JP2007242554A - Catalyst material for fuel cell, its manufacturing method, catalyst membrane, electrode-membrane assembly, and fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst material for a fuel cell used for improving utilization efficiency of catalyst particles, and having high durability and catalyst activity. <P>SOLUTION: This catalyst material for a fuel cell contains a carbon material, a solvolysis-resistant and heat-resistant polymer X connected to a surface of the carbon material at two or more points through a connection group having solvolysis resistance and heat resistance, and having an ionic functional group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fuel cell that uses pure hydrogen, methanol, ethanol, dimethyl ether, methanol or reformed hydrogen from fossil fuel as a fuel, and uses air or oxygen as an oxidant, and in particular, a solid polymer fuel The present invention relates to a catalyst material used in a battery, an electrode membrane assembly, and a fuel cell.

A solid polymer fuel cell is a fuel cell characterized by the fact that the ionic conductor, that is, the electrolyte, is a solid and a polymer. Specifically, an ion exchange resin is used as the solid polymer electrolyte. , Disposing both the negative electrode and the positive electrode across this electrolyte, for example, generating hydrogen by supplying hydrogen as fuel to the negative electrode side and oxygen or air to the positive electrode side to generate electricity It is.
That is, when hydrogen is used as the fuel, the following reaction occurs at the negative electrode:
H ₂ → 2H ⁺ + 2e ⁻
Further, when oxygen is used as the oxidizing agent, the following reaction occurs at the positive electrode, and water is generated.
1 / 2O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O

  In order for the above reaction to proceed smoothly and to maximize the performance of the fuel cell, in the electrode catalyst layer, an ion exchange resin as a proton conductor, a carbon carrier as an electron conductor, and a reaction gas are simultaneously used. A catalyst (such as platinum) needs to be present at the contacting three-phase interface. For this reason, attempts have been made to increase the amount of catalyst existing at the three-phase interface by increasing the functionality of the catalyst layer structure. For example, Nafion 117 (Nafion: registered trademark) (manufactured by Du Pont), which is a kind of sulfonated fluororesin, is used as the solid polymer electrolyte, a noble metal catalyst having platinum or the like supported on its inner surface, and a catalyst layer A method for improving the working area by three-dimensionalizing the reaction site is disclosed (Non-patent Document 1). According to this technique, not only the contact surface between the electrolyte and the membrane but also the catalyst inside the catalyst layer can be used, and the utilization rate of platinum can be improved by this catalyst layer.

In addition, as a basis for designing more sophisticated electrodes, the pore distribution of the electrode structure has been studied, and the catalyst layer has pores with a diameter of 0.04 to 1.0 μm, and proton conduction is conducted in the pores. Patent Document 1 describes that it is effective to distribute an electrolyzing electrolyte.
Furthermore, these catalyst layers have pores that change with a diameter of 0.04 μm as a boundary, pores with a diameter of 0.02 μm to 0.04 μm are primary pores, and pores with a diameter of 0.04 μm to 1 μm. It is considered as a secondary pore (nonpatent literature 2). Then, a fluorine-based polymer such as Nafion cannot enter a pore having a diameter of 0.04 μm or less because of its molecular weight, and catalyst particles in such a pore do not form a three-phase interface. It does not become a reaction field.

  Therefore, various methods for effectively utilizing the catalyst particles existing in the pores having small pores (for example, a diameter of 0.04 μm or less) that are difficult for the solid polymer electrolyte to enter as described above are studied. Has been. For example, as a method for preparing a cathode catalyst material for a fuel cell using hydrogen as a fuel, proton conduction is also conducted in the primary pores by grafting a sulfonic acid site or a sulfonic acid group-containing polymer onto the surface of carbon black as a catalyst carrier. A method of introducing a site and forming a three-phase interface in catalyst particles in primary pores is disclosed (Non-Patent Document 3). However, in Non-Patent Document 3, when the weight of the polymer to be grafted increases, the graft polymer fills the carbon pores and oxygen permeability decreases, and the output decreases in a high current density region. There is a problem that the amount of conductive sites is limited.

