JP2002008447A - Composite membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite membrane made from sulfonated polyallylane, improved in the toughness of membrane, which maintains the gas barrier property without deteriorating its proton conductivity. SOLUTION: A composite membrane is made by laminating membranes made from tetrafluoroethylene copolymer having proton conductivity and from sulfonated polyallylane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for forming a gaseous layer without impairing proton conductivity by laminating a membrane of sulfonated polyarylene on an elastomeric membrane made of tetrafluoroethylene copolymer having proton conductivity. The present invention relates to a composite membrane having improved toughness of a membrane made of sulfonated polyarylene while maintaining barrier properties.

[0002]

2. Description of the Related Art Electrolytes are often used as (water) solutions. However, in recent years, the tendency to replace this with a solid system has been increasing. 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 so-called cation exchange resins, for example, sulfonated products of vinyl polymers such as polystyrene sulfonic acid,
Sulfonic acid and phosphate groups are 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 onto an electrode by utilizing the fact that it is 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 dependence on humidity conditions. However, there is a problem that the size is large, the adhesion to the electrode is not sufficiently satisfactory, the strength is reduced due to excessive swelling during operation due to the water-containing polymer structure, and the shape is collapsed. 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 comprising a sulfonated rigid polyphenylene (ie, a sulfonate having a polyarylene structure as a main component). This polymer is mainly composed of a polymer having a phenylene chain obtained by polymerizing an aromatic compound (the structure described in column 9 in the same specification), and is reacted with a sulfonating agent to introduce a sulfonic acid group. . However, an increase in the amount of sulfonic acid groups introduced leads to an improvement 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, a 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 maintains gas barrier properties without impairing proton conductivity, and further comprises a membrane made of sulfonated polyarylene. An object of the present invention is to provide a composite film having improved toughness.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a membrane comprising a tetrafluoroethylene copolymer having proton conductivity (hereinafter also referred to as "membrane (1)") and a membrane comprising sulfonated polyarylene (hereinafter referred to as "membrane"). (2) "). Here, as the tetrafluoroethylene copolymer having proton conductivity,
A polymer comprising the structural unit represented by the general formula (1) (hereinafter also referred to as “polymer (1)”) is preferable.

[0008]

Embedded image

[In the general formula (1), x is a number from 1 to 30, y is
Is a number of 10 to 2,000, m is a number of 0 to 10, n is 1 to
10 The number of, A is in -SO ₃ Z or -COOZ (wherein
Z is a hydrogen atom or an alkali metal atom). The sulfone polyarylene is preferably a sulfonated polymer of a structural unit represented by the general formula (2) (hereinafter also referred to as “polymer (2)”).

[0010]

Embedded image

[In the general formula (2), 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. A preferred embodiment of the composite membrane of the present invention is a composite membrane in which a membrane made of a tetrafluoroethylene copolymer having proton conductivity is sandwiched on both sides by a membrane made of a sulfonated polyarylene. Next, the present invention is characterized in that N-vinylpyrrolidone and a polymerizable compound having at least one polymerizable functional group are added to polyethylene glycol on the bonding surface of each film, and then laminated and heated. And a method for producing the above composite membrane.
In addition, the present invention provides a method for producing the above composite membrane using, as an adhesive, a tetrafluoroethylene copolymer having proton conductivity dissolved in an alcohol solvent and / or a sulfonated polyarylene dissolved in an alcohol solvent. About.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The composite membrane of the present invention is obtained by laminating a membrane made of a tetrafluoroethylene copolymer having proton conductivity and a membrane made of sulfonated polyarylene without impairing proton conductivity. And a composite membrane having improved toughness of a membrane made of sulfonated polyarylene while maintaining gas barrier properties.

