WO2015030084A1 - 新規なビニルアルコール系共重合体、その製造方法およびイオン交換膜 - Google Patents
新規なビニルアルコール系共重合体、その製造方法およびイオン交換膜 Download PDFInfo
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- WO2015030084A1 WO2015030084A1 PCT/JP2014/072503 JP2014072503W WO2015030084A1 WO 2015030084 A1 WO2015030084 A1 WO 2015030084A1 JP 2014072503 W JP2014072503 W JP 2014072503W WO 2015030084 A1 WO2015030084 A1 WO 2015030084A1
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- copolymer
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- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Images
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- 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
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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- 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
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- 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
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- 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 is a copolymer (P) comprising a vinyl alcohol monomer unit (A), a vinylene monomer unit (B), and a polymer component (C) having a polar group other than a hydroxyl group,
- the present invention relates to a production method and an ion exchange membrane.
- the copolymer having a polar group includes an ion exchange membrane, an ion exchange resin, an ion adsorption material, a solid electrolyte for a fuel cell, a conductive polymer material, an antistatic material, a primary battery, a secondary battery, a solid electrolytic capacitor, an ink, It is widely used as a base material and modifier for various materials such as binders (adhesives), health care products such as pharmaceuticals and cosmetics, food additives, and detergents.
- styrene-divinylbenzene-based ion exchange resins and fluorocarbon-based ion exchange resins, and these resins are often used in a film form (ion-exchange membrane).
- anionic groups such as sulfonic acid groups and cationic groups such as quaternary ammonium groups are introduced into the styrene-divinylbenzene copolymer by post-modification.
- Patent Documents 1 and 2 anionic groups such as sulfonic acid groups and cationic groups such as quaternary ammonium groups are introduced into the styrene-divinylbenzene copolymer by post-modification.
- Patent Document 3 a perfluoroalkylsulfonic acid type polymer in which a sulfonic acid group is bonded to a side chain of a perfluoro skeleton is used as a fluorocarbon ion exchange resin.
- the styrene-divinylbenzene ion exchange membrane has poor processability of the polymer, it needs to be provided with a support at the time of polymerization, and the production cost is increased due to post-modification treatment. I have a point.
- Fluorocarbon-based ion exchange membranes also have the problem of using fluorocarbon-based materials that are difficult to significantly reduce costs because the polymer production process is complicated.
- a bifunctional hydroxyl crosslinking agent such as glutaraldehyde or a hydroxyl modifier such as formaldehyde is usually used.
- the insolubilization treatment by is indispensable, and even after the insolubilization treatment, the water content is high and the dimensional stability may be poor, and further improvement is demanded.
- the present inventors have modified, modified, and modified the vinyl alcohol copolymer so that the water content of the vinyl alcohol copolymer used in an ion exchange membrane or the like is lowered to give practical shape stability. Obtaining an ion exchange membrane from a quality vinyl alcohol copolymer was set as a problem to be solved.
- the present inventors introduced a vinylene monomer unit into the vinyl alcohol copolymer by a simple method of heat-treating the vinyl alcohol copolymer, and the vinylene monomer.
- the present inventors have found that a low water content can be achieved by introducing a monomer unit.
- the first configuration of the present invention is a copolymer comprising a vinyl alcohol monomer unit (A), a vinylene monomer unit (B), and a polymer component (C) having a polar group other than a hydroxyl group as constituent components.
- Combined (P) is a copolymer comprising a vinyl alcohol monomer unit (A), a vinylene monomer unit (B), and a polymer component (C) having a polar group other than a hydroxyl group as constituent components.
- the copolymer (P) may be a copolymer (P1) represented by the following general formula (1).
- the copolymer (P) may be a copolymer (P2) represented by the following general formula (2).
- R 1 is a hydrogen atom or a carboxyl group
- R 2 is a hydrogen atom, a methyl group, a carboxyl group or a carboxymethyl group
- L may contain a nitrogen atom and / or an oxygen atom.
- a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and when R 1 is a carboxyl group or R 2 is a carboxyl group or a carboxymethyl group, it may form a ring with an adjacent hydroxyl group.
- M is a monomer unit having a polar group other than a hydroxyl group. ]
- the polymer component (C) having a polar group other than the hydroxyl group may be a polymer component (CA) having an ionic group, and the ionic group may be an anionic group, It may be a sex group.
- the monomer unit M having the polar group is represented by any one of the following general formulas (3), (4), and (5).
- R 3 represents a hydrogen atom or an alkali metal atom.
- an acetal-modified site by monoaldehyde treatment or a cross-linking bond by dialdehyde treatment may be introduced.
- a copolymer (precursor) (P ′) containing a vinyl alcohol polymer component (A ′) and a polymer component (C) having a polar group other than a hydroxyl group is subjected to acidic conditions.
- the method for producing a copolymer (P) is characterized in that the vinylene monomer unit (B) is introduced by heat treatment with dehydration polyene.
- the third configuration of the present invention is a vinyl alcohol monomer unit (A), a vinylene type, wherein the polymer component (C) having a polar group other than the hydroxyl group is a polymer component (CA) having an ionic group. It is an ion exchange membrane containing as a main component a copolymer (PA) having a monomer unit (B) and a polymer component (CA) having an ionic group as constituent components.
- PA copolymer
- CA polymer component having an ionic group
- the ion exchange membrane may contain a reinforcing material.
- the reinforcing material is a continuous support made of a porous film, a mesh, or a nonwoven fabric.
- the nonwoven fabric may be a wet nonwoven fabric of polyvinyl alcohol short fibers.
- a film-like molded product comprising a copolymer (P ′′) containing a vinyl alcohol polymer component (A ′) and a polymer component (CA) having an ionic group as main components. It heat-processes on acidic conditions, and uses dehydrated polyene-ized as a structural component the vinyl alcohol-type monomer unit (A), vinylene-type monomer unit (B), and the polymer component (CA) which has an ionic group.
- a method for producing an ion exchange membrane characterized by introducing a copolymer (PA).
- the copolymer (P) according to the first configuration of the present invention is a precursor copolymer before heat treatment is obtained as a copolymer aqueous solution, it has excellent processability and can easily be imparted with various forms. Furthermore, vinylene monomer units can be introduced by heat treatment, a low water content is achieved, and water resistance is imparted. For this reason, by using this copolymer, it is possible to provide a copolymer that can form a member that is less swelled by water and has excellent dimensional stability and excellent ion exchange ability, adsorption ability, and selective permeability. is there.
- a copolymer containing a vinyl alcohol polymer component (A ′) and a polymer component (C) having a polar group other than the hydroxyl group is obtained.
- the vinylene monomer unit (B) by dehydration polyene can be introduced into the copolymer, and the copolymer (P) according to the present invention is produced.
- the ion exchange membrane formed from the copolymer (P) according to the third configuration of the present invention by introducing a vinylene monomer unit, a low water content is achieved and water resistance is imparted. . For this reason, an ion exchange membrane with little swelling due to water content and excellent dimensional stability can be obtained.
- a copolymer (P ′) containing a vinyl alcohol polymer component (A ′) and a polymer component (C) having an ionic group Is subjected to dehydration polyene by a simple method of heat-treating a film-like composition containing as a main component under acidic conditions, and vinyl alcohol monomer units (A), vinylene monomer units (B), and ions It is possible to obtain an ion exchange membrane mainly comprising a copolymer (P) having a polymer component (C) having a functional group as a constituent component.
- the copolymer according to the present invention comprises a vinyl alcohol monomer unit (A), a vinylene monomer unit (B), and a polymer component (C) having a polar group other than a hydroxyl group as constituent components.
- a polymer (P) is contained as a main component.
- a block copolymer represented by the above general formula (1) or a graft copolymer represented by the above general formula (2) can be mentioned.
- Formula in (1) (o 1 + p 1) / (n 1 + o 1 + p 1) is vinyl acetate contained in the vinyl alcohol-based monomer unit (A) and vinylene monomer units (B)
- the mole fraction of components other than units is shown. About a minimum, it is 0.5000 or more, More preferably, it is 0.7000 or more, More preferably, it is 0.8000 or more.
- the upper limit is preferably 0.9999, more preferably 0.999 or less, and still more preferably 0.995 or less. When the ratio of the lower limit is too small, that is, when the degree of saponification is too low, the performance of the membrane such as membrane resistance tends to deteriorate due to the influence of lowering the moisture content. Making it larger than 9999 involves manufacturing difficulties.
- Formula (1) in the p 1 / (n 1 + o 1 + p 1) is a vinylene monomer units contained in the vinyl alcohol-based monomer unit (A) and vinylene monomer units (B) (B ) And the polyene conversion rate.
- the lower limit of the polyene conversion rate is 0.100 or more, more preferably 0.250 or more, and further preferably 0.500 or more.
- the upper limit is preferably 0.999 or less, more preferably 0.99 or less, and still more preferably 0.95 or less. Increasing the upper limit of the polyene conversion ratio to more than 0.999 is accompanied by difficulty in production, and if the ratio of the lower limit of the polyene conversion ratio is too small, it becomes difficult to obtain water resistance of the film.
- the mole fraction of the polymer component (C) having a polar group other than the hydroxyl group contained in the coalescence component (C) is shown. About a minimum, it is 0.01 or more, More preferably, it is 0.03 or more, More preferably, it is 0.5 or more.
- the upper limit is 0.50 or less, more preferably 0.30 or less, and preferably 0.25 or less. If the above lower limit value is too low, no ion path is formed, so that the performance as an ion exchange membrane is not sufficiently developed, and if the above upper limit value is too high, the shape retention of the membrane tends to be insufficient. It is in.
