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    • 专利摘要:
    An inexpensive and durable polymer electrolyte composition exhibiting highionic conductivity even in the absence of water or a solvent, characterized bycomprising a molten salt and an aromatic polymer having a carbonyl bond and/or asulfonyl bond in the main chain thereof and containing a cation exchange group. Thearomatic polymer is preferably an aromatic polyether sulfone having a specificstructural unit and containing a cation exchange group, an aromatic polyether ketonehaving a specific structural unit and containing a cation exchange group, or an aromaticpolyether sulfone block copolymer and/or an aromatic polyether ketone blockcopolymer, the block copolymers comprising a hydrophilic segment containing a cationexchange group and a cation exchange group-free hydrophobic segment. The polymerelectrolyte composition containing the block copolymer as an aromatic polymer exhibitshigh structural retention even in high temperatures.
    公开号:EP1449886A1
    申请号:EP02788687
    申请日:2002-11-29
    公开日:2004-08-25
    发明作者:Masayuki c/o Ube Industries Ltd. KINOUCHI；Tetsuji C/O Ube Industries Ltd. Hirano；Nobuharu c/o Ube Industries Ltd. HISANO
    申请人:Ube Industries Ltd；
    IPC主号:C08G-65
    专利说明:
    [0001] The present invention relates to a polymer electrolyte composition and, inparticular, a polymer electrolyte composition useful in fuel cells, secondary batteries,electric double layer capacitors, electrolytic capacitors, etc. Background Art:
    [0002] It is known that ammonium salts of certain kinds, such as imidazolium saltsand pyridinium salts, become liquid molten salts at 100°C or lower, particularly aroundroom temperature, and exhibit high ionic conductivity at relatively low temperatures of200°C or lower even in the absence of water or an organic solvent. In view of theunique non-volatility of these molten salts, application as an electrolyte of batteries, etc.has been studied. Being liquid, however, they are not easy to handle. In order tofacilitate handling of the molten salts, several proposals have been made on a polymerelectrolyte comprising a molten salt immobilized with a polymer.
    [0003] For example, JP-A-8-245828 discloses a composition comprising an aliphaticquaternary ammonium salt of an organic carboxylic acid and a polymer, such aspolyvinyl chloride, polyacrylonitrile or an aliphatic polyether. JP-A-7-118480discloses a combination of a room-temperature molten salt and a polymer of a vinylmonomer having an alkyl quaternary ammonium salt structure. JP-A-10-83821,JP-A-2000-3620, and JP-A-2000-11753 propose an aliphatic molten salt type polymersynthesized from an imidazolium compound and an acid or an acid monomer. A.Noda, et al., Electrochim Acta, vol. 45, 1265 (2000) and JP-A-11-86632 report acomposition of a vinyl polymer and a molten salt. Because all these compositions usea polymer the main chain of which is composed mainly of an aliphatic hydrocarbongroup, they are inferior in durability characteristics including resistance to oxidation.
    [0004] JP-A-11-306858 discloses a composition of a vinylidene fluoride polymer andan imidazolium salt, and J. Electrochem. Soc., vol. 147, 34 (2000), Electrochimica Acta,vol. 46, 1703 (2001), and JP-A-11-86632 teach compositions comprising aperfluoropolymer having an acid group and a molten salt. A composition containing afluoropolymer is expected to have improved durability but is disadvantageous from thepoint of view of cost and environmental burdens involved in the production of fluoropolymers. It has therefore been demanded to develop an inexpensive anddurable molten salt composition containing a hydrocarbon polymer.
    [0005] JP-A-10-265673 proposes a polymer composite having an ionic liquidsolidified with a non-fluoropolymer. However, an electrolyte composition having amolten salt combined with an aromatic polyether ketone excellent in durability,particularly resistance to oxidative deterioration, is not mentioned in the publication norknown from any other literature. Neither does the publication suggest an electrolytecomposition containing a molten salt and a polystyrene-based polymer, which is one ofgeneral-purpose resins and inexpensive.
    [0006] While an aromatic polyether sulfone is inexpensive and excellent in durabilitysuch as resistance to oxidative deterioration, an electrolyte composition containing thesame and a molten salt is unknown. Disclosure of the Invention:
    [0007] An object of the present invention is to provide inexpensive and durablepolymer electrolyte composition and membrane which comprise an aromatic polymerand a molten salt and exhibit high ionic conductivity even in the absence of water or asolvent and processes of producing them.
    [0008] The great bar to achievement of the above object of the invention is that anaromatic polyether sulfone and an aromatic polyether ketone that are superior indurability such as oxidative deterioration resistance is hardly miscible with a molten saltonly to provide an unstable composition liable to suffering from molten salt's bleeding.
    [0009] The present inventors have found that a stable composition can be obtainedfrom an aromatic polyether sulfone or an aromatic polyether ketone and an ammoniummolten salt by introducing cation exchange groups into the polymer and thus completedthe present invention.
    [0010] Although an aromatic polyether sulfone and an aromatic polyether ketone areinexpensive polymers with high durability such as oxidative deterioration resistance,molded articles, such as membranes, of compositions of these polymers combined witha liquid molten salt can be plasticized in high temperatures, resulting in reduction ofstrength.
    [0011] Accordingly, an object of the invention is to provide inexpensive and durablepolymer electrolyte composition and membrane which exhibit high ionic conductivityeven in the absence of water or a solvent and excellent structure retention even in hightemperatures and processes of producing them.
    [0012] The present inventors have found that an aromatic polyether sulfone blockcopolymer and/or an aromatic polyether ketone block copolymer each of whichcomprises a hydrophilic segment containing a cation exchange group and a hydrophobicsegment containing no cation exchange group and an ammonium molten salt form astable composition having excellent structure retention even in high temperatures.
    [0013] In synthesizing aromatic polyether sulfone block copolymers, it is known thatthe reaction between a halogen-terminated prepolymer and a hydroxyl-terminatedprepolymer gives a block copolymer having an aromatic polyether sulfone structure inboth segments. A fluorine-terminated prepolymer is mostly used as thehalogen-terminated prepolymer. When a chlorine-terminated one is used, it is difficultto synthesize a block copolymer because ether exchange reaction occurs to form arandom copolymer, as is reported, e.g., in Z. Wang, et al., Polym. Int., vol. 50, 249(2001). The problem is that the synthesis of a fluorine-terminated prepolymer requiresa large quantity of an expensive aromatic difluoro compound.
    [0014] For the purpose of averting ether exchange reaction, it has been practiced tosynthesize the block copolymer using a prepolymer having a specific group introducedinto the terminal thereof. For instance, JP-A-64-9230 proposes using a prepolymerhaving an active chloromethyl group introduced into the terminal thereof. Y.Bourgeois et al., Polymer, vol. 37, 5503 (1996) teaches a process in which anamino-terminated prepolymer and an acid anhydride-terminated prepolymer are allowedto react to form an imido linkage.
    [0015] However, these proposed processes result in formation of a bonding group of adifferent kind in the molecular chain, which impairs the heat resistance or waterresistance of the polymer.
    [0016] Accordingly, still another object of the invention is to provide an economicalprocess of producing an aromatic polyether sulfone block copolymer having no bondinggroup of a different kind in the molecular chain thereof.
    [0017] Polystyrene, which is another inexpensive polymer, is also hardly misciblewith a molten salt and can provide an unstable composition from which a molten saltmay bleed out. The inventors have found that a polystyrene polymer and anammonium molten salt form a stable composition by incorporating a cation exchangegroup into the polystyrene polymer and has thus reached the present invention.
    [0018] The above objects of the invention are accomplished by the following polymerelectrolyte composition, polymer electrolyte membrane, processes of producing them,and process of producing an aromatic polyether sulfone block copolymer.
    [0019] The present invention provides a polymer electrolyte compositioncharacterized by comprising a molten salt and an aromatic polymer having a carbonylbond and/or a sulfonyl bond in the main chain thereof and containing a cation exchangegroup.
    [0020] The aromatic polymer preferably includes the one having a structural unitrepresented by chemical formula (1) shown below and/or a structural unit representedby chemical formula (2) shown below and containing a cation exchange group.
    [0021] The aromatic polymer preferably includes an aromatic polyether sulfonehaving a structural unit represented by chemical formula (3) shown below and/or astructural unit represented by chemical formula (4) shown below and containing acation exchange group.
    [0022] The aromatic polymer preferably includes an aromatic polyether ketone havinga structural unit represented by chemical formula (5) shown below and containing acation exchange group.
    [0023] The aromatic polymer preferably includes an aromatic polyether sulfone blockcopolymer and/or an aromatic polyether ketone block copolymer. Each of thearomatic polyether sulfone block copolymer and the aromatic polyether ketone blockcopolymer comprises a hydrophilic segment containing a cation exchange group and ahydrophobic segment containing no cation exchange group.
    [0024] The present invention also provides a polymer electrolyte membranecharacterized by comprising the above-described polymer electrolyte composition of thepresent invention.
    [0025] The present invention also provides a method of preparing the above-describedpolymer electrolyte composition of the invention, which is characterized by comprisingdissolving predetermined amounts of the aromatic polymer and the molten salt in asolvent capable of dissolving both and removing the solvent by drying.
    [0026] The present invention also provides a method of producing the above-describedpolymer electrolyte membrane of the invention, which is characterized by comprisingdissolving predetermined amounts of the aromatic polymer and the molten salt in asolvent capable of dissolving both, casting the resulting solution, and removing thesolvent by drying.
    [0027] The present invention also provides a method of producing the above-describedpolymer electrolyte composition or polymer electrolyte membrane according to theinvention, which is characterized by comprising immersing a molded article of thearomatic polymer in the molten salt to impregnate the aromatic polymer with the moltensalt
    [0028] The present invention also provides a preferred process of preparing theabove-described aromatic polyether sulfone block copolymer that can be used in theinvention. That is, the present invention provides a process of preparing an aromaticpolyether sulfone block copolymer comprising (a) a segment represented by chemicalformula (10) shown below and (b) a segment represented by chemical formula (11)shown below, which is characterized by comprising allowing (A) an aromatic polyethersulfone prepolymer having the segment (a) and (B) a prepolymer having the segment (b) and bearing at least one terminal hydroxyl group in the form of an alkali metal saltto react in a solution.
    [0029] The present invention also provides a polymer electrolyte compositioncharacterized by comprising a molten salt and a polystyrene polymer having a structuralunit represented by chemical formula (12) shown below and/or a structural unitrepresented by chemical formula (13) shown below.
    [0030] Fig. 1 is a graph showing the temperature dependence of ionic conductivity ofthe polymer electrolyte membrane prepared in Example 3.Fig. 2 is a graph showing the results of comparison of heat resistance betweenthe BPS-2 and the PHEMA films prepared in Reference Example 1.
    [0031] The aromatic polymers used in the present invention which contain a carbonylbond and/or a sulfonyl bond in the main chain thereof and have a cation exchange grouppreferably include an aromatic polymer comprising the structural unit represented bychemical formula (1) and/or the structural unit represented by chemical formula (2) andcontaining a cation exchange group; particularly an aromatic polyether sulfonecomprising the structural unit represented by chemical formula (3) and/or the structuralunit represented by chemical formula (4); an aromatic polyether ketone comprising thestructural unit represented by chemical formula (5); and an aromatic polyether sulfoneblock copolymer and/or an aromatic polyether ketone block copolymer both of whichcomprise a hydrophilic segment containing a cation exchange group and a hydrophobicsegment containing no cation exchange group.
    [0032] The aromatic polyether sulfone comprising the structural unit represented bychemical formula (3) and/or the structural unit represented by chemical formula (4) andcontaining a cation exchange group will be described in more detail.
    [0033] The aromatic polyether sulfone which is a copolymer may be a randomcopolymer or a block copolymer.
    [0034] The aromatic divalent group represented by Ar3 in chemical formula (4)preferably includes the following ones.
    [0035] The cation exchange group the aromatic polyether sulfone contains preferablyincludes a sulfonic acid group and a carboxyl group.
    [0036] The ion exchange capacity of the cation exchange group-containing aromaticpolyether sulfone is preferably 0.3 to 7 meq/g, more preferably 0.4 to 7 meq/g. Withan ion exchange capacity below the lower limit, the polymer is not sufficiently mixedwith a molten salt (described infra), and the resulting composition tends to suffer frombleeding out of the molten salt.
    [0037] The position of the cation exchange group is not particularly limited.Examples of the aromatic polyether sulfone structural unit having a cation exchangegroup in, for example, Ar3 in chemical formula (4) are shown below.
    [0038] The aromatic polyether sulfone which is a block copolymer preferably includesone comprising a hydrophobic segment represented by chemical formula (14) shownbelow and a hydrophilic segment represented by chemical formula (15) shown below.
    [0039] The cation exchange group-containing aromatic polyether sulfone used in thepresent invention can be synthesized by, for example, (1) a process including synthesisof a polymer and introduction of a cation exchange group and (2) polymerization of amonomer containing a cation exchange group.
    [0040] Synthesis of an aromatic polyether sulfone is known in the art. For instance,an aromatic polyether sulfone is synthesized by the reaction between a dialkali metalsalt of a dihydric phenol and an aromatic dihalide as taught in R.N. Johnson et al., J.polym. Sci., A-1, vol. 5,2375 (1967) and JP-B-46-21458.
    [0041] The aromatic dihalide used in the synthesis of an aromatic polyether sulfoneincludes bis(halogenophenyl) sulfones, such as bis(4-chlorophenyl) sulfone,bis(4-fluorophenyl) sulfone, bis(4-bromophenyl) sulfone, bis(2-iodophenyl) sulfone,bis(2-chlorophenyl) sulfone, and bis(2-fluorophenyl) sulfone. In view of reactivityand availability, bis(4-chlorophenyl) sulfone and bis(4-fluorophenyl) sulfone arepreferred.