Proton-conductive tetrafluoroe
As the polymer constituting the tylene copolymer film (1), for example, a proton-conductive tetrafluoroethylene copolymer represented by the general formula (1) is used. The proton-conductive tetrafluoroethylene copolymer is, for example, a sulfonated polymer obtained by hydrolyzing a copolymer of tetrafluoroethylene and a perfluorovinyl ether having a sulfonylfluoride group at a terminal to obtain a sulfonic acid group, or This is a carboxylated polymer in which some or all of the sulfonic acid groups are substituted with carboxyl groups. In the above general formula (1), x is 1 to 30, preferably 1
The number of -20, y is 10-2,000, preferably 100
M is a number of 0-10, preferably 0-5, and n is a number of 1-10, preferably 1-5. Here, if x is less than 1, it becomes water-soluble. Meanwhile, 3
If it exceeds 0, the proton conductivity will decrease. When y is less than 10, the proton conductivity decreases. On the other hand, 2,
If it exceeds 000, the mechanical strength decreases. Furthermore, m
Exceeds 10, the proton conductivity decreases. Further, when n exceeds 5, the proton conductivity decreases. In the general formula (1), A represents —SO ₃ Z or —C
OOZ, where Z is a hydrogen atom or an alkali metal atom such as sodium or potassium.

The ion exchange capacity of the tetrafluoroethylene copolymer having proton conductivity is 0.7 to 1.5.
meq / g, preferably 0.8 to 1.2 meq / g.

[0015] Specific examples of the polymer (1) include:
Nafion (x = 5-13.5, y =
1,000, m ≧ 1, n = 2, ion exchange capacity = 0.9
_{1meq / g, A = -SO 3} H), US Dow Chemical Company known as Dow membrane (m = 0, n = 2 , the ion exchange capacity = 0.8meq / g, A = -SO 3 H), Asahi Kasei Acipex manufactured by Kogyo Co., Ltd. (x = 1.5
-14, m = 0-3, n = 2-5, ion exchange capacity =
_{0.9~1.0meq / g, A = -SO 3} H, -COO
H), Flemion manufactured by Asahi Glass Co., Ltd.
(M = 0 to 1, n = 1 to 5, ion exchange capacity = 0.9 m
eq / g, A = -COOH).

The sulfonated polyarylene constituting the sulfonated polyarylene membrane (2) is preferably a sulfonated product obtained by sulfonating the polyarylene represented by the general formula (2). Here, the polymer (2) has a repeating structural unit represented by the general formula (2). Hereinafter, in the general formula (2), the structural unit enclosed by p is “structural unit p”, the structural unit enclosed by q is “structural unit q”, and the structural unit enclosed by r is “structural unit r”. , S is also referred to as a “structural unit s”.

In the above general formula (2), 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, and a pentafluorophenyl group. No. In the above general formula (2), 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). 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 above general formula (2), Y represents -O-, -CO-,-.
COO -, - CONH-, and -SO ₂ - is at least one selected from the group of radicals, 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 (2), the monomer constituting the structural unit p (hereinafter also referred to as “monomer p”) includes:
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-trifluoromethylsulfur) 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 (2), the monomers constituting the structural unit q (hereinafter also referred to as “monomer q”) include, 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 (2), the monomer constituting the structural unit r (hereinafter also referred to as “monomer r”) includes, 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.

The above-mentioned monomer r includes, 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 (2), 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 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,
4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether, 3,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether and the like can be mentioned.

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, 4,4'-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, examples of the monomer s include 4,4'-bis [(4-chlorophenyl) tetrafluoroethyl] diphenyl ether and 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 such that in the above formula (2), 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, nickel acetylacetonate, palladium chloride, and the like.
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 preferred.

Examples of the ligand include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, 1,3-bis (diphenylphosphino) propane and the like. 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 that can be used in such a catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium and calcium, and zinc and manganese are preferred. These reducing agents can be used more 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,
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,
Sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide are preferred.

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 mol. 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, it may be difficult to purify the resulting polyarylene.

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 of the total amount of the above 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 obtained polyarylene.

Examples of the polymerization solvent which 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 from 0 to 200 ° C., preferably from 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 polymer (2) (sulfonated polyarylene) used in the composite membrane of the present invention
Can be obtained by introducing a sulfonic acid group into the polymer (2) having no sulfonic acid group by a conventional method using a sulfonating agent. As a method for introducing a sulfonic acid group, for example, the polymer (2) is converted into a sulfonate under a known condition using a known sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid, sodium hydrogen sulfite, or the like. [Polymer P
reprints, Japan, Vol. 42, no.
3, p. 730 (1993); Polymer Pre
prints, Japan, Vol. 42, no. 3,
p. 736 (1994); Polymer Prepr
ints, Japan, Vol. 42, no. 7, p.
2490-2492 (1993)].

