JP4135728B2 - Sulfonic acid group-containing polyarylene ether compound and method for producing the same, resin composition containing sulfonic acid group-containing polyarylene ether compound, polymer electrolyte membrane, electrolyte membrane / electrode composite, fuel cell, and adhesive - Google Patents

Description

  The present invention relates to a polymer electrolyte membrane, and a polyarylene ether-based compound containing a sulfonic acid group useful as an adhesive for an electrolyte membrane / electrode composite, a production method thereof, a resin composition containing the same, a polymer electrolyte membrane, The present invention relates to an electrolyte membrane / electrode composite, a fuel cell, and an adhesive.

  As an example of an electrochemical device using a polymer solid electrolyte as an ionic conductor instead of a liquid electrolyte, a water electrolysis tank and a fuel cell can be mentioned. The polymer electrolyte membrane and membrane / electrode composite resin used in these materials have good proton conductivity as a cation exchange membrane and are chemically, thermally, electrochemically and mechanically sufficient. What is stable is required. For this reason, perfluorocarbon sulfonic acid membranes, typically “Nafion (registered trademark)” manufactured by DuPont, have been used as long-term usable products. However, if the perfluorocarbon sulfonic acid membrane is to be operated at a temperature of 100 ° C. or higher, the moisture content of the membrane is drastically lowered and the membrane is also softened. Further, in a fuel cell using methanol as a fuel, power generation performance is reduced due to methanol permeation in the membrane, and sufficient fuel cell performance cannot be exhibited. Furthermore, it is pointed out as an obstacle to the establishment of fuel cell technology that the cost of the membrane is too high even in a fuel cell that operates near 80 ° C. using hydrogen as fuel. The same problem has been pointed out when perfluorocarbon sulfonic acid resin is used as the adhesive resin.

In order to overcome such drawbacks, various polymer electrolyte membranes in which a sulfonic acid group is introduced into a non-fluorinated aromatic ring-containing polymer have been studied. As the polymer skeleton, polyarylene ether compounds such as polyarylene ether ketones and polyarylene ether sulfones can be considered as promising structures in consideration of heat resistance and chemical stability. (For example, see Non-Patent Document 1), sulfonated polyether ether ketone (for example, see Patent Document 1), and the like have been reported. In these, a sulfonic acid group is introduced by reacting a polymer with a sulfonating agent. On the other hand, a method for directly obtaining a sulfonated polymer by polymerization using a sulfonated monomer has also been reported (see, for example, Patent Documents 2 to 4). However, these aromatic hydrocarbon-based membranes are also required to have even better proton conductivity. In addition, when used as an adhesive resin in the production of an electrolyte membrane / electrode complex, a resin having stronger bonding properties with a polymer electrolyte membrane is required.
JP-A-6-93114 US Patent Application Publication No. 2002/0091225 International Publication No. 2003/095509 Specification International Publication No. 2004/033534 Specification Journal of Membrane Science (Netherlands) 1993, 83, p. 211-220

  An object of the present invention is to obtain a polymer material having excellent ion conductivity, heat resistance, processability and dimensional stability, and useful as a polymer electrolyte membrane and a resin for bonding an electrolyte membrane / electrode assembly. It is in.

  In the present invention, the following general formula (1),

(However, X is hydrogen or a monovalent cation species, Y is a sulfone group or a ketone group, and n is an arbitrary integer of 2 or more.)
It relates to a sulfonic acid group-containing polyarylene ether compound containing a constituent represented by

  The sulfonic acid group-containing polyarylene ether compound of the present invention has the following general formula (2),

(However, n represents an arbitrary integer of 2 or more.)
It is preferable to contain further the structural component shown by these.

  The sulfonic acid group content in the sulfonic acid group-containing polyarylene ether compound of the present invention is preferably in the range of 0.3 to 5.0 meq / g.

  The sulfonic acid group-containing polyarylene ether compound of the present invention has the following general formula (3),

(However, o represents an arbitrary integer of 0 or more.)
A terminal dihydroxy compound represented by the formula (1), comprising a plurality of components having different o and having an average composition in the range of 1 < o ≦ 10 as a part of the monomer component preferable.

  In the sulfonic acid group-containing polyarylene ether compound of the present invention, the glass transition temperature is preferably in the range of 130 ° C to 220 ° C.

The present invention also relates to a resin composition containing the sulfonic acid group-containing polyarylene ether compound in a range of 50% by mass to less than 100% by mass .

  The present invention also relates to a polymer electrolyte membrane containing the sulfonic acid group-containing polyarylene ether compound.

The present invention also relates to a polymer electrolyte membrane containing the above resin composition.
The present invention also relates to an electrolyte membrane / electrode composite containing the above polymer electrolyte membrane and an electrode.

The present invention also relates to a fuel cell containing the above electrolyte membrane / electrode composite.
The fuel cell of the present invention can preferably use methanol as a fuel.

  The present invention also relates to an adhesive containing the sulfonic acid group-containing polyarylene ether compound.

The present invention further provides a production method for obtaining the sulfonic acid group-containing polyarylene ether compound, wherein the sulfonic acid group-containing polyarylene ether compound is represented by the following general formula ( 4 ):

(However, n represents an arbitrary integer of 2 or more.)
The present invention relates to a method for producing a sulfonic acid group-containing polyarylene ether compound obtained by polymerization by an aromatic nucleophilic substitution reaction using the compound represented by formula (1) as at least one monomer component.

  The present invention further relates to a method for producing a polymer electrolyte membrane containing the sulfonic acid group-containing polyarylene ether compound, wherein a solution containing the sulfonic acid group-containing polyarylene ether compound and a solvent is cast. The present invention relates to a method for producing a polymer electrolyte membrane, comprising a step of casting so as to have a thickness in the range of 10 to 1500 μm and a step of drying the cast solution.

  The polymer material showing outstanding performance as a polymer electrolyte used in fuel cells, etc., excellent in ion conductivity, heat resistance, processability and dimensional stability by the sulfonic acid group-containing polyarylene ether compound of the present invention Can be provided. The sulfonic acid group-containing polyarylene ether compound of the present invention is also useful as an adhesive resin for an electrolyte membrane / electrode assembly exhibiting good bonding properties with a polymer electrolyte membrane.

  The present invention relates to a specific polyarylene ether compound in which a sulfonic acid group is introduced on an aromatic ring, and is excellent in ion conductivity, heat resistance, processability and dimensional stability, and particularly useful as an ion conductive membrane About. The sulfonic acid group-containing polyarylene ether compound of the present invention contains a structural unit represented by the following general formula (1) in the molecular chain.

(Where Y is a sulfone group or ketone group, X is hydrogen or a monovalent cation species, and n is an arbitrary integer of 2 or more).

  In the general formula (1), examples of the monovalent cation species for X include monovalent metal salts such as sodium and potassium, salts with organic base compounds such as ammonium salts, and the like. The structure of the above general formula (1) is composed of 3,3′-disulfo-4,4′-dihalogenated diphenylsulfone, 3,3′-disulfo-4,4′-dihalogenated benzophenone or a derivative thereof, and a terminal hydroxyl group. It can be formed from a group-containing phenylene ether oligomer by an aromatic nucleophilic substitution reaction. Here, in the structure part comprised from a phenylene ether oligomer, n in the said General formula (1) is shown with the arbitrary integers of 2 or more. The sulfonic acid group-containing polyarylene ether compound of the present invention may contain only a single structural unit consisting of a specific single number as a structural unit represented by the general formula (1). , N may include a plurality of structural units which are a plurality of different numbers. In addition, the sulfonic acid group-containing polyarylene ether compound of the present invention may contain a structural unit represented by the general formula (1), that is, a structural unit in which n is an integer of 2 or more. A diphenyl ether unit or a diphenoxybenzene unit corresponding to the case of n = 0 or n = 1 in the structure represented by

  In order to effectively contain a sufficient amount of the sulfonic acid group in the molecular chain of the sulfonic acid group-containing polyarylene ether compound according to the present invention, the structural unit represented by the general formula (1) has an average composition n of 10 or less. It is preferable that In addition, the average composition in this specification means the number average number of bonds when n is a plurality of bonds different from each other, and can be determined by NMR or the like.

