JP2003335835A - Sulfo group-containing resin varnish and sulfo group- containing crosslinked resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a varnish which is a raw material for a protonic acid group-containing crosslinked resin having a high ionic conductivity, excellent resistance to water and methanol, and a low methanol permeability; an ionically conductive polymer film for a fuel cell comprising the crosslinked resin; and a fuel cell using the film. <P>SOLUTION: The sulfo group-containing resin varnish contains a polymer and a curing agent. The polymer contains specific sulfo group-containing structural units in a specified ratio to all the repeating structural units and has active hydrogen-containing groups at the molecular chain terminals. The sulfo group-containing crosslinked resin is obtained by heat-treating the varnish. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sulfonic acid group-containing crosslinked resin forming an ion conductive polymer membrane applicable to a fuel cell using hydrogen, alcohol, etc. as a fuel and a sulfonic acid group-containing resin varnish which is a raw material thereof. Regarding
More specifically, the present invention relates to a sulfonic acid group-containing crosslinked resin having high ionic conductivity, excellent water resistance and methanol resistance, and low methanol permeability, and a sulfonic acid group-containing resin varnish which is a raw material of the crosslinked resin.

[0002]

2. Description of the Related Art In recent years, new energy storage or power generation elements have been strongly demanded in society from the viewpoint of environmental problems.
Fuel cells are also attracting attention as one of them, and are the most promising power generation elements because of their characteristics of low pollution and high efficiency. A fuel cell is a cell in which a fuel such as hydrogen or methanol is electrochemically oxidized using oxygen or air to convert the chemical energy of the fuel into electric energy and to extract it.

Such fuel cells are classified into phosphoric acid type, molten carbonate type, solid oxide type and polymer electrolyte type depending on the type of electrolyte used. The phosphoric acid fuel cell is
It has already been put to practical use for electric power. However, the phosphoric acid fuel cell needs to be operated at a high temperature (around 200 ° C.), so that the startup time is long, it is difficult to downsize the system, and the proton conductivity of phosphoric acid is low. It has a drawback that it cannot take out an electric current.

On the other hand, the operating temperature of the polymer fuel cell is about 80 to 100 ° C. at the highest. Further, since the internal resistance in the fuel cell can be reduced by thinning the electrolyte membrane used, it is possible to operate at a high current, and therefore the size can be reduced. Due to these advantages, research on polymer fuel cells has been actively conducted.

The polymer electrolyte membrane used in this polymer fuel cell is required to have high ionic conductivity of protons involved in the electrode reaction of the fuel cell. As such an ion conductive polymer electrolyte membrane material, a super strong acid group-containing fluoropolymer such as perfluorocarbon sulfonic acid is known. However, since these polymer electrolyte materials are fluorine-based polymers, they have a problem of being extremely expensive. Moreover, since the glass transition temperature of these polymers is low and the water retention at around 100 ° C. which is the operating temperature is not sufficient, the ionic conductivity sharply decreases at a temperature of 100 ° C. or higher, and the polymer can function as a battery. There was a problem of disappearing. Further, it cannot be applied to a direct methanol fuel cell due to its high methanol permeability.

In order to overcome these problems, many attempts have been made to introduce sulfonic acid groups into engineering plastics such as polyetherketone and polysulfone having high heat resistance and chemical resistance to form an ion conductive membrane. In order to increase the proton conductivity of the ion conductive polymer electrolyte membrane, it is necessary to increase the sulfonation degree of the polymer and reduce the ion exchange group equivalent. However, when the amount of sulfonic acid groups in the polymer is increased, water resistance and methanol resistance of the polymer are lowered, and problems such as decomposition of the polymer and dissolution in water or methanol occur. For this reason, only polyetherketone or polysulfone having a reduced sulfonation degree and a small proton conductivity can be applied to the fuel cell.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems of the prior art. A crosslinked resin having a high ionic conductivity, that is, a small ion exchange group equivalent and excellent water resistance and methanol resistance, a crosslinked resin having a sulfonic acid group, a varnish which is a raw material thereof, and an ion conductive polymer for a fuel cell, which comprises the crosslinked resin It is intended to provide a membrane and a fuel cell.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a polymer solution having a sulfonic acid group whose molecular chain end is an alcoholic hydroxyl group or an amino group,
By adding an isocyanate compound, a modified isocyanate compound or an epoxy compound as a curing agent,
It was found that a crosslinked structure can be formed between polymer molecules. Further, they have found that the obtained sulfonic acid group-containing crosslinked resin has excellent ion conductivity, excellent methanol resistance and methanol barrier property, and completed the present invention.

The present invention is specified by the matters described in [1] to [9] below. [1] General formula (1) for all repeating structural units

[Chemical 6]

[In the general formula (1), A is -CO- or-
SO ₂ -, B stands direct _{bond, -CH 2 -, - C (} CH
_{3) 2 -, - C (} CF 3) 2 -, - O -, - S -, - SO 2
Represents -or-CO-. h and i are integers of 0 or more and 2 or less, and h + i is a number of 1 or more. M represents hydrogen, lithium, sodium or potassium. m is 0 or a positive integer of 2 or less. ] 20-99 mol% of repeating structural units having a sulfonic acid group represented by
General formula (2)

[0011]

[Chemical 7]

[In the general formula (2), B and n are the general formula (1)
Has the same meaning as B and n. E is a direct bond, -CH
_{2 -, - C (CH 3} ) 2 -, - C (CF 3) 2 -, - O-,
-S -, - representing the or -CO- - SO _2. n is 0 or a positive integer of 2 or less. ] A sulfonic acid group-containing resin varnish comprising a polymer having a repeating structural unit represented by 1 to 80 mol% and having an active hydrogen-containing group at a molecular chain terminal, and a curing agent.

[2] General formula (1) and general formula (2)
The group containing active hydrogen at the terminal of the molecular chain of the polymer consisting of the repeating structural unit of

[Chemical 8]

[In the general formula (3), B and m are the general formula (1).
It has the same meaning as B and m in the inside. R is an alkyl group having 2 to 4 carbon atoms. k is a positive integer of 1 or more and 9 or less. ] It is an alcoholic hydroxyl group represented by these, The resin varnish containing a sulfonic acid group as described in [1].

[3] General formula (1) and general formula (2)
The group containing active hydrogen at the molecular chain end of the polymer consisting of the repeating structural unit of

[Chemical 9]

[In the general formula (4), Ar is

[Chemical 10] Is. G and G 'is a direct bond, -CH ₂ -, - C
_{(CH 3) 2 -, -} C (CF 3) 2 -, - O -, - SO 2 -
Alternatively, it represents -CO-. ] The sulfonic-acid-group containing resin varnish as described in [1].

[4] The curing agent is an isocyanate compound having two or more isocyanate groups in the molecule, or a modified isocyanate compound obtained by masking (blocking) the isocyanate groups with phenols. The resin varnish containing a sulfonic acid group according to any one of [3].

[5] The resin varnish containing a sulfonic acid group according to any one of [1] to [3], wherein the curing agent is an epoxy compound having two or more epoxy groups in the molecule.

[6] A sulfonic acid group-containing crosslinked resin obtained by heat-treating the sulfonic acid group-containing resin varnish according to any one of [1] to [5].

[7] An ion conductive polymer membrane for a fuel cell, which comprises the sulfonic acid group-containing crosslinked resin according to [6].

[8] Ion exchange group equivalent is 1000 g /
The ion conductive membrane for a fuel cell according to [7], which is less than or equal to mol and has a methanol solubility of less than 15 wt%.

[9] The present invention provides a fuel cell obtained by using the ion conductive polymer membrane for a fuel cell according to [7] or [8].

INDUSTRIAL APPLICABILITY The present invention provides a sulfonic acid group-containing crosslinked resin which can be easily crosslinked under the same conditions as general urethane resins and epoxy resins, and which is excellent in methanol resistance and is useful as a proton conductive membrane for fuel cells. Provided is a sulfonic acid group-containing crosslinked resin varnish which is a raw material thereof.

The ion conductive polymer film according to the present invention has high ion conductivity, and is excellent in water resistance and solvent resistance. In particular, when a fuel cell is formed using the ion conductive polymer film according to the present invention, a fuel cell having excellent durability, low resistance and high current operation can be obtained.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The sulfonic acid group-containing crosslinked resin according to the present invention and the varnish of the sulfonic acid group-containing resin which is the raw material thereof will be specifically described below.

The sulfonic acid group-containing resin varnish of the present invention is
It is characterized by containing a polymer having a sulfonic acid group in the molecular chain and having a group containing active hydrogen at the terminal of the molecular chain, and a curing agent. In addition, the active hydrogen in the present invention is hydrogen bonded to an oxygen atom or a nitrogen atom, and specifically represents hydrogen of a hydroxyl group or an amino group.