- Formula (2) in (o 2 + p 2) / (n 2 + o 2 + p 2) are vinyl acetate contained in the vinyl alcohol-based monomer unit (A) and vinylene monomer units (B)
- the mole fraction of components other than units is shown. About a minimum, it is 0.5000 or more, More preferably, it is 0.7000 or more, More preferably, it is 0.8000 or more.
- the upper limit is preferably 0.9999, more preferably 0.999 or less, and still more preferably 0.995 or less. When the ratio of the lower limit is too small, that is, when the degree of saponification is too low, the performance of the membrane such as membrane resistance tends to deteriorate due to the influence of lowering the moisture content. Making it larger than 9999 involves manufacturing difficulties.
- p 2 / (n 2 + o 2 + p 2 ) is a vinylene monomer unit (B) contained in the vinyl alcohol monomer unit (A) and the vinylene monomer unit (B). ) And the polyene conversion rate.
- the lower limit of the polyene conversion rate is 0.100 or more, more preferably 0.250 or more, and further preferably 0.500 or more.
- the upper limit is preferably 0.999 or less, more preferably 0.99 or less, and still more preferably 0.95 or less. Increasing the upper limit of the polyene conversion ratio to more than 0.999 is accompanied by difficulty in production, and if the ratio of the lower limit of the polyene conversion ratio is too small, it becomes difficult to obtain water resistance of the film.
- q 2 / (n 2 + o 2 + p 2 + q 2 ) represents a mole fraction of units having a branched structure contained in the copolymer (P2).
- the lower limit is preferably 0.001 or more, more preferably 0.002 or more, and still more preferably 0.003 or more.
- the upper limit is preferably 0.050 or less, more preferably 0.02 or less, and still more preferably 0.01 or less.
- q 2 m 2 / (q 2 m 2 + n 2 + o 2 + p 2 ) is a polarity other than the vinyl alcohol monomer unit (A), the vinylene monomer unit (B), and the hydroxyl group.
- the molar fraction of the polymer component (C) having a polar group other than the hydroxyl group contained in the polymer component (C) having a group is shown.
- the lower limit is 0.01 or more, preferably 0.03 or more, and more preferably 0.5 or more.
- the repeating units n 1 , o 1 , p 1 , n 2 , o 2 , p 2 and q 2 of the monomer units are arranged as shown. Does not mean that each unit exists and is usually randomly arranged, but the same unit may be continuous.
- L may be any divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain a nitrogen atom and / or an oxygen atom, and is not particularly limited.
- the number of nitrogen atoms and oxygen atoms contained in L is not particularly limited.
- the aliphatic hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched. When the aliphatic hydrocarbon group is branched, the number of carbon atoms at the site branched from the main chain of the aliphatic hydrocarbon group (a chain in which atoms are continuous between a sulfur atom and a nitrogen atom) is 1 to 5 is preferable.
- the aliphatic hydrocarbon group is a carbonyl bond (—CO 2) in which a nitrogen atom and / or an oxygen atom is inserted into the aliphatic hydrocarbon group.
- - An ether bond (-O-), an amino bond [-NR- (R is a hydrogen atom or a group containing carbon bonded to N)], an amide bond (-CONH-), etc.
- the hydrocarbon group may contain a nitrogen atom and / or an oxygen atom as a carboxyl group (—COOH), a hydroxyl group (—OH) or the like that replaces the aliphatic hydrocarbon group.
- L is preferably a linear or branched alkylene group having a total carbon number of 1 to 20 and optionally having a carboxyl group, more preferably A linear or branched alkylene group having a total carbon number of 2 to 15 and optionally having a carboxyl group, more preferably a total of 2 to 10 carbon atoms having a carboxyl group A good linear or branched alkylene group.
- Examples of polar groups other than hydroxyl groups include ionic groups, and examples of ionic groups include anionic groups and cationic groups.
- anionic group examples include a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, a boronic acid group, and a sulfonylimide group. Although it does not specifically limit as a cation of a counter, Monovalent cations, such as an alkali metal ion, H ⁇ +> , quaternary ammonium ion, are preferable.
- Examples of the cationic group which is an embodiment of a polar group other than a hydroxyl group include an amino group such as an unsubstituted amino group, an N-alkylamino group and an N-dialkylamino group, a nitrogen-containing heterocycle such as a pyridyl group and an imidazolyl group, Quaternary ammonium groups such as N-trialkylammonium group, N-alkylpyridinium group, N-alkylimidazolium group, thiouronium group, isothiouronium group and the like can be mentioned.
- the anion of the quaternary ammonium group counter is not particularly limited, but a halogenated anion of a Group 5B element such as PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , a halogenated anion of a Group 3B element such as BF 4 ⁇ , I - (I 3 -), Br -, Cl - and a halogen anion, ClO 4 - halogen anion such as, AlCl 4 -, FeCl 4 - , SnCl 5 - represented by - metal halide anions such as, NO 3 Nitrate anion, p-toluenesulfonate anion, naphthalenesulfonate anion, organic sulfonate anions such as CH 3 SO 3 ⁇ , CF 3 SO 3 — , carboxylate anions such as CF 3 COO ⁇ , C 6 H 5 COO ⁇ , OH - 1 monovalent
- Examples of the monomer having a polar group other than a hydroxyl group and capable of forming the constituent component M include a structural unit derived from at least one ethylenically unsaturated monomer that is covalently bonded to the polar group.
- ethylenically unsaturated monomer examples include ⁇ -olefins such as ethylene, propylene, n-butene, and isobutylene; styrenes such as styrene and ⁇ -methylstyrene; acrylic acid, methyl acrylate, ethyl acrylate, acrylic Acrylic acid or esters thereof such as n-propyl acid, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid Methacrylic acid or esters thereof such as n-propyl, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide
- Examples of the monomer unit M having a polar group other than a hydroxyl group include the following general formulas (6) to (26).
- R 3 represents a hydrogen atom or an alkali metal atom.
- R 3 has the same meaning as described above, and R 4 represents a hydrogen atom or a methyl group.
- X ⁇ represents a halogenated anion of a group 5B element such as PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , a halogenated anion of a group 3B element such as BF 4 ⁇ , I ⁇ (I 3 ⁇ ), Halogen anions such as Br ⁇ and Cl ⁇ , halogen acid anions such as ClO 4 ⁇ , metal halide anions such as AlCl 4 ⁇ , FeCl 4 ⁇ and SnCl 5 ⁇ , nitrate anions represented by NO 3 ⁇ , p-toluenesulfone Acid anions, naphthalene sulfonate anions, organic sulfonate anions such as CH 3 SO 3 ⁇ and CF 3 SO 3 — , carboxylic acid anions such as CF 3 COO ⁇ and C 6 H 5 COO ⁇ , and monovalent OH ⁇ An anion, and R 4
- R 4 has the same meaning as described above and may be the same as or different from each other. ]
- the method for producing a molded body comprising the copolymer (P) according to the present invention usually comprises a vinyl alcohol polymer component (A ′) and a polymer component (C) having a polar group other than a hydroxyl group as constituent components.
- a step I for producing an intermediate (precursor) containing a copolymer (P ′) to be produced, a step II for producing a molded body by imparting a desired form to the intermediate, and a dehydration polyeneation reaction Step I and Step III are indispensable for the production of the copolymer (P).
- Step I includes (Ia) a method of producing a desired intermediate containing a copolymer (P ′) by bonding a polar group other than a hydroxyl group after producing a vinyl alcohol polymer, or (Ib) vinyl In any of the methods for producing an intermediate containing a copolymer (P ′) composed of an alcohol-based polymer component (A ′) and at least one monomer unit having a polar group other than a hydroxyl group is there.
- one or more hydroxyl modifiers (butyraldehyde sulfonic acid or its alkali metal salt, benzaldehyde sulfonic acid or its alkali metal salt, cationic ammonium aldehyde, etc.) in the presence of vinyl alcohol polymer ) Is reacted, and a polar group other than a hydroxyl group is introduced to produce an intermediate.
- an industrial process is a method of producing an intermediate by radical polymerization of at least one monomer containing a polar group other than a hydroxyl group in the presence of a vinyl alcohol polymer containing a mercapto group. It is preferable because of its ease. In particular, since the type and amount of each component can be easily controlled, the production method (Ib) is preferable.
- a block copolymer (P1 ′) represented by the following general formula (27) or a graft copolymer (P2 ′) represented by the following general formula (28) is used as a preferable structure of the copolymer (P ′).
- a block copolymer (P1 ′) represented by the following general formula (27) or a graft copolymer (P2 ′) represented by the following general formula (28) is used.
- o 3 / (n 3 + o 3 ) represents a ratio of vinyl alcohol units contained in the vinyl alcohol polymer component (A ′). About a minimum, it is 0.5000 or more, More preferably, it is 0.7000 or more, More preferably, it is 0.8000 or more. On the other hand, the upper limit is preferably 0.9999, more preferably 0.999 or less, and still more preferably 0.995 or less.
- the vinyl alcohol polymer component (A ′) is converted into a polymer component containing a vinyl alcohol monomer unit (A) and a vinylene monomer unit (B) by a dehydration polyene conversion reaction
- the block copolymer (P1 ′) represented by the formula (27) is used as an intermediate, o 3 / (n 3 + o 3 ) in the general formula (27) and (o in the general formula (1) 1 + p 1 ) / (n 1 + o 1 + p 1 ) are equivalent.
- M 3 / (m 3 + n 3 + o 3 ) in the general formula (27) has an ionic group contained in the vinyl alcohol polymer component (A ′) and the polymer component (C) having an ionic group.