    [0042] The dihydric phenol used in the synthesis of an aromatic polyether sulfoneincludes dihydroxybenzenes, such as hydroquinone and resorcinol;dihydroxynaphthalenes, such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; dihydroxybiphenyls, such as4,4'-biphenol and 2,2'-biphenol; bisphenyl ethers, such as bis(4-hydroxyphenyl) etherand bis(2-hydroxyphenyl) ether; bisphenylpropanes, such as2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, and2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; bisphenylmethanes, such asbis(4-hydroxyphenyl)methane; bisphenylsulfones, such as bis(4-hydroxyphenyl)sulfone; bisphenyl sulfides, such as bis(4-hydroxyphenyl) sulfide; bisphenyl ketones,such as bis(4-hydroxyphenyl) ketone; bisphenylhexafluoropropanes, such as2,2-bis(3,5-dimethyl-4-hydroxyphenyl)hexafluoropropane; and bisphenylfluorenes,such as 9,9-bis(4-hydroxyphenyl)fluorene. Dipotassium salts and disodium salts ofthese dihydric phenols are preferably used. These compounds can be used eitherindividually or as a combination of two or more thereof. Preferred of them aredipotassium salts and disodium salts of hydroquinone, 4,4'-biphenol,2,2-bis(4-hydroxyphenyl)propane or bis(4-hydroxyphenyl) sulfone.
    [0043] The aromatic polyether sulfones synthesized from the above-recited materialsinclude those having the following structural units.
    [0044] The aromatic polyether sulfone which is a random copolymer can besynthesized at a time by using two or more kinds of dihydric phenols as taught inJP-B-62-28169.
    [0045] Synthesis of the aromatic polyether sulfone which is a block copolymer is alsoknown. For example, it is synthesized by preparing corresponding prepolymersterminated with a halide or a phenol group so as to be copolymerized with each otherand allowing them to react as described in Z. Wang, et al., Polym. Int., vol. 50, 249(2001) or by linking corresponding prepolymers via a linking group having higher reactivity as described in JP-A-63-258930.
    [0046] The above-mentioned non-sulfonated aromatic polyether sulfone preferablyhas a solution viscosity ηsp/c (measured as a 0.5 g/dl solution inN-methyl-2-pyrrolidone) of 0.1 to 5, particularly 0.2 to 4.
    [0047] The method of introducing a cation exchange group into the previouslyprepared aromatic polyether sulfone is not particularly limited, and known techniquescan be utilized.
    [0048] Introduction of a sulfonic acid group is achieved by reaction with a knownsulfonating agent, such as sulfuric acid, fuming sulfuric acid or chlorosulfonic acid, asdescribed in JP-A-61-43630 and J. Membr. Sci., vol. 83, 211 (1993).
    [0049] JP-A-61-43630 teaches that an aromatic polyether sulfone having an aromaticring that is not bonded to an electron attractive group such as a sulfonyl group can havethe aromatic group selectively sulfonated by dissolving the polymer in sulfuric acid andstirring the solution for several hours.
    [0050] Cation exchange group introduction can also be achieved by lithiumizationfollowed by conversion into sulfonic acid as described, e.g., in J. Polym. Sci., Part A,Polym. Chem., vol. 34, 2421 (1996). More specifically an aromatic polyether sulfoneis lithiumized with butyllithium, etc. and then reacted with SO2, followed by treatmentwith hydrochloric acid to yield an aromatic polyether sulfone having a sulfonic acidgroup introduced therein.
    [0051] Introduction of a carboxyl group can be effected by, for example, the methodof Polymer, vol. 27, 1626 (1986). More specifically an aromatic polyether sulfone islithiumized with butyllithium, etc., reacted with CO2, and treated with hydrochloric acidto give an aromatic polyether sulfone having a carboxyl group introduced therein.
    [0052] An aromatic polyether sulfone containing a cation exchange group can also besynthesized by starting with a monomer containing a cation exchange group.
    [0053] For example, synthesis starting with a monomer containing a sulfonic acidgroup is carried out in accordance with the process described in J. Polym. Sci., Part A,Polym. Chem., vol. 31, 853 (1993) and U.S. Patent 2000/0021764A1. Morespecifically, synthesis is carried out in the same manner as for the above-describedaromatic polyether sulfone but by using a sulfonic acid group-containing monomer,such as 3,3'-sulfonyl bis(6-hydroxybenzenesulfonic acid), 3,3'-sulfonylbis(6-fluorobenzenesulfonic acid), and 3,3'-sulfonyl bis(6-chlorobenzenesulfonic acid).The sulfonic acid group-containing aromatic polyether sulfone synthesized from such asulfonic acid group-containing monomer may have additional sulfonic acid groups introduced in accordance with the above-described method for sulfonic acid groupintroduction.
    [0054] Synthesis starting with a carboxyl-containing monomer is carried out inaccordance with the process described in Polymer, vol. 42, 5973 (2001) and ibid, vol.34, 2836 (1993). More Specifically, the synthesis is carried out in the same manner asfor the above-described aromatic polyether sulfone but by using a carboxyl-containingmonomer, such as 5-[(4-fluorophenyl)sulfonyl]-2-fluorobenzoic acid or diphenolic acid.
    [0055] The aromatic polyether ketone used in the invention which has the structuralunit represented by chemical formula (5) and contains a cation exchange group is thendescribed in more detail.
    [0056] The cation exchange group-containing aromatic polyether ketone can besynthesized by, for example, the following processes (1) and (2) similarly to the cationexchange group-containing polyether sulfone. (1) A process including synthesis of a polymer and introduction of a cationexchange group into the polymer (2) A process including polymerization of a cation exchange group-containingmonomer.
    [0057] Synthesis of an aromatic polyether ketone is known in the art. For instance,an aromatic polyether ketone is synthesized by the reaction between a dialkali metal saltof a dihydric phenol and an aromatic dihalide as taught in R.N. Johnson, et al., J. polym.Sci., A-1, vol. 5, 2375 (1967) and JP-A-54-90296.
    [0058] The aromatic dihalide used in the synthesis of an aromatic polyether ketoneincludes bis(4-chlorophenyl) ketone, bis(4-fluorophenyl) ketone, bis(4-bromophenyl)ketone, bis(4-iodophenyl) ketone, bis(2-chlorophenyl) ketone, bis(2-bromophenyl)ketone, bis(2-fluorophenyl) ketone, 1,4-bis(4-chlorobenzoyl)benzene, and4,4'-bis(4-chlorobenzoyl) biphenyl. Bis(4-chlorophenyl) ketone andbis(4-fluorophenyl) ketone are preferred.
    [0059] The dihydric phenol used in the synthesis of an aromatic polyether ketoneincludes hydroquinone, methylhydroquinone, resorcinol, 4,4'-biphenol, 2,2'-biphenol,bis(4-hydroxyphenyl) ether, bis(2-hydroxyphenyl) ether, and bis(4-hydroxyphenyl)ketone. Dipotassium salts and disodium salts of these dihydric phenols are preferablyused. These compounds can be used either individually or as a combination of two ormore thereof. Preferred of them are a dipotassium salt and a disodium salt ofhydroquinone, 4,4'-biphenol, bis(4-hydroxyphenyl) ether or bis(4-hydroxyphenyl)ketone.
    [0060] An aromatic polyether ketone can also be synthesized through Friedel-Craftspolycondensation between an aromatic dicarboxylic acid dihalide and an aromatic etheras taught in Y. Iwakura, et al., J. Polym. Sci., A-1, vol. 6, 3345 (1968) andJP-A-6-263871.
    [0061] The aromatic dicarboxylic acid dihalide used in the synthesis preferablyincludes terephthaloyl dichloride, isophthaloyl dichloride, 4,4'-oxybisbenzoyldichloride, 4,4'-biphenyldicarboxylic acid dichloride, 2,2'-biphenyldicarboxylic aciddichloride, 2,6-naphthalenedicarboxylic acid dichloride, and2,7-naphthalenedicarboxylic acid dichloride.
    [0062] The aromatic ether used in the synthesis preferably includes diphenyl ether,1,4-bisphenoxybenzene, 4,4'-bisphenoxybiphenyl, and 4,4'-bisphenoxybenzophenone.
    [0063] The aromatic polyether ketones synthesized from the above-describedmaterials include those having the following structural units.
    [0064] The number of the kinds of the structural units represented by chemicalformula (5) making up the aromatic polyether ketone is not limited to one. Thearomatic polyether ketone may be one comprising two or more kinds of the structuralunits represented by chemical formula (5) that is synthesized from three or more kindsof monomers. The aromatic polyether ketone comprising the two or more kinds of thestructural units may be a random copolymer or a block copolymer.
    [0065] The method of introducing a cation exchange group into the previouslyprepared aromatic polyether ketone is not particularly limited, and known techniquescan be used. The cation exchange group preferably includes a sulfonic acid group and a carboxyl group.
    [0066] Introduction of a sulfonic acid group is achieved by reaction with a knownsulfonating agent, such as sulfuric acid, fuming sulfuric acid or chlorosulfonic acid, asdescribed in JP-A-57-25328, JP-A-63-291920, JP-A-6-93114, J. Membr. Sci., vol. 199,167 (2002), ibid, vol. 173, 17 (2000), Polymer, vol. 28, 1009 (1987), Solid State Ionics,vol. 106, 219 (1998), and Br. Polym. J., vol. 17,4 (1985).
    [0067] For instance, JP-A-57-25328 teaches that an aromatic polyether ketone havingan aromatic ring that is not bonded to a carbonyl group can have the aromatic groupselectively sulfonated by dissolving the polymer in sulfuric acid and stirring the solutionfor several hours. JP-T-11-502245 discloses a process for sulfonating an aromatic ringhaving a carbonyl group as well which comprises dissolving a polyether ketone in 94 to97% sulfuric acid and adding a sulfonating agent such as fuming sulfuric acid orchlorosulfonic acid to the solution to increase the sulfuric acid concentration.
    [0068] Introduction of a carboxyl group can be achieved by, for example, the processreported in Macromolecules, vol. 26, 5295 (1993). More specifically, a methylatedaromatic polyether ketone prepared by using methylhydroquinone is dibrominated withbromine, the dibromomethyl group is hydrolyzed into an aldehyde group, which is thenoxidized with sodium chlorite to obtain a carboxyl-containing aromatic polyetherketone.
    [0069] The cation exchange group-containing aromatic polyether ketone can also besynthesized from a cation exchange group-containing monomer.
    [0070] In starting with a sulfonic acid group-containing monomer, the desired polymeris obtained by the process described in Polym. Int., vol. 50, 812 (2001). Morespecifically, the synthesis is carried out in the same manner as for the above-describedaromatic polyether ketone from 5,5'-carbonylbis(sodium 2-fluorobenzenesulfonate) andhydroquinone. The sulfonic acid group-containing aromatic polyether ketonesynthesized from the sulfonic acid group-containing monomer may have additionalsulfonic acid groups introduced in the same manner as described above.
    [0071] The cation exchange group-containing aromatic polyether ketone preferablyhas an ion exchange capacity of 0.3 to 7 meq/g. With an ion exchange capacity belowthe lower limit, the polymer is not sufficiently mixed with a molten salt (describedinfra), and the resulting composition tends to suffer from the molten salt's bleeding out.
    [0072] The aromatic polyether sulfone block copolymer and/or the aromatic polyetherketone block copolymer each comprising a hydrophilic segment containing a cationexchange group and a hydrophobic segment containing no cation exchange group will then be described in more detail.
    [0073] The cation exchange group-containing aromatic polyether sulfone blockcopolymer and/or aromatic polyether ketone block copolymer can be synthesized by, forexample, the following processes (1) and (2). (1) A process comprising synthesizing a block copolymer that does not contain acation exchange group and selectively introducing a cation exchange group to form ahydrophilic segment. (2) A process comprising previously preparing a hydrophobic segment prepolymerand a hydrophilic segment prepolymer having a cation exchange group and allowing theprepolymers to react to produce a block copolymer.
    [0074] The hydrophobic segment prepolymer, the hydrophilic segment prepolymer,and a prepolymer that is to be rendered hydrophilic by introducing a cation exchangegroup, each of which is useful to synthesize the aromatic polyether sulfone blockcopolymer and/or the aromatic polyether ketone block copolymer, are well known as anaromatic polyether sulfone or an aromatic polyether ketone. They can be synthesizedby the reaction between a dialkali metal salt of a dihydric phenol and an aromaticdihalide as disclosed in R.N. Johnson, et al., J. Polym. Sci., A-1, vol. 5, 2375 (1967),JP-B-46-21458, and JP-A-54-90296.
    [0075] The aromatic dihalide used in the synthesis includes bis(4-chlorophenyl)sulfone, bis(4-fluorophenyl) sulfone, bis(4-bromophenyl) sulfone, bis(4-iodophenyl)sulfone, bis(2-chlorophenyl) sulfone, bis(2-fluorophenyl) sulfone,bis(2-methyl-4-chlorophenyl) sulfone, bis(2-methyl-4-fluorophenyl) sulfone,bis(3,5-dimethyl-4-chlorophenyl)sulfone, bis(3,5-dimethyl-4-fluorophenyl) sulfone,bis(4-chlorophenyl) ketone, bis(4-fluorophenyl) ketone, bis(4-bromophenyl) ketone,bis(4-iodophenyl) ketone, bis(2-chlorophenyl) ketone, bis(2-bromophenyl) ketone,bis(2-fluorophenyl) ketone, 1,4-bis(4-chlorobenzoyl)benzene, and4,4'-bis(4-chlorobenzoyl) biphenyl. These aromatic dihalides can be used eitherindividually or as a combination of two or more thereof. Preferred of them arebis(4-chlorophenyl) sulfone, bis(4-fluorophenyl) sulfone, bis(4-chlorophenyl) ketone,and bis(4-fluorophenyl) ketone are preferred.
