JP2002008440A - Proton conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a proton conductive film with improved ductility of the film made of sulfonated polyarylene without damaging proton conductivity. SOLUTION: This proton conductive film with excellent proton conductivity and ductility is made by means of compounding (A) polyethyleneglycol or its derivatives and (B) sulfonated polyarylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method of mixing polyethylene glycol or a derivative thereof with a sulfonated polyarylene to form a complex, without impairing proton conductivity.
The present invention relates to a proton conductive membrane having improved ductility of a membrane made of sulfonated polyarylene.

[0002]

2. Description of the Related Art Electrolytes are often used as (water) solutions. However, in recent years, there has been an increasing tendency to replace this with a solid system. The first reason is, for example, the easiness of processing when applied to the above-mentioned electric and electronic materials, and the second reason is the shift to lighter, thinner, smaller and higher power. Conventionally, both proton conductive materials and inorganic materials are known. Examples of the inorganic substance include uranyl phosphate, which is a hydrated compound. However, these inorganic compounds have insufficient contact at the interface, and there are many problems in forming a conductive layer on a substrate or an electrode.

On the other hand, examples of organic compounds include polymers belonging to the so-called cation exchange resin, for example, sulfonated products of vinyl polymers such as polystyrene sulfonic acid,
Sulfonate and phosphate groups were introduced into perfluoroalkylsulfonic acid polymers and perfluoroalkylcarboxylic acid polymers represented by Nafion (manufactured by DuPont), and heat-resistant polymers such as polybenzimidazole and polyetheretherketone. Polymer [Polymer P
reprints, Japan, Vol. 42, no.
7, p. 2490-2492 (1993), Polym
er Preprints, Japan, Vol. 4
3, No. 3, p. 735-736 (1994), Po
lymer Preprints, Japan, Vo
l. 42, no. 3, p730 (1993)].

[0004] These organic polymers are usually used in the form of a film, but a conductive film can be bonded to an electrode by utilizing the fact that they are soluble in a solvent or thermoplastic. However, many of these organic polymers not only have insufficient proton conductivity, but also have poor durability, low proton conductivity at high temperatures (100 ° C. or higher), and are highly dependent on humidity conditions. In addition, there is a problem that the adhesion to the electrode is not sufficiently satisfactory, or the strength is reduced and the shape is collapsed due to excessive swelling during operation due to the structure of the water-containing polymer. Therefore, these organic polymers have various problems when applied to the above electric / electronic materials.

Further, US Pat. No. 5,403,675 proposes a solid polymer electrolyte composed of a sulfonated rigid polyphenylene (ie, a sulfonate having a polyarylene structure as a main component). This polymer has, as a main component, a polymer having a phenylene chain (structure described in column 9 in the same specification) obtained by polymerizing an aromatic compound, and reacts it with a sulfonating agent to introduce a sulfonic acid group. . However, an increase in the amount of sulfonic acid groups introduced leads to an increase in the proton conductivity, but the mechanical properties of the resulting sulfonated polymer are significantly impaired. Therefore, it is necessary to maintain an excellent mechanical property and to adjust an appropriate sulfonation concentration for exhibiting proton conductivity. In fact, in this polymer, the sulfonation reaction easily proceeds, and it is very difficult to control an appropriate amount of sulfonic acid groups to be introduced.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and a proton conductive membrane having improved ductility of a membrane made of sulfonated polyarylene without impairing proton conductivity. Is to provide.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a proton conducting membrane comprising (A) polyethylene glycol or a derivative thereof and (B) sulfonated polyarylene. The number average molecular weight of the (A) polyethylene glycol or a derivative thereof is preferably 3,000 or more. The sulfonated polyarylene (B) is preferably a sulfonated polyarylene having a structural unit represented by the following general formula (1).