Further, the sulfonic acid group-containing crosslinked resin of the present invention comprises a sulfonic acid group-containing resin varnish containing a polymer having a sulfonic acid group in the molecular chain and having an alcoholic hydroxyl group at the molecular chain end and a curing agent. can get.

The sulfonic acid group-containing crosslinked resin of the present invention is obtained from a sulfonic acid group-containing resin varnish containing a polymer having a sulfonic acid group in the molecular chain and having an amino group at the molecular chain end and a curing agent. To be

The sulfonic acid group-containing polymer of the present invention is preferably 20 to 99 mol% of the repeating structural unit represented by the following general formula (1), based on all repeating structural units.
And a repeating structural unit 1 represented by the following general formula (2)
80 mol% and has an alcoholic hydroxyl group terminal represented by the following general formula (3) or an amino group terminal represented by the following general formula (4).

[0030]

[Chemical 11]

In the general formula (1), A is --CO-- or --S.
O ₂ -, B stands direct _{bond, -CH 2 -, - C (} C
_{H 3) 2 -, - C} (CF 3) 2 -, - O -, - S -, - SO
Represents _2- or -CO-. h and i are integers of 0 or more and 2 or less, and h + i is a number of 1 or more. M represents hydrogen, lithium, sodium or potassium. m is 0 or a positive integer of 2 or less.

In the general formula (2), B and n have the same meanings as B and n in the general formula (1). E is a direct bond, -CH ₂ -,
_{-C (CH 3) 2 -,} - C (CF 3) 2 -, - O -, - S
-, - representing the or -CO- - SO _2. n is 0 or 2
The following positive integers.

In the general formulas (1) and (2),
Hydrogen on the aromatic ring may be substituted with halogen or an alkyl group.

In the general formula (3), B and m have the same meanings as B and m in the general formula (1). R is an alkyl group having 2 to 4 carbon atoms. k is a positive integer of 1 or more and 9 or less.

The term "1 mol of the terminal alcoholic hydroxyl group" means 1 mol of the terminal structural unit represented by the general formula (3).

Examples of the alkylene group represented by R in the general formula (3) include ethylene group, 1,2-propylene group, 1,2-butylene group and 1,4-butylene group.

In the general formula (4), Ar is

[Chemical 12] Is. G and G 'is a direct bond, -CH ₂ -, - C
_{(CH 3) 2 -, -} C (CF 3) 2 -, - O -, - SO 2 -
Alternatively, it represents -CO-. Further, in the general formula (4), hydrogen of the aromatic ring may be substituted with halogen, an alkyl group or an amino group.

Further, 1 mol of the terminal amino group described below means 1 mol of the terminal structure represented by the general formula (4).

The sulfonic acid group-containing resin of the present invention is roughly classified into sulfonated polyether ketones in which A in the general formula (1) is —CO— and sulfonated polysulfones in which A is —SO ₂ —. To be done.

The sulfonated polyether ketones in which A in the general formula (1) is —CO— and the molecular chain terminal is an alcoholic hydroxyl group represented by the general formula (3), and a method for producing the same will be described. To do.

The sulfonated polyether ketones that can be used in the present invention preferably contain 20 to 99 mol% of the repeating structural unit represented by the general formula (1) based on the total repeating structural units of the polymer. 1 to 80 mol% of the repeating structural unit represented by the general formula (2),
More preferably, the repeating structural unit represented by the general formula (1) has 30 to 80 mol% and the repeating structural unit represented by the general formula (2) has 20 to 70 mol%, and the general formula It has an alcoholic hydroxyl group terminal represented by (3). The arrangement of the repeating structural unit represented by the general formula (1) and the repeating structural unit represented by the general formula (2) may be random or block.

The sulfonated polyether ketones having an alcoholic hydroxyl group terminal which can be used in the present invention are prepared by adding an alkylene oxide or a cyclic ether to a sulfonated polyether ketone having a phenolic hydroxyl group terminal by a known method. Can be obtained by The sulfonated polyetherketones having a phenolic hydroxyl group terminal are less than an equivalent amount of the sulfonated benzophenone compound represented by the following general formula (5) with respect to the aromatic diol represented by the following general formula (7) and the following. General formula (6)
It can be obtained by reacting a mixture with a dihalogenated aromatic compound represented by

[0043]

[Chemical 13]

In the general formula (5), M, h and i have the same meanings as M, h and i in the general formula (1). Z ¹ is fluorine or chlorine.

In the general formula (6), E and n have the same meanings as E and n in the general formula (2). Z ² is fluorine or chlorine.

In the general formula (7), B and m have the same meanings as B and m in the general formula (1).

A raw material, a sulfonated benzophenone compound,
There is no limitation on the order of charging the dihalogenated aromatic compound and the aromatic diol, the reaction concentration, the temperature and the time. In addition, normally, polyetherketones are in the atmosphere of an inert gas such as nitrogen and argon, in an aprotic polar solvent, in the coexistence of a sulfonated benzophenone compound and an aromatic diol with a basic catalyst, at about 0 to 200 ° C. It can be obtained by reacting for several hours.

Specific examples of the sulfonated benzophenone represented by the general formula (5) that can be used in the present invention include 5,5'-carbonylbis (2-fluorobenzenesulfonic acid) and 4,4 '. -Carbonylbis (2-fluorobenzenesulfonic acid), 6,6'-carbonylbis (3-fluorobenzenesulfonic acid), 2-fluoro-5-[(4-fluorophenyl) carbonyl] benzenesulfonic acid, 2-fluoro -4-[(3-fluorophenyl) carbonyl] benzenesulfonic acid, 5,5'-
Carbonylbis (lithium 2-fluorobenzenesulfonate), 4,4′-carbonylbis (lithium 2-fluorobenzenesulfonate), 6,6′-carbonylbis (lithium 3-fluorobenzenesulfonate), 2-fluoro- 5-[(4-fluorophenyl) carbonyl]
Lithium benzenesulfonate, 2-fluoro-4-
[(3-Fluorophenyl) carbonyl] benzenesulfonate lithium, 5,5′-carbonylbis (sodium 2-fluorobenzenesulfonate), 4,4′-carbonylbis (sodium 2-fluorobenzenesulfonate), 6, 6'-Carbonylbis (sodium 3-fluorobenzenesulfonate), 2-fluoro-5-[(4
-Fluorophenyl) carbonyl] sodium benzenesulfonate, 2-fluoro-4-[(3-fluorophenyl) carbonyl] sodium benzenesulfonate,
5,5'-carbonylbis (potassium 2-fluorobenzenesulfonate), 4,4'-carbonylbis (potassium 2-fluorobenzenesulfonate), 6,6'-carbonylbis (potassium 3-fluorobenzenesulfonate) , 2-fluoro-5-[(4-fluorophenyl)
Carbonyl] potassium benzenesulfonate, 2-fluoro-4-[(3-fluorophenyl) carbonyl] potassium benzenesulfonate, 5,5′-carbonylbis (2-chlorobenzenesulfonic acid), 4,4′-carbonylbis ( 2-chlorobenzenesulfonic acid), 6,6 '
-Carbonylbis (3-chlorobenzenesulfonic acid),
2-chloro-5-[(4-chlorophenyl) carbonyl] benzenesulfonic acid, 2-chloro-4-[(3-chlorophenyl) carbonyl] benzenesulfonic acid, 5,
5'-carbonylbis (lithium 2-chlorobenzenesulfonate), 4,4'-carbonylbis (lithium 2-chlorobenzenesulfonate), 6,6'-carbonylbis (lithium 3-chlorobenzenesulfonate), 2-chloro- Lithium 5-[(4-chlorophenyl) carbonyl] benzenesulfonate, lithium 2-chloro-4-[(3-chlorophenyl) carbonyl] benzenesulfonate, 5,5′-carbonylbis (sodium 2-chlorobenzenesulfonate), 4,4'-carbonylbis (2
-Sodium chlorobenzene sulfonate), 6,6'-
Carbonylbis (sodium 3-chlorobenzenesulfonate), sodium 2-chloro-5-[(4-chlorophenyl) carbonyl] benzenesulfonate, sodium 2-chloro-4-[(3-chlorophenyl) carbonyl] benzenesulfonate, 5 , 5'-carbonylbis (2
-Potassium chlorobenzenesulfonate), 4,4'-carbonylbis (potassium 2-chlorobenzenesulfonate), 6,6'-carbonylbis (potassium 3-chlorobenzenesulfonate), 2-chloro-5-[(4-chlorophenyl ) Carbonyl] potassium benzenesulfonate, potassium 2-chloro-4-[(3-chlorophenyl) carbonyl] benzenesulfonate, and the like.
These sulfonated benzophenone compounds can be used alone or in admixture of two or more.

