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WO2004078822A1 - Amine-cured type epoxy resin electrolyte having a sulfonic acid group and method for preparation thereof - Google Patents

Amine-cured type epoxy resin electrolyte having a sulfonic acid group and method for preparation thereof Download PDF

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Publication number
WO2004078822A1
WO2004078822A1 PCT/JP2004/002571 JP2004002571W WO2004078822A1 WO 2004078822 A1 WO2004078822 A1 WO 2004078822A1 JP 2004002571 W JP2004002571 W JP 2004002571W WO 2004078822 A1 WO2004078822 A1 WO 2004078822A1
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Prior art keywords
amine
acid
epoxy resin
electrolyte membrane
type epoxy
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PCT/JP2004/002571
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French (fr)
Inventor
Eiichi Akiyama
Takashi Kawakami
Hitoshi Ito
Hiroshi Yokota
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Ebara Corp
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Ebara Corp
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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/46—Epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. in situ polymerisation or in situ crosslinking
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1093—After-treatment of the membrane other than by polymerisation mechanical, e.g. pressing, puncturing
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/182—Regeneration by thermal means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a resin electrolyte and a resin electrolyte membrane suited for use in various electrochemical devices such as electro de-ionization pure water production equipment, secondary batteries, fuel cells, humidity sensors, ion sensors, gas sensors, electro ⁇ hromic devices and desi ⁇ cants, and method for preparation thereof, and electrochemical devices using them.
  • electrochemical devices such as electro de-ionization pure water production equipment, secondary batteries, fuel cells, humidity sensors, ion sensors, gas sensors, electro ⁇ hromic devices and desi ⁇ cants, and method for preparation thereof, and electrochemical devices using them.
  • Electrolytes are used in various electrochemical devices such as electro de-ionisation pure water production equipment, secondary batteries, fuel cells, humidity sensors, ion sensors, gas sensors, electrochromic devices and desiccants, and they are the members exerting a great influence on the performance of these devices .
  • polyvinylbenzene sulfonic acids typified by "DIAION" (trade mark, product of Mitsubishi Chemical) are used widely as an ion exchanger.
  • Polyvinylbenzene sulfonic acids are prepared either by radical polymerization of vinylbenzenesulfonic acid or a derivative of vinylbenzenesulfonate salt, or sulfonation of general- purpose polystyrene by a polymer reaction. Because of low cost, easy control of ion exchange capacity and free selection of their form from fibers , porous membrane and beads, they have been widely employed in the above- described technical field.
  • polyethers typified by polyethylene oxide are useful as an ion conductive material.
  • polyethers typified by polyethylene oxide are useful as an ion conductive material.
  • Fluorine-based polymer electrolytes are known as highly chemically stable electrolytes. Fluorine-based polymer electrolytes typified by "Nafion” (trade mark, product of DuPont) have been used for membrane for sodium chloride electrolysis, proton conducting membrane for fuel cell and the like which need chemical durability (for example, refer to Patent Documents 1 to 4).
  • Patent Document 1 As another polymer electrolytes, polymer electrolytes having an aromatic group in the main chain and a sulfonic acid group bonded to this aromatic group are known (for example, refer to Patent Documents 5 and 6). [Patent Document 1]
  • Patent Document 4 Japanese Patent Laid-Open No. 1991-15175 (the fourth page) [Patent Document 4]
  • Patent Document 5 Japanese Patent Laid-Open No. 1989-253631 (the third page) [Patent Document 5]
  • polyvinylben ⁇ enesul onic acids are esspected to be used for a wide variety of applications .
  • Upon increase of the density of the sulfonic acid group however, they become water soluble and simultaneous use of a crosslinking monomer such as divinylbenzene is required in order to stabilize the form in water.
  • a crosslinking monomer such as divinylbenzene is required in order to stabilize the form in water.
  • radical polymerization which is a chain reaction, they become insoluble in a solvent. It is easy to obtain the polymer as a swollen gel or beads powder, but is difficult to form a mesh sheet or uniform thin membrane.
  • Polyethers are, on the other hand, superior in ion conductivity but , they are usually in the gel form and cannot be used for the applications requiring mechanical strength.
  • Fluorine-based polymer electrolytes are superior in chemical durability and mechanical strength but are known to undergo a dimensional change owing to swelling or the like.
  • fluorine-based monomers which are raw materials for obtaining such polymers are very expensive compared with monomers having the corresponding fluorine replaced with hydrogen so that their use in electrochemical devices is limited.
  • their production procedure requires halogen-based organic solvents having high affinity with the fluorine-based compounds. In recent social circumstances, there is a fear of halogen-based compounds having a harmful influence on the environment .
  • Polymer electrolytes having an aromatic group to which a sulfonic acid group has been bonded have heat resistance and when formed into a membrane, have high strength, but involve drawbacks such as inferior membrane forming property.
  • an object of the present invention is to provide a method for preparing a polymer (resin) electrolyte or polymer (resin) electrolyte membrane which shows electrolyte properties such as ion conductivity enough for use in electrochemical devices , has sufficient heat resistance and mechanical strength depending on the using purpose, is free of a halogen element having a large environment load, and can be produced at a sufficient low cost, and in addition, from the viewpoint of the application to electrochemical devices, can be expected to have excellent bonding or adhesion property to electrodes because the swelling of the membrane owing to impregnation with water, alcohol, non-protic polar solvent or auxiliary electrolyte solution is suppressed; and an electrochemical device using the polymer electrolyte membrane .
  • the amine-cured type epoxy resin can be produced at a lower cost compared with that for the conventional polymer electrolyte membranes because epoxy compounds and amine compounds ordinarily employed as a chemical product can be used as raw materials.
  • a three-dimensionally crosslinked structure can be introduced into the resin, making it possible to suppress the swelling owing to the impregnation with water.
  • alcohol, non-protic polar solvent or auxiliary electrolyte solution and to provide an electrolyte membrane contributing to a reduction in environmental load during production and upon after-use disposal because a halogen element has not been introduced into the skeleton of polymer by a covalent bond.
  • the present invention relates to a sulfonic-acid- containing amine-cured type epoxy resin having at least one structure selected from the structures represented by the following formulas (1) and (2):
  • R 1 and R 3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms, or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond, and R 2 represents a hydrocarbon chain having 3 or 4 carbon atoms ) ; or a molded product thereof .
  • the present invention also relates to an electrolyte or electrolyte membrane comprising the above-described sulfonic-acid-containing amine-cured type epoxy resin.
  • the present invention further relates to the above- described electrolyte or electrolyte membrane further comprising a lithium ion.
  • the present invention further relates to an electrolyte membrane comprising an amine-cured type epoxy resin which has a free sulfonic acid group and has at least one structure selected from the structures represented by the following formulas (3 ) and ( 4) :
  • R 1 and R 3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms , or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond
  • R 2 represents a hydrocarbon chain having 3 or 4 carbon atoms
  • R 4 represents a hydrogen atom or a hydrocarbon chain having 1 to 18 carbon atoms
  • X " represents a monovalent, divalent or trivalent anion
  • the present invention further relates to a method for preparing a sulfonic-acid-containing amine-cured type epoxy resin, which comprises reacting an epoxy compound having, in a molecule thereof, at least 2 epoxy groups with an amine compound having an amine value of 2 or greater, and then reacting the amine in the reaction system with a cyclic sulfonate ester.
  • the present invention further relates to a method for preparing an electrolyte membrane comprising a sulfonic- acid-containing amine-cured type epoxy resin, which comprises mixing an epoxy compound having, in a molecule thereof, at least 2 epoxy groups with an amine compound having an amine value of 2 or greater, adding a cyclic sulfonate ester to form a membrane prior to completion of the curing reaction between the epoxy compound and amine compound, and then completing the curing reaction and the reaction between the amine and the cyclic sulfonate ester in the reaction system.
  • the present invention further relates to the above- described method for preparing an electrolyte membrane, wherein the membrane is formed by solvent casting method, spin coating method, transfer method or printing method.
  • the present invention further relates to the above- described method for preparing an electrolyte membrane, wherein upon membrane formation, hot rolling and/or drawing treatment is conducted.
  • the present invention relates to a method for preparing an electrolyte or electrolyte membrane comprising a lithium ion, which comprises impregnating the electrolyte membrane obtained by the above-described method, or the above-described electrolyte or electrolyte membrane in a lithium-ion-containing solvent.
  • the present invention further relates to a method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating the electrolyte membrane, which has been obtained by the above-described method for preparation, in a solvent containing an inorganic acid.
  • the present invention further relates to a method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating the electrolyte membrane, which has been obtained by the above-described method for preparation, in a solvent containing an organic acid.
  • the present invention further relates to a method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating the electrolyte membrane, which has been obtained by the above-described method for preparation, in a solvent containing methylsulfuric acid, dimethylsulfuric acid, alkyl halide having 1 to 10 carbon atoms or allyl halide.
  • epoxy compound to be used in the present invention having, in a molecule thereof, at least two epoxy groups insofar as it can provide ion conductivity enough for the use in the intended electrochemical devices and thermal and mechanical properties capable of enduring the using environment .
  • Specific examples include the below-described ones.
  • the epoxy compounds for use in the present invention also include low molecular compounds and polymer compounds such as oligomer and polymer.
  • x stands for an integer of 1 or greater.
  • iz stands for an integer of from 1 to 100 are preferred.
  • epoxy compounds are given as examples of the component, in the amine-cured type epoxy resin available by the present invention, preferably employed for providing a flexible and soft electrolyte membrane.
  • bifunctional compounds represented by the formula (18) in which.
  • B 2 represents any one of substituents -H, -CH 3 and -OCH 3
  • b 1 stands for an integer of from 0 to 4
  • epoxy compounds are given as e ⁇ amples of the component, in the amine-cured type epoxy resin available by the present invention, preferably employed for providing an electrolyte membrane excellent in heat resistance.
  • a 13 represents methylene or a divalent linking group represented by the formula (25) or (26), in which b 2 stands for an integer of from 0 to 4, b 3 stands for an integer of from 1 to 3 and b 4 stands for an integer of from 0 to 2) and the formula (24).
  • epoxy compounds are given as examples of the component, in the amine-cured type epoxy resin available by the present invention, preferably employed for providing an electrolyte membrane excellent in mechanical strength.
  • At least two polyfunctional epoxy compounds represented by the formulas (5) to (24) may be used simultaneously.
  • the sulfonic-acid-containing amine-cured type epoxy resin of the present invention is also available by using, as a polyvalent epoxy compound, a polyfunctional epoxy resin as described in Japanese Patent Laid-Open No. 1986-247720, Japanese Patent Laid-Open Mo. 1986-246219, Japanese Patent Laid-Open No. 1988-10613 and the like either singly or in combination with the epoxy compound as shown by the formulas (5) to (24).
  • the amine compound to be used in the present invention includes low molecular compounds , and high molecular compounds such as oligomers and polymers .
