JP2004346305A - Aromatic polyether-based ion-conducting ultra-high-molecular-weight polymer, intermediate for the same, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film of an aromatic polyether-based ion-conducting polymer, improved in mechanical strength. <P>SOLUTION: The aromatic polyether-based ion-conducting ultra-high-molecular-weight polymer has an ion exchange capacity of ≥0.1 meq/g, and further has such a structure that acid groups are introduced into the aromatic polyether-based ultra-high-molecular-weight polymer, wherein the aromatic polyether-based ultra-high-molecular-weight polymer has at least one kind of structural unit selected from formula (1) (Ar<SP>1</SP>is an aromatic divalent group, and pluralities of Ar<SP>1</SP>may be different from each other; and m is a number of repeating units, and is 10 or more) and formula (2) (Ar<SP>2</SP>is an aromatic divalent group, may be different from Ar<SP>1</SP>, and pluralities of Ar<SP>2</SP>may be different from each other; and n is a number of repeating units, and is 10 or more, and may be different from m) and a sum of (a) and (b) of 2 or more [(a) is a number of structural units of formula (1); and (b) is a number of structural units of formula (2)]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to an aromatic polyether-based ion-conductive ultrapolymer, an intermediate thereof, a production method thereof, and a use thereof.

  BACKGROUND ART A polymer electrolyte made of a polymer having ion conductivity is used as a diaphragm of an electrochemical device such as a primary battery, a secondary battery, and a polymer electrolyte fuel cell. For example, perfluorosulfonic acid-based materials such as Nafion (registered trademark of DuPont) have been conventionally mainly used because of their excellent properties when used in fuel cells. However, it has been pointed out that this material is very expensive, has low heat resistance, has a low film strength and is not practical without some kind of reinforcement.

  Under these circumstances, the development of inexpensive polymers that can replace the above-mentioned ion-conductive polymers has recently been active. Above all, a polymer in which an acid group such as a sulfonic acid group is introduced into an aromatic polyether having excellent heat resistance and high film strength, that is, the main chain is an aromatic type, and the main chain has a sulfonic acid group or the like. Promising are aromatic polymers to which acid groups are directly bonded. For example, aromatic polyether-based ion conductive polymers such as sulfonated polyether ketones (Patent Document 1) and sulfonated polyether sulfones (Patent Documents 2 and 3) have been proposed.

Japanese Patent Publication No. 11-502249 JP-A-10-45913 JP-A-10-21943

  However, the film strength of the aromatic polyether-based ion-conductive polymer as described above is higher than that of a perfluorosulfonic acid-based material, but can be sufficiently satisfied when used as an electrolyte membrane of a fuel cell or the like. Rather, it has been desired to develop an electrolyte in which this point is improved.

  The present inventors have conducted intensive studies to provide an aromatic polyether-based ion-conductive polymer having improved mechanical strength. As a result, a condensation reaction using a terminal group of the polymer, that is, a halogen as a terminal group was carried out. By coupling aromatic polyether-based polymers with each other, it is possible to further increase the molecular weight and find that an ultra-high-molecular-weight aromatic polyether can be obtained. The present inventors have found that an ion-conductive ultrapolymer having a sulfonic acid group or the like introduced therein can be an electrolyte membrane having excellent film strength, and have made various studies to complete the present invention.

（式中、Ａｒ^１、Ａｒ^２は独立に芳香族の２価の基を表す。ｍ、ｎは繰返し数を表し、ｍ、ｎは独立に１０以上の数値を表す。複数のＡｒ^１、Ａｒ^２、ｍ、ｎはそれぞれ異なっていても良い。）
から選ばれる少なくとも１種の構造単位を含有し、式（１）の構造単位の数ａと式（２）の構造単位の数ｂの和は２以上であることを特徴とする芳香族ポリエーテル系イオン伝導性超高分子を提供するものである。
さらに本発明は、
［２］酸基がスルホン酸基であることを特徴とする上記［１］記載の芳香族ポリエーテル系イオン伝導性超高分子を提供するものである。
また、本発明は、
［３］上記［１］記載の式（１）、（２）から選ばれる少なくとも１種の構造単位を含有し、式（１）の構造単位数ａと式（２）の構造単位数ｂの和は２以上である芳香族ポリエーテル系超高分子に酸基を導入することを特徴とする上記［１］記載の芳香族ポリエーテル系イオン伝導性超高分子の製造方法、
［４］酸基がスルホン酸基であることを特徴とする上記［３］記載の製造方法
を提供するものである。
また、本発明は、
［５］上記［１］記載の式（１）、（２）から選ばれる少なくとも１種の構造単位を含有し、式（１）の構造単位の数ａと式（２）の構造単位の数ｂの和は２以上であることを特徴とする芳香族ポリエーテル系超高分子を提供するものである。
また、本発明は、
［６］ゼロ価遷移金属錯体の共存下、下式（３）、（４）