    [0076] The dihydric phenol used in the synthesis includes hydroquinone,methylhydroquinone, resorcinol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, 2,2'-biphenol,bis(4-hydroxyphenyl) ether, bis(2-hydroxyphenyl) ether,2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)ketone, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)hexafluoropropane, and9,9-bis(4-hydroxyphenyl)fluorenone. Dipotassium salts and disodium salts of thesedihydric phenols are preferably used. These compounds can be used eitherindividually or as a combination of two or more thereof. Preferred of them are adipotassium salt and a disodium salt of hydroquinone, 4,4'-biphenol,2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl)ether or bis(4-hydroxyphenyl) ketone.
    [0077] In synthesizing the prepolymers as segments, molecular weight regulation andformation of terminal groups used to yield a desired block copolymer are accomplishedby using either one of the dihydric phenol and the aromatic dihalide in excess.Otherwise, the same purpose can be achieved by using the dihydric phenol and thearomatic dihalide in an equimolar ratio and adding to the reaction system either one of amonohydric phenol (e.g., phenol, cresol, 4-phenylphenol or 3-phenylphenol) and anaromatic halide (e.g., 4-chlorophenyl phenyl sulfone, 1-chloro-4-nitrobenzene,1-chloro-2-nitrobenzene, 1-chloro-3-nitrobenzene, 4-fluorobenzophenone,1-fluoro-4-nitrobenzene, 1-fluoro-2-nitrobenzene or 1-fluoro-3-nitrobenzene).
    [0078] The aromatic polyether ketone can also be synthesized through Friedel-Craftspolycondensation between an aromatic dicarboxylic acid dihalide and an aromatic etheras taught in Y. Iwakura, et al., J. Polym. Sci., A-1, vol. 6, 3345 (1968) andJP-A-6-263871.
    [0079] The aromatic dicarboxylic acid dihalide used in the synthesis preferablyincludes terephthaloyl dichloride, isophthaloyl dichloride, 4,4'-oxybisbenzoyldichloride, 4,4'-biphenyldicarboxylic acid dichloride, 2,2'-biphenyldicarboxylic aciddichloride, 2,6-naphthalenedicarboxylic acid dichloride, and2,7-naphthalenedicarboxylic acid dichloride.
    [0080] The aromatic ether used in the synthesis preferably includes diphenyl ether,1,4-bisphenoxybenzene, 4,4'-bisphenoxybiphenyl, and 4,4'-bisphenoxybenzophenone.
    [0081] The prepolymers of the respective segments preferably have a degree ofpolymerization of 3 to 1500, more preferably 5 to 1000. A prepolymer whose degreeof polymerization is 3 or fewer hardly produces a block copolymer with desiredcharacteristics. A prepolymer whose degree of polymerization exceeds 1500 isdifficult to copolymerize to give a block copolymer.
    [0082] The cation exchange group possessed by the aromatic polyether sulfone block copolymer and/or the aromatic polyether ketone block copolymer preferably includes asulfonic acid group and a carboxyl group.
    [0083] The aromatic polyether sulfone block copolymer and/or aromatic polyetherketone block copolymer containing a sulfonic acid group as a cation exchange groupcan be synthesized by a process comprising synthesizing a non-sulfonated blockcopolymer and selectively sulfonating the block copolymer or a process comprisingpreviously preparing a hydrophobic segment prepolymer and a hydrophilic segmentprepolymer containing a sulfonic acid group and allowing the prepolymers to react toproduce a block copolymer.
    [0084] Where the sulfonic acid group-containing aromatic polyether sulfone blockcopolymer and/or aromatic polyether ketone block copolymer is obtained by selectivesulfonation of a previously prepared non-sulfonated block copolymer, it is necessarythat the aromatic ring constituting the hydrophobic segment should be bonded to anelectron attracting group in order to achieve selective sulfonation to form a hydrophilicsegment. In this situation the most preferred hydrophobic segment prepolymer is onehaving a structural unit represented by chemical formula (6):
    [0085] On the other hand, the prepolymer that is to be sulfonated to become ahydrophilic segment should be prepared from an aromatic dihalide and theabove-recited dihydric phenol the aromatic ring of which is not bonded to an electronattractive group. A prepolymer having a structural unit represented by chemicalformula (7) shown below is the most preferred.
    [0086] The hydrophobic segment prepolymer and the prepolymer that becomes ahydrophilic segment on sulfonation may be commercially available polymers having acorresponding structure. It is also possible to use such a commercially availablepolymer having been subjected to ether exchange to have a regulated molecular weightor to introduce a terminal group. The ether exchange is carried out using an alkalimetal salt of the above-recited dihydric phenol or a monohydric phenol described infraunder the same conditions as for the polyether sulfone synthesis described in R.N.Johnson et al., j. Polym. Sci., A-1, vol. 5, 2375 (1967) and JP-B-46-21458.
    [0087] The non-sulfonated block copolymer comprising the hydrophobic segmentprepolymer and the prepolymer that becomes a hydrophilic segment after sulfonation issynthesized by reacting the hydrophobic segment prepolymer having a halogen terminalgroup or a phenol alkyl metal salt terminal group with the prepolymer that becomes ahydrophilic segment after sulfonation and carries a terminal group reactive with thatterminal group in accordance with known processes described, e.g., in Z. Wu et al.,Angw. Makromol. Chem., vol. 173, 163 (1989), and Z. Wu et al., Polym. Int., vol. 50,249 (2001). It is also obtainable by reacting the two segment prepolymers. bothterminated with a phenol alkali metal end group with a linking agent in the samemanner. The linking agent includes the above-mentioned aromatic dihalides,preferably highly reactive aromatic dihalides having fluorine as a halogen.
    [0088] Methods of sulfonating polyether sulfone or polyether ketone are known. Ofthe aromatic rings of the non-sulfonated block copolymer prepared by theabove-described process, those which are not bonded to an electron attracting group areselectively sulfonated to form a hydrophilic segment in accordance with, for example,the methods of JP-A-57-25328, JP-A-61-36781, JP-B-1-54323, and JP-B-2-17571.The aromatic polyether sulfone block copolymer and/or aromatic polyether ketone block copolymer which can be used in the present invention are thus obtained.
    [0089] The sulfonic acid group-containing aromatic polyether sulfone blockcopolymer and/or aromatic polyether ketone block copolymer used in the presentinvention can also be synthesized by allowing a hydrophobic segment prepolymer and asulfonic acid group-containing hydrophilic segment prepolymer that have separatelybeen prepared to react with each other in the same manner for the non-sulfonated blockcopolymer.
    [0090] The sulfonic acid group-containing hydrophilic segment prepolymer isobtained by a process in which the prepolymer that is to become a hydrophilic segmenton sulfonation is sulfonated before block copolymerization. It is also obtainable by aprocess in which a monomer containing a sulfonic acid group is polymerized. In thiscase, the hydrophilic segment prepolymer may have sulfonated not only its aromaticrings that are not bonded to an electron attractive group but those which are bonded toan electron attractive group.
    [0091] The above-mentioned hydrophilic segment prepolymer can be obtained bysulfonating a prepolymer by the known sulfonation methods described supra. Thesulfonic acid group-containing hydrophilic segment prepolymer can also be obtained bylithiumizing a prepolymer with butyllithium, etc., allowing the lithio-prepolymer toreact with SO2, and treating the product with hydrochloric acid as described in J. Polym.Sci., Part A, Polym. Chem., vol. 34, 2421 (1996).
    [0092] The hydrophilic segment prepolymer can also be synthesized from a monomercontaining a sulfonic acid group. For example, the sulfonic acid group-containinghydrophilic segment prepolymer can be synthesized by using a pre-sulfonated aromaticdihalide, such as sodium 5,5'-sulfonylbis(2-chlorobenzenesulfonate) described in M.Ueda et al., J. Polym. Sci.: Part A: Polym. Chem., vol. 31, 853 (1993) and sodium5,5'-carbonylbis(2-fluorobenzenesulfonate) described in F. Wang et al., Macromol.Chem. Phys., vol. 199, 1421 (1998) and D. Gan et al., Polym. Int., vol. 50, 812 (2001).The hydrophilic segment may have more sulfonic acid groups introduced by theabove-mentioned method for sulfonic acid group introduction.
    [0093] The aromatic polyether sulfone block copolymer and/or aromatic polyetherketone block copolymer containing a carboxyl group as a cation exchange group whichcan be used in the present invention can be synthesized by a process comprisingsynthesizing a non-carboxylated block copolymer and selectively carboxylating theblock copolymer or a process comprising separately preparing a hydrophobic segmentprepolymer and a carboxyl-containing hydrophilic segment prepolymer and allowing the prepolymers to react to form a block copolymer.
    [0094] Where the carboxyl group-containing aromatic polyether sulfone blockcopolymer and/or aromatic polyether ketone block copolymer used in the presentinvention is obtained by carboxylation of a previously prepared non-carboxylated blockcopolymer, carboxyl group introduction is carried out by, for example, the methodtaught in Macromolecules, vol. 26, 5295 (1993). Specifically, a hydrophobic segmentprepolymer and a prepolymer synthesized by using methylhydroquinone are allowed toreact to synthesize a non-carboxylated block copolymer in the same manner as for thepreparation of the non-sulfonated block copolymer. The methyl groups originated inthe methylhydroquinone are then dibrominated with bromine. The dibromomethylgroups are hydrolyzed into aldehyde groups, which are oxidized with sodium chlorite toobtain a block copolymer having a carboxyl group-containing hydrophilic segment.
    [0095] Where the aromatic polyether sulfone block copolymer and/or the aromaticpolyether ketone block copolymer used in the present invention is obtained bypreviously preparing a hydrophobic segment prepolymer and a carboxylgroup-containing hydrophilic segment prepolymer and block copolymerizing theprepolymers, a prepolymer is synthesized by using methylhydroquinone, and the methylgroups of the resulting prepolymer are converted into carboxyl groups in the samemanner as described above to make a hydrophilic segment prepolymer. The resultinghydrophilic segment prepolymer is reacted with a hydrophobic segment prepolymer tosynthesize a block copolymer having a carboxyl group-containing hydrophilic segment.
    [0096] The carboxyl group-containing hydrophilic segment prepolymer that is to bereacted with a hydrophobic segment prepolymer may be one synthesized by the processdisclosed, e.g., in Polymer, vol. 27, 1626 (1986). Specifically, the carboxylgroup-containing hydrophilic segment is obtainable by lithiumizing a prepolymer withbutyllithium, etc., reacting the lithio-prepolymer with CO2, and treating the product withhydrochloric acid.
    [0097] The block copolymer of the invention can also be obtained by using ahydrophilic segment prepolymer synthesized from a carboxyl group-containingmonomer. Such a prepolymer is synthesized from a carboxyl-containing monomer,such as 5-[(4-fluorophenyl)sulfonyl]-2-fluorobenzoic acid or diphenolic acid, asdescribed, e.g., in Polymer, vol. 42, 5973 (2001) and Polymer, vol. 34, 2836 (1993).
    [0098] The ion exchange capacity of the aromatic polyether sulfone block copolymerand/or aromatic polyether ketone block copolymer used in the invention is preferably0.1 to 10 meq/g. With an ion exchange capacity below the lower limit, the copolymer is not sufficiently mixed with a molten salt (described infra), and the resultingcomposition tends to suffer from bleeding out of the molten salt.
    [0099] The weight fraction of the hydrophilic segment in the aromatic polyethersulfone block copolymer and/or aromatic polyether ketone block copolymer used in theinvention is not particularly limited as long as the ion exchange capacity of thecopolymer falls within the above-recited range. It is preferably 0.05 to 0.95. Theweight fraction of the hydrophilic segment is defined to be the weight of the hydrophilicsegment divided by the weight of the block copolymer.
    [0100] The non-sulfonated aromatic polyether sulfone block copolymer and/or thenon-sulfonated aromatic polyether ketone block copolymer used in the presentinvention preferably have a reduced viscosity ηsp/c (measured in a 0.5 g/dl solution inN-methyl-2-pyrrolidone) of 0.1 to 3.0 dl/g.
    [0101] Where, in particular, the aforementioned aromatic polyether sulfone blockcopolymer and/or aromatic polyether ketone block copolymer is used as the aromaticpolymer having a carbonyl bond and/or a sulfonyl bond in the main chain thereof andcontaining a cation exchange group as specified in the present invention, a polymerelectrolyte composition excellent in high-temperature structure retention and a polymerelectrolyte membrane less susceptible to thickness reduction can be obtained.
    [0102] The non-sulfonated aromatic polyether sulfone block copolymer that can beused in the present invention is preferably prepared by the following process accordingto the present invention. That is, an aromatic polyether sulfone block copolymerhaving no bonding group of a different kind in the molecular chain thereof can beprepared at low cost by a process of producing an aromatic polyether sulfone blockcopolymer comprising (a) a segment represented by chemical formula (10) shownbelow and (b) a segment represented by chemical formula (11) shown below,characterized by comprising allowing (A) an aromatic polyether sulfone prepolymerhaving the segment (a) and (B) a prepolymer having the segment (b) and having at leastone terminal hydroxyl group in the form of an alkali metal salt to react with each other in a solution.
    [0103] The aromatic polyether sulfone prepolymer (A) is prepared by nucleophilicsubstitution between a dihydric phenol dialkali metal salt and an aromatic dihalide asdisclosed, e.g., in R.N. Johnson et al., J. Polym. Sci., A-1, vol. 5, 2375 (1967) andJP-B-46-21458.