  • Examples include amine compounds having an amine value (the number of hydrogen atoms derived from the amino group contained in one molecule) of 2 and represented by the formulas (25) to (27), (28) (wherein, B 3 represents a hydrocarbon group having 2 to 20 carbon atoms or a group having at least one ether bond in a hydrocarbon chain having 4 to 20 carbon atoms) and (29), amine compounds having an amine value of 3 and represented by the formulas (30), (31) (wherein, a 1 stands for an integer of from 2 to 18, and B 4 represents a hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon chain having 3 to 20 carbon atoms with at least one ether bond in the chain) and (32), amine compounds having an amine value of 4 and represented by the formulas (33) (wherein, a 1 stands for an integer of from 2 to 18), (34), (35) (wherein, a 2 stands for an integer of from 1 to 10000), (35) and (37), and amine compounds having an amine value of 5 or
  • amine compounds are given as examples of the component preferably employed in the amine- cured type epoxy resin available by the present invention.
  • Two or more amine compounds represented by the formula (25) to (42) may be used simultaneously in order to control the ion conductivity, heat resistance, mechanical properties and productivity of an electrolyte membrane.
  • cyclic sulfonate ester to be used in the present invention insofar as it can be introduced into the epoxy resin through a covalent bond by the reaction with an amine and can provide ion conductivity enough for use in the intended electrochemical device and thermal and mechanical properties enough to stand the using environment .
  • Those represented by the formulas (43) and (44) and easily available in practice can be used in the present invention.
  • Means for chemical analysis in order to identify the detailed chemical structure of the sulfonic-acid-containing amine-cured type epoxy resin available by the present invention is limited, because the resinous product obtained as a final product cannot be re-dissolved in an organic solvent because it has been three-dimensionally crosslinked.
  • IR infrared absorption
  • R 1 and R 3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms, or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond, and R 2 represents a hydrocarbon chain having 3 or 4 carbon atoms).
  • a low-mole ⁇ ular-weight model compound which is soluble to solvent, having a partial structure represented by the formula (1) or (2) existing in the resin is synthesized separately.
  • the resin is confirmed to have at least one structure selected from the formulas (1) and (2).
  • these structures can be identified based on the nuclear magnetic resonance (NMR) spectrum and IR spectrum of the reaction products represented by the below-described reaction scheme ⁇ 1> by using phenyl glycidyl ether as the epoxy compound, n-butylamine as the amine compound and 1,3-propanesultone as the cyclic sulfonate ester.
  • NMR nuclear magnetic resonance
  • Reaction scheme ⁇ 1> The spectrum data of Compounds (45) to (48) in the reaction scheme ⁇ 1> will be described later in Referential Examples. It has been confirmed that Compound (49) is not formed when an excess amount of propanesultone is reacted with Compound (45), or propanesultone is further added to Compound (48).
  • the infrared absorption bands identifying the structure of the formula (1) or (2) which is a constituent of the resin are determined as shown in Table 1 based on the analysis results of the spectrum data of the model compound.
  • the formation of the structure represented by the formula (1) or (2) in the sulfonic-acid-containing amine-cured type epoxy resin can be determined when absorptions characteristic of the amine compound and epoxy compound used as its raw materials cannot be observed in the spectrum of the epoxy resin or observed but they are very weak, and absorptions characteristic of the structure of the formula (1) or (2) can be recognized.
  • a membrane can be formed prior to the completion of the curing reaction by the membrane forming method such as solvent casting method, spin coating method, transfer method or printing method, or by mechanical treatment such as rolling or drawing.
  • an organic solvent can be used as needed to conduct the reaction uniformly. Any organic solvent can be used unless it reacts with the epoxy compound, considerably lowers the nucleophilicity of amine, reacts with the cyclic sulfonate ester or adversely affects the properties of the membrane formed.
  • Examples include n- hexane, cyclohexane, n-heptane, n-octane, ethyl cellosolve, butyl cellosolve, benzene, toluene, xylene, anisole, methanol, ethanol, isopropanol, butanol, ethylene glycol, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, N,N- dimethylformamide, N,N-dimethylacetamide, N-methyl-2- pyrrolidinone and dimethylsulfoxide.
  • organic solvents can be used as a mixture or the organic solvents may be added with water.
  • Organic solvents containing a halogen element such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2,- tetrachloroethane, chlorobenzene and dichlorobenzene may be used for promoting the reaction, but from the viewpoint of the "small environmental load", which is one of the object of this application, they are not desirable as an embodiment of the present invention. If it can be judged that the possibility of leakage to the environment can be avoided without spending a large energy, however, such solvents are not undesirable.
  • a resin electrolyte obtained by reacting a liquid epoxy compound and a liquid amine compound with a cyclic sulfonate ester is expected to have a high transference number of ion, but its mechanical strength is sometimes weak.
  • a resin electrolyte obtained by reacting a solid epoxy compound and a solid amine compound with a cyclic sulfonate ester tends to be hard and fragile. In applications requiring high mechanical strength, a three-dimensional crosslinking density is an important influencing factor. Synthesis of a resin electrolyte having properties contrary in molecular design such as high ion transference number and mechanical strength can be achieved by mixing appropriate raw materials .
  • a resin electrolyte having high ion transference number and improved mechanical properties can be obtained, for example, by mixing a liquid component and a solid component, by mixing a bifunctional component and a polyfunctional component, or by reacting components respectively to some extent to extend their chains and mixing them; and then reacting the mixture with a cyclic sulfonate ester. Heightening of the ion transference number can be expected if sulfonic acid can be introduced at a high density in a region of a flexibility-imparting resin component having a great influence on an ion transference number.
  • a resin electrolyte whose swelling with a good solvent of the resulting resin electrolyte is suppressed and which has excellent mechanical properties and high ion transference number can also be synthesized by adding a cyclic sulfonate ester only to a pre-cured solution of a flexibility-imparting resin component, which has been reacted separately, to react them, and then, mixing the reaction mixture with a pre-cured solution of a rigidity-imparting resin component to which the cyclic sulfonate ester has not been added.
  • a sulfonic acid group By reacting the cyclic sulfonate ester with a primary, secondary or tertiary amine in the reaction system, a sulfonic acid group can be introduced into the resin through a covalent bond.
  • a polyfunctional amine as a flexibility-imparting resin component makes it possible to introduce sulfonic acid at high density in a region of a flexibility-imparting resin component so that it is effective for improving the ion transference number. It is preferred to adjust the mole number of the cyclic sulfonate ester used for the reaction not to exceed that of nitrogen atoms derived from the amino group in the reaction system.
  • the molded product of the present invention can be obtained by molding the sulfonic-acid-containing amine- cured type epoxy resin available by the present invention. No particular limitation is imposed on the molding method insofar as it is ordinarily employed.
  • the intended molded product is available, for example, by transfer molding.
  • the electrochemical devices of the present invention can be produced.
  • the electrochemical device is a device in which electrochemical reaction is effected.
  • Examples include electro de-ionization pure water production equipment, secondary cell, fuel cell, humidity sensor, ion sensor, gas sensor, electrochromic device and desiccant.
  • the electrochemical device of the present invention can be obtained by replacing the electrolyte or electrolyte membrane ordinarily employed in the above-described device with the electrolyte or electrolyte membrane of the present invention. In some applications, enough electrolyte properties cannot be attained because the sulfonic acid group and the amine group in the sulfonic-acid-containing amine-cured type epoxy resin available by the present invention strongly reacts each other.
  • Sulfuric acid is desirable in view of handling ease and low cost.
  • No particular limitation is imposed on the solvent insofar as it does not damage the membrane and not disturb the action of the conversion agent in the solvent.
  • Water, alcohols having 1 to 4 carbon atoms, acetic acid, acetone, tetrahydrofuran, 1,4-dioxane, N,N- imethylformamide, N,N- dimethylacetamide, N-methyl-2-pyrrolidinone and dimethylsulfoxide can be used either singly or in combination of two or more.
  • the conversion treatment is not particular limited insofar as the membrane can be brought into contact with a solution obtained by mixing the conversion agent in the solvent.
  • the treatment temperature may de determined, for example, within a range of from 0 to 150° C, depending on the kind of the solvent or in consideration of the influence on the membrane.
  • the sulfonic-acid-containing amine-cured type epoxy resin of the present invention as an electrolyte for lithium ion secondary battery by doping lithium ions in the resin.
  • an epoxy compound or amine compound to be used upon synthesis of the epoxy resin, containing a number of ether bonds and to control the composition of the epoxy resin to have properties of a soft gel electrolyte.
  • doping of lithium ions known methods as described, for example, in "High-density Lithium Secondary Battery” (Technosystems, 1998) may be used.
  • Lithium ions can be doped by dipping the electrolyte or electrolyte membrane of the present invention in an aqueous solution, organic solvent, or an organic solvent containing an aqueous solution, each containing lithium ions.
  • the epoxy resin electrolyte can be used for them after washing.
  • the above-described conversion treatment employed for the formation of free sulfonic acid can be utilized as is as the washing treatment .
  • the impurities can be eluted by dipping the resin electrolyte in a solvent such as water, an alcohol having 1 to 4 carbon atoms, acetone, tetrahydrofuran, 1,4- dioxane, N,N-dimethylformamide, or N,N-dimethylacetamide. It is preferred to complete the washing by boiling it for from several hours to several days in distilled water. [Example] Examples of the present invention will next be described. It should however be borne in mind that the present invention is not limited to or by the following examples .
  • Epoxy compounds (E) used in Examples and infrared absorption bands characteristic of the epoxy compounds will next be shown in Table 2.
  • Table 2 Chemical structure of epoxy compound and infrared absorption band characteristic of epoxy ring
  • raw material compounds for them commercially available ones can mainly be used as are. It is however needless to say that raw material compounds not commercially available can be synthesized for use in the present invention.
  • IR, v (cm "1 , KBr disk) 3365 (m, phenolO-H) , 3035 (w) , 2932 (m, C-H), 2916 (m) , 2900 (m) , 2877 (s), 1516 (s, arC- C), 1489 (m), 1477 (m) , 1458 (m) , 1379 (m) , 1350 (w) , 1303 (m) , 1281 (m), 1233 (s, arC-O-alC) , 1175 (m) , 1134 (s), 1111 (s), 1045 (m) , 991 (s), 822 (s), 805 (m) , 767 (s), 516 (m).
  • Amine-cured type epoxy resins obtained in the above- described Examples can be prepared using raw materials which are relatively easily available and inexpensive. Since they contain a sulfonic acid group in their structure, they can be expected to have properties as an electrolyte.
  • a wide variety of membranes from gel membranes to self-supporting, flexible and tough ones can be prepared by changing the composition and thereby controlling their properties so that they can be applied to various electrochemical devices .
  • the membranes obtained in Examples 1, 2, 9, 28 and 29 were each cut into a piece of 2 cm x 5 cm and boiled for 1 hour in a 1 mol/1 aqueous solution of sulfuric acid. After boiling for 1 hour in distilled water, the resulting membrane pieces were each sandwiched with 2 gold electrodes in size of 0.5 cm 4 cm, followed by impedance measurement within a frequency range of from 0.5 Hz to 10 MHz by using an impedance analyzer ("Solartron 1260") while controlling the temperature and humidity in a thermo-hygrostat at 90° C and RH90%, respectively. From the results of the Nyquist Plot thus obtained, the ion conductivity was calculated. The calculation results are shown in Table 5.