（式中、Ａｒ^１、Ａｒ^２、ｍ、ｎは前記と同じ意味を表す。Ｘは、縮合反応時に脱離する基を表し、複数のＸは異なる種類であっても良い。）
から選ばれる少なくとも１種の高分子を縮合反応により重合することを特徴とする上記［５］記載の芳香族ポリエーテル系超高分子の製造方法、
［７］Ｘが、クロロ、ブロモ、ヨード、ｐ−トルエンスルホニルオキシ基、メタンスルホニルオキシ基、またはトリフルオロメタンスルホニルオキシ基であることを特徴とする上記［６］に記載の芳香族ポリエーテル系超高分子量高分子の製造方法、
また、本発明は、
［８］上記［１］記載の芳香族ポリエーテル系イオン伝導性超高分子を有効成分とする高分子電解質、
［９］上記［８］記載の高分子電解質からなる高分子電解質膜、
［１０］上記［８］記載の高分子電解質を用いてなることを特徴とする触媒組成物、
［１１］上記［９］記載の高分子電解質膜および／または上記［１０］記載の触媒組成物を用いてなることを特徴とする燃料電池
を提供するものである。 That is, the present invention
[1] The ion exchange capacity is 0.1 meq / g or more, the aromatic polyether-based ultrapolymer has a structure in which an acid group is introduced, and the aromatic polyether-based ultrapolymer is represented by the following formula ( 1), (2)

(Wherein, Ar ¹ and Ar ² independently represent an aromatic divalent group; m and n each represent a number of repetitions; m and n each independently represent a numerical value of 10 or more; a plurality of Ar ¹ and Ar ² , m and n may be different from each other.)
Wherein the sum of the number a of the structural units of the formula (1) and the number b of the structural units of the formula (2) is 2 or more, containing at least one structural unit selected from the group consisting of: The present invention provides a system-based ion conductive ultrapolymer.
Further, the present invention
[2] The present invention provides the aromatic polyether-based ion conductive ultrapolymer according to the above [1], wherein the acid group is a sulfonic acid group.
Also, the present invention
[3] It contains at least one type of structural unit selected from the formulas (1) and (2) according to the above [1], and has a number of structural units a of the formula (1) and a number of structural units b of the formula (2). The method for producing an aromatic polyether-based ion-conductive ultrapolymer according to the above [1], wherein an acid group is introduced into the aromatic polyether-based ultrapolymer having a sum of 2 or more;
[4] The method according to the above [3], wherein the acid group is a sulfonic acid group.
Also, the present invention
[5] It contains at least one structural unit selected from the formulas (1) and (2) described in the above [1], and the number a of the structural units of the formula (1) and the number of the structural units of the formula (2) The present invention provides an aromatic polyether-based ultrapolymer, wherein the sum of b is 2 or more.
Also, the present invention
[6] In the presence of a zero-valent transition metal complex, the following formulas (3) and (4)

(In the formula, Ar ¹ , Ar ² , m, and n represent the same meaning as described above. X represents a group that is eliminated during the condensation reaction, and a plurality of Xs may be of different types.)
The method for producing an aromatic polyether-based ultrapolymer according to the above [5], wherein at least one polymer selected from the group consisting of:
[7] X is a chloro, bromo, iodo, p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group, wherein the aromatic polyether-based polymer according to the above [6]. A method for producing a high molecular weight polymer,
Also, the present invention
[8] A polymer electrolyte containing the aromatic polyether ion conductive ultrapolymer according to the above [1] as an active ingredient,
[9] A polymer electrolyte membrane comprising the polymer electrolyte according to the above [8],
[10] A catalyst composition comprising the polymer electrolyte according to the above [8],
[11] A fuel cell comprising the polymer electrolyte membrane according to the above [9] and / or the catalyst composition according to the above [10].

According to the present invention, a higher molecular weight can be further achieved by a condensation reaction utilizing a terminal group of the polymer, that is, by coupling aromatic polyether-based polymers having a halogen or the like as a terminal group, thereby achieving an ultra-high molecular weight aromatic compound. Group polyethers can be easily prepared.
In addition, the aromatic polyether-based ion-conductive ultrapolymer in which an acid group such as a sulfonic acid group is introduced into the aromatic polyether-based ultrapolymer can be an electrolyte membrane having excellent mechanical strength.

Hereinafter, the present invention will be described in detail.
The ion exchange capacity of the aromatic polyether-based ion conductive ultrapolymer of the present invention is 0.1 meq / g or more, preferably about 0.1 to 4 meq / g, and more preferably 0.8 to 2.2 meq / g. It is about 5 meq / g. When used as a polymer electrolyte for a fuel cell, if the ion exchange capacity is too small, the proton conductivity may be low and the function as an electrolyte may be insufficient. On the other hand, if it is too large, water resistance may be poor, which is not preferable.