[0008]

Embedded image

[In the general formula (1), X is -CQQ'- (where Q and Q 'are the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) And R ^{1 to} R ³⁶ are the same or different and represent a hydrogen atom, a halogen atom or a monovalent organic group, and Y represents —O—, —CO—, -COO-, -CONH-
And -SO ₂ - is a group selected from the group of radicals, p is 0
-100 mol%, q is 0-100 mol%, r is 0-10
0 mol%, s is 0 to 100 mol% (provided that p + q + r
+ S = 100 mol%), and t is 0 or 1. Next, the present invention provides a proton conductive membrane comprising applying a composition obtained by dissolving (A) polyethylene glycol or a derivative thereof and (B) a sulfonated polyarylene in a solvent onto a substrate, and heating the composition. And a method for producing the same. here,
The polyethylene glycol is preferably a macromer containing a polymerizable functional group.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The proton conducting membrane of the present invention
By forming a membrane from a mixture containing (A) polyethylene glycol or a derivative thereof and (B) a sulfonated polyarylene represented by the general formula (1) as a main component, without impairing the proton conductivity, B) A proton conductive membrane having improved ductility of a membrane made of sulfonated polyarylene.

Component (A) The component (A) is polyethylene glycol or a derivative thereof, and preferably has a number average molecular weight of 3,000.
Above, more preferably 5,000 to 300,000. When the number average molecular weight is less than 3,000, mechanical properties and durability are not sufficient. Examples of the component (A) include polyethylene glycol and various derivatives of polyethylene glycol. As a derivative of polyethylene glycol, as a compound having no polymerizable functional group,
For example, polyoxyethylene coconut oil fatty acid monoethanolamide, polyoxyethylene coconut oil fatty acid sorbitan, polyoxyethylene sorbitan monostearate,
Polyoxyethylene sorbitan monooleate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol dilaurate, polyethylene glycol distearate, polyethylene glycol dioleate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene Oleyl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene alkyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene polyoxypropylene glycol block copolymer, polyoxyethylene polyoxypropylene butyl ether, Polyoxyethylene polyoxypropylene hex Glycol ethers, polyoxyethylene polyoxypropylene trimethylolpropane, polyoxyethylene polyoxypropylene glycol glyceryl ether and the like.

Examples of macromers having a polymerizable functional group as derivatives of polyethylene glycol include:
Polyethylene glycol acrylate, polyethylene glycol methacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane ethoxylate methyl ether diacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane ethoxylate methyl ether dimethacrylate, trimethylolpropane ethoxy Rate trimethacrylate and the like. The use of a macromer of polyethylene glycol having a polymerizable functional group is preferable because the polyethylene glycol has a cross-linked structure, so that the durability when a conductive film is used is improved.

The sulfonated polyarylene is preferably a sulfonated polyarylene represented by the above general formula (1) (hereinafter also referred to as “polymer (1)”). Here, the polymer (1) has a repeating structural unit represented by the general formula (1). Hereinafter, the general formula (1)
In the above, the structural unit enclosed by p is referred to as “structural unit p”, q
The structural unit enclosed by "" is also referred to as "structural unit q", the structural unit enclosed by r is also referred to as "structural unit r", and the structural unit enclosed by s is also referred to as "structural unit s".

In the above general formula (1), X is -CQQ'-
(Where Q and Q ′ are the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) and a group selected from the group consisting of a fluorenylene group. Here, of Q and Q ', the halogenated alkyl group includes a trifluoromethyl group and a pentafluoroethylene group, and the aryl group includes a phenyl group, a biphenyl group, a tolyl group, a pentafluorophenyl group and the like. No. In the above general formula (1), R ^{1 to} R ³⁶ are the same or different and each represent a hydrogen atom, an alkyl group, a halogen atom, a monovalent organic group (for example, a polymerization reaction for producing a halogenated alkyl group or polyarylene). (A monovalent organic group containing a non-functional group). In R ^{1 to} R ³⁶ , the alkyl group is a methyl group,
Examples include an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group. Examples of the halogen atom include fluorine. Examples of the halogenated alkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Furthermore, examples of the monovalent organic group containing a functional group that does not inhibit the polymerization reaction for producing polyarylene include aryloxy, aryloxo, arylthiocarbonyl, aryloxycarbonyl, arylthio, and arylsulfone. These also include monovalent organic groups containing two or more functional groups, for example, aryloxyaryloxo, aryloxyarylsulfone, arylthioaryloxo, and the like. Further, these may be used in place of the aryl group, instead of the alkyl group, the alkylaryl group, and the arylalkyl group. Further, in the general formula (1), Y represents -O-, -CO-,-.
At least one selected from the group consisting of COO—, —CONH—, and —SO ₂ — groups, p is 0 to 100 mol%, q is 0 to 100 mol%, r is 0 to 100 mol%, s
Is 0 to 100 mol% (however, p + q + r + s = 100
Mol%), t is 0 or 1. ]