- the ratio of the polymer component (C) is shown.
- the lower limit is 0.01 or more, preferably 0.03 or more, and more preferably 0.5 or more.
- the upper limit is 0.50 or less, more preferably 0.30 or less, and preferably 0.25 or less.
- o 4 / (n 4 + o 4 ) represents a ratio of vinyl alcohol units contained in the vinyl alcohol polymer component (A ′). About a minimum, it is 0.5000 or more, More preferably, it is 0.7000 or more, More preferably, it is 0.8000 or more. On the other hand, the upper limit is preferably 0.9999, more preferably 0.999 or less, and still more preferably 0.995 or less.
- q 4 / (n 4 + o 4 + p 4 + q 4 ) represents a mole fraction of units having a branched structure contained in the copolymer (P2 ′).
- the lower limit is preferably 0.001 or more, more preferably 0.002 or more, and still more preferably 0.003 or more.
- the upper limit is preferably 0.050 or less, more preferably 0.02 or less, and still more preferably 0.01 or less.
- Q 4 m 4 / (q 4 m 4 + o 4 + n 4 ) in the general formula (28) is an ion contained in the vinyl alcohol polymer component (A ′) and the polymer component (C) having an ionic group.
- the ratio of the polymer component (C) having a functional group is shown.
- the lower limit is 0.01 or more, preferably 0.03 or more, and more preferably 0.5 or more.
- the upper limit is 0.50 or less, more preferably 0.30 or less, and preferably 0.25 or less.
- the vinyl alcohol polymer component (A ′) is converted into a polymer containing the vinyl alcohol monomer unit (A) and the vinylene monomer unit (B) by the dehydration polyene conversion reaction.
- the block copolymer (P2 ′) represented by (28) is used as an intermediate, q 4 m 4 / (q 4 m 4 + o 4 + n 4 ) in the general formula (28) is the above general formula ( It is equivalent to q 2 m 2 / (q 2 m 2 + n 2 + o 2 + p 2 ) in 2 ).
- the monomer repeating units n 3 , n 4 , o 3 , o 4 and q 4 are not meant to be arranged as shown. It simply indicates that each unit exists and is usually arranged at random to each other, but the same unit may be continuous.
- Patent Document 4 As a method for producing the copolymer (P1 ′), for example, Patent Document 4, Patent Document 5, and the like using a terminal mercapto group-containing vinyl alcohol polymer and a monomer having a polar group other than a hydroxyl group are used. It can be obtained by the polymerization method described in 1.
- the content rate of the vinyl alcohol unit in the above-mentioned terminal mercapto group-containing vinyl alcohol polymer is not particularly limited, but 100 mol of all the structural units in the polymer. % Is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more. On the other hand, regarding the upper limit, the total structural unit in the polymer is 100 mol%, preferably 99.99 mol% or less, more preferably 99.9 mol% or less, and further preferably 99.5 mol%. It is as follows.
- the viscosity average degree of polymerization of the above-mentioned terminal mercapto group-containing vinyl alcohol polymer measured according to JIS K6726 is not particularly limited, and is preferably 100 to 5,000, more preferably 200 to 4,000. . When the viscosity average degree of polymerization is less than 100, the mechanical strength of the derived copolymer may be lowered. A vinyl alcohol polymer having a viscosity average polymerization degree exceeding 5,000 is difficult to produce industrially.
- a side chain mercapto group-containing vinyl represented by the following general formula (30) composed of a structural unit represented by the following general formula (29) and a vinyl alcohol-based structural unit Using an alcohol-based polymer and a monomer unit having a polar group other than a hydroxyl group, it can be obtained by a polymerization method described in Patent Document 4, Patent Document 5, and the like.
- R 1 and R 2 are as defined above.
- n 4 , o 4 , q, L, R 1 and R 2 are as defined above].
- the structural unit represented by the general formula (29) can be derived from an unsaturated monomer that can be converted into the structural unit, and preferably has an unsaturated double bond represented by the following general formula (31). It can derive from the thioester type monomer which has.
- R 1a and R 1b are a hydrogen atom or a carboxyl group, at least one is a hydrogen atom, and R 3 is a methyl group, or a cyclic bond with a specific carbon atom contained in L A structure is formed, and R 2 and L are as defined above.
- the thioester monomer having an unsaturated double bond represented by the general formula (31) can be produced according to a known method.
- Preferred specific examples of the thioester monomer having an unsaturated double bond represented by the general formula (31) include thioacetic acid S- (3-methyl-3-buten-1-yl) ester, thio Acetic acid S-17-octadecene-1-yl ester, thioacetic acid S-15-hexadecene-1-yl ester, thioacetic acid S-14-pentadecene-1-yl ester, thioacetic acid S-13-tetradecene-1-yl ester Thioacetic acid S-12-tridecen-1-yl ester, thioacetic acid S-11-dodecen-1-yl ester, thioacetic acid S-10-undecen-1-yl ester, thioacetic acid S-9-decene-1- Yl ester, thioacetic acid S-8-nonen-1-yl ester, thioacetic acid S-7-octen
- thioacetic acid S-7-octen-1-yl ester (b-6), (b-7), (b-9), (B-10), (b-11), (b-12), (b-14), (b-15), (b-16), (b-17), (b-19), (b -20), (b-21), (b-22), (b-24), (b-25), (b-26), (b-27), (b-29), (b-30) ) Is preferred.
- the content of the structural unit represented by the general formula (29) in the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (30) is not particularly limited, but 100 moles of all structural units in the polymer.
- the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (30) can have one or more structural units represented by the formula (29). When it has 2 or more types of the said structural unit, it is preferable that the sum total of the content rate of these 2 or more types of structural units exists in the said range.
- the content of vinyl alcohol units in the side-chain mercapto group-containing vinyl alcohol polymer represented by the general formula (30) is not particularly limited.
- the total structural unit in the coalescence is 100 mol%, preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more.
- the total structural unit in the polymer is 100 mol%, preferably 99.99 mol% or less, more preferably 99.9 mol% or less, and further preferably 99.5 mol%. It is as follows.
- the vinyl alcohol unit in the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (30) can be derived from the vinyl ester unit by hydrolysis, alcoholysis or the like. Although it does not specifically limit as vinyl ester of a vinyl ester unit, Vinyl acetate is preferable from an industrial viewpoint.
- the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (30) has a constitution other than the constitutional unit represented by the formula (29), the vinyl alcohol unit and the vinyl ester unit as long as the effect of the present invention is obtained. It can further have units.
- the structural unit includes, for example, an unsaturated monomer that can be copolymerized with a vinyl ester and that can be converted into a structural unit represented by the formula (29), and an ethylenically unsaturated monomer that can be copolymerized with a vinyl ester. It is a derived structural unit.
- the ethylenically unsaturated monomer has the same meaning as described above.
- the viscosity average degree of polymerization measured according to JIS K6726 of the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (30) is not particularly limited, and is preferably 100 to 5,000, more preferably. Is 200 to 4,000. When the viscosity average degree of polymerization is less than 100, the mechanical strength of the derived copolymer may be lowered. A vinyl alcohol polymer having a viscosity average polymerization degree exceeding 5,000 is difficult to produce industrially.
- the method for producing the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (30) is not particularly limited as long as the target side chain mercapto group-containing vinyl alcohol polymer can be produced.
- a manufacturing method (I) a vinyl ester; (Ii) an unsaturated monomer copolymerizable with a vinyl ester and convertible to a structural unit represented by the formula (29);
- the vinyl ester unit of the obtained copolymer is converted into a vinyl alcohol unit, while the unsaturated unit that can be converted into a structural unit represented by the formula (29)
- thioester monomer (31) a copolymer obtained by copolymerizing a vinyl ester and a thioester monomer having an unsaturated double bond represented by the general formula (31) (hereinafter referred to as thioester monomer (31)) was obtained.
- a method of hydrolysis or alcoholysis of the ester bond of the vinyl ester unit of the polymer and the thioester bond of the structural unit derived from the thioester monomer (31) is simple and preferably used, and this method will be described below.
- the copolymerization of the vinyl ester and the thioester monomer (31) can be performed by employing known methods and conditions for homopolymerizing the vinyl ester.
- a monomer copolymerizable with the vinyl ester and thioester monomer (31) may be further copolymerized.
- the copolymerizable monomer is the same as the ethylenically unsaturated monomer.
- the ester bond of the vinyl ester unit of the obtained copolymer and the thioester bond of the structural unit derived from the thioester monomer (31) can be hydrolyzed or alcoholically decomposed under substantially the same conditions. Therefore, hydrolysis or alcoholysis of the ester bond of the vinyl ester unit of the obtained copolymer and the thioester bond of the structural unit derived from the thioester monomer (31) is used to saponify the vinyl ester homopolymer.
- the known methods and conditions can be employed.
- the form of the intermediate containing the copolymer (P ′) is not particularly limited, but considering the processability in Step II, it is preferably a solution, and the solvent is not particularly limited, and water, methanol, Polar solvents such as ethanol, isopropanol, diethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, N-methyl pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide, or the like
- a mixed solvent may be mentioned, and water is more preferable from the viewpoint of solubility.
- the concentration of the solution is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the solvent.
- the intermediate containing the copolymer (P ′) may contain any additive as necessary, and the order of addition is also arbitrarily selected. Can do.
- the additive can be appropriately selected from known additives, for example, metal fine particles, inorganic fine particles, inorganic salts, ultraviolet absorbers, antioxidants, deterioration inhibitors, dispersants, surfactants, Examples thereof include polymerization inhibitors, thickeners, conductive assistants, surface modifiers, antiseptics, antifungal agents, antibacterial agents, antifoaming agents, and plasticizers. These may be used alone or in combination of two or more.