Further, the aromatic polyether ion conductive ultrapolymer of the present invention has a structure in which an acid group is introduced into the aromatic polyether ultrapolymer, and the aromatic polyether ultrapolymer has the above formula ( It contains at least one structural unit selected from 1) and (2), and the sum of the number a of structural units in Formula (1) and the number b of structural units in Formula (2) is 2 or more.
Here, Ar ¹ and Ar ² in the formulas (1) and (2) independently represent an aromatic divalent group, and typical examples of such an aromatic divalent group include, for example, 1,4 -Phenylene, 1,3-phenylene, 1,2-phenylene, 2-phenyl-1,4-phenylene, 2-phenoxy-1,4-phenylene, 1,4-naphthylene, 2,3-naphthylene, 1,5 -Naphthylene, 2,6-naphthylene, 2,7-naphthylene, biphenyl-4,4'-diyl, biphenyl-3,3'-diyl, biphenyl-3,4'-diyl, 3,3'-diphenylbiphenyl- 4,4′-diyl, 3,3′-diphenoxybiphenyl-4,4′-diyl, 2,2-diphenylpropane-4 ′, 4 ″ -diyl, diphenylether-4,4′-diyl, diphenylsulfone -4,4'-diyl, ben Phenone-4,4'-diyl, etc. divalent group having an ether bond shown below and the like.

These aromatic divalent groups may have a substituent, and as the substituent, those which do not inhibit the condensation reaction described below are preferable, for example, alkyl having 1 to 6 carbon atoms, carbon number Examples include 1 to 6 alkoxy, phenyl, phenoxy and the like. Especially, methyl, ethyl, methoxy, ethoxy, phenyl, phenoxy and the like are preferable. The substitution positions of these substituents are not particularly limited.
The plurality of Ar ¹ and Ar ² may be different from each other.

M and n representing the number of repetitions independently represent a numerical value of 10 or more, preferably a numerical value of about 20 to 250, more preferably about 50 to 200. A plurality of m and n may be different from each other.
The sum of the number a of the structural units of the formula (1) and the number b of the structural units of the formula (2) is 2 or more, and preferably about 3 to 10.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a sulfonylimide group, and a phosphonic acid group. When used as a polymer electrolyte for a fuel cell or the like, a sulfonic acid group and a sulfonylimide group are preferred.
These acid groups may be directly substituted on the aromatic ring constituting the main chain of the polymer, or may be introduced into a substituent or a side chain on the aromatic ring constituting the main chain. , Or a combination thereof.
The number average molecular weight in terms of polystyrene is usually about 2000 to 100,000, preferably about 5000 to 80,000 in the structural units of the formulas (1) and (2), respectively. It is about 100,000 or more, preferably about 150,000 or more, more preferably about 200,000 to 400,000.

The aromatic polyether-based ion-conductive ultrapolymer of the present invention may have any structure in which an acid group is introduced into the aromatic polyether-based ultrapolymer as described above, and the production method is particularly limited. However, it can be produced, for example, by introducing an acid group into the aromatic polyether-based ultrapolymer as described above.
Here, a known method can be used as a method for introducing an acid group. For example, when a sulfonic acid group is introduced into an aromatic ring, a method of dispersing or dissolving an aromatic polyether-based ultrapolymer in concentrated sulfuric acid, heating if necessary, or adding fuming sulfuric acid may be used ( For example, Patent Documents 2 and 3 described above). When a sulfonic acid group is introduced via an alkylene group, J. Am. Amer. Chem. Soc. , 76, 5357-5360 (1954). When a sulfonic acid group is introduced via an alkyleneoxy group, a monomer or polymer having a hydroxy group is reacted with an alkali metal compound and / or an organic base compound to form an alkali metal salt and / or an amine salt. For example, a reaction with an alkylsulfonic acid having a leaving group.
When a carboxylic acid group is introduced, the carboxylic acid group is brominated using a known method (for example, JP-A-2002-241493, Polymer, 1989, Vol. 30, June, 1137-1142.), And then Grignard reaction is performed. After introducing an acyl group or an alkyl group using a known method such as a method of introducing a carboxylic acid group by the action of carbon dioxide using Friedel-Crafts reaction, and then converting it to a carboxylic acid group by a known oxidation reaction Such methods may be used.

When a sulfonylimide group is introduced, for example, the sulfonic acid group introduced by the above-described method is reacted with thionyl chloride or the like to form a sulfonyl halide group such as a sulfonyl chloride, or an aromatic polyether-based ultrapolymer is used as necessary. In an organic solvent, chlorosulfuric acid is allowed to act to introduce a sulfonyl chloride group, and then a sulfonylamide compound such as methanesulfonylamide or benzenesulfonylamide is acted on in the co-presence of a deoxidizing agent, if necessary, to introduce a sulfonylimide group. Such methods may be used.
In the case of introducing a phosphonic acid group, for example, after introducing a bromo group according to a known method, a phosphonic acid diester group is introduced by reacting a trialkyl phosphite in the presence of a nickel compound such as nickel chloride. This is hydrolyzed by a known method (for example, Chem. Ber., 103, 2428-2436. (1970).), And in the presence of a Lewis acid catalyst, phosphorus trichloride or pentane is reacted by Friedel-Crafts reaction. A method of forming a CP bond using phosphorus chloride or the like, followed by oxidation and hydrolysis as necessary to form a phosphonic acid group, or a method of reacting phosphoric anhydride at a high temperature (for example, J. Amer. Chem. Soc., 76, 1045-1051. (1954). Etc.).