    [0104] The dihydric phenol includes bis(4-hydroxyphenyl)sulfone, and the alkalimetal includes sodium and potassium.
    [0105] The aromatic dihalide includes chlorosulfones, such as bis(4-chlorophenyl)sulfone, bis(2-chlorophenyl) sulfone, bis(2-methyl-4-chlorophenyl) sulfone, andbis(3,5-dimethyl-4-chlorophenyl) sulfone.
    [0106] In chemical formula (10), r3 is an integer of 5 to 1500, preferably an integer of5 to 1000.
    [0107] The prepolymer (A) may be a commercially available one, such asSUMIKAEXCEL (registered trademark) from Sumitomo Chemical Co., Ltd. andULTRASON (registered trademark) from BASF.
    [0108] Synthesis of the prepolymer (B) is known. The prepolymer (B) is synthesizedby the reaction between an aromatic dihalide and excess of a dihydric phenol dialkalimetal salt in the same manner as for the aromatic polyether sulfone represented bychemical formula (10).
    [0109] The dihydric phenol used above is one having no electron attractive groupbonded to its aromatic ring, such as hydroquinone, resorcinol,1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 4,4'-biphenol, 2,2'-biphenol, bis(4-hydroxyphenyl) ether,bis(2-hydroxyphenyl) ether, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis-(4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)hexafluoropropane,and 9,9-bis(4-hydroxyphenyl)fluorene. These compounds can be used eitherindividually or as a combination of two or more thereof.The alkali metal includes sodium and potassium.
    [0110] The aromatic dihalide includes chlorosulfones, such as bis(4-chlorophenyl)sulfone, bis(2-chlorophenyl) sulfone, bis(2-methyl-4-chlorophenyl) sulfone, andbis(3,5-dimethyl-4-chlorophenyl) sulfone, and bis(4-chlorophenyl) ketone.
    [0111] Synthesis of the prepolymer (B) using bis(4-chlorophenyl)ketone is carried outin the same manner as in the synthesis using the chlorosulfone as taught, e.g., inJP-A-10-120743.
    [0112] In chemical formula (11), r4 is an integer of 5 to 300, preferably an integer of 5to 200.
    [0113] The prepolymer (B) is also synthesized by allowing an aromatic polyethersulfone having a biphenyl structure that is sold under the trade name Radel (registeredtrademark) or an aromatic polysulfone marketed under the trade name Udel (registeredtrademark), both available from Solvay Advanced Polymers, or an aromatic polyetherketone marketed under the trade name Victrex (registered trademark) from Victrex-MCInc. to react with the dihydric phenol alkali metal salt having no electron attractinggroup bonded to the aromatic ring thereof to give a prepolymer having a controlledmolecular weight and a modified terminal group.
    [0114] Synthesis of the block copolymer is conducted by mixing a solution of theprepolymer (A) and a solution of the prepolymer (B) to cause the prepolymers to react.The temperature of the mixture is preferably 120 to 200°C, still preferably 130 to195°C, particularly preferably 140 to 190°C. At reaction temperatures lower than120°C, the reaction hardly proceeds. At temperatures higher than 200°C, the etherexchange reaction tends to proceed excessively, resulting in formation of a randomcopolymer. The reaction time ranges from 15 minutes to 48 hours. With a shorterreaction time, the reaction tends to be insufficient. With a longer time, the etherexchange reaction tends to proceed excessively, resulting in formation of a randomcopolymer.
    [0115] Each of the solutions of the prepolymers used in the block copolymer synthesismay be either the one as obtained in the prepolymer synthesis or one prepared byre-dissolving the prepolymer isolated from the synthesis system in a solvent.
    [0116] Where the isolated prepolymer (B) is re-dissolved in a solvent, it is necessaryto convert the hydroxyl group into an alkali metal salt.
    [0117] The solvent which can be used for the block copolymer synthesis includesthose capable of dissolving both the prepolymers, such as polar solvents, e.g., dimethylsulfoxide, sulfolane, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,N,N-dimethylformamide, N,N-dimethylacetamide, and diphenyl sulfone.
    [0118] In the block copolymer synthesis, cases are sometimes met with in which thehydroxyl terminals in the form of an alkali metal salt are in excess over the halogenterminals, and the block copolymer hardly gains a desired molecular weight. In suchcases, it is advisable that a requisite amount of bis(4-fluorophenyl) sulfone be added tothe solution as obtained by the block copolymerization to cause the block copolymer tofurther react at 120 to 190°C for 15 minutes to 48 hours to increase the molecularweight. The amount of bis(4-fluorophenyl) sulfone to be added is nearly such as tocounteract the imbalance of the terminal groups. For example, it is 1/5 or less of themole number of the aromatic dihalide used in the synthesis of the prepolymer (B).
    [0119] The manner of isolating the block copolymer from the resulting reactionsolution is not particularly restricted. For instance, the reaction solution is poured intoa poor solvent, such as water and an alcohol, to precipitate the block copolymer, or theresidual and the produced inorganic salts are removed by filtration, and the solvent isremoved from the filtrate by drying
    [0120] The non-sulfonated aromatic polyether sulfone block copolymer obtained bythe above-described process of the invention preferably has a solution viscosity (ηsp/c)of 0.1 to 5.
    [0121] The polymer electrolyte composition according to the present invention cancontain a polystyrene polymer having a structural unit represented by chemical formula(12) shown below and/or a structural unit represented by chemical formula (13) shownbelow in place of the "aromatic polymer having a carbonyl bond and/or a sulfonyl bondin the main chain thereof and containing a cation exchange group".
    [0122] The polystyrene polymer having a structural unit represented by chemicalformula (12) and/or a structural unit represented by chemical formula (13) may be eithera homopolymer or a copolymer having one or more other repeating units.
    [0123] The polystyrene polymer having a structural unit represented by chemicalformula (12) and/or a structural unit represented by chemical formula (13) can besynthesized by, for example, (1) a process in which a monomer containing a cationexchange group is polymerized or (2) a process in which a cation exchange group isintroduced into a previously prepared polymer. The copolymer may be either a blockcopolymer or a random copolymer. The cation exchange group includes a sulfonicacid group, a carboxyl group, and a phosphonic acid group.
    [0124] A polystyrene polymer having a structural unit represented by chemicalformula (12) wherein the cation exchange group is a sulfonic acid group, for example,can be obtained by homopolymerizing styrenesulfonic acid or a salt thereof orcopolymerizing styrenesulfonic acid or a salt thereof with a comonomer. The onewherein the cation exchange group is a carboxyl group can be obtained byhomopolymerizing vinylbenzoic acid or a salt thereof or copolymerizing vinylbenzoicacid or a salt thereof with a comonomer.
    [0125] A polystyrene polymer having a structural unit represented by chemicalformula (13) can be obtained by homopolymerizing, for example, vinylbenzylsulfonicacid or a salt thereof or copolymerizing the same with a comonomer.
    [0126] The copolymerizable comonomers are not particularly limited and includearomatic compounds, such as styrene and α-methylstyrene, acrylic or methacrylicesters, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethylmethacrylate, and aliphatic conjugated dienes, such as butadiene and isoprene. Acopolymer with an aliphatic conjugated diene may have the unsaturated bonds in themain chain thereof saturated by hydrogenation.
    [0127] The method for introducing a cation exchange group into a previouslysynthesized polymer is not particularly limited, and known methods can be used. Forexample, a polystyrene polymer having a sulfonic acid group-containing structural unitof chemical formula (12) can be obtained by introducing a sulfonic acid group into apreviously synthesized polymer. This can be done by, for example, reactingpolystyrene or a copolymer having a styrene unit with a known sulfonating agent, suchas sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or acetyl sulfate.
    [0128] For example, JP-T-2002-509152 and European Polymer Journal, vol. 36, 61(2000) disclose a process in which acetyl sulfate prepared from concentrated sulfuricacid and acetic anhydride is used to introduce a sulfonic acid group into astyrene-(ethylene-butylene)-styrene triblock copolymer or astyrene-(ethylene-propylene) block copolymer.
    [0129] The process of producing a polystyrene polymer having a carboxylgroup-containing structural unit of chemical formula (12) by introducing a carboxylgroup into a previously prepared polymer includes a process comprising acetylatingpreviously prepared polystyrene or copolymer having a styrene unit throughFriedel-Crafts reaction and oxidizing the acetyl group with an oxidizing agent.
    [0130] For example, Macromolecules, vol. 28, 8702 (1995) and European PolymerJournal, vol. 36, 61 (2000) teach a process including acetylating astyrene-(ethylene-butylene)-styrene triblock copolymer or astyrene-(ethylene-propylene) block copolymer with acetyl chloride, etc. and oxidizingthe acetyl group with an oxidizing agent, e.g., sodium hypochlorite, to introduce acarboxyl group.
    [0131] A polystyrene polymer having a sulfonic acid group-containing structural unitof chemical formula (13) can also be obtained by a process including chloromethylatingpreviously prepared polystyrene or a previously prepared copolymer having a styreneunit with chloromethyl methyl ether and allowing the polymer to react with sodiumsulfite to introduce a sulfonic acid group into the polymer. A polystyrene polymerhaving a sulfonic acid group-containing structural unit of chemical formula (13) canalso be obtained by allowing chloromethylated polystyrene synthesized byhomopolymerization of chloromethylstyrene or a copolymer having a chloromethylatedstyrene unit synthesized by copolymerizing chloromethylstyrene and other monomer(s)to react with sodium sulfite to introduce a sulfonic acid group into the polymer.
    [0132] A polystyrene polymer having a phosphonic acid group-containing structuralunit represented by chemical formula (13) can be obtained by applying the processdescribed in JP-A-2000-11755. That is, the polymer is obtained by chloromethylatingpreviously synthesized polystyrene or copolymer having a styrene unit withchloromethyl methyl ether, allowing the chloromethylated polymer to react with triethylphosphite, and hydrolyzing the product. A polystyrene polymer having a phosphonicacid group-containing structural unit of chemical formula (13) can also be obtained byallowing chloromethylated polystyrene obtained by homopolymerization ofchloromethylstyrene or a copolymer having a chloromethylated styrene unit obtained by copolymerizing chloromethylstyrene with other monomer(s) to react with triethylphosphite and hydrolyzing the product.
    [0133] The previously synthesized polymer may be either a homopolymer of styreneor chloromethylstyrene or a copolymer of the same with one or more other monomers.The other monomers providing the constituent unit of the copolymer are not particularlylimited and include aromatic compounds, such as styrene and α-methylstyrene, acrylicor methacrylic esters, such as methyl acrylate, ethyl acrylate, methyl methacrylate, andethyl methacrylate, and aliphatic conjugated dienes, such as butadiene and isoprene. Acopolymer with an aliphatic conjugated diene may have the unsaturated bonds in themain chain thereof saturated by hydrogenation.
    [0134] The polystyrene polymer used in the present invention preferably has a weightaverage molecular weight of 10,000 to 2,000,000. With the weight average molecularweight smaller than the lower limit, the polymer electrolyte composition or the polymerelectrolyte membrane will have reduced strength.
    [0135] The polystyrene polymer used in the invention preferably has an ion exchangecapacity of 0.3 to 7 meq/g. With an ion exchange capacity below the lower limit, thepolymer is not sufficiently mixed with a molten salt (hereinafter described), and theresulting composition tends to suffer from bleeding out of the molten salt.
    [0136] The molten salt which can be used in the present invention has a melting pointof 100°C or lower, preferably 80°C or lower, still preferably 60°C or lower. Knownmolten salts can be used. The molten salt is composed of a cation component and ananion component. Preferred molten salts include those that are liquid at roomtemperature, room-temperature molten salts, and ionic liquids.
    [0137] The cation component composing the molten salt is preferably an ammoniumion in view of molten salt's stability and the like. Cations having the followingstructures can be mentioned as examples. Cations having a cyclic structure preferablyinclude those having an imidazole ring, a triazole ring, a pyrrolidine ring, a pyridinering, a cyclohexane ring or a benzene ring. Each of these rings may be substituted.Cations having a straight-chain or branched alkyl group preferably include those havingan alkyl group containing 1 to 10 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl.
    [0138] The anion component composing the molten salt preferably includes sulfonicacid, a sulfonic acid compound, a carboxylic acid, and an inorganic acid. Specificexamples are (CF3SO2)3C-, (CF3SO2)2N-, CF3SO3 -, C4F9SO3 -, CF3CO2 -, C3F7CO2 -, BF4 -,PF6 -, ClO4 -, CH3CO2 -, NO3 -, NO2 -, HSO3 -, and halide ions.
    [0139] Methods for synthesizing molten salts composed of the anion and cationcomponents are already known. For example, the molten salts are synthesized by themethods described in Hiroyuki Ohno, Lithium Nijidenchino GijyutukakushintoSyoraitenbo, NTS Inc., Tokyo, p. 79 (2001), R. Hagiwara et al., J. Fluorine Chem., vol.105, 221 (2000), J. Sun et al., Electrochimica Acta., vol. 46, 1703 (2001), P. Bonhote etal., Inorg. Chem., vol. 35, 1168 (1996), and D.R. McFarlane et al., Electrochim. Acta.,vol. 45, 1271 (2000).
    [0140] More specifically, the molten salts are obtained by reacting a basicnitrogen-containing compound and/or a halogen salt thereof with an acid and/or a metalsalt thereof.
    [0141] Examples of preferred molten salts for use in the present invention are listedbelow.