“Electrochemistry” Vol. 53, No. 10 (1985), 812-817. J. Electrochemical Society Vol.142, No.2, p.463 Journal of Power Sources 138, 25 (2004) Japanese Patent No. 3275652

  In order to improve the performance of the electrode catalyst, it is necessary to effectively supply protons and oxygen into the pores of carbon black as a catalyst carrier. However, as described above, when a large amount of ionic functional group-containing polymer is grafted to improve proton conductivity, there is a problem in that the output is not increased because oxygen permeability is lowered. It is a subject of this case to make compatible the proton conductivity and oxygen permeability in a carbon pore.

By linking one ionic functional group-containing polymer to the carbon material through at least two or more linking points, the ionic functional group-containing polymer is prevented from spreading in the pores of the carbon material and is placed near the carbon surface. It became possible to make it. This makes it possible to improve proton conductivity while maintaining oxygen permeability.
Specifically, the inventors have found that the above problems can be solved by the following means, and have reached the present invention.
(1) A solvent-resistant solvent having an ionic functional group, which is linked to a carbon material and a surface of the carbon material via a linking group having solvent-resistant decomposition resistance and heat resistance at least at two or more points. A fuel cell catalyst material comprising a decomposable and heat-resistant polymer (X).
(2) The catalyst material for a fuel cell according to (1), wherein the polymer (X) is connected to the surface of the carbon material at at least two points via a connecting group having the same structure.
(3) The fuel cell catalyst material according to (1), wherein the polymer (X) is connected to the surface of the carbon material at least at two or more points via connecting groups having different structures.
(4) The fuel cell catalyst material according to any one of (1) to (3), wherein the carbon material contains an electrode catalyst.
(5) The fuel cell catalyst material according to any one of (1) to (4), wherein the carbon material is carbon black or carbon nanotube.
(6) The fuel cell catalyst material according to any one of (1) to (5), wherein at least one of the linking groups is a linking group represented by the following formula (1).
Formula (1)

（式（１）中、Ｒ¹およびＲ²はそれぞれ２〜４価の連結基を表し、Ａｒ¹は芳香族炭化水素および／またはヘテロ環を含む２〜６価の連結基を表し、ｎ₁、ｎ₂およびｎ₃はそれぞれ０以上の整数であり、ｎ₁とｎ₂とｎ₃との和は１以上の整数である。ｎ₄は１〜１０の整数であり、ｎ₅は１〜３の整数である。Ｌｃはカーボン材料側と連結する連結箇所を、Ｌｐは前記ポリマー（Ｘ）側と連結する連結箇所を表す。）
（７）前記ポリマー（Ｘ）は、下記式（２）で表される繰り返し単位を主鎖構造として含み、かつ、前記主鎖が有する芳香環には、下記式（３）〜（５）より選ばれる少なくとも１つの部分構造が結合している、（１）〜（６）のいずれか１項に記載の燃料電池用触媒材料。

(In formula (1), R ¹ and R ² each represent a divalent to tetravalent linking group, Ar ¹ represents a divalent to hexavalent linking group containing an aromatic hydrocarbon and / or a heterocycle, and n ₁ , N ₂ and n ₃ are each an integer of 0 or more, and the sum of n ₁ , n ₂ and n ₃ is an integer of 1 or more, n ₄ is an integer of 1 to 10, and n ₅ is 1 to (It is an integer of 3. Lc represents a connection point connected to the carbon material side, and Lp represents a connection point connected to the polymer (X) side.)
(7) The polymer (X) includes a repeating unit represented by the following formula (2) as a main chain structure, and the aromatic ring included in the main chain is represented by the following formulas (3) to (5). The fuel cell catalyst material according to any one of (1) to (6), wherein at least one selected partial structure is bonded.