That is, as the reaction conditions for the sulfonation, the polymer (2) is reacted with the sulfonating agent in the absence of 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, 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 product of the polymer (2) (sulfonated polyarylene) thus obtained is usually based on 1 unit of the units p to s constituting the polymer. , 0.05 to 2, preferably 0.3 to 1.5. If the number is less than 0.05, 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.

Further, the sulfonated product of the polymer (2) thus obtained (sulfonated polyarylene)
Means that the molecular weight of the base polymer before sulfonation is 1,000 to 1,000 in terms of polystyrene equivalent weight average molecular weight.
000, preferably 1,500-300,000. 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, when it exceeds 1,000,000, there are problems such as insufficient solubility, high solution viscosity, and poor workability.

The membrane (2) used in the present invention comprises a sulfonated product of the polymer (2) (sulfonated polyarylene).
An inorganic acid such as phosphoric acid, an organic acid containing a carboxylic acid, and an appropriate amount of water may be used in combination.

To produce the composite membrane of the present invention having excellent proton conductivity, for example, a sulfonated polymer (sulfonated polyarylene) of the polymer (1) or the polymer (2) can be prepared by using a solvent, respectively. After being dissolved in, by casting method, which is formed into a film by casting, or by melt molding method,
A method for producing the film (1) and the film (2) is exemplified. Here, as the solvent in the casting method, N, N-
Examples include aprotic polar solvents such as dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide, and alcohol solvents such as methanol. The dry film thickness of each of the films (1) and (2) is usually 10 to 150 µm, preferably 10 to 100 µm. The dry film thickness of the obtained composite film is usually 10 to 100 μm, preferably 20 to 80 μm.

Here, embodiments of the composite membrane of the present invention include:
The membrane (1) made of a tetrafluoroethylene copolymer having proton conductivity may be laminated with the membrane (2) made of a sulfonated polyarylene, but from the viewpoint of gas barrier properties and the effect of exhibiting toughness, the membrane ( An embodiment in which both surfaces of 1) are sandwiched between films (2) is preferable.

Here, in order to laminate the film (1) and the film (2), a polymerizable compound having one or more polymerizable functional groups or one of them is added to N-vinylpyrrolidone and polyethylene glycol, and then laminated. And heating (lamination method), or using, as an adhesive, a tetrafluoroethylene copolymer having proton conductivity dissolved in an alcohol-based solvent and / or a sulfonated polyarylene dissolved in an alcohol-based solvent (Lamination method) and the like.

Laminating method: The polymerizable compound used in the laminating method is a polyethylene glycol derivative having at least one polymerizable functional group. Specific examples thereof include polyethylene glycol acrylate, polyethylene glycol methacrylate, polyethylene glycol diacrylate, and the like.
Examples include polyethylene glycol dimethacrylate, trimethylolpropane ethoxylate methyl ether diacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane ethoxylate methyl ether dimethacrylate, and trimethylolpropane ethoxylate trimethacrylate.

N-vinylpyrrolidone and the above-mentioned polymerizable compounds are usually used as radical polymerization initiators such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide,
t-butyl peroxyacetate, 1,1-bis (t-
Organic peroxides such as butylperoxy) cyclohexane, t-cumyl peroxide and bis (4-t-butylcyclohexyl) peroxydicarbonate are usually 0.01 to 10% by weight, preferably 0.01 to 10% by weight, based on these monomers. Is used in an amount of about 0.1 to 5% by weight. At this time,
N-vinylpyrrolidone and the polymerizable compound are methanol,
It is used as an organic solvent solution such as an alcohol solvent such as ethanol and hexafluoroisopropanol and an amide solvent such as N-methylpyrrolidone and N, N-dimethylacetamide.

In the laminating method, N-vinylpyrrolidone and a polymerizable compound are dissolved in the above-mentioned organic solvent, the above-mentioned radical initiator is added thereto, and this mixed solution is used for forming the film (1) or the film (2). Coating or dipping on the bonding surface, then drying at room temperature to 200 ° C., preferably at room temperature, for 10 to 180 minutes, preferably for 10 to 60 minutes, and then laminating both films, about several hundred g / cm ² Under pressure, 50-200
C., preferably at 50 to 150.degree. The composite membrane obtained in this manner has N-
Vinylpyrrolidone and a polymerizable compound are polymerized, and the film (1) and the film (2) can be strongly bonded. In addition, since polyvinylpyrrolidone and polyethylene glycol derivatives present on this bonding surface are hydrophilic polymers,
The resulting composite membrane has the effect that the decrease in proton conductivity is small.

