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    • 专利摘要:
    The present invention relates to a polymer electrolyte having excellent proton conductivity, excellent heat resistance and excellent strength, characterized by having a structural unit of formula (1) in the main chain. Formula 1 In Formula 1 above, Ar 1 and Ar 2 independently represent a divalent aromatic group, m is an integer from 0 to 3, X + represents an ion selected from hydrogen ions, alkali metal ions and ammonium ions. The polymer electrolyte is soluble in solvents, has excellent film forming properties and is excellent in recyclability.
    公开号:KR20020079424A
    申请号:KR1020020018062
    申请日:2002-04-02
    公开日:2002-10-19
    发明作者:시노다히로시；이와사키가쓰히코；데라하라아쓰시
    申请人:스미또모 가가꾸 고교 가부시끼가이샤；
    IPC主号:
    专利说明:

    Polymer electrolyte and process for producing same
    [1] The present invention relates to polymer electrolytes, and in particular to polymer electrolytes which are suitably used as separators in electrochemical devices such as batteries, fuel cells and the like.
    [2] Polymer electrolytes having ion conductivity are used as separators in cell chemistry devices such as primary batteries, secondary batteries, and solid polymer fuel cells. As such a polymer electrolyte, polymer materials having acidic groups such as sulfonic acid groups, carboxylic acid groups, phosphoric acid groups or metal salts thereof are used.
    [3] For example, in a solid polymer fuel cell, Nafion [Nafion; this. children. Perfluorosulfonic acid-based polymer electrolytes including DuPont de Nemours Co. (registered trademark of E. I. Dupont de Nemours Co.) have been used. However, such an electrolyte has a problem of low membrane strength, heat resistance and the like. In addition, sulfonates of random copolymers obtained from 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybiphenyl and 4,4'-dichlorodiphenylsulfone have also been proposed, but protons thereof Since the conductivity is not necessarily satisfactorily obtained, a polymer electrolyte showing higher proton conductivity is desired.
    [4] On the other hand, as a polymer electrolyte which has a disulfonylimide unit, the compound which has a disulfonylimide unit in a crosslinking residue is known. For example, a polymer electrolyte prepared by crosslinking a perfluoro-based sulfonyl fluoride membrane with perfluorobutane-1,4-disulfonamide (Japanese Patent Laid-Open No. 2000-188013), a chlorosulfonated poly Polymer electrolytes prepared by crosslinking ether-ether ketones with 2,5-dichlorobenzene-1,4-disulfoneamide (WO 99/61141) and the like have been proposed. Since these crosslinked polymer electrolyte membranes are insoluble and infusible, when they are used as separators in batteries, separation from electrode materials becomes difficult, and there is a fear that recovery of materials and reuse thereof are very difficult. In addition, since a crosslinking step is required after film production, there is a problem that its manufacturing process is complicated.
    [5] Under such circumstances, the present inventors have conducted a study on the polymer compound having a disulfonylimide unit, and as a result, the polymer compound having a specific disulfonylimide unit which is a bis (arylsulfonyl) imide in the main chain is used as a polymer electrolyte. It has been found to be excellent in heat resistance, easy to manufacture membrane, recoverable material, and excellent in recyclability, and also high in the case of preparing the polymer compound as a composite membrane with a porous membrane. It was found to maintain ionic conductivity.
    [6] The present invention therefore provides a practically good polymer electrolyte [1] characterized by having a structural unit of formula (1) in the main chain:
    [7]
    [8] In Formula 1 above,
    [9] Ar 1 and Ar 2 independently represent a divalent aromatic group,
    [10] m is an integer from 0 to 3,
    [11] X + represents an ion selected from hydrogen ions, alkali metal ions and ammonium ions.
    [12] The present invention also provides a polymer electrolyte [2] according to [1], which is characterized by further having a polymerized unit of formula (2) in the main chain:
    [13]
    [14] In Formula 2 above,
    [15] Ar 3 represents a divalent aromatic group.
    [16] The present invention provides a polymer electrolyte [3] according to [2], further comprising a polymerized unit of formula (2a) different from formula (2) in the main chain:
    [17]
    [18] In Formula 2a above,
    [19] Ar 4 represents a divalent aromatic group.
    [20] This invention also provides the practically excellent composite membrane [4] containing the polymer electrolyte and porous membrane of [1], [2], or [3].
    [21] In Formula 1, Ar 1 and Ar 2 independently represent a divalent aromatic group. Examples of divalent aromatic groups include the following groups.
    [22]
    [23] In the above formula,
    [24] R 1 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group, an acetyl group, a benzoyl group, a nitrile group, a sulfonic acid, a carboxylic acid, a phosphonic acid or a halogen atom Represents;
    [25] a represents an integer of 0 to 4;
    [26] b and c represent integers from 0 to 4, and the sum of b and c is an integer from 0 to 6;
    [27] When there are a plurality of R 1 , they may be the same or different;
    [28] Y is a direct bond, -O-, -S-, -C (O)-, -SO 2 -or -C (R 3 ) 2- (wherein R 3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, Halogenated alkyl group or aryl group having 1 to 10 carbon atoms, and two R 3 's may be the same or different or may form a ring;
    [29] When there are a plurality of Y's, they may be the same or different.
    [30] Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, phenyl group, naphthyl group and the like. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group and the like. Halogenated alkyl groups having 1 to 10 carbon atoms include trifluoromethyl groups, pentafluoroethyl groups, and the like. Examples of aryl groups include phenyl groups, naphthyl groups, phenoxy groups, and the like. Examples of halogen atoms include fluorine atoms, chlorine atoms and bromine atoms.
    [31] Examples of the halogenated alkyl group having 1 to 10 carbon atoms of R 3 include trifluoromethyl group and the like. Examples of the ring formed by two R 3 include a cyclohexane ring, a fluorene ring, and the like.
    [32] The ion dissociation degree of the sulfonylimide group is changed by the substituents of the adjacent aromatic groups Ar 1 and Ar 2 , and the higher the electron attraction of the substituent, the higher the ion dissociation degree. Therefore, as Ar 1 and Ar 2 , a compound substituted with a substituent having high electron withdrawing properties, for example, a compound substituted with a halogen atom is preferable, and a compound substituted with a fluorine atom is more preferable. In particular, when Ar 1 or Ar 2 is tetrafluorophenylene, the disulfonylimide group has a high ion dissociation degree, which is particularly preferable.
    [33] X + includes hydrogen ions, alkali metal ions and ammonium ions. When using a polymer electrolyte as a fuel, X + is preferably hydrogen ions.
    [34] The polymer electrolyte of the present invention is characterized in that it has a polymerized unit of formula 1 as mentioned above in the main chain, but usually the electrolyte has such a polymerized unit and another polymerized unit, and is an alternating copolymer, a random copolymer or a block. It may be a copolymer.