（上記式（２）中、Ｒ³は芳香環を含む２価の基であり、Ｘ¹は２価の連結基である。式（３）中、Ｂ¹は単結合または２〜６価の連結基、Ａ¹はイオン性官能基を表し、ｎ₆は１〜５の整数を表す。式（４）中、Ｂ²は単結合または２〜６価の連結基を、Ｄは少なくとも１つのイオン性官能基を有するラジカル重合性モノマーの重合物を表す。式（５）においてＥ¹は酸素透過性の高い置換基を表す。）
（８）前記ポリマー（Ｘ）の主鎖部分が、ポリエーテルスルホン系化合物、ポリエーテルエーテルスルホン系化合物、ポリエーテルエーテルケトン系化合物、ポリフェニレンスルフィド系化合物、ポリフェニレンエーテル系化合物、ポリスルホン系化合物またはポリエーテルケトン系化合物である、（１）〜（７）のいずれか１項に記載の燃料電池用触媒材料。
（９）前記ポリマー（Ｘ）の主鎖部分が、下記式(６)で表される繰り返し単位を含み、かつ、前記主鎖が有する芳香環に、下記式(７)で表される部分構造および／または下記式(８)で表される部分構造が結合している、（１）〜（６）のいずれか１項に記載の燃料電池用触媒材料。

(In the above formula (2), R ³ is a divalent group containing an aromatic ring, and X ¹ is a divalent linking group. In formula (3), B ¹ is a single bond or a 2-6 valent group. A linking group, A ¹ represents an ionic functional group, n ₆ represents an integer of 1 to 5. In formula (4), B ² represents a single bond or a bivalent to hexavalent linking group, and D represents at least one This represents a polymer of a radically polymerizable monomer having an ionic functional group.In formula (5), E ¹ represents a substituent having high oxygen permeability.
(8) The main chain portion of the polymer (X) is a polyether sulfone compound, a polyether ether sulfone compound, a polyether ether ketone compound, a polyphenylene sulfide compound, a polyphenylene ether compound, a polysulfone compound or a polyether. 6. The fuel cell catalyst material according to any one of (1) to (7), which is a ketone compound.
(9) The partial structure represented by the following formula (7) in the main chain portion of the polymer (X) includes a repeating unit represented by the following formula (6) and the aromatic ring of the main chain has And / or the fuel cell catalyst material according to any one of (1) to (6), wherein a partial structure represented by the following formula (8) is bonded.

（式(６)中、Ｗ¹¹、Ｗ¹²およびＷ¹³はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表す。式(７)中、Ｂ³は単結合または２〜６価の連結基を表し、Ａ²はイオン性官能基を表し、ｎ₇は１〜５の整数である。式(８)中、Ｅ²は酸素透過性の高い置換基を表す。）
（１０）少なくとも２つ以上のラジカル発生基を有するポリマーからラジカルを発生させ、カーボン材料に前記ラジカルを捕捉させることにより、ポリマー−カーボン材料間を少なくとも２点以上で連結させることを含む、（１）〜（９）のいずれか１項に記載の燃料電池用触媒材料の製造方法。
（１１）耐加溶媒分解性および耐熱性を有する連結基を有するポリマーを、該連結基を介してカーボン材料に連結させ、前記ポリマーに少なくとも１つ以上のラジカル発生基を導入してラジカルを発生させ、前記カーボン材料に前記ラジカルを捕捉させることにより、ポリマー−カーボン材料間を少なくとも２点以上で連結させることを含む、（１）〜（９）のいずれか１項に記載の燃料電池用触媒材料の製造方法。
（１２）（１）〜（９）のいずれか１項に記載の燃料電池用触媒材料と、固体電解質を含む触媒膜。
（１３）第一の燃料電池用触媒材料と、第二の燃料電池用触媒材料と、固体電解質を含む触媒膜であって、前記第一の燃料電池用触媒材料は、（１）〜（９）のいずれか１項に記載の燃料電池用触媒材料であり、前記第二の燃料電池用触媒材料は、カーボン表面に、イオン性官能基を有する耐加溶媒分解性および耐熱性ポリマーを有さない燃料電池用触媒材料である、触媒膜。
（１４）前記固体電解質が、下記式（２）で表される繰り返し単位を主鎖構造として含み、かつ、前記主鎖が有する芳香環には、下記式（３）〜（５）より選ばれる少なくとも１つの部分構造が結合しているポリマーを含む、（１２）または（１３）に記載の触媒膜。