Specific examples of the dihalogenated aromatic compound represented by the general formula (6) include 1,4-difluorobenzene, 1,3-difluorobenzene, 2,5-difluorotoluene and 2,5-difluoroethylbenzene. , 2,
5-difluoro-p-xylene, 4,4'-difluorobiphenyl, 3,3'-dimethyl-4,4'-difluorobiphenyl, 2,2'-difluorobiphenyl, 3,
3'-dibromo-4,4'-difluorobiphenyl,
4,4'-difluorobenzophenone, 2,2'-dimethyl-4,4'-difluorobenzophenone, 3,3 '
-Dimethyl-4,4'-difluorobenzophenone,
3,3 ′, 5,5′-tetramethyl-4,4′-difluorobenzophenone, 2,2′-difluorobenzophenone, 4,4′-bis (4-fluorobenzoyl) benzene, 4,4′-bis ( 4-fluorobenzoyl) biphenyl, 4,4′-difluorodiphenyl sulfide,
2,2'-difluorodiphenyl sulfide, 4,4 '
-Difluorodiphenylmethane, 2,2'-difluorodiphenylmethane, 4,4'-difluorodiphenyl ether, 2,2'-difluorodiphenyl ether,
4,4'-difluorodiphenyl sulfone, 2,2'-
Difluorodiphenyl sulfone, 2,2-bis (4-fluorophenyl) propane, 2,2-bis (2-fluorophenyl) propane, α, α′-bis (4-fluorophenyl) -1,4-diisopropylbenzene, α,
α'-bis (2-fluorophenyl) -1,4-diisopropylbenzene, α, α'-bis (4-fluorophenyl) -1,3-diisopropylbenzene, α, α'-
Bis (2-fluorophenyl) -1,3-diisopropylbenzene, 1,4-dichlorobenzene, 1,3-dichlorobenzene, 4,4′-dichlorobiphenyl, 2,
2'-dichlorobiphenyl, 3,3'-dibromo-4,
4'-dichlorobiphenyl, 4,4'-dichlorobenzophenone, 2,2'-dichlorobenzophenone, 4,
4'-dichlorodiphenyl sulfide, 2,2'-dichlorodiphenyl sulfide, 4,4'-dichlorodiphenylmethane, 2,2'-dichlorodiphenylmethane,
4,4'-dichlorodiphenyl ether, 2,2'-dichlorodiphenyl ether, 4,4'-dichlorodiphenyl sulfone, 2,2'-dichlorodiphenyl sulfone, 2,2-bis (4-chlorophenyl) propane,
2,2-bis (2-chlorophenyl) propane, α,
α'-bis (4-chlorophenyl) -1,4-diisopropylbenzene, α, α'-bis (2-chlorophenyl) -1,4-diisopropylbenzene, α, α'-bis (4-chlorophenyl) -1, 3-diisopropylbenzene, α, α′-bis (2-chlorophenyl) -1,
3-diisopropylbenzene etc. are mentioned. These bifunctional aromatic compounds may be used alone or in admixture of two or more.

The charging ratio of the dihalogenated aromatic compound is
The amount of the sulfonated benzophenone compound and the dihalogenated aromatic compound is 1 to 80 mol%, preferably 10% by mol.
˜70 mol%.

Specific examples of the aromatic diols represented by the general formula (7) that can be used in the present invention include:
Hydroquinone, resorcin, 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-hexylhydroquinone, 2-octylhydroquinone, 2-decanylhydroquinone, 2,3-dimethylhydroquinone,
2,3-diethylhydroquinone, 2,5-dimethylhydroquinone, 2,5-diethylhydroquinone, 2,
6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 4,4′-dihydroxybiphenyl, 2,
2'-dihydroxybiphenyl, 3,3'-dimethyl-
4,4'-dihydroxybiphenyl, 3,3 ', 5
5'-tetramethyl-4,4'-dihydroxybiphenyl, 3,3'-dichloro-4,4'-dihydroxybiphenyl, 3,3 ', 5,5'-tetrachloro-4,4'
-Dihydroxybiphenyl, 3,3'-dibromo-4,
4'-dihydroxybiphenyl, 3,3 ', 5,5'-
Tetrabromo-4,4'-dihydroxybiphenyl,
3,3'-difluoro-4,4'-dihydroxybiphenyl, 3,3 ', 5,5'-tetrafluoro-4,4'
-Dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenylmethane, 3,3'-dimethyl-4,4'-dihydroxydiphenylmethane, 3,3 ', 5,5'-tetramethyl-
4,4'-dihydroxydiphenylmethane, 3,3'-
Dichloro-4,4'-dihydroxydiphenylmethane,
3,3 ', 5,5'-tetrachloro-4,4'-dihydroxydiphenylmethane, 3,3'-dibromo-4,
4'-dihydroxydiphenylmethane, 3,3 ', 5
5'-tetrabromo-4,4'-dihydroxydiphenylmethane, 3,3'-difluoro-4,4'-dihydroxydiphenylmethane, 3,3 ', 5,5'-tetrafluoro-4,4'-dihydroxydiphenylmethane,
4,4'-dihydroxydiphenyl ether, 2,2 '
-Dihydroxydiphenyl ether, 3,3'-dimethyl-4,4'-dihydroxydiphenyl ether, 3,
3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl ether, 3,3'-dichloro-4,4'
-Dihydroxydiphenyl ether, 3,3 ', 5,
5'-tetrachloro-4,4'-dihydroxydiphenyl ether, 3,3'-dibromo-4,4'-dihydroxydiphenyl ether, 3,3 ', 5,5'-tetrabromo-4,4'-dihydroxydiphenyl ether,
3,3'-difluoro-4,4'-dihydroxydiphenyl ether, 3,3 ', 5,5'-tetrafluoro-
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dihydroxydiphenyl sulfide, 2,2'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-
4,4'-dihydroxydiphenyl sulfide, 3,
3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dichloro-4,
4'-dihydroxydiphenyl sulfide, 3,3 ',
5,5'-tetrachloro-4,4'-dihydroxydiphenyl sulfide, 3,3'-dibromo-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'
-Tetrabromo-4,4'-dihydroxydiphenyl sulfide, 3,3'-difluoro-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetrafluoro-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone,
2,2'-dihydroxydiphenyl sulfone, 3,3 '
-Dimethyl-4,4'-dihydroxydiphenyl sulfone, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfone, 3,3'-dichloro-
4,4'-dihydroxydiphenyl sulfone, 3,
3 ', 5,5'-tetrachloro-4,4'-dihydroxydiphenyl sulfone, 3,3'-dibromo-4,4'
-Dihydroxydiphenyl sulfone, 3,3 ', 5
5'-tetrabromo-4,4'-dihydroxydiphenyl sulfone, 3,3'-difluoro-4,4'-dihydroxydiphenyl sulfone, 3,3 ', 5,5'-tetrafluoro-4,4'-dihydroxydiphenyl Sulfone, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (2-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane,
2,2-bis (3,5-didibromo-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-)
Hydroxyphenyl) propane, 2,2-bis (3,5
-Difluoro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, α, α′-
Bis (2-hydroxyphenyl) -1,4-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -1,3-diisopropylbenzene, α, α′-bis (2-hydroxyphenyl) -1, 3-diisopropylbenzene, α, α′-bis (3-methyl-4-hydroxyphenyl) -1,4-diisopropylbenzene,
α, α′-bis (3,5-dimethyl-4-hydroxyphenyl) -1,4-diisopropylbenzene, α, α ′
-Bis (3-methyl-4-hydroxyphenyl) -1,
3-diisopropylbenzene, α, α′-bis (3,5
-Dimethyl-4-hydroxyphenyl) -1,3-diisopropylbenzene and the like. These aromatic diols can be used alone or in admixture of two or more.

The method of charging the aromatic diols, the sulfonated benzophenone compounds and the dihalogenated aromatic compounds into the polymerization system and carrying out the reaction is not particularly limited, but preferably a) the aromatic diols, the sulfonated benzophenone compounds and the dihalogenated compounds. A method in which all of the aromatic compounds and a basic catalyst are further charged into the polymerization system to carry out the reaction, or (b) after reacting the aromatic diols with the basic catalyst to form a salt, a sulfonated benzophenone compound, Any method of adding an aromatic bifunctional compound and carrying out the reaction is desirable.

The type of catalyst and reaction conditions are not particularly limited, and known catalysts and reaction conditions can be applied. As the catalyst, alkali metal, alkaline earth metal, basic metal compounds such as zinc oxide, carbonates and acetates of various metals,
Examples thereof include hydroxides, quaternary ammonium salts, phosphonium salts and organic bases. The amount of these catalysts to be used is usually 0.1 to 5. with respect to 1 mol of the aromatic diol used.
It is 0 molar ratio. The molar ratio is preferably 0.5 to 2.0.