    [35] Examples of preferred polymerization units other than the polymerization unit of the formula (1) include the polymerization units of the following formula (2) and the like. In addition to the polymerized units of formula (2), the electrolyte may have polymerized units different from these polymerized units. Examples of such polymerized units include, but are not limited to, polymerized units of Formula 2a.
    [36] Formula 2
    [37]
    [38] Formula 2a
    [39]
    [40] In Formula 2 and Formula 2a above,
    [41] Ar 3 and Ar 4 independently represent a divalent aromatic group.
    [42] The divalent aromatic group usually has 6 to 24 carbon atoms, preferably 6 to 18 carbon atoms, and may have substituents such as methyl group, ethyl group and sulfonic acid group.
    [43] Examples of divalent aromatic groups include the same groups as Ar 1 and Ar 2 as mentioned above.
    [44] The polymer electrolyte having the polymerization units of Chemical Formula 1 and Chemical Formula 2 may be prepared by, for example, using a compound of Formula 3, an aromatic diol of Formula 4, and the like, and polymerizing them.
    [45]
    [46]
    [47] In Formula 3 and Formula 4 above,
    [48] Ar 1 , Ar 2 , Ar 3 , m and X + are as defined in Formula 1 above;
    [49] Z represents a halogen atom or a nitro group.
    [50] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like. Preferable examples are a fluorine atom and a chlorine atom, and a fluorine atom is more preferable.
    [51] Representative examples of the aromatic diol of the formula (4) include hydroquinone, resorcinol, catechol, 2-methylhydroquinone, 2,6-dimethylhydroquinone, 2-methoxyhydroquinone, 2-phenylhydroquinone, 2,6-di Phenylhydroquinone, 2-sulfohydroquinone, 2,6-disulfohydroquinone, 2-methyl resorcinol, 2,4-dimethyl resorcinol, 2-phenyl resorcinol, 2,4-diphenyl resorciene Nol, 1,2-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6,7 -Dihydroxy-2-naphthalenesulfonic acid, 2,7-dihydroxynaphthalene-3,6-disulfonic acid, 4,5-dihydroxynaphthalene-2,7-disulfonic acid, 4,4'-dihydro Oxybiphenyl, 4,4'-dihydroxy-3,3'-disulfobiphenyl, 4,4'-dihydroxy-3,3'-diphenylbiphenyl, 2,4'-dihydroxybi Phenyl, 2,2a-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 1,1-bi (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclo Hexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, Bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4'-dihydroxydiphenylether, bis (4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3 '-Disulfodiphenyl sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, alkali metal salts thereof (sodium salt, potassium salt) and the like. Among these, two or more types can be used.
    [52] Among them, hydroquinone, 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxy-3,3'-diphenylbiphenyl, 4 Since 4'- dihydroxy diphenyl ether and these alkali metal salts are highly reactive, they are used preferably.
    [53] As other raw materials, the compound of formula 3 may be prepared in the following manner.
    [54] The compound in which m is 0 can be easily prepared, for example, by reacting a sulfonyl chloride compound of formula 10 with a sulfonamide compound of formula 8. Usually, the reaction is carried out in a solvent in which the pH value in the reaction system is adjusted to 7 to 8 and two or more equivalents of base are added.
    [55]
    [56]
    [57] In Formula 8 and Formula 10 above,
    [58] Z and Ar 1 are as defined above.
    [59] Examples of the solvent include acetone, 2-butanone, tetrahydrofuran, 1,4-dioxane, acetonitrile, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, and two or more of these. Mixtures and the like. Bases which can be used include sodium hydride, lithium hydride, triethylamine, pyridine, dimethylaminopyridine and the like. The reaction temperature is preferably about 0 to 150 ° C, more preferably 20 to 80 ° C. The reaction time is usually about 1 to 20 hours.
    [60] The sulfonamide compound used in the present invention may be prepared, for example, by reacting a sulfonyl chloride compound of Formula 10 with ammonia, ammonium chloride, or the like in the presence of a base of two times or more.
    [61] Among the compounds of formula (3), the compound of m is 1, for example, by reacting a sulfonamide compound of formula (8) with a bissulfonyl chloride compound of formula (9), or a sulfonyl chloride compound of formula (10) It can be easily prepared by reacting with an amide compound. The reaction can be carried out, for example, under reaction conditions similar to those for the compound in which m is zero. Bissulfonamide compounds used in the present invention can also be prepared by, for example, reacting a corresponding bissulfonyl chloride compound with ammonia, ammonium chloride, or the like.
    [62]
    [63]
    [64] In Formula 9 and Formula 11 above,
    [65] Ar 2 is as defined above.
    [66] Among the compounds of the formula (3), a compound having m of 2 or 3 may be prepared by, for example, reacting a bissulfonyl chloride compound and a bissulfonamide compound with a sulfonyl chloride compound or sulfonamide compound in a ternary system. The length of the oligomer chain can be controlled by its molar ratio. However, since it is difficult to increase the molecular weight of the final polymer because it is difficult to purify at the stage of the compound of formula 3 due to the distribution of chain lengths, it is preferable to use the compound of formula 3 wherein m is 0 or m is 1 Do.
    [67] Representative examples of the sulfonyl chloride compound used in the preparation of the compound of formula 3 include 4-fluorobenzenesulfonyl chloride, 3-fluorobenzenesulfonyl chloride, 2-fluorobenzenesulfonyl chloride, difluorobenzenesulfonyl chloride , Trifluorobenzenesulfonyl chloride, tetrafluorobenzenesulfonyl chloride, pentafluorobenzenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride, 3-chlorobenzenesulfonyl chloride, 2-chlorobenzenesulfonyl chloride, dichloro Benzenesulfonyl chloride, trichlorobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride, 3-brorobenzenesulfonyl chloride, 2-bromobenzenesulfonyl chloride, dibromobenzenesulfonyl chloride, 4-nitro Benzenesulfonyl chloride, 3-nitrobenzenesulfonyl chloride, and the like. Among these, two or more types can be used. It is also possible to use sulfonyl fluoride compounds in place of these sulfonyl chloride compounds.
    [68] Representative examples of bissulfonyl chloride compounds used in the preparation of the compound of formula 3 include 1,4-benzenedisulfonyl chloride, 1,3-benzenedisulfonyl chloride, 1,2-benzenedisulfonyl chloride, 4,4'-ratio Phenyldisulfonyl chloride, naphthalenedisulfonyl chloride and the like. Among these, two or more types can be used. It is also possible to use bissulfonyl fluoride compounds in place of these bissulfonyl chloride compounds.
