JP2003082012A - Method for producing cross-linked polyelectrolyte and cross-linked polyelectrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cross-linked polyelectrolyte having excellent permanency and useful as a proton conductive membrane such as an electrolyte for primary batteries, an electrolyte for secondary batteries, a solid polyelectrolyte for fuel cells, a display element, various kinds of sensors, a signal transmission medium, a solid capacitor or an ion exchange membrane while maintaining essentially possessed high proton conductivity. SOLUTION: This cross-linked polyelectrolyte having a high cross-linking density is produced by subjecting a monomer having at least >=2 radically polymerizable groups in one molecule to a polymerizing reaction in the presence of a proton conductive polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly durable solid polymer electrolyte, more specifically, an oxidation resistance suitable for use in a polymer electrolyte membrane such as polymer electrolyte fuel cells and water electrolysis cells. The present invention relates to a highly durable solid polymer electrolyte and a method for producing the same.

[0002]

2. Description of the Related Art A solid polymer electrolyte is a solid polymer material having an electrolyte group such as a sulfonic acid group or a carboxylic acid group in the polymer chain, and is firmly bound to a specific ion, or a cation or anion. Since it has the property of selectively permeating ions, it is used as a polymer electrolyte membrane in polymer electrolyte fuel cells and water electrolysis cells.

A polymer electrolyte fuel cell is provided with a pair of electrodes on both sides of a proton-conducting solid polymer electrolyte membrane, and one electrode using pure hydrogen or reformed hydrogen gas as a fuel gas.
(Electrode) is supplied to a different electrode (air electrode) by using oxygen gas or air as an oxidant to obtain an electromotive force. In water electrolysis, the electrolysis of water using a solid polymer electrolyte membrane causes a reverse reaction of a fuel cell reaction to produce hydrogen and oxygen.

However, in actual fuel cells and water electrolysis, side reactions occur in addition to these main reactions. A typical example is the production of hydrogen peroxide (H ₂ O ₂ ). To generate this hydrogen peroxide (H ₂ O ₂ ), at the hydrogen electrode, oxygen mixed in the gas as an impurity or by intentional mixing, or the oxygen electrode melts into the electrolyte and diffuses to the hydrogen electrode. Oxygen is considered to be involved in the reaction, while in water electrolysis, a side reaction that produces hydrogen peroxide (H ₂ O ₂ ) may occur in almost the same manner.

The hydrogen peroxide generated on these electrodes is separated from the electrodes by diffusion or the like and moves into the electrolyte. Since this hydrogen peroxide has a strong oxidizing power, it oxidizes many organic substances that make up the electrolyte. Although the detailed mechanism has not been clarified, it is considered that hydrogen peroxide is radicalized in many cases, and the generated hydrogen peroxide radical is a direct reactant of the oxidation reaction.

Japanese Patent Laid-Open No. 2001-118591 discloses a highly durable polymer electrolyte excellent in oxidation resistance against peroxide generated by a battery reaction in order to improve the durability of the polymer electrolyte. . In this publication, specifically, a transition metal oxide having a catalytic ability for catalytically decomposing a peroxide is dispersed and blended in a polymer electrolyte, or a peroxide such as a metal peroxide which suppresses decomposition of the peroxide. The substance stabilizer is dispersed and blended, or the phenolic hydroxyl group is introduced into the electrolyte polymer by a chemical bond. However, if a metal peroxide is blended in the polymer electrolyte, the membrane strength will drop extremely, so the polymer electrolyte membrane will not be formed during the mounting work when actually using the polymer electrolyte membrane to make a fuel cell. It causes serious problems such as breaking. Also, in order to express high radical resistance by the method of introducing a phenolic hydroxyl group into the electrolyte polymer by a chemical bond, it is necessary to introduce a large number of phenolic hydroxyl groups,
Since there is a fatal problem that the proton conductivity of the polymer electrolyte decreases, the method of maintaining high radical resistance and tough film strength while maintaining high proton conductivity is limited and still insufficient. .

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polymer electrolyte which maintains its original high proton conductivity and is excellent in durability.

[0008]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention comprises polymerizing a monomer having at least two radically polymerizable groups in one molecule in the presence of a proton conductive polymer. The present invention relates to a method for producing a crosslinked polyelectrolyte. The content of insoluble matter in N-methylpyrrolidone obtained by this production method is 40% by weight.
The present invention relates to the crosslinked polyelectrolyte itself.

1. [Proton Conductive Polymer] The proton conductive polymer has an electrolyte group and a hydrocarbon moiety, and examples of the electrolyte group include ion-forming functional groups such as a sulfonic acid group and a carboxylic acid group. Further, in the hydrocarbon part of the proton conductive polymer, the electrolyte group is introduced at a predetermined introduction rate with respect to the part into which the electrolyte group can be introduced.

Specific examples of the polymer compound having a hydrocarbon moiety into which the above-mentioned electrolyte group is introduced include polyarylene sulfone resin, polyether sulfone resin, polyether ether ketone resin, straight-chain phenol-formaldehyde resin, cross-linking type. Phenol formaldehyde resin, linear polystyrene resin, crosslinked polystyrene resin, linear poly (trifluorostyrene) resin, crosslinked (trifluorostyrene) resin, poly (2,3-diphenyl-1,4-phenylene oxide) Resin, poly (allyl ether ketone) resin, poly (arylene ether sulfone) resin, poly (phenylquinosan phosphorus) resin, poly (benzylsilane) resin, polystyrene-graft-ethylene tetrafluoroethylene resin, polystyrene-graft-polyvinylidene fluoride Resin, polystyrene-gra Examples thereof include futo-tetrafluoroethylene resin.

In the present invention, a sulfonated polyarylene is preferably used as the proton conductive polymer. Further, when the proton conductive polymer has a radical reactive group, the insoluble N-methylpyrrolidone is insoluble even when the amount of the monomer having at least two radical polymerizable groups in one molecule used in the present invention is small. It is preferable because a crosslinked polyelectrolyte having a large content can be obtained. Examples of the radical-reactive group include an alkyl group having a tertiary carbon atom from which a hydrogen atom is easily abstracted by a free radical (specific example: isopropyl group), an aryl group, a vinyl group, a mercapto group, an acryloyl group, a methacryloyl group and the like. be able to. In particular, in the case of an alkyl group having a tertiary carbon, the alkyl group having a tertiary carbon is likely to remain in the polymer even after sulfonation, so that this functional group acts efficiently as a cross-linking reaction point, and more highly It is preferable because a crosslinked crosslinked polymer electrolyte is obtained.

The polyarylene before the sulfonation reaction is (a) a polyarylene polymer containing an aromatic compound unit having an electron-withdrawing group in the main chain (hereinafter referred to as unit (A)), Since the unit (A) has a flexible structure in the main chain, it has high toughness and is preferable.

Further, it is a polyarylene copolymer containing the above unit (A) and (b) an aromatic compound unit having no electron-withdrawing group in the main chain (hereinafter referred to as unit (B)). However, the upper limit of the amount of sulfonic acid groups introduced can be controlled by the unit (B), the toughness and hot water resistance do not easily decrease even when sulfonated, and the toughness, mechanical strength, elastic modulus, and anti-swelling property are excellent. , Better than this.