Laminating method: As the alcoholic solvent used in the laminating method, an alcoholic solvent capable of dissolving a polymer (1) such as methanol, ethanol or hexafluoroisopropanol and a sulfonated product of polymer (2) (sulfonated polyarylene). A solvent is used.

In the laminated layer, a sulfonated product of polymer (1) and polymer (2) (sulfonated polyarylene) or one of them is dissolved in the above-mentioned alcohol-based solvent to form an adhesive. ) And membrane (2)
Are laminated. At this time, the polymer concentration in the adhesive is usually 5 to 50% by weight, preferably 10 to 30% by weight. In the lamination method, the adhesive obtained as described above is applied or immersed on the bonding surface of the film (1) or the film (2), and then applied at room temperature to 80 ° C., preferably at room temperature.
Dried for ~ 180 minutes, preferably 10-60 minutes, then
After laminating both films, pressurize under several hundred g / cm ²
Bonding is performed by heating at 0 to 200C, preferably 50 to 150C. In the laminating method, this joining surface is formed by the polymer (1)
Alternatively, since it is a sulfonated product of polymer (2) itself (sulfonated polyarylene), the resulting composite membrane has an effect that the decrease in proton conductivity is extremely small.

The composite membrane of the present invention is obtained by laminating a membrane of a sulfonated polyarylene on an elastomeric membrane made of a tetrafluoroethylene copolymer having proton conductivity, without impairing the proton conductivity, and preventing gas blocking. The toughness of the membrane comprising the sulfonated polyarylene is improved while maintaining the properties. Therefore, the composite membrane of the present invention
For example, it can be used for proton conductive conductive membranes that can be used for primary battery electrolytes, secondary battery electrolytes, polymer solid electrolytes for fuel cells, display elements, various sensors, signal transmission media, solid capacitors, ion exchange membranes, etc. It is.

[0057]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. 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. Was.

Sulfonation equivalent The obtained polymer was washed until the washing water became neutral. Except for the free remaining acid, the polymer was thoroughly washed with water, dried, weighed 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 of the resulting film at room temperature.
It was calculated from the initial slope of the strain curve. Using a film bending resistance tester, the number of bending was 166 times / min, and the load was 200.
g, the bending deformation angle was measured at 135 °.

The water absorption was determined by immersing the film in distilled water at room temperature for 1 hour and measuring the weight change before and after.

Measurement of Proton Conductivity A 13 mm-diameter film 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.

Gas Permeability Using a high vacuum gas permeation tester, the gas permeation amount at 30 ° C. was determined and standardized to unit time, film thickness, pressure and area.

Example 1 A commercially available polymer membrane (produced by DuPont, trade name; Nafion 112, film thickness: 50 μm) made of a tetrafluoroethylene copolymer having proton conductivity was rolled by a heating roll. The thickness was 20 μm. On the other hand, 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% based on the repeating unit) was prepared using an NMP solvent. The film was cast on a PET film and dried to prepare a film having a thickness of 20 μm. Each film was immersed in a solution consisting of 90 parts of ethanol containing 0.01 part of benzoyl peroxide and 10 parts of N-vinylpyrrolidone of the monomer for 1 hour at room temperature. After immersion, the film surface is dried at room temperature for 20 minutes, then a membrane made of a tetrafluoroethylene copolymer having proton conductivity is arranged at the center, and both sides are sandwiched by sulfonated polyarylene to form a composite membrane, and a spacer is interposed. Using a heating press, pre-pressing was performed at 100 g / cm ² for 3 minutes, and further, curing and bonding were performed at 100 ° C. for 30 minutes under a pressure of 1 kg / cm ² . Table 1 shows the evaluation results of the obtained laminated composite film.
Shown in

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) Copolymer comprising repeating unit (A) and repeating unit (B) of (diphenylmethane-4,4'-diyl) [copolymer composition; (A) / (B) = 90 /
10%] sulfonated membrane [90 mol% of unit (A)
Was sulfonated, while the unit (B) was not sulfonated.], And a composite membrane was obtained in the same manner as in Example 1. Table 1 shows the results.