    [69] The polymer electrolyte of the present invention can be prepared by using the compound of the formula (3), the aromatic diol of the formula (4), etc. as a raw material and polymerizing them. Although it does not specifically limit as this specific manufacturing method, For example, Process of reacting the compound of the said Formula (3) with the aromatic diol of the said Formula (4) in presence of alkali [1]; Reacting the compound of formula 3 above, the aromatic diol of formula 4 above, and the compound of formula 5 [2]; Reacting the compound of formula 3 with the aromatic diol of formula 4, followed by reacting with a compound having a hydroxyl group of formula [3]; Reacting the compound of formula 3 above with the aromatic diol of formula 4 above, and then reacting it with the compound of formula 7 [4]; Reacting the compound of Formula 3 with the aromatic diol of Formula 4, followed by reacting it with a compound having the following Formula 5 and a compound having a hydroxyl group of the following Formula [5]; And reacting the compound of Formula 3 with the aromatic diol of Formula 4, followed by reacting it with the aromatic diol of Formula 4 and the compound of Formula 7 [6].
    [70]
    [71]
    [72]
    [73] In Chemical Formulas 5, 6, and 7, above,
    [74] Ar 4 is as mentioned above,
    [75] Ar 5 and Ar 6 independently represent a divalent aromatic group,
    [76] W represents a halogen atom or a nitro group,
    [77] j represents an integer of 1 to 5,000.
    [78] The divalent aromatic group usually has 6 to 24 carbohydrates, preferably 6 to 18 carbon atoms, and may be substituted with a substituent such as a methyl group, a phenyl group or a halogen atom. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and the like.
    [79] Examples of the halogen atom (W) used in the above Formula 5 or Formula 7 include a fluorine atom, a chlorine atom, a bromine atom and the like.
    [80] Representative examples of the compound of formula 5 include 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 2,4-difluorobenzophenone, 4,4'-dibromobenzophenone, 3 , 4'-dinitrobenzophenone, 4,4'-difluorodiphenylsulfone, 4,4'-difluoro-3,3'-disulfodiphenylsulfone, 4,4'-difluoro-3, 3'-disulfodiphenylsulfone dipotassium salt, 4,4'-difluoro-3,3'-disulfodiphenylsulfone disodium salt, 4,4'-dichlorodiphenylsulfone, 4,4'-dichloro- 3,3'-disulfodiphenylsulfone, 4,4'-dichloro-3,3'-disulfodiphenylsulfone dipotassium salt, 4,4'-dichloro-3,3'-disulfodiphenylsulfone disodium salt, 4,4'-dibromodiphenylsulfone, 4,4'-dinitrodiphenylsulfone, 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile, hexafluorobenzene, decafluorobiphenyl, Octafluoronaphthalene and the like. Among these, two or more types can be used.
    [81] Among them, 4,4'-difluorobenzophenone, 4,4'-difluorodiphenylsulfone, 4,4'-dichlorodiphenylsulfone, decafluorobiphenyl and the like are preferable.
    [82] Examples of Ar 5 in the compound having a hydroxyl group of formula 6 include divalent aromatic groups as mentioned above. Ar 5 may be the same as or different from Ar 3 , Ar 4 and the like. Examples of the compound of the formula (6) having a hydroxyl group are not particularly limited, but polyphenylene ether, polyether ketone, polyether-ether ketone, polysulfone, polyether sulfone, polyphenylene having hydroxyl groups at its ends Aromatic polymers such as sulfides. Among these, two or more types can be used.
    [83] Examples of Ar 6 in the compound of formula 7 include divalent aromatic groups as mentioned above. Ar 6 may be the same as or different from Ar 3 , Ar 4 , Ar 5, and the like. Examples of the compound of Formula 7 are not particularly limited, but polyphenylene ether, polyether ketone, polyether-ether ketone, polysulfone, polyether sulfone, polyphenylene sulfide and the like having a halogen atom or a nitro group at its terminal Aromatic polymers. Among these, two or more types can be used.
    [84] The number average molecular weight of the compound of formula 6 and the compound of formula 7 mentioned above is preferably 2,000 to 500,000, more preferably 5,000 to 200,000, most preferably 8,000 to 100,000. When the number average molecular weight is less than 2,000, the film strength or the heat resistance of the block copolymer may decrease, and when the number average molecular weight is 500,000 or more, the solubility may decrease.
    [85] The polymerization reaction can be carried out according to known methods for carrying out the reaction in the presence of alkali. As the alkali, a known alkali having polymerization activity can be used in the present invention. Preferably, alkali metal hydroxide, alkali metal carbonate, etc. are used as alkali. Among these, potassium carbonate is used preferably.
    [86] In addition, the polymerization reaction can be carried out in a molten state without using a solvent, but is preferably carried out in a solvent. Solvents that can be used include aromatic hydrocarbon solvents, ether solvents, ketone solvents, amide solvents, sulfone solvents, sulfoxide solvents, and the like, but dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, N, N-dimethylacetic Amide, N-methylpyrrolidone, N, N-dimethylimidazolidinone, diphenylsulfone and the like are preferably used.
    [87] The reaction temperature of a polymerization reaction is 20-300 degreeC normally, Preferably it is 50-200 degreeC. In terms of heat resistance and film strength, the number average molecular weight of the polymer is preferably 5,000 to 100,000, more preferably 10,000 to 500,000.
    [88] After completion of the reaction, the polymer electrolyte can be taken, for example, by dropwise addition of the reaction solution into the non-solvent of the polymer electrolyte to form a precipitate which is filtered or decanted. Examples of nonsolvents include methanol, water, hydrochloric acid, diethyl ether, acetone, and the like. These can be used individually or in mixture of 2 or more types as needed. Water, methanol, a mixture of hydrochloric acid and methanol, a mixture of hydrochloric acid and water, and the like are particularly preferably used.
    [89] Moreover, a substituent can be introduce | transduced into an aromatic ring after superposition | polymerization. For example, the obtained polymer electrolyte may be reacted with concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like to introduce sulfonic acid groups.
    [90] In the above-mentioned manner, the polymer electrolyte of the present invention having the polymerized unit of the formula (1) in the main chain can be prepared, and when the polymer electrolyte of the present invention is used as a separator of cell chemistry devices such as lithium batteries, fuel cells, etc. Used in form. There is no particular limitation on the method of converting the polymer electrolyte of the present invention to a film, but a method of preparing the film in a solution state (solvent casting process) is preferable.
    [91] As a specific example of the solution casting method, a method of producing a membrane is obtained by dissolving a polymer electrolyte in a suitable solvent, casting the solution onto a glass plate, a Teflon plate, or the like, and then removing the solvent by heating under reduced pressure, if necessary. Include.
    [92] The solvent used to prepare the membrane is not particularly limited as long as it can dissolve and subsequently remove the polymer electrolyte, but for example, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like); Chlorine solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and the like; Alcohols (eg, methanol, ethanol, propanol, etc.); Alkylene glycol monoalkyl ethers (eg ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.) are preferably used. The solvents may be used alone or in combination of two or more solvents as necessary. Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, a mixed solvent of methylene chloride and methanol are particularly preferable because of high solubility of the polymer electrolyte. .