    [0142] Trifluoromethanesulfonates, including 1,3-dimethylimidazoliumtrifluoromethanesulfonate, 1,3-diethylimidazolium trifluoromethanesulfonate,1,2-dimethylimidazolium trifluoromethanesulfonate, 1,2-diethylimidazoliumtrifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate,1-methyl-3-propylimidazolium trifluoromethanesulfonate, 2-ethyl-1-methylimidazoliumtrifluoromethanesulfonate, 1-ethyl-2-methylimidazolium trifluoromethanesulfonate,1,2,3-trimethylimidazolium trifluoromethanesulfonate,1,2-dimethyl-3-propylimidazolium trifluoromethanesulfonate, 1-methylimidazolium trifluoromethanesulfonate, 1-ethylimidazolium trifluoromethanesulfonate,1-vinylimidazolium trifluoromethanesulfonate, 2-methylimidazoliumtrifluoromethanesulfonate, 1-methylpyrrolidinium trifluoromethanesulfonate, and2,4-lutidinium trifluoromethanesulfonate.
    [0143] Trifluoroacetates such as 1,3-dimethylimidazolium trifluoroacetate and1-ethyl-3-methylimidazolium trifluoroacetate.
    [0144] Tetrafluoroborates, such as 1,3-dimethylimidazolium tetrafluoroborate,1,3-diethylimidazolium tetrafluoroborate, 1,2-dimethylimidazolium tetrafluoroborate,1,2-diethylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazoliumtetrafluoroborate, 1-methyl-3-propylimidazolium tetrafluoroborate,2-ethyl-1-methylimidazolium tetrafluoroborate, 1-ethyl-2-methylimidazoliumtetrafluoroborate, 1,2,3-trimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazoliumtetrafluoroborate, 1-methylimidazolium tetrafluoroborate,1-ethylimidazolium tetrafluoroborate, 1-vinylimidazolium tetrafluoroborate,2-methylimidazolium tetrafluoroborate, 1-methylpyrrolidinium tetrafluoroborate,2,4-lutidinium tetrafluoroborate, and 1-butylpyridinium tetrafluoroborate.
    [0145] Hexafluorophosphates, such as 1,3-dimethylimidazolium hexafluorophosphateand 1-butyl-3-methylimidazolium hexafluorophosphate.
    [0146] Tris(trifluoromethylsulfonyl)methides, such as 1,3-dimethylimidazoliumtris(trifluoromethylsulfonyl)methide, 1,3-diethylimidazolium tris-(trifluoromethylsulfonyl)methide, 1,2-dimethylimidazolium tris-(trifluoromethylsulfonyl)methide, 1,2-diethylimidazolium tris(trifluoromethylsulfonyl)-methide,1-ethyl-3-methylimidazolium tris(trifluoromethylsulfonyl)methide,1-methyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methide, 2-ethyl-1-methylimidazoliumtris(trifluoromethylsulfonyl)methide, 1-ethyl-2-methylimidazoliumtris(trifluoromethylsulfonyl)methide, 1,2,3-trimethylimidazolium tris-(trifluoromethylsulfonyl)methide, 1,2-dimethyl-3-propylimidazolium tris-(trifluoromethylsulfonyl)methide, 1-methylimidazolium tris(trifluoromethylsulfonyl)-methide,and 2-methylimidazolium tris(trifluoromethylsulfonyl)methide.
    [0147] Methanesulfonates, such as 1,3-dimethylimidazolium methanesulfonate,1-methylimidazolium methanesulfonate, 1-ethylimidazolium methanesulfonate, and1-vinylimidazolium methanesulfonate.
    [0148] Acetates, such as 1,3-dimethylimidazolium acetate,1-ethyl-3-methylimidazolium acetate, 1-methylimidazolium acetate, and1-ethylimidazolium acetate.
    [0149] Nitrates, such as 1,3-dimethylimidazolium nitrate,1-ethyl-3-methylimidazolium nitrate, 1-methylimidazolium nitrate, 1-ethylimidazoliumnitrate, and 1-vinylimidazolium nitrate.
    [0150] Nitrites, such as 1,3-dimethylimidazolium nitrite and1-ethyl-3-methylimidazolium nitrite.
    [0151] Sulfites, such as 1,3-dimethylimidazolium sulfite, 1-methylimidazolium sulfite,1-ethylimidazolium sulfite, and 1-vinylimidazolium sulfite.
    [0152] Chlorides, such as 1,3-dimethylimidazolium chloride,1-ethyl-3-methylimidazolium chloride, 1-methylimidazolium chloride,1-ethylimidazolium chloride, 1-vinylimidazolium chloride,1,2-dimethyl-1,2,4-triazolium chloride, and 1-butylpyridinium chloride.
    [0153] Bromides, such as 1,3-dimethylimidazolium bromide,1-ethyl-3-methylimidazolium bromide, 1-methylimidazolium bromide,1-ethylimidazolium bromide, 1-vinylimidazolium bromide, and 1-butylpyridiniumbromide.
    [0154] Bis(trifluoromethylsulfonyl)imides, such as 1,3-dimethylimidazoliumbis(trifluoromethylsulfonyl)imide, 1,3-diethylimidazolium bis(trifluoromethylsulfonyl)-imide,1,2-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-diethylimidazoliumbis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, 1-methyl-3-propylimidazolium bis-(trifluoromethylsulfonyl)imide, 2-ethyl-1-methylimidazolium bis-(trifluoromethylsulfonyl)imide, 1-ethyl-2-methylimidazolium bis-(trifluoromethylsulfonyl)imide, 1,2,3-trimethylimidazolium bis-(trifluoromethylsulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis-(trifluoromethylsulfonyl)imide, 1-methylimidazolium bis(trifluoromethylsulfonyl)-imide,1-ethylimidazolium bis(trifluoromethylsulfonyl)imide, 1-vinylimidazoliumbis(trifluoromethylsulfonyl)imide, and 2-methylimidazolium bis-(trifluoromethylsulfonyl)imide.
    [0155] Of these molten salts, imidazolium salts are preferred for their low viscosity atroom temperature. Specifically, 1-ethyl-3-methylimidazoliumtrifluoromethanesulfonate, 1-ethyl-3-methylimidazolium tetrafluoroborate,1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, I-ethyl-3-methylimidazoliumacetate, 1-ethylimidazolium trifluoromethanesulfonate,1-ethylimidazolium tetrafluoroborate, 1-ethylimidazolium nitrate, 1-ethylimidazoliumbis(trifluoromethylsulfonyl)imide, and the like are preferred.
    [0156] The polymer electrolyte composition of the present invention can be producedby (1) dissolving predetermined amounts of the aromatic polymer and the molten salt ina solvent capable of dissolving both and drying the solution to remove the solvent or (2)immersing a molded article of the aromatic polymer in the molten salt to impregnate thearomatic polymer with the molten salt.
    [0157] The molten salt in (2) above may be in the form of a solution in a solventincapable of dissolving the aromatic polymer. In this case, impregnation of thearomatic polymer with the molten salt solution is followed by solvent removal bydrying thereby to produce the polymer electrolyte composition.
    [0158] The drying temperature for solvent removal in (1) and (2) above is notparticularly limited as long as it is between the boiling point of the solvent and thedecomposition temperatures of the cation exchange group-containing aromatic polymerand the molten salt. For example, where the aromatic polymer is an aromaticpolyether sulfone, drying is carried out at a temperature of 0 to 200°C. The drying forsolvent removal may be conducted under reduced pressure. If sufficient for solventremoval, the drying time is not particularly limited. For example, the drying ispreferably continued for 2 to 100 hours.
    [0159] The polymer electrolyte membrane of the present invention can be produced by(1) dissolving predetermined amounts of the aromatic polymer and the molten salt in asolvent capable of dissolving both, casting the solution, and removing the solvent bydrying or (2) immersing a molded article of the aromatic polymer in the molten salt toimpregnate the aromatic polymer with the molten salt.
    [0160] The molten salt in (2) above may be in the form of a solution in a solventincapable of dissolving the aromatic polymer. In this case, impregnation of thearomatic polymer with the molten salt solution is followed by solvent removal bydrying thereby to produce the polymer electrolyte membrane.
    [0161] The drying temperature for solvent removal in (1) and (2) above is notparticularly limited as long as it is between the boiling point of the solvent and thedecomposition temperatures of the cation exchange group-containing aromatic polymerand the molten salt. For example, where the aromatic polymer is an aromaticpolyether sulfone, drying is carried out at a temperature of 0 to 200°C. The drying forsolvent removal may be conducted under reduced pressure. If sufficient for solventremoval, the drying time is not particularly limited. For example, the drying ispreferably continued for 2 to 100 hours.
    [0162] A preferred weight fraction of the molten salt in the polymer electrolyte composition of the invention is in the range of 3 to 90% by weight, particularly 5 to80% by weight. With a higher amount of the molten salt, the composition may fail toretain its shape, e.g., a film shape after molding, or the molten salt tends to bleed out.With a lower amount of the molten salt, the composition will have reduced ionicconductivity.
    [0163] Similarly, a preferred weight fraction of the molten salt in the polymerelectrolyte membrane of the invention is in the range of 3 to 90% by weight,particularly 5 to 80% by weight. With a higher amount of the molten salt, themembrane may fail to retain its shape, or the molten salt tends to bleed out. With alower amount of the molten salt, the composition will have reduced ionic conductivity.
    [0164] The solvent used to dissolve both the aromatic polymer and the molten salt isnot particularly limited. Basically, any solvent capable of dissolving them can beused, including amides, sulfones, alcohols, and ethers. Examples of suitable solventsare water, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfolane, diphenyl sulfone,methanol, ethanol, isopropyl alcohol, ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, propylene glycol monomethyl ether, diethyl ether, acetone, andtetrahydrofuran. Preferred are those which can be removed by drying at temperaturesnot higher than the decomposition temperatures of the aromatic polymer and the moltensalt.
    [0165] The molded articles made of the cation exchange group-containing aromaticpolymer include membranes, fibers, nonwoven fabrics, fillers, and porous films.
    [0166] When the molded article is immersed in and impregnated with the molten salt,the immersion temperature is not limited as long as it ranges from the melting point ofthe molten salt up to the melting or decomposition temperature of the cation exchangegroup-containing aromatic polymer or from the melting point to the decompositiontemperature of the molten salt. For example, in using the aromatic polyether sulfoneor the aromatic polyether ketone as the aromatic polymer, the immersion is carried outat a temperature of 0 to 250°C. In using the polystyrene polymer as the aromaticpolymer, the immersion is conducted at 0 to 200°C.
    [0167] If necessary, a part or all of the cation exchange groups possessed by thearomatic polymer used in the present invention may be in the form of a metal salt, e.g.,a sodium salt or a potassium salt. The molded article of the aromatic polymer may bereinforced by fiber, a porous film, etc. If desired, the polymer electrolyte compositionof the invention may contain an inorganic acid, e.g., phosphoric acid, hypophosphorous acid or sulfuric acid, or a salt thereof; a perfluoroalkylsulfonic acid having 1 to 14carbon atoms or a salt thereof; a perfluoroalkylcarboxylic acid having 1 to 14 carbonatoms or a salt thereof; an inorganic substance, such as platinum, silica gel, silica orzeolite; a tertiary amine compound, e.g., an imidazole compound, a pyridine compoundor an aliphatic tertiary amine; an alkali metal salt, e.g., a lithium salt; or a polymer ofdifferent kind.
    [0168] The present invention provides a desired polymer electrolyte compositionhaving an ionic conductivity, e.g., of 10-4 Scm-1 or higher at 150°C, especially at 100°C.
    [0169] The present invention will now be illustrated in greater detail with reference toExamples and Comparative Examples. In Examples and Comparative Examples,measurements were made in accordance with the following methods. 1) Measurement of reduced viscosity ηsp/c of polyether sulfone
    [0170] Measurement was made on a 0.5 g/dl sample solution inN-methyl-2-pyrrolidone at 25°C with a Ubbellohde viscometer. The reduced viscositywas calculated according to equation (1):(1)   η sp/c = ts - t 0 t 0 .1 c wherein ts is a solution flow time; t0 is a solvent flow time; and c is a solutionconcentration. 2) Measurement of ionic conductivity
    [0171] A membrane having been vacuum dried at 60°C for 16 hours was sandwichedbetween stainless steel plates having a radius of 0.65 cm and put into a closed container.The ionic conductivity was obtained by complex impedance measurement with 3532LCR Hi-Tester supplied by Hioki E.E. Corp. in a thermostat set at a prescribedtemperature. 3) Measurement of ion exchange capacity
    [0172] A sample was stirred in a 0.01N sodium hydroxide aqueous solution at roomtemperature for 16 hours, followed by nitration. The filtrate was titrated with a 0.01Nhydrochloric acid aqueous solution to obtain the amount of consumed sodiumhydroxide, from which the ion exchange capacity was calculated. 4) Transmission electron microscopic observation
    [0173] A membrane was sliced in the thickness direction, and the slice was observedunder JEM 200CX supplied from JEOL Ltd. at a magnification of 90000 times. 5) Melting point
    [0174] Measured in a helium stream at a rate of temperature rise of 10°C/min withDSC-7 supplied by Perkin Elmer Inc. 6) Thermogravimetry
    [0175] Measurement was made in air at a rate of temperature rise of 10°C/min withTGA-50 supplied by Shimadzu Corp. SYNTHESIS EXAMPLE 1: Synthesis of sulfonic acid group-containing aromaticpolyether sulfone random copolymer (RPS-1)
    [0176] To a mixture of 51.4 g of bis(4-fluorophenyl) sulfone, 25 g ofbis(4-hydroxyphenyl) sulfone, 18.9 g of 4,4'-biphenol, and 36 g of potassium carbonatewere added 300 ml of N,N-dimethylacetamide and 200 ml of toluene, and the mixturewas heated while stirring in a nitrogen stream. The temperature was elevated up to165°C while removing produced water together with toluene. The stirring wascontinued for 3 hours at that temperature. The solution was poured into a largequantity of water to precipitate a white solid, which was collected by filtration, washedtwice with hot water and once with methanol, and dried under reduced pressure to givecopolymer RP-1. The solution viscosity ηsp/c of the resulting polymer was 0.55.