  The sulfonic acid group-containing polyarylene ether compound of the present invention includes the structure of the above general formula (1) in the polymer chain, but may consist only of the structure represented by the above general formula (1). As a component other than the structural unit having the structure represented by the general formula (1), for example, one or more of an aromatic dihydroxy compound and an aromatic dihalogenated compound may be included in the form of a copolymer. In any case, when the structural unit represented by the general formula (1) is present in the sulfonic acid group-containing polyarylene ether compound, the ionic conductivity, heat resistance, processability and dimensional stability of the compound are included. Property is improved. In the present invention, by including the structural unit of the above general formula (1) in which n is an integer of 2 or more, the flexibility of the molecular chain of the sulfonic acid group-containing polyarylene ether compound is improved. Since it is possible to express the property of excellent workability at the time of preparing an electrolyte membrane / electrode composite in use, the structural unit represented by the above general formula (1) is contained in the sulfonic acid group-containing polyarylene ether compound. Is preferably contained in an amount of 10% by mass or more, more preferably 20% by mass or more.

  As described above, in the sulfonic acid group-containing polyarylene ether compound of the present invention, it is important that the structural unit represented by the general formula (1) is contained in the polymer chain. The method for introducing the structure (1) is not particularly limited. As a general method, 4,4′-dihalogenated benzophenone and / or 4,4′-dihalogenated diphenylsulfone containing a sulfonic acid group or a sulfonic acid group derivative capable of giving the above general formula (1) and a terminal are used. It can be synthesized by an aromatic nucleophilic substitution reaction using a hydroxyl group-containing phenylene ether oligomer as at least part of the monomer component.

  Specific examples of 4,4′-dihalogenated benzophenone and / or 4,4′-dihalogenated diphenylsulfone containing sulfonic acid groups or sulfonic acid group derivatives include 3,3′-disulfo-4,4′-dichloro Diphenyl sulfone, 3,3′-disulfo-4,4′-difluorodiphenyl sulfone, 3,3′-disulfo-4,4′-dichlorobenzophenone, 3,3′-disulfo-4,4′-difluorobenzophenone, and Examples thereof include those in which those sulfonic acid groups are converted to salts with monovalent cation species. Examples of the monovalent cation species include, but are not limited to, sodium, potassium, other metal species, various amines, and the like.

  The sulfonic acid group-containing polyarylene ether-based compound of the present invention preferably further includes a structural unit represented by the following general formula (2) in addition to the structure represented by the general formula (1).

(However, n is represented by an arbitrary integer of 2 or more.)
The sulfonic acid group-containing polyarylene ether compound of the present invention may contain only a single structural unit in which n is a specific single number as the structural unit represented by the general formula (2). , N may include a plurality of structural units which are a plurality of different numbers.

  Since the proportion of the phenylene ether oligomer in the structural unit represented by the general formula (2) is larger than that of the structural unit represented by the general formula (1), the sulfonic acid group-containing polyarylene ether compound of the present invention When the compound contains a structural unit represented by the general formula (2), an effect that good flexibility is imparted by the molecular chain of the compound is exhibited. In addition, when the sulfonic acid group-containing polyarylene ether compound of the present invention includes both the structural units represented by the general formula (1) and the general formula (2), If the total of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is contained in all the structural units in an amount of 40% by mass or more, a sulfonic acid group having excellent flexibility. It is preferable at the point from which a containing polyarylene ether type compound is obtained, and if it is 60 mass% or more, it is more preferable.

  The method for introducing the structural unit represented by the general formula (2) in the sulfonic acid group-containing polyarylene ether compound of the present invention is not particularly limited. As a general method, an aromatic using 2,6-dihalogenated benzonitrile and a terminal hydroxyl group-containing phenylene ether oligomer which can give the structural unit represented by the general formula (2) as at least a part of the monomer component Examples include a method of synthesis by a nucleophilic substitution reaction.

  Examples of 2,6-dihalogenated benzonitrile include 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and the like.

In the aromatic nucleophilic substitution reaction for obtaining the sulfonic acid group-containing polyarylene ether compound of the present invention, the above-mentioned terminal hydroxyl group-containing compound which can give the structural unit represented by the general formulas (1) and (2) As the phenylene ether oligomer, for example, an oligomer represented by the following general formula ( 4 ) may be used.

(However, n represents an arbitrary integer of 2 or more). As the terminal hydroxyl group-containing phenylene ether oligomer represented by the general formula ( 4 ), a single component in which n is a single number may be used, or a mixture of a plurality of components having different numbers of n is used. You may do it. When a plurality of components having different numbers of n are included, a monomer component having an average composition of the terminal hydroxyl group-containing phenylene ether oligomer represented by the general formula ( 4 ) in the range of 1 <n ≦ 10 is used. It is preferable to use it as a part. More preferably, an average composition having a range of 2 ≦ n ≦ 10 is used as a part of the monomer component. If n as the average composition is 1 or less, the glass transition temperature of the resulting polymer tends to be high, and the processability as a fuel cell material tends to decrease. If n as the average composition is greater than 10, glass This is because the transition temperature becomes lower and the heat resistance when used as a fuel cell material tends to be insufficient. In the present invention, when the terminal hydroxyl group-containing phenylene ether oligomer represented by the general formula (3) or the general formula (4) includes a plurality of components different from o or n, the average composition of the oligomer is NMR. The abundance ratios of different components of o or n can be determined by GPC or the like.

  In the aromatic nucleophilic substitution reaction for obtaining the sulfonic acid group-containing polyarylene ether compound of the present invention, active as a monomer component for giving a structure other than the structures represented by the general formulas (1) and (2) Difluoroaromatic compounds and dichloroaromatic compounds can be used. Specifically, for example, decafluorobiphenyl, decafluorodiphenyl ether, decafluorobenzophenone, 2,4-dichlorobenzonitrile, 2,4-difluorobenzonitrile, 4,4′-dichlorobenzophenone, 4,4′-dichlorodiphenyl Examples of the compounds such as sulfone, 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylsulfone, and the like, but not limited thereto, are other aromatic dihalogens active in aromatic nucleophilic substitution reaction. Compound, aromatic dinitro compound, aromatic dicyano compound and the like can also be used. These compounds may be used alone or as a mixture of two or more.

  Moreover, an aromatic diol component can also be used as a monomer component for giving structures other than the structure shown by General formula (1) and General formula (2). Specifically, for example, 4,4′-biphenol, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) ) Propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-2,5-dimethylphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) Diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxy) Loxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, hydroquinone, resorcin, 1,4-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) thioether, bis (4-hydroxyphenoxy) -1,4-benzene, bis (4-hydroxyphenoxy) -1,3-benzene and the like can be mentioned. Other fragrances You can use various aromatic diols which can be used for the polymerization of polyarylene ether-based compound by nucleophilic substitution reaction. In addition, a substituent such as a methyl group, a halogen, a cyano group, a sulfonic acid group, and a salt compound thereof may be bonded to these aromatic diols. The kind of substituent is not particularly limited, and is preferably 0 to 2 per aromatic ring. Furthermore, diphenylthioether-4,4'-dithiol etc. which can react like an aromatic diol can also be used. These aromatic diols may be used alone or as a mixture of two or more.