（式中、Ａｒ^１、Ａｒ^２、ｍ、ｎは前記と同じ意味を表す。Ｘは、縮合反応時に脱離する基を表し、複数のＸは異なる種類であっても良い。）
から選ばれる少なくとも１種の高分子を縮合反応により重合することにより製造し得る。 Next, a method for producing an aromatic polyether-based ultrapolymer will be described.
The aromatic polyether-based superpolymer is obtained by the following formulas (3) and (4) in the presence of a zero-valent transition metal complex.

(In the formula, Ar ¹ , Ar ² , m, and n represent the same meaning as described above. X represents a group that is eliminated during the condensation reaction, and a plurality of Xs may be of different types.)
Can be produced by polymerizing at least one polymer selected from

  Here, X represents a group which is eliminated during the condensation reaction, and specific examples thereof include halogens such as chloro, bromo and iodine, and p-toluenesulfonyloxy, methanesulfonyloxy and trifluoromethanesulfonyloxy groups. And the like.

The polymerization by condensation reaction of the polymer is carried out in the presence of a zero-valent transition metal complex. Examples of the zero-valent transition metal complex include a zero-valent nickel complex and a zero-valent palladium complex. Of these, a zero-valent nickel complex is preferably used.
As the zero-valent transition metal complex, a commercially available product or a separately synthesized product may be supplied to a polymerization reaction system, or may be generated from a transition metal compound by the action of a reducing agent in a polymerization reaction system. In the latter case, for example, a method in which zinc, magnesium, or the like is allowed to act on the transition metal compound, or the like, may be used.
In any case, it is preferable to add a ligand described below from the viewpoint of improving the yield.
Here, examples of the zero-valent palladium complex include palladium (0) tetrakis (triphenylphosphine) and the like.

Examples of the zero-valent nickel complex include nickel (0) bis (cyclooctadiene), nickel (0) (ethylene) bis (triphenylphosphine), and nickel (0) tetrakis (triphenylphosphine). Among them, nickel (0) bis (cyclooctadiene) is preferably used.
When a reducing agent is allowed to act on a transition metal compound to generate a zero-valent transition metal complex, a divalent transition metal compound is usually used as the transition metal compound to be used, but a zero-valent one may also be used. You can also. Among them, a divalent nickel compound and a divalent palladium compound are preferable. Examples of the divalent nickel compound include nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel acetylacetonate, nickel chloride bis (triphenylphosphine), nickel bromide (triphenylphosphine), and nickel bis (iodide) ( Triphenylphosphine), and examples of the divalent palladium compound include palladium chloride, palladium bromide, palladium iodide, and palladium acetate.

Examples of the reducing agent include metals such as zinc and magnesium and alloys thereof with, for example, copper, sodium hydride, hydrazine and its derivatives, and lithium aluminum hydride. If necessary, ammonium iodide, trimethylammonium iodide, triethylammonium iodide, lithium iodide, sodium iodide, potassium iodide and the like can be used in combination.
When no reducing agent is used, the amount of the zero-valent transition metal complex is usually 0.1 to 5 times the total amount of the polymers represented by the formulas (3) and (4). If the amount used is too small, the molecular weight tends to decrease, so it is preferably at least 1.5 mol times, more preferably at least 1.8 mol times, even more preferably at least 2.1 mol times. The upper limit of the amount used is desirably 5.0 mol times or less, since if the amount used is too large, post-processing tends to be complicated.
When a reducing agent is used, the amount of the transition metal compound used is 0.01 to 1 mole times the total amount of the polymers represented by the formulas (3) and (4). If the amount is too small, the molecular weight tends to be small, so it is preferably at least 0.03 mol times. The upper limit of the amount used is desirably not more than 1.0 mol times because if the amount used is too large, post-processing tends to be complicated.

  The amount of the reducing agent to be used is usually 0.5 to 10 times the total amount of the polymers represented by the formulas (3) and (4). If the amount used is too small, the molecular weight tends to be small, so it is preferably at least 1.0 mole times. The upper limit of the amount used is desirably 10 mol times or less, since an excessive amount tends to complicate post-processing.

Examples of the ligand include 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N, N′N′-tetramethylethylenediamine, triphenylphosphine, tolylphosphine, tributylphosphine, Triphenoxyphosphine, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane, and the like, and triphenylphosphine, 2,2 in terms of versatility, low cost, high reactivity, and high yield. '-Bipyridyl is preferred. In particular, 2,2′-bipyridyl is preferably used because the yield of the polymer is improved when combined with bis (1,5-cyclooctadiene) nickel (0).
When a ligand coexists, it is usually used in an amount of about 0.2 to 2 mol, preferably about 1 to 1.5 mol, based on the metal atom, based on the zero-valent transition metal complex.