(1) Monomer constituting unit (A) As the monomer constituting the unit (A) (hereinafter referred to as "monomer (A)"), the following general formula (a) is preferred.
1-1m), (a1-2m) and those represented by (a2m) Monomers (hereinafter, “monomer (A1)”,
"Monomer (A2)" and "monomer (A3)"
Is mentioned.

[0015]

[Chemical 8] During ... (a1-1m) (general formula (a1-1m), X is independently a chlorine atom, a bromine atom, an iodine atom or -OSO ₂ Y (wherein, Y is an alkyl group, a halogenated alkyl group or an aryl group And A is an electron-withdrawing group, and R ^{1 to} R ⁸ are the same or different and each is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group.)

In the above general formula (a1-1m), electron withdrawing property
As the group (A), -CO-, -CONH-,-(CF
₂) P- (where p is an integer of 1 to 10), -C
(CF ₃)₂ -, -COO-, -SO-, -SO₂− Etc.
Is mentioned.

Similarly, the alkyl group may be a methyl group, an ethyl group, an isopropyl group or the like, and the fluoroalkyl group may be a trifluoromethyl group, a pentafluoroethyl group or the like. An isopropyl group or the like having a tertiary carbon acts as a cross-linking point in the cross-linking reaction, and the cross-linking reaction occurs efficiently, which is preferable.

Similarly, as Z in -OSO ₂ Y,
An alkyl group such as a methyl group or an ethyl group, a halogenated alkyl group such as a trifluoromethyl group or a pentafluoroethyl group, an aryl group such as a phenyl group, p
-A tolyl group and the like.

Specific examples of the monomer (A1) are shown below. (A1-1) 4,4'-dichlorobenzophenone, 2,4'-dichlorobenzophenone, 3,3'-dichlorobenzophenone,
4,4'-dibromobenzophenone, 2,4'-dibromobenzophenone, 3,3'-dibromobenzophenone, 4,4'-diiodobenzophenone, 2,4'-diiodobenzophenone, 3,3'-
Diiodobenzophenone, bis (4-trifluoromethylsulfonyloxyphenyl) ketone, bis (3-trifluoromethylsulfonyloxyphenyl) ketone.

(A1-2) 4,4'-dichlorobenzanilide, 3,
3'-dichlorobenzanilide, 3,4'-dichlorobenzanilide, 4,4'-dibromobenzanilide, 3,3'-dibromobenzanilide, 3,4'-dibromobenzanilide, 4,4'-diiodo Benzanilide, 3,3'-diiodo Benzanilide, 3,4'-diiodo Benzanilide.

(A1-3) bis (chlorophenyl) difluoromethane, bis (chlorophenyl) tetrafluoroethane,
Bis (chlorophenyl) hexafluoropropane, bis
(Chlorophenyl) octafluorobutane, bis (chlorophenyl) decafluoropentane, bis (chlorophenyl) dodecafluorohexane, bis (chlorophenyl) tetradecafluoroheptane, bis (chlorophenyl) hexadecafluorooctane, bis (chlorophenyl) octadecafluorononane, Bis (chlorophenyl) eicosafluorodecane, bis (bromophenyl) difluoromethane, bis (bromophenyl) tetrafluoroethane, bis
(Bromophenyl) hexafluoropropane, bis (bromophenyl) octafluorobutane, bis (bromophenyl) decafluoropentane, bis (bromophenyl) dodecafluorohexane, bis (bromophenyl) tetradecafluoroheptane, bis (bromophenyl) Hexadecafluorooctane, bis (bromophenyl) octadecafluorononane, bis (bromophenyl) eicosafluorodecane, bis (iodophenyl) difluoromethane, bis
(Iodophenyl) tetrafluoroethane, bis (iodophenyl) hexafluoropropane, bis (iodophenyl) octafluorobutane, bis (iodophenyl) decafluoropentane, bis (iodophenyl) dodecafluorohexane, bis (iodophenyl) tetra Decafluoroheptane, bis (iodophenyl) hexadecafluorooctane, bis (iodophenyl) octadecafluorononane, bis (iodophenyl) eicosafluorodecane.

(A1-4) 2,2-bis (4-chlorophenyl) hexafluoropropane, 2,2-bis (3-chlorophenyl) hexafluoropropane, 2,2-bis (4-bromophenyl) hexafluoropropane 2,2-bis (3-bromophenyl) hexafluoropropane, 2,2-bis (4-iodophenyl) hexafluoropropane, 2,2-bis (3-iodophenyl) hexafluoropropane, bis (4- Trifluoromethylsulfonyloxyphenyl) hexafluoropropane, bis
(3-Trifluoromethylsulfonyloxyphenyl) hexafluoropropane.

(A1-5) 4-chlorophenyl 4-chlorobenzoate, 3-chlorophenyl 4-chlorobenzoate, 3-chlorophenyl 3-chlorobenzoate, 4-chlorophenyl 3-chlorobenzoate, 4- Bromobenzoic acid-4-bromophenyl, 4-bromobenzoic acid-3-bromophenyl, 3-bromobenzoic acid-3-
Bromophenyl, 4-bromobenzoic acid-4-bromophenyl
(A1-6) bis (4-chlorophenyl) sulfoxide, bis (3-
Chlorophenyl) sulfoxide, bis (4-bromophenyl) sulfoxide, bis (3-bromophenyl) sulfoxide, bis (4-iodophenyl) sulfoxide, bis (3-iodophenyl) sulfoxide, bis (4-trifluoromethylsulfonyloxy) Phenyl) sulfoxide, bis (3-trifluoromethylsulfonyloxyphenyl) sulfoxide.

(A1-7) Bis (4-chlorophenyl) sulfone, bis (3-chlorophenyl) sulfone, bis (4-bromophenyl) sulfone, bis (3-bromophenyl) sulfone, bis (4-iodophenyl) sulfone , Bis (3-iodophenyl) sulfone, bis (4-trifluoromethylsulfonyloxyphenyl) sulfone, bis (3-trifluoromethylsulfonyloxyphenyl) sulfone.

[0025]

[Chemical 9] ... (a1-2m) (In general formula (a1-2m), X and R < ¹ > -R < ⁸ > are formula (a1).
−1m), A is independently an electron-withdrawing group as defined for formula (a1-1m), R ^{1 ′ to} R ^{8 ′} are the same or different and are hydrogen atoms,
It is a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group. ) The alkyl group and fluoroalkyl group in the general formula (a1-2m) are as defined for the general formula (a1-1m).

Specific examples of the monomer (A2) are shown below. (A2-1) 4,4'-bis (4-chlorobenzoyl) diphenyl ether, 4,4'-bis (3-chlorobenzoyl) diphenyl ether, 4,4'-bis (4-bromobenzoyl) diphenyl ether, 4,4 '-Bis (3-bromobenzoyl) diphenyl ether, 4,4'-bis (4-iodobenzoyl) diphenyl ether, 4,4'-bis (3-iodobenzoyl) diphenyl ether, 4,4'-bis (4-trifluoro Methylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-Methylsulfonyloxyphenyl) diphenyl ether.