- polyvinyl alcohol may be added to the intermediate containing the copolymer (P ′) as appropriate for the purpose of improving the strength of the copolymer molded product.
- the viscosity average degree of polymerization measured according to JIS K6726 is not particularly limited, and is preferably 500 to 8,000, more preferably 1000 to 7,000.
- the intermediate solution containing the copolymer (P ′) preferably has a pH of less than 3.0 and has a pH of less than 2.0 in order to facilitate the introduction of the vinylene monomer unit in Step III. More preferably.
- An acidic compound such as sulfuric acid, hydrochloric acid, acetic acid, ammonium chloride or a basic compound such as sodium hydroxide, potassium hydroxide, ammonia, sodium acetate may be added as appropriate to adjust the pH.
- an ion exchange resin such as a resin, the pH may be adjusted, the pH may be adjusted by electrodialysis, and the pH adjusting method is not particularly limited.
- Process II is a process in which a desired form is imparted to the intermediate obtained in Process I to produce a molded body.
- Examples of the form include molded bodies such as particles, fibers, and films.
- a method for producing a polyvinyl alcohol-based particulate molded body is not particularly limited, but a known method (Patent No. 3763904) in which a solution containing the intermediate obtained in Step I is dropped into a solidified solution and molded into a particulate form. ) And the like.
- the production method of the polyvinyl alcohol-based fibrous molded body is not particularly limited, but is a method of plasticizing by heating, a method of dry spinning a concentrated aqueous solution (Japanese Patent Publication No. 43-8992), and dehydrating properties such as mirabilite.
- a method of wet-spinning into an aqueous salt solution JP-A-62-215011
- a method of dry-wet spinning of an organic solvent solution of PVA into methanol, which is a solidification solvent having 1 carbon atom JP-A-1-229805
- the obtained fibrous molded body may have a structure such as a modified cross-section yarn, a hollow cross-section yarn or a composite fiber, or may be processed into a fiber structure such as a woven or knitted fabric or a nonwoven fabric. good.
- the method for producing a polyvinyl alcohol film-shaped molded article is not particularly limited.
- a melt molding method for example, an extrusion molding method, an injection molding method, an inflation molding method for plasticizing and molding a polyvinyl alcohol polymer by heating the polymer.
- Method, press molding method, blow molding method solvent casting method in which the solution is cast into a film and then the solvent is removed by drying to form a film.
- thermoplastic resin When using the melt molding method, an arbitrary thermoplastic resin may be added as necessary, and the order of addition may be arbitrarily selected.
- the thermoplastic resin is not particularly limited, and a general thermoplastic resin can be used.
- the solvent casting method When using the solvent casting method, it can be carried out using a casting machine, a film applicator, etc., but is not particularly limited thereto, on a polymer film such as polyethylene terephthalate film, nylon film, polypropylene film, or copper It may be laminated on a metal foil such as foil, aluminum foil, or an inorganic substrate such as a glass substrate or silicon substrate, may have a multilayer structure, or may be a porous film, mesh, nonwoven fabric, porous ceramic, It may be combined with a porous material such as zeolite, or may be formed on the surface of a three-dimensionally processed molded body such as a polymer, metal, ceramics or glass.
- a polymer film such as polyethylene terephthalate film, nylon film, polypropylene film, or copper
- a metal foil such as foil, aluminum foil, or an inorganic substrate such as a glass substrate or silicon substrate
- Step II in addition to the above-described production method, reinforcement by adding a reinforcing material made of an inorganic material, an organic material, or an organic-inorganic hybrid material can be performed.
- the reinforcing material may be a fibrous material, a particulate material, or a flaky material.
- a continuous support such as a porous film, a mesh, and a nonwoven fabric may be used.
- the mechanical strength and dimensional stability can be improved by performing the reinforcement by the addition of the reinforcing material.
- a fibrous material or the above-described continuous support is used as a reinforcing material, the reinforcing effect is high.
- the reinforcing material may be added to and mixed with the polyvinyl alcohol polymer when it is processed into a film-shaped molded body, or may be impregnated with a solution containing the polyvinyl alcohol polymer, You may laminate.
- the nonwoven fabric is preferably a wet nonwoven fabric formed from short fibers (fiber length: 1 to 30 mm).
- Wet non-woven fabric is made by dispersing main fibers and a small amount of binder fibers that bond between the main fibers in water and making them uniform slurry under gentle agitation.
- a sheet can be formed and manufactured using a papermaking apparatus having at least one of the wires.
- the polymer forming the nonwoven fabric is not particularly limited, and examples thereof include polyester (PET, PTT, etc.), polyvinyl alcohol and the like, and polyvinyl alcohol is particularly preferable.
- a particularly preferable nonwoven fabric sheet includes a wet nonwoven fabric mainly composed of polyvinyl alcohol short fibers.
- the polyvinyl alcohol-based main fiber does not dissolve in water at 90 ° C. or less and has a saponification degree of 99.9 mol% or more.
- the polyvinyl alcohol-based fibers are preferably subjected to acetalization treatment.
- the degree of acetalization is preferably 15 to 40 mol%, more preferably 25 to 35 mol%.
- the polymerization degree of polyvinyl alcohol constituting any of the fibers is preferably 1000 to 2500.
- a method for producing the polyvinyl alcohol fiber used in the present invention a known method can be adopted, and any one of a wet spinning method, a dry wet spinning method, and a dry spinning method may be adopted. Since the polyvinyl alcohol-based main fiber used in the present invention is used as a wet nonwoven fabric, the fineness thereof is preferably 0.3 to 10 dtex, and more preferably 0.5 to 5 dtex.
- the inorganic material used as the reinforcing material is not particularly limited as long as it has a reinforcing effect.
- the organic material used as the reinforcing material is not particularly limited as long as it has a reinforcing effect.
- polyvinyl alcohol polyphenylene sulfide, polyphenylene ether, polysulfone, polyether sulfone, polyether ether sulfone, polyether ketone, polyether ether ketone.
- An organic-inorganic hybrid material can also be used as a reinforcing material, and examples thereof include an organic silicon polymer compound having a silsesquioxane structure or a siloxane structure, such as POSS (Polyhedral Oligomeric Silsesquioxanes) or silicone rubber.
- POSS Polyhedral Oligomeric Silsesquioxanes
- Step III is a precursor of the vinyl alcohol polymer component (A ′) obtained in Step II and a polymer component having a polar group other than a hydroxyl group, preferably dehydrated into a molded body containing the precursor.
- a reaction is performed, thereby constituting a polymer component containing a vinyl alcohol monomer unit (A) and a vinylene monomer unit (B), and a polymer component (C) having a polar group other than a hydroxyl group.
- This is a process for producing a copolymer (P) as a component.
- the form of the copolymer is not particularly limited.
- the step III is a precursor of the vinyl alcohol polymer component (A ′) obtained in the step II and the polymer component (C) having an ionic group, preferably Are subjected to a dehydration polyeneation reaction on the film-shaped molded product containing the precursor as a main component, whereby a polymer containing a vinyl alcohol monomer unit (A) and a vinylene monomer unit (B) and
- This is a step of producing an ion exchange membrane mainly comprising a copolymer (P) having a polymer component (C) having an ionic group as a constituent component.
- the dehydration polyene reaction includes heat treatment and can be changed depending on the type and form of the resin molded body, but generally known methods can be used, such as a hot air dryer, hot press, hot plate, infrared heater, A roller heater or the like can be used.
- a planar heating means is preferable, and a hot press, a hot plate, an infrared heater, a roller heater, and the like are more preferable.
- the heat treatment conditions are not particularly limited, and the heat treatment temperature is preferably 100 to 250 ° C., more preferably 140 to 200 ° C., and the heating time is preferably in the atmosphere, an inert gas atmosphere such as nitrogen, or reduced pressure. The time is 5 seconds to 4 hours, more preferably 1 minute to 2 hours, and the heat treatment may be performed in multiple steps.
- the copolymer (P) obtained in Step III may be subjected to a crosslinking treatment as necessary.
- a crosslinking treatment By performing the crosslinking treatment, the water resistance can be further improved.
- the method for the crosslinking treatment is not particularly limited as long as it is a method capable of bonding the molecular chains of the polymer by chemical bonding. Usually, a method of immersing in a solution containing a crosslinking agent is used.
- the crosslinking agent include formaldehyde or dialdehyde compounds such as glyoxal and glutaraldehyde.
- the above crosslinking agent is mixed in advance, and the crosslinking treatment is performed simultaneously with Step III.
- the heat treatment water, alcohol under acidic conditions
- the method of performing a crosslinking process by immersing in the solution formed by dissolving a dialdehyde compound in those mixed solvents is mentioned, It is preferable to carry out by the latter method in consideration of process passability.
- the concentration of the crosslinking agent is usually 0.001 to 10% by volume of the crosslinking agent with respect to the solution.
- the conversion rate was defined as the polyene conversion rate as a result of the weight reduction due to the conversion to.
- the reinforcing material made the weight of the copolymer what subtracted the weight of the reinforcing material from the total weight of the film
- n 1 , n 2 ; o 1 , o 2 ; p 1 , p 2 ; m 1 , q 2 in the structure of the copolymer represented by the general formula (1) or (2) are as follows: It is determined as follows.
- n 1 , n 2 It is considered that the remaining acetic acid groups in the block copolymer PVA or graft copolymer PVA of the starting material (before polyeneization) remain as they are without being affected by polyeneization.