In the formula (1), the monomers constituting the structural unit p (hereinafter also referred to as “monomer p”) include:
2,2-bis (4-methylsulfonyloxyphenyl)
Hexafluoropropane, bis (4-methylsulfonyloxyphenyl) methane, bis (4-methylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4
-Methylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy- 3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxyphenyl) propane, 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) propane, 2,2 -Bis (4-methylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-
Bis (4-methylsulfonyloxy-3-fluorophenyl) propane, 2,2-bis (4-methylsulfonyloxy-3,5-difluorophenyl) propane, 2,
2-bis (4-trifluoromethylsulfonyloxyphenyl) propane, 2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy) Phenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) propane, 2,2-
Bis (4-phenylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane,
2,2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, 2,2-bis (p
-Tolylsulfonyloxyphenyl) propane, 2,2
-Bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane, 2,2-
Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-
Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane, bis (p-tolylsulfonyloxy-3-fluoro) Phenyl) propane, bis (p-tolylsulfonyloxy)
3,5-difluorophenyl) propane, 9,9-bis (4-methylsulfonyloxyphenyl) fluorene,
9,9-bis (4-methylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4- Methylsulfonyloxy-3-
Propenylphenyl) fluorene, 9,9-bis (4-
Methylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-methylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4- Methylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-
Difluorophenyl) diphenylmethane, 9,9-bis (4-methylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4 -Methylsulfonyloxyphenyl) methane, bis (4-methylsulfonyloxy-3-methylphenyl) methane, bis (4-methylsulfonyloxy-3,
5-dimethylphenyl) methane, bis (4-methylsulfonyloxy-3-propenylphenyl) methane, bis (4-methylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-methylsulfonyloxyphenyl) phenyl Methane, 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane, bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) diphenylmethane,
2,2-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) hexafluoropropane,
2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-trifluoromethylsulfonyloxyphenyl) fluorene, 9,9-bis (4-
Trifluoromethylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfone) Phonyloxy-3-propenylphenyl) fluorene,
9,9-bis (4-trifluoromethylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy) -3,5-dimethylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) diphenylmethane,
Bis (4-trifluoromethylsulfonyloxy-3-
(Fluorophenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) fluorene, 9,9 -Bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) ) Methane, bis (4-trifluoromethylsulfonyloxy-3,5-)
Dimethylphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4
-Trifluoromethylsulfonyloxyphenyl),
2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane, bis (4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxyphenyl) diphenylmethane, 2,2-
Bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfur Phonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-phenylsulfonyloxyphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-
3,5-dimethylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-phenylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5)
-Difluorophenyl) diphenylmethane, 9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3,5-difluorophenyl) fluorene, bis ( 4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxy-3-methylphenyl) methane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-
Phenylsulfonyloxy-3-propenylphenyl)
Methane, bis (4-phenylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-phenylsulfonyloxyphenyl) phenylmethane,
2,2-bis (p-tolylsulfonyloxyphenyl)
Hexafluoropropane, bis (p-tolylsulfonyloxyphenyl) methane, bis (p-tolylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (p
-Tolylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyloxy- 3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (p-tolylsulfonyloxyphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-methylphenyl) fluorene, 9,9 -Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-propenylphenyl) fluorene,
9,9-bis (p-tolylsulfonyloxy-3-phenylphenyl) fluorene, bis (p-tolylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-dimethyl) Phenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-difluoro) Phenyl) diphenylmethane, 9,9-bis (p-tolylsulfonyloxy)
3-fluorophenyl) fluorene, 9,9-bis (p
-Tolylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (p-tolylsulfonyloxyphenyl) methane, bis (p-tolylsulfonyloxy-)
3-methylphenyl) methane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) methane, bis (p-tolylsulfonyloxy-3-propenylphenyl) methane, bis (p-tolylsulfonyloxyphenyl) ) Trifluoromethylphenylmethane, bis (p-tolylsulfonyloxyphenyl) phenylmethane and the like. The monomers p may be used alone or in combination of two or more.