  • an epoxy resin can be crosslinked three-dimensionally so that a change in dimension can be suppressed to the minimum even under conditions which permit considerable swelling of ordinary uncrosslinked type electrolyte membranes.
  • a dimensional change due to swelling was compared between the resin electrolyte membrane of the present invention and a fluorine-based polymer electrolyte membrane (Nafion (trade mark) 115, product of Dupont) as a Comparative Example, which is popular as uncrosslinked electrolyte membrane.
  • the electrolyte membranes obtained in Examples 1, 2 and 29 and the electrolyte of Comparative Example were each cut into a piece of 1 cm x 1 cm under dry condition. Their length and width were measured precisely. Each test piece was boiled in distilled water for 1 hour. Immediately after it was taken out from the distilled water, its length and width were measured precisely.
  • a dimensional change was calculated in accordance with Equation ( 1 ) and the results are shown in Table .
  • Equation ( 1 )
  • the electrolyte membranes obtained in Examples 1, 2, 26, 27, 28 and 29 and the electrolyte membrane of Comparative Example were each cut into a piece of 1 cm x 1 cm under dry condition. Their length and width were measured precisely. Each test piece was boiled in a 1:1 (molar ratio) mixed solution of methanol and water for 1 hour. Immediately after it was taken out from the solution, its length and width were measured precisely. A dimensional change was calculated in accordance with Equation (1) and the results are shown in Table 7.
  • sulfonic-acid-containing amine-cured type epoxy resins having wide variety of properties ranging from a gel to a self-supporting, flexible and tough membrane can be obtained.
  • these resins can improve the adhesion of the electrolyte or membrane to electrodes and the like because a dimensional change due to swelling is small.
  • electrolytes, electrolyte membranes and electrochemical devices featuring a lower cost and a smaller environmental load can be provided.

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Abstract

Provided are a sulfonic-acid-containing amine-cured type epoxy resin having at least one structure selected from structures represented by the following formulas (1)and (2) (wherein, R1 and R3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms, or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond, and R2 represents a hydrocarbon chain having 3 or 4 carbon atoms); electrolyte or electrolyte membrane containing the resin; method for preparation thereof; electrochemical device using the membrane. The electrolyte and electrolyte membrane according to the present invention have electrolyte properties such as ion conductivity enough for use in electrochemical devices, have heat resistance and mechanical strength, and can be prepared at a low cost. In addition, bonding or adhesion to electrodes is excellent owing to suppressed swelling of the membrane when impregnated with a solvent.

Description

DESCRIPTION
AMINE-CURED TYPE EPOXY RESIN ELECTROLYTE HAVING A SULFONIC ACID GROUP AND METHOD FOR PREPARATION THEREOF
TECHNICAL FIELD
The present invention relates to a resin electrolyte and a resin electrolyte membrane suited for use in various electrochemical devices such as electro de-ionization pure water production equipment, secondary batteries, fuel cells, humidity sensors, ion sensors, gas sensors, electroσhromic devices and desiσcants, and method for preparation thereof, and electrochemical devices using them.
BACKGROUND ART
Electrolytes are used in various electrochemical devices such as electro de-ionisation pure water production equipment, secondary batteries, fuel cells, humidity sensors, ion sensors, gas sensors, electrochromic devices and desiccants, and they are the members exerting a great influence on the performance of these devices . Of the electrolytes , polyvinylbenzene sulfonic acids typified by "DIAION" (trade mark, product of Mitsubishi Chemical) are used widely as an ion exchanger. Polyvinylbenzene sulfonic acids are prepared either by radical polymerization of vinylbenzenesulfonic acid or a derivative of vinylbenzenesulfonate salt, or sulfonation of general- purpose polystyrene by a polymer reaction. Because of low cost, easy control of ion exchange capacity and free selection of their form from fibers , porous membrane and beads, they have been widely employed in the above- described technical field.
It is known that of electrolytes , polyethers typified by polyethylene oxide are useful as an ion conductive material. By using the controllability of their viscosity by the molecular weight or the like, and metal ion conductivity appearing by doping various metal salts, they have been applied to polymer batteries and various sensors .
Fluorine-based polymer electrolytes are known as highly chemically stable electrolytes. Fluorine-based polymer electrolytes typified by "Nafion" (trade mark, product of DuPont) have been used for membrane for sodium chloride electrolysis, proton conducting membrane for fuel cell and the like which need chemical durability (for example, refer to Patent Documents 1 to 4).
As another polymer electrolytes, polymer electrolytes having an aromatic group in the main chain and a sulfonic acid group bonded to this aromatic group are known (for example, refer to Patent Documents 5 and 6). [Patent Document 1]
Japanese Patent Laid-Open No. 1996-164319 (the second page)
[Patent Document 2]
Japanese Patent Laid-Open No. 1992-305219 (the second page )
[Patent Document 3]
Japanese Patent Laid-Open No. 1991-15175 (the fourth page) [Patent Document 4]
Japanese Patent Laid-Open No. 1989-253631 (the third page) [Patent Document 5]
Japanese Patent Laid-Open No. 2001-250567 (the second page)
[Patent Document 6]
Japanese Patent Laid-Open No. 1988-283707 (the first page)
Because of free selection of the form from fibers , porous membrane and beads as well as low cost and controllability of ion exchange capacity, polyvinylben∑enesul onic acids are esspected to be used for a wide variety of applications . Upon increase of the density of the sulfonic acid group, however, they become water soluble and simultaneous use of a crosslinking monomer such as divinylbenzene is required in order to stabilize the form in water. With the progress of radical polymerization, which is a chain reaction, they become insoluble in a solvent. It is easy to obtain the polymer as a swollen gel or beads powder, but is difficult to form a mesh sheet or uniform thin membrane. Use of electron beam induced graft polymerization makes it possible to chemically link polystyrene base to the surface of a polymer having a form suited for the using purpose and by sulfonating the resulting polystyrene-linked base, a graft polymer in the form of cloth, porous membrane or film is relatively easily available. The sulfonation reaction is however an electrophilic substitution reaction so that a polymer base which can be employed in this reaction is limited to polyolefin resins such as polyethylene. The polyvinylbenzene sulfonic acids therefore do not always satisfy applications requiring heat resistance, mechanical strength and the like.
Polyethers are, on the other hand, superior in ion conductivity but , they are usually in the gel form and cannot be used for the applications requiring mechanical strength.
Fluorine-based polymer electrolytes are superior in chemical durability and mechanical strength but are known to undergo a dimensional change owing to swelling or the like. In addition, fluorine-based monomers which are raw materials for obtaining such polymers are very expensive compared with monomers having the corresponding fluorine replaced with hydrogen so that their use in electrochemical devices is limited. Moreover, their production procedure requires halogen-based organic solvents having high affinity with the fluorine-based compounds. In recent social circumstances, there is a fear of halogen-based compounds having a harmful influence on the environment . It is therefore necessary to give special consideration so as not to cause leakage of halogen compounds to environments during production, or even upon disposal after use of the products, so as not to release harmful halogen- containing compounds to environments by incineration and the like. From such points of view, use of non-halogen- based compounds having a smaller environmental load is preferred.
Polymer electrolytes having an aromatic group to which a sulfonic acid group has been bonded have heat resistance and when formed into a membrane, have high strength, but involve drawbacks such as inferior membrane forming property.
With the foregoing problems in view, an object of the present invention is to provide a method for preparing a polymer (resin) electrolyte or polymer (resin) electrolyte membrane which shows electrolyte properties such as ion conductivity enough for use in electrochemical devices , has sufficient heat resistance and mechanical strength depending on the using purpose, is free of a halogen element having a large environment load, and can be produced at a sufficient low cost, and in addition, from the viewpoint of the application to electrochemical devices, can be expected to have excellent bonding or adhesion property to electrodes because the swelling of the membrane owing to impregnation with water, alcohol, non-protic polar solvent or auxiliary electrolyte solution is suppressed; and an electrochemical device using the polymer electrolyte membrane .
DISCLOSURE OF THE INVENTION As a result of an extensive effort and investigation with a view to overcoming the above-described problems, the present inventors have completed the present invention. Described specifically, they have found that by properly selecting an epoxy compound and amine compound upon synthesis of an amine-cured type epoxy resin, properties such as form, processability, strength, heat resistance and flexibility which an electrolyte membrane is required to have when used in an intended electrochemical device can be controlled; and that by reacting a cyclic sulfonate ester with a primary, secondary or tertiary amine existing in the reaction system prior to curing, chemically fixes the sulfonic acid group in the resin by covalent bonding to impart the electrolyte membrane with electrolyte properties such as ion conductivity enough for practical use. The amine-cured type epoxy resin can be produced at a lower cost compared with that for the conventional polymer electrolyte membranes because epoxy compounds and amine compounds ordinarily employed as a chemical product can be used as raw materials. By selecting proper amine and epoxy compounds, a three-dimensionally crosslinked structure can be introduced into the resin, making it possible to suppress the swelling owing to the impregnation with water. alcohol, non-protic polar solvent or auxiliary electrolyte solution, and to provide an electrolyte membrane contributing to a reduction in environmental load during production and upon after-use disposal because a halogen element has not been introduced into the skeleton of polymer by a covalent bond.
The present invention relates to a sulfonic-acid- containing amine-cured type epoxy resin having at least one structure selected from the structures represented by the following formulas (1) and (2):
Figure imgf000008_0001
(wherein, R1 and R3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms, or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond, and R2 represents a hydrocarbon chain having 3 or 4 carbon atoms ) ; or a molded product thereof . The present invention also relates to an electrolyte or electrolyte membrane comprising the above-described sulfonic-acid-containing amine-cured type epoxy resin.
The present invention further relates to the above- described electrolyte or electrolyte membrane further comprising a lithium ion.
The present invention further relates to an electrolyte membrane comprising an amine-cured type epoxy resin which has a free sulfonic acid group and has at least one structure selected from the structures represented by the following formulas (3 ) and ( 4) :
Figure imgf000009_0001
(wherein, R1 and R3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms , or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond, R2 represents a hydrocarbon chain having 3 or 4 carbon atoms, R4 represents a hydrogen atom or a hydrocarbon chain having 1 to 18 carbon atoms, and X" represents a monovalent, divalent or trivalent anion) . The present invention further relates to an electrochemical device using the above-described resin, molded product, electrolyte or electrolyte membrane.
The present invention further relates to a method for preparing a sulfonic-acid-containing amine-cured type epoxy resin, which comprises reacting an epoxy compound having, in a molecule thereof, at least 2 epoxy groups with an amine compound having an amine value of 2 or greater, and then reacting the amine in the reaction system with a cyclic sulfonate ester.