    [93] Although the thickness of a film is not specifically limited, Preferably it is 10-200 micrometers, More preferably, it is 20-150 micrometers. If the thickness of the film is thinner than 10 mu m, the practical strength may not be sufficient, and if it is thicker than 200 mu m, the film resistance becomes large, and the characteristics of the electrochemical device tend to be insufficient. The film thickness can be controlled by the concentration of the polymer electrolyte solution and the thickness of the film on the substrate.
    [94] In addition, the membrane obtained by the above method, for example, can be washed with ion-exchanged water to remove the solvent, salt and the like contained in the membrane. The membrane is immersed in hydrochloric acid and washed with ion-exchanged water to prepare an electrolyte membrane of Formula 1 wherein X + is H + .
    [95] The ion exchange capacity (mole number of acidic groups per gram of polymer electrolyte) of the polymer electrolyte is preferably 0.5 to 3.0 meq / g, more preferably 0.8 to 1.8 meq / g. If the ion exchange capacity is lower than 0.5 meq / g, sufficient ionic conductivity cannot be obtained and the performance as a polymer electrolyte is degraded. If the ion exchange capacity is higher than 3.0 meq / g, the water resistance is lowered.
    [96] In the present invention, for the purpose of improving various physical properties of the film, plasticizers, stabilizers, mold release agents, and the like, which are usually used in polymers, can be added to the polymer electrolyte of the present invention. It is also possible to produce a complex alloy of the polymer electrolyte of the present invention with another polymer by a method such as a mixed co-casting process mixed in the same solvent. In particular, it is preferable to use an aromatic polyimide together, whereby film strength, water resistance and the like can be improved.
    [97] For the purpose of improving the ion conductivity and the like, a method including adding a low molecular weight electrolyte, an acid compound or other polymer electrolyte or impregnating a solvent is known. In fuel cell applications, it is also known to add inorganic particulates or organic particulates as water retention agents in order to facilitate water control. All these known methods can also be used as long as they do not contradict the object of the present invention.
    [98] In addition, in the present invention, for the purpose of improving the mechanical strength of the film, the product can be crosslinked by irradiation with an electron beam, radiation or the like. It is also known to prepare a composite by impregnating a porous film or sheet (porous membrane) or to reinforce the film by mixing fibers or pulp. All these known methods can also be used as long as they do not contradict the object of the present invention.
    [99] Since the porous membrane is used to further improve the strength, flexibility and durability of the polymer electrolyte, it can be used regardless of its shape or material as long as its purpose of use is satisfied. When the porous membrane is used as a separator of a solid polymer fuel cell, its thickness is usually 1 to 100 µm, preferably 3 to 30 µm, more preferably 5 to 20 µm, and the pore diameter is usually 0.01 to 10 µm. Preferably, it is 0.02-7 micrometers, and a porosity is 20-98% normally, Preferably it is 30-95%. As a material of a porous film, an aliphatic polymer or a fluorine-containing polymer is preferable in view of heat resistance and reinforcing effect of mechanical strength.
    [100] Examples of aliphatic polymers include polyethylene, polypropylene, ethylene-propylene copolymers, and the like. Polyethylene referred to herein refers to ethylene polymers having a polyethylene crystal structure, examples being copolymers of ethylene with other monomers. Specifically, the copolymer of ethylene and alpha-olefin called so-called linear low density polyethylene (LLDPE) is contained. Polypropylene as referred to herein means a propylene polymer having a polypropylene crystal structure and includes commonly used propylene block copolymers, random copolymers, and the like (copolymers of ethylene and 1-butene).
    [101] As the fluorine-containing porous membrane, any thermoplastic resin having at least one carbon-fluorine bond in the molecule may be used without limitation. Usually, resins having a structure in which all or most of hydrogen atoms in aliphatic polymers are replaced by fluorine atoms are preferably used. Examples thereof include polytrifluoroethylene, polytetrafluoroethylene, polychlorotrifluoroethylene, poly (tetrafluoroethylene-hexafluoropropylene), poly (tetrafluoroethylene-perfluoroalkyl ether), poly Vinylidene fluoride and the like. Among them, polytetrafluoroethylene and poly (tetrafluoroethylene-hexafluoropropylene) are preferable, and polytetrafluoroethylene is particularly preferable. The average molecular weight of these fluororesins is preferably 100,000 or more in consideration of excellent mechanical strength.
    [102] The manufacturing method of the composite material which has a porous film is not specifically limited. As an example, a method of impregnating a porous membrane into a polymer electrolyte solution, taking it out, and then removing the solvent to obtain a composite membrane, a method of applying the polymer electrolyte solution onto the porous membrane, and then removing the solvent to obtain a composite membrane, and depressurizing the porous membrane Contact with the polymer electrolyte solution, and then applying atmospheric pressure to impregnate the solution into the pores of the porous membrane, and remove the membrane from the solvent to obtain a composite membrane.
    [103] The fuel cell according to the invention is described next.
    [104] The fuel cell of the present invention comprises a membrane-electrode assembly comprising a positive electrode and a negative electrode including a gas diffusion electrode containing a catalyst, and a polymer electrolyte positioned between the positive electrode and the negative electrode, hydrogen gas, air or oxygen. It is obtained by inserting into a battery by inserting it between separators including a conductive carbon plate having grooves serving as passages of gas.
    [105] The catalyst is not particularly limited as long as it can activate a redox reaction of hydrogen or oxygen, and may be a known product. Preferred products are platinum fine powders or platinum alloy fine powders. The fine powder is often contained in granular or fibrous carbon such as activated carbon or graphite.
    [106] The gas diffusion layer in the gas diffusion electrode may be a known material, preferably a porous carbon nonwoven fabric or carbon paper.
    [107] The manufacturing method of the membrane-electrode assembly may be a known method. Examples thereof include a method of forming two plates having a gas diffusion layer and a catalyst bonded thereto, inserting a polymer electrolyte membrane therebetween to bond therebetween, and bonding the catalyst to the polymer electrolyte membrane, and the obtained conjugate is a gas diffusion layer. There is a method of inserting in between.