In the formula (1), as the monomer constituting the structural unit q (hereinafter also referred to as “monomer q”), for example, 4,4′-dimethylsulfonyloxybiphenyl, 4,4′-dimethylsulfone Phoniloxy-3,
3'-dipropenylbiphenyl, 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, 3,3'-diallyl-4,4'-bis (4-fluorobenzenesulfonyloxy) biphenyl, 4,4 '
-Dichloro-2,2'-trifluoromethylbiphenyl, 4,4'-dibromo-2,2'-trifluoromethylbiphenyl, 4,4'-diiodo-2,2'-trifluoromethylbiphenyl, bis (4 -Chlorophenyl)
Sulfone, 4,4'-dichlorobenzophenone, 2,
4-dichlorobenzophenone and the like can be mentioned. The monomers q can be used alone or in combination of two or more.

Further, in the formula (1), the monomers constituting the structural unit r (hereinafter also referred to as “monomer r”) include, for example, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, p-diiodobenzene, Dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5
-Dibromotoluene, 2,5-diiodotoluene, 2,
5-dimethylsulfonyloxybenzene, 2,5-dichloro-p-xylene, 2,5-dibromo-p-xylene, 2,5-diiodo-p-xylene, 2,5-dichlorobenzotrifluoride, 2,5 -Dibromobenzotrifluoride, 2,5-diiodobenzotrifluoride, 1,4-dichloro-2,3,5,6-tetrafluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluoro Benzene, 1,4-diiodo-2,3
5,6-tetrafluorobenzene, 2,5-dichlorobenzoic acid, 2,5-dibromobenzoic acid, methyl 2,5-dichlorobenzoate, methyl 2,5-dibromobenzoate,
Examples include t-butyl 2,5-dichlorobenzoate, t-butyl 2,5-dibromobenzoate, and 3,6-dichlorophthalic anhydride, and preferably p-dichlorobenzene and p-dimethyl. Sulfonyloxybenzene,
2,5-dichlorotoluene, 2,5-dichlorobenzotrifluoride, 2,5-dichlorobenzophenone,
2,5-dichlorophenoxybenzene and the like.

Further, as the monomer r, for example,
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-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 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, 2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4-dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-dichloro-t-butoxycarbonyloxy Phenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, 2, Methyl 4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, 3,
Methyl 5-dibromobenzoate, methyl 2,4-dibromobenzoate, t-butyl 2,4-dichlorobenzoate,
Examples thereof include t-butyl 3,5-dichlorobenzoate, t-butyl 2,4-dibromobenzoate, and t-butyl 3,5-dibromobenzoate.
Dichlorobenzene, 2,4-dichlorotoluene, 3,5
-Dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dichlorobenzophenone, 2,4-dichlorophenoxybenzene and the like.

Further, in the formula (1), as a monomer constituting the structural unit s (hereinafter also referred to as “monomer s”), for example, 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-trifluoromethylsulfonyloxyphenyl) diphenyl ether,
4,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-methylsulfonyloxyphenyl) ) Diphenyl ether and the like.

Examples of the monomer s include, for example, 4'-bis (4-chlorobenzoylamino) diphenyl ether, 3,4'-bis (4-chlorobenzoylami) diphenyl ether and 4,4'-bis (3-chloro Benzoylamino) 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-trifluoromethylsulfonyloxyphenyl) 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,
Examples thereof include 4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether and 3,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether.

Further, as the monomer s, for example, 4,4'-bis (4-chlorophenylsulfonyl) diphenyl ether, 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, 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, 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, 4'-bis (4-trifluoromethylsulfonyloxy) Phenylsulfonyl) diphenyl ether, 4,4'-bis (3-trifluoromethylsulfonyloxyphenylisulfonyl) diphenyl ether, 3,4'-bis (3-trifluoromethylsulfonyloxyphenylsulfonyl) diphenyl ether, 4,4'- Bis (4-methylsulfonyloxyphenisulfonyl) diphenyl ether, 4'-bis (4-
Methylsulfonyloxyphenylsulfonyl) diphenyl ether, 4,4'-bis (3-methylsulfonyloxyphenisulfonyl) diphenyl ether, 3,4 '
-Bis (3-methylsulfonyloxyphenylsulfonyl) diphenyl ether and the like.

Further, as the monomer s, for example, 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'-bis (4-iodophenyl) diphenyl ether dicarboxylate, 3,4'-bis (4-iodophenyl) diphenyl ether dicarboxylate, 4,
4'-bis (3-iodophenyl) diphenyl ether dicarboxylate, 3,4'-bis (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-trifluoromethylsulfonyloxyphenyl) 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.