  In the polymerization of the sulfonic acid group-containing polyarylene ether compound of the present invention, a halogenated aromatic hydroxy compound can be added as a reactive monomer component to perform polymerization. The halogenated aromatic hydroxy compound used in this case is not particularly limited, but 4-hydroxy-4′-chlorobenzophenone, 4-hydroxy-4′-fluorobenzophenone, 4-hydroxy-4′-chlorodiphenylsulfone. 4-hydroxy-4′-fluorodiphenylsulfone, 4-chloro-4 ′-(p-hydroxyphenyl) diphenylsulfone, 4-fluoro-4 ′-(p-hydroxyphenyl) benzophenone, and the like. it can. These may be used alone or as a mixture of two or more.

  In addition, a component that crosslinks with heat and / or light may be contained in the molecular chain of the sulfonic acid group-containing polyarylene ether compound of the present invention, that is, as the main chain, side chain, or terminal group of the polymer. Examples of the thermally crosslinkable component include reactive unsaturated bond-containing groups such as an ethylene group, an ethynyl group, and an ethynylene group, but are not limited to these. Any material that can form a bond may be used. Examples of photocrosslinkable components include benzophenone groups, α-diketone groups, acyloin groups, acyloin ether groups, benzyl alkyl ketal groups, acetophenone groups, polynuclear quinones, thioxanthone groups, acylphosphine groups, and ethylenically unsaturated groups. Mention may be made of functional groups. Among them, a combination of a group capable of generating a radical by light such as a benzophenone group and an aromatic group having a hydrocarbon group such as a methyl group or an ethyl group and capable of reacting with the radical is preferable. When using an ethylenically unsaturated group, photopolymerization of benzophenones, α-diketones, acyloins, acyloin ethers, benzyl alkyl ketals, acetophenones, polynuclear quinones, thioxanthones, acylphosphines, etc. It is preferable to add an initiator.

  In the case of introducing a crosslinkable group at the terminal, a monofunctional endblocker which gives a terminal structure containing a crosslinkable group is added during the polymerization of the sulfonic acid group-containing polyarylene ether compound of the present invention. Sex groups can be introduced. Examples of monofunctional end-capping agents are specifically 3-fluoropropene, 3-fluoro-1-propyne, 4-fluoro-1-butene, 4-fluoro-1-butyne, 3-fluorocyclohexene, 4 -Fluorostyrene, 3-fluorostyrene, 2-fluorostyrene, 4-fluoroethynylbenzene, 3-fluoroethynylbenzene, α-fluoro-4-ethynyltoluene, 4-fluorostilbene, 4- (phenylethynyl) fluorobenzene, 3 -(Phenylethynyl) fluorobenzene, 3-chloropropene, 3-chloro-1-propyne, 4-chloro-1-butene, 4-chloro-1-butyne, 3-chlorocyclohexene, 4-chlorostyrene, 3-chloro Styrene, 2-chlorostyrene, 4-chloroethynylbenzene, 3-chloroethini Benzene, α-chloro-4-ethynyltoluene, 4-chlorostilbene, 4- (phenylethynyl) chlorobenzene, 3- (phenylethynyl) chlorobenzene, 3-hydroxypropene, 3-hydroxy-1-propyne, 4-hydroxy-1 -Butene, 4-hydroxy-1-butyne, 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, 4-hydroxyethynylbenzene, 3-ethynylphenol, 4-ethynylbenzyl alcohol, 4-hydroxystilbene, 4- (Phenylethynyl) phenol, 3- (phenylethynyl) phenol, 4-chlorobenzophenone, 4-fluorobenzophenone, 4-hydroxybenzophenone, 4-methylphenol, 3-methylphenol, 2-methylphenol, 4 Ethylphenol, 3-ethylphenol, 4-propyl phenol, 4-butylphenol, 4-pentylphenol, 4-benzyl-phenol, and the like. These end-blocking agents may be used alone or in admixture of two or more.

  Specific examples of the crosslinkable group-containing monomer include 1-butene-3,4-diol, 3,5-dihydroxystyrene, 3,5-dihydroxystilbene, 1-butyne-3,4-diol, and 1-butene. -3,4-diol, 2,4-hexadiyne-1,6-diol, 2-ethynylhydroquinone, 2- (phenylethynyl) hydroquinone, 5-ethynylresorcin, 2-butene-1,4-diol, 4,4 '-Dihydroxystilbene, 1,4-butynediol, 1,2-bis (4-hydroxyphenyl) acetylene, 1,2-bis (3-hydroxyphenyl) acetylene, 3,3-difluoropropene, 3,3-difluoro Propyne, 3,3,3-trifluoropropyne, 3,4-difluoro-1-butene, 1,4-difluoro-2-butene, 3 , 4-Difluoro-1-butyne, 1,4-difluoro-2-butyne, 1,6-difluoro-2,4-hexadiyne, 3,4-difluorostyrene, 2,6-difluorostyrene, 2,5-difluoro Ethynylbenzene, 3,5-difluoroethynylbenzene, α, α-difluoro-4-ethynyltoluene, α, α, α-trifluoro-4-ethynyltoluene, 2,4-difluorostilbene, 4,4′-difluorostilbene 1,2-bis (4-fluorophenyl) acetylene, 3,4-difluoro (phenylethynyl) benzene, 3,3-dichloropropene, 3,3-dichloropropyne, 3,3,3-trichloropropyne, 3,4-dichloro-1-butene, 1,4-dichloro-2-butene, 3,4-dichloro-1-butyne, 1,4-dichloro 2-butyne, 3,4-dichlorostyrene, 2,6-dichlorostyrene, 2,4-difluorocinamic acid, 2,5-dichloroethynylbenzene, 3,5-dichloroethynylbenzene, α, α-dichloro-4 -Ethynyltoluene, α, α, α-trichloro-4-ethynyltoluene, 2,4-dichlorostilbene, 4,4'-dichlorostilbene, 1,2-bis (4-chlorophenyl) acetylene, 3,4-dichloro ( Phenylethynyl) benzene, 4,4′-dihydroxybenzophenone, 4,4′-dichlorobenzophenone, 4,4′-difluorobenzophenone, 4-chlorobenzophenone, 4-fluorobenzophenone, 4-hydroxybenzophenone 1,1-bis (4 -Hydroxyphenyl) ethane, 2,2-bis (4-hydroxypheny) ) Propane, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-2,5-dimethylphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, 4-benzyl Resorcin, 2,5-dimethylresorcin, 4-ethylresorcin, and the like. By adding these crosslinkable group-containing monomers during the polymerization of the polyarylene ether compound of the present invention, a crosslinkable group can be introduced into the molecular chain.

  The sulfonic acid group-containing polyarylene ether compound of the present invention preferably has a sulfonic acid group content in the range of 0.3 to 5.0 meq / g. When it is less than 0.3 meq / g, there is a tendency that it does not show sufficient ionic conductivity when used as a polymer electrolyte membrane. Tend to be. The sulfonic acid group content can be determined by a titration method described later after the sulfonic acid group is converted to an acid type structure by an acidic aqueous solution treatment. In addition, Preferably it is 0.5-3.5 meq / g.