    [108] Example
    [109] The present invention is described below with reference to Examples, but the present invention should not be construed as being limited by the Examples.
    [110] How to measure
    [111] (1) 10% weight loss temperature
    [112] A 10% weight loss temperature is measured using a thermal mass spectrometer (TGA-50, manufactured by Shimadzu Corporation) under an elevated temperature rate of 10 ° C. per minute under a nitrogen atmosphere.
    [113] (2) molecular weight (Mn)
    [114] Using a N, N-dimethylacetamide solvent containing 0.05M LiBr, the polystyrene-reduced number average molecular weight was measured using a GPC [HLC-8020, equipped with a UV detector [UV-8010, manufactured by TOSOH Corporation]. Manufacturer: Doso Corp.].
    [115] (3) ion exchange capacity
    [116] After impregnating the polymer electrolyte film in 0.1N NaOH aqueous solution, the aqueous solution is neutralized titrated with 0.1N HCl aqueous solution, and the value of the ion exchange capacity is calculated.
    [117] (4) proton conductivity
    [118] SI 1260 High Performance Impedance / Gain-Phase Analyzer (manufacturer: Solartoron Company) and 1287-type constant potentiometers (ELECTROCHEMICAL INTERFACE), manufacturer: Solarton Corporation ], The proton conductivity is measured by the AC impedance method in a constant temperature oven at 80 ° C. and 90% RH.
    [119] Synthesis Example 1
    [120] Synthesis Example of Disulfonylimide
    [121] An acetone solution of 1,3-benzenedisulfonyl chloride is added dropwise to an aqueous ammonium chloride solution at room temperature. During the addition, the pH is adjusted to 7 using aqueous sodium hydroxide solution. The precipitate is filtered off and recrystallized from ethanol to give 1,3-benzenedisulfonamide. The structure is confirmed by 1 H-NMR and IR.
    [122] Next, 4-fold molar NaH is added to a tetrahydrofuran solution of 1,3-benzenedisulfonamide. Then, 2 moles of pentafluorobenzenesulfonyl chloride is slowly added to the mixture and reacted at 60 ° C. The reaction is filtered and the filtrate is concentrated. The residue is dissolved in methanol and combined with a methanol solution of KOH to give the desired sulfonylimide (which may be referred to as BSI 1) in the form of potassium salt. The product is recrystallized from a mixed solvent of acetone and methanol.
    [123]
    [124] 1 H-NMR in ppm: 7.52, 7.64, 7.71; 19 F-NMR in ppm: -129, -143, -154.
    [125] Example 1 (Alternative Copolymer Containing BSI 1 and Biphenol)
    [126] 0.500 g of BSI 1, 0.121 g of 4,4'-dihydroxybiphenyl, 94 mg of potassium carbonate and 3 mL of dimethylsulfoxide (hereinafter referred to as DMSO) are placed under nitrogen and heated with stirring at 100 ° C. for 18 hours. . The reaction solution is added dropwise to 10% aqueous hydrochloric acid solution. The precipitate obtained is collected by filtration, washed with methanol and dried at 60 ° C. under reduced pressure to yield 0.48 g of a disulfonylimide polymer in the form of a white solid. Table 1 shows the molecular weight measurement results (conversion to polystyrene).
    [127] The obtained polymer was dissolved in DMAc at a concentration of about 10% by weight, cast in a glass dish, dried at 80 ° C. to remove the solvent, thereby preparing a colorless transparent rigid film having a thickness of 105 μm. The proton conductivity of the film is measured by alternating current under conditions of temperature of 80 ° C. and humidity of 90%. In addition, the ion exchange capacity is measured by a titration method. The results are shown in Table 1.
    [128] Example 2 (random copolymer comprising BSI 1, bisphenol A and decafluorobiphenyl)
    [129] 0.773 g of BSI 1, 0.435 g of bisphenol A, 0.334 g of decafluorobiphenyl, 0.290 g of calcium carbonate and 7.5 mL of DMSO are placed under a stream of nitrogen and heated with stirring at 80 ° C. for 30 hours. After completion of the reaction, the reaction solution is added dropwise to 10% methanolic hydrochloric acid solution. The precipitate obtained is collected by filtration, washed with methanol and dried at 60 ° C. under reduced pressure to give 0.93 g of a disulfonylimide polymer in the form of a light brown solid. The molecular weight measurement results and the 10% weight loss temperature results are shown in Table 1.
    [130] The polymer obtained was converted to a film in the same manner as in Example 1 to prepare a clear pale brown rigid film having a thickness of 36 탆. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [131] Example 3 (block copolymer prepared by reacting a disulfonylimide oligomer having a terminal fluorine group and consisting of BSI 1 and bisphenol A with a polyether sulfone having a terminal hydroxy group)
    [132] 4,4'-dihydroxydiphenylsulfone and 4,4'-dichlorodiphenylsulfone were polycondensed at a temperature of 200 to 290 DEG C with diphenylsulfone as a solvent in a molar ratio of 16:15 to give a terminal hydroxy group. A polyether sulfone oligomer having a molecular weight (molecular weight (Mn): 2.0 × 10 4 ) is synthesized.
    [133] 1.267 g of BSI 1, 0.310 g of bisphenol A, 0.220 g of potassium carbonate and 6 mL of DMAc are placed under a stream of nitrogen in a flask and heated with stirring at 80 ° C. for 12 hours. Subsequently, 1.00 g of a polyether sulfone oligomer having a terminal hydroxy group synthesized above is added, and the reaction is continued at 80 ° C. for 20 hours. After the reaction was completed, the polymer was recovered in the same manner as in Example 2 to obtain 2.01 g of a block copolymer having a disulfonylimide block in the form of a pale yellow solid. The molecular weight measurement results and the 10% weight loss temperature results are shown in Table 1.
    [134] The polymer obtained was converted to a film in the same manner as in Example 1 to prepare a translucent colorless rigid film having a thickness of 147 μm. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [135] Synthesis Example 2
    [136] Synthesis Example of Disulfonylimide
    [137] An acetone solution of pentafluorobenzenesulfonyl chloride is added dropwise to an aqueous ammonium chloride solution at room temperature. During the addition, the pH is adjusted to 7 using aqueous sodium hydroxide solution. The precipitate is filtered off and recrystallized from toluene to give pentafluorobenzenesulfonamide. The structure is confirmed by 1 H-NMR, 19 F-NMR and IR.
    [138] A 2-fold molar NaH is added to a tetrahydrofuran solution of pentafluorobenzenesulfonamide. Then, an equimolar amount of pentafluorobenzenesulfonyl chloride is slowly added to the mixture and reacted at 60 ° C. The reaction is filtered and the filtrate is concentrated. The residue is dissolved in methanol and combined with a methanol solution of KOH to give the desired sulfonylimide (which may be referred to as BSI 2) in the form of potassium salt. The product is recrystallized from a mixed solvent of acetone and methanol.
    [139] 19 F-NMR in ppm: -130, -142, -154.
    [140]
    [141] Example 4 (Alternative Copolymer Containing BSI 2 and Hydroquinone)