The present invention further relates to a method for preparing an electrolyte membrane comprising a sulfonic- acid-containing amine-cured type epoxy resin, which comprises mixing an epoxy compound having, in a molecule thereof, at least 2 epoxy groups with an amine compound having an amine value of 2 or greater, adding a cyclic sulfonate ester to form a membrane prior to completion of the curing reaction between the epoxy compound and amine compound, and then completing the curing reaction and the reaction between the amine and the cyclic sulfonate ester in the reaction system.
The present invention further relates to the above- described method for preparing an electrolyte membrane, wherein the membrane is formed by solvent casting method, spin coating method, transfer method or printing method.
The present invention further relates to the above- described method for preparing an electrolyte membrane, wherein upon membrane formation, hot rolling and/or drawing treatment is conducted.
The present invention relates to a method for preparing an electrolyte or electrolyte membrane comprising a lithium ion, which comprises impregnating the electrolyte membrane obtained by the above-described method, or the above-described electrolyte or electrolyte membrane in a lithium-ion-containing solvent. The present invention further relates to a method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating the electrolyte membrane, which has been obtained by the above-described method for preparation, in a solvent containing an inorganic acid.
The present invention further relates to a method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating the electrolyte membrane, which has been obtained by the above-described method for preparation, in a solvent containing an organic acid.
The present invention further relates to a method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating the electrolyte membrane, which has been obtained by the above-described method for preparation, in a solvent containing methylsulfuric acid, dimethylsulfuric acid, alkyl halide having 1 to 10 carbon atoms or allyl halide.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will hereinafter be described more specifically.
No particular limitation is imposed on the epoxy compound to be used in the present invention and having, in a molecule thereof, at least two epoxy groups insofar as it can provide ion conductivity enough for the use in the intended electrochemical devices and thermal and mechanical properties capable of enduring the using environment . Specific examples include the below-described ones. The epoxy compounds for use in the present invention also include low molecular compounds and polymer compounds such as oligomer and polymer.
Specific examples include bifunctional epoxy compounds represented by the formulas (5) to (10), and bifunctional epoxy compounds represented by the formulas (11) and (12). In the formulas, x stands for an integer of 1 or greater. There is no particular limitation on the upper limit, but compounds in which iz stands for an integer of from 1 to 100 are preferred.
Figure imgf000012_0001
Figure imgf000013_0001
These epoxy compounds are given as examples of the component, in the amine-cured type epoxy resin available by the present invention, preferably employed for providing a flexible and soft electrolyte membrane.
Additional examples include bifunctional epoxy compounds represented by the formulas (13), (14) and (15), bifunctional epoxy compounds represented by the formulas (16) and (17) (wherein. A1, A2, A3 and A4 each independently represents a divalent linking group selected from -O- , - C(=0)0-, -NHC(=0)0- or -OC(=0)0-, and B1 represents any one of substituents -H, -CH3 and -OCH3) , and bifunctional compounds represented by the formula (18) (in which. A5 and A6 each independently represents a divalent linking group selected from -0-, -C(=0)0-, -NHC(=0)0- or -OC(=0)0-, B2 represents any one of substituents -H, -CH3 and -OCH3, b1 stands for an integer of from 0 to 4, and D represents a single bond or any one of divalent linking groups -0- , - C(=0)-, -C(=0)0~, -NHC(=0)-, -NH-, -N=N- , -CH=N-, -CH=CH-, -C(CN)=N-, -C≡C-, -CH2-, -CH2CH2, -CH2CH2CH2- , -C(CH3)2-, -0- (CH2)m-0- and -0- (CH2CH20)n- (wherein, m stands for an integer of from 2 to 12 and n stands for an integer of from 1 to 5) ) .
Figure imgf000014_0001
These epoxy compounds are given as e≤amples of the component, in the amine-cured type epoxy resin available by the present invention, preferably employed for providing an electrolyte membrane excellent in heat resistance.
Additional examples of epoxy compounds include trifunctional epoxy compounds represented by the formula (19) (wherein, x, y, and z each independently stands for an integer of from 1 to 20), the formula (20), the formula (21) (wherein. A7, A8 and A9 each independently represents a divalent linking group selected from -0- , -C(=0)0-, - NHC(=0)0- or -OC(=0)0-, and the formula (22) (wherein. A10, A11 and A12 each independently represents a divalent linking group selected from -O- , -C(=0)0-, -NHC(=0)0- or -OC(=0)0-), and tetrafunctional epoxy compounds represented by the formula (23) (wherein. A13 represents methylene or a divalent linking group represented by the formula (25) or (26), in which b2 stands for an integer of from 0 to 4, b3 stands for an integer of from 1 to 3 and b4 stands for an integer of from 0 to 2) and the formula (24).
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000015_0003
Figure imgf000016_0001
The above-described epoxy compounds are given as examples of the component, in the amine-cured type epoxy resin available by the present invention, preferably employed for providing an electrolyte membrane excellent in mechanical strength.
In order to control ion conductivity, heat resistance, mechanical properties and productivity of an electrolyte membrane, at least two polyfunctional epoxy compounds represented by the formulas (5) to (24) may be used simultaneously. The sulfonic-acid-containing amine-cured type epoxy resin of the present invention is also available by using, as a polyvalent epoxy compound, a polyfunctional epoxy resin as described in Japanese Patent Laid-Open No. 1986-247720, Japanese Patent Laid-Open Mo. 1986-246219, Japanese Patent Laid-Open No. 1988-10613 and the like either singly or in combination with the epoxy compound as shown by the formulas (5) to (24). No particular limitation is imposed on the amine compound to be used in the present invention insofar as it can provide ion conductivity enough for use in the intended electrochemical device and thermal and mechanical properties which can endure the using environment . Specific examples will be described below. The amine compounds to be used in the present invention include low molecular compounds , and high molecular compounds such as oligomers and polymers .
Examples include amine compounds having an amine value (the number of hydrogen atoms derived from the amino group contained in one molecule) of 2 and represented by the formulas (25) to (27), (28) (wherein, B3 represents a hydrocarbon group having 2 to 20 carbon atoms or a group having at least one ether bond in a hydrocarbon chain having 4 to 20 carbon atoms) and (29), amine compounds having an amine value of 3 and represented by the formulas (30), (31) (wherein, a1 stands for an integer of from 2 to 18, and B4 represents a hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon chain having 3 to 20 carbon atoms with at least one ether bond in the chain) and (32), amine compounds having an amine value of 4 and represented by the formulas (33) (wherein, a1 stands for an integer of from 2 to 18), (34), (35) (wherein, a2 stands for an integer of from 1 to 10000), (35) and (37), and amine compounds having an amine value of 5 or greater and represented by the formulas (38) (wherein a3 stands for an integer of 2 or greater), (39), (40) (wherein x, y and z each independently represents an integer of from 1 to 20), (41) (wherein, a4 stands for an integer of 2 or greater and B5 represents a hydrogen atom or a methyl group), and (42) (wherein, p, q, r and s each independently stands for an integer of from 1 to 20).
Figure imgf000018_0001
HN ,N-CH2CH2-N NH \ / \ / (27) H2N-Bd (28)
Figure imgf000018_0002
HN N-CH2CH2NH2 B' — N-(cH2-f— NH2
(30) H x 'a1 (31)
Figure imgf000018_0003
Figure imgf000019_0001
The above-described amine compounds are given as examples of the component preferably employed in the amine- cured type epoxy resin available by the present invention. Two or more amine compounds represented by the formula (25) to (42) may be used simultaneously in order to control the ion conductivity, heat resistance, mechanical properties and productivity of an electrolyte membrane.
No particular limitation is imposed on the cyclic sulfonate ester to be used in the present invention insofar as it can be introduced into the epoxy resin through a covalent bond by the reaction with an amine and can provide ion conductivity enough for use in the intended electrochemical device and thermal and mechanical properties enough to stand the using environment . Those represented by the formulas (43) and (44) and easily available in practice can be used in the present invention.
Figure imgf000019_0002
Means for chemical analysis in order to identify the detailed chemical structure of the sulfonic-acid-containing amine-cured type epoxy resin available by the present invention is limited, because the resinous product obtained as a final product cannot be re-dissolved in an organic solvent because it has been three-dimensionally crosslinked. For example, it is possible to confirm by infrared absorption (IR) spectrum of the sulfonic-acid-containing amine-cured type epoxy resin that it has at least one structure selected from the structures represented by the following formulas ( 1 ) and ( 2 ) :
Figure imgf000020_0001
(wherein, R1 and R3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms, or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond, and R2 represents a hydrocarbon chain having 3 or 4 carbon atoms). Upon identification, a low-moleσular-weight model compound, which is soluble to solvent, having a partial structure represented by the formula (1) or (2) existing in the resin is synthesized separately. By making the attribution of its IR spectrum to correspond to the IR spectrum of the sulfonic-acid-containing amine-cured type epoxy resin, the resin is confirmed to have at least one structure selected from the formulas (1) and (2). Described specifically, these structures can be identified based on the nuclear magnetic resonance (NMR) spectrum and IR spectrum of the reaction products represented by the below-described reaction scheme <1> by using phenyl glycidyl ether as the epoxy compound, n-butylamine as the amine compound and 1,3-propanesultone as the cyclic sulfonate ester.
Figure imgf000021_0001
Reaction scheme <1> The spectrum data of Compounds (45) to (48) in the reaction scheme <1> will be described later in Referential Examples. It has been confirmed that Compound (49) is not formed when an excess amount of propanesultone is reacted with Compound (45), or propanesultone is further added to Compound (48). The infrared absorption bands identifying the structure of the formula (1) or (2) which is a constituent of the resin are determined as shown in Table 1 based on the analysis results of the spectrum data of the model compound.
Table 1 : Identification of structure by infrared absorption spectrum
Figure imgf000022_0001
As is apparent from the reaction scheme and Table 1, the formation of the structure represented by the formula (1) or (2) in the sulfonic-acid-containing amine-cured type epoxy resin can be determined when absorptions characteristic of the amine compound and epoxy compound used as its raw materials cannot be observed in the spectrum of the epoxy resin or observed but they are very weak, and absorptions characteristic of the structure of the formula (1) or (2) can be recognized.
No particular limitation is imposed on the reaction between the epoxy compound and amine compound insofar as a membrane can be formed prior to the completion of the curing reaction by the membrane forming method such as solvent casting method, spin coating method, transfer method or printing method, or by mechanical treatment such as rolling or drawing. In general, an organic solvent can be used as needed to conduct the reaction uniformly. Any organic solvent can be used unless it reacts with the epoxy compound, considerably lowers the nucleophilicity of amine, reacts with the cyclic sulfonate ester or adversely affects the properties of the membrane formed. Examples include n- hexane, cyclohexane, n-heptane, n-octane, ethyl cellosolve, butyl cellosolve, benzene, toluene, xylene, anisole, methanol, ethanol, isopropanol, butanol, ethylene glycol, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, N,N- dimethylformamide, N,N-dimethylacetamide, N-methyl-2- pyrrolidinone and dimethylsulfoxide. If necessary, two or more of these organic solvents can be used as a mixture or the organic solvents may be added with water. Organic solvents containing a halogen element such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2,- tetrachloroethane, chlorobenzene and dichlorobenzene may be used for promoting the reaction, but from the viewpoint of the "small environmental load", which is one of the object of this application, they are not desirable as an embodiment of the present invention. If it can be judged that the possibility of leakage to the environment can be avoided without spending a large energy, however, such solvents are not undesirable.