(A2-2) 4,4'-bis (4-chlorobenzoylamino) diphenyl ether, 3,4'-bis (4-chlorobenzoylami) diphenyl ether, 4,4'-bis (3-chlorobenzoylamino) ) Diphenyl ether, 3,4'-bis (3-chlorobenzoyl) diphenyl ether, 4,4'-bis (4-bromobenzoylamino) diphenyl ether, 3,4'-bis
(4-Bromobenzoylamino) diphenyl ether, 4,4 '
-Bis (3-bromobenzoylamino) diphenyl ether, 3,4'-bis (3-bromobenzoylamino) diphenyl ether, 4,4'-bis (4-iodobenzoylamino) diphenyl ether, 3,4'-bis (4- Iodobenzoylamino) diphenyl ether, 4,4'-bis (3-iodobenzoylamino) diphenyl ether, 3,4'-bis (3-iodobenzoylamino) diphenyl ether, 4,4'-bis (4-trifluoromethylsulfonyl) Roxyphenyl) diphenyl ether, 3,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-
Trifluoromethylsulfonyloxyphenyl) diphenyl ether, 3,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (4
-Methylsulfonyloxyphenyl) diphenyl ether, 3,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether, 3,4'-bis ( 3-Methylsulfonyloxyphenyl) diphenyl ether.

(A2-3) 4,4'-bis (4-chlorophenylsulfonyl) diphenyl ether, 3,4'-bis (4-chlorophenylsulfonyl) diphenyl ether, 4,4'-bis (3-chlorophenylsulfonyl) diphenyl ether, 3,4'-bis (3-chlorophenylsulfonyl) diphenyl ether,
4,4'-bis (4-bromophenylsulfonyl) diphenyl ether, 3,4'-bis (4-bromophenylsulfonyl) diphenyl ether, 4,4'-bis (3-bromophenylsulfonyl) diphenyl ether, 3,4'- Bis (3-bromophenylsulfonyl) diphenyl ether, 4,4-bis (4-iodophenylsulfonyl) diphenyl ether, 3,4'-bis (4-
Iodophenylsulfonyl) diphenyl ether, 4,4'-
Bis (3-iodophenylsulfonyl) diphenyl ether, 3,4'-bis (3-iodophenylsulfonyl) diphenyl ether, 4,4'-bis (4-trifluoromethylsulfonyloxyphenisulfonyl) diphenyl ether, 3,4'-
Bis (4-trifluoromethylsulfonyloxyphenylsulfonyl) diphenyl ether, 4,4'-bis (3-trifluoromethylsulfonyloxyphenisulfonyl) diphenyl ether, 3,4'-bis (3-trifluoromethylsulfonyloxy) Phenylsulfonyl) diphenyl ether, 4,4'-bis (4-methylsulfonyloxyphenisulfonyl) diphenyl ether, 3,4'-bis (4-methylsulfonyloxyphenylsulfonyl) diphenyl ether,
4,4'-bis (3-methylsulfonoxyphenisulfonyl) diphenyl ether, 3,4'-bis (3-methylsulfonyloxyphenylsulfonyl) diphenyl ether.

(A2-4) 4,4'-bis (4-chlorophenyl) diphenyl ether dicarboxylate, 3,4'-bis (4-chlorophenyl) diphenyl ether dicarboxylate,
4,4'-bis (3-chlorophenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-chlorophenyl) diphenyl ether dicarboxylate, 4,4'-bis (4-bromophenyl) diphenyl ether dicarboxylate, 3 ,
4'-bis (4-bromophenyl) diphenyl ether dicarboxylate, 4,4'-bis (3-bromophenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-bromophenyl) diphenyl ether dicarboxylate, 4 ,Four'-
Bis (4-iodophenyl) diphenyl ether dicarboxylate, 3,4′-bis (4-iodophenyl) diphenyl ether dicarboxylate, 4,4′-bis (3-iodophenyl) diphenyl ether dicarboxylate, 3,4 ′ -Screw
(3-iodophenyl) diphenyl ether dicarboxylate, 4,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate,
3,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 4,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-Trifluoromethylsulfonoxyphenyl) diphenyl ether dicarboxylate, 4,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 3,4'-bis (4-methylsulfonyloxyphenyl) ) Diphenyl ether dicarboxylate, 4,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate.

(A2-5) 4,4'-bis [(4-chlorophenyl)-
1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4 , 4'-bis [(3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-chlorophenyl) -1,1,1,3 , 3,3-Hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) -1,1,
1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4-bromophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4 ' -Bis [(3-bromophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-bromophenyl) -1,1,1,3, 3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) -1,1,1,
3,3,3-hexafluoropropyl] diphenyl ether,
3,4'-bis [(4-iodophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-
Iodophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-iodophenyl) -1,1,1,3,3,3-hexafluoro Propyl] diphenyl ether, 4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4 -Trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl)-
1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3,3-hexa Fluoropropyl]
Diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4-methylsulfoni Roxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-methylsulfonyloxyphenyl) -1,1,1,3,3,3 -Hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-methylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether.

(A2-6) 4,4'-bis [(4-chlorophenyl) tetrafluoroethyl] diphenyl ether, 4,4'bis [(3-chlorophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [ (4-chlorophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-
Chlorophenyl) hexafluoropropyl] diphenyl ether, 4,4'bis [(4-chlorophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(3-chlorophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [ (4-chlorophenyl) decafluoropentyl] diphenyl ether, 4,4′-bis [(3-chlorophenyl) decafluoropentyl] diphenyl ether, 4,
4'-bis [(4-bromophenyl) tetrafluoroethyl]
Diphenyl ether, 4,4'-bis [(3-bromophenyl)
Tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-Bromophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) decafluoropentyl] diphenyl ether , 4,4'-bis [(3-bromophenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) tetrafluoroethyl] diphenyl ether,
4,4'-bis [(3-iodophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) hexafluoropropyl] diphenyl ether, 4,
4'-bis [(3-iodophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) octafluorobutyl] diphenyl ether, 4,4'-
Bis [(3-iodophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3-iodophenyl) decafluoropentyl] Diphenyl ether, 4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4, 4'-bis [(4-trifluoromethylsulfonyloxyphenyl) octafluorobutyl] di Phenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) decafluoropentyl] diphenyl ether , 4,4'-bis [(3-trifluoromethylsulfonyloxy) decafluoropentyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether, 4,4 ' -
Bis [(3-methylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-methyl Sulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(3-methylsulfonyloxyphenyl)
Octafluorobutyl] diphenyl ether, 4,4′-bis [(4-methylsulfonoxyphenyl) decafluoropentyl] diphenyl ether, 4,4′-bis [(3-methylsulfonyloxy) decafluoropentyl] diphenyl ether.

[0032]

[Chemical 10] (A2m) (In general formula (a2m), A is independently an electron-withdrawing group as defined in formula (a1-1m), and B is independently an electron-donating atom or a divalent group. , X is independently a chlorine atom, a bromine atom or an iodine atom, R ^{1 to} R ⁸ are the same or different and each is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group, and n is 2 or more, It is preferably an integer of 2 to 100, particularly preferably 2 to 80.)

Examples of the electron-donating atom or the divalent group (B) in the above general formula (a2m) include --O--, --S--,-.
CH = CH-, -C≡C-,

[0034]

[Chemical 11]

[0035]

[Chemical 12] And so on.

Specific examples of the above monomer (A3) include:
For example, 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,3-hexafluoropropane,
Bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl]
Examples thereof include sulfone, and those represented by the following chemical formulas.