(In the formula (6), W ¹¹ , W ¹² and W ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. In the formula (7), B ³ is a single bond or 2-6. Represents a valent linking group, A ² represents an ionic functional group, and n ₇ represents an integer of 1 to 5. In formula (8), E ² represents a substituent having high oxygen permeability.
(10) generating radicals from a polymer having at least two radical generating groups and capturing the radicals in the carbon material, thereby connecting the polymer and the carbon material at at least two points; )-(9) The manufacturing method of the catalyst material for fuel cells of any one of (9).
(11) A polymer having a linking group having solvolysis resistance and heat resistance is linked to a carbon material through the linking group, and at least one radical generating group is introduced into the polymer to generate radicals. The catalyst for fuel cells according to any one of (1) to (9), wherein the carbon-material is coupled with at least two points by capturing the radicals in the carbon material. Material manufacturing method.
(12) A catalyst membrane comprising the fuel cell catalyst material according to any one of (1) to (9) and a solid electrolyte.
(13) A catalyst film including a first fuel cell catalyst material, a second fuel cell catalyst material, and a solid electrolyte, wherein the first fuel cell catalyst material comprises (1) to (9) ), The second fuel cell catalyst material has a solvolysis-resistant and heat-resistant polymer having an ionic functional group on the carbon surface. There is no catalyst material for fuel cells, catalyst membrane.
(14) The solid electrolyte includes a repeating unit represented by the following formula (2) as a main chain structure, and the aromatic ring included in the main chain is selected from the following formulas (3) to (5). The catalyst membrane according to (12) or (13), comprising a polymer having at least one partial structure bonded thereto.

（上記式（２）中、Ｒ³は芳香環を含む２価の基であり、Ｘ¹は２価の連結基である。式（３）中、Ｂ¹は単結合または２〜６価の連結基、Ａ¹はイオン性官能基を表し、ｎ₆は１〜５の整数を表す。式（４）中、Ｂ²は単結合または２〜６価の連結基を、Ｄは少なくとも１つのイオン性官能基を有するラジカル重合性モノマーの重合物を表す。式（５）においてＥ¹は酸素透過性の高い置換基を表す。）
（１５）多孔質導電シートと、該多孔質導電シートに接して設けられた触媒膜と、該触媒膜に接して設けられた固体電解質膜とを有し、かつ、前記触媒膜が、（１２）〜（１４）のいずれか１項に記載の触媒膜である、電極膜接合体。
（１６）前記固体電解質膜が、下記式（２）で表される繰り返し単位を主鎖構造として含み、かつ、前記主鎖が有する芳香環には、下記式（３）〜（５）より選ばれる少なくとも１つの部分構造が結合しているポリマーを含む、（１５）に記載の電極膜接合体。

(In the above formula (2), R ³ is a divalent group containing an aromatic ring, and X ¹ is a divalent linking group. In formula (3), B ¹ is a single bond or a 2-6 valent group. A linking group, A ¹ represents an ionic functional group, n ₆ represents an integer of 1 to 5. In formula (4), B ² represents a single bond or a bivalent to hexavalent linking group, and D represents at least one This represents a polymer of a radically polymerizable monomer having an ionic functional group.In formula (5), E ¹ represents a substituent having high oxygen permeability.
(15) A porous conductive sheet, a catalyst film provided in contact with the porous conductive sheet, and a solid electrolyte film provided in contact with the catalyst film, and the catalyst film comprises (12 An electrode membrane assembly, which is the catalyst membrane according to any one of (14) to (14).
(16) The solid electrolyte membrane includes a repeating unit represented by the following formula (2) as a main chain structure, and the aromatic ring of the main chain is selected from the following formulas (3) to (5) The electrode membrane assembly according to (15), comprising a polymer having at least one partial structure bonded thereto.