The condensation reaction is usually performed in the presence of a solvent. Examples of such a solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, n-butylbenzene, mesitylene, and naphthalene: ether solvents such as diisopropyl ether, tetrahydrofuran, 1,4-dioxane, and diphenyl ether; -Aprotic polar solvents substituted for amide solvents such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethylsulfoxide: aliphatic hydrocarbons such as tetralin and decalin Solvent: Ether solvents such as tetrahydrofuran, 1,4-dioxane, dibutyl ether, tert-butyl methyl ether, dimethoxyethane and the like: Ester solvents such as ethyl acetate, butyl acetate and methyl benzoate: chloroform, And halogenated alkyl solvents chloroethane, and the like.
In order to further increase the molecular weight of the resulting ultrapolymer, it is desirable that the polymer and the ultrapolymer are sufficiently dissolved. Therefore, tetrahydrofuran, 1,4- Dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene and the like are preferred. These may be used in combination of two or more. Among them, toluene, tetrahydrofuran, N, N-dimethylformamide, and a mixture of two or more thereof are preferably used.

The solvent is usually used in an amount of 5 to 500 times, preferably about 20 to 100 times the weight of the monomer, ie, the polymer.
The condensation temperature is usually in the range of 0 to 250 ° C, preferably about 10 to 100 ° C, and the condensation time is usually about 0.5 to 24 hours. Above all, in order to further increase the molecular weight of the resulting ultrapolymer, the zero-valent transition metal complex and the polymer represented by the formula (3) and / or (4) are allowed to act at a temperature of 45 ° C. or higher. Is preferred. The preferred working temperature is usually 45 ° C to 200 ° C, particularly preferably about 50 ° C to 100 ° C.
The method of reacting the zero-valent transition metal complex with the polymer represented by the formula (3) and / or the formula (4) is a method of adding one to the other, or a method of simultaneously adding both to the reaction vessel. It may be. When adding, it may be added all at once, but it is preferable to add it little by little in consideration of heat generation, and it is also preferable to add it in the presence of a solvent.
After allowing the zero-valent transition metal complex to react with the polymer represented by the formula (3) and / or the formula (4), the temperature is generally maintained at about 45 ° C to 200 ° C, preferably about 50 ° C to 100 ° C.

When Ar ¹ and Ar ² in the formulas (3) and (4) are the same as the aromatic polyether-based ultrapolymer to be produced, for example, a simple re-extended polymer of the polymer represented by the formula (3) Is obtained, while if different, a block copolymer of the polymer represented by the formula (3) and the polymer represented by the formula (4) is obtained.
Normally, in the method of producing a condensation block copolymer, in order to adjust the composition ratio of each block, it is necessary to control the molecular weight of each block precursor polymer and accurately adjust the equivalent of the reactive terminal group. However, according to this production method, a block copolymer having a preferable composition can be synthesized only by controlling the weight ratio of the charged components.

An ordinary method can be used to take out the aromatic polyether-based ultrapolymer produced by the condensation reaction from the reaction mixture. For example, the polymer can be precipitated by adding a poor solvent or the like, and the target substance can be taken out by filtration or the like. Further, if necessary, it can be further purified by an ordinary purification method such as washing with water or reprecipitation using a good solvent and a poor solvent.
The analysis of the degree of polymerization of the aromatic polyether-based ultrapolymer and the structure of the polymer can be carried out by ordinary means such as GPC measurement and NMR measurement.

Thus, an aromatic polyether-based ultrapolymer is obtained. The degree of polymerization is represented by (mxa + nb). According to the present invention, a polymer having an extremely high molecular weight that cannot be produced by a conventional ordinary method, for example, a polymer having a degree of polymerization of 500 or more is used. Can be manufactured.
The number average molecular weight in terms of polystyrene is usually about 100,000 or more, preferably 150,000 or more, more preferably about 200,000 to 400,000.

Next, the case where the aromatic polyether-based ion conductive superpolymer of the present invention is used as a diaphragm of an electrochemical device such as a fuel cell will be described.
In this case, the film is usually used in the form of a film, but the method of converting the film is not particularly limited, and for example, a method of forming a film from a solution state (solution casting method) is preferably used.
Specifically, a film is formed by dissolving the copolymer in an appropriate solvent, casting and applying the solution on a substrate such as a glass plate, and removing the solvent. The solvent used for film formation is not particularly limited as long as it can dissolve the copolymer and can be removed thereafter. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Aprotic polar solvents such as 2-pyrrolidone and dimethyl sulfoxide: chlorinated solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and dichlorobenzene: alcohols such as methanol, ethanol and propanol: ethylene glycol monomethyl ether, ethylene Alkylene glycol monoalkyl ethers such as glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether are preferably used. These may be used as a mixture of two or more solvents as necessary. Among them, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like are preferable because of high solubility of the polymer.