A resin electrolyte obtained by reacting a liquid epoxy compound and a liquid amine compound with a cyclic sulfonate ester is expected to have a high transference number of ion, but its mechanical strength is sometimes weak. On the contrary, a resin electrolyte obtained by reacting a solid epoxy compound and a solid amine compound with a cyclic sulfonate ester tends to be hard and fragile. In applications requiring high mechanical strength, a three-dimensional crosslinking density is an important influencing factor. Synthesis of a resin electrolyte having properties contrary in molecular design such as high ion transference number and mechanical strength can be achieved by mixing appropriate raw materials .
A resin electrolyte having high ion transference number and improved mechanical properties can be obtained, for example, by mixing a liquid component and a solid component, by mixing a bifunctional component and a polyfunctional component, or by reacting components respectively to some extent to extend their chains and mixing them; and then reacting the mixture with a cyclic sulfonate ester. Heightening of the ion transference number can be expected if sulfonic acid can be introduced at a high density in a region of a flexibility-imparting resin component having a great influence on an ion transference number. In this case, a resin electrolyte whose swelling with a good solvent of the resulting resin electrolyte is suppressed and which has excellent mechanical properties and high ion transference number can also be synthesized by adding a cyclic sulfonate ester only to a pre-cured solution of a flexibility-imparting resin component, which has been reacted separately, to react them, and then, mixing the reaction mixture with a pre-cured solution of a rigidity-imparting resin component to which the cyclic sulfonate ester has not been added. By reacting the cyclic sulfonate ester with a primary, secondary or tertiary amine in the reaction system, a sulfonic acid group can be introduced into the resin through a covalent bond. In the above-described example, use of a polyfunctional amine as a flexibility-imparting resin component makes it possible to introduce sulfonic acid at high density in a region of a flexibility-imparting resin component so that it is effective for improving the ion transference number. It is preferred to adjust the mole number of the cyclic sulfonate ester used for the reaction not to exceed that of nitrogen atoms derived from the amino group in the reaction system.
The molded product of the present invention can be obtained by molding the sulfonic-acid-containing amine- cured type epoxy resin available by the present invention. No particular limitation is imposed on the molding method insofar as it is ordinarily employed. The intended molded product is available, for example, by transfer molding. By using the sulfonic-acid-containing amine-cured type epoxy resin, molded product, or electrolyte or electrolyte membrane of the resin, which are obtained by the present invention, the electrochemical devices of the present invention can be produced.
No particular limitation is imposed on the electrochemical device insofar as it is a device in which electrochemical reaction is effected. Examples include electro de-ionization pure water production equipment, secondary cell, fuel cell, humidity sensor, ion sensor, gas sensor, electrochromic device and desiccant. The electrochemical device of the present invention can be obtained by replacing the electrolyte or electrolyte membrane ordinarily employed in the above-described device with the electrolyte or electrolyte membrane of the present invention. In some applications, enough electrolyte properties cannot be attained because the sulfonic acid group and the amine group in the sulfonic-acid-containing amine-cured type epoxy resin available by the present invention strongly reacts each other. This is considered to occur by the influence of a betaine structure attributable to the coordination of the proton derived from sulfonic acid at the amine residue or reaction of the tertiary amine with the cyclic sulfonate ester. By treating, after the epoxy resin is formed into a membrane or the like, the membrane with a solution containing sulfuric acid to convert the chemical structure of the formula ( 1) or ( 2 ) into that of the formula (3) or (4), in other words, to introduce a free sulfonic acid group into the membrane, the membrane is able to have improved electrolyte properties . Monovalent, divalent or trivalent anion species (X") introduced simultaneously into the membrane will function as an auxiliary electrolyte. No particular limitation is imposed on the conversion ratio from the formula ( 1) or ( 2) to the formula (3) or (4) insofar as it permits sufficient manifestation of electrolyte properties in the electrochemical device for which it is used. Although there is no particular limitation imposed on the conversion agent insofar as it can form a free sulfonic acid group in the membrane, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide and phosphoric acid, organic acids such as benzensulfonic acid, toluenesulfonic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, trifluoroacetic acid and trichloroacetic acid, and compounds such as methyl sulfuric acid, dimethylsulfuric acid, alkyl halides having 1 to 10 carbon atoms and allyl halides can be used. Sulfuric acid is desirable in view of handling ease and low cost. No particular limitation is imposed on the solvent insofar as it does not damage the membrane and not disturb the action of the conversion agent in the solvent. Water, alcohols having 1 to 4 carbon atoms, acetic acid, acetone, tetrahydrofuran, 1,4-dioxane, N,N- imethylformamide, N,N- dimethylacetamide, N-methyl-2-pyrrolidinone and dimethylsulfoxide can be used either singly or in combination of two or more. The conversion treatment is not particular limited insofar as the membrane can be brought into contact with a solution obtained by mixing the conversion agent in the solvent. The treatment temperature may de determined, for example, within a range of from 0 to 150° C, depending on the kind of the solvent or in consideration of the influence on the membrane.
It is possible to use the sulfonic-acid-containing amine-cured type epoxy resin of the present invention as an electrolyte for lithium ion secondary battery by doping lithium ions in the resin. In order to achieve a lithium ion transference number sufficient for practical use, it is recommended to use an epoxy compound or amine compound, to be used upon synthesis of the epoxy resin, containing a number of ether bonds and to control the composition of the epoxy resin to have properties of a soft gel electrolyte. For doping of lithium ions, known methods as described, for example, in "High-density Lithium Secondary Battery" (Technosystems, 1998) may be used. Lithium ions can be doped by dipping the electrolyte or electrolyte membrane of the present invention in an aqueous solution, organic solvent, or an organic solvent containing an aqueous solution, each containing lithium ions.
When there is a possibility of elution of impurities in the membrane adversely affecting the performance of electric devices, the epoxy resin electrolyte can be used for them after washing. The above-described conversion treatment employed for the formation of free sulfonic acid can be utilized as is as the washing treatment . Alternatively, the impurities can be eluted by dipping the resin electrolyte in a solvent such as water, an alcohol having 1 to 4 carbon atoms, acetone, tetrahydrofuran, 1,4- dioxane, N,N-dimethylformamide, or N,N-dimethylacetamide. It is preferred to complete the washing by boiling it for from several hours to several days in distilled water. [Example] Examples of the present invention will next be described. It should however be borne in mind that the present invention is not limited to or by the following examples .
First, synthesis reaction of model compounds represented by the reaction scheme 1 will be described below as Reference Examples . Referential Example 1> Synthesis of Compound (45) In an argon atmosphere, 40 ml of DMF was charged in a 50 ml two-necked eggplant type flask. It was stirred and then heated to 60° C. After 6.8 ml (50 mmol) of phenyl glycidyl ether was added to dissolve it in DMF, 5.0 ml (50 mmol) of n-butylamine was added in portions. The resulting mixture was stirred for 18 hours, followed by concentration under reduced pressure to remove the solvent. The residue was purified by chromatography on a silica gel column (developing solvent: dichloromethane) , whereby 4.5 g (yield: 40%) of a compound represented by the formula (45) was obtained in the white powdery form. Spectrum data of Compound (45)
^-NMR, δ (ppm, DMSO-de, 400 MHz): 0.87 (3H, t, CH3), 1.31 (2H, m, CH2), 1.40 (2H, m, CH2) , 2.51 (2H, m, CH2) , 2.57 (IH, dd, CH2), 2.65 (IH, dd, CH2) , 3.86 (IH, m, CH) , 3.86 (IH, m, CH2), 3.94 (IH, m, CH2) , 4.93 (IH, d, OH), 6.91 (3H, m, Ph) , 7.27 (2H, , Ph) .
13C-NMR, δ (ppm, DMSO-de, 400 MHz): 14.8 (CH3) , 20.8 (CH2) , 32.7 (CH2), 50.1 (CH2), 53.4 (CH2) , 69.0 (CH) , 71.5 (CH2) , 115.3 (Ph), 121.3 (Ph), 130.3 (Ph) , 159.6 (Ph) .
IR (cm"1, KBr disk): 3267 (s, OH st), 3065, 2929 (s, CH st), 2869 (s, CH st), 2832, 1600 (s, arC-C st), 1587 (m, NH deform), 1499 (s, arC-C st), 1485, 1456, 1293, 1247 (vs, arC-O-alC st as), 1175 (m, arC-O-alC st as), 1142, 1109, 1084, 1037 (arC-O-alC st sy) , 1007, 914, 894, 810, 753, 692. Referential Example 2> Synthesis of Compound (46)
In an argon atmosphere, 40 ml of DMF was charged in a 50 ml two-necked eggplant type flask. It was stirred and then heated to 60° C. After 6.8 ml (50 mmol) of phenyl glycidyl ether was added to dissolve it in the resulting DMF, 2.5 ml (25 mmol) of n-butylamine was added in portions. The resulting mixture was stirred for 24 hours, followed by concentration under reduced pressure to remove the solvent. The residue was purified by chromatography on a silica gel column (developing solvent: ethyl acetate/n-hexane = 3/7, by volume), whereby 8.4 g (yield: 90%) of a compound represented by the formula (46) was obtained in the form of a pale yellow viscous liquid. Spectrum data of Compound (46)
XH-NMR, δ (ppm, DMSO-d6, 400 MHz): 0.78 (3H, dt, CH3) , 1.20 (2H, m, CH2), 1.35 (2H, m, CH2) , 2.62 (2H, m, CH2) , 2.47 (4H, m, CH2 2), 3.84 (4H, m, CH2χ2), 3.94 (2H, m, CHχ2), 4.86 (2H, d, OHχ2), 6.88 (6H, m, Ph) , 7.25 (4H, m, Ph) . 13C-MMR, δ (ppm, DMSO-d6, 400 MHz): 14.8 (CH3) , 20.9 (CH2) , 29.8 (CH2), 56.1 (CH2) , 58.7 (CH2) , 59.3 (CH2) , 68.1 (CH) , 68.4 (CH), 71.3 (CH2*2), 115.2 (Ph) , 121.2 (Ph) , 130.3 (Ph) , 159.6 (Ph).