The reaction for producing the sulfonated polyether ketones that can be used in the present invention is usually carried out in a solvent. The following are mentioned as a preferable solvent. a) aprotic amide solvent N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N -Methylcaprolactam, hexamethylphosphorotriamide and the like. b) Ether solvent 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy)
Ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane and the like. c) Amine-based solvents pyridine, quinoline, isoquinoline, α-picoline, β
-Picoline, γ-picoline, isophorone, piperidine,
2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine and the like. d) Other solvents Dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole and the like.

These solvents may be used alone or in admixture of two or more. Further, the solvent shown in the item e) below may be used, and one or more of them may be further mixed and used. When mixed and used, it is not always necessary to select a combination of solvents that dissolve each other, and a heterogeneous mixed system may be used without mixing.

There is no limitation on the concentration of the reaction substance (hereinafter referred to as polymerization concentration) carried out in these solvents. In the present invention, the polymerization concentration carried out in the solvent is defined as a value indicating the ratio of the total mass of the used monomers to the total amount of the total mass of all the solvents used and the total mass of the monomers, as a percentage.
The preferred polymerization concentration is 5 to 40%, more preferably 8 to 35%, and the most preferred polymerization concentration is 10%.
To 30%.

By subjecting aromatic diols, sulfonated benzophenone compounds and dihalogenated aromatic compounds to polycondensation in the above solvent, the sulfonic acid group-containing crosslinkable polyether ketones of the present invention can be obtained.

A particularly preferred solvent for this reaction is a) above.
The aprotic amide solvent in the item and dimethyl sulfoxide in the item d) are mentioned. Air, nitrogen, helium, neon, or argon is used as the atmospheric gas, and there is no particular limitation, but nitrogen or argon, which is an inert gas, is preferably selected.

Further, in order to remove the water generated by the reaction out of the system, another solvent can be made to coexist. Examples of the solvent used here include those described in the following item e). e) benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene,
Brombenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene and the like. These solvents may be used alone or in combination of two or more.

It is also possible to use the solvent shown in the above items a) to e) and further mix them with one kind or two or more kinds. When mixed and used, it is not always necessary to select a combination of solvents that dissolve each other, and a heterogeneous mixed system may be used without mixing.
There is no limitation on the amount of the dehydrating agent used.

The reaction temperature, reaction time and reaction pressure include
There is no particular limitation and known conditions can be applied. That is, the reaction temperature is approximately 100 to 300 ° C.
However, it is more preferably in the range of about 120 to 280 ° C, and most preferably 140 ° C to 2 in terms of implementation.
It is 50 ° C. The reaction time varies depending on the type of monomer used, the type of solvent, and the reaction temperature.
~ 48 hours is preferred. It is more preferably a few hours to several tens of hours, and most preferably 5 to 20 hours in terms of implementation. Further, the reaction pressure is usually atmospheric pressure.

The sulfonated polyether ketones that can be used in the present invention can be prepared by adjusting the total amount of the sulfonated benzophenone compound and the dihalogenated aromatic compound with respect to the aromatic diols to obtain the amount of terminal hydroxyl groups and varnish of the resulting polymer. And the crosslink density (distance between crosslink points) of the obtained crosslinked resin can be controlled. In the synthesis of the sulfonated polyether ketones that can be used in the present invention, the total amount of the sulfonated benzophenone compound and the dihalogenated aromatic compound is 0.8 to 0.99 mol with respect to 1 mol of the aromatic diol. Is preferred. When the amount of diamine used is less than 0.8 mol, the strength of the obtained polymer tends to be too low, and the coating film may crack when the varnish is applied and cured, which is not preferable. On the other hand, if the amount is more than 0.99 mol, the sulfonated polyether ketones obtained will have too few phenolic hydroxyl group terminals, and therefore sufficient crosslinking may not be possible in some cases.

When 1 mol of the aromatic diol, and the total amount α mol of the sulfonated benzophenone compound and the dihalogenated aromatic compound are used, the amount of terminal hydroxyl groups of the sulfonated polyether ketones obtained is (1-α) × 2 mol.

Next, a method of reacting phenolic hydroxyl group-terminated sulfonated polyether ketones with alkylene oxides or cyclic ethers to obtain alcoholic hydroxyl group termini will be described.

The alcoholic hydroxyl group-terminated sulfonated polyetherketone which can be used in the present invention is a phenolic hydroxyl group-terminated sulfonated polyetherketone, and an epoxy group in the molecule of ethylene oxide, propylene oxide, butylene oxide, styrene oxide or the like. Alkylene oxides having OH, or cyclic ethers such as tetrahydrofuran and 1,4-dioxane are used without catalyst or KOH, CsOH.
It can be produced by an addition reaction according to a known production method of a usual polyol using an alkali metal hydroxide, a tertiary amine, a Lewis acid or the like as a catalyst.

In the present invention, it is preferable to use 1 to 10 moles of alkylene oxide or cyclic ether for 1 mole of the terminal phenolic hydroxyl group. When the amount of alkylene oxide or the amount of cyclic ether is too small, the number of crosslinked polymer chains is small, and the effect of improving physical properties by crosslinking is small. On the other hand, if the amount is too large, the number of alkyl chain portions having not so high heat resistance increases and the heat resistance of the crosslinked film decreases, which is not preferable.

The molecular weight of the sulfonated polyetherketones having an alcoholic hydroxyl group at the molecular end which can be used in the present invention is not particularly limited, and the viscosity of the varnish and the obtained sulfonated crosslinked polyetherketones are It can be arbitrarily set according to the physical properties and the like, but when it is expressed by logarithmic viscosity, it is in the range of 0.3 to 2.0 dl / g (measured in dimethyl sulfoxide at a concentration of 0.5 g / dl at 35 ° C.). Is preferred. Logarithmic viscosity is 0.3
If it is less than the above range, the strength of the polymer may be too low, and the coating film may be broken when the varnish is applied and cured. On the other hand, when it exceeds 2.0, the number of alcoholic hydroxyl group terminals of the obtained sulfonated polyetherketone may be too small, and it tends to be difficult to obtain the effect of improving the physical properties by crosslinking.

Next, the sulfonated polyether ketones whose molecular chain ends are amino groups represented by the above general formula (4) will be described.

The sulfonated polyether ketones whose molecular chain terminal which can be used in the present invention is an amino group represented by the above general formula (4) can be used in the production of the above polyether ketones having a phenolic hydroxyl group. Further, it can be obtained by further adding an aromatic amine having one hydroxyl group in the molecule represented by the following general formula (8) and reacting it with a sulfonated benzophenone, a dihalogen compound and an aromatic diol.

[0070]

[Chemical 14]

In the general formula (8), Ar is the above general formula (4).
Has the same meaning as Ar. The polymerization method and the polymerization conditions may be the same as those for the synthesis of polyether ketones having a phenolic hydroxyl group.

Examples of the aromatic amine having one hydroxyl group represented by the above general formula (8) include p-hydroxyaniline, m-hydroxyaniline, o-hydroxyaniline, 4-hydroxy-4'-aminobiphenyl and 3 -Hydroxy-3'-aminobiphenyl, 4-hydroxy-
4'-aminodiphenyl ether, 4-hydroxy-
4'-aminobenzophenone, 4-hydroxy-4'-
Aminodiphenyl sulfone, 4-hydroxy-4′-aminodiphenyl sulfide, (4-hydroxyphenyl) (4-aminophenyl) methane, 2,2- (4-hydroxyphenyl) (4-aminophenyl) propane,
2,2- (4-hydroxyphenyl) (4-aminophenyl) hexafluoropropane, (4-hydroxyphenyl) (4-aminophenyl) benzene, (4-hydroxyphenoxy) (4-aminophenoxy) benzene,
(4-Hydroxybenzyl) (4-aminobenzyl) benzene, (4-hydroxybenzoyl) (4-aminobenzoyl) benzene, 3-hydroxy-1,3-diaminobenzene and the like can be mentioned. The amount of the aromatic amine having a hydroxyl group used varies depending on the type of the monomer, the molar ratio of the sulfonated benzophenone compound and the aromatic diol, etc., but is preferably 0.01 per 1 mol of the aromatic diol.
˜0.2 mol, more preferably 0.02 to 0.1 mol.

The molecular weight of the sulfonated polyetherketones having an amino group at the terminal of the molecular chain that can be used in the present invention is not particularly limited, and may be optionally adjusted according to the viscosity of the varnish, the physical properties of the resulting crosslinked resin and the like. Although it can be set, it is 0.3 to 2.0 dl / g expressed in logarithmic viscosity (concentration: 0.5 in dimethyl sulfoxide, as in sulfonated polyether ketones having an alcoholic hydroxyl group).
g / dl, measured at 35 ° C. ) Is preferable. The total amount of the sulfonated benzophenone compound and the dihalogenated aromatic compound is preferably 0.8 with respect to 1 mol of the total amount of the aromatic diol and the aromatic amine having a hydroxyl group.
It is 5 to 1.1 mol, and more preferably 0.9 to 1.05 mol.