    [142] 2.577 g of BSI 2, 0.551 g of hydroquinone, 0.795 g of calcium carbonate and 12 mL of dimethylsulfoxide are placed under a stream of nitrogen and heated with stirring at 80 ° C. for 19 hours in a flask. After the reaction was completed, the polymer was recovered in the same manner as in Example 2 to obtain 3.00 g of a disulfonylimide polymer in the form of a brown solid. The molecular weight measurement results and the 10% weight loss temperature results are shown in Table 1.
    [143] The obtained polymer was converted to a film in the same manner as in Example 1 to prepare a translucent pale brown rigid film having a thickness of 54 mu m. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [144] Example 5 (Alternative Copolymer Containing BSI 2 and 4,4'-Dihydroxy-3,3'-diphenylbiphenyl)
    [145] 2.000 g of BSI 2, 1.313 g of 4,4'-dihydroxy-3,3'-diphenylbiphenyl, 0.563 g of calcium carbonate and 8 mL of dimethylsulfoxide were placed in a flask under a nitrogen stream and stirred at 80 ° C. for 20 hours. While heating. After the reaction was completed, the polymer was recovered in the same manner as in Example 2 to obtain 3.00 g of a disulfonylimide polymer in the form of a white solid. The molecular weight measurement results and the 10% weight loss temperature results are shown in Table 1.
    [146] The obtained polymer was dissolved in a mixed solvent of methylene chloride and methanol at a concentration of about 10% by weight in a volume ratio of 9: 1, cast on a glass plate, dried at room temperature to remove the solvent, and a semi-transparent colorless stiffness of 58 µm in thickness. Prepare a film. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [147] Example 6 (block copolymer prepared by reacting a disulfonylimide oligomer having a terminal fluorine group with BSI 2 and hydroquinone with a polyether sulfone having a terminal hydroxy group)
    [148] 0.500 g of BSI 2, 0.105 g of hydroquinone, 0.140 g of calcium carbonate and 4 mL of DMSO are placed in a flask under a stream of nitrogen and heated with stirring at 80 ° C. for 15 hours. Then, 0.150 g of polyether sulfone oligomer having a terminal hydroxy group is added similarly as in Example 3, and the reaction is continued for 24 hours at 80 ° C. After the reaction was completed, the polymer was recovered in the same manner as in Example 2 to give 0.57 g of a block copolymer having a disulfonylimide block in the form of a brown solid. The molecular weight measurement results and the 10% weight loss temperature results are shown in Table 1.
    [149] The obtained polymer was converted to a film in the same manner as in Example 1 to prepare a translucent pale brown rigid film having a thickness of 26 μm. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [150] Example 7 (block copolymer prepared by reacting a disulfonylimide oligomer having a terminal fluorine group with BSI 2 and hydroquinonesulfonic acid with a polyether sulfone having a terminal hydroxy group)
    [151] 2.000 g of BSI 2, 0.780 g of potassium hydroquinonesulfonate, 0.563 g of calcium carbonate and 17 mL of DMSO are placed under a nitrogen stream and heated with stirring at 80 ° C. for 6 hours. Then, 3.352 g of a polyether sulfone oligomer having a terminal hydroxy group is added similarly as in Example 3, and the reaction is continued at 80 ° C. for 15 hours. After the reaction was completed, the polymer was recovered in the same manner as in Example 2 to give 6.00 g of a block copolymer having disulfonylimide blocks in the form of a brown solid. The molecular weights are listed in Table 1.
    [152] The obtained polymer was converted to a film in the same manner as in Example 5 to prepare a translucent pale brown rigid film having a thickness of 27 μm. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [153] Example 8 (block copolymer prepared by reacting a disulfonylimide oligomer having a terminal fluorine group with BSI 2 and hydroquinonesulfonic acid with a polyether sulfone having a terminal hydroxy group)
    [154] 5.153 g of BSI 2, 1.940 g of potassium hydroquinonesulfonate, 1.589 g of calcium carbonate and 40 mL of DMSO are placed under a nitrogen stream and heated with stirring at 80 ° C. for 6 hours. Then, 10.800 g of polyether sulfone oligomer having a terminal hydroxy group is added similarly as in Example 3, and the reaction is continued at 80 ° C. for 10 hours. After the reaction was completed, the polymer was recovered in the same manner as in Example 2 to give 14.40 g of a block copolymer having disulfonylimide blocks in the form of a brown solid. The molecular weight measurement results and the 10% weight loss temperature results are shown in Table 1.
    [155] The obtained polymer was converted to a film in the same manner as in Example 5 to prepare a translucent pale brown rigid film having a thickness of 45 μm. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [156] Example 9 (Polymer Electrolyte Membrane Combining the Polymer Electrolyte Obtained in Example 8 with a Polytetrafluoroethylene Porous Membrane)
    [157] The polymer obtained in Example 8 was dissolved in a mixed solvent of methylene chloride and methanol at a volume ratio of about 9: 1 at a concentration of about 9: 1 to fix a polytetrafluoroethylene porous membrane (film thickness: 15 μm, porosity) fixed on a glass plate. : 90%, pore diameter: 3.0 mu m), dried at room temperature to remove the solvent to prepare a translucent light brown rigid film having a thickness of 57 mu m. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [158] Comparative Example 1
    [159] 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybiphenyl and 4,4'-dichlorodiphenylsulfone, together with potassium carbonate in a molar ratio of 7: 3: 10, diphenylsulfone It polycondenses at a temperature of 200-290 degreeC as a solvent. The obtained polymer is sulfonated with concentrated sulfuric acid to give a random copolymer in which sulfonic acid groups are introduced into biphenyl units.
    [160] The polymer obtained was converted to a film in the same manner as in Example 1 to prepare a colorless transparent rigid film having a thickness of 42 μm. The result of measuring the proton conductivity and ion exchange capacity of the film is shown together in Table 1.
    [161]
    [162] Example 10 (evaluation of characteristics of fuel cell)
    [163] The polymer electrolyte obtained in Example 9 was inserted between carbon cloths having a carbonaceous platinum film to obtain a membrane-electrode assembly (MEA). A fuel cell is manufactured by inserting the MEA between fuel cell separators.
    [164] To activate the fuel cell, humidified hydrogen is supplied to one side of the cell and humidified air to the other side. While maintaining the operating temperature at 80 ° C, the characteristics of the fuel cell are evaluated. The relationship between the current density and the cell voltage is shown in Table 2.
    [165]
    [166] Since the polymer electrolyte of the present invention provides a film having excellent proton conductivity, excellent heat resistance and excellent strength, it is suitable for proton conductive membranes for fuel cells. In addition, since the electrolyte contains little crosslinking structure and is soluble in a solvent, it can be easily converted into a film and has excellent recyclability. In addition, when composed of porous membranes, they exhibit a high degree of proton conductivity.
    权利要求:
    Claims (21)
    [1" claim-type="Currently amended] A polymer electrolyte, characterized in that it has a structural unit of formula 1 in the main chain.
    Formula 1