- o 1 , o 2 When the vinyl alcohol polymer component [0 3 , 0 4 in formula (27) or formula (28)] of the starting material (before polyeneization) is prepared as a sample dry weight and copolymer Calculated from the ratio of PVA / modified monomer (monomer having an ionic group, etc.) and saponification degree.
- p 1 , p 2 Vinyl alcohol polymer component (A ′) [o 3 , o 4 in formula (27) or formula (28)] of the starting material (before polyene formation) is reduced in weight by polyene formation. From the change to o 1 + p 1 or o 2 + p 2 in the formula (1) or (2), the polyene conversion rate is calculated as follows.
- the dynamic transport number of the ion exchange membrane is obtained by sandwiching the ion exchange membrane in a two-chamber cell having a platinum black electrode plate shown in FIG. 1, and filling both sides of the ion exchange membrane with a 0.5 mol / L-NaCl solution. Went. Using ion chromatography, the change in the amount of ions before and after dialysis was calculated, and the dynamic transport number td + was calculated by substituting it into the following equation.
- F Faraday constant
- the membrane resistance was determined by sandwiching an ion exchange membrane in a two-chamber cell having a platinum black electrode plate shown in FIG. 2, filling a 0.5 mol / L-NaCl solution on both sides of the membrane, and an AC bridge (frequency 1000 cycles / second). Then, the resistance between the electrodes at 25 ° C. was measured, and the resistance was calculated from the difference between the resistance between the electrodes and the resistance between the electrodes when no ion exchange membrane was installed. The membrane used for the above measurement was previously equilibrated in a 0.5 mol / L-NaCl solution.
- the obtained PVA-2 had a viscosity average polymerization degree of 1,500 and a saponification degree of 97.4 mol%, measured according to JIS K6726.
- the obtained PVA-3 had a viscosity average polymerization degree of 500 and a saponification degree of 99.8 mol%, measured according to JIS K6726.
- a methanol solution (concentration of 4% by mass) of the thioester monomer (b-11) was prepared as a comonomer sequential addition solution (hereinafter referred to as a delay solution), and argon was bubbled for 30 minutes.
- the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.1 part by mass of 2,2′-azobisisobutyronitrile was added to initiate polymerization. While the polymerization reaction was in progress, the prepared delay solution was dropped into the system so that the monomer composition (molar ratio of vinyl acetate and thioester monomer (b-11)) in the polymerization solution became constant. . After polymerization at 60 ° C.
- a gelled product was formed about 8 minutes after the addition of the sodium hydroxide methanol solution. This was pulverized by a pulverizer and further allowed to stand at 40 ° C. for 52 minutes to allow saponification to proceed. Methyl acetate was added thereto to neutralize the remaining alkali, and then thoroughly washed with methanol and dried in a vacuum dryer at 40 ° C. for 12 hours to obtain a side chain mercapto group-containing PVA (PVA-4). .
- chemical shift values obtained by 1 H-NMR measurement are shown below. The content (modified amount) of the structural unit represented by the formula (I) determined by 1 H-NMR measurement was 1.0 mol%.
- the viscosity average degree of polymerization measured according to JIS K6726 was 1000, and the degree of saponification was 97.9 mol%.
- Example 1 The copolymer (P-1 to P-9) aqueous solution obtained in Synthesis Examples 4 to 12 was poured into an acrylic cast plate having a length of 27 0 mm ⁇ width of 21 0 mm without adjusting the pH, and the excess After removing the liquid and air bubbles, it was dried at 80 ° C. for 30 minutes using a hot air dryer, and then heat-treated at 160 ° C. for 30 minutes using a high-temperature heat treatment machine. Film-shaped copolymers Q-1 to Q-9 containing
- Example 2 Concentrated sulfuric acid was added to the aqueous solution of copolymers P-10 to P-14 obtained in Synthesis Examples 13 to 17 to adjust the pH to 1.0, and then the length was 27 0 mm ⁇ width 21 0 mm. Pour onto an acrylic cast plate, remove excess liquid and bubbles, then dry at 80 ° C for 30 minutes using a hot air dryer, then heat-treat at 160 ° C for 30 minutes using a high-temperature heat treatment machine. Copolymers Q-10 to Q-14 containing polyeneated monomer units were obtained.
- Example 3 Comparative Example 3> To 1 L of 350 g / L sodium sulfate aqueous solution, sulfuric acid was added to adjust pH (25 ° C.) to 1.0, and then 40 ml of 25% glutaraldehyde aqueous solution was added to prepare a treatment solution. After the treatment liquid is heated to 50 ° C., the polyene copolymers Q-1 to Q-14 (Example 3) and the copolymers R-1 to R-14 (Comparative Example 3) are immersed for 30 minutes. Then, a crosslinking treatment was performed.
- Table 1 (Examples) and Table 2 (Comparative Examples) show the polyene conversion rate measurement results and moisture content measurement results of the copolymers described in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3.
- each polyene copolymer of the examples corresponds to the copolymer represented by the general formula (1) or (2).
- 3 shows.
- n 1 or n 2 it is considered that the remaining acetic acid groups in the starting block copolymer PVA or graft copolymer PVA remain as they are without being affected by the polyene formation. The same applies to m 1 and q 2 .
- Example 4 The aqueous solutions of copolymers P-1 to P-9 obtained in Synthesis Examples 4 to 12 were applied on a PET film with an applicator bar at a gap of 500 ⁇ m without adjusting the pH, and then applied to a hot air dryer. And dried at 80 ° C. for 30 minutes. Thereafter, the PET film was peeled off and heat-treated at 160 ° C. for 30 minutes using a high-temperature heat treatment machine to obtain ion exchange membranes QF-1 to QF-9 containing polyeneated monomer units. The polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 4.
- Example 5 Concentrated sulfuric acid was added to the aqueous solutions of copolymers P-10 to P-14 obtained in Synthesis Examples 13 to 17 to adjust the pH to 1.0, and a gap was then formed on the PET film using an applicator bar. After coating at 500 ⁇ m, it was dried at 80 ° C. for 30 minutes with a hot air dryer. Thereafter, the PET film was peeled off, and heat treatment was performed at 160 ° C. for 30 minutes using a high-temperature heat treatment machine to obtain ion exchange membranes QF-10 to QF-14 containing polyeneated monomer units. The polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 4.
- Example 6 PET aqueous solution prepared by adding concentrated sulfuric acid to the aqueous copolymer P-3 solution obtained in Synthesis Example 6 and the aqueous copolymer P-10 solution obtained in Synthesis Example 13 to adjust the pH to 1.0
- the vinylon nonwoven fabric BNF No. 2 (made by Kuraray Co., Ltd.) was bonded and dried at 80 ° C. for 30 minutes using a hot air dryer. Thereafter, the PET film was peeled off, and heat treatment was performed at 160 ° C. for 30 minutes using a high-temperature heat treatment machine to obtain QF-15 and QF-16 containing polyeneated monomer units.
- the polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 4.
- ⁇ Comparative Example 5> The aqueous solutions of copolymers P-10 to P-14 obtained in Synthesis Examples 13 to 17 were applied on a PET film with an applicator bar at a gap of 500 ⁇ m without adjusting the pH, and then applied to a hot air dryer. And dried at 80 ° C. for 30 minutes. Thereafter, the PET film was peeled off and heat-treated at 160 ° C. for 30 minutes using a high-temperature heat treatment machine to obtain ion exchange membranes RF-10 to RF-14. The polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 5. The resulting ion exchange membrane was so leached into water that membrane resistance and dynamic transport number could not be measured.
- the copolymer of the present invention includes an ion exchange membrane, an ion exchange resin, an ion adsorption material, a solid electrolyte for a fuel cell, a conductive polymer material, an antistatic material, a primary battery, a secondary battery, a solid electrolytic capacitor, an ink, and a binder. Since it can be widely used as a base material and a modifier for various materials such as (adhesives), health care products such as pharmaceuticals and cosmetics, food additives, and detergents, it has industrial applicability.