Next, A in the general formula (1) is —SO ₂ —
And the sulfonated polysulfones having the molecular chain terminal of the alcoholic hydroxyl group represented by the general formula (3) will be described. Sulfonated polysulfones having a molecular chain terminal of an alcoholic hydroxyl group use a sulfonated diphenyl sulfone compound represented by the following general formula (9) in place of sulfonated benzophenone, and other than the sulfonated polyether ketones. Can be produced by polymerizing with the dihalogenated aromatic compound represented by the general formula (6) and the aromatic diol represented by the general formula (7).

[0075]

[Chemical 15] In the general formula (9), M, h, and i are M in the general formula (1),
It has the same meaning as h and i. Z ³ is fluorine or chlorine.

Examples of the sulfonated diphenyl sulfones that can be used include bis (4-fluoro-3-benzenesulfonic acid) sulfone, bis (4-fluoro-2-benzenesulfonic acid) sulfone and 3-fluoro-4-benzenesulfonic acid. ) Sulfone, bis (sodium 4-fluoro-3-benzenesulfonate) sulfone, bis (sodium 4-fluoro-2-benzenesulfonate) sulfone, 3-
Sodium fluoro-4-benzenesulfonate) sulfone, bis (sodium 4-fluoro-3-benzenesulfonate) sulfone, bis (sodium 4-fluoro-2-benzenesulfonate) sulfone, 3-fluoro-4-
Sodium benzenesulfonate) sulfone, bis (4-
Sodium fluoro-3-benzenesulfonate) sulfone, bis (sodium 4-fluoro-2-benzenesulfonate) sulfone, sodium 3-fluoro-4-benzenesulfonate) sulfone, bis (4-fluoro-3-)
Potassium benzenesulfonate) sulfone, bis (4-fluoro-2-potassium benzenesulfonate) sulfone,
3-Fluoro-4-benzenesulfonic acid potassium) sulfone, bis (4-chloro-3-benzenesulfonic acid) sulfone, bis (4-chloro-2-benzenesulfonic acid)
Sulfone, 3-chloro-4-benzenesulfonic acid) sulfone, bis (4-chloro-3-benzenesulfonic acid sodium) sulfone, bis (4-chloro-2-benzenesulfonic acid sodium) sulfone, 3-chloro-4- Sodium benzenesulfonate) sulfone, bis (sodium 4-chloro-3-benzenesulfonate) sulfone, bis (sodium 4-chloro-2-benzenesulfonate)
Sulfone, sodium 3-chloro-4-benzenesulfonate) sulfone, bis (sodium 4-chloro-3-benzenesulfonate) sulfone, bis (4-chloro-2-)
Sodium benzene sulfonate) sulfone, 3-chloro-4-sodium benzenesulfonate) sulfone, bis (potassium 4-chloro-3-benzenesulfonate) sulfone, bis (potassium 4-chloro-2-benzenesulfonate) sulfone, 3-chloro-4-benzenesulfonic acid potassium) sulfone, bis (3-methyl-4-fluorophenyl) sulfone, bis (3-ethyl-4-fluorophenyl) sulfone, bis (3-methyl-5-fluorophenyl) Sulfone, bis (3,5-dimethyl-4-fluorophenyl) sulfone, bis (3,5-diethyl-
4-fluorophenyl) sulfone, bis (3-methyl-)
4-chlorophenyl) sulfone, bis (3-ethyl-4)
-Chlorophenyl) sulfone, bis (3-methyl-5-
Chlorophenyl) sulfone, bis (3,5-dimethyl-
4-chlorophenyl) sulfone, bis (3,5-diethyl-4-chlorophenyl) sulfone, bis (3-methyl-5-nitrophenyl) sulfone and the like can be mentioned.

As the dihalogenated aromatic compound, the same compounds as the sulfonated polyether ketones can be used. The obtained sulfonated polysulfones having a phenolic hydroxyl group end, like the sulfonated polyether ketones,
Alcoholic terminated sulfonated polysulfones are obtained by reaction with alkylene oxides or cyclic ethers.

The molecular weight of the protonated polysulfone having an alcoholic hydroxyl group terminal is not particularly limited and can be arbitrarily set according to the viscosity of the varnish, the physical properties of the resulting crosslinked resin and the like. As in the case of the modified polyether ketones, it may be in the range of 0.3 to 2.0 dl / g (measured in N, N-dimethylacetamide at a concentration of 0.5 g / dl at 35 ° C.) in terms of logarithmic viscosity. preferable.

Next, A in the general formula (1) is -SO _2-.
And the sulfonated polysulfones having an amino group molecular chain terminal represented by the general formula (4) will be described.

As the sulfonated polysulfone having a molecular chain terminal of an amino group, a sulfonated diphenylsulfone compound represented by the general formula (9) is used instead of the sulfonated benzophenone, and other amino group terminated sulfonated polyethers. It can be obtained by reacting with an aromatic diol and an aromatic amine having one hydroxyl group like the ketones. As the aromatic amine having one hydroxyl group, the compounds listed as the sulfonated polyether ketones can be used.

The molecular weight of the sulfonated polysulfones having amine terminals that can be used in the present invention is not particularly limited and can be arbitrarily set depending on the viscosity of the varnish, the physical properties of the resulting crosslinked resin, etc. As with the sulfonated polyether ketones having a hydroxyl group terminal, the logarithmic viscosity is 0.3 to 2.0 dl / g (N,
Concentration 0.5 g / dl, 3 in N-dimethylacetamide
Measured at 5 ° C. ) Is preferable.

Next, the curing agent contained in the varnish of the present invention will be described. The curing agent that can be used in the present invention is roughly classified into an isocyanate compound or a modified isocyanate compound having two or more isocyanate groups in the molecule and an epoxy compound having two or more epoxy groups in the molecule. .

The isocyanate compound of the present invention is a known compound having two or more isocyanate groups in the molecule. Specifically, tolylene diisocyanate having two isocyanate groups in the molecule, 4,4'- Diphenylmethane diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc., and tris (4-isocyanatophenyl) methane having three isocyanate groups in the molecule, tris (3- Isocyanate phenyl) methane, thiophosphoric acid tris (4-isocyanate phenyl ester), N-isocyanatohexaaminocarbonyl-N ', N "-bis (isocyanatehexyl) urea, 1,3,5-tol Sus (3-isocyanate-4-methylphenyl) -2,4,6-trioxohexahydro-1,3,5-triazine (TDI trimer) and the like, and polymethylene polyphenyl polyisocyanate (polymeric MDI). Examples of the modified isocyanate compound include known compounds in which the isocyanate group of the above isocyanate compound is blocked with a phenol compound such as phenol, cresol, or chlorophenol.

These isocyanate compounds or modified isocyanate compounds can be used alone or in combination of two or more kinds. Since a varnish containing an isocyanate compound as a curing agent easily gels, it is preferable to use a modified isocyanate compound as a curing agent when the varnish is not used immediately after its production but is stored.

In the present invention, the amount of the isocyanate compound or modified isocyanate compound used varies depending on the number of isocyanate groups in the molecule, the type of the terminal group of the polymer, the type of the isocyanate compound, etc., but the alcohol of the sulfonic acid group-containing polymer used. The amount is 0.2 to 4.0 mol, preferably 0.3 to 2.0 mol, based on 1 mol of the terminal hydroxyl group or amino group. When the amount of the isocyanate compound used is large or small, the proportion of uncrosslinked molecular chains in the obtained polymer is large, and the effect of improving heat resistance and chemical resistance is small. Further, when the amount used is large, unreacted isocyanate groups remain in the polymer, which is not preferable.

By dissolving the sulfonated polymer and the isocyanate compound or the modified isocyanate compound in a solvent, adding the isocyanate compound or the modified isocyanate compound to the solution of the sulfonated polymer, or mixing the polymer solution and the isocyanate compound solution, The varnish of the invention can be obtained. As the solvent, the solvents mentioned in the production of sulfonated polyether ketones can be used.

There is no particular limitation on the concentration of the polymer having an alcoholic hydroxyl group or an amino group at the molecular chain end contained in the varnish of the present invention, and it can be optionally prepared depending on the storage stability and coating property of the varnish. In order to obtain a good sulfonic acid group-containing crosslinked resin thin film, the polymer concentration is preferably 5 to 50 wt%, more preferably 10 to 40 wt%.
It is preferably in the range of%.

A known catalyst for accelerating the reaction of the isocyanate group may be added to the varnish of the present invention. As the catalyst, amines, aziridines, quaternary ammonium compounds, alkali metal salts, lead compounds, tin compounds, alcoholate compounds, which are usually used in the production of urethane resins,
A phenolate compound, a metal halogen compound, a metal complex compound or the like can be used, and a mixture thereof may be used.