（上記式（２）中、Ｒ³は芳香環を含む２価の基であり、Ｘ¹は２価の連結基である。式（３）中、Ｂ¹は単結合または２〜６価の連結基、Ａ¹はイオン性官能基を表し、ｎ₆は１〜５の整数を表す。式（４）中、Ｂ²は単結合または２〜６価の連結基を、Ｄは少なくとも１つのイオン性官能基を有するラジカル重合性モノマーの重合物を表す。式（５）においてＥ¹は酸素透過性の高い置換基を表す。）
（１７）（１５）または（１６）に記載の電極膜接合体を有する、燃料電池。

(In the above formula (2), R ³ is a divalent group containing an aromatic ring, and X ¹ is a divalent linking group. In formula (3), B ¹ is a single bond or a 2-6 valent group. A linking group, A ¹ represents an ionic functional group, n ₆ represents an integer of 1 to 5. In formula (4), B ² represents a single bond or a bivalent to hexavalent linking group, and D represents at least one This represents a polymer of a radically polymerizable monomer having an ionic functional group.In formula (5), E ¹ represents a substituent having high oxygen permeability.
(17) A fuel cell comprising the electrode membrane assembly according to (15) or (16).

  According to the present invention, it has become possible to produce a fuel cell catalyst material having both high catalytic activity and high durability. An electrode membrane assembly can be easily produced, and a fuel cell having high performance can be produced.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
Various physical property values in the present invention are those at room temperature (for example, 25 ° C.) unless otherwise specified. Further, the polymerization in the present invention includes so-called copolymerization. Therefore, the polymer referred to in the present invention is intended to include a copolymer. Further, in the present specification, the acetyl group may be indicated as Ac, the ethyl group as Et, the methyl group as Me, and the phenyl group or phenylene group as Ph.
In addition, the “film” in the present invention is intended to include plate-shaped and flat-plate-shaped materials.

(1) The fuel cell catalyst material of the present invention is connected to a carbon material, the surface of the carbon material, and at least two points through a linking group having solvolysis resistance and heat resistance. And a solvolysis-resistant and heat-resistant polymer (X) having an ionic functional group.
Here, being connected at least two or more points means that one polymer (X) is connected to the surface of the carbon material at two or more points. In addition, within the range which does not deviate from the meaning of this invention, it does not exclude that the polymer connected with the surface of carbon material by the connection aspect other than this exists.
Here, the structure of the linking group portion connecting one polymer (X) and the carbon material may be the same or different.
Further, a part of the linking group may have a configuration that also serves as the carbon material or the polymer (X) (for example, a configuration that becomes a linking group including a connection point with the carbon material or the polymer (X)).
The group having solvolysis resistance is easily solvolyzed under high temperature and strongly acidic conditions in the working environment of the fuel cell (for example, 10% or more is solvolyzed at 100 ° C. and pH 2 or less). A group containing no bond, such as an ester bond, an amide bond, and a siloxane bond. Examples of the solvolysis-resistant linking group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group,

からなる群から選ばれる１つ以上の組み合わせからなる基が挙げられる。

And a group consisting of one or more combinations selected from the group consisting of:

Here, the aliphatic hydrocarbon group may be a saturated hydrocarbon or an unsaturated hydrocarbon, and may be linear, branched, or cyclic. Further, the hydrogen atom may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom) within a range not departing from the gist of the present invention. 1-12 are preferable and, as for carbon number of an aliphatic hydrocarbon group, 1-6 are more preferable. Specific examples of the aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, a decylene group, an isobutylene group, — (CH ₂ ) _n CH═CH— (n is , And preferably an integer of 1 to 6.), —CH ₂ CH ₂ CH═CH—, C ((CH ₂ ) _n —) ₄ (n is an integer, preferably 0 to 6), CH ((CH ₂ ) _n −) ₃ (n is an integer, preferably an integer of 0 to 6), CH ₃ C ((CH ₂ ) _n −) ₃ (n Is an integer, preferably an integer from 0 to 6), EtC ((CH ₂ ) _n —) ₃ (n is an integer, preferably an integer from 0 to 6), —C (( _{CH 2) n -) 3 (} n is an integer, preferably an integer of 0~6), - CH ((CH 2) n -) 2 (n is an integer, preferably 0 to 6 Is an integer).
6-25 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-16 are more preferable, and 6-12 are more preferable. The cyclic hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom) without departing from the gist of the present invention. The aromatic hydrocarbon group is preferably a group having a triphenylene ring, pyrene ring, anthracene ring, naphthalene ring, biphenylene ring or benzene ring, more preferably a group having a naphthalene ring, biphenylene ring or benzene ring, and a benzene ring. Groups are most preferred.
The heterocyclic group preferably contains any of a sulfur atom, a nitrogen atom and an oxygen atom, and preferably contains a sulfur atom or a nitrogen atom. Moreover, 3-16 are preferable and, as for carbon number which a heterocyclic group has, 3-12 are more preferable. The hydrogen atom on the ring of the heterocyclic group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention. Specifically, the heterocyclic group is preferably a group having a pyridine ring, a furan ring, a thieten ring, or a triazine ring, and more preferably a group having a triazine ring.

Preferred examples of the group having solvolysis resistance include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, a decylene group, a phenylene (—Ph—) group, —CH ₂ —O— ( CH _{2) n} - (n is an integer, preferably an integer from 1 to _{6), - CH 2 -Ph -,} - CH 2 CH 2 OCH 2 CH 2 -, - (CH 2 CH 2 O ) ₂ CH ₂ CH ₂ —, —CH ₂ CH═CH—, —CH ₂ CH ₂ CH═CH—, C ((CH ₂ ) _n —) ₄ (n is an integer of 0 or more, preferably Each of which is an integer of 0 to 6), CH ((CH ₂ ) _n —) ₃ (n is an integer of 0 or more, preferably each of 0 to 6), CH ₃ C ((CH _{2) n} -) _{3 (n} are each an integer of 0 or more, each an integer of preferably 0 to 6) _{EtC ((CH 2) n -} ) 3 (n is an integers of 0 or more, preferably an integer of 0~6), - C ((CH 2) n -) 3 (n , respectively An integer of 0 or more, preferably each of 0 to 6), —CH ((CH ₂ ) _n —) ₂ (n is an integer of 0 or more, preferably each of 0 to 6) As well as these (including groups in which two or more of the above groups are combined) and —CO—, —SO—, —CS—, —SO ₂ —,

の１つ以上との組み合わせが挙げられる。

And a combination with one or more of the above.