Further, as the monomer s, for example, 4,4'-bis [(4-chlorophenyl) -1,1,1
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, , 4'-bis [(3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) -1,1,1,1 3,3,3-
Hexafluoropropyl] diphenyl ether, 3,
4'-bis [(4-bromophenyl) -1,1,1,1
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) -1,1,1,1 3,3,3-
Hexafluoropropyl] diphenyl ether, 4'-
Bis [(3-iodophenyl) -1,1,1,3,3
3-hexafluoropropyl] diphenyl ether,
3,4'-bis [(3-iodophenyl) -1,1,1
1,3,3,3-hexafluoropropyl] 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'-bis [(3-
Trifluoromethylsulfonyloxyphenyl) -1,
1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4′-bis [(3-trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3
3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'- Screw [(4-
Methylsulfonyloxyphenyl) -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'- Screw [(3-
Methylsulfonyloxyphenyl) -1,1,1,3,
3,3-hexafluoropropyl] diphenyl ether.

Further, as the monomer s, for example, 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'-bis [(4-bromophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) hexa Fluoropropyl] 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'-bis [(3-trifluoromethylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-
Trifluoromethylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether, 4,4′-bis [(3-trifluoromethylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether,
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'-bis [(4-methylsulfonyloxyphenyl)
Hexafluoropropyl] diphenyl ether, 4,
4'-bis [(3-methylsulfonyloxyphenyl)
Hexafluoropropyl] diphenyl ether, 4,
4'-bis [(4-methylsulfonyloxyphenyl)
Octafluorobutyl] diphenyl ether, 4,4 '
-Bis [(3-methylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3- Methylsulfonyloxy) decafluoropentyl] diphenyl ether and the like.

In addition to the above monomers p to s, for example, o-dichlorobenzene, o-dibromobenzene, o-dichlorobenzene,
-Diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3 2,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4-dimethylsulfonyloxybenzene,
3,4-dichlorobenzotrifluoride, 3,4-dibromobenzotrifluoride, 3,4-diiodobenzotrifluoride, 1,2-dibromo-3,4,5
6-Tetrafluorobenzene, 4,5-dichlorophthalic anhydride and the like can be copolymerized.

The proportion of the repeating structural unit in the polyarylene is as follows: in the above formula (1), p is 0 to 100 mol%;
q is 0 to 100 mol%, r is 0 to 100 mol%, and s is 0
-100 mol%, preferably p is 50-100 mol%, q is 0-50 mol%, r is 50-100 mol%, s
Is 0 to 50 mol% (however, p + q + r + s = 100 mol%).

The catalyst used for producing the polyarylene used in the present invention is preferably a catalyst system containing a transition metal compound. As the catalyst system, a transition metal salt and a ligand or a ligand are used. Transition metal (salt),
In addition, a reducing agent may be used as an essential component, and a “salt” may be added to increase the polymerization rate.

Here, the transition metal salt includes nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate; palladium chloride;
Examples 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 preferred.

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

Further, as the transition metal (salt) to which a ligand has been previously coordinated, for example, nickel chloride 2 triphenylphosphine, nickel bromide 2 triphenylphosphine, nickel iodide 2 triphenylphosphine, nickel nitrate 2 -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)
Nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like can be mentioned, and nickel chloride2triphenylphosphine and nickel chloride2,2'bipyridine are preferable.

Examples of the above-mentioned reducing agent which can be used in such a catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium and the like, and zinc and manganese are preferred. These reducing agents can be used after being activated by contact with an acid or an organic acid.

The "salt" which can be used in such a catalyst system includes sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide and sodium sulfate, potassium fluoride, and the like.
Potassium compounds such as potassium chloride, potassium bromide, potassium iodide, and potassium sulfate; and ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate can be given. But sodium bromide,
Preferred are sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide.

The proportion of each component used in such a catalyst system is such that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is usually 0 to 1 mol of the total amount of the monomers p to s. 0.0001 to 10 mol, preferably 0.01 to
0.5 mole. When the amount is less than 0.0001 mol, the polymerization reaction does not sufficiently proceed.
The molecular weight may decrease.