Examples of amines include trimethylaminoethylpiperazine, triethylamine, tripropylamine,
N-methylmorpholine, N-ethylmorpholine, triethylenediamine, dimethylethanolamine, tetramethylhexamethylenediamine, dimethylcyclohexylamine, diazobicycloundecene, 1,3,5-
Tris (dimethylaminopropyl) hexahydro-S-
Examples thereof include ethylaziridine. Examples of the quaternary ammonium compound include carboxylic acid salts of tertiary amines. As alkali metal salts,
Examples thereof include potassium octylate and sodium acetate. Examples of the lead compound include lead naphthenate and lead octylate. Examples of the tin compound include dibutyltin diacetate, dibutyltin dilaurate, tin laurate, and tin octoate. Examples of the alcoholate compound include sodium methoxide and sodium ethoxide. Examples of the phenolate compound include potassium phenoxide, lithium phenoxide, sodium phenoxide and the like.
Examples of metal halides include iron chloride, zinc chloride, zinc bromide, tin chloride and the like. Examples of the metal complex compound include metal complex compounds such as acetylacetone metal salt.

It is also possible to use a cocatalyst together. As a cocatalyst, for example, ethylene carbonate, a carbonate compound such as propylene carbonate or a phosphoric acid ester,
Examples thereof include phosphoric acid compounds such as phosphite. These catalysts can be used alone or in combination of two or more kinds.

Next, the epoxy compound having two or more epoxy groups in the molecule which can be used as a curing agent in the present invention will be described. As the epoxy compound, a known epoxy compound used for producing an epoxy resin or the like can be used. Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol C diglycidyl ether, bisphenol M diglycidyl obtained by reacting an aromatic polyhydric alcohol or an aromatic polyhydric amine with epichlorohydrin Ether, bisphenol S diglycidyl ether, tetramethylbisphenol A diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diether, dihydroxybiphenyl diglycidyl ether, bisphenol hexatrifluoroacetone diglycidyl ether, phlorogricinol triglycidyl ether, tetraglycidyl benzophenone , Bisresorcinol tetraglycidyl ether, 1,1,2,2-
Tetrakis (4- (2,3-epoxypropyl) phenyl) ethane, tris (4- (2,3-epoxypropyl) phenyl) methane, tetraglycidyldiaminodiphenylmethane, tetraglycidylxylenediamine, triglycidyl p-aminophenol, and the like, 2,2-bis (3,4-epoxycyclohexyl) propane, 4-epoxyethyl-, obtained by oxidizing a cyclic alkene
1,2-epoxycyclohexane etc. are mentioned.

In the present invention, the amount of the epoxy compound used varies depending on the number of epoxy groups in the molecule, the type of the terminal group of the polymer, the type of the epoxy compound, and the like, but the alcoholic hydroxyl group or amino group of the sulfonic acid group-containing polymer used. It is preferably 0.1 to 4.0 with respect to 1 mol of the terminal group.
The amount is more preferably 0.2 to 2.0 mol. When the amount of the epoxy compound used is small, the proportion of uncrosslinked molecular chains in the obtained polymer increases,
The effect of improving heat resistance and chemical resistance is small. If the amount is large, unreacted epoxy groups remain in the polymer, which is not preferable.

The varnish of the present invention can be obtained by dissolving the sulfonated polymer and the epoxy compound in a solvent, adding the epoxy compound to the sulfonated polymer solution, or mixing the polymer solution and the epoxy compound solution. . As the solvent, the solvents mentioned above in the production of the sulfonated polyether ketones can be used. A known catalyst that accelerates the reaction of epoxy groups may be added to the varnish of the present invention.

There is no particular limitation on the concentration of the polymer having an alcoholic hydroxyl group or an amino group at the molecular chain end contained in the varnish of the present invention, and it can be optionally prepared depending on the storage stability and the coating property of the varnish. In order to obtain a good sulfonic acid group-containing crosslinked resin thin film, the polymer concentration is preferably 5 to 50 wt%, more preferably 10 to 40 wt%.
It is preferably in the range of%.

Next, the crosslinked resin obtained by heat treating the varnish of the present invention and the method for producing the same will be described. The sulfonic acid group-containing crosslinked resin of the present invention has a repeating structural unit of 20 to 99 mol% having a sulfonic acid group represented by the general formula (1), based on all repeating structural units of the polymer.
And the repeating structural units 1 to 1 represented by the general formula (2).
A urethane bond having 80 mol% and formed by reacting an alcoholic hydroxyl group at the molecular chain terminal represented by the general formula (3) with an isocyanate group of an isocyanate compound,
Further, it is a resin in which polymer terminals are cross-linked by an allophanate bond due to a reaction between a urethane bond and an isocyanate group.

The sulfonic acid group-containing crosslinked resin of the present invention contains 20 to 99 mol% of the repeating structural unit having a sulfonic acid group represented by the general formula (1), based on the total repeating structural units of the polymer. Having 1 to 80 mol% of the repeating structural unit represented by the general formula (2) and reacting the amino group at the terminal of the molecular chain represented by the general formula (4) with the isocyanate group of the isocyanate compound. It is a resin in which the polymer ends are cross-linked by the resulting urea bond and further by the biuret bond resulting from the reaction of the urea bond and the isocyanate group.

Further, the sulfonic acid group-containing crosslinked resin of the present invention comprises 20 to 99 mol% of repeating structural units having a sulfonic acid group represented by the general formula (1), based on all repeating structural units of the polymer. Having 1 to 80 mol% of the repeating structural unit represented by the general formula (2) and reacting the alcoholic hydroxyl group at the terminal of the molecular chain represented by the general formula (3) with the epoxy group of the epoxy compound. It is a resin in which polymer ends are cross-linked by an ether bond formed by the above, or an ether bond by a reaction between a hydroxyl group generated by a reaction of an epoxy group and another epoxy group.

The sulfonic acid group-containing crosslinked resin of the present invention contains 20 to 99 mol% of the repeating structural unit having a sulfonic acid group represented by the general formula (1) with respect to the total repeating structural units of the polymer. Having 1 to 80 mol% of the repeating structural unit represented by the general formula (2) and reacting the amino group at the terminal of the molecular chain represented by the general formula (4) with the epoxy group of the epoxy compound. Ether bond that can be made,
Further, it is a resin in which polymer terminals are cross-linked by an ether bond due to a reaction between a hydroxyl group generated by a reaction of an epoxy group and another epoxy group.

The crosslinked resin of the present invention exhibits higher chemical resistance than conventional linear sulfonated polyetherketones and sulfonated polysulfones having no crosslinked structure. Further, the crosslinked resin of the present invention has higher mechanical strength and methanol blocking property than sulfonated polyetherketone and sulfonated polysulfone having no crosslinked structure.

The sulfonic acid group-containing crosslinked resin of the present invention can be obtained by coating the substrate with the varnish of the present invention, removing the solvent, and then curing the coating film. The curing method is not particularly limited, and a conventionally known thermal curing method can be used. Known methods include, for example, a method in which the varnish applied on the base material is dried with hot air, and then the cast film is peeled from the base material and heat-treated, and a method in which the cast film is heat-treated while attached to the base material.

When a sulfonic acid group-containing crosslinked resin is produced by heat-treating a film obtained by casting the varnish of the present invention, the usual urethane bond forming conditions and epoxy curing conditions are sufficient. It is not necessary to perform high temperature annealing for a long time. The temperature at the time of curing is not limited, but it is particularly preferably 250 ° C. or lower in order to suppress deterioration of the obtained sulfonic acid group-containing crosslinked polyetherketone and polyethersulfone due to oxidation or the like and decomposition of urethane bonds.

The sulfonic acid group at the time of heat treatment may be of a protic acid type, but when heated to 200 ° C. or higher, it is preferably a lithium, sodium or potassium metal salt type in order to suppress elimination of the sulfonic acid group.

The ion conductive polymer membrane of the present invention is a membrane obtained by thermally crosslinking the sulfonic acid group-containing resin varnish. The thickness of the ion conductive polymer film is not particularly limited, but is usually 10 to 100 μm, and particularly 30 to
80 μm is preferable. Within the above range, the mechanical strength of the film that can withstand practical use can be obtained, and the film resistance can be reduced to a level that is practically sufficient, that is, sufficient power generation performance can be obtained. The film thickness can be controlled by the polymer concentration of the varnish or the coating thickness on the substrate.

The ion-exchange group equivalent of the ion-conductive polymer membrane is preferably 1,000 g / mol or less, more preferably 250 to 950 g / mol, though it varies depending on the type and application of the fuel cell. Further, as a state of the sulfonic acid group of the sulfonic acid group-containing crosslinked resin when used as the ion conductive polymer membrane, a free protonic acid state having the highest proton conductivity is preferable.