[0037]

[Chemical 13] [In the above formula, X is as defined for the general formula (a2m). ]

The above monomer (A3) that can be used in the present invention
In addition to the monomer represented by n = 2, "oligomer" or "polymer" in which n is larger than 2 can be used. As an example, the specific structural formula of an oligomer or polymer having a structure having an aromatic chloride at the molecular end is as follows.

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

The monomer (A3) includes, for example, when the electron donating group is --O--, bisphenol linked with the electron withdrawing group (A) and fluorine activated with the electron withdrawing group.
Aromatic dihalide compound substituted with a halogen atom such as chlorine, for example, 4,4'-difluorobenzophenone, 4,4'-
Dichlorobenzophenone, 4,4'-chlorofluorobenzophenone, bis (4-chlorophenyl) sulfone, bis (4-
(Fluorophenyl) sulfone, 4-fluorophenyl-4'-
Chlorophenyl sulfone, bis (3-nitro-4-chlorophenyl) sulfone, 2.6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, hexafluorobenzene, decafluorobiphenyl, 2,5-difluorobenzophenone, 1,3-bis ( It can be synthesized by reacting 4-chlorobenzoyl) benzene or the like. It is preferable to use a chlorofluoro compound having one halogen atom with different reactivity as the active aromatic dihalide, and since the fluorine atom preferentially causes the nucleophilic substitution reaction with the phenoxide as in the following reaction, the purpose is It is convenient to obtain the activated terminal chloro form of.

[0043]

[Chemical 17]

(2) Monomer constituting unit (B) Monomer constituting unit (B) (hereinafter referred to as monomer (B))
), Preferably the following general formula (b1m)
Monomers represented by (b4m) (hereinafter, referred to as “monomer (B1)”, “monomer (B2)”, “monomer (B3)”, and “monomer (B4)”, respectively).

[0045]

[Chemical 18] … (B1m) (In general formula (b1m), A is constant with respect to formula (a1-1m).
It is an electron-withdrawing group as defined, and B is independently a group represented by the formula (a
2m) electron-donating atom as defined for
X is independently a chlorine atom, a bromine atom or iodine.
An atom, R ⁹~ R¹⁵Are the same or different and
Child, fluorine atom, allyl group, alkyl group or fluoro
Alkyl group, Z is aryl group, m is 0, 1
Alternatively, it is an integer of 2. ) The alkyl group or fluoroalkyl group has the formula
As defined for (a1-1m). Aesop
When it is an alkyl group having a tertiary carbon atom such as a ropyl group,
During the cross-linking reaction, it acts as a cross-linking reaction point, resulting in a high degree of cross-linking.
It is preferable because a crosslinked polyelectrolyte can be obtained.

Examples of the aryl group relating to Z are, for example, a phenyl group, a naphthyl group and a formula:

[0047]

[Chemical 19] (In the formula, R ^{25 to} R ³³ are R ^{9 to} R ^{15 with} respect to the formula (b1m).
Is the same as that defined in. ) And a biphenylyl group represented by.

Examples of the monomer (B1) include compounds represented by the following formula.

[0049]

[Chemical 20] [In the formula, X and Z are as defined in the general formula (b1m). ]

More specifically, examples of the monomer (B1) include 2,4-dichloro-4'-phenoxybenzophenone, 4'-phenoxyphenyl 2,5-dichlorobenzoate and 4'-phenoxyphenyl 2,4. -Dichlorobenzoate, and also those represented by the following formula.

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

[0055]

[Chemical 25]

[0056]

[Chemical formula 26]

The monomer (B1) is, for example, 2,5-dichloro-4 '-[(4-phenoxy) phenoxy] benzophenone, which is 2,5-dichloro-4'-fluorobenzophenone and p-phenoxy. Phenol is used as a starting reaction material, and potassium carbonate is added to this to convert it into a highly reactive phenoxide, and as a reaction solvent, aprotic dipolar polar solvents such as dimethylacetamide, toluene, N-methylpyrrolidone, and dimethylsulfoxide. Can be used for the synthesis for 1 to 30 hours at a reaction temperature of 80 to 200 ° C.

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29] (The above general formulas (b2m), (b3m) and (b4m)
Wherein X is independently a chlorine atom, a bromine atom, an iodine atom or —OSO ₂ Y (wherein Y represents an alkyl group, a halogenated alkyl group or an aryl group), and R ^{17 to} R ^17
24 are the same or different and each is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group. )

In the general formulas (b2m) to (b4m),
When R ^{17 to} R ²⁴ are an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and the like can be mentioned, and in the case of a fluoroalkyl group, a trifluoromethyl group, a pentafluoroethyl group and the like can be mentioned. Can be mentioned.

Specific examples of the above-mentioned monomer (B2) include:
These include: p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5-dibromotoluene, 2,5-diiodotoluene, 2,5- Dimethylsulfonoxybenzene, 2,5-dichloro-p-xylene, 2,5-dibromo-p-xylene, 2,5-diiodo-p-xylene, 2,5-dichlorobenzotrifluoride, 2,5-dibromo Benzotrifluoride, 2,5-diiodobenzotrifluoride, 1,4-dichloro-2,3,5,6-tetrafluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluorobenzene, 1,4-diiodo-2,3,5,6-tetrafluorobenzene. Among the above, preferred are p-dichlorobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, and 2,5-dichlorobenzotrifluoride.

Specific examples of the above-mentioned monomer (B3) include:
These include: 4,4'-Dimethylsulfonoxybiphenyl, 4,4'-Dimethylsulfonyloxy-3,3'-
Dipropenyl biphenyl, 4,4'-dibromobiphenyl,
4,4'-diiodobiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-dimethylbiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-difluorobiphenyl, 4,4'- Dimethylsulfonyloxy-3,3 ', 5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl, 4,4'-
Methylsulfonyloxyoctafluorobiphenyl. Among the above, 4,4'-dimethylsulfonoxybiphenyl, 4,4'-dibromobiphenyl, 4,4'- are preferable.
Diiodobiphenyl, 4,4'-dimethylsulfonyloxy-
It is 3,3'-dipropenyl biphenyl.

Specific examples of the above-mentioned monomer (B4) include:
These include: m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene, 2,4-diiodotoluene, 3,5- Dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2,
6-diiodotoluene, 3,5-dimethylsulfonoxytoluene, 2,6-dimethylsulfonoxytoluene, 2,4-
Dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzotrifluoride , 1,3-Dibromo-2,4,5,6-tetrafluorobenzene. Among the above, preferred are m-dichlorobenzene, 2,4-dichlorotoluene, 3,5-dimethylsulfonyloxytoluene, and 2,4-dichlorobenzotrifluoride.

The monomer (B) for constituting the unit (b) of the polyarylene copolymer of the present invention is
Among the above monomers (B1) to (B4), solubility,
From the viewpoint of high molecular weight, dichlorobenzoic acid derivative,
For example, 2,5-dichloro-4'-phenoxybenzophenone,
Preference is given to using 2,4-dichloro-4′-phenoxybenzophenone, 2,5-dichloro-4′-phenoxyphenylbenzoate, 2,4-dichloro-4′-phenoxyphenylbenzoate.