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Abstract
Description
以下、本発明について詳細に説明する。本発明に係る共重合体は、ビニルアルコール系単量体単位(A)、ビニレン系単量体単位(B)及び、水酸基以外の極性基を有する重合体成分(C)を構成成分とする共重合体(P)を主成分として含有する。
上記の下限の比率が小さすぎると、すなわち、けん化度が低すぎると含水率が低くなるなどの影響で、膜抵抗などの膜の性能が悪化する傾向にあり、上記の上限の比率を0.9999よりも大きくすることは製造上の困難を伴う。
ポリエン化率の上限を0.999よりも大きくすることは製造上の困難を伴い、また、ポリエン化率の下限の比率が小さすぎると膜の耐水性が得られにくくなる。
上記の下限の値が低すぎるとイオンパスが形成されないため、イオン交換膜としての性能の発現が十分でなく、また、上記の上限の値が高すぎると膜の形状保持性が不十分となる傾向にある。
上記の下限の比率が小さすぎると、すなわち、けん化度が低すぎると含水率が低くなるなどの影響で、膜抵抗などの膜の性能が悪化する傾向にあり、上記の上限の比率を0.9999よりも大きくすることは製造上の困難を伴う。
ポリエン化率の上限を0.999よりも大きくすることは製造上の困難を伴い、また、ポリエン化率の下限の比率が小さすぎると膜の耐水性が得られにくくなる。
上記の下限の値が低すぎるとイオンパスが形成されず、イオン交換膜としての性能の発現が十分でなく、また、上記の上限の値が高すぎると膜の形状保持性が不十分となる傾向にある。
本発明に係る共重合体(P)からなる成形体を製造する方法は、通常、ビニルアルコール系重合体成分(A’)及び水酸基以外の極性基を有する重合体成分(C)を構成成分とする共重合体(P’)を含有する中間体(前駆体)を作製する工程Iと、中間体に所望の形態を付与し成形体を作製する工程IIと、脱水ポリエン化反応により本発明に係る共重合体(P)を作製する工程IIIと、から構成されるが、共重合体(P)の製造としては、工程Iと工程IIIが必須である。
このうち(Ia)については、ビニルアルコール系重合体の存在下、1つ或いは複数の水酸基変性剤(ブチルアルデヒドスルホン酸またはそのアルカリ金属塩、ベンズアルデヒドスルホン酸またはそのアルカリ金属塩、カチオン性アンモニウムアルデヒドなど)を反応させ、水酸基以外の極性基を導入し中間体を製造する方法が好ましい。(Ib)については、メルカプト基を含有するビニルアルコール系重合体の存在下、水酸基以外の極性基を含有する少なくとも1つの単量体をラジカル重合させることにより中間体を製造する方法が、工業的な容易さから好ましい。特に各成分の種類や量を容易に制御できることから、(Ib)の製造方法が好ましい。
(i)ビニルエステルと、
(ii)ビニルエステルと共重合可能であり、かつ式(29)で示される構成単位に変換可能な不飽和単量体と、
を共重合する共重合工程と、加溶媒分解により、得られた共重合体のビニルエステル単位をビニルアルコール単位に変換し、一方、式(29)で示される構成単位に変換可能な不飽和単量体に由来する単位を式(29)で示される構成単位に変換する変換工程とを含む方法が挙げられる。
共重合体(P’)を含有する中間体には、共重合体と溶媒の他に、共重合体成形物の強度向上を目的として、適宜ポリビニルアルコールを添加してもよく、添加されるポリビニルアルコールとしては、JIS K6726に準拠して測定した粘度平均重合度は特に限定されず、好ましくは500~8,000であり、より好ましくは1000~7,000である。
イオン交換膜を製造する場合には、工程IIIは、前記工程IIで得られる、ビニルアルコール系重合体成分(A’)と、イオン性基を有する重合体成分(C)との前駆体、好ましくは、前記前駆体を主成分とする膜状成形体に脱水ポリエン化反応を施し、これにより、ビニルアルコール系単量体単位(A)とビニレン系単量体単位(B)を含む重合体及びイオン性基を有する重合体成分(C)を構成成分とする共重合体(P)を主成分とするイオン交換膜を製造する工程である。
共重合体を含む水溶液を、余分な液、気泡を除去した後、熱風乾燥機を用いて80℃で30分乾燥させた後、熱風乾燥機を用いて80℃で30 分乾燥させた後の重量を[ポリエン化前重量]とし、高温熱処理機を用いて160℃30分間の条件で熱処理を行った後の重量を[ポリエン化後重量]とし、上記の重量減少([ポリエン化前重量]-[ポリエン化後重量])全てが、共重合体中に含まれるビニルアルコール系単量体単位(44.05g/mol)が、熱処理により脱水されてビニレン系重合体成分(26.04g/mol)に変換されたことによる重量減少によるものとして、その変換率をポリエン化率と規定した。なお、補強材料を含むものは、膜の総重量から補強材料の重量を引いたものを共重合体の重量とした。
ポリエン化率の測定から、一般式(1)または(2)で示される共重合体の構造におけるn1,n2; o1,o2;p1,p2; m1,q2は下記のようにして決定される。
n1,n2: 出発原料(ポリエン化前)のブロック共重合体PVAまたはグラフト共重合体PVA中の残存酢酸基がポリエン化の影響を受けることなく、そのまま残存していると考えている。
o1,o2:出発原料(ポリエン化前)のビニルアルコール系重合体成分[式(27)または式(28)における03,04]をサンプル乾燥重量と共重合体を作成するとき時のPVA/変性モノマー(イオン性基を有するモノマー等)の比率、けん化度から算出。
p1,p2:出発原料(ポリエン化前)のビニルアルコール系重合体成分(A’)[式(27)または式(28)におけるo3,o4]は、ポリエン化により重量減少して、式(1)または(2)におけるo1+p1またはo2+p2に変化することから、ポリエン化率は下記のように計算される。
ΔW/(W-Wr-Wm-Wq)=(ポリエン化による重量減少量)/(n3またはn4単量体単位の重量およびo3またはo4単量体単位の重量)
=Rp×(44.05-26.04)/{(1-Rs)×86.09+Rs×44.05}
ΔW:重量減少量(測定値)
W:乾燥重量(測定値)
Wr:補強材料重量(測定値)
Wm:水酸基以外の極性基を有する重合体成分の重量・・・共重合体製造条件から算出
Wq:枝分かれ構造を有するユニットの重量・・・側鎖メルカプト基含有ポリビニルアルコールおよび共重合体製造条件から算出(式2のみ)
Rs:けん化度=(o1+p1)/(n1+o1+p1)または(o2+p2)/(n2+o2+p2) (ポリエン化前の)ビニルアルコール系重合体成分のモル%、共重合体分析から算出
1-Rs:酢酸ビニル単量体単位のモル%(酢酸ビニル単量体単位:86.09g/mol) [(n1)/(n1+o1+p1)または(n2)/(n2+o2+p2)]
Rp:ポリエン化度
共重合体をイオン交換水に室温5時間含浸させた後、ろ紙にて膜表面の余分な水分をふき取り除去した共重合体の重量を膨潤重量とし、その後、40℃、5時間の条件で真空乾燥した後の重量を乾燥重量とし、含水率を[膨潤重量-乾燥重量]/[(膨潤重量-乾燥重量)+乾燥重量]×100と規定した。
イオン交換膜の動的輸率は、図1に示される白金黒電極板を有する2室セル中にイオン交換膜を挟み、イオン交換膜の両側に0.5mol/L-NaCl溶液を満たし電気透析を行った。イオンクロマトグラフィーを用いて、透析前後のイオン量の変化を計算し、下式に代入することで動的輸率td+を算出した。
td +=Δm/Ea
td +:動的輸率
Ea:理論当量=I・t/F
Δm:移動当量
F:Faraday定数
膜抵抗は、図2に示される白金黒電極板を有する2室セル中にイオン交換膜を挟み、膜の両側に0.5mol/L-NaCl溶液を満たし、交流ブリッジ(周波数1000サイクル/秒)により25℃における電極間の抵抗を測定し、該電極間抵抗とイオン交換膜を設置しない場合の電極間抵抗との差により求めた。上記測定に使用する膜は、あらかじめ0.5mol/L-NaCl溶液中で平衡にしたものを用いた。
末端メルカプト基含有ポリビニルアルコールの合成
<PVA-1、-2、-3>
特開昭59-187003号公報に記載された方法(末端にメルカプト基を有するポリビニルアルコール系重合体およびその方法)によって、末端にメルカプト基を有するポリビニルアルコール(PVA-1,-2,-3)を合成した。得られたPVA-1のJIS K6726に準拠して測定した粘度平均重合度は1500、けん化度は99.9モル%であった。得られたPVA-2のJIS K6726に準拠して測定した粘度平均重合度は1500、けん化度は97.4モル%であった。得られたPVA-3のJIS K6726に準拠して測定した粘度平均重合度は500、けん化度は99.8モル%であった。
チオエステル系単量体変性ポリビニルアセテートの合成(側鎖メルカプト基含有ポリビニルアルコール合成の前段階)
攪拌機、還流冷却管、アルゴン導入管、コモノマー添加口及び重合開始剤の添加口を備えた反応器に、酢酸ビニル450質量部、コモノマーとして前記化学式(b-11)で示されるチオエステル系単量体、0.64質量部、及びメタノール330質量部を仕込み、アルゴンバブリングをしながら30分間系内をアルゴン置換した。これとは別に、コモノマーの逐次添加溶液(以降ディレー溶液と表記する)としてチオエステル系単量体(b-11)のメタノール溶液(濃度4質量%)を調製し、30分間アルゴンをバブリングした。反応器の昇温を開始し、内温が60℃となったところで、2,2’-アゾビスイソブチロニトリル0.1質量部を添加し重合を開始した。重合反応の進行中は、調製したディレー溶液を系内に滴下することで、重合溶液におけるモノマー組成(酢酸ビニルとチオエステル系単量体(b-11)のモル比率)が一定となるようにした。60℃で210分間重合した後、冷却して重合を停止した。重合停止時の重合率は40%であった。次に、30℃の減圧下でメタノールを追加しながら未反応の酢酸ビニルモノマーを留去し、チオエステル系単量体(b-11)が導入された変性ポリビニルアセテートのメタノール溶液を得た。
側鎖メルカプト基含有ポリビニルアルコールの合成
<PVA-4>
合成例2で得られたチオエステル系単量体(b-11)が導入されたポリ酢酸ビニルのメタノール溶液にメタノールを加え、さらに水酸化ナトリウムメタノール溶液(濃度12.8%)を添加して、40℃でけん化を行った(けん化溶液のチオエステル系単量体(b-11)が導入されたポリ酢酸ビニル濃度30%、チオエステル系単量体(b-11)が導入されたポリ酢酸ビニル中の酢酸ビニルユニットに対する水酸化ナトリウムのモル比0.040)。水酸化ナトリウムメタノール溶液を添加後約8分でゲル化物が生成したので、これを粉砕機にて粉砕し、さらに40℃で52分間放置してけん化を進行させた。これに酢酸メチルを加えて残存するアルカリを中和した後、メタノールでよく洗浄し、真空乾燥機中40℃で12時間乾燥することにより、側鎖メルカプト基含有PVA(PVA-4)を得た。また、1H-NMR測定により得られた化学シフト値を以下に示す。1H-NMR測定により求めた式(I)で表される構成単位の含有量(変性量)は1.0mоl%であった。また、JIS K6726に準拠して測定した粘度平均重合度は1000、けん化度は97.9モル%であった。
還流冷却管、攪拌翼を備え付けた500mLの四つ口セパラブルフラスコに、水115g、末端メルカプト基含有ポリビニルアルコール(PVA-1)を25.0gと2-アクリルアミド-2-メチルプロパンスルホン酸(AMPS、純度97%:和光純薬工業(株)製)を6.2g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液5.6mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に4時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールと2-アクリルアミド-2-メチルプロパンスルホン酸のブロック共重合体PVA-b-AMPS(P-1)の水溶液を作製した。該水溶液のpHは0.9であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、AMPS単位の変性量は5モル%であった。