    [0177] Ten gram of copolymer RP-1 prepared above was dissolved in 100 ml of 98%sulfuric acid, and the solution was stirred at room temperature for 24 hours. Thesolution was poured into a large amount of water. The precipitated white solid wasseparated by filtration, washed twice with hot water and once with methanol, and driedunder reduced pressure to give copolymer RPS-1. The resulting polymer had an ionexchange capacity of 1.73 mmol/g. A solution of the polymer inN,N-dimethylacetamide was cast and dried to form a membrane. TEM observation ofthe membrane revealed no phase separation structure, proving the polymer to be arandom copolymer. SYNTHESIS EXAMPLE 2: Synthesis of sulfonic acid group-containing aromaticpolyether sulfone block copolymer (BPS-1)
    [0178] In a four-necked flask equipped with a stirrer, a water content meter, athermometer, and a nitrogen inlet were put 51.4 g of bis(4-fluorophenyl) sulfone, 50 gof bis(4-hydroxyphenyl) sulfone, and 36 g of potassium carbonate. To the mixturewere added 300 ml of N,N-dimethylacetamide and 200 ml of toluene, and the mixturewas heated while stirring in a nitrogen stream. The temperature was elevated up to165°C while removing produced water together with toluene. The stirring wascontinued for 3 hours at that temperature. The solution was poured into a largequantity of water to precipitate a white solid, which was collected by filtration, washed twice with hot water and once with methanol and dried under reduced pressure to givehydrophobic segment prepolymer al. The solution viscosity ηsp/c of the resultingpolymer was 0.42.
    [0179] To a mixture of 25.7 g of bis(4-fluorophenyl) sulfone, 18.9 g of 4,4'-biphenol,and 18 g of potassium carbonate were added 150 ml of N,N-dimethylacetamide and100 ml of toluene. The mixture was heated with stirring in a nitrogen stream up to165°C while removing produced water together with toluene. The stirring wascontinued at that temperature for 3 hours to prepare polymer b1 solution. Separately,42.6 g of hydrophobic segment prepolymer a1 and 0.5 g of potassium carbonate wereadded to a mixture of 150 ml of N,N-dimethylacetamide and 100 ml of toluene, and themixture was heated in a nitrogen stream up to 165°C while removing produced watertogether with toluene to prepare a solution of a potassium salt of polymer a1. Thesolution of the hydrophobic segment prepolymer a1 potassium salt was added to thepolymer b1 solution, and the mixture was stirred at 160°C for 1 hour. The mixedsolution was poured into a large amount of water to precipitate a white solid. Thesolid was collected by filtration, washed twice with hot water and once with methanol,and dried in vacuo to obtain copolymer BP-1. The resulting polymer had a solutionviscosity ηsp/c of 0.63.
    [0180] Ten grams of copolymer BP-1 was dissolved in 100 ml of 98% sulfuric acid.The solution was stirred at room temperature for 24 hours, followed by pouring into alarge quantity of water. The white solid thus precipitated was separated by filtration,washed twice with hot water and once with methanol, and vacuum dried to yieldpolymer BPS-1. The resulting polymer had an ion exchange capacity of 1.78 mmol/g.The hydrophilic segment weight fraction was 0.49 as calculated by 1H-NMR analysis.A membrane prepared by casting a solution of polymer BPS-1 inN,N-dimethylacetamide and drying revealed a phase separation structure under TEMobservation, proving that the polymer to be a block copolymer. SYNTHESIS EXAMPLE 3: Synthesis of sulfonic acid group-containing aromaticpolyether sulfone block copolymer (BPS-2)
    [0181] In a four-necked flask equipped with a stirrer, a water content meter, athermometer, and a nitrogen inlet were put 75.5 g (0.263 mol) of bis(4-chlorophenyl)sulfone, 50 g (0.269 mol) of 4,4'-biphenol, and 48 g of potassium carbonate. To themixture were added 400 ml of dimethyl sulfoxide and 50 ml of toluene, and the mixturewas heated while stirring in a nitrogen stream. The temperature was elevated up to180°C while removing produced water together with toluene. The stirring was continued for 3 hours at that temperature to prepare a solution of polymer b2(prepolymer (B)). The number of the repeating units of polymer b2, r4, was about 44as calculated from the feed ratio.
    [0182] Separately, 160.9 g of SUMIKAEXCEL 4100G (Sumitomo Chemical Co.,Ltd.) having the structural unit shown below was dissolved in 480 ml of dimethylsulfoxide to prepare a solution of a prepolymer (A). The number of the repeatingunits, r3, of the polymer was about 78 as obtained by 1H-NMR analysis.
    [0183] Ten grams of copolymer BP-2 was dissolved in 100 ml of 98% sulfuric acid,followed by stirring at room temperature for 24 hours thereby to sulfonate thecomponent derived from polymer b2 (prepolymer (B)). The solution was put into alarge quantity of water to precipitate a white solid. The solid was separated byfiltration, washed twice with hot water and once with methanol, and dried underreduced pressure to give polymer BPS-2. The resulting polymer had an ion exchangecapacity of 1.63 mmol/g, which indicates that the sulfonated component based onpolymer b2 (prepolymer (B)) was not dissolved and removed by washing with hot waterand that polymer b2 had reacted with the prepolymer (A). A membrane prepared bycasting a solution of polymer BPS-2 in N,N-dimethylacetamide and drying the cast filmrevealed a phase separation structure under TEM observation, proving that the polymerto be a block copolymer. SYNTHESIS EXAMPLE 4: Synthesis of sulfonic acid group-containing aromaticpolyether sulfone block copolymer (BPS-3)
    [0184] In a four-necked flask equipped with a stirrer, a water content meter, athermometer, and a nitrogen inlet were put 42.7 g (0.149 mol) of bis(4-chlorophenyl)sulfone, 28.2 g (0.151 mol) of 4,4'-biphenol, and 27.2 g of potassium carbonate. Tothe mixture were added 240 ml of dimethyl sulfoxide and 30 ml of toluene, and themixture was heated while stirring in a nitrogen stream. The temperature was elevated up to 180°C while removing produced water together with toluene. The stirring wascontinued for 3 hours at that temperature to prepare a solution of polymer b3(prepolymer (B)). The number of the repeating units of polymer b3, r4, was about 55as calculated from the feed ratio.
    [0185] Separately, 115 g of SUMIKAEXCEL 4100G (available from SumitomoChemical Co., Ltd.; repeating unit number r3=ca. 78) was dissolved in 345 ml ofdimethyl sulfoxide, and the resulting solution was added to the polymer b3 solution.The mixed solution was stirred at 170°C for 1.5 hours, followed by pouring into a largequantity of water. The white solid thus precipitated was recovered by filtration,washed twice with hot water and once with methanol, and dried under reduced pressureto give copolymer BP-3. The solution viscosity ηsp/c of the resulting polymer was0.46.
    [0186] Ten grams of copolymer BP-3 was dissolved in 100 ml of 98% sulfuric acid,followed by stirring at room temperature for 24 hours thereby to sulfonate thecomponent derived from polymer b3 (prepolymer (B)). The solution was put into alarge quantity of water to precipitate a white solid. The solid was separated byfiltration, washed twice with hot water and once with methanol, and dried underreduced pressure to give polymer BPS-3. The resulting polymer had an ion exchangecapacity of 1.38 mmol/g, which indicates that the sulfonated component based onpolymer b3 (prepolymer (B)) was not dissolved and removed by washing with hot waterand that polymer b3 had reacted with the prepolymer (A). A membrane prepared bycasting a solution of polymer BPS-3 in N,N-dimethylacetamide and drying the cast filmrevealed a phase separation structure under TEM observation, proving that the polymerto be a block copolymer. SYNTHESIS EXAMPLE 5: Synthesis of sulfonic acid group-containing aromaticpolyether sulfone block copolymer (BPS-4)
    [0187] In the same manner as in Synthesis Example 3, a solution of polymer b4(prepolymer (B)) and a dimethyl sulfoxide solution of SUMIKAEXCEL 4100G wereprepared. The dimethyl sulfoxide solution of SUMIKAEXCEL was added to thepolymer b4 solution, followed by stirring at 170°C for 1.5 hours. To the solution wasadded 1.05 g (4.1 x 10-3 mol) of bis(4-fluorophenyl) sulfone, followed by stirring at170°C for 1.5 hours. The solution was poured into a large amount of water toprecipitate a white solid, which was collected by filtration, washed twice with hot waterand once with methanol, and dried in vacuo to yield copolymer BP-4. The resultingpolymer had a solution viscosity ηsp/c of 0.58.
    [0188] Ten grams of copolymer BP-4 was dissolved in 100 ml of 98% sulfuric acid,and the solution was stirred at room temperature for 24 hours to sulfonate thecomponent derived from polymer b4 (prepolymer (B)). The solution was poured intoa large amount of water. The white solid thus precipitated was separated by filtration,washed twice with hot water and once with methanol, and vacuum dried to yieldpolymer BPS-4. The resulting polymer had an ion exchange capacity of 1.67 mmol/g,which indicates that the sulfonated component based on polymer b4 (prepolymer (B))was not dissolved and removed by washing with hot water and that polymer b4 hadreacted with the prepolymer (A). A membrane prepared by casting a solution ofpolymer BPS-4 in N,N-dimethylacetamide and drying the cast film revealed a phaseseparation structure under TEM observation, proving that the polymer BPS-4 to be ablock copolymer. SYNTHESIS EXAMPLE 6: Synthesis of aromatic polyether sulfone random copolymerand TEM observation of a sulfonation product of the copolymer
    [0189] In a four-necked flask equipped with a stirrer, a water content meter, athermometer, and a nitrogen inlet were put 18.6 g of bis(4-chlorophenyl) sulfone, 4.5 gof 4,4'-biphenol, 10.1 g of bis(4-hydroxyphenyl) sulfone, and 11.8 g of potassiumcarbonate. To the mixture were added 50 ml of dimethyl sulfoxide and 25 ml oftoluene, and the mixture was heated while stirring in a nitrogen stream. Thetemperature was raised to 195°C while removing produced water together with toluene.The stirring was continued for 3 hours at that temperature to prepare a polymer solution.The solution was put into a large quantity of water. The white solid thus precipitatedwas recovered by filtration, washed twice with hot water and once with methanol, anddried under reduced pressure to give copolymer RP-2. The solution viscosity ηsp/c ofthe resulting polymer was 0.52.
    [0190] Five grams of copolymer RP-2 was dissolved in 50 ml of 98% sulfuric acid,followed by stirring at room temperature for 24 hours. The solution was poured into alarge amount of water to precipitate a white solid. The solid was separated byfiltration, washed twice with hot water and once with methanol, and dried underreduced pressure to give polymer RPS-2. By this treatment, only those aromatic ringswith no electron attracting groups bonded thereto were selectively sulfonated asdescribed, e.g., in JP-A-61-43630. The resulting polymer had an ion exchangecapacity of 1.5 mmol/g. A membrane prepared by casting a solution of polymerRPS-2 in N,N-dimethylacetamide and drying the cast film showed a uniform structureunder TEM observation. This provides confirmation that a block copolymer is not produced unless a prepolymer is used and that a sulfonated random copolymer revealsno phase separation structure. SYNTHESIS EXAMPLE 7: Confirmation of water solubility of sulfonated prepolymer(B)
    [0191] In a four-necked flask equipped with a stirrer, a water content meter, athermometer, and a nitrogen inlet were put 7.71 g of bis(4-chlorophenyl) sulfone, 5 g of4,4'-biphenol, and 4.9 g of potassium carbonate. To the mixture were added 50 ml ofdimethyl sulfoxide and 25 ml of toluene, and the mixture was heated while stirring in anitrogen stream. The temperature was increased up to 180°C while removingproduced water together with toluene. The stirring was continued for 3 hours at thattemperature to prepare a polymer solution. The solution was poured into a largequantity of water. The white solid thus precipitated was recovered by filtration,washed twice with hot water and once with methanol, and dried under reduced pressureto give polymer HP-1. Polymer HP-1 structurally corresponds to the prepolymers (B)in Synthesis Examples 3 to 5. The solution viscosity ηsp/c of polymer HP-1 was 0.41.