  The sulfonic acid group-containing polyarylene ether compound of the present invention preferably has a glass transition temperature in the range of 130 ° C to 220 ° C. When the glass transition temperature is lower than 130 ° C, the heat resistance when used as a polymer electrolyte membrane tends to be insufficient, and when the glass transition temperature is higher than 220 ° C, an electrolyte membrane / electrode composite is produced. There is a tendency for workability to decrease. When the glass transition temperature is in the range of 130 ° C. to 220 ° C., the processability when producing the electrolyte membrane / electrode composite is excellent, and the heat resistance when used as a fuel cell is particularly good. . In addition, the glass transition temperature said here can be determined by the dynamic viscoelasticity measurement mentioned later.

  When the sulfonic acid group-containing polyarylene ether compound of the present invention is polymerized by an aromatic nucleophilic substitution reaction, the activated difluoroaromatic compound and / or the dichloroaromatic compound and the aromatic diol are reacted in the presence of a basic compound. A polymer can be obtained by reacting. The polymerization can be carried out in the temperature range of 0 to 350 ° C., but is preferably 50 to 250 ° C. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed. The reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent. Examples of the solvent that can be used include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane, and the like. And any solvent that can be used as a stable solvent in the aromatic nucleophilic substitution reaction. These organic solvents may be used alone or as a mixture of two or more. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and those that can convert an aromatic diol into an active phenoxide structure may be used. It can use without being limited to. In the aromatic nucleophilic substitution reaction, water may be generated as a by-product. In this case, regardless of the polymerization solvent, water can be removed from the system as an azeotrope by coexisting toluene or the like in the reaction system. As a method for removing water out of the system, a water-absorbing agent such as molecular sieve can also be used. When the aromatic nucleophilic substitution reaction is performed in a solvent, it is preferable to charge the monomer so that the resulting polymer concentration is 5 to 50% by mass. When the amount is less than 5% by mass, the degree of polymerization tends to be difficult to increase. On the other hand, when the amount is more than 50% by mass, the viscosity of the reaction system becomes too high, and the post-treatment of the reaction product tends to be difficult. For the polymerization, it is preferable to add monomers at the beginning of the reaction to form a polymer having a highly random chain distribution. After completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation, and the residue is washed as necessary to obtain the desired polymer. In addition, the polymer can be obtained by precipitating the polymer as a solid by adding the reaction solution in a solvent having low polymer solubility, and collecting the precipitate by filtration. If necessary, a filtration treatment may be performed before the precipitation.

  The sulfonic acid group-containing polyarylene ether compound of the present invention preferably has a polymer log viscosity measured by a method described later of 0.1 or more. When the logarithmic viscosity is less than 0.1, the membrane tends to be brittle when molded as a polymer electrolyte membrane. The logarithmic viscosity is more preferably 0.3 or more. On the other hand, when the logarithmic viscosity exceeds 5, problems in processability such as difficulty in dissolving the polymer tend to occur. In addition, as a solvent for measuring logarithmic viscosity, polar organic solvents such as N-methyl-2-pyrrolidone and N, N-dimethylacetamide can be generally used. However, when the solubility of the polymer in these is low It can also be measured using concentrated sulfuric acid.

When the sulfonic acid group-containing polyarylene ether compound of the present invention is used as a polymer electrolyte membrane, the sulfonic acid group-containing polyarylene ether compound can be used alone, but a resin in combination with other polymers. It can also be used as a composition. Examples of other polymers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamides such as nylon 6, nylon 6,6, nylon 6,10, and nylon 12, polymethyl methacrylate, and polymethacrylate. Acrylate resins such as polymethyl acrylate, polyacrylic acid esters, polyacrylic acid resins, polymethacrylic acid resins, polyethylene, polypropylene, various polyolefins including polystyrene and diene polymers, polyurethane resins, cellulose acetate, Cellulosic resins such as ethyl cellulose, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyether Thermal curing of aromatic polymers such as ruphone, polyetheretherketone, polyetherimide, polyimide, polyamideimide, polybenzimidazole, polybenzoxazole, polybenzthiazole, epoxy resin, phenol resin, novolac resin, benzoxazine resin There are no particular restrictions on the conductive resin. A resin composition with a basic polymer such as polybenzimidazole or polyvinylpyridine can be said to be a preferable combination for improving polymer dimensional stability. When an acidic group-containing basic polymer in which an acidic group such as a sulfonic acid group or a phosphonic acid group is further introduced into these basic polymers is used, the processability of the resin composition becomes more preferable. When used as these resin compositions, the sulfonic acid group-containing polyarylene ether-based compound of the present invention is preferably contained in a range of 50% by mass or more and less than 100% by mass of the entire resin composition. More preferably, it is 70 mass% or more and less than 100 mass%. When the content of the sulfonic acid group-containing polyarylene ether compound of the present invention is less than 50% by mass of the entire resin composition, the polymer electrolyte membrane containing this resin composition has a low sulfonic acid group concentration, which is favorable. There is a tendency that ion conductivity cannot be obtained, and a unit containing a sulfonic acid group becomes a discontinuous phase, and the mobility of ions to conduct tends to be lowered. In addition, the sulfonic acid group-containing polyarylene ether compound of the present invention, and the resin composition containing the same, for example, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, Various additives such as a viscosity modifier, an antistatic agent, an antibacterial agent, an antifoaming agent, a dispersant, and a polymerization inhibitor may be included.

As the acidic group-containing basic polymer, an acidic group-containing polybenzimidazole containing a structural unit represented by the following general formula ( 5 ) can be preferably used.

(Where m ¹ represents an integer of 1 to 4, R ¹ represents a tetravalent aromatic bond unit capable of forming an imidazole ring, R ² represents a divalent aromatic unit, and R ¹ and R ² are Z ³ may be a monocyclic aromatic ring, a combination of a plurality of aromatic rings or a condensed ring, and may have a stable substituent, and Z ³ may be a sulfonic acid group and / or a phosphonic acid group. Represents a group, part of which may have a salt structure).

The route for synthesizing the acidic group-containing polybenzimidazole compound containing the structural unit represented by the general formula ( 5 ) is not particularly limited, but usually aromatic tetramines capable of forming an imidazole ring in the compound and It can be synthesized by a reaction of one or more compounds selected from the group consisting of those derivatives and one or more compounds selected from the group consisting of aromatic dicarboxylic acids and derivatives thereof. At that time, by using a dicarboxylic acid containing a sulfonic acid group or a phosphonic acid group or a salt thereof as at least a part of the dicarboxylic acid to be used, a sulfonic acid group or a phosphonic acid group is added to the obtained polybenzimidazole. Can be introduced. The dicarboxylic acids containing a sulfonic acid group or a phosphonic acid group can be used in combination of one or more, but a sulfonic acid group-containing dicarboxylic acid and a phosphonic acid group-containing dicarboxylic acid can also be used simultaneously.

  Here, a benzimidazole-based binding unit that is a constituent element of a polybenzimidazole-based compound, an aromatic dicarboxylic acid-bonding unit having a sulfonic acid group and / or a phosphonic acid group, neither a sulfonic acid group nor a phosphonic acid group The aromatic dicarboxylic acid bonding unit and other bonding units are preferably bonded by random polymerization and / or alternating polymerization. Moreover, these polymerization formats are not limited to one type, and two or more polymerization types may coexist in the same compound.