還流冷却管、攪拌翼を備え付けた500mLの四つ口セパラブルフラスコに、水136g、末端メルカプト基含有ポリビニルアルコール(PVA-1)を25.0gと2-アクリルアミド-2-メチルプロパンスルホン酸(AMPS、純度97%:和光純薬工業(株)製)を13.1g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液11.9mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に4時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールと2-アクリルアミド-2-メチルプロパンスルホン酸のブロック共重合体PVA-b-AMPS(P-2)の水溶液を作製した。該水溶液のpHは0.9であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、AMPS酸単位の変性量は10モル%であった。
還流冷却管、攪拌翼を備え付けた500mLの四つ口セパラブルフラスコに、水154g、末端メルカプト基含有ポリビニルアルコール(PVA-1)を25.0gと2-アクリルアミド-2-メチルプロパンスルホン酸(AMPS、純度97%:和光純薬工業(株)製))を19.2g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液17.4mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に4時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールと2-アクリルアミド-2-メチルプロパンスルホン酸のブロック共重合体PVA-b-AMPS(P-3)の水溶液を作製した。該水溶液のpHは0.9であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、AMPS酸単位の変性量は14モル%であった。
還流冷却管、攪拌翼を備え付けた500mLの四つ口セパラブルフラスコに、水185g、末端メルカプト基含有ポリビニルアルコール(PVA-1)を25.0gと2-アクリルアミド-2-メチルプロパンスルホン酸(AMPS、純度97%:和光純薬工業(株)製)を29.4g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液26.8mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に4時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールと2-アクリルアミド-2-メチルプロパンスルホン酸のブロック共重合体PVA-b-AMPS(P-4)の水溶液を作製した。該水溶液のpHは0.8であった。該水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、AMPS酸単位の変性量は20モル%であった。
還流冷却管、攪拌翼を備え付けた500mLの四つ口セパラブルフラスコに、水247g、末端メルカプト基含有ポリビニルアルコール(PVA-1)を25.0gと2-アクリルアミド-2-メチルプロパンスルホン酸(AMPS、純度97%:和光純薬工業(株)製)を50.5g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液45.9mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に4時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールと2-アクリルアミド-2-メチルプロパンスルホン酸のブロック共重合体PVA-b-AMPS(P-5)の水溶液を作製した。該水溶液のpHは0.8であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、AMPS単位の変性量は30モル%であった。
実施例3の末端メルカプト基含有ポリビニルアルコール(PVA-1)の代りに末端メルカプト基含有ポリビニルアルコール(PVA-2)を用いた以外は同様の操作を行い、ポリビニルアルコールと2-アクリルアミド-2-メチルプロパンスルホン酸(AMPS)のブロック共重合体PVA-b-AMPS(P-6)の水溶液を作製した。該水溶液のpHは0.9であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、AMPS単位の変性量は14モル%であった。
実施例3の末端メルカプト基含有ポリビニルアルコール(PVA-1)の代りに末端メルカプト基含有ポリビニルアルコール(PVA-3)を用いた以外は同様の操作を行い、ポリビニルアルコールと2-アクリルアミド-2-メチルプロパンスルホン酸(AMPS)のブロック共重合体PVA-b-AMPS(P-7)の水溶液を作製した。該水溶液のpHは0.9であった。該水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、AMPS単位の変性量は14モル%であった。
実施例1の末端メルカプト基含有ポリビニルアルコール(PVA-1)の代りに側鎖メルカプト基含有ポリビニルアルコール(PVA-4)を用いた以外は同様の操作を行い、ポリビニルアルコールと2-アクリルアミド-2-メチルプロパンスルホン酸(AMPS)のグラフト共重合体PVA-g-AMPS(P-8)の水溶液を作製した。該水溶液のpHは0.9であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、AMPS単位の変性量は14モル%であった。
還流冷却管、攪拌翼を備え付けた500mLの四つ口セパラブルフラスコに、水117g、末端メルカプト基含有ポリビニルアルコール(PVA-1)を25.0gとビニルスルホン酸(VSA、純度95%:旭化成ファインケム(株)製)を7.0g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液6.2mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に24時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールとビニルスルホン酸のブロック共重合体PVA-b-VSA(P-9)の水溶液を作製した。該水溶液のpHは0.9であった。水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、VSA単位の変性量は10モル%であった。
還流冷却管、攪拌翼を備え付けた300mLの四つ口セパラブルフラスコに、水136g、末端にメルカプト基を有するポリビニルアルコールとしてPVA-1を25.0gとパラスチレンスルホン酸ナトリウム(PSS、純度90%:東ソー有機化学(株)製)を14.0g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液11.8mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に4時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールとパラスチレンスルホン酸ナトリウムのブロック共重合体PVA-b-PSS(P-10)の水溶液を作製した。該水溶液のpHは7.0であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、PSS単位の変性量は10モル%であった。
還流冷却管、攪拌翼を備え付けた300mLの四つ口セパラブルフラスコに、水138g、末端にメルカプト基を有するポリビニルアルコールとしてPVA-1を25.0gと(3-アクリルアミドプロピル)トリメチルアンモニウムクロリド(MAPTAC、純度96%:東京化成工業(株)製)を14.1g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液12.7mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に4時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールと(3-アクリルアミドプロピル)トリメチルアンモニウムクロリドのブロック共重合体PVA-b-MAPTAC(P-11)の水溶液を作製した。該水溶液のpHは9.3であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、MAPTAC単位の変性量は10モル%であった。
還流冷却管、攪拌翼を備え付けた300mLの四つ口セパラブルフラスコに、水138g、末端にメルカプト基を有するポリビニルアルコールとしてPVA-1を25.0gとN-[3-(ジメチルアミノ)プロピル]メタクリルアミド(DAPMA、純度97%:和光純薬工業(株)製)を10.7g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液9.8mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に4時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールとN-[3-(ジメチルアミノ)プロピル]メタクリルアミドのブロック共重合体PVA-b-DAPMA(P-12)の水溶液を作製した。該水溶液のpHは10.3であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、DAPMA単位の変性量は10モル%であった。
還流冷却管、攪拌翼を備え付けた500mLの四つ口セパラブルフラスコに、水137g、末端メルカプト基含有ポリビニルアルコール(PVA-1)を25.0gとビニルベンジルトリメチルアンモニウムクロライド(VBTAC、純度97%:AGCセイミケミカル(株)製)を13.4g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液12.2mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に24時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールとビニルベンジルトリメチルアンモニウムクロライドのブロック共重合体PVA-b-VBTAC(P-13)の水溶液を作製した。該水溶液のpHは8.0であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、VBTAC単位の変性量は10モル%であった。
還流冷却管、攪拌翼を備え付けた500mLの四つ口セパラブルフラスコに、水155g、末端メルカプト基含有ポリビニルアルコール(PVA-1)を25.0gとビニルベンジルトリメチルアンモニウムクロライド(VBTAC、純度97%:AGCセイミケミカル(株)製)を19.6g仕込み、攪拌下90℃まで加熱して窒素をバブリングしつつ溶解した。窒素置換後、上記水溶液に2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)-2-プロピオンアミド]の2.0%水溶液17.8mLを1.5時間かけて逐次的に添加して重合を開始させ、進行させた後、系内温度を90℃に24時間維持して重合をさらに進行させ、ついで冷却して、ポリビニルアルコールとビニルベンジルトリメチルアンモニウムクロライドのブロック共重合体PVA-b-VBTAC(P-14)の水溶液を作製した。該水溶液のpHは8.8であった。前記水溶液の一部を乾燥した後、重水に溶解し、500MHzでの1H-NMR測定に付した結果、VBTAC単位の変性量は14モル%であった。