(3) Synthesis of Polyarylene Copolymer (a) An aromatic compound unit having an electron-withdrawing group in the main chain, and (b) an aromatic compound unit having no electron-withdrawing group in the main chain The polyarylene-based copolymer having is a monomer (A1), a monomer (A2) and a monomer (A
At least one monomer (A) selected from the group consisting of 3), the above-mentioned monomer (B1), monomer (B2),
It can be synthesized by a coupling reaction with at least one monomer (B) selected from the group consisting of the monomer (B3) and the monomer (B4).

The catalyst used in the production of the polyarylene copolymer is a catalyst system containing a transition metal compound, and this catalyst system includes (1) a transition metal salt and a compound which becomes a ligand ( Hereinafter, referred to as a ligand component), or a transition metal complex (including a copper salt) coordinated with a ligand, and
(2) A reducing agent is an essential component, and a “salt” may be added to further increase the polymerization rate.

As the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate, palladium chloride,
Examples thereof include palladium compounds such as palladium bromide and palladium iodide, iron compounds such as iron chloride, iron bromide and iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferable.

Examples of the ligand component include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene and 1,3-bis (diphenylphosphino) propane. Phosphine and 2,2'-bipyridine are preferred. The compound that is the ligand component may be used alone or in combination of two or more.

Further, examples of the transition metal complex having a ligand coordinated in advance include, for example, nickel chloride bis (triphenylphosphine), nickel bromide bis (triphenylphosphine), and nickel iodide bis (triphenylphosphine). , Nickel nitrate bis (triphenylphosphine),
Nickel chloride (2,2'-bipyridine), nickel bromide (2,2'-
Bipyridine), nickel iodide (2,2'-bipyridine), nickel nitrate (2,2'-bipyridine), bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine)
Examples thereof include nickel, tetrakis (triphenylphosphite) nickel and tetrakis (triphenylphosphine) palladium, and nickel chloride bis (triphenylphosphine) and nickel chloride (2,2′-bipyridine) are preferable.

Examples of the reducing agent that can be used in the above catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium and the like, but zinc, magnesium and manganese are preferable. These reducing agents can be further activated and used by bringing them into contact with an acid such as an organic acid.

As the "salt" which can be used in the catalyst system, sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide and sodium sulfate, potassium fluoride, potassium chloride and bromide. Potassium compounds such as potassium, potassium iodide, and potassium sulfate, ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate can be used. Sodium bromide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide are preferred.

The proportion of each component used in the catalyst system is usually 0.0001 to 10 moles, preferably 0.01 to 0, moles of transition metal salt or transition metal complex per 1 mole of the above-mentioned monomers.
It is 5 mol. If it is less than 0.0001 mol, the polymerization reaction will not proceed sufficiently, while if it is more than 10 mol, the molecular weight will decrease.

When a transition metal salt and a ligand component are used in the catalyst system, the ratio of the ligand component used is usually 0.1 to 100 mol, preferably 1 to 10 mol, based on 1 mol of the transition metal salt. Is. If it is less than 0.1 mol, the catalytic activity will be insufficient, while if it exceeds 100 mol, the molecular weight will decrease.

The ratio of the reducing agent used in the catalyst system is usually 0.1 to 100 with respect to 1 mol of the above-mentioned monomers in total.
The molar amount is preferably 1 to 10 mol. If it is less than 0.1 mol, the polymerization does not proceed sufficiently, while if it exceeds 100 mol,
There is a problem that purification of the obtained polymer becomes difficult.

Further, when a "salt" is used in the catalyst system,
The use ratio thereof is usually 0.001 to 100 mol, preferably 0.01 to 1 mol, based on 1 mol of the total amount of the above monomers.
If it is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient, while if it exceeds 100 mol, there is a problem that purification of the resulting polymer becomes difficult.

Examples of the polymerization solvent that can be used for synthesizing the polyarylene copolymer include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- 2-pyrrolidone, γ-butyrolactone, γ-butyrolactam and the like can be mentioned, and tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are preferable.
It is preferable to use these polymerization solvents after drying them sufficiently. The total concentration of the above-mentioned monomers in the polymerization solvent is usually 1 to 90% by weight, preferably 5 to 40% by weight.

The polymerization temperature for polymerizing the polyarylene copolymer is usually 0 to 200 ° C., preferably 50 to 1
20 ° C. The polymerization time is usually 0.5 to 100 hours,
It is preferably 1 to 40 hours.

Here, for example, by polymerizing the monomer (A3) and the monomer (B1) under the above conditions,
General formula:

[0080]

[Chemical 30] (Here, A, B, Z, R ^{1 to} R ¹⁵ , m and n are as described above, p and q each independently represent the number of repeating units, and the ratio of p / q (that is, the above The molar ratio of the two repeating units is from 99/1 to 20/80)).

The structure of the polyarylene copolymer is, for example, 1,230 to 1,250 cm according to the infrared absorption spectrum.
^-1 C-O-C absorption, 1,640 to 1,660 cm ^-1 C = O absorption, etc., and the nuclear magnetic resonance spectrum ( ¹
Its structure can be confirmed by the peak of the aromatic proton at 6.8 to 8.0 ppm by (H-NMR).

(4) Synthesis of polyarylene-based polymer According to the same method and conditions as in the case of the above-mentioned polyarylene-based copolymer, only the monomer (A3) is used as a raw material and the polyarylene of the following structural formula (A) Based polymers can be synthesized.

[0083]

[Chemical 31] (A) (where A, B, Z, R ^{1 to} R ⁸ , and n are as described above, and s is the number of repeating units).

(5) Sulfonation of polyarylene type (co) polymer Next, the (co) polymer having a sulfonic acid group is treated with a sulfonating agent to the above (co) polymer having no sulfonic acid group. It can be obtained by using a conventional method and introducing a sulfonic acid group.

As a method of introducing a sulfonic acid group, for example, a known sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid or sodium hydrogen sulfite is prepared from the copolymer having no sulfonic acid group. It can be used for sulfonation under known conditions without a solvent or in the presence of a solvent.

Examples of the solvent include hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, aprotic polar solvents such as dimethylacetamide, dimethylformamide and dimethylsulfoxide, and tetrachloroethane, dichloroethane, Examples thereof include halogenated hydrocarbons such as chloroform and methylene chloride. The reaction temperature is not particularly limited,
Usually, it is -50 to 200 ° C, preferably -10 to 100 ° C. The reaction time is usually 0.5 to 1,000 hours, preferably 1
~ 200 hours.

The amount of sulfonic acid group in the sulfonic acid group-containing (co) polymer of the present invention thus obtained is 0.5
~ 3 milliequivalents / g, preferably 0.8-2.8 milliequivalents / g. If it is less than 0.5 milliequivalent / g, the proton conductivity will not increase, while if it exceeds 3 milliequivalent / g, the hydrophilicity will be improved to become a water-soluble polymer, or the durability will be improved even if water solubility is not reached. descend.

The above-mentioned amount of sulfonic acid group is based on the amount of monomer (A).
It can be easily adjusted by changing the use ratio of the monomer (B) and the type and combination of the monomer (A) and the monomer (B).

Further, the molecular weight of the thus obtained precursor of the sulfonic acid group-containing polyarylene type (co) polymer before sulfonation is 10 × 10 ³ to 1,000 × in terms of polystyrene equivalent weight average molecular weight. 10 ³ , preferably 20 × 10 ³
~ 800 x 10 ³ . When it is less than 10 × 10 ³ , the coating film properties are insufficient, such as cracks in the molded film, and the strength properties are also problematic. On the other hand, when it exceeds 1,000 × 10 ³ , there are problems that the solubility becomes insufficient, the solution viscosity is high, and the workability becomes poor.