IR (cm-1, KBr disk): 3396 (broad, OH st), 3063, 3041, 2955 (s, CH st), 2872 (m, CH st), 1600 (s, arC-C st), 1497 (s, arC-C st), 1457, 1301, 1246 (vs, arC-O-alC st as), 1173 (m, arC-O-alC st as), 1079, 1043 (arC-O-alC st sy) , 753, 691. Referential Example 3> Synthesis of Compound (47)
In a 50 ml two-necked eggplant type flask was charged 1.9 g (5.0 mmol) of the compound obtained in Referential Example 2. In an argon atmosphere, the compound was heated to 60° C. After 0.5 ml of acetone was added to dissolve the compound therein, 0.44 ml (5.0 mmol) of 1,3-propanesultone was added in portions . The resulting mixture was heated to 80° C. Three hours later, 0.5 ml of acetone was added and the resulting viscous solution was stirred slowly. Three hours later, the reaction mixture was cooled to room temperature. Ether was added to precipitate a solid. The solid was vacuum dried at 60° C, whereby 2.15 g (yield: 87%) of a compound represented by the formula (47) was obtained in the colorless powdery form. Spectrum data of Compound (47)
^- MR, δ (ppm, DMSO-de, 400 MHz): 0.91 (3H, t, CH3), 1.28 (2H, m, CH2), 1.7 (2H, m, CH2), 2.1 (2H, m, CH2) , 2.49 (2H, m, CH2), 3.46 (2H, m, CH2) , 3.5 (4H, m, CH2*2), 3.62 (2H, m, CH2), 3.93 (4H, m, CH2χ2), 4.5 (2H, m, CH*2), 6.96 (6H, m, Ph), 7.30 (4H, m, Ph) .
IR (cm"1, KBr disk): 3301 (broad, OH st) , 2964 (m, CH st), 2877 (m, CH st), 1600 (s, arC-C st), 1497 (s, arC-C st), 1472, 1295, 1245 (vs, arC-O-alC st as), 1172 (s, arC-O-alC st as), "1165 (as shoulder, S=0 st as), 1080, "1045 (as shoulder, S=0 st sy) , 1037 (arC-O-alC st sy) , 756, 693, 520 Referential Example 4> Synthesis of Compound (48)
In a 50 ml two-necked eggplant type flask was charged 1.1 g (5.0 mmol) of Compound (45) obtained in Referential Example 1, followed by stirring. In an argon atmosphere, the compound was heated to 50° C. After 5 ml of acetone was added to dissolve the compound therein, 0.44 ml (5.0 mmol) of 1,3-prophnesultone was added in portions, by which the solution gradually became milky white. Five hour later, the reaction mixture was cooled to room temperature. Ether was added to precipitate a solid. The solid was collected and vacuum dried at 60° C, whereby 0.86 g (yield: 50%) of a compound represented by the formula (48) was obtained in the form of colorless powder. Spectrum data of Compound (48) ^-NMR, δ (ppm, DMSO-de, 400 MHz): 0.90 (3H, t, CH3) , 1.32
(2H, m, CH2), 1.62 (2H, m, CH2) , 2.00 (2H, m, CH2) , 2.61 (2H, m, CH2), 3.19 (2H, m, CH2) , 3.19 (IH, m, CH2) , 3.29 (IH, m, CH2), 3.29 (2H, m, CH2) , 3.96 (2H, d, CH2) , 4.27 (IH, m, CH) , 5.86 (IH, br-s, OH), 6.95 (3H, m, Ph) , 7.29 (2H, m, Ph) , 9.51 (IH, br-s, OH).
IR (cm"1, KBr disk): 3371 (broad, OH st), 2968 (m, CH st), 2774 (broad), 1600 (m, arC-C st) , 1500 (m, arC-C) , 1249 (s, arC-O-alC st as), 1222, "1165 (as shoulder, S=0 st as), 1150 (vs, S=0 st), "1045 (as shoulder, S=0 st sy) , 1032 (s, arC-O-alC st sy) , 756, 695, 600, 590, 531, 522.
The structures of Epoxy compounds (E) used in Examples and infrared absorption bands characteristic of the epoxy compounds will next be shown in Table 2. Table 2: Chemical structure of epoxy compound and infrared absorption band characteristic of epoxy ring
Figure imgf000034_0001
Figure imgf000035_0001
The structure of the amine compounds (A) used in
Examples and infrared absorption bands characteristic of the amine compounds will next be shown in Table 3.
Table 3 : Chemical structure of amine compound and infrared absorption band characteristic of amino group
Figure imgf000035_0002
Figure imgf000036_0001
As cyclic sulfonate ester (S), that represented by the below-described formula (43) or (44) was employed.
AΛ <
(43)
1344 cm"1 (s) -S(=0)20- asymmetric stretching vibration 1167 cm"1 (s) -S(=0)20- symmetric stretching vibration 779 cm-1 (s) S-0 stretching vibration
Figure imgf000036_0002
1351 cm"1 (s) -S(=0)20- asymmetric stretching vibration 1171 cm"1 (s) -S(=0)20- symmetric stretching vibration
783 cm ,-"ι (s) S-0 stretching vibration In these cyclic sulfonate esters , the cleavage of the ring easily occurs in the presence of an amine compound derivative, followed by bonding with the amine compound derivative to form sulfonic acid. Of the infrared absorption bands shown above, absorption at -1350 cm"1 attributable to a sulfonate ester structure is less subject to another absorption band and progress of the reaction can easily be judged by the disappearance or drastic reduction of this absorption band. This suggests the formation of sulfonic acid.
As raw material compounds for them, commercially available ones can mainly be used as are. It is however needless to say that raw material compounds not commercially available can be synthesized for use in the present invention.
A description will next be made of synthesis examples of epo∑ry compounds . Referential Example 5> Synthesis of E-6
In 260 ml of acetone were dissolved 34.8 g (174 mmol) of 4- (benzyloxy)phenol and 11.9 ml (87.0 mmol) of 1,5- dibromopentane . To the resulting solution were added 30.1 g of potassium carbonate and 1.4 g of potassium iodide, followed by stirring for 18 hours at reflux temperature. At room temperature, 800 ml of acetone was added and insoluble matters were filtered off. After concentration of the filtrate, the concentrate was purified by recrystallization with acetone: tetrahydrofuran= 1:1 (by volume) to obtain 36.0 g of a colorless powdery solid. As a result of spectrum measurement, the solid was confirmed to be l,5-bis(4-benzyloxyphenoxy)pentane.
^- MR, δ (ppm, CDC13, 400MHz): 1.64 (2H, m, CH2) , 1.82 (4H, m, CH2 χ2), 3.91 (4H, t, CH2χ2), 5.00 (4H, m, CH2) , 6.82 (4H, d, J=9.2Hz, Ph), 6.90 (4H, d, J=9.2Hz, Ph) , 7.40 (10H, m, Ph) .
IR, v (cm"1, KBr disk): 2929 (m, C-H) , 2862 (m) , 1510 (s, arC-C), 1468 (m) , 1454 (m) , 1397 (w) , 1382 (m) , 1287 (m) , 1240 (s, arC-O-alC), 1116 (m) , 1067 (m) , 1018 (s), 946 (m) , 828 (s), 741 (m), 734 (m) , 692(s), 509 (m) .
In a mixed solvent of ethanol (53.4 ml) and tetrahydrofuran (53.4 ml) was dissolved 2.50 g (5.34 mmol) of the powder solid obtained by the above-described operation while heating, followed by dispersion of 0.227 g of 5% palladium held on carbon powder in the resulting solution. The reaction container was cooled to -60° C. After vacuum degassing for 1 hour, a hydrogen gas was introduced into the container and stirring was conducted at 75° C for 14 hours. The catalyst was removed through Celite and the residue was purified by chromatography on a silica gel column (developing solvent: chloroform), whereby 1.40 g of a colorless powdery solid was obtained. From the results of the spectrum measurement , the solid was confirmed to be 1, 5-bis(4-hydroxyphenoxy)pentane. Yield: 91.5%. ^-NMR, δ (ppm, CDC13, 400MHz): 1.63 (2H, m, CH2) , 1.81 (4H, m, CH2χ 2 ) , 3 . 92 ( 4H , t , J=6 . 4Hz , CH2 χ 2 ) , 4 . 1 - 4 . 9 ( 2H , broad, PhOH) , 6 . 76 ( 8H , m, J=9 . 2Hz , Ph) .
IR, v (cm"1, KBr disk): 3357 (m, phenolO-H) , 3040 (w) , 2949 (w, C-H), 2928 (m), 2860 (w) , 1607 (vw, arC-C) , 1513 (s, arC-C), 1472 (m) , 1462 (m) , 1393 (w) , 1376 (m) , 1271 (m) ,
1235 (s, arC-O-alC), 1106 (m) , 1068 (m, arC-O-alC) , 951 (m) , 823 (s), 778 (w), 741 (m) , 524 (m) .
In 29.5 ml (378 mmol) of epichlorohydrin was dissolved 10.8 g (37.8 mmol) of the colorless powder obtained in the above operation. At intervals of 30 minutes at 95° C, 0.45 g (11.3 mmol) of sodium hydroxide was added 10 times, followed by stirring at 95° C for 43 hours. After the reaction mixture was allowed to cool down, 500 ml of hexane was added to collect insoluble matters . Chloroform and water were added and the organic layer was concentrated. The residue was purified by chromatography on a silica gel column (developing solvent: dichloromethane/ethyl acetate = 12/1, by volume), whereby 9.91 g of a colorless solid was obtained. From the results of the spectrum measurement, the solid was confirmed to be l,5-bis(4-glyσidyloxyphenoxy)pentane (E-6). Yield: 65.9%. ^-NMR, δ (ppm, CDC13, 400MHz): 1.63 (2H, m, CH2), 1.83 (4H, m, CH2χ2), 2.74 (2H, dd, J=2.8, 5.2H , ) , 2.90 (2H, dd, J=4.4, 4.8Hz)), 3.34 (2H, m, CHχ2), 3.92 (2H, dd, J=5.2, 11.0Hz), 3.93 (4H, t, J=6.4Hz), 4.16 (2H, dd, J=3.4,
11.0Hz, ), 6.82 (4H, d, J=9.1Hz, Ph) , 6.85 (4H, d, J=9.1Hz, Ph) . IR, v (cm"1, KBr disk): 3055 (vw, epoxyC-H) , 3005 (vw) , 2941 (w, C-H), 2911 (w) , 2856 (w) , 1509 (s, arC-C) , 1466 (m), 1389 (w), 1290 (w) , 1237 (s, arC-O-alC) , 1130 (w) , 1114 (w), 1070 (w), 1039 (m) , 991 (w) , 914 (w) , 848 (w) , 820 (m, epoxyC-O) , 786 (w) , 525 (w) .