  The thickness of the film is not particularly limited, but is preferably from 10 to 300 µm, more preferably from 15 to 100 µm. If the film is thinner than 10 μm, the practical strength may not be sufficient, and if the film is thicker than 300 μm, the film resistance tends to increase and the characteristics of the electrochemical device tend to decrease. The film thickness can be controlled by the concentration of the solution and the thickness applied on the substrate.

For the purpose of improving various physical properties of the film, a plasticizer, a stabilizer, a release agent, and the like used in the field of polymers can be added to the aromatic polyether-based ion conductive ultrapolymer of the present invention. Further, it is also possible to form a composite alloy of another polymer with the copolymer of the present invention by a method such as mixing and co-casting in the same solvent.
In fuel cell applications, it is also known to add inorganic or organic fine particles as a water retention agent to facilitate water management. Any of these known methods can be used as long as the object of the present invention is not violated.

  Further, for the purpose of improving the mechanical strength of the film, the film can be cross-linked by irradiation with an electron beam or radiation. Furthermore, a method of impregnating and compounding a porous film or sheet, or a method of reinforcing the film by mixing fibers or pulp is known, and any of these known methods is not contrary to the object of the present invention. Can be used.

Next, the fuel cell of the present invention will be described.
The fuel cell of the present invention can be manufactured by bonding a catalyst and a conductive material as a current collector to both surfaces of a film made of an aromatic polyether-based ion conductive ultrapolymer. Further, it is also possible to use the aromatic polyether-based ion conductive ultrapolymer of the present invention as an ion conductive component of a catalyst layer. That is, the aromatic polyether-based ionic superpolymer of the present invention can be used both as an electrolyte membrane of a polymer electrolyte membrane-electrode assembly used in a fuel cell and as an ion conductive component of a catalyst layer. A polymer electrolyte membrane-electrode assembly can be obtained by using both.
The catalyst is not particularly limited as long as it can activate the oxidation-reduction reaction with hydrogen or oxygen, and known catalysts can be used, but it is preferable to use platinum or platinum alloy fine particles. Platinum fine particles are often used by being supported on particulate or fibrous carbon such as activated carbon and graphite, and are preferably used.

Known materials can also be used for the conductive substance as the current collector, but porous carbon woven fabric, carbon nonwoven fabric, or carbon paper is preferable for efficiently transporting the raw material gas to the catalyst.
A method for bonding platinum fine particles or carbon carrying platinum fine particles to a porous carbon nonwoven fabric or carbon paper and a method for bonding the same to a polymer electrolyte film are described in, for example, J. Mol. Electrochem. Soc. : A known method such as the method described in Electrochemical Science and Technology, 1988, 135 (9), 2209 can be used.
The fuel cell of the present invention manufactured as described above can be used in various types using hydrogen gas, reformed hydrogen gas, or methanol as a fuel.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The molecular weight in the examples is a number average molecular weight (Mn) and a weight average molecular weight (Mw) in terms of polystyrene measured by GPC.
The mechanical properties of the film were measured by the following method.
After dissolving an aromatic polyether-based ion conductive ultrapolymer or the like in DMAc and adjusting it to 10 wt%, it is cast and applied on a glass substrate, and the solvent is removed to form a film. A test piece was punched out with a dumbbell cutter SDMK-1223 manufactured by Dumbbell Co., and the elongation at break was measured at room temperature and 50% relative humidity at a test speed of 10 mm / min.

（特開平１０−２１９４３号公報実施例３に記載の方法に準拠して製造。Ｍｎ＝５．５０×１０^４）２０ｇと、２，２'−ビピリリジル０．４６８ｇ（３．００ｍｍｏｌ）をＤＭＡｃ８００ｍＬに溶解し、３０分間アルゴンガスのバブリングを実施、Ｎｉ（ＣＯＤ）_２ ０．８２４ｇ（３．００ｍｍｏｌ）を加えて８０℃まで昇温し、同温度で８時間保温攪拌した後放冷した。次いで反応混合物を４Ｎ塩酸５００ｍＬに注ぎ、生じた白色沈殿をろ過、通常の方法で再沈精製を行い、下記芳香族ポリエーテル系超高分子ａ−１を得た。超高分子は定量的に回収された。得られた超高分子の分子量を測定したところ、Ｍｎ＝２．２０×１０^５、Ｍｗ＝３．９３×１０^５（ＧＰＣ、ポリスチレン標準）であり、約４倍に延長された。

Example 1
<Production of aromatic polyether superpolymer a-1>
Under an argon atmosphere, the following polyethersulfone copolymer (the subscripts 0.85 and 0.15 in each repeating unit of the random copolymer represent mol%)