Example 3 A polyarylene poly (4-phenoxybenzoyl-1,4) was formed on both surfaces of a 20 μm-thick proton-conductive tetrafluoroethylene copolymer membrane (Nafion) prepared in Example 1. A 10% methanol solution of a sulfonated product of (phenylene) is applied and preliminarily dried at room temperature. As in Example 1, this proton conductive tetrafluoroethylene copolymer membrane is disposed in the center, A composite membrane was sandwiched between the same sulfonated polyarylene membranes as in Example 1, and was prepressed at 100 g / cm ² for 3 minutes using a hot press with a spacer, and further under pressure at a pressure of 1 kg / cm ^2. The adhesive was cured at 100 ° C. for 30 minutes. Table 1 shows the properties of the obtained laminated composite film.

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

Comparative Example 2 A repeating unit (A) of (4-phenoxybenzoyl-1,4-phenylene) which is a polyarylene used in Example 2 and a repeating unit (B) of (diphenylmethane-4,4'-diyl) ) Of the copolymer [copolymer composition; (A) / (B) = 90/10%] (90 mol% of the unit (A) is sulfonated, while the unit (B) is Table 1 shows the evaluation results of the film thickness (not sulfonated) of 50 μm.

Comparative Example 3 A commercially available membrane of a proton-conductive tetrafluoroethylene copolymer used in Example 1 (manufactured by DuPont, Naf
(ion 117, film thickness 50 μm) are shown in Table 1.

[0070]

[Table 1]

[0071]

The composite membrane of the present invention is obtained by laminating a membrane of a sulfonated polyarylene on an elastomeric membrane made of a tetrafluoroethylene copolymer having proton conductivity, without impairing the proton conductivity. It is possible to improve the toughness of a film made of sulfonated polyarylene while maintaining gas barrier properties. Therefore, the composite film of the present invention has high proton conductivity as a conductive film 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 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) C08F 216/14 C08F 216/14 5G301 C08G 61/12 C08G 61/12 5G307 75/20 75/20 C08J 5 / 12 CEU C08J 5/12 CEU CEZ CEZ H01B 1/06 H01B 1/06 A // C08L 27:18 C08L 27:18 65:00 65:00 (72) Inventor Hisao Nagai 2-11 Tsukiji, Chuo-ku, Tokyo No. 24 F-term in JASR Co., Ltd. BA09 BC08 BC13 BD03 BF13 BG06 4J032 CA04 CB03 CB05 CD09 CE03 CF01 CG01 4J100 AC26P AE38Q BA02Q BA17Q BA56Q BB13Q CA04 5G301 CA30 CD01 5G307 BA07 BB09 BC10

Claims (6)

[Claims] 1. A composite membrane in which a membrane made of a tetrafluoroethylene copolymer having proton conductivity and a membrane made of a sulfonated polyarylene are laminated. 2. The composite membrane according to claim 1, wherein the proton-conductive tetrafluoroethylene copolymer comprises a structural unit represented by the general formula (1). Embedded image [In the general formula (1), x is a number of 1 to 30, y is 10 to 2,
000, m is a number from 0 to 10, n is a number from 1 to 10, A
(In this case, Z is a is hydrogen atom or an alkali metal atom) -SO ₃ Z or -COOZ showing the. ] 3. The sulfone polyarylene represented by the general formula (2)
The composite membrane according to claim 1, which is a sulfonated product of a polymer comprising a structural unit represented by: Embedded image [In the general formula (2), X is -CQQ '-(where Q,
Q 'is the same or different and represents a group represented by a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) and 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. The composite membrane according to claim 1, wherein both sides of a membrane made of a tetrafluoroethylene copolymer having proton conductivity are sandwiched between membranes made of a sulfonated polyarylene. 5. A method in which N-vinylpyrrolidone and / or a polymerizable compound having one or more polymerizable functional groups are provided to polyethylene glycol on the bonding surface of each film, and then laminated and heated. The method for producing a composite membrane according to claim 1. 6. The adhesive according to claim 1, wherein a proton-conductive tetrafluoroethylene copolymer dissolved in an alcohol-based solvent and a sulfonated polyarylene dissolved in an alcohol-based solvent are used.
4. The method for producing a composite membrane according to any one of 4.