    In Formula 1 above,
    Ar 1 and Ar 2 independently represent a divalent aromatic group,
    m is an integer from 0 to 3,
    X + represents an ion selected from hydrogen ions, alkali metal ions and ammonium ions.
    [2" claim-type="Currently amended] 2. The polymer electrolyte of claim 1, further comprising a polymerized unit of formula 2 in the main chain.
    Formula 2

    In Formula 2 above,
    Ar 3 represents a divalent aromatic group.
    [3" claim-type="Currently amended] 3. The polymer electrolyte of claim 2, further comprising polymerized units of formula 2a different from formula 2 in the main chain.
    Formula 2a

    In Formula 2a above,
    Ar 4 represents a divalent aromatic group.
    [4" claim-type="Currently amended] The polymer electrolyte of claim 1, wherein the divalent aromatic group is at least one group selected from the following structures.

    In the above formula,
    R 1 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group, an acetyl group, a benzoyl group, a nitrile group, a sulfonic acid, a carboxylic acid, a phosphonic acid or a halogen atom Represents;
    a represents an integer of 0 to 4;
    b and c represent integers from 0 to 4, and the sum of b and c is an integer from 0 to 6;
    When there are a plurality of R 1 , they may be the same or different;
    Y is a direct bond, -O-, -S-, -C (O)-, -SO 2 -or -C (R 3 ) 2- (wherein R 3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, Halogenated alkyl group or aryl group having 1 to 10 carbon atoms, and two R 3 's may be the same or different or may form a ring;
    When there are a plurality of Y's, they may be the same or different.
    [5" claim-type="Currently amended] The polymer electrolyte of claim 1, wherein Ar 1 is tetrafluorophenylene.
    [6" claim-type="Currently amended] The polymer electrolyte of claim 1, wherein m is 0 or 1.
    [7" claim-type="Currently amended] The polymer electrolyte according to claim 2, wherein the polymer electrolyte is a block copolymer comprising a block having a polymer unit of Formula 1 and a polymer unit of Formula 2.
    [8" claim-type="Currently amended] A process for preparing the polymer electrolyte according to claim 2, characterized in that the compound of formula 3 is polymerized with the aromatic diol of formula 4.
    Formula 3