    [0192] Five grams of polymer HP-1 was dissolved in 50 ml of 98% sulfuric acid,followed by stirring at room temperature for 24 hours. The solution was put into alarge quantity of water, but no precipitate was formed. The solution was poured into a1N hydrochloric acid aqueous solution to form a precipitate, which was washed withacetone three times and dried under reduced pressure. The resulting solid alsodissolved in water. From these results it was confirmed that the resulting polymerHPS-1 was water soluble and that, when the segment (of the block copolymer) derivedfrom the prepolymer (B) was a homopolymer, a sulfonation product of the segment wasremoved during the step of washing with water. SYNTHESIS EXAMPLE 8: Synthesis of sulfonic acid group-containing polyether etherketone
    [0193] In 100 ml of 98% sulfuric acid was dissolved 10 g of a commercially availablepoly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) (weight averagemolecular weight: ca. 20,800; number average molecular weight: 10,300; melting point:322°C) (polyether ether ketone). The solution was stirred at room temperature for 45hours and then poured into a large amount of water to precipitate a white solid. Thesolid was separated by filtration, washed with a large quantity of water until thewashing became neutral, and dried under reduced pressure to give a sulfonic acidgroup-containing polyether ether ketone. The resulting polymer had an ion exchangecapacity of 1.54 mmol/g. SYNTHESIS EXAMPLE 9: Synthesis of carboxyl group-containing aromatic polyethersulfone
    [0194] In a four-necked flask equipped with a stirrer, a water content meter, athermometer, and a nitrogen inlet were put 15 g of 4,4'-bis(p-hydroxyphenyl)valericacid, 13 g of potassium carbonate, 250 ml of dimethyl sulfoxide, and 90 ml of toluene,followed by heating while stirring in a nitrogen stream. The temperature was elevatedup to 150°C while removing produced water together with toluene. The stirring wascontinued for 3 hours at that temperature. To the system was further added 15 g of4,4'-dichlorodiphenyl sulfone, and the temperature was raised to 185°C while removingtoluene, at which temperature the mixture was stirred for 16 hours. Potassium chloridethus precipitated was removed by filtration, and the filtrate was poured into a largequantity of diluted hydrochloric acid to precipitate a white solid. The solid wascollected by filtration, washed with methanol repeatedly, and dried under reducedpressure to give a carboxyl-containing aromatic polyether sulfone. In the 1H-NMRspectrum measured on the resulting polymer, the signals at 7.906 ppm (d) and7.100 ppm (d) were assigned to the protons of the phenyl rings originated in4,4'-dichlorodiphenyl sulfone, the signals at 7.262 ppm (d) and 7.039 ppm (d) wereattributed to the protons of the phenyl rings originated in4,4'-bis(p-hydroxyphenyl)valeric acid, signals at 2.382 ppm to 2.367 ppm (t)corresponded to the methylene groups next to the carboxyl groups originated in4,4'-bis(p-hydroxyphenyl)valeric acid, those at 2.047 ppm to 2.026 ppm (t) wereassigned to the adjacent methylene groups, and the peak at 1.597 ppm (s) was attributedto the protons of the methyl groups. The ion exchange capacity was 2.00 mmol/g,calculated from the integral intensity ratio of the protons of the methylene groups nextto the carboxyl groups and the protons of the phenyl rings originated in4,4'-dichlorodiphenyl sulfone. SYNTHESIS EXAMPLE 10: Synthesis of N-ethylimidazole trifluoromethanesulfonate
    [0195] Twenty-five grams of trifluoromethanesulfonic acid was added dropwise to asolution of 16 g of N-ethylimidazole in 20 ml of ethanol at 0°C. The solution wasreturned to room temperature, stirred overnight, and dried in vacuo at 60°C for 16 hoursto give N-ethylimidazole trifluoromethanesulfonate (EtIm+TfS-) as a colorlesstransparent liquid. The resulting salt had a melting point of 8.3°C (literature value:7.8°C). SYNTHESIS EXAMPLE 11: Synthesis of 2,4-lutidine trifluoromethanesulfonate
    [0196] Eight-point-five grams of trifluoromethanesulfonic acid was added dropwise to a solution of 6.1 g of 2,4-lutidine in 15 ml of ethanol at 0°C. The solution wasreturned to room temperature, stirred overnight, and dried in vacuo at 60°C for 16 hoursto yield 2,4-lutidine trifluoromethanesulfonate (Lut+TfS-) as a colorless transparentliquid. The resulting salt had a melting point of 64.9°C. SYNTHESIS EXAMPLE 12: Synthesis of 1-methylpyrrolidine trifluoromethanesulfonate
    [0197] Twenty-five grams of trifluoromethanesulfonic acid was added dropwise to asolution of 14.2 g of 1-methylpyrrolidine in 25 ml of ethanol at 0°C. The solution wasreturned to room temperature, stirred overnight, and dried in vacuo at 60°C for 16 hoursto furnish 1-methylpyrrolidine trifluoromethanesulfonate (MePy+TfS-) as a brownsolid. The resulting salt had a melting point of 97.5°C. SYNTHESIS EXAMPLE 13: Synthesis of N-ethylimidazole bis(trifluoromethyl-sulfonyl)imide
    [0198] To 1.0 g of bis(trifluoromethylsulfonyl)imide was added dropwise 0.34 g ofN-ethylimidazole in a nitrogen atmosphere in a glove box, and the solution was stirredovernight to obtain N-ethylimidazole bis(trifluoromethylsulfonyl)imide (EtIm+TFSI-)as a colorless transparent liquid. The resulting salt had a melting point of 6.6°C. EXAMPLE 1
    [0199] One-point-three grams of the sulfonic acid group-containing aromaticpolyether sulfone random copolymer RPS-1 prepared in Synthesis Example 1 and 3 g ofEtIm+TfS- obtained in Synthesis Example 10 were dissolved in 20 ml ofN,N-dimethylacetamide. The solution was cast on a glass plate and dried in vacuo at60°C for 5 hours and 120°C for 16 hours to obtain a transparent membrane. Even afterthe membrane was allowed to stand at 50°C for one week, neither did EtIm+TfS- bleedout, nor was observed weight loss. The ionic conductivity of the membrane was ashigh as 2 x 10-3 Scm-1 at 100°C in spite of the absence of water. EXAMPLE 2
    [0200] Three grams of the sulfonic acid group-containing aromatic polyether sulfonerandom copolymer RPS-1 synthesized in Synthesis Example 1 and 3 g of EtIm+TfS-obtained in Synthesis Example 10 were dissolved in 20 ml of N,N-dimethylacetamide.The solution was cast on a glass plate and dried in vacuo at 60°C for 5 hours and 120°Cfor 16 hours to obtain a transparent membrane having a thickness of 124 µm. Evenwhen left to stand at 50°C for one week, the membrane suffered from neither bleedingout of EtIm+TfS- nor weight loss. The ionic conductivity of the membrane was ashigh as 2 x 10-3 Scm-1 at 100°C in spite of the absence of water. Although the membrane sandwiched between electrode plates was partly pressed out of the plateedges, and the part held between the plates was reduced in thickness to 60 µm, such wasnon-problematic for practical use. EXAMPLE 3
    [0201] Three grams of the sulfonic acid group-containing aromatic polyether sulfoneblock copolymer BPS-2 obtained in Synthesis Example 3 and 3 g of EtIm+TfS-synthesized in Synthesis Example 10 were dissolved in 20 ml ofN,N-dimethylacetamide. The solution was cast on a glass plate and dried in vacuo at60°C for 5 hours and 120°C for 16 hours to obtain a transparent membrane. Even afterthe membrane was left to stand at 50°C for one week, neither did EtIm+TfS- bleed out,nor was observed weight loss. The temperature dependence of the ionic conductivityof the resulting membrane is shown in Fig. 1. In spite of the absence of water, theionic conductivity at 100°C was as high as 1.2 x 10-3 Scm-1. The membrane retainedits shape even after the measurement. EXAMPLE 4
    [0202] Three grams of the sulfonic acid group-containing aromatic polyether sulfoneblock copolymer BPS-1 prepared in Synthesis Example 2 and 5.5 g of EtIm+TfS- obtained in Synthesis Example 10 were dissolved in 20 ml of N,N-dimethylacetamide.The solution was cast on a glass plate and dried in vacuo at 60°C for 5 hours and 120°Cfor 16 hours to obtain a transparent membrane. Even after the membrane was left tostand at 50°C for one week, neither did EtIm+TfS- bleed out, nor was observed weightloss. In spite of the absence of water, the ionic conductivity of the membrane at 50°Cwas as high as 1.2 x 10-3 Scm-1. The membrane retained its shape even after themeasurement. EXAMPLE 5
    [0203] Three grams of the sulfonic acid group-containing aromatic polyether sulfoneblock copolymer BPS-2 prepared in Synthesis Example 3 and 12 g of EtIm+TfS-obtained in Synthesis Example 10 were dissolved in 20 ml of N,N-dimethylacetamide.The solution was cast on a glass plate and dried in vacuo at 60°C for 5 hours and 120°Cfor 16 hours to obtain a white turbid membrane. Even after the membrane was left tostand at 50°C for one week, neither did EtIm+TfS- bleed out, nor was observed weightloss. In spite of the absence of water, the ionic conductivity of the membrane at 50°Cwas as high as 6.2 x 10-3 Scm-1. The membrane retained its shape even after themeasurement. EXAMPLE 6
    [0204] Three grams of the sulfonic acid group-containing aromatic polyether sulfoneblock copolymer BPS-2 prepared in Synthesis Example 3 was dissolved in 20 ml ofN,N-dimethylacetamide. The solution was cast on a glass plate and dried in vacuo at60°C for 5 hours and 120°C for 16 hours to obtain a transparent membrane. A 0.100 gportion of the resulting membrane was immersed in EtIm+TfS- obtained in SynthesisExample 10 at room temperature for 18 hours. The membrane was taken out ofEtIm+TfS-, wiped to remove the attached EtIm+TfS- from both sides thereof, andweighed. The membrane showed 9.8% increase in weight over the dry weight beforeimmersion, which was due to absorption of EtIm+TfS-. Even after the membrane wasleft to stand at 50°C for one week, neither did EtIm+TfS- bleed out, nor was observedweight loss. COMPARATIVE EXAMPLE 1
    [0205] A membrane was prepared in the same manner as in Example 1, except forreplacing the sulfonated aromatic polyether sulfone RPS-1 with the non-sulfonatedaromatic polyether sulfone random copolymer RP-1 synthesized in Synthesis Example1. The membrane after drying was white turbid, and EtIm+TfS- bled out of themembrane. COMPARATIVE EXAMPLE 2
    [0206] A membrane was prepared in the same manner as in Example 2, except forreplacing the sulfonated aromatic polyether sulfone BPS-1 with the non-sulfonatedaromatic polyether sulfone block copolymer BP-1 synthesized in Synthesis Example 2.The membrane after drying was white turbid, and EtIm+TfS- bled out of the membrane. COMPARATIVE EXAMPLE 3
    [0207] Three grams of the sulfonated aromatic polyether sulfone block copolymerBPS-1 obtained in Synthesis Example 2 and 3 g of N-ethylimidazole were dissolved in20 ml of N,N-dimethylacetamide. A membrane was prepared in the same manner as inExample 2, except by using the resulting solution. The ionic conductivity of theresulting membrane at 100°C was as low as 6 x 10-7 Scm-1. EXAMPLE 7
    [0208] Three grams of the sulfonic acid group-containing polyether ether ketonesynthesized in Synthesis Example 8 and 3 g of EtIm+TfS- obtained in SynthesisExample 10 were dissolved in 20 ml of N-methyl-2-pyrrolidone. The solution wascast on a glass plate and dried in vacuo at 60°C for 5 hours and 150°C for 16 hours toobtain a semi-transparent membrane having a thickness of 76 µm. Even after themembrane was left to stand at 50°C for one week, neither did EtIm+TfS- bleed out, nor was observed weight loss. The ionic conductivity of the membrane was as high as 3 x10-3 Scm-1 at 100°C in spite of the absence of water. Although the membranesandwiched between electrode plates was partly pressed out of the plate edges to haveits thickness reduced to 40 µm, such was non-problematic for practical use. EXAMPLE 8
    [0209] Three grams of the sulfonic acid group-containing aromatic polyether etherketone prepared in Synthesis Example 8 was dissolved in 20 ml ofN-methyl-2-pyrrolidone. The solution was cast on a glass plate and dried in vacuo at60°C for 5 hours and 150°C for 16 hours to obtain a membrane having a thickness of75 µm. A 1.00 g portion of the resulting membrane was immersed in EtIm+TfS- andleft to stand at 60°C for 6 hours. The membrane was taken out of EtIm+TfS-, wiped toremove the attached EtIm+TfS- from both sides thereof, and weighed. The membraneshowed 26% increase in weight over the dry weight before immersion, which was dueto absorption of EtIm+TfS-. Even after the membrane was allowed to stand at 50°Cfor one week, neither did EtIm+TfS- bleed out, nor was observed weight loss. COMPARATIVE EXAMPLE 4
    [0210] Three grams of the polyether ether ketone before introduction of sulfonic acidgroups was once melted on a hot plate at 400°C and allowed to cool to prepare adisk-shaped solid having a thickness of about 1 mm and weighing 1.00 g. The thussolidified polyether ether ketone was immersed in EtIm+TfS- at 60°C for 6 hours. Thesolid taken out of EtIm+TfS- and wiped to remove EtIm+TfS- from both sides thereofweighed 1.00 g, showing no gain in weight. That is, the polyether ether ketone failedto hold EtIm+TfS-. EXAMPLE 9
    [0211] A transparent membrane was prepared in the same manner as in Example 3,except for replacing EtIm+TfS- with Lut+TfS- obtained in Synthesis Example 11.When the membrane was allowed to stand at 50°C for one week, neither did Lut+TfS-bleed out, nor was observed weight loss. The ionic conductivity of the membrane at150°C was as high as 8.4 x 10-4 Scm-1 despite the absence of water. EXAMPLE 10
    [0212] A white turbid membrane was obtained in the same manner as in Example 3,except for replacing EtIm+TfS- with MePy+TfS- obtained in Synthesis Example 12.When the membrane was allowed to stand at 50°C for one week, neither did MePy+TfS- bleed out, nor was observed weight loss. The ionic conductivity of themembrane at 150°C was as high as 4.1 x 10-3 Scm-1 despite the absence of water. EXAMPLE 11
    [0213] A transparent membrane was obtained in the same manner as in Example 3,except for replacing EtIm+TfS- with EtIm+TFSI- obtained in Synthesis Example 13.When the membrane was allowed to stand at 50°C for one week, neither didEtIm+TFSI- bleed out, nor was observed weight loss. The ionic conductivity of themembrane at 100°C was as high as 4.4 x 10-4 Scm-1 despite the absence of water. EXAMPLE 12
    [0214] Three grams of the carboxyl group-containing aromatic polyether sulfoneprepared in Synthesis Example 9 and 3 g of EtIm+TfS- obtained in Synthesis Example10 were dissolved in 20 ml of N,N-dimethylacetamide. The solution was cast on aglass plate and dried in vacuo at 60°C for 5 hours and 120°C for 16 hours to obtain awhite turbid membrane. Even after the membrane was left to stand at 50°C for oneweek, neither did EtIm+TfS- bleed out, nor was observed weight loss. In spite of theabsence of water, the ionic conductivity of the membrane at 150°C was as high as 7.5 x10-4 Scm-1. REFERENCE EXAMPLE 1
    [0215] Three grams of BPS-2 obtained in Synthesis Example 3 was dissolved in 20 mlof N,N-dimethylacetamide. The solution was cast on a glass plate and vacuum dried at60°C for 5 hours and 120°C for 16 hours to form a transparent film. Separately, amethanol solution of commercially available poly(2-hydroxyethyl methacrylate)(PHEMA) having an aliphatic hydrocarbon group in the main chain was cast on a glassplate and dried in vacuo at 70°C for 6 hours to obtain a transparent film. The BPS-2film and the PHEMA film were compared in pyrolysis behavior by thermogravimetry.The results obtained are shown in Fig. 2. It is apparent seen that the BPS-2 film wassuperior in heat resistance. SYNTHESIS EXAMPLE 14: Synthesis of styrene-p-styrenesulfonic acid copolymer
    [0216] In 80 ml of 40°C water was dissolved 6.0 g of sodium p-styrenesulfonate, andthe solution was bubbled with nitrogen for 30 minutes. To the solution were added9.1 g of styrene and, as a polymerization initiator, 0.065 g of 4,4'-azobis(4-cyanovalericacid) to carry out polymerization at 60°C for 24 hours in a nitrogen atmosphere. Aftercompletion of the polymerization, the solution was poured into a large amount of2-propanol to precipitate a white solid, which was collected by filtration. The solidwas washed twice with 2-propanol and once with acetone and dried under reduced pressure to give a polystyrene copolymer containing a sulfonic acid group in sodiumsalt form. The resulting copolymer was treated with 1N hydrochloric acid for 2 hours,and the insoluble matter was recovered by filtration and dried under reduced pressure toyield sulfonic acid group-containing polystyrene PS-1. PS-1 had an Mw of 1.8 x 106,an Mw/Mn ratio of 2.8, and an ion exchange capacity of 1.75 mmol/g.