[0090] The structure of the sulfonic acid group-containing polyarylene (co) polymer by the infrared absorption spectrum, 1,030～1,045Cm ^-1, the 1,160~1,190cm ^-1 S = O
Absorption, C-O-C absorption at 1,130 to 1,250 cm ^-1 , 1,640 to
It can be confirmed by C═O absorption at 1,660 cm ⁻¹ , and their composition ratio can be known by neutralization titration of sulfonic acid and elemental analysis. In addition, the nuclear magnetic resonance spectrum ( ¹ H
-NMR), the structure can be confirmed from the peak of the aromatic proton at 6.8 to 8.0 ppm.

Further, an inorganic acid such as sulfuric acid and phosphoric acid, an organic acid such as carboxylic acid, and an appropriate amount of water may be used together with the sulfonic acid group-containing (co) polymer according to the present invention.

2. [Polymerization of Crosslinkable Monomer in the Presence of Proton Conductive Polymer] The crosslinked polymer electrolyte according to the present invention can be obtained by radically polymerizing the crosslinkable monomer in the presence of the proton conductive polymer. The ratio of the proton conductive polymer and the crosslinkable monomer used is 99.9 to 50/0.
The weight ratio is 1 to 50, preferably 99.9 to 70 / 0.1 to 30.

As the polymerization reaction, it is more preferable to react the crosslinkable monomer in the presence of a radical polymerization initiator which generates radicals by the action of heat, light or a reducing agent.

Examples of the radical polymerization initiator include organic peroxides and azobis radical polymerization initiators.
The use of an organic peroxide is preferable because the crosslinking reaction will proceed further.

Specific examples of the organic peroxide include (1) acetyl peroxide, benzoyl peroxide, isobutyroyl peroxide, 2,4-dichlorobenzoyl peroxide and 3,5,5-trimethylhexanoyl peroxide. , Octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, and other diacyl peroxides;

(2) Methyl ethyl ketone peroxide,
Ketone peroxides such as cyclohexanone peroxide, methylcyclohexanone peroxide and acetylacetone peroxide;

(3) Hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Hydroperoxides such as t-hexyl hydroperoxide;

(4) Di-t-butyl peroxide, dicumyl peroxide, dilauryl peroxide, α, α '
-Bis (t-butylperoxy) diisopropylben, 2,5-
Dimethyl-2,5-bis (t-butylperoxy) hexane, t-
Butyl cumyl peroxide, 2,5-dimethyl-2,5-bis
Dialkyl peroxides such as (t-butylperoxy) hexyne-3;

(5) t-butyl peroxyacetate, t-
Butyl peroxypivalate, t-hexyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexa Noylperoxy) hexane, 1-cyclohexyl-
1-Methylethylperoxy 2-ethylhexanoate, t-
Hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t -Butylperoxy 2-ethylhexyl monocarbonate, t-butylperoxyallyl monocarbonate, t-butylperoxy maleate, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate , 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, 1,1, 3,3-Tetramethylbutylperoxy neodecanoate, 1-Cyclohexyl-1-methylethylperoxy neodecanoate, t-hex Sylperoxy neodecanoate, t-butylperoxy neododecanoate, t-butylperoxybenzoate, t-hexylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2, Peroxyesters such as 5-bis (benzoylperoxy) hexane, t-butylperoxy m-toluoyl benzoate, and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

(6) 1,1-bis (t-hexylperoxy) 3,3,
5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) (Oxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, Peroxyketals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane;

(7) Di-n-propyl peroxydicarbonate, disopropyl peroxydicarbonate, bis (4
-t-butylcyclohexyl) peroxydicarbonate,
Di-2-ethoxyethyl peroxydicarbonate, di-2-
Ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, di (3-methyl-3-
Examples thereof include peroxydicarbonates such as methoxybutyl) peroxydicarbonate, and t-butyltrimethylsilyl peroxide.

Specific examples of the azobis radical polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) Isobutyronitrile, 2,2'-
Azobis [2-methyl-N- {1,1-bis (hydroxymethyl) -2-
Hydroxyethyl} propionamide], 2,2'-azobis
[2-Methyl-N- {2- (1-hydroxybutyl)} propionamide], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl)]
-Propionamide], 2,2'-azobis [N- (2-propenyl)]
-2-Methylpropionamide], 2,2'-azobis (N-butyl
-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis
[2- (5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazoline-2-
Ile) propane] dihydrochloride, 2,2'-azobis
[2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- {1- (2-hydroxyethyl) -2-imidazolin-2-yl} propane] dihydrochloride,
2,2'-azobis [2- (2-imidazolin-2-yl) propane],
2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl)
-2-Methyl-propionamidine], 2,2'-azobis (2-methylpropionamidoxime), dimethyl 2,2'-azobisbutyrate, 4,4'-azobis (4-cyanopentanoic acid), 2,2′-azobis (2,4,4-trimethylpentane), a polymer represented by the following formula and the like can be mentioned.

[0103]

[Chemical 32] (Molecular weight: about 30,000-40,000)

[0104]

[Chemical 33] (Molecular weight: about 70,000 to 90,000)

[0105]

[Chemical 34] (Molecular weight: about 15,000 to 30,000)

[0106]

[Chemical 35] (Molecular weight: about 25,000 to 40,000) Incidentally, persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate can also be used as the radical polymerization initiator.

The number of polymerizable groups of the monomer having two or more radically polymerizable groups in one molecule is preferably 3 or more,
It is more preferably 4 or more, and particularly preferably 5 to 6. Examples of the monomer having two or more radically polymerizable groups in one molecule include dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta.
(Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di
(Meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris
(2-hydroxyethyl) isocyanurate di (meth) acrylate, bis (hydroxymethyl) tricyclodecanedi
(Meth) acrylate, diol di (meth) acrylate which is an adduct of ethylene oxide or propylene oxide of bisphenol A, di (meth) acrylate of diol which is an adduct of hydrogenated bisphenol A of ethylene oxide or propylene oxide, bisphenol Epoxy (meth) acrylate obtained by adding hydroxyalkyl (meth) acrylate such as hydroxy (meth) acrylate to diglycidyl ether of A, di (meth) acrylate of polyoxyalkylenated bisphenol A,
Examples thereof include p- or m-divinylbenzene and triethylene glycol divinyl ether.

Examples of commercially available products of monomers having two or more radically polymerizable groups in one molecule include KAYAR.
AD-DPHA, KAYARAD R-604, DPC
A-20, -30, -60, -120, HX-620,
D-310, D-330 (above, manufactured by Nippon Kayaku Co., Ltd.) Iupimer UV SA1002, SA2007 (above, manufactured by Mitsubishi Chemical Corporation), Viscoat # 195, # 230, #
215, # 260, # 335HP, # 295, # 30
0, # 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate 4EG-A, 9EG-A, NP-A, DC
P-A, BP-4EA, BP-4PA, PE-3A, P
E-4A, DPE-6A (above, Kyoeisha Chemical Co., Ltd.
Made), Aronix M-208, M-210, M-2
15, M-220, M-240, M-305, M-30
9, M-315, M-325 (above, Toa Gosei Co., Ltd.
Manufactured) and the like.

