in Example 1. The film was evaluated.
  • the intrinsic conductivity of the obtained film was 251 S / cm.
  • a polyaniline composition showing almost the same electrical conductivity could be produced even when scaled up twice. It seems that even if scaled up, polyaniline with equivalent performance can be obtained.
  • the amount of AOT was set to 2.7 g (6 mmol), and 0.333 g of Surfmer FP-120 was added, and the mixture was stirred for 30 minutes in advance, to produce a polyaniline complex in the same manner as in Example 1.
  • the polyaniline composition was formed into a film and evaluated. As a result, the intrinsic conductivity of the obtained film was 402 S / cm.
  • component (b) instead of Surfmer FP-120, Kohacool L-300 (manufactured by Toho Chemical Co., Ltd., sulfosuccinic acid surfactant) 0.8 g (0.1 equivalent of AOT) was used.
  • a polyaniline complex was produced, and a polyaniline composition was formed into a film and evaluated.
  • the intrinsic conductivity of the obtained film was 170 S / cm.
  • the intrinsic conductivity of the obtained film was 223 S / cm.
  • component (b) instead of Surfmer FP-120, Peganol TH-8 (Toho Chemical Co., Ltd., polyoxyethylene alkyl ether type nonionic surfactant) 0.18 g (AOT 0.84)
  • the polyaniline complex was produced in the same manner as in Example 1 except that the equivalent weight was used, and a polyaniline composition was formed into a film and evaluated.
  • the intrinsic conductivity of the obtained film was 223 S / cm.
  • component (b) instead of Surfmer FP-120, Peganol L 12S (manufactured by Toho Chemical Co., Ltd., polyoxyethylene alkyl ether type nonionic surfactant) 0.32 g (0.11 equivalent of AOT)
  • a polyaniline complex was produced, and a polyaniline composition was formed into a film and evaluated.
  • the intrinsic conductivity of the obtained film was 98 S / cm.
  • component (b) instead of Surfmer FP-120, Sorbone S-20 (Toho Chemical Co., Ltd., sorbitan fatty acid ester type nonionic surfactant) 0.14 g (0.1 equivalent of AOT) was used. Others were produced in the same manner as in Example 1, and a polyaniline complex was produced, and a polyaniline composition was formed into a film and evaluated.
  • Sorbone S-20 Toho Chemical Co., Ltd., sorbitan fatty acid ester type nonionic surfactant 0.14 g (0.1 equivalent of AOT) was used.
  • Others were produced in the same manner as in Example 1, and a polyaniline complex was produced, and a polyaniline composition was formed into a film and evaluated.
  • the intrinsic conductivity of the obtained film was 157 S / cm.
  • component (b) instead of Surfmer FP-120, Sorbon T 20 (manufactured by Toho Chemical Industry Co., Ltd., polyoxyethylene sorbitan fatty acid ester type nonionic surfactant)
  • a polyaniline complex was produced in the same manner as in Example 1 except that 0.5 g (0.1 equivalent of AOT) was used, and a polyaniline composition was formed and evaluated.
  • the intrinsic conductivity of the obtained film was 121 S / cm.
  • the polyaniline composite obtained by the production method of the present invention is particularly useful in the field of power electronics and optoelectronics, and is used for electrostatic antistatic materials, transparent electrodes and conductive film materials, materials for electroluminescent devices, It can be used for materials, capacitor dielectrics, electrolytes, solar and secondary battery electrode materials, fuel cell separator materials, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Electrochemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Photovoltaic Devices (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Fuel Cell (AREA)

Abstract

La présente invention concerne un procédé de production d'un composite de polyaniline, l'aniline ou un dérivé d'aniline étant polymérisé dans un solvant de polymérisation à deux phases, lequel est composé d'un solvant organique essentiellement non-miscible dans l'eau et d'eau ou d'une solution aqueuse, en présence des composants (a) et (b). (a) un composé possédant un groupe sulfone (b) un agent tensio-actif
PCT/JP2007/068498 2006-09-25 2007-09-25 Procédé de production d'un composite conducteur de polyaniline Ceased WO2008038609A1 (fr)

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WO2009034816A1 (fr) * 2007-09-14 2009-03-19 Idemitsu Kosan Co., Ltd. Composition de polyaniline conductrice
WO2009084418A1 (fr) * 2007-12-27 2009-07-09 Idemitsu Kosan Co., Ltd. Complexe de polyaniline, et composition et article moulé le comprenant
WO2009084419A1 (fr) * 2007-12-27 2009-07-09 Idemitsu Kosan Co., Ltd. Complexe de polyaniline, et composition et article moulé le comprenant the same
WO2010143450A1 (fr) * 2009-06-12 2010-12-16 出光興産株式会社 Composition de polymère π-conjugué
WO2012102017A1 (fr) * 2011-01-27 2012-08-02 出光興産株式会社 Composite de polyaniline, son procédé de production et sa composition

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JP5289899B2 (ja) * 2008-11-10 2013-09-11 東海ゴム工業株式会社 導電性エラストマーの製造方法
TWI478957B (zh) 2009-09-07 2015-04-01 Idemitsu Kosan Co Conductive composition
WO2012140881A1 (fr) * 2011-04-13 2012-10-18 パナソニック株式会社 Procédé pour la production d'une solution ayant un polymère électroconducteur dispersé dans celle-ci et condensateur électrolytique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009034816A1 (fr) * 2007-09-14 2009-03-19 Idemitsu Kosan Co., Ltd. Composition de polyaniline conductrice
WO2009084418A1 (fr) * 2007-12-27 2009-07-09 Idemitsu Kosan Co., Ltd. Complexe de polyaniline, et composition et article moulé le comprenant
WO2009084419A1 (fr) * 2007-12-27 2009-07-09 Idemitsu Kosan Co., Ltd. Complexe de polyaniline, et composition et article moulé le comprenant the same
JP2015199969A (ja) * 2009-06-12 2015-11-12 出光興産株式会社 π共役高分子組成物
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CN102803388A (zh) * 2009-06-12 2012-11-28 出光兴产株式会社 π共轭高分子组合物
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WO2010143450A1 (fr) * 2009-06-12 2010-12-16 出光興産株式会社 Composition de polymère π-conjugué
JP5839683B2 (ja) * 2009-06-12 2016-01-06 出光興産株式会社 π共役高分子組成物
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KR20160084484A (ko) * 2009-06-12 2016-07-13 이데미쓰 고산 가부시키가이샤 π 공액 고분자 조성물
KR101636837B1 (ko) 2009-06-12 2016-07-07 이데미쓰 고산 가부시키가이샤 π 공액 고분자 조성물
US9384866B2 (en) 2011-01-27 2016-07-05 Idemitsu Kosan Co., Ltd. Polyaniline composite, method for producing same, and composition
JP5894089B2 (ja) * 2011-01-27 2016-03-23 出光興産株式会社 ポリアニリン複合体、その製造方法及び組成物
WO2012102017A1 (fr) * 2011-01-27 2012-08-02 出光興産株式会社 Composite de polyaniline, son procédé de production et sa composition
JP2016172847A (ja) * 2011-01-27 2016-09-29 出光興産株式会社 ポリアニリン複合体、その製造方法及び組成物

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