  The sulfonic acid group-containing polyarylene ether compound and the resin composition containing the sulfonic acid group-containing compound of the present invention can be formed into a molded body such as a fiber or a film by an arbitrary method such as extrusion, spinning, rolling, or casting. Among these, it is preferable to mold from a solution dissolved in an appropriate solvent. Examples of the solvent include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and hexamethylphosphonamide, alcohols such as methanol and ethanol, A mixed solvent selected from a combination of ketones, water and the like can be used, but is not limited thereto. A plurality of these solvents may be used as a mixture within a possible range. The compound concentration in the solution is preferably in the range of 0.1 to 50% by mass. If the compound concentration in the solution is less than 0.1% by mass, it tends to be difficult to obtain a good molded product, and if it exceeds 50% by mass, the workability tends to deteriorate. A method of obtaining a molded body from a solution can be performed using a conventionally known method. For example, the molded product can be obtained by removing the solvent by heating, drying under reduced pressure, immersion in a compound non-solvent that can be mixed with a solvent that dissolves the compound, or the like. When the solvent is an organic solvent, it is preferable to distill off the solvent by heating or drying under reduced pressure. At this time, it can be formed into various shapes such as a fiber shape, a film shape, a pellet shape, a plate shape, a rod shape, a pipe shape, a ball shape, and a block shape in a composite form with other compounds as necessary. . When combined with a compound having a similar dissolution behavior, it is preferable in that good molding can be achieved. The sulfonic acid group in the molded article thus obtained may contain a salt form with a cationic species, but it can be converted to a free sulfonic acid group by acid treatment as necessary. You can also.

In the present invention, a polymer electrolyte membrane can be produced from a sulfonic acid group-containing polyarylene ether compound and a resin composition containing the same. The most preferable method for forming the polymer electrolyte membrane is casting from a solution, and the polymer electrolyte membrane can be obtained by removing the solvent from the cast solution as described above. Examples of the solution include a solution using an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and in some cases alcohols, ketones, water, etc. Examples thereof include a mixed solvent selected from combinations. The removal of the solvent is preferably performed by drying in view of the uniformity of the ion conductive membrane. In order to avoid decomposition or alteration of the compound or solvent, it is also preferable to dry at a temperature as low as possible under reduced pressure. Further, when the viscosity of the solution is high, when the substrate or the solution is heated and cast at a high temperature, the viscosity of the solution is lowered and the casting can be easily performed. The thickness of the solution at the time of casting is not particularly limited, but is preferably 10 to 1500 μm. More preferably, it is 50-500 micrometers. If the thickness of the solution is thinner than 10 μm, the shape as a polymer electrolyte membrane tends to be not maintained, and if it is thicker than 1500 μm, a non-uniform polymer electrolyte membrane tends to be easily formed. A known method can be used as a method for controlling the cast thickness of the solution. For example, the thickness can be controlled with the amount and concentration of the solution with a constant cast area using an applicator, a doctor blade or the like, or with a frame that prevents the solution from flowing out. The cast solution can be formed into a more uniform film by adjusting the solvent removal rate. For example, when the solvent is removed by heating, the evaporation rate can be reduced by lowering the temperature in the first stage. In addition, when immersed in a non-solvent such as water, the coagulation rate and solvent removal rate of the compound can be adjusted by leaving the solution in air or an inert gas for an appropriate time. The polymer electrolyte membrane of the present invention can have any film thickness depending on the purpose, but is preferably as thin as possible from the viewpoint of ion conductivity. Specifically, it is preferably 5 to 250 μm, more preferably 5 to 100 μm, and most preferably 5 to 50 μm. If the thickness of the polymer electrolyte membrane is less than 5 μm, the handling of the polymer electrolyte membrane becomes difficult and a short circuit or the like tends to occur when a fuel cell is manufactured. If the thickness is more than 250 μm, the electric resistance value of the ion conductive membrane is high. Therefore, the power generation performance of the fuel cell tends to decrease. When used as an ion conductive membrane, the sulfonic acid group in the membrane may contain a metal salt, but it can be converted to free sulfonic acid by an appropriate acid treatment. In this case, it is also effective to immerse the membrane in an aqueous solution of sulfuric acid, hydrochloric acid or the like with or without heating. The ionic conductivity of the polymer electrolyte membrane is preferably 1.0 × 10 ⁻³ S / cm or more. When the ion conductivity of 1.0 × 10 ^-3 S / cm or higher, tend to better output can be obtained in the fuel cell using a polymer electrolyte membrane, 1.0 × 10 ^-3 S / When it is less than cm, the output of the fuel cell tends to decrease.

The polymer electrolyte membrane of the present invention is also useful for a direct methanol fuel cell using methanol as a fuel. In particular, a polymer electrolyte membrane in which a membrane having an average thickness of 50 μm is prepared and the methanol permeation rate measured at 25 ° C. using a 5 M aqueous methanol solution shows a value of 7 mmol / m ² · sec or less is preferable. In this case, excellent power generation characteristics are imparted to the fuel cell. The methanol permeation rate is further preferably 4 mmol / m ² · sec or less, and more preferably 1 mmol / m ² · sec or less. The methanol permeation characteristics may depend on the film thickness, and in the above methanol permeation rate, the case where a sample having an average thickness of 50 μm is prepared is described. When actually used as an ion conductive membrane for a fuel cell, In particular, the film thickness is not limited. The film having an average thickness of 50 μm substantially indicates a film having an average thickness of 48 μm to an average thickness of 52 μm.

When the polymer electrolyte membrane obtained from the sulfonic acid group-containing polyarylene ether compound of the present invention and the resin composition containing the same contains a component that crosslinks by heat and / or light, heat treatment and / or light By introducing a crosslinked structure into the molecular chain by irradiation treatment, the dimensional stability of the film can be further improved. The heating temperature at the time of thermal crosslinking varies depending on the structure of the crosslinkable polyarylene ether, the type of the crosslinkable group, the amount of the crosslinkable group introduced, and the like, but is usually 150 to 450 ° C, preferably 200 to 400 ° C. The heating time varies depending on the heating temperature and the structure of the crosslinkable polyarylene ether, but is usually 0.01 to 50 hours, preferably 0.02 to 24 hours. The pressure may be normal pressure, reduced pressure, or increased pressure. The gas atmosphere may be an air atmosphere, a nitrogen atmosphere, or an argon atmosphere. When the heating temperature is high, the sulfonic acid group is preferably heat-treated in a salt state. The light source used for photocrosslinking is not particularly limited, but a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. The irradiation dose may vary depending on the polymer structure and its thickness, usually, 100~50000mJ / cm ^2, preferably 300~30000mJ / cm ^2.

  Further, by joining the above-described polymer electrolyte membrane or film of the present invention to an electrode, a joined body of the polymer electrolyte membrane or film or the like and the electrode as the electrolyte membrane / electrode composite of the present invention is obtained. Can do. As a method for producing this joined body, a conventionally known method can be used. For example, a method of applying an adhesive to the electrode surface and bonding the polymer electrolyte membrane and the electrode, or a polymer electrolyte membrane and There is a method of heating and pressing the electrode. Among these, a method of applying and bonding an adhesive mainly composed of the sulfonic acid group-containing polyarylene ether compound of the present invention and a resin composition containing the compound to the electrode surface is preferable. This is because the adhesion between the polymer electrolyte membrane and the electrode is improved, and it is considered that the ion conductivity of the polymer electrolyte membrane is less impaired.