The group having heat resistance means a group that exists stably even under high temperature conditions (for example, 100 ° C. or higher) in the actual working environment of the fuel cell. For example, in the case where the ionic functional group is a sulfo group, it is known that if the sulfo group is directly bonded to the aromatic ring, the sulfo group is in a dissociation equilibrium state, so that it is eliminated over time at a high temperature. (Col. Czech. Chem. Commun., Vol. 9, pp. 465 (1937)), it cannot be said that a single bond to an aromatic ring has heat resistance. Therefore, here, the group having heat resistance represents all organic groups except a single bond to an aromatic ring. However, even when a sulfo group is linked to an aromatic ring via a single bond, it is known that the heat resistance of the sulfo group is improved when an electron-withdrawing group is present in the aromatic ring. (NEDO Achievement Report 100004243 “FY2003 Achievement Report Solid Polymer Fuel Cell System Technology Development Project Solid Polymer Fuel Cell Element Technology Development Business, etc.) Highly durable hydrocarbon-based electrolyte membranes for polymer electrolyte fuel cells Research and Development"). Therefore, even when a sulfo group is linked to an aromatic ring via a single bond, if the sum of substituent constants σ of substituents other than the sulfo group on the aromatic ring is a certain value or more, the sulfo group is It can be regarded as having heat resistance. The sum of the substituent constants σ for heat resistance is preferably 0.3 or more, more preferably 0.35 or more, and most preferably 0.4 or more. In addition, the value of the para position shall be substituted for the substituent constant of the substituent located in the ortho position with respect to the sulfo group.
Hereinafter, what satisfies the conditions for the above-mentioned linking group having heat resistance may be referred to as Condition B.
As a preferable example of the linking group having heat resistance, from the preferable examples of the linking group having solvolysis resistance, an ionic functional group is connected to an aromatic group through a single bond (the above substituent constants). excluding those satisfying the condition for σ).

(2) The carbon material (catalyst-carrying carbon material) used for the fuel cell catalyst material of the present invention is not particularly defined, and a known carbon material can be used, and carbon black, carbon nanotube (CNT), carbon Nanohorn (CNH), fullerene, and graphite are preferably used. Carbon black and carbon nanotubes can be used particularly preferably because ionic functional groups can be introduced starting from functional groups present on the surface.

Carbon black The carbon black used in the present invention is a fine powder produced by gas phase pyrolysis or incomplete combustion of natural gas or hydrocarbon gas, and is spherical or chain-like carbon. , Thermal black and lamp black. These differ in particle size, oxygen content, volatile components, specific surface area, microstructure, etc., and are described in the latest collection of the latest carbon black technologies, Chapter 4 (published in 2005 by Technical Information Association). In the present invention, one or more of the above carbon blacks can be used, and commercially available products such as ketjen black and Vulcan XC-72 can also be used.

  There are oxygen-containing functional groups such as phenolic hydroxyl groups, carboxyl groups, quinone-type carbonyl groups, and lactone groups on the surface of carbon black, and polymers can be introduced onto the surface of carbon black using these functional groups. . The number of these functional groups can be increased by subjecting them to an oxidation treatment in addition to those originally present on the carbon black surface. Examples of the oxidation treatment method include corona discharge, plasma treatment, gas phase oxidation, liquid phase oxidation, etc., and oxidation treatment is performed using one or more of these methods to increase the number of functional groups on the carbon black surface. It is preferable. Examples of the oxidizing agent in the gas phase oxidation include molecular oxygen, atomic oxygen, ozone, dry air, and wet air, and these may be used in combination of two or more kinds as much as possible. As oxidizing agents in liquid phase oxidation, nitric acid, potassium permanganate, chlorous acid, chloric acid and perchloric acid sodium salt, oxygen saturated water, ozone aqueous solution, bromine aqueous solution, sodium hypochlorite, potassium chromate And a mixed aqueous solution of phosphoric acid and a mixture of silver dichromate and sulfuric acid.

  As for the carboxyl group and lactone group on the surface of carbon black, as it is, the polymer can only be introduced via an ester bond or amide bond with low heat resistance and solvolysis resistance, so it is reduced to a hydroxymethyl group, It is preferable to introduce the segment using the hydroxymethyl group.

  Carbon black is also known to act as a strong radical scavenger (for example, N. Tsubokawa et al., J. Polym. Sci., Part A: Polym. Chem., 36, 3165). (1998) etc.), for example, captures a carbon radical generated by thermal decomposition of an azo group, and forms a carbon-carbon bond or a carbon-oxygen bond excellent in solvolysis resistance and heat resistance. Therefore, a polymer can also be introduced using such radical scavenging properties.