(Manufactured according to the method described in Example 3 of JP-A-10-21943. Mn = 5.50 × 10 ⁴ ) 20 g and 2,2′-bipyridylyl 0.468 g (3.00 mmol) in 800 mL of DMAc. After dissolving, bubbling of argon gas was performed for 30 minutes, 0.824 g (3.00 mmol) of Ni (COD) ₂ was added, the temperature was raised to 80 ° C., the mixture was stirred at the same temperature for 8 hours, and then allowed to cool. Next, the reaction mixture was poured into 500 mL of 4N hydrochloric acid, and the resulting white precipitate was filtered and reprecipitated and purified by a usual method to obtain the following aromatic polyether-based superpolymer a-1. The ultrapolymer was recovered quantitatively. When the molecular weight of the obtained ultrapolymer was measured, it was Mn = 2.20 × 10 ⁵ and Mw = 3.93 × 10 ⁵ (GPC, polystyrene standard), and was extended about four times.

Example 2
<Production of aromatic polyether-based ion-conductive superpolymer b-1>
10 g of the above-mentioned aromatic polyether-based superpolymer a-1 was dissolved in 80 g of concentrated sulfuric acid, sulfonated at room temperature for 48 hours, purified by a conventional method, and the aromatic polyether-based ionic conductive ultra-high polymer shown below was obtained. The molecule b-1 was obtained. Its ion exchange capacity was 1.15 meq / g. The elongation at break was 25%.

Comparative Example 1
<Production of aromatic polyether ion conductive polymer b′-1>
The same procedure as in Example 2 was followed, except that 5 g of the same polyethersulfone copolymer as used in Example 1 was used instead of the aromatic polyether-based superpolymer 1 to obtain the following. An aromatic polyether ion conductive polymer b′-1 was obtained. Its ion exchange capacity was 1.10 meq / g. The elongation at break was 7%.

（住友化学工業製スミカエクセルＰＥＳ５２００Ｐ、Ｍｎ＝５．４４×１０^４、Ｍｗ＝１．２３×１０^５：ＧＰＣ、ポリスチレン標準）２．５ｇ、下記ポリエーテルスルホン共重合体

（特開２００２−２２０４６９号公報の実施例１に記載の方法に準拠して製造した。Ｍｎ＝３．１６×１０^４、Ｍｗ＝８．６８×１０^４）２．５０ｇ、２，２'−ビピリリジル０．１１７ｇ（０．７５ｍｍｏｌ）をＤＭＡｃ２００ｍＬに溶解し、３０分間アルゴンガスのバブリングを実施、Ｎｉ（ＣＯＤ）_２ ０．２０６ｇ（０．７５ｍｍｏｌ）を加えて８０℃まで昇温し、同温度で６時間保温攪拌した後放冷した。次いで反応混合物を４規定塩酸５００ｍＬに注ぎ、生じた白色沈殿をろ過、常法により再沈精製を行い、下記芳香族ポリエーテル系超高分子ａ−２を得た。
Ｍｎ＝１．８９×１０^６、Ｍｗ＝２．１７×１０^６（ＧＰＣ、ポリスチレン標準）であった。

Example 3
<Production of aromatic polyether superpolymer a-2>
The following polyether sulfones, which are chloro-terminated, under an argon atmosphere

(Sumitomo Chemical Industries Sumika Excel PES5200P, Mn = 5.44 × 10 ⁴ , Mw = 1.23 × 10 ⁵ : GPC, polystyrene standard) 2.5 g, the following polyether sulfone copolymer

(Manufactured according to the method described in Example 1 of JP-A-2002-220469. Mn = 3.16 × 10 ⁴ , Mw = 8.68 × 10 ⁴ ) 2.50 g, 2,2′- 0.117 g (0.75 mmol) of bipyridyl is dissolved in 200 mL of DMAc, bubbling of argon gas is performed for 30 minutes, 0.206 g (0.75 mmol) of Ni (COD) ₂ is added, and the temperature is raised to 80 ° C. The mixture was stirred for 6 hours while keeping it to cool. Next, the reaction mixture was poured into 500 mL of 4 N hydrochloric acid, and the resulting white precipitate was filtered and purified by reprecipitation by a conventional method to obtain the following aromatic polyether-based superpolymer a-2.
Mn = 1.89 × 10 ⁶ , Mw = 2.17 × 10 ⁶ (GPC, polystyrene standard).

Example 4
<Production of aromatic polyether-based ion-conductive superpolymer b-2>
Sulfonation and purification were carried out in accordance with Example 2 except that 5 g of the aromatic polyether-based superpolymer a-2 was used, thereby obtaining an aromatic polyether-based ion-conductive superpolymer b-2 shown below. Got. Its ion exchange capacity was 1.77 meq / g.