Referential Example 6> Synthesis of E-7
In 200 ml of acetone were dissolved 30.0 g (65.4 mmol) of triethylene glycol di-p-tosylate and 26.7 g (131 mmol) of 4- (benzyloxy)phenol. To the resulting solution was added 22.6 g of potassium carbonate and the mixture was stirred for 30 hours at reflux temperature. At room temperature, 1.0 1 of acetone was added and insoluble matters were filtered off. After concentration of the filtrate, the concentrate was purified by re- crystallization with acetone :hexane=5 : 1 (by volume), whereby 12.1 g of a pale yellow solid was obtained. From the results of spectrum measurement, the solid was confirmed to be triethyleneglycol di-4-benzyloxyphenyl ether. Yield: 35.8% ^-NMR, δ (ppm, CDC13, 400MHz): 3.75 (4H, m, CH2χ2), 3.84
(4H, m, CH2 χ2), 4.08 (4H, m, CH2x2), 5.00 (4H, m, CH2) , 6.84 (4H, d, J=9.4Hz, Ph), 6.89 (4H, d, J=9.4Hz, Ph) , 7.37 (10H, m, Ph) . IR, v (cm"1, KBr disk): 3065 (w) , 2915 (m, C-H), 2860 (m) , 1511(s, ArC-C), 1467 (m) , 1454 (s), 1384 (m) , 1287(s), 1240 (s, arC-O-alC), 1145 (s), 1115 (s), 1064 (m) , 1019(s), 987 (s), 924(m), 862 (m) , 827 (s), 766 (m) , 732 (s), 692 (s). 522 ( m ) .
11.3 g (22.1 mmol) of the pale yellow solid obtained in the above-described step was dissolved in a mixed solvent of 100 ml of tetrahydrofuran and 100 ml of ethanol, 0.94 g of 5% palladium on carbon powder was dispersed in the resulting solution. In a hydrogen gas atmosphere, the dispersion was stirred at 75° C for 18 hours. The catalyst was removed through Celite and the residue was concentrated, whereby 7.23 g of white powder was obtained. From the results of spectrum measurement, the powder was confirmed to be triethyleneglycol di-4-hydroxyphenyl ether. Yield: 98. Ό -S .
^- MR, δ (ppm, CDC13, 400MHz): 3.75 (4H, m, CH2χ2), 3.84 (4H, m, CH2x2), 4.07 (4H, m, CH2χ2), 6.73 (4H, d, J=9.4Hz, Ph), 6.78 (4H, d, J=9.4Hz, Ph) .
IR, v (cm"1, KBr disk) : 3365 (m, phenolO-H) , 3035 (w) , 2932 (m, C-H), 2916 (m) , 2900 (m) , 2877 (s), 1516 (s, arC- C), 1489 (m), 1477 (m) , 1458 (m) , 1379 (m) , 1350 (w) , 1303 (m) , 1281 (m), 1233 (s, arC-O-alC) , 1175 (m) , 1134 (s), 1111 (s), 1045 (m) , 991 (s), 822 (s), 805 (m) , 767 (s), 516 (m).
In 16.5 ml (210 mmol) of epichlorohydrin was dissolved 7.00 g (21.1 mmol) of the white powder obtained above and 0.23 g (6.32 mmol) of sodium hydroxide was added 10 times at intervals of 30 minutes at 100° C. The resulting mixture was then stirred for 20 hours at 100° C. After the reaction mixture was allowed to cool down, 500 ml of hexane was added. Insoluble matters collected were washed with 500 ml of acetone. After concentration of a portion soluble in acetone, the residue was purified by chromatography on a silica gel column ( developing solvent : dichloromethane/ethyl acetate=9/l, by volume), whereby 5.96 g of a white solid was obtained. From the results of spectrum measurement, the solid was confirmed to be triethyleneglycol di-4-glycidyloxyphenyl ether (E-7). Yield: 63.6%. ^-NMR, δ (ppm, CDC13, 400MHz): 2.74 (2H, dd, J=2.6, 5.2Hz), 2.90 (2H, dd, J=4.0, 4.6Hz), 3.33 (2H, m, CHχ2), 3.74 (4H, m, CH2χ2), 3.84 (4H, m, CH2χ2), 3.90 (2H, dd, J=3.2, 11Hz), 4.08 (4H, m, CH2χ2), 4.16 (2H, dd, J=3.2, 11Hz), 6.84 (8H, m, Ph) . IR, v (cm-1, KBr disk): 3118 (w) , 3076 (w) , 3055 (w, epoxyC-H), 2927 (m, C-H), 2891 (s), 2856 (m) , 2833 (m) , 1509 (s, arC-C), 1456 (s), 1433 (s), 1378 (m) , 1344 (m) , 1322 (m), 1288 (s), 1233 (s, arC-O-alC) , 1131 (s), 1076 (s), 1049 (s), 971 (m), 928 (m) , 913 (m) , 880 (m) , 865 (m) , 846 (m), 827 (s, epoxyC-O) , 771 (s), 747 (m) , 529 (m) , 454 (m) . Referential Example 7> Synthesis of E-12
In an argon atmosphere, 5.0 g (25 mmol) of 4,4'- diaminodiphenyl ether, 11.0 g (100 mmol) of sodium carbonate and 20.0 ml (250 mmol) of epichlorohydrin were charged in a 100 ml three-necked eggplant type flask. They were stirred and heated to 110° C. After three hours stirring, the reaction mixture was returned to room temperature. Dichloromethane was added. From the mixture, sodium carbonate was filtered off. Dichloromethane was distilled off under reduced pressure. In an argon gas atmosphere, 5.0 g (125 mmol) of sodium hydroxide and 10 ml (125 mmol) of epichlorohydrin were added and the mixture was heated to 60° C. After three hours stirring, the reaction mixture was returned to room temperature and 50 ml of hexane was added. Stirring for 30 minutes produced a yellowish white viscous product. The supernatant was removed and then, dichloromethane was added to dissolve the former in the latter. Insoluble matters were filtered off and the solvent was distilled off under reduced pressure. The residue was purified by chromatography on a silica gel column (developing solvent: hexane/ethyl acetate = 1/1, by volume) to yield 5.3 g of a pale yellow viscous liquid. As a result of spectrum measurement, it was confirmed to be 4, ' -bi (N,N-diglycidylamino)phenyl ether (E-12). Yield:
XH-NMR, δ (ppm, CDC13, 400MHz): 2.58 (4H, m, CH2) , 2.80 (4H, m, CH2), 3.17(4H, m, CHχ4), 3.38 (4H, m, CH2) , 3.70 (4H, m,
CH2), 6.78 (4H, m, Ph) , 6.90 (4H, m, Ph) .
13C-NMR, δ (ppm, CDC13, 400MHz): 45.8 (CH2) , 51.1 (CH) , 54.1
( CH2 ) , 114 . 6 ( Ph) , 119 . 9 ( Ph) , 144 . 9 ( Ph ) , 150 . 2 ( Ph) .
IR, v (cm-1, KBr disk): 3051 (m, epoxyC-H) , 2995 (s, C-H), 2922 (m), 1609 (m, arC-C), 1505 (vs, arC-C) , 1412 (m) , 1386
(s), 1331 (m), 1226 (vs, arC-O-alC) , 1190 (s), 1153 (m) ,
1126 (m), 1006 (w) , 974 (m) , 941 (m) , 907 (m) , 871 (m) , 828 (s, epoxyC-O) , 754 (m) , 517 (m) . Referential Example 8> Synthesis of E-13
In an argon atmosphere, 5.5 g (15 mmol) of 4,4'- bis(4-aminophenoxy) -biphenyl, 6.4 g (60 mmol) of sodium carbonate and 12 ml (150 mmol) of epichlorohydrin were charged in a 100 ml three-necked eggplant type flask. They were stirred and heated to 110° C. After three hours stirring, the reaction mixture was returned to room temperature. Dichloromethane was added. From the mixture, sodium carbonate was filtered off. Dichloromethane was distilled off under reduced pressure. In an argon gas atmosphere, 3.0 g (75 mmol) of sodium hydroxide and 10 ml (130 mmol) of epichlorohydrin were added and the mixture was heated to 60° C. After three hours stirring, the reaction mixture was returned to room temperature and 50 ml of hexane was added. Stirring for 30 minutes produced a yellowish white precipitate . The supernatant was removed and then, chloroform was added to dissolve the former in the latter. Insoluble matters were filtered off, followed by purification by chromatography on a silica gel column (developing solvent: chloroform) to yield 3.1 g of a pale yellow powder. As a result of spectrum measurement, it was confirmed to be 4,4 ' -bis[4-(N,N- diglycidylamino)phenoxy]biphenyl (E-13). Yield: 35%. XH-NMR, δ (ppm, CDC13 , 400MHz): 2.61 (4H, m, CH2), 2.82 (4H, m, CH2), 3.20 (4H, m, CH) , 3.41 (4H, m, CH2), 3.75 (4H, m, CH2), 6.83 (4H, m, Ph) , 6.99 (8H, m, Ph) , 7.46 (4H, m, Ph) . 13C-NMR, δ (ppm, CDC13 , 400MHz): 45.8 (CH2), 51.1 (CH) , 54.0 (CH2), 114.4 (Ph) , 118.0 (Ph) , 121.4 (Ph) , 128.3 (Ph) , 135.2 (Ph), 145.6 (Ph), 148.3 (Ph) , 158.5 (Ph) . IR, v (cm"1, KBr disk): 3044 (w, epoxyC-H) , 2983 (w, C-H), 2917 (w), 1611 (m, arC-C), 1513 (s, arC-C) , 1490 (s, arC-C) , 1387 (m) , 1340 (w) , 1266 (s, epoxyC-O-C) , 1231 (s, arC-O- alC), 1191 (m), 1172 (m) , 1000 (w) , 968 (m) , 941 (w) , 907 (w) , 869 (m) , 826 (s, epoxyC-O-C) , 761 (m) , 645 (w) , 509 (m). Referential Example 9> Synthesis of E-14
In an eggplant type flask, 4, 4 ' -diphenol (30.0 g, 161 mmol), potassium carbonate (37.8 g, 273.9 mmol) and potassium iodide (2.67 g, 16.1 mmol) were weighed. To the mixture was added 480 ml of acetone. Then, 3-bromo-l- propene (39.0 g, 322 mmol) was added, followed by stirring for 4 hours at reflux temperature. Further, 3-bromo-l- propene (39.0 g, 322 mmol) was added and the misϊture was stirred for 17 hours at reflux temperature. The reaction mixture was filtered and the salt collected by filtration was washed with acetone. The acetone was distilled off from the filtrate, followed by drying, whereby 42.9 g of a colorless powdery solid was obtained. As a result of spectrum measurement , it was confirmed to be 4,4'- diallyloxybiphenyl. Yield: 100% ^-NMR, δ (ppm, CDC13, 400 MHz): 4.58 (4H, dt , J=1.6,
5.2Hz), 5.31 (2H, ddd, J=1.6, 3.2, 10.4Hz), 5.44 (2H, ddd, J=1.6, 3.2, 17.2Hz), 6.08 (2H, ddt , J=5.2, 10.4, 17.2Hz), 6.97 (4H, d, J=8.8Hz), 7.47 (4H, d, J=8.8Hz). IR, v (cm-1, KBr disk): 3085 (w, =C-H) , 3022 (w) , 2987 (w, C-H), 2915 (w) , 2869 (w) , 1650 (w, C=C) , 1607 (m, arC-C) , 1499 (s, arC-C), 1460 (w) , 1428 (m) , 1365 (w) , 1270 (s), 1245 (s, arC-O-alC), 1178 (m) , 1031 (m, arC-O-alC) , 1010 (m), 993 (m), 943 (m) , 824 (s), 803 (m) , 570 (w) , 519 (w) .