合成例4~12で得られた共重合体(P-1~P-9)水溶液を、pHを調整することなく、縦27 0 mm × 横21 0 mm のアクリル製のキャスト板に流し込み、余分な液、気泡を除去した後、熱風乾燥機を用いて80℃で30 分乾燥させた後、高温熱処理機を用いて160℃30分間の条件で熱処理を行い、ポリエン化された単量体単位を含むフィルム形状の共重合体Q-1~Q-9を得た。
合成例13~17で得られた共重合体P-10~P-14水溶液に対して、濃硫酸を添加してpHを1.0に調整した後、縦27 0 mm × 横21 0 mm のアクリル製のキャスト板に流し込み、余分な液、気泡を除去した後、熱風乾燥機を用いて80℃で30 分乾燥させた後、高温熱処理機を用いて160℃30分間の条件で熱処理を行い、ポリエン化された単量体単位を含む共重合体Q-10~Q-14を得た。
合成例4~12で得られた共重合体P-1~P-9水溶液に対して、1.0M水酸化ナトリウムを添加してpHを7.0に調整した後、縦27 0 mm × 横21 0 mm のアクリル製のキャスト板に流し込み、余分な液、気泡を除去した後、熱風乾燥機を用いて80℃で30 分乾燥させた後、高温熱処理機を用いて160℃30分間の条件で熱処理を行い、共重合体R-1~R-9を得た。
合成例13~17で得られた共重合体P-10~P-14水溶液を、pHを調整することなく、縦27 0 mm × 横21 0 mm のアクリル製のキャスト板に流し込み、余分な液、気泡を除去した後、熱風乾燥機を用いて80℃で30 分乾燥させた後、高温熱処理機を用いて160℃30分間の条件で熱処理を行い、共重合体R-10~R-14を得た。
350g/Lの硫酸ナトリウム水溶液に1Lに対して、硫酸を添加し、pH(25℃)を1.0に調整した後に、40mlの25%グルタルアルデヒド水溶液を添加して、処理液を作製した。処理液を50℃に加温した後、ポリエン化された共重合体Q-1~Q-14(実施例3)および共重合体R-1~R-14(比較例3)を30分浸漬し、架橋処理を施した。
合成例4~12で得られた共重合体P-1~P-9水溶液を、pHを調整せずに、PETフィルム上にアプリケーターバーを用いてギャップ500μmにて塗布した後、熱風乾燥機にて80℃で30分乾燥させた。その後、PETフィルムを剥離して、高温熱処理機を用いて160℃30分間の条件で熱処理を行い、ポリエン化された単量体単位を含むイオン交換膜QF-1~QF-9を得た。得られたイオン交換膜のポリエン化率、膜抵抗、動的輸率を測定した。結果を表4に示す。
合成例13~17で得られた共重合体P-10~P-14水溶液に対して、濃硫酸を添加してpHを1.0に調整した後、PETフィルム上にアプリケーターバーを用いてギャップ500μmにて塗布した後、熱風乾燥機にて80℃で30分乾燥させた。その後、PETフィルムを剥離して、高温熱処理機を用いて160℃30分間の条件で熱処理を行い、ポリエン化された単量体単位を含むイオン交換膜QF-10~QF-14を得た。得られたイオン交換膜のポリエン化率、膜抵抗、動的輸率を測定した。結果を表4に示す。
合成例6で得られた共重合体P-3水溶液、および合成例13で得られた共重合体P-10水溶液に対して濃硫酸を添加してpHを1.0に調整した水溶液をPETフィルム上にアプリケーターバーを用いてギャップ500μmにて塗布した後、ビニロン不織布BNF No.2(株式会社クラレ製)を貼合し、熱風乾燥機を用いて80℃で30分乾燥させた。その後、PETフィルムを剥離して、高温熱処理機にて160℃30分間の条件で熱処理を行い、ポリエン化された単量体単位を含むQF-15およびQF-16を得た。得られたイオン交換膜のポリエン化率、膜抵抗、動的輸率を測定した。結果を表4に示す。
合成例4~12で得られた共重合体P-1~P-9水溶液に対して、1.0M水酸化ナトリウムを添加してpHを7.0に調整した後、PETフィルム上にアプリケーターバーを用いてギャップ500μmにて塗布した後、熱風乾燥機にて80℃で30分乾燥させた。その後、PETフィルムを剥離して、高温熱処理機にて160℃30分間の条件で熱処理を行い、イオン交換膜RF-1~RF-9を得た。得られたイオン交換膜のポリエン化率、膜抵抗、動的輸率を測定した。結果を表5に示す。得られたイオン交換膜は水への溶出が激しく膜抵抗、動的輸率の測定が出来なかった。
合成例13~17で得られた共重合体P-10~P-14水溶液を、pHを調整せずに、PETフィルム上にアプリケーターバーを用いてギャップ500μmにて塗布した後、熱風乾燥機にて80℃で30分乾燥させた。その後、PETフィルムを剥離して、高温熱処理機を用いて160℃30分間の条件で熱処理を行い、イオン交換膜RF-10~RF-14を得た。得られたイオン交換膜のポリエン化率、膜抵抗、動的輸率を測定した。結果を表5に示す。得られたイオン交換膜は水への溶出が激しく膜抵抗、動的輸率の測定が出来なかった。
したがって、そのような変更および修正は、請求の範囲から定まる発明の範囲内のものと解釈される。
B:アンペアメーター
C:クーロンメーター
D:ボルトメーター
E:モーター
F:スターラー
G:カソード電極
H:アノード電極
I:0.5MNaCl水溶液
J:イオン交換膜(有効膜面積8.0cm2)
K:イオン交換膜(有効面積1.0cm2)
L:白金電極
M:NaCl水溶液
N:水浴
O:LCRメーター
Claims (15)
- ビニルアルコール系単量体単位(A)、ビニレン系単量体単位(B)及び、水酸基以外の極性基を有する重合体成分(C)を構成成分として含む共重合体(P)。
- 前記共重合体(P)が下記一般式(2)
- 前記水酸基以外の極性基を有する重合体成分(C)がイオン性基を有する重合体成分(CA)である請求項1~3のいずれか一項に記載の共重合体(PA)。
- 前記イオン性基を有する重合体成分(CA)がアニオン性基である請求項4に記載の共重合体。
- 前記イオン性基を有する重合体成分(CA)がカチオン性基である請求項4に記載の共重合体。
- 前記共重合体(P)にモノアルデヒド処理によるアセタール変性部位またはジアルデヒド処理による架橋結合が導入されていることを特徴とする請求項1~7のいずれか一項に記載の共重合体。
- ビニルアルコール系重合体成分(A’)及び水酸基以外の極性基を有する重合体成分(C)を含有する共重合体(P’)を酸性条件下で加熱処理し、脱水ポリエン化してビニレン系単量体単位(B)を導入することを特徴とする、請求項1~7のいずれか一項に記載の共重合体(P)の製造方法。
- 請求項4~6のいずれか一項に記載の共重合体(PA)を主成分として含有するイオン交換膜。
- 前記共重合体(PA)に架橋結合が導入されている請求項10に記載のイオン交換膜。
- 補強材料を含む請求項10または11に記載のイオン交換膜。
- 前記補強材料が多孔膜、メッシュまたは不織布からなる、連続した支持体である請求項12に記載のイオン交換膜。
- 前記不織布が、ポリビニルアルコール系短繊維の湿式不織布である、請求項12に記載のイオン交換膜。
- ビニルアルコール系重合体成分(A’)及びイオン性基を有する重合体成分(CA)を含有する共重合体(P”)を主成分として含む膜状成形体を酸性条件下で加熱処理し、脱水ポリエン化によりビニルアルコール系単量体単位(A)、ビニレン系単量体単位(B)及びイオン性基を有する重合体成分(CA)と、を構成成分とする共重合体(PA)を導入することを特徴とするイオン交換膜の製造方法。
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EP14839384.6A EP3040350A4 (en) | 2013-08-30 | 2014-08-27 | Novel vinyl alcohol based copolymer, production method for same, and ion exchange membrane |
KR1020167008237A KR20160049542A (ko) | 2013-08-30 | 2014-08-27 | 신규의 비닐알코올계 공중합체, 그 제조 방법 및 이온 교환막 |
JP2015534274A JPWO2015030084A1 (ja) | 2013-08-30 | 2014-08-27 | 新規なビニルアルコール系共重合体、その製造方法およびイオン交換膜 |
US15/050,723 US20160168346A1 (en) | 2013-08-30 | 2016-02-23 | Novel vinyl alcohol based copolymer, production method for same, and ion exchange membrane |
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Cited By (3)
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WO2016133170A1 (ja) * | 2015-02-20 | 2016-08-25 | 株式会社クラレ | イオン交換膜 |
JP2016155110A (ja) * | 2015-02-25 | 2016-09-01 | 株式会社クラレ | 酸の回収方法 |
CN107887642A (zh) * | 2016-09-30 | 2018-04-06 | 东丽先端材料研究开发(中国)有限公司 | 聚合物电解质膜及其制备方法 |
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KR20150092175A (ko) * | 2012-12-04 | 2015-08-12 | 가부시키가이샤 구라레 | 비닐알코올계 그래프트 중합체, 그 제조 방법 및 그것을 사용하는 이온 교환막 |
WO2017111922A1 (en) * | 2015-12-21 | 2017-06-29 | United Technologies Corporation | Solvent cast electrocaloric polymer films |
US10873106B2 (en) * | 2016-03-16 | 2020-12-22 | University Of Utah Research Foundation | Composite solid electrolytes for lithium batteries |
CN107666004B (zh) * | 2017-09-13 | 2020-06-16 | 大连理工大学 | 一种简单绿色的交联复合型阴离子交换膜及其制备方法 |
WO2019118662A1 (en) * | 2017-12-13 | 2019-06-20 | Evoqua Water Technologies Llc | Anion exchange membranes for redox flow batteries |
CN114976229B (zh) * | 2022-05-25 | 2024-04-19 | 济南大学 | 一种制备锂电池用四氟乙烯基聚合物电解质的方法 |
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CN107887642A (zh) * | 2016-09-30 | 2018-04-06 | 东丽先端材料研究开发(中国)有限公司 | 聚合物电解质膜及其制备方法 |
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EP3040350A4 (en) | 2017-04-05 |
TW201516062A (zh) | 2015-05-01 |
JPWO2015030084A1 (ja) | 2017-03-02 |
US20160168346A1 (en) | 2016-06-16 |
KR20160049542A (ko) | 2016-05-09 |
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