  A fuel cell can also be produced using the above-described assembly of a polymer electrolyte membrane or film and an electrode. The polymer electrolyte membrane or film of the present invention is excellent in heat resistance, workability, ion conductivity and dimensional stability, so it can withstand operation at high temperatures, is easy to produce, and has good output. Can be provided. It is also preferable to use it as a fuel cell using methanol as a direct fuel.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. Various measurements were performed as follows.
Solution viscosity: The polymer powder was dissolved in N-methylpyrrolidone at a concentration of 0.5 g / dl, and the viscosity was measured using a Ubbelohde viscometer in a constant temperature bath at 30 ° C., and the logarithmic viscosity (ln [ta / tb] / C) (ta is the drop time of the sample solution, tb is the drop time of the solvent only, and c is the polymer concentration).
TGA: Using a thermogravimetry meter (TGA-50) manufactured by Shimadzu Corporation, measurement was performed in an argon atmosphere at a heating rate of 10 ° C./min (while maintaining at 150 ° C. for 30 minutes to sufficiently remove water) .
Ion conductivity measurement: A platinum wire (diameter: 0.2 mm) is pressed against the surface of a strip-shaped membrane sample on a self-made measurement probe (Teflon (registered trademark)), and a constant temperature and humidity oven at 80 ° C. and 95% RH. The sample was held in (Nagano Scientific Machinery Co., Ltd., LH-20-01), and the impedance between the platinum wires was measured by SOLARTRON 1250 FREQUENCY RESPONSE ANALYSER. Conductivity with the contact resistance between the film and the platinum wire canceled by the following formula from the slope of the measured resistance value estimated from the distance between the poles and the C-C plot. The rate was calculated. Moreover, the same measurement was performed by immersing the measurement probe in ultrapure water maintained at 25 ° C., and the proton conductivity in water was also calculated.
Conductivity [S / cm] = 1 / film width [cm] × film thickness [cm] × resistance interelectrode gradient [Ω / cm]
Sulfonic acid group content: The weight of a sample dried overnight under a nitrogen atmosphere was weighed, and after stirring with an aqueous sodium hydroxide solution, the ion exchange capacity (IEC) (meq / g) was determined by back titration with an aqueous hydrochloric acid solution. .
Methanol permeation rate: A membrane immersed in a 5M (mol / liter) aqueous methanol solution adjusted to 25 ° C. for 24 hours is sandwiched between H-type cells, 100 ml of 5M aqueous methanol solution is placed on one side of the cell, and 100 ml of ultrapure is placed on the other cell. Calculated by injecting water (18 MΩ · cm) and measuring the amount of methanol diffusing into the ultrapure water through the ion exchange membrane while stirring the cells on both sides at 25 ° C. (The area of the ion exchange membrane is 2.0 cm ² ).
Glass transition temperature: Using a Rheogel-E4000 manufactured by Orientec, a tensile sine wave was applied to a film sample having a sample width of 5 mm and an effective sample length of 15 mm, and dynamic viscoelasticity measurement was performed at a heating rate of 2 ° C./min. The temperature at which the elastic modulus begins to decrease as the temperature rises is defined as the glass transition point.
HNMR measurement: The sample was dissolved in deuterated dimethyl sulfoxide and measured at 80 ° C. using a Varian GEMINI 200 NMR spectrometer.
Power generation evaluation: After adding a small amount of ultrapure water and isopropyl alcohol to Pt / Ru catalyst-supporting carbon (TEC61E54) and moistening, a 20% Nafion (registered trademark) solution manufactured by DuPont (product number: SE-) 2011) was added so that the mass ratio of Pt / Ru catalyst-supported carbon to Nafion (registered trademark) was 2.5: 1. Next, stirring was performed to prepare an anode catalyst paste. This catalyst paste was applied and dried by screen printing on Toray carbon paper TGPH-060 to be a gas diffusion layer so that the adhesion amount of platinum was 2 mg / cm ² , thereby producing a carbon paper with an electrode catalyst layer for anode. . Further, after adding a small amount of ultrapure water and isopropyl alcohol to a Pt catalyst-supporting carbon (Tanaka Kikinzoku Kogyo Co., Ltd. TEC10V40E) and moistening, a 20% Nafion (registered trademark) solution (product number: SE-20192) manufactured by DuPont is used. A cathode catalyst paste was prepared by adding a Pt catalyst-carrying carbon and Nafion (registered trademark) in a mass ratio of 2.5: 1 and stirring. This catalyst paste was applied and dried on Toray carbon paper TGPH-060 that had been subjected to water repellent treatment so that the amount of platinum deposited was 1 mg / cm ² , thereby producing a carbon paper with an electrode catalyst layer for cathode. . By sandwiching the membrane sample between the two types of carbon paper with the electrode catalyst layer so that the electrode catalyst layer is in contact with the membrane sample, pressurizing and heating at 130 ° C. and 8 MPa for 3 minutes by a hot press method, An electrolyte membrane / electrode assembly was obtained. This joined body was incorporated into an evaluation fuel cell FC25-02SP manufactured by Electrochem, and a power generation test was performed using a fuel cell power generation tester (manufactured by Toyo Corporation). Power generation was performed while supplying a 2 mol / l aqueous methanol solution (1.5 ml / min) and high-purity oxygen gas (80 ml / min) adjusted to 40 ° C. to the anode and cathode, respectively, at a cell temperature of 40 ° C.

(Example 1)
3,3'-disulfo-4,4'-dichlorodiphenylsulfone disodium salt (abbreviation: S-DCDPS) 9.6228 g (0.019588 mole), 2,6-dichlorobenzonitrile (abbreviation: DCBN) 3.1102 g ( 0.018082 mole), terminal hydroxyl group-containing phenylene ether oligomer (abbreviation: DPE) (Dainippon Ink & Co., Ltd. SPECIANOL DPE-PL, lot C106) (in the general formula (3), a mixture containing components of o = 1 to 7. NMR. The average composition according to the above formula is o = 4.0.) 20.71319 g (0.037670 mole) and 5.9873 g (0.043321 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen. 100 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. to react for 13 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and a polymer composed of a sulfonic acid group-containing polyarylene ether compound was obtained. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.36.

20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 day to convert the acidic group in the polymer from a salt type structure to an acid type structure, and then in pure water for 1 hour. The acid component was removed by dipping twice and dried. When the ionic conductivity of this film was measured, it showed a value of 0.15 S / cm at 80 ° C. and 95% RH and 0.032 S / cm in 25 ° C. water. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) of the film by thermogravimetry was 286 ° C., and the 3% weight reduction temperature was 352 ° C. The IEC determined by titration was 1.23 meq / g. The methanol permeation rate was 2.6 mmol / m ² · sec. FIG. 1 is a diagram showing a 1HNMR spectrum of a film made of a sulfonic acid group-containing polyarylene ether compound obtained in Example 1, and a structural formula belonging to the spectrum. From the integral value of the spectrum in FIG. 1, it can be seen that the average value of n in the structural formula in the figure is about 4.4.

(Example 2)
S-DCDPS 10.24552 g (0.020855 mole), DCBN 9.2246 g (0.053628 mole), DPE (Dai Nippon Ink SPECIANOL DPE-PL, lot C106) 20.0.4777 g (0.03724 mole), 4,4′-dihydroxydiphenyl ether 7.5307 g (0.03724 mole) and potassium carbonate 11.8385 g (0.08566 mole) were weighed into a 200 ml four-necked flask and flushed with nitrogen. 140 ml of N-methyl-2-pyrrolidone was added, the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. for 16 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and a polymer composed of a sulfonic acid group-containing polyarylene ether compound was obtained. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.90.