Next, a fuel cell obtained by using the ion conductive polymer membrane of the present invention will be described. The fuel cell of the present invention can be roughly classified into a general polymer electrolyte fuel cell (PEMFC) using hydrogen as a fuel and a direct methanol polymer electrolyte fuel cell (DMFC) using methanol as a fuel.
Any of them can be manufactured by a known method in which a conductive material as a catalyst for an electrode and a current collector is bonded to both surfaces of an ion conductive polymer film.

The PEMFC electrode catalyst is not particularly limited as long as it can activate the redox reaction between hydrogen and oxygen, and known ones can be used. It is preferable to use fine particles. Platinum fine particles are often used by being supported on particulate or fibrous carbon such as activated carbon or graphite. Known materials can be used for the conductive substance as the current collector, but a porous carbon nonwoven fabric or carbon paper is preferable for efficiently transporting the raw material gas to the catalyst.

Also in the case of DMFC, a known catalyst can be used for the electrode. For example, as the catalyst for the methanol electrode, a platinum catalyst, an alloy catalyst such as a platinum-ruthenium alloy or a platinum-tin alloy, or a supported catalyst in which fine particles of these catalysts are dispersed and supported on a carrier such as carbon is used. As the catalyst for the air electrode, platinum fine particles similar to PEMFC are used. As the conductive material as the current collector, a known material such as porous carbon nonwoven fabric or carbon paper can be used as in the PEMFC.

As a method for producing a bonded body of a gas diffusion electrode and an ion conductive polymer film, a method of directly forming a gas diffusion electrode on the ion conductive polymer film, a PTFE (polytetrafluoroethylene) film, or the like is used. A method in which a gas diffusion electrode is once formed into a layer on a substrate and then transferred to an ion exchange membrane, a method in which a gas diffusion electrode and an ion conductive polymer membrane are hot-pressed, and a method in which they are adhered to each other with an adhesive liquid Various known methods can be applied.

The fuel cell of the present invention is less expensive to manufacture than the conventional fuel cell using expensive perfluorocarbon sulfonic acid. Moreover, since the sulfonic acid group-containing crosslinked resin of the present invention has higher heat resistance than conventional perfluorocarbon sulfonic acids, it can be used at high temperatures. Furthermore, since the sulfonic acid group-containing crosslinked resin of the present invention has a small ion exchange group equivalent, it has a high ionic conductivity, which makes it possible to produce a fuel cell capable of operating at high current.

[0110]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

The test methods of various tests in the examples are as follows. (B) 0.50 g of a polymer powder having a logarithmic viscosity was added to dimethyl sulfoxide (D
MSO) or dimethylacetamide (DMAc) solvent dissolved in 100 ml, or polymer solution at a concentration of 0.00
Dilute to 5g / ml with DMSO or DMAc, 35 ° C
In Ubbelohde viscometer. (B) Proton exchange The metal salt of protonic acid was returned to free protonic acid by the following method. 1) The protonic acid group-containing crosslinked resin film was immersed in 2N sulfuric acid overnight. 2) The acid-treated membrane was immersed in distilled water overnight. 3) The membrane treated with acid and washed with distilled water was dried at 150 ° C. for 4 hours to obtain a membrane containing free protonic acid.

(C) Ion conductivity After cutting out the ionic conductive membrane to a width of 5 mm and a length of 40 mm, it was placed on a polytetrafluoroethylene (PTFE) holder, and four electrodes were pressure-welded to each other, and an alternating current of a four-terminal method was used. The resistivity was measured from the arc of the Cole-Cole plot obtained by the impedance method. The distance between the voltage terminals was 20 mm. The impedance was measured using an LCR meter (3532 manufactured by Hioki Electric Co., Ltd.). The temperature change was carried out by placing a sample to which an electrode was connected in a thermostat made of an aluminum block, and measuring the conductivity in the range of 30 ° C to 110 ° C. All measurements were carried out under humidification, but this humidification was carried out by introducing steam into a thermostatic chamber at normal pressure. If the temperature measured by the steam generator was less than 100 ° C, the thermostatic chamber temperature was + 5 ° C, 100 ° C.
In the above, the distilled water was heated to a constant temperature of 120 ° C. and the generated steam was used. Further, the film thickness required for calculation of ionic conductivity was measured in a dry state using a micrometer. (D) Methanol solubility The ion conductive membrane dried at 150 ° C. for 4 hours was immersed in methanol and allowed to stand at 25 ° C. for 24 hours. The taken out ion exchange membrane was dried again at 150 ° C. for 4 hours, and then the weight loss rate was measured.

(V) Methanol permeability Distilled water and a 1 mol / L methanol aqueous solution were contacted at room temperature through a proton conductive membrane having a diameter of 23 mmφ, and changes in methanol concentration on the distilled water side for up to 3 hours were measured by gas chromatography. . The methanol permeability was calculated from the slope of the obtained methanol concentration increase straight line. (F) The ion-exchange group equivalent sulfonated photocurable film was precisely weighed in a glass container capable of being sealed, an excess amount of calcium chloride aqueous solution was added thereto, and the mixture was stirred overnight. The hydrogen chloride generated in the system was titrated with a 0.1N sodium hydroxide standard aqueous solution using a phenolphthalein indicator and calculated.

(Example 1) A 300 ml five-necked reactor equipped with a nitrogen introducing tube, a thermometer, a cooling tube and a stirrer was used.
5,5′-Carbonylbis (sodium 2-fluorobenzenesulfonate) 4.22 g (10 mmol), 4,
1.96 g of 4'-difluorobenzophenone (9 mmo
l) and 4.57 g of bisphenol A (20 mmo
1) and 3.46 g (25 mmol) of potassium carbonate were weighed. Dimethyl sulfoxide (DMSO) 40
ml and 30 ml of toluene were added, and the mixture was stirred under a nitrogen atmosphere and heated at 130 ° C. for 2 hours to remove produced water out of the system, and then toluene was distilled off. 1 at 160 ℃
The reaction was carried out for 4 hours to obtain a viscous polymer solution. The resulting solution was diluted with 30 ml of DMSO and then filtered. The polymer solution was discharged into 400 ml of acetone,
The precipitated polymer powder was filtered and then dried at 160 ° C. for 4 hours to obtain 8.49 g (yield 85%) of polymer powder. The obtained polyetherketone powder has an inherent viscosity of 0.65 dl /
g (DMSO, 35 ° C).

Next, in a pressure vessel, 6.16 g of the obtained sulfonated polyether ketone, 20 ml of DMSO, and KO
Charge H 0.10g and toluene 10ml, 120 ℃
The resulting water was removed from the system by heating for 2 hours, and then toluene was distilled off. After cooling the system, propylene oxide 0.28
g was charged and reacted at 120 ° C. for 2 hours under pressure. DMS
After adding 40 ml of O and filtering, the polymer solution was added with acetone 4
It is discharged to 00 ml and dried at 160 ° C. for 4 hours to give a sulfonated polyether sulfone having alcoholic hydroxyl groups.
Obtained 5.80 g.

DMSO 14.2 was obtained by adding 4.20 g of the obtained polyetherketone having an alcoholic hydroxyl group and 0.52 g of tris (4-isocyanatophenyl) methane masked with phenol as a modified isocyanate compound.
It was dissolved in g to prepare a varnish. The obtained varnish was applied on a glass substrate, heated from room temperature to 170 ° C. in 4 hours in an inert oven under a normal pressure nitrogen atmosphere, and then heated to 170 ° C.
The solvent was removed and cross-linking was carried out by maintaining the temperature for 2 hours. The glass plate was immersed in water to remove the sulfonated crosslinked polyetherketone film, and the sulfonic acid group of the polymer was returned to the free protonic acid type from the sodium salt type by the method described in (b). The obtained film was flexible and tough. For this membrane, the ion conductivity was measured by the method described in (c), the methanol solubility was measured by the method described in (d), the methanol permeability was measured by the method described in (e), and the ion exchange group equivalent was measured by the method described in (f). .. The measurement results are shown in Table 1.

Example 2 2.18 g (10.0 mmol) of 4,4′-difluorobenzophenone and 4.45 g (19.5 mmol) of bisphenol A were added, and p-
0.22 g (2.0 mmol) of hydroxyaniline was added, and the sulfonated polyetherketone having an amino group terminal was synthesized in the same manner as in Example 1 except for the above. The yield of the sulfonated polyether ketone was 9.04 g (yield 88%), and the inherent viscosity η was 0.71 dl / g (DMSO, 35 ° C.).