Example 5
<Production of aromatic polyether superpolymer a-3>
Under an argon atmosphere, 5 g of the same polyether sulfone (SUMIKAEXCEL PES5200P manufactured by Sumitomo Chemical Co., Ltd.) used in Example 3, which was a terminal chloro type, 0.12 g (1.10 mmol) of 2,2′-bipyridyl, and 15 ml of toluene were added. After dissolving in 100 mL of DMSO and distilling off toluene by heating at a bath temperature of 150 ° C., water in the system was removed. After allowing to cool, 0.382 g (1.39 mmol) of Ni (COD) ₂ was added and heated, followed by stirring at 60 ° C. for 3 hours and then at 80 ° C. for 4 hours, followed by cooling. The reaction mixture was poured into water, and the precipitate was washed with 10% hydrochloric acid and then with water, and then dried.
When the molecular weight of the obtained aromatic polyether-based superpolymer a-3 was measured, it was Mn = 1.40 × 10 ⁵ , Mw = 3.33 × 10 ⁵ (GPC, polystyrene standard), which was about 3 times. Had been extended.

Example 6
<Production of aromatic polyether-based superpolymer a-4>
Under an argon atmosphere, 5 g of a copolymer (Mn = 5.50 × 10 ⁴ ) represented by the same formula as the polyethersulfone copolymer used in Example 1 and 0.117 g of 2,2′-bipyridyl (0.10 g) were used. 75 mmol) was dissolved in 200 mL of DMAc, and bubbling with argon gas was performed for 30 minutes. Next, the temperature was raised to 80 ° C., 0.206 g (0.75 mmol) of Ni (COD) ₂ was added, and the mixture was stirred at the same temperature for 8 hours, and then allowed to cool. The reaction mixture was poured into 500 mL of 4N hydrochloric acid, and the resulting white precipitate was filtered and purified by reprecipitation in a usual manner to obtain an aromatic polyether superpolymer a-4 represented by the same formula as the product of Example 1. Obtained. The ultrapolymer was recovered quantitatively. When the molecular weight of the obtained ultrapolymer was measured, it was Mn = 3.02 × 10 ⁵ and Mw = 9.91 × 10 ⁶ (GPC, polystyrene standard), which was extended to about 5.5 times.

Example 7
<Production of Aromatic Polyether-Based Ion-Conducting Ultrapolymer b-3>
5 g of the above aromatic polyether-based superpolymer a-4 was dissolved in 40 g of concentrated sulfuric acid, sulfonated at room temperature for 48 hours, and purified by a conventional method to give a product of the same formula as in Example 2. Thus, an aromatic polyether-based ion conductive ultrapolymer b-3 was obtained. Its ion exchange capacity was 1.18 meq / g. The elongation at break was 60%.

Claims (11)

The ion exchange capacity is 0.1 meq / g or more, the aromatic polyether-based ultrapolymer has a structure in which an acid group is introduced, and the aromatic polyether-based ultrapolymer is represented by the following formula (1): (2)

(Wherein, Ar ¹ and Ar ² independently represent an aromatic divalent group; m and n each represent a number of repetitions; m and n each independently represent a numerical value of 10 or more; a plurality of Ar ¹ and Ar ² , m and n may be different from each other.)
Wherein the sum of the number a of the structural units of the formula (1) and the number b of the structural units of the formula (2) is 2 or more, containing at least one structural unit selected from the group consisting of: -Based ion-conductive ultrapolymer   2. The aromatic polyether ion conductive ultrapolymer according to claim 1, wherein the acid group is a sulfonic acid group.   It contains at least one type of structural unit selected from the formulas (1) and (2) according to claim 1, and the sum of the number a of structural units in the formula (1) and the number b of structural units in the formula (2) is 2 or more. 2. The method according to claim 1, wherein an acid group is introduced into the aromatic polyether-based ultrapolymer.   The method according to claim 3, wherein the acid group is a sulfonic acid group.   It contains at least one type of structural unit selected from the formulas (1) and (2) according to claim 1, and the sum of the number a of the structural units of the formula (1) and the number b of the structural units of the formula (2) is 2. An aromatic polyether-based ultrapolymer, wherein the number is 2 or more. In the presence of a zero-valent transition metal complex, the following formulas (3) and (4)

(In the formula, Ar ¹ , Ar ² , m, and n represent the same meaning as described above. X represents a group that is eliminated during the condensation reaction, and a plurality of Xs may be of different types.)
6. The method for producing an aromatic polyether-based ultrapolymer according to claim 5, wherein at least one kind of polymer selected from the group consisting of: is polymerized by a condensation reaction.   X is a chloro, bromo, iodo, p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group, The aromatic polyether-based ultrahigh molecular weight polymer according to claim 6, wherein Manufacturing method.   A polymer electrolyte comprising the aromatic polyether ion conductive ultrapolymer according to claim 1 as an active ingredient.   A polymer electrolyte membrane comprising the polymer electrolyte according to claim 8.   A catalyst composition comprising the polymer electrolyte according to claim 8. A fuel cell comprising the polymer electrolyte membrane according to claim 9 and / or the catalyst composition according to claim 10.