    [0217] GPC of polystyrene polymers prepared was carried out as follows. A0.5 wt% solution of a polymer was prepared using, as a solvent,N-methyl-2-pyrrolidone having dissolved therein lithium chloride and phosphoric acideach in concentration of 50 mM. GPC was performed using a Shodex GPC KD-806Mcolumn available from Showa Denko KK and a differential refractive index detectorRID-10A from Shimadzu Corp. to obtain standard polystyrene equivalent weightaverage molecular weight Mw, number average molecular weight Mn, and molecularweight distribution Mw/Mn. SYNTHESIS EXAMPLE 15: Synthesis of styrene-vinylbenzylsulfonic acid copolymer
    [0218] Sulfonic acid group-containing polystyrene (PS-2), which was astyrene-vinylbenzylsulfonic acid copolymer, was synthesized in the same manner as inSynthesis Example 14, except for using 6.4 g of sodium vinylbenzylsulfonate in placeof sodium p-styrenesulfonate. PS-2 had an Mw of 1.7 x 106 and an Mw/Mn ratio of2.1. The ion exchange capacity of PS-2 was 1.06 mmol/g. EXAMPLE 13
    [0219] Two grams of the sulfonic acid group-containing polystyrene PS-1 prepared inSynthesis Example 14 and 2 g ofEtIm+TfS- obtained in Synthesis Example 10 weredissolved in 20 ml of N-methyl-2-pyrrolidone. The solution was cast on a glass plateand dried in vacuo at 60°C for 5 hours and 150°C for 16 hours to obtain a membrane.The membrane, while opaque, did not suffer from bleeding of EtIm+TfS- nor weightloss even when allowed to stand at 50°C for one week. The ionic conductivity of themembrane was as high as 3.6 x 10-3 Scm-1 at 100°C in spite of the absence of water. EXAMPLE 14
    [0220] A membrane was obtained in the same manner as in Example 13, except forreplacing PS-1 with the sulfonic acid group-containing polystyrene PS-2 obtained inSynthesis Example 15. The membrane, while opaque, did not suffer from bleeding ofEtIm+TfS- nor weight loss even after it was allowed to stand at 50°C for one week.The ionic conductivity of the membrane was as high as 3.1 x 10-3 Scm-1 at 100°C inspite of the absence of water. EXAMPLE 15
    [0221] Five grams of a commercially available 5 wt% solution of a sulfonatedstyrene-(ethylene-butylene)-styrene triblock copolymer (styrene content: 29 wt%;sulfonation degree of the styrene unit: 45 to 55%; solvent: 1-propanol/dichloroethanemixture) and 0.25 g of EtIm+TfS- obtained in Synthesis Example 10 were mixed up.The solution was cast on a glass plate and vacuum dried at 40°C for 2 hours and 80°Cfor 16 hours to form a membrane. The membrane, while opaque, did not suffer frombleeding of EtIm+TfS- nor weight loss even after it was allowed to stand at 50°C forone week. The ionic conductivity of the membrane was as high as 2.3 x 10-3 Scm-1 at50°C in spite of the absence of water. COMPARATIVE EXAMPLE 5
    [0222] A membrane was prepared in the same manner as in Example 13, except forreplacing PS-1 with a commercially available polystyrene (Mw: 280,000). Themembrane obtained after drying was white turbid and suffered from bleeding ofEtIm+TfS-. COMPARATIVE EXAMPLE 6
    [0223] One-point-five grams of a commercially available styrene-(ethylene-butylene)-styrenetriblock copolymer (styrene content: 29 wt%; Mw: 89,000) and 1.5 g ofEtIm+TfS- obtained in Synthesis Example 10 were dissolved in 20 ml oftetrahydrofuran. The solution was cast on a glass plate and dried in vacuo at roomtemperature for 4 hours and 60°C for 16 hours to form a membrane. The driedmembrane was white turbid and suffered from bleeding of EtIm+TfS-. COMPARATIVE EXAMPLE 7
    [0224] Two grams of the sulfonic acid group-containing polystyrene PS-1 obtained inSynthesis Example 14 and 2 g of N-ethylimidazole were dissolved in 20 ml ofN-methyl-2-pyrrolidone. A membrane was formed in the same manner as in Example13, except for using the solution. The ionic conductivity of the membrane at 100°Cwas as low as 4 x 10-7 Scm-1. Industrial Applicability:
    [0225] The present invention provides a polymer electrolyte composition and apolymer electrolyte membrane which are inexpensive and durable, comprise anaromatic polymer and a molten salt, exhibit high ionic conductivity even in the absenceof water or a solvent, and are useful in fuel cells, secondary batteries, electric doublelayer capacitors, electrolytic capacitors, etc. The present invention also provides a process of producing them.
    [0226] The present invention also provides a polymer electrolyte composition which isinexpensive and durable, shows high ionic conductivity even in the absence of water ora solvent, and exhibits high structure retention even in high temperatures.
    [0227] The present invention also provides an economical process of producing anaromatic polyether sulfone block copolymer free from a bond of different kind in themolecular chain and useful as an aromatic polymer used in the present invention.
    权利要求:
    Claims (27)
    [1] A polymer electrolyte composition characterized by comprising a molten saltand an aromatic polymer having a carbonyl bond and/or a sulfonyl bond in the mainchain thereof and containing a cation exchange group.
    [2] The polymer electrolyte composition according to claim 1, wherein thearomatic polymer has a structural unit represented by chemical formula (1):
    [3] The polymer electrolyte composition according to claim 1, wherein thearomatic polymer is an aromatic polyether sulfone having a structural unit representedby chemical formula (3):
    [4] The polymer electrolyte composition according to claim 1, wherein thearomatic polymer is an aromatic polyether ketone having a structural unit representedby chemical formula (5):
    [5] The polymer electrolyte composition according to claim 1, wherein thearomatic polymer is an aromatic polyether sulfone block copolymer and/or an aromaticpolyether ketone block copolymer, the aromatic polyether sulfone block copolymer andthe aromatic polyether ketone block copolymer comprising a hydrophilic segmentcontaining a cation exchange group and a hydrophobic segment containing no cationexchange group.
    [6] The polymer electrolyte composition according to claim 5, wherein thehydrophobic segment has a structural unit represented by chemical formula (6):
    [7] The polymer electrolyte composition according to claim 5, wherein thehydrophilic segment has a structural unit represented by chemical formula (7):
    [8] The polymer electrolyte composition according to claim 1, wherein the moltensalt has an ammonium ion as a cation component.
    [9] The polymer electrolyte composition according to claim 1, wherein the moltensalt is present in an amount of 3 to 90% by weight.
    [10] The polymer electrolyte composition according to claim 1, wherein the cationexchange group is a sulfonic acid group or a carboxyl group, and the cation exchangegroup-containing aromatic polymer has an ion exchange capacity of 0.3 to 7 meq/g.
    [11] The polymer electrolyte composition according to claim 5, wherein the cationexchange group is a sulfonic acid group or a carboxyl group, and the cation exchangegroup-containing block copolymer has an ion exchange capacity of 0.1 to 10 meq/g.
    [12] The polymer electrolyte composition according to claim 5, wherein anon-sulfonated compound of the aromatic polyether sulfone block copolymer and/or anon-sulfonated compound of the aromatic polyether ketone block copolymer have areduced viscosity ηsp/c of 0.1 to 3.0 dl/g.
    [13] The polymer electrolyte composition according to claim 5, wherein anon-sulfonated compound of the aromatic polyether sulfone block copolymer isobtained by allowing (A) an aromatic polyether sulfone prepolymer having a segmentrepresented by chemical formula (8):
    [14] A polymer electrolyte membrane characterized by comprising the polymerelectrolyte composition according to claim 1.
    [15] A method of preparing the polymer electrolyte composition according to claim1, which is characterized by comprising dissolving predetermined amounts of thearomatic polymer and the molten salt in a solvent capable of dissolving both andremoving the solvent by drying.
    [16] A method of producing the polymer electrolyte membrane according to claim14, which is characterized by comprising dissolving predetermined amounts of thearomatic polymer and the molten salt in a solvent capable of dissolving both, casting theresulting solution, and removing the solvent by drying.
    [17] A method of producing the polymer electrolyte composition according to claim1 or the polymer electrolyte membrane according to claim 14, which is characterized bycomprising immersing a molded article of the aromatic polymer in the molten salt toimpregnate the aromatic polymer with the molten salt.
    [18] A process of preparing an aromatic polyether sulfone block copolymercomprising (a) a segment represented by chemical formula (10):
    [19] The process of preparing an aromatic polyether sulfone block copolymeraccording to claim 18, wherein the reaction of the prepolymers (A) and (B) is carriedout at a temperature of 120 to 200°C.
    [20] A polymer electrolyte composition characterized by comprising a molten saltand a polystyrene polymer having a structural unit represented by chemical formula(12):
    [21] The polymer electrolyte composition according to claim 20, wherein themolten salt has an ammonium ion as a cation component.
    [22] The polymer electrolyte composition according to claim 20, wherein the polystyrene polymer has an ion exchange capacity of 0.3 to 7 meq/g.
    [23] The polymer electrolyte composition according to claim 20, wherein themolten salt is present in an amount of 3 to 90% by weight.
    [24] A polymer electrolyte membrane characterized by comprising the polymerelectrolyte composition according to claim 20.
    [25] A method of preparing the polymer electrolyte composition according to claim20, which is characterized by comprising dissolving predetermined amounts of thepolystyrene polymer and the molten salt in a solvent capable of dissolving both andremoving the solvent by drying.
    [26] A method of producing the polymer electrolyte membrane according to claim24, which is characterized by comprising dissolving predetermined amounts of thepolystyrene polymer and the molten salt in a solvent capable of dissolving both, castingthe resulting solution, and removing the solvent by drying.
    [27] A method of producing the polymer electrolyte composition according to claim20 or the polymer electrolyte membrane according to claim 24, which is characterizedby comprising immersing a molded article of the polystyrene polymer in the molten saltto impregnate the polystyrene polymer with the molten salt.
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    同族专利:
    公开号 | 公开日
    DE60238512D1|2011-01-13|
    AT467242T|2010-05-15|
    US7563850B2|2009-07-21|
    EP2058889A1|2009-05-13|
    EP2058889B1|2010-12-01|
    AT490568T|2010-12-15|
    WO2003046080A1|2003-06-05|
    DE60236314D1|2010-06-17|
    EP2147947B1|2012-07-25|
    US20050069780A1|2005-03-31|
    EP1449886B1|2010-05-05|
    EP1449886A4|2007-05-30|
    EP2147947A1|2010-01-27|
    US20090212253A1|2009-08-27|
    AU2002355055A1|2003-06-10|
    US7923492B2|2011-04-12|
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    优先权:
    申请号 | 申请日 | 专利标题
    JP2001364298||2001-11-29||
    JP2001364298||2001-11-29||
    JP2002004683||2002-01-11||
    JP2002004683A|JP4032749B2|2002-01-11|2002-01-11|Process for producing aromatic polyethersulfone block copolymer|
    JP2002060407||2002-03-06||
    JP2002060407||2002-03-06||
    JP2002116550||2002-04-18||
    JP2002116550||2002-04-18||
    JP2002130568||2002-05-02||
    JP2002130568||2002-05-02||
    PCT/JP2002/012510|WO2003046080A1|2001-11-29|2002-11-29|Polyelectrolyte compositions|EP09014174A| EP2147947B1|2001-11-29|2002-11-29|Process for preparing an aromatic polyether sulfone blockcopolymer|
    EP09001023A| EP2058889B1|2001-11-29|2002-11-29|Polymer electrolyte composition|
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