After 4,4 ' -diallyloxybiphenyl (20.0 g, 75.1 mmol) was dissolved in 260 ml of dichloromethane, the resulting solution was cooled in an ice bath. While the temperature of the solution was returned gradually to room temperature by adding m-chloroperbenzoic acid (cont. 65%) (49.9 g, 188 mmol), the mixture was stirred for 20 hours. Then, m- chloroperbenzoic acid (cont. 65%) (22.4 g, 84.'4 mmol) was added further and the mixture was stirred at room temperature for 6 hours. The organic layer was washed twice with 300 ml of a 1 mol/1 of aqueous sodium bicarbonate solution and then, once with 300 ml of water. The organic layer was dried over sodium sulfate and then distilled to remove the solvent. The residue was purified by chromatography on a silica gel column (developing solvent: dichloromethane/methanol = 400/1) to yield 7.72 g of a pale yellow powdery solid. As a result of spectrum measurement, it was confirmed to be E-14 in Table 2. Yield: 34.5%. XH-NMR, δ (ppm, CDC13, 400 MHz): 2.78 (2H, dd, J=2.8,
4.8Hz), 2.93 (2H, dd, J=4.4, 4.8Hz), 3.38 (2H, m, CHχ2), 4.00 (2H, dd, J=5.6, 11.0Hz), 4.26 (2H, dd, J=3.2, 11.0Hz), 6.98 (4H, d, J=8.8Hz), 7.47 (4H, d, J=8.8Hz). IR, v (cm"1, KBr disk): 3062 (w, epoxyC-H) , 3012 (w, C-H), 2928 (w, C-H), 1606 (m, arC-C) , 1501 (s, arC-C) , 1452 (w) , 1432 (w) , 1347 (w) , 1272 (s, epoxyC-O-C) , 1243 (s, arC-O- alC), 1180 (m) , 1133 (w) , 1037 (s, arC-O-alC) , 1015 (m) , 998 (w) , 910 (m), 864 (w) , 814 (s, epoxyC-O-C) , 761 (w) , 588 (w), 518 (w) . <Example 1>
The preparation of an amine-cured type epoxy resin electrolyte membrane by using E-1 as an epoxy compound, A-1, as an amine compound and (43) as a cyclic sulfonate ester will next be described specifically.
In an eggplant type flask, 3.1 g (9.0 mmol) of 2,2- bis( 4-glycidyloxyphenyl)propane (E-1) was weighed. In an argon atmosphere, 12 ml of dry N,N-dimethylformamide (DMF) was added. To the resulting mixture was added 0.45 ml (3.0 mmol) of triethylenetetramine (A-1) and the mixture was stirred at 80® C for 2 hours. To a 8.9 ml portion of the reaction mixture was added 0.39 ml (4.5 mmol) of 1,3- propanesultone (S-l), followed by stirring at room temperature for 15 minutes. On a 10χ5 cm2 glass plate (having edges sealed with Teflon (trade mark)) disposed horizontally in a thermostat, 2.5 ml of the reaction mixture was cast. After treatment at 60° C for 16 hours and then, at 120° C for 6 hours, a pale brown transparent film having a thickness of 99 μm was obtained. As a result of IR analysis of E-1, A-1 and the film thus obtained. absorption peaks at 3057 cm"1 and 829 cm"1 derived from the epoxy ring of E-1, and absorption peaks near at 3300 cm -"1
and at 1571 cm"1 derived from the amino group of A-1 disappeared, while an absorption peak at 3387 cm"1 derived from a hydroxyl group, and absorption peaks at 1164 cm-1 (observed as a shoulder peak of the absorption peak at 1183 cm"1 derived from the ether bond) and at 1035 cm"1 each derived from sulfonic acid were observed. From the above- described results, the formation of the structure (1) or (2) was confirmed.
In a similar manner, amine-cured type epoxy resins were prepared by using various compounds in combination. The results are shown in Table 4.
Table 4: Preparation results of amine-cured type epoxy resin electrolyte membranes
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Amine-cured type epoxy resins obtained in the above- described Examples can be prepared using raw materials which are relatively easily available and inexpensive. Since they contain a sulfonic acid group in their structure, they can be expected to have properties as an electrolyte. In addition, a wide variety of membranes from gel membranes to self-supporting, flexible and tough ones can be prepared by changing the composition and thereby controlling their properties so that they can be applied to various electrochemical devices . <Example 33>
As one example of the properties of the sulfonic- acid-containing amine-cured type epoxy resin electrolytes prepared in the above-described Examples, their conductivity was determined by measuring the AC impedance.
The membranes obtained in Examples 1, 2, 9, 28 and 29 were each cut into a piece of 2 cm x 5 cm and boiled for 1 hour in a 1 mol/1 aqueous solution of sulfuric acid. After boiling for 1 hour in distilled water, the resulting membrane pieces were each sandwiched with 2 gold electrodes in size of 0.5 cm 4 cm, followed by impedance measurement within a frequency range of from 0.5 Hz to 10 MHz by using an impedance analyzer ("Solartron 1260") while controlling the temperature and humidity in a thermo-hygrostat at 90° C and RH90%, respectively. From the results of the Nyquist Plot thus obtained, the ion conductivity was calculated. The calculation results are shown in Table 5.
Table 5 : Measuring results of conductivity
Figure imgf000053_0001
<Example 34>
According to the present invention, an epoxy resin can be crosslinked three-dimensionally so that a change in dimension can be suppressed to the minimum even under conditions which permit considerable swelling of ordinary uncrosslinked type electrolyte membranes. A dimensional change due to swelling was compared between the resin electrolyte membrane of the present invention and a fluorine-based polymer electrolyte membrane (Nafion (trade mark) 115, product of Dupont) as a Comparative Example, which is popular as uncrosslinked electrolyte membrane. Described specifically, the electrolyte membranes obtained in Examples 1, 2 and 29 and the electrolyte of Comparative Example were each cut into a piece of 1 cm x 1 cm under dry condition. Their length and width were measured precisely. Each test piece was boiled in distilled water for 1 hour. Immediately after it was taken out from the distilled water, its length and width were measured precisely. A dimensional change was calculated in accordance with Equation ( 1 ) and the results are shown in Table .
Equation ( 1 ) :
Average of length and width after boiling(mm)
Dimensional change (%) =- 100 (% Averageof length and width under dry condition (mm)
Figure imgf000054_0001
<Example 35>
The electrolyte membranes obtained in Examples 1, 2, 26, 27, 28 and 29 and the electrolyte membrane of Comparative Example were each cut into a piece of 1 cm x 1 cm under dry condition. Their length and width were measured precisely. Each test piece was boiled in a 1:1 (molar ratio) mixed solution of methanol and water for 1 hour. Immediately after it was taken out from the solution, its length and width were measured precisely. A dimensional change was calculated in accordance with Equation (1) and the results are shown in Table 7.
Table 7 : Dimensional change after boiling in methanol/water
Figure imgf000055_0001
As shown in the above-described results, swelling due to solvent or the like is greatly suppressed in the electrolyte membrane of the sulfonic-acid-containing amine- cured type epoxy resin according to the present invention, compared with the uncrosslinked type electrolyte membrane. When it is applied to electrochemical devices, therefore, an improvement in adhesion to electrodes can be expected. INDUSTRIAL APPLICABILITY
According to the present invention, by controlling the composition of raw materials, sulfonic-acid-containing amine-cured type epoxy resins having wide variety of properties ranging from a gel to a self-supporting, flexible and tough membrane can be obtained. When these resins are used as an electrolyte or electrolyte membrane, they can improve the adhesion of the electrolyte or membrane to electrodes and the like because a dimensional change due to swelling is small. In addition, electrolytes, electrolyte membranes and electrochemical devices featuring a lower cost and a smaller environmental load can be provided.

Claims

1. A sulfonic-acid-containing amine-cured type epoxy resin, comprising at least one structure selected from the structures represented by the following formulas (1) and
(2):
Figure imgf000057_0001
(wherein, R1 and R3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms, or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond, and
R2 represents a hydrocarbon chain having 3 or 4 carbon atoms ) .
2. A molded product obtained by molding the sulfonic-acid-containing amine-cured type epoxy resin of Claim 1.
3. An electrolyte comprising the sulfonic-acid- containing amine-cured type epoxy resin of Claim 1.
4. The electrolyte of Claim 3 , further comprising a lithium ion .
5. An electrolyte membrane comprising the sulfonic- acid-containing amine-cured type epoxy resin of Claim 1.
6. An electrolyte membrane comprising a sulfonic- acid-containing amine-cured type epoxy resin having at least one structure selected from the structures represented by the following formulas ( 3 ) and (4 ) :
Figure imgf000058_0001
(wherein, R1 and R3 each independently represents a hydrocarbon chain having 1 to 50 carbon atoms, or a hydrocarbon chain having 1 to 50 carbon atoms and having a hydroxyl group, amino group, ether bond or imine bond, R2 represents a hydrocarbon chain having 3 or 4 carbon atoms, R4 represents a hydrogen atom or a hydrocarbon chain having 1 to 18 carbon atoms, and X" represents a monovalent, divalent or trivalent anion) .
7. An electrochemical device obtained by using the sulfonic-acid-containing amine-cured type epoxy resin of Claim 1 .
8. A method for preparing a sulfonic-acid-containing amine-cured type epoxy resin, which comprises reacting an epoxy compound having, in a molecule thereof, at least 2 epoxy groups with an amine compound having an amine value of 2 or greater, and reacting the amine in the reaction system with a cyclic sulfonate ester.
9. A method for preparing an electrolyte membrane having a sulfonic-acid-containing amine-cured type epoxy resin, which comprises mixing an epoxy compound having, in a molecule thereof, at least 2 epoxy groups with an amine compound having an amine value of 2 or greater, adding a cyclic sulfonate ester to form a membrane prior to completion of the curing reaction between the epoxy compound and amine compound, and completing the curing reaction and the reaction between the amine and cyclic sulfonate ester in the reaction system.
10. The method for preparing an electrolyte membrane of Claim 9 , wherein the membrane is formed by solvent casting method, spin coating method, transfer method or printing method.
11. The method for preparing an electrolyte membrane of Claim 9, wherein upon membrane formation, hot rolling and/or drawing treatment is conducted.
12. A method for preparing a lithium-ion-containing electrolyte membrane, which comprises impregnating an electrolyte membrane obtained by the method for preparation of Claim 9 in a lithium-ion-containing solvent.
13. A method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating an electrolyte membrane obtained by the method for preparation of Claim 9 in a solvent containing an inorganic acid.
14. A method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating an electrolyte membrane obtained by the method for preparation of Claim 9 in a solvent containing an organic acid.
15. A method for preparing an electrolyte membrane comprising an amine-cured type epoxy resin having a free sulfonic acid group, which comprises impregnating an electrolyte membrane obtained by the method for preparation of Claim 9 in a solvent containing methylsulfuric acid, dimethylsulfuric acid, alkyl halide having 1 to 10 carbon atoms or allyl halide.
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