When a transition metal salt and a ligand are used in such a catalyst system, the ligand is used in an amount of usually 0.1 to 100 mol, preferably 1 to 100 mol, per mol of the transition metal salt. 10 to 10 mol. If the amount is less than 0.1 mol, the catalytic activity becomes insufficient.
There is a problem that the molecular weight decreases.

The proportion of the reducing agent used in the catalyst system is usually 0.1 to 1 mol of the total amount of the monomers p to s.
１００100 mol, preferably 1-10 mol. 0.1
If it is less than 100 moles, the polymerization does not proceed sufficiently, and if it exceeds 100 moles, the resulting polyarylene may be difficult to purify.

Further, when a “salt” is used in the catalyst system,
The use ratio is usually 0.001 to 100 mol, preferably 0.0 to 1 mol based on 1 mol of the total amount of the monomers p to s.
1 to 1 mol. If the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient, and if it exceeds 100 mol, it may be difficult to purify the resulting polyarylene.

Examples of the polymerization solvent that can be used in the present invention include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2.
-Pyrrolidone, γ-butyrolactone, γ-butyrolactam, etc., and tetrahydrofuran, N,
N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone are preferred. These polymerization solvents are preferably used after being sufficiently dried.

The concentration of the total amount of the monomers p to s in the polymerization solvent is usually 1 to 100% by weight, preferably 5 to 100% by weight.
４０40% by weight.

The polymerization temperature for polymerizing the polyarylene of the present invention is usually 0 to 200 ° C., preferably 50 to 200 ° C.
８０80 ° C. The polymerization time is usually 0.5 to 1
00 hours, preferably 1 to 40 hours. The polyarylene used in the present invention generally has a weight average molecular weight in terms of polystyrene of 1,000 to 1,000,000.
0.

The sulfonated polyarylene used in the proton conductive membrane of the present invention can be obtained by introducing a sulfonic acid group into the above-mentioned polyarylene having no sulfonic acid group by using a sulfonating agent and using a conventional method. . As a method for introducing a sulfonic acid group, for example, the above polyarylene is sulfonated under known conditions using a known sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid, sodium hydrogen sulfite, or the like. [Polymer Preprints, Japan
n, Vol. 42, no. 3, p. 730 (199
3); Polymer Preprints, Japan
n, Vol. 42, no. 3, p. 736 (199
4); Polymer Preprints, Japan
n, Vol. 42, no. 7, p. 2490-2492
(1993)].

That is, as the reaction conditions for the sulfonation, the polyarylene is reacted with the sulfonating agent in the absence or presence of a solvent. Examples of the solvent include hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, N, N
Aprotic polar solvents such as -dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfoxide, and halogenated hydrocarbons such as tetrachloroethane, dichloroethane, chloroform and methylene chloride. Can be The reaction temperature is not particularly limited, but is generally -50 to 200C, preferably -10 to 100C. The reaction time is usually 0.5 to 1,000 hours, preferably 1 to 200 hours.

The amount of the sulfonic acid group in the sulfonated polyarylene thus obtained is usually 0.05 to 1 unit of the units p to r constituting the polymer.
２2, preferably 0.3-1.5. 0.05
If the number is less than 2, the proton conductivity does not increase. On the other hand, if the number exceeds 2, the hydrophilicity is improved and the polymer becomes a water-soluble polymer.

The sulfonated polyarylene thus obtained has a weight average molecular weight in terms of polystyrene of 1,000 before the sulfonation of the base polymer.
~ 1,000,000, preferably 1,500 ~ 30
000. If it is less than 1,000, the film properties are insufficient, such as cracks in the molded film, and there is a problem in the strength properties. On the other hand, 1,000,000
If it exceeds 0, there are problems such as insufficient solubility, high solution viscosity, and poor processability.

The sulfonated polyarylene used in the present invention may be used in combination with an inorganic acid such as sulfuric acid or phosphoric acid, an organic acid containing a carboxylic acid, or an appropriate amount of water, in addition to the above sulfonated product.

In the above components (A) and (B), the components (A) and (B) are used in an amount of 2 to 40% by weight, preferably 2 to 25% by weight, ) 98 to 6 components
0% by weight, preferably 2 to 40% by weight [however, (A)
+ (B) = 100% by weight]. When the amount of the component (A) is less than 2% by weight (the amount of the component (B) exceeds 98% by weight), there is almost no effect of improving the toughness, while the amount of the component (A) exceeds 40% by weight (the amount of the component (B) is 60%). % By weight] undesirably greatly reduces the strength and elastic modulus.