4.11 g of the obtained amino group-terminated sulfonated polyether ketone and 0.52 g of tris (4-isocyanatophenyl) methane masked with phenol as an isocyanate compound were added to DMSO solvent 13.
It was dissolved in 9 g to prepare a varnish. After heat-treating the cast film in the same manner as in Example 1, the sulfonic acid group of the polymer was ion-exchanged into a protonic acid type, and various measurements were performed. The results are shown in Table 1.

(Example 3) 4.11 g of the amino group-terminated sulfonated polyether ketone obtained in Example 2 and 0.34 g of tetraglycidyldiaminodiphenylmethane as an epoxy compound were dissolved in 13.4 g of DMSO solvent to prepare a varnish. did. A cast film was prepared in the same manner as in Example 1, and various measurements were performed after ion exchange with a protonic acid type by the method described in (b). The results are shown in Table 1.

Example 4 In place of 5,5'-carbonylbis (sodium 2-fluorobenzenesulfonate), 5,5'-sulfonylbis (sodium 2-chlorobenzenesulfonate) was 4.91 g (10 mmol),
4,4'-difluorobenzophenone instead of 4,
2.58 g of 4'-dichlorodiphenyl sulfone (9 mm
ol), dimethylacetamide (D
The reaction was performed in the same manner as in Example 1 except that MAc) was used in the same amount. 8.79 g (yield 82%) of polymer powder was obtained. The polysulfone obtained had an inherent viscosity of 0.62d.
It was 1 / g (DMAc, 35 ° C).

6.41 g of polymer as in Example 1
Was reacted with propylene oxide to obtain 5.96 g of sulfonated polysulfone having an alcoholic hydroxyl group. A varnish was prepared by dissolving 4.36 g of the obtained polymer and 0.52 g of tris (4-isocyanatephenyl) methane masked with phenol as a modified isocyanate compound in 14.6 g of DMAc. As in Example 1, the varnish was cast on a glass plate to form a crosslinked film. After ion exchange with the protonic acid type, various measurements were performed. The results are shown in Table 1.

Example 5 In place of 5,5′-carbonylbis (sodium 2-fluorobenzenesulfonate), 5,5′-sulfonylbis (sodium 2-chlorobenzenesulfonate), 4.92 g (10 mmol),
4,4'-difluorobenzophenone instead of 4,
2.87 g of 4'-dichlorodiphenyl sulfone (10 m
mol) was used and otherwise the same as in Example 2 to synthesize an amino group-terminated sulfonated polysulfone. Yield 9.4
6 g (86% yield), logarithmic viscosity η 0.69 dl / g (D
MAc, 35 ° C).

DMAc was added with 4.40 g of amino group-terminated sulfonated polysulfone obtained in the same manner as in Example 2 and 0.52 g of tris (4-isocyanatophenyl) methane masked with phenol as an isocyanate compound.
It melt | dissolved in 14.8 g and the cast film was created from the obtained varnish. After ion exchange with the protonic acid type, various measurements were performed. The results are shown in Table 1.

Example 6 A varnish was prepared by dissolving 4.40 g of the amino group-terminated sulfonated polyether ketone obtained in Example 5 and 0.34 g of tetraglycidyldiaminodiphenylmethane as an epoxy compound in 14.2 g of DMAc. . A cast membrane was prepared in the same manner as in Example 1, and after performing ion exchange of the sulfonic acid group into a protonic acid type, various measurements were performed. The results are shown in Table 1.

Comparative Example 1 Polyether ketone was synthesized in the same manner as in Example 1 except that difluorobenzophenone (10 mmol) was used. Yield 8.25g (Yield 8
1%). A cast membrane was prepared in the same manner as in Example 1, and after performing ion exchange of the sulfonic acid group into a protonic acid type, various measurements were performed. The results are shown in Table 1.

(Comparative Example 2) Polysulfone was synthesized in the same manner as in Example 1 except that dichlorodiphenyl sulfone (10 mmol) was used. Yield 10.13 g (yield 93
%)Met. A cast membrane was prepared in the same manner as in Example 1, and after performing ion exchange of the sulfonic acid group into a protonic acid type, various measurements were performed. The results are shown in Table 1.

Comparative Example 3 Various measurements were carried out in the same manner as in Example 1 using a perfluorocarbon sulfonic acid film (Nafion (registered trademark) film, Aldrich reagent). The measurement results are shown in Table 1.

[0128]

[Table 1]

It is clear that Examples 1 to 6 have a lower methanol solubility, that is, a significantly improved methanol resistance, as compared with the non-crosslinked polymers of Comparative Examples 1 and 2. Further, it can be seen that although the ionic conductivity is on the same order as that of the Nafion (registered trademark) membrane of Comparative Example 4, the methanol permeability is low.

[0130]

EFFECTS OF THE INVENTION By using the varnish of the present invention, a fuel cell having excellent durability, low resistance and high current operation can be obtained, and the ionic conductivity is high and the methanol resistance and the methanol barrier property are excellent. There is provided an ion conductive polymer membrane made of a crosslinked resin containing a protonic acid group. Furthermore, an excellent fuel cell using the same is provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/22 CFF C08J 5/22 CFF H01M 8/02 H01M 8/02 P 8/10 8/10 // C08L 63:00 C08L 63:00 A 75:04 75:04 (72) Inventor Takehiko Omi 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72) Masaji Tamai 580- Nagaura, Sodegaura City, Chiba Prefecture 32 Mitsui Chemicals Co., Ltd. In-house F-term (reference) 4F071 AA42 AA53 AH15 FA05 FB07 FC01 FD02 4J034 BA03 DA01 DA02 DB01 DB04 DB07 DC02 DC42 DC43 DD02 DN03 HA01 HA06 HA07 HA08 HB05 HB09 HB15 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC61 HC52 HC61 HC61 HC52 HC61 HC HC71 HC73 HD03 JA06 QB06 RA14 4J036 AC03 AC05 AD07 AD08 AD09 AD20 AH07 AH09 AJ09 FB12 FB15 JA15 5H026 AA06 BB01 CX05 EE18 HH00

Claims (9)

[Claims] 1. A compound represented by the general formula (1): [In general formula (1), A represents —CO— or —SO ₂ —, B is a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —
_{C (CF 3) 2 -,} - O -, - S -, - SO 2 - or -
Represents CO-. h and i are integers of 0 or more and 2 or less, and h + i is a number of 1 or more. M represents hydrogen, lithium, sodium or potassium. m is 0 or 2
The following positive integers. A repeating structural unit having a sulfonic acid group represented by the following formula: 20 to 99 mol% and a compound represented by the general formula (2): [In the general formula (2), B and n have the same meanings as B and n in the general formula (1). E is a direct _{bond, -CH 2 -, - C (} C
_{H 3) 2 -, - C} (CF 3) 2 -, - O -, - S -, - SO
Represents _2- or -CO-. n is 0 or a positive integer of 2 or less. ] A sulfonic acid group-containing resin varnish comprising a polymer having a repeating structural unit represented by 1 to 80 mol% and having a group containing active hydrogen at a molecular chain terminal, and a curing agent. 2. A group comprising an active hydrogen at the terminal of the molecular chain of a polymer composed of repeating structural units of the general formulas (1) and (2) has the general formula (3): [In the general formula (3), B and m have the same meanings as B and m in the general formula (1). R is an alkyl group having 2 to 4 carbon atoms. k is a positive integer of 1 or more and 9 or less. ] An alcoholic hydroxyl group represented by the formula [1].
The sulfonic acid group-containing resin varnish described. 3. A group comprising an active hydrogen at the terminal of the molecular chain of a polymer comprising repeating structural units of the general formulas (1) and (2) has the general formula (4): [In the general formula (4), Ar is Is. G and G 'is a direct bond, -CH ₂ -, - C
_{(CH 3) 2 -, -} C (CF 3) 2 -, - O -, - SO 2 -
Alternatively, it represents -CO-. ] The resin varnish containing a sulfonic acid group according to claim 1, wherein 4. The curing agent is an isocyanate compound having two or more isocyanate groups in the molecule, or a modified isocyanate compound obtained by masking (blocking) the isocyanate groups with phenols. 7. A resin varnish containing a sulfonic acid group according to any one of 1. 5. The curing agent is an epoxy compound having two or more epoxy groups in the molecule.
A resin varnish containing a sulfonic acid group according to any one of to 3. 6. A sulfonic acid group-containing crosslinked resin obtained by heat-treating the sulfonic acid group-containing resin varnish according to claim 1. 7. An ion conductive polymer membrane for a fuel cell, which comprises the sulfonic acid group-containing crosslinked resin according to claim 6. 8. The ion conductive polymer membrane for a fuel cell according to claim 7, which has an ion exchange group equivalent of 1000 g / mol or less and a methanol solubility of less than 15 wt%. 9. A fuel cell obtained by using the ion conductive polymer membrane for a fuel cell according to claim 7.