20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 day to convert the acidic group in the polymer from a salt type structure to an acid type structure, and then in pure water for 1 hour. The acid component was removed by dipping twice and dried. When the ionic conductivity of this film was measured, it showed a value of 0.05 S / cm at 80 ° C. and 95% RH and 0.019 S / cm in water at 25 ° C. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) by thermogravimetry of this film was 297 ° C., and the 3% weight reduction temperature was 362 ° C. The IEC determined by titration was 0.90 meq / g. The methanol permeation rate was 1.2 mmol / m ² · sec. The glass transition temperature measured by dynamic viscoelasticity was 153 ° C. FIG. 2 is a diagram showing a 1H NMR spectrum of a film made of a sulfonic acid group-containing polyarylene ether compound obtained in Example 2, and a structural formula assigned from the spectrum. From the integral value of the spectrum of FIG. 2, it can be seen that the average value of n in the structural formula in the figure shows about 2.0.

(Example 3)
S-DCDPS 11.0125 g (0.022417 mole), DCBN 4.0134 g (0.02333 mole), DPE (Dai Nippon Ink SPECIANOL DPE-PL, lot C106) 12.57779 g (0.022875 mole), 4,4′-dihydroxydiphenyl ether 4.6255 g (0.022875 mole) and 7.2715 g (0.05261 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen. 100 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. to react for 15 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and a polymer composed of a sulfonic acid group-containing polyarylene ether compound was obtained. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.56.

20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 day to convert the acidic group in the polymer from a salt type structure to an acid type structure, and then in pure water for 1 hour. The acid component was removed by dipping twice and dried. When the ionic conductivity of this film was measured, it showed a value of 0.19 S / cm at 80 ° C. and 95% RH and 0.090 S / cm in water at 25 ° C. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) by thermogravimetry of this film was 284 ° C., and the 3% weight reduction temperature was 346 ° C. The IEC determined by titration was 1.52 meq / g. The methanol permeation rate was 4.4 mmol / m ² · sec. The glass transition temperature measured by dynamic viscoelasticity was 162 ° C.

Example 4
S-DCDPS 10.0608 g (0.02048 mole), DCBN 5.7477 g (0.03341 mole), DPE (Dai Nippon Ink SPECIANOL DPE-PL, lot C106) 14.8173 g (0.026947 mole), 4,4′-dihydroxydiphenyl ether 5.4490 g (0.026947 mole) and potassium carbonate 8.5661 g (0.061979 mole) were weighed into a 200 ml four-necked flask and flushed with nitrogen. 110 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. to react for 15 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and a polymer composed of a sulfonic acid group-containing polyarylene ether compound was obtained. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.51.

20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 day to convert the acidic group in the polymer from a salt type structure to an acid type structure, and then in pure water for 1 hour. The acid component was removed by dipping twice and dried. When the ionic conductivity of this film was measured, it showed a value of 0.11 S / cm at 80 ° C. and 95% RH and 0.042 S / cm in 25 ° C. water. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) by thermogravimetry of this film was 303 ° C., and the 3% weight reduction temperature was 361 ° C. The IEC determined by titration was 1.21 meq / g. The methanol permeation rate was 2.6 mmol / m ² · sec.

(Example 5)
S-DCDPS 8.1896 g (0.016771 mole), DCBN 9.6001 g (0.055811 mole), DPE (Dai Nippon Ink SPECIANOL DPE-PL, Lot C106) 10.5332 g (0.018121 mole), 4,4′-dihydroxydiphenyl ether 10.9925 g (0.054362 mole) and 11.5205 g (0.083336 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen. 110 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. for 14 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and a polymer composed of a sulfonic acid group-containing polyarylene ether compound was obtained. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.93.

20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 day to convert the acidic group in the polymer from a salt type structure to an acid type structure, and then in pure water for 1 hour. The acid component was removed by dipping twice and dried. When the ion conductivity of this film was measured, it showed a value of 0.05 S / cm at 80 ° C. and 95% RH and 0.018 S / cm in water at 25 ° C. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) by thermogravimetry of this film was 304 ° C., and the 3% weight reduction temperature was 365 ° C. The IEC determined by titration was 0.93 meq / g. The methanol permeation rate was 1.1 mmol / m ² · sec. The glass transition temperature measured by dynamic viscoelasticity was 173 ° C.

(Example 6)
3,3′-disulfo-4,4′-difluorobenzophenone disodium salt 6.1115 g (0.01447 mole), DCBN 5.8085 g (0.03377 mole), DPE (Dai Nippon Ink SPECIANOL DPE-PL, lot C106) 13 .7812 g (0.02412 mole), 4,4′-dihydroxydiphenyl ether 4.8774 g (0.02412 mole), and potassium carbonate 6.6675 g (0.05548 mole) were weighed into a 200 ml four-necked flask and flushed with nitrogen. 90 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. to carry out the reaction for 18 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and a polymer composed of a sulfonic acid group-containing polyarylene ether compound was obtained. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.58.

20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 day to convert the acidic group in the polymer from a salt type structure to an acid type structure, and then in pure water for 1 hour. The acid component was removed by dipping twice and dried. When the ionic conductivity of this film was measured, it was 0.06 S / cm at 80 ° C. and 95% RH, and 0.021 S / cm in 25 ° C. water. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) by thermogravimetry of this film was 297 ° C., and the 3% weight reduction temperature was 362 ° C. The IEC determined by titration was 1.03 meq / g. The methanol permeation rate was 1.3 mmol / m ² · sec.

(Example 7)
S-DCDPS 7.1016 g (0.01446 mole), DCBN 6.3941 g (0.03717 mole), DPE (Dai Nippon Ink SPECIANOL DPE-PL, lot C106) 14.7491 g (0.025815 mole), 4,4′-biphenol 4 8069 g (0.025815 mole) and potassium carbonate 8.2060g (0.059373 mole) were weighed into a 200 ml four-necked flask and flushed with nitrogen. 100 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. to react for 15 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.79.

20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 day to convert the acidic group in the polymer from a salt type structure to an acid type structure, and then in pure water for 1 hour. The acid component was removed by dipping twice and dried. When the ionic conductivity of this film was measured, it was 0.08 S / cm at 80 ° C. and 95% RH, and 0.040 S / cm in 25 ° C. water. The IEC determined by titration was 0.95 meq / g. The methanol permeation rate was 1.0 mmol / m ² · sec.

(Example 8)
S-DCDPS 8.3450 g (0.016987 mole), 4,4′-dichlorodiphenylsulfone 9.9040 g (0.03449 mole), DPE (Dai Nippon Ink SPECIANOL DPE-PL, lot C106) 14.7056 g (0.025738 mole) 4,4′-dihydroxydiphenyl ether (5.2045 g, 0.025738 mole) and 8.1817 g (0.05920 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen. 115 ml of N-methyl-2-pyrrolidone was added, and the mixture was stirred with heating, the reaction temperature was raised to 195 to 200 ° C., and the reaction was carried out for 19 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and a polymer composed of a sulfonic acid group-containing polyarylene ether compound was obtained. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.67.

20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 day to convert the acidic group in the polymer from a salt type structure to an acid type structure, and then in pure water for 1 hour. The acid component was removed by dipping twice and dried. When the ionic conductivity of this film was measured, it was 0.08 S / cm at 80 ° C. and 95% RH and 0.037 S / cm in 25 ° C. water. The IEC determined by titration was 0.94 meq / g. The methanol permeation rate was 2.9 mmol / m ² · sec.