    Formula 4

    In Formula 3 and Formula 4 above,
    Ar 1 , Ar 2 , Ar 3 , m and X + are as defined above,
    Z represents a halogen atom or a nitro group.
    [9" claim-type="Currently amended] A method of preparing a polymer electrolyte according to claim 3, characterized by reacting a compound of Formula 3, an aromatic diol of Formula 4, and a compound of Formula 5.
    Formula 3

    Formula 4

    Formula 5

    In Formula 3, Formula 4 and Formula 5 above,

    Ar 1 , Ar 2 , Ar 3 , Ar 4 , m, X + and Z are as defined above,
    W represents a halogen atom or a nitro group.
    [10" claim-type="Currently amended] A process for preparing a polymer electrolyte according to claim 2 characterized by polymerizing a compound of formula 3 with an aromatic diol of formula 4 and then reacting a compound having a hydroxyl group of formula 6.
    Formula 3

    Formula 4

    Formula 6

    In Formula 3, Formula 4 and Formula 6 above,
    Ar 1 , Ar 2 , Ar 3 , m, X + and Z are as defined above,
    Ar 5 represents a divalent aromatic group,
    j represents an integer of 1 to 5,000.
    [11" claim-type="Currently amended] A process for preparing a polymer electrolyte according to claim 2 characterized by polymerizing a compound of formula 3 with an aromatic diol of formula 4 and then reacting a compound having a hydroxyl group of formula 7.
    Formula 3

    Formula 4

    Formula 7

    In the above Formula 3, Formula 4 and Formula 7,
    Ar 1 , Ar 2 , Ar 3 , m, X + , Z and j are as defined above,
    Ar 6 represents a divalent aromatic group,
    W represents a halogen atom or a nitro group.
    [12" claim-type="Currently amended] A polymer electrolyte membrane, characterized in that it comprises a polymer electrolyte according to any one of claims 1 to 7.
    [13" claim-type="Currently amended] The polymer electrolyte composite membrane according to any one of claims 1 to 7, wherein the polymer electrolyte and the porous membrane are combined.
    [14" claim-type="Currently amended]
    The polymer electrolyte composite membrane according to claim 13, wherein the porous membrane comprises an aliphatic polymer or a fluorine-containing polymer.
    [15" claim-type="Currently amended] The polymer electrolyte composite membrane according to claim 14, wherein the porous membrane comprises polytetrafluoroethylene.
    [16" claim-type="Currently amended] A fuel cell comprising the polymer electrolyte membrane according to any one of claims 12 to 15.
    [17" claim-type="Currently amended] Disulfonylimide compound of the formula

    In Formula 3a above,
    Ar 1 , Ar 2 , X + and Z are as defined above,
    n represents the integer of 1-3.
    [18" claim-type="Currently amended] 18. The disulfonylimide compound of claim 17, wherein n is 1.
    [19" claim-type="Currently amended] 18. The disulfonylimide compound of claim 17, wherein n is 2 or 3.
    [20" claim-type="Currently amended] Reacting a sulfonamide compound of formula (8) with a bissulfonyl chloride compound of formula (9) or a sulfonyl chloride compound of formula (10) with a bissulfonamide compound of formula (11) The method for producing the disulfonylimide compound according to any one of claims 17 to 19.
    Formula 8

    Formula 9

    Formula 10

    Formula 11

    In Formula 8, Formula 9, Formula 10, and Formula 11 above,
    Ar 1 , Ar 2 and Z are as defined above.
    [21" claim-type="Currently amended] Reacting a bissulfonyl chloride compound of formula (9) with a bissulfonamide compound of formula (11) with a sulfonyl chloride compound of formula (10) or a sulfonamide compound of formula (8) , The method for producing a disulfonylimide compound according to claim 19.
    Formula 8

    Formula 9

    Formula 10

    Formula 11

    In Formula 8, Formula 9, Formula 10, and Formula 11 above,
    Ar 1 , Ar 2 and Z are as defined above.
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    同族专利:
    公开号 | 公开日
    EP1248313A2|2002-10-09|
    CA2379277A1|2002-10-04|
    US6939646B2|2005-09-06|
    US20020187377A1|2002-12-12|
    DE60225204T2|2008-06-12|
    DE60225204D1|2008-04-10|
    EP1248313A3|2006-04-05|
    JP2003173799A|2003-06-20|
    EP1248313B1|2008-02-27|
    CA2379277C|2010-02-09|
    KR100810922B1|2008-03-10|
    JP3969077B2|2007-08-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-04-04|Priority to JP2001105596
    2001-04-04|Priority to JPJP-P-2001-00105596
    2001-09-27|Priority to JPJP-P-2001-00297814
    2001-09-27|Priority to JP2001297814
    2001-12-11|Priority to JP2001376904A
    2001-12-11|Priority to JPJP-P-2001-00376904
    2002-04-02|Application filed by 스미또모 가가꾸 고교 가부시끼가이샤
    2002-10-19|Publication of KR20020079424A
    2008-03-10|Application granted
    2008-03-10|Publication of KR100810922B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2001105596|2001-04-04|
    JPJP-P-2001-00105596|2001-04-04|
    JPJP-P-2001-00297814|2001-09-27|
    JP2001297814|2001-09-27|
    JP2001376904A|JP3969077B2|2001-04-04|2001-12-11|Polymer electrolyte and method for producing the same|
    JPJP-P-2001-00376904|2001-12-11|
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