Proton Conducting Membrane To produce the conductive membrane having excellent proton conductivity of the present invention, for example, (A) polyethylene glycol or a derivative thereof and (B) sulfonated polyarylene are dissolved in, for example, a common solvent. After that, by casting method such as forming into a film by casting,
A method for producing a conductive film composed of a mixture of the components (A) and (B) is exemplified.

Here, the solvent in the casting method includes aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfoxide, and alcohol solvents such as methanol. Solvents and the like. The polymer concentration at this time is usually 5 to 50% by weight, preferably 10 to 30% by weight. After film formation by the casting method, the film is dried at 30 to 100 ° C., preferably 50 to 80 ° C. for 10 to 180 minutes, preferably 15 to 60 minutes, and then preferably dried under reduced pressure of 500 mmHg to 0.1 mmHg. Vacuum drying at a temperature of about 150 ° C. for 0.5 to 24 hours can provide a proton conductive membrane.

When a macromer of polyethylene glycol containing a polymerizable functional group is used as the component (A), benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t
Organic peroxides such as -butylperoxyacetate, 1,1-bis (t-butylperoxy) cyclohexane, t-cumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, and the like; On the other hand, it is usually used in an amount of about 0.01 to 10% by weight, preferably about 0.1 to 5% by weight. At this time, after the film is formed by casting, the film is formed at 50 to 200 ° C., preferably 60 to 150 ° C., for 10 to 180 minutes, preferably 15 to 180 minutes.
Dry for ~ 60 minutes, then preferably at 500 mmHg
0.5 to 0.1 mmHg under reduced pressure at 50 to 150 ° C.
By heating and vacuum drying for 24 hours, a cured proton conductive membrane is obtained.

The dry thickness of the proton conducting membrane of the present invention is usually 10 to 150 μm, preferably 20 to 100 μm.

The proton conducting membrane of the present invention is made to be ductile without impairing proton conductivity by compounding (A) polyethylene glycol or a derivative thereof with (B) sulfonated polyarylene. be able to. Therefore, the proton conductive membrane 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, a signal transmission medium,
It can be used for proton conductive conductive membranes that can be used for solid capacitors, ion exchange membranes, etc.

[0051]

EXAMPLES 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. In addition, various measurement items in the examples were obtained as follows.

Number average molecular weight, weight average molecular weight The number average molecular weight and weight average molecular weight of the polymer before sulfonation were determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and the molecular weight in terms of polystyrene was determined. Was.

Sulfonation equivalent The obtained polymer was washed until the washing water became neutral, freed of remaining acid, washed well with water, dried, weighed out, and weighed in THF / water. Dissolved in a mixed solvent of
Using phenolphthalein as an indicator, titration was performed with a standard solution of NaOH, and the sulfonation equivalent was determined from the neutralization point.

Tensile Strength Tensile strength was measured by a tensile test at room temperature of the obtained film. The modulus of elasticity is the stress minus the tensile test at room temperature of the resulting film.
Calculated from the initial slope of the strain curve. Using a folding tester for film bending resistance , the number of bending times was 166 times / min, and the load was 200
g, the bending deformation angle was measured at 135 °. Water absorption The film was immersed in distilled water for 1 hour at room temperature, and was determined from the change in weight before and after.

Measurement of Proton Conductivity A 13 mm-diameter film-like sample placed under 100% relative humidity was sandwiched between platinum electrodes, sealed in a closed cell, and analyzed using an impedance analyzer (HYP4192A).
Frequency 5-13MHz, applied voltage 12mV, temperature 20
The absolute value of the impedance of the cell and the phase angle were measured at 50 ° 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 proton conductivity.

Example 1 100 g of a sulfonated product obtained by sulfonating poly (4-phenoxybenzoyl-1,4-phenylene) having a weight-average molecular weight of 145,000 with concentrated sulfuric acid (85 mol% of the repeating unit was sulfonated). , And 10 g of polyethylene glycol (manufactured by Sanyo Chemical Industry Co., Ltd., PEG-20000, number average molecular weight = 20,000) in 1,000 ml of NMP.
To obtain a uniform solution. The obtained polymer solution was cast on a PET film and dried at 100 ° C. for 1 hour, and further dried at 100 ° C. for one day and night with a vacuum drier to obtain a dry film thickness of 5 μm.
A 0 μm film was prepared. The strength, elastic modulus, film folding test, and proton conductivity of the obtained film were measured and evaluated by a tensile test. Table 1 shows the results.