In the method for producing a crosslinked polymer electrolyte according to the present invention, in order to obtain an electrolyte membrane (proton conductive membrane), for example, a sulfonic acid group-containing copolymer is dissolved in a solvent and then a polyfunctional radical-polymerizable monomer is used. A mixture of the radical polymerization initiator and the radical polymerization initiator may be formed into a film by casting and then heated to volatilize the solvent, and thereafter, the radical polymerization / crosslinking reaction may be performed at a higher temperature. The obtained crosslinked film is no longer soluble or slightly soluble in a solvent and can be used as an electrolyte membrane (proton conductive membrane).

As the solvent in the above casting method, dimethylacetamide, dimethylformamide,
Examples include aprotic polar solvents such as N-methyl-2-pyrrolidone and dimethyl sulfoxide. An alcohol solvent such as methanol may be further mixed with these solvents.

The crosslinked polymer electrolyte obtained by the production method of the present invention is, for example, an electrolyte for a primary battery, an electrolyte for a secondary battery, a polymer solid electrolyte for a fuel cell, a display element, various sensors, and signal transmission as a film body. Medium, solid condenser,
It can be used as a proton conductive membrane that can be used as an ion exchange membrane.

[0112]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Various measurement items in the examples were determined as follows. [Weight Average Molecular Weight] The weight average molecular weight of the precursor polymer before sulfonation is determined by using tetrahydrofuran (THF) as a solvent.
Gel permeation chromatography (G
The molecular weight in terms of polystyrene was determined by (PC).

[Amount of Sulfonic Acid Group] Washing water of the obtained sulfonated polymer was washed until the pH was adjusted to 4 to 6 to remove free residual acid, followed by thorough washing with water and drying. Weigh a fixed amount, dissolve in a mixed solvent of THF / water,
Phenolphthalein was used as an indicator and titrated with a standard solution of NaOH to determine the amount of sulfonic acid groups (milligram equivalent / g) from the neutralization point.

[Measurement of Proton Conductivity] A film sample having a diameter of 13 mm placed under 100% relative humidity was sandwiched between platinum electrodes and enclosed in a closed cell, and an impedance analyzer (HYP4192A) was used to measure the frequency 5 to 5. 13 MH
The absolute value of the impedance of the cell and the phase angle were measured at z, applied voltage 12 mV, temperature 20 ° C., 50 ° C. and 100 ° C. The obtained data was subjected to complex impedance measurement at an oscillation level of 12 mV using a computer to calculate the proton conductivity.

[Measurement of Tensile Strength, Tensile Elongation and Young's Modulus] The tensile strength, tensile elongation and Young's modulus were measured by a tensile test of the obtained film at room temperature.

[Fenton Test] A Fenton reagent was prepared by adding iron sulfate heptahydrate to 3 wt% hydrogen peroxide so that the concentration of iron ions was 20 ppm. Collect 200 g of Fenton's reagent in a 250 cc polyethylene solution, 3 cm
A polymer electrolyte membrane cut into a size of 4 cm and a film thickness of 55 μm was charged, sealed, and then immersed in a constant temperature water bath at 45 ° C. to perform a Fenton test for 150 hours. After the Fenton test, the film was taken out and washed with ion-exchanged water, then at 25 ℃ ・ 50% RH ・ 12
The h state was prepared and various physical properties were measured. The weight retention rate in the Fenton test was calculated by the following mathematical formula. Weight retention rate in Fenton test (%) = film weight after Fenton test / film weight before Fenton test x 100

-Synthesis Example 1- [Synthesis of Sulfonated Polymer 1] (Synthesis of Oligomer) Stirrer, Thermometer, Cooling Tube, Dean-S
In a 1 L three-necked flask equipped with a tark tube and a three-way cock for introducing nitrogen, 2,2-bis (4-hydroxyphenyl) -1,
1,1,3,3,3-hexafluoropropane (bisphenol A
F) 67.3 g (0.20 mol), 4,4'-dichlorobenzophenone
(4,4'-DCBP) 60.3 g (0.24 mol), potassium carbonate 71.
9 g (0.52 mol), N, N-dimethylacetamide (DMA
c) Take 300 mL and 150 mL of toluene, and in an oil bath,
The mixture was heated under a nitrogen atmosphere and reacted at 130 ° C under stirring. When the water produced by the reaction was azeotropically distilled with toluene and the reaction was carried out while removing it out of the system with a Dean-Stark tube, almost no water production was observed in about 3 hours. The reaction temperature was gradually increased from 130 ° C to 150 ° C. Then gradually increase the reaction temperature to 1
Most of the toluene was removed while raising the temperature to 50 ℃
After continuing the reaction for 10 hours at 4,4'-DCBP 10.0 g (0.04
(0 mol) was added and the reaction was continued for 5 hours. After allowing the obtained reaction solution to cool, the precipitate of the inorganic compound by-produced is removed by filtration,
The filtrate was poured into 4 L of methanol. The precipitated product was separated by filtration, collected, dried and then dissolved in 300 mL of tetrahydrofuran. This was reprecipitated in 4 L of methanol to obtain 95 g of the desired compound (yield 85%).

The polystyrene-equivalent number average molecular weight of the obtained polymer determined by GPC (THF solvent) was 4,200, and the weight average molecular weight was 8,300. The obtained polymer has T
Soluble in HF, NMP, DMAc, sulfolane, etc.
The g was 110 ° C and the thermal decomposition temperature was 498 ° C.

The resulting oligomer has the formula (I):

[0121]

[Chemical 36] It was presumed to have a structure represented by (I), and the average value of n was determined to be 7.8 in view of the structure and the number average molecular weight.

(Synthesis of Polyarylene Copolymer) 28.4 g (2.87 mmol) of the oligomer of the formula (I), 2,5-dichloro-4 ′-(4-phenoxy) phenoxybenzophenone (D
CPPB) 29.2 g (67.1 mmol), bis (triphenylphosphine) nickel dichloride 1.37 g (2.1 mmo
l), sodium iodide 1.36 g (9.07 mmol), triphenylphosphine 7.34 g (28.0 mmol), zinc dust 1
1.0 g (168 mmol) was placed in a flask and purged with dry nitrogen. Add 130 ml of N-methylpyrrolidone (NMP),
Polymerization was carried out by heating to 80 ° C. and stirring for 4 hours. The polymerization solution was diluted with THF, coagulated and recovered with hydrochloric acid / methanol, repeatedly washed with methanol, dissolved in THF, purified by reprecipitation into methanol, and the collected polymer was vacuum dried to obtain 50.7 g of the target copolymer (96 %) Was obtained. GPC
The polystyrene-reduced number average molecular weight calculated with (THF) is
The weight average molecular weight was 40,000 and 145,000.

(Preparation of Sulfonated Polymer 1) 25 g of the copolymer obtained above was placed in a 500 ml separable flask, 250 ml of 96% sulfuric acid was added, and the mixture was stirred under a nitrogen stream for 24 hours. The obtained solution was poured into a large amount of ion-exchanged water to precipitate the polymer. The polymer was washed repeatedly until the pH of the wash water became neutral. After drying, 29 g (96
%) Of the sulfonated polymer was obtained. The sulfonation equivalent of the sulfonated polymer was 1.70 milligram equivalent / g.