Example 9
3,3 ', 4,4'-tetra-diaminodiphenyl sulfone ^{1.500g (5.389 × 10 -3 mole)} , 2,5- dicarboxylate benzenesulfonic acid 1.445g (5.389 × 10 ^-3 mole) , 20.5 g of polyphosphoric acid (phosphorus pentoxide content 75% by mass) and 16.5 g of phosphorus pentoxide are weighed into a polymerization vessel. The temperature is raised to 100 ° C. while slowly stirring on an oil bath while flowing nitrogen. After maintaining at 100 ° C. for 1 hour, the temperature was raised to 150 ° C. for 1 hour, and the temperature was raised to 200 ° C. for 4 hours to polymerize. Was allowed to cool after completion of the polymerization, water was polymerized product was taken out by adding, repeatedly washed with water until the pH test paper became neutral using a household mixer to obtain a port Rimmer. The obtained polymer was dried under reduced pressure at 80 ° C. overnight. The logarithmic viscosity of the polymer was 2.19. 1 g of this polymer was dissolved by heating in 10 ml of N-methyl-2-pyrrolidone, mixed with 40 ml of the film-forming solution prepared in Example 3, and then the same as in Example 1 except that the cast thickness was adjusted.
A blend film having a thickness of 50 μm made of a resin composition containing the sulfonic acid group-containing polyarylene ether compound of the present invention was prepared. The content of the sulfonic acid group-containing polyarylene ether compound in the resin composition is 91% by mass.

When the ion conductivity of this film was measured, it showed a value of 0.06 S / cm in 25 ° C. water. The methanol permeation rate was 3.5 mmol / m ² · sec.

(Example 10)
3,3 ', 4,4'-tetra-diaminodiphenyl sulfone ^{1.830g (6.575 × 10 -3 mole)} , 3,5- dicarboxyphenyl phosphonic acid 1.084g (4.405 × 10 ^-3 mole) , 0.360 g (2.170 × 10 ⁻³ mole) of terephthalic acid, 20.5 g of polyphosphoric acid (phosphorus pentoxide content: 75 mass%) and 16.5 g of phosphorus pentoxide are weighed in a polymerization vessel. The temperature is raised to 100 ° C. while slowly stirring on an oil bath while flowing nitrogen. After maintaining at 100 ° C. for 1 hour, the temperature was raised to 150 ° C. for 1 hour, and the temperature was raised to 200 ° C. and polymerized for 7 hours. Was allowed to cool after completion of the polymerization, water was polymerized product was taken out by adding, repeatedly washed with water until the pH test paper became neutral using a household mixer to obtain a port Rimmer. The obtained polymer was dried under reduced pressure at 80 ° C. overnight. The logarithmic viscosity of the polymer measured using sulfuric acid was 1.07.

  A blend comprising the resin composition containing the sulfonic acid group-containing polyarylene ether compound of the present invention mixed with 40 ml of the film-forming solution prepared in Example 3 in the same manner as in Example 9 using 1 g of this polymer A film was prepared. The content of the sulfonic acid group-containing polyarylene ether compound in the resin composition is 91% by mass.

When the ion conductivity of this film was measured, it showed a value of 0.04 S / cm in 25 ° C. water. The methanol permeation rate was 2.9 mmol / m ² · sec.

(Example 11)
When the film produced in Example 2 was used as the film sample and the power generation evaluation was performed by the above-described method, a favorable power generation characteristic of 0.34 V was obtained at a current density of 100 mA.

(Example 12)
Except for using a 10% by mass N-methyl-2-pyrrolidone solution of the polymer synthesized in Example 1 in place of the Nafion (registered trademark) solution, the same method as the method for preparing the electrolyte membrane / electrode assembly in the power generation evaluation described above By using the film prepared in Example 2 as a membrane sample, an electrolyte membrane / electrode assembly was prepared. When the obtained electrolyte membrane / electrode assembly was visually observed, it was a good assembly with no electrode peeling.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  The sulfonic acid group-containing polyarylene ether compound of the present invention can provide a polymer electrolyte material that is excellent not only in ion conductivity but also in heat resistance, workability, and dimensional stability. These can be used for fuel cells and water electrolyzers that use hydrogen or methanol as raw materials as ion conductive membranes, but various battery electrolytes, humidifying membranes, humidity adjusting membranes, display elements, sensors, binders, It is expected to be used as an additive.

It is a figure which shows the 1HNMR spectrum of the film which consists of a sulfonic acid group containing polyarylene ether type compound obtained in Example 1, and the structural formula which belongs from this spectrum. It is a figure which shows the 1HNMR spectrum of the film which consists of a sulfonic-acid-group containing polyarylene ether type compound obtained in Example 2, and the structural formula which belongs from this spectrum.

Claims (16)

A sulfonic acid group-containing polyarylene ether having a logarithmic viscosity of 0.1 or more, which contains a constituent represented by the following general formula (1) and a constituent represented by the following general formula (2) in the molecular chain A compound based on
The logarithmic viscosity is obtained by using the sulfonic acid group-containing polyarylene ether compound as a sample, a solution obtained by dissolving the sample in a solvent composed of N-methylpyrrolidone at a sample concentration of 0.5 g / dl, and 30 Ln [ta / tb] / c when viscosity is measured using a Ubbelohde viscometer in a constant temperature bath at 0 ° C. (where ta is the number of seconds that the sample solution is dropped and tb is the number of seconds that the solvent is dropped) , C is the sample concentration), and a sulfonic acid group-containing polyarylene ether compound.

(However, X is hydrogen or a monovalent cation species, Y is a sulfone group or a ketone group, and n is an arbitrary integer of 2 or more.)

(However, n represents an arbitrary integer of 2 or more.)   The sulfonic acid group-containing polyarylene ether compound according to claim 1, wherein the sulfonic acid group content is in the range of 0.3 to 5.0 meq / g. The following general formula (3),

(However, o represents an arbitrary integer of 0 or more.)
It is obtained by using a terminal dihydroxy compound represented by the formula (1) as a part of the monomer component comprising a plurality of components having different o and having an average composition in the range of 1 <o ≦ 10. Item 3. The sulfonic acid group-containing polyarylene ether compound according to Item 1 or 2.   The sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 3, wherein the glass transition temperature is in the range of 130C to 220C. The sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 4 is contained in a range of 50% by mass or more and less than 100% by mass, and the sulfonic acid group-containing polyarylene ether compound is combined with a polymer. Resin composition.   A polymer electrolyte membrane containing the sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 4.   A polymer electrolyte membrane comprising the resin composition according to claim 5. An electrolyte membrane / electrode composite comprising the polymer electrolyte membrane according to claim 6 and an electrode.   A fuel cell containing the electrolyte membrane / electrode composite according to claim 8.   The fuel cell according to claim 9, wherein methanol is used as a fuel. An electrolyte membrane / electrode composite comprising the polymer electrolyte membrane according to claim 7 and an electrode . A fuel cell containing the electrolyte membrane / electrode composite according to claim 11 . The fuel cell according to claim 12, wherein methanol is used as a fuel . An adhesive containing the sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 4 . A production method for obtaining a sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 4,
The sulfonic acid group-containing polyarylene ether compound is represented by the following general formula (4):

(However, n represents an arbitrary integer of 2 or more.)
A method for producing a sulfonic acid group-containing polyarylene ether compound obtained by polymerization using an aromatic nucleophilic substitution reaction using the compound represented by formula (1) as at least one monomer component . A method for producing a polymer electrolyte membrane comprising the sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 4,
Casting the solution containing the sulfonic acid group-containing polyarylene ether compound and the solvent so that the cast thickness is in the range of 10 to 1500 μm;
Drying the cast solution;
A method for producing a polymer electrolyte membrane, comprising:

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