Example 2 Instead of the homopolymer of poly (4-phenoxybenzoyl-1,4-phenylene), which is the polyarylene used in Example 1, (4-phenoxybenzoyl-1,4-phenylene) was used. Copolymer of repeating unit (A) and repeating unit (B) of (diphenylmethane-4,4'-diyl) [copolymer composition; (A) / (B) = 90 /
10%] (90 mol% of the unit (A))
Is not sulfonated, while the unit (B) is not sulfonated.] A proton conducting membrane was obtained in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 Table 1 shows the evaluation results of the membrane (film thickness 50 μm) of the sulfonated product of poly (4-phenoxybenzoyl-1,4-phenylene) which is the polyarylene used in Example 1.

Comparative Example 2 A repeating unit (A) of (4-phenoxybenzoyl-1,4-phenylene), which is the polyarylene used in Example 2, and a repeating unit (B) of (diphenylmethane-4,4'-diyl) 90% by weight of a sulfonated product [copolymer composition; (A) / (B) = 90/10%] (unit (A) is sulfonated, while unit (B) is Table 1 shows the evaluation results for the film thickness of 50 μm.

[0060]

[Table 1]

[0061]

The proton conductive membrane of the present invention improves the ductility of a membrane made of sulfonated polyarylene without impairing proton conductivity by compounding polyethylene glycol or a derivative thereof with sulfonated polyarylene. be able to. Therefore, the proton conductive membrane of the present invention has high proton conductivity as a conductive membrane over a wide temperature range, has excellent adhesion to substrates and electrodes, is not brittle, and has excellent strength. It can be used as an electrolyte for a secondary battery, a polymer solid electrolyte for a fuel cell, a display element, various sensors, a signal transmission medium, a solid capacitor, a conductive membrane such as an ion exchange membrane, and the industrial significance is extremely large.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/00 C08L 71/00 A 5H024 71/02 71/02 5H026 H01M 6/18 H01M 6/18 E 5H029 8/02 8/02 P 10/40 10/40 B F term (reference) 4F071 AA33 AA51 AA69 AF07 AF36 AG28 AH15 BA02 BB02 BC02 BC17 4J002 BK001 CA001 CH022 GQ00 4J011 AA05 AB02 PA87 PB08 PC13 4J027 AC01 AC03 AC36 AJ01 CA10 CC02 5G301 CA30 CD01 5H024 BB01 BB08 DD09 EE09 FF21 HH01 5H026 AA06 BB01 BB04 CX04 EE18 HH00 5H029 AJ11 AM16 CJ02 CJ22 DJ04 DJ09 EJ12 HJ11

Claims (5)

[Claims] 1. A proton conducting membrane comprising (A) polyethylene glycol or a derivative thereof and (B) sulfonated polyarylene. 2. The proton conductive membrane according to claim 1, wherein (A) polyethylene glycol or a derivative thereof has a number average molecular weight of 3,000 or more. 3. The proton conductive membrane according to claim 1, wherein (B) the sulfonated polyarylene is a sulfonated polyarylene having a structural unit represented by the following general formula (1). Embedded image [In the general formula (1), X represents -CQQ '-(where Q,
Q ′ is the same or different and represents a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) and a group selected from the group consisting of a fluorenylene group, and R ^{1 to} R ³⁶ are the same. Or differently, represents a hydrogen atom, a halogen atom or a monovalent organic group, and Y is -O
-, -CO-, -COO-, -CONH- and -SO
A group selected from the group consisting of _2- groups, p is 0 to 100 mol%, q is 0 to 100 mol%, r is 0 to 100 mol%, s
Is 0 to 100 mol% (however, p + q + r + s = 100
Mol%), t is 0 or 1. ] 4. A method for producing a proton conducting membrane, comprising applying a composition obtained by dissolving (A) polyethylene glycol or a derivative thereof and (B) sulfonated polyarylene in a solvent onto a substrate and heating the composition. . 5. The method according to claim 4, wherein the polyethylene glycol is a macromer containing a polymerizable functional group.