-Synthesis Example 2- [Synthesis of Sulfonated Polymer 2] 193.5 g of 2,5-dichloro-4'-phenoxybenzophenone (5
40 mmol), 4,4'-dichlorobenzophenone 15.1 g (6
0mmol), sodium iodide 11.7g (78mmo
l), bistriphenylphosphine nickel dichloride 11.8 g (1.8 mmol), triphenylphosphine 63.
0 g (240 mmol) and 94.1 g (1.44 mol) zinc were placed in a three-necked flask equipped with a reflux tube and a three-way cock, and the temperature was 70 ° C.
Immerse in an oil bath and replace with nitrogen, then N-
1,000 ml of methyl-2-pyrrolidone was added to start the reaction.
After reacting for 20 hours, dilute with 500 ml of N-methyl-2-pyrrolidone, pour the polymerization reaction solution into a 1:10 hydrochloric acid / methanol solution,
The polymer was precipitated, washed, filtered, and vacuum dried to obtain a white powder. The yield was 153g. The weight average molecular weight was 159,000. The obtained polymer was formed into a film using N-methyl-2-pyrrolidone and immersed in methanol, but no swelling was observed.

To 150 g of the polymer obtained above, 1,500 ml of concentrated sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours to carry out a sulfonation reaction. After the reaction, it was poured into a large amount of pure water to precipitate the sulfonated polymer. Continue washing the polymer with water until the pH reaches 7, and after filtration, collect the sulfonated polymer and
It was vacuum dried at ° C. The yield of sulfonated polymer is 179
It was g. The sulfonation equivalent of the sulfonated polymer is
It was 2.45 milligram equivalent / g.

Example 1 10% N of Sulfonated Polymer 1 obtained in Synthesis Example 1 above
900 parts by weight of MP solution (sulfonated polymer 1 solid content 90
(Parts by weight), a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a crosslinkable monomer (trade name: KAYARAD-D
10 parts by weight of PHA (manufactured by Nippon Kayaku Co., Ltd.) and 1 part of peroxide (di-t-butyl peroxide) were mixed to prepare a uniform NMP solution.

This NMP solution was applied on a glass substrate to a thickness of 55 μm using a doctor blade, and then pre-dried in an oven at 70 ° C. for 1 hour to remove the coating film from the glass substrate. After fixing the film on an aluminum plate with a heat-resistant tape, it was further heat-treated at 170 ° C. for 1 hour to polymerize and cross-link the cross-linkable monomer to obtain a desired cross-linked polymer electrolyte membrane. Then, in order to completely remove the NMP remaining in the coating film, the remaining NMP was immersed in distilled water at room temperature for 7 days.
The MP was removed. Then, the film was dried.

The insoluble content in N-methylpyrrolidone (NMP) of this film-like crosslinked polymer electrolyte was measured and found to be 95% by weight, which was a film having a highly crosslinked structure. Film at 25 ℃, 50%
After preparing the RH for 12 hours, various physical properties were measured. The results are shown in Table 1. The film has high proton conductivity before and after the Fenton test without deterioration of the film,
It maintained a high tensile strength and had an excellent balance of physical properties.

-Comparative Example 1-A film was obtained by using 100 parts by weight of the sulfonated polymer 1 without polymerizing and crosslinking in the above-mentioned Example 1. Table 1 shows the results of measuring various physical properties.

Example 2-A film-like crosslinked polymer was prepared in the same manner as in Example 1 except that the sulfonated polymer 2 obtained in Synthesis Example 2 was used instead of the sulfonated polymer 1 in Example 1. An electrolyte was obtained. Table 1 shows the results of measuring various physical properties.

-Comparative Example 2- A film was obtained by using 100 parts by weight of the sulfonated polymer 2 without polymerizing and crosslinking in the above-mentioned Example 2. Table 1 shows the results of measuring various physical properties.

[0132]

[Table 1]

[0133]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a crosslinked polymer electrolyte which maintains the originally required high proton conductivity and is extremely excellent in durability. Since the proton conductive polymer is highly crosslinked by the crosslinkable monomer, the crosslinked polymer electrolyte can be suitably used as a proton conductive membrane of a highly durable fuel cell. Further, it can be used as an electrolyte for primary batteries, an electrolyte for secondary batteries, a display element, various sensors, a signal transmission medium, a solid capacitor, a conductive film such as an ion exchange film, and its industrial significance is extremely great. Is.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01M 8/10 H01M 8/10 F term (reference) 4J011 PA83 PA90 PA94 PC02 4J026 AC36 BA28 GA02 5G301 CD01 5H026 AA06 CX05 EE17 EE18

Claims (8)

[Claims] 1. In the presence of a proton conducting polymer, 1
A method for producing a crosslinked polymer electrolyte, which comprises polymerizing a monomer having at least two radically polymerizable groups in a molecule. 2. The method for producing a crosslinked polymer electrolyte according to claim 1, wherein the two or more radically polymerizable groups are the same or different and are an acryloyl group or a methacryloyl group. 3. The proton-conducting polymer is sulfonated polyarylene.
2. The method for producing a crosslinked polymer electrolyte according to 2. 4. The sulfonated polyarylene is
4. The method for producing a crosslinked polymer electrolyte according to claim 3, wherein (a) is a sulfonated product of a polyarylene polymer containing an aromatic compound unit having an electron-withdrawing group in the main chain. 5. The unit (a) is represented by the following general formula (a2):
The method for producing a crosslinked polymer electrolyte according to claim 4, which is a unit represented by: [Chemical 1] (A2) (In the general formula (a2), A is independently an electron-withdrawing group, B is independently an electron-donating atom or a divalent group,
R ^{1 to} R ⁸ are the same or different and each is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group, and n is an integer of 2 or more. ) 6. The polyarylene-based polymer,
A polyarylene-based copolymer comprising (a) an aromatic compound unit having an electron-withdrawing group in the main chain and (b) an aromatic compound unit having no electron-withdrawing group in the main chain. The method for producing a crosslinked polymer electrolyte according to claim 4. 7. The unit (a) is the following general formula (a1):
And at least one unit selected from the group consisting of units represented by (a2), and the unit (b)
Is at least one unit selected from the group consisting of units represented by the following general formulas (b1) to (b4), and the method for producing a crosslinked polymer electrolyte according to claim 6, wherein [Chemical 2] (A1) (In the general formula (a1), A is independently an electron-withdrawing group, R ^{1 to} R ⁸ and R ^{1 ′ to} R ^{8 ′} are the same or different,
It is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group, and r is an integer of 0 or 1. ) [Chemical 3] (A2) (In the general formula (a2), A is independently an electron-withdrawing group, B is independently an electron-donating atom or a divalent group,
R ^{1 to} R ⁸ are the same or different and each is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group, and n is an integer of 2 or more. ) [Chemical 4] (B1) (In the general formula (b1), A is an electron-withdrawing group, B is independently an electron-donating atom or a divalent group, and R ⁹ to
R ¹⁵ is the same or different and is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group,
Z is an aryl group, and m is an integer of 0, 1 or 2. ) [Chemical 5] ... (b2) … (B3) (B4) (In the general formulas (b2) to (b4), R ^{17 to} R ²⁴ are the same or different and each is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group.) 8. The crosslinked polymer electrolyte obtained by the production method according to claim 1, wherein the insoluble content in N-methylpyrrolidone is 40% by weight or more.