WO2004078822A1 - Electrolyte en resine epoxyde de type durci par amines comprenant un groupe d'acide sulfonique et son procede de preparation - Google Patents

Electrolyte en resine epoxyde de type durci par amines comprenant un groupe d'acide sulfonique et son procede de preparation Download PDF

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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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amine
acid
epoxy resin
electrolyte membrane
type epoxy
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PCT/JP2004/002571
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English (en)
Inventor
Eiichi Akiyama
Takashi Kawakami
Hitoshi Ito
Hiroshi Yokota
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Ebara Corporation
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Publication of WO2004078822A1 publication Critical patent/WO2004078822A1/fr

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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. insitu polymerisation or insitu 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

La présente invention a trait à une résine époxyde de type durci par amines contenant de l'acide sulfonique présentant une structure choisie parmi les structures représentées par les formules (1) et (2), dans lesquelles : R1 et R3 sont indépendamment l'un de l'autre une chaîne hydrocarbonée ayant 1 à 50 atomes de carbone, ou une chaîne hydrocarbonée ayant 1 à 50 atomes de carbone et ayant un groupe hydroxyle, un groupe amino, une liaison éther ou une liaison imine, et R2 représente une chaîne hydrocarbonée à 3 ou 4 atomes de carbone. L'invention a également trait à un électrolyte ou membrane d'électrolyte contenant ladite résine ; un procédé pour sa préparation ; un dispositif électrochimique utilisant une telle membrane. L'électrolyte et la membrane d'électrolyte selon la présente invention présentent des propriétés telles qu'une conductivité d'ions suffisante pour une utilisation dans des dispositifs électrochimiques, présentent une tenue à la chaleur et une résistance mécanique, et peuvent être préparés à un coût économique. En outre, leur liaison ou adhérence à des électrodes est excellente en raison de l'absence de gonflement de la membrane lorsqu'elle est imprégnée de solvant.
PCT/JP2004/002571 2003-03-04 2004-03-02 Electrolyte en resine epoxyde de type durci par amines comprenant un groupe d'acide sulfonique et son procede de preparation WO2004078822A1 (fr)

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WO2007096382A2 (fr) * 2006-02-23 2007-08-30 Qiagen Gmbh Procédé de production d'une cellule transformée
EP1837365A1 (fr) * 2005-01-07 2007-09-26 Asahi Kasei Kabushiki Kaisha Resine epoxy poreuse durcie
US7939216B2 (en) 2006-01-13 2011-05-10 Samsung Sdi Co., Ltd. Polymer electrolyte membrane, method of preparing the same and fuel cell employing the same
WO2013155173A2 (fr) * 2012-04-13 2013-10-17 Regents Of The University Of Minnesota Procédés et compositions associés à des élastomères époxydés biodégradables
CN113150244A (zh) * 2021-05-20 2021-07-23 广东工业大学 一种磺酸盐型环氧丙烯酸酯树脂及其制备方法和应用

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US7854854B2 (en) * 2005-01-12 2010-12-21 Otsuka Chemical Co., Ltd. Quaternary ammonium salt, electrolyte, electrolyte solution and electrochemical device
US8415490B2 (en) 2008-10-20 2013-04-09 Toray Fine Chemicals Co., Ltd. Epoxy compound and manufacturing method thereof
KR101989660B1 (ko) 2013-07-09 2019-06-14 에보니크 데구사 게엠베하 전기활성 중합체, 그의 제조 방법, 전극 및 그의 용도
JP6159199B2 (ja) * 2013-08-27 2017-07-05 積水化学工業株式会社 ゲル電解質前駆体、ゲル電解質の製造方法、リチウムイオン二次電池の製造方法、及びリチウムイオン二次電池
US10756348B2 (en) 2015-08-26 2020-08-25 Evonik Operations Gmbh Use of certain polymers as a charge store
WO2017032583A1 (fr) 2015-08-26 2017-03-02 Evonik Degussa Gmbh Utilisation de certains polymères comme accumulateurs de charges

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US4087391A (en) * 1975-10-15 1978-05-02 Rhone-Poulenc Industries Ion-exchanger alkylsulphonated phenoxy polymers for membranes
US4265745A (en) * 1977-05-25 1981-05-05 Teijin Limited Permselective membrane
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Cited By (11)

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EP1837365A1 (fr) * 2005-01-07 2007-09-26 Asahi Kasei Kabushiki Kaisha Resine epoxy poreuse durcie
EP1837365A4 (fr) * 2005-01-07 2011-04-20 Emaus Kyoto Inc Resine epoxy poreuse durcie
US8186519B2 (en) 2005-01-07 2012-05-29 Emaus Kyoto, Inc. Porous cured epoxy resin
US7939216B2 (en) 2006-01-13 2011-05-10 Samsung Sdi Co., Ltd. Polymer electrolyte membrane, method of preparing the same and fuel cell employing the same
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WO2013155173A3 (fr) * 2012-04-13 2014-04-10 Regents Of The University Of Minnesota Procédés et compositions associés à des élastomères époxydés biodégradables
CN113150244A (zh) * 2021-05-20 2021-07-23 广东工业大学 一种磺酸盐型环氧丙烯酸酯树脂及其制备方法和应用
CN113150244B (zh) * 2021-05-20 2022-06-07 广东工业大学 一种磺酸盐型环氧丙烯酸酯树脂及其制备方法和应用

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