Carbon nanotube The carbon nanotube used in the present invention has a carboxyl group on its surface, and an ionic functional group can be introduced on the surface of the carbon nanotube starting from this carboxyl group. In addition, since the number of carboxyl groups on the surface can be increased by the oxidation treatment, it is preferable to perform the oxidation treatment when used in the present invention. As an oxidation treatment method, it is preferable to use an oxidation reaction with nitric acid.

  The carboxyl group on the surface of the carbon nanotube can be reduced to a hydroxymethyl group because the polymer can only be introduced via an ester bond or an amide bond with low heat resistance and solvolysis resistance, as it is. It is preferable to introduce a polymer using

 Carbon nanotubes are also known to act as radical scavengers (for example, A. Adronov et al., Research report, Macromolecules, 38, 1172 (2005)). The generated carbon radical is captured, and a carbon-carbon bond or a carbon-oxygen bond excellent in solvolysis resistance and heat resistance is formed. Therefore, a hydrophilic segment and a hydrophobic segment can also be introduced using such radical scavenging properties.

(4) Detailed description of linking group having solvolysis resistance and heat resistance The linking group having solvolysis resistance and heat resistance is preferably a linking group represented by formula (1).

Formula (1)

(In formula (1), R ¹ and R ² each represent a divalent to tetravalent linking group, Ar ¹ represents a divalent to hexavalent linking group containing an aromatic hydrocarbon and / or a heterocycle, and n ₁ , N ₂ and n ₃ are each an integer of 0 or more, and the sum of n ₁ , n ₂ and n ₃ is an integer of 1 or more, n ₄ is an integer of 1 to 10, and n ₅ is 1 to (It is an integer of 3. Lc represents a connection point connected to the carbon material side, and Lp represents a connection point connected to the polymer (X) side.)
Here, each of the formula (1), R ¹ and R ² are aliphatic hydrocarbon radicals, -O-,

からなる群から選ばれる１以上の組み合わせからなる基であることが好ましい。
ここで、脂肪族炭化水素基は、飽和炭化水素でも不飽和炭化水素でもよく、また、直鎖、分岐、環状のいずれであってもよい。さらに、水素原子が、本発明の趣旨を逸脱しない範囲内において、置換基（例えば、ハロゲン原子、好ましくはフッ素原子など）で置換されていてもよい。脂肪族炭化水素基の炭素数は１〜２４が好ましく、１〜６がより好ましい。
Ｒ¹およびＲ²の好ましい例としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、オクチレン基、デシレン基、イソブチレン基、−ＣＨ₂−Ｏ−（ＣＨ₂）_n−（ｎは、０以上の整数であり、好ましくは、１〜６の整数である）、−ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−、−（ＣＨ₂ＣＨ₂Ｏ）₂ＣＨ₂ＣＨ₂−、Ｃ（(ＣＨ₂) _n−）₄(ｎは、それぞれ０以上の整数であり、好ましくはそれぞれ０〜６の整数である)、ＣＨ（(ＣＨ₂) _n−）₃(ｎは、それぞれ０以上の整数であり、好ましくはそれぞれ０〜６の整数である)、ＣＨ₃Ｃ（(ＣＨ₂) _n−）₃(ｎは、それぞれ０以上の整数であり、好ましくはそれぞれ０〜６の整数である)、ＥｔＣ（(ＣＨ₂) _n−）₃(ｎは、それぞれ０以上の整数であり、好ましくはそれぞれ０〜６の整数である)、−Ｃ((ＣＨ₂）_n−）₃(ｎは、それぞれ０以上の整数であり、好ましくはそれぞれ０〜６の整数である)、−ＣＨ((ＣＨ₂）_n−）₂(ｎは、それぞれ０以上の整数であり、好ましくはそれぞれ０〜６の整数である)、ならびに、これら（前記基を２以上組み合わせた基を含む）と、−Ｏ−、−ＣＯ−、−ＳＯ−、−ＣＳ−、−ＳＯ₂−、

A group consisting of one or more combinations selected from the group consisting of
Here, the aliphatic hydrocarbon group may be a saturated hydrocarbon or an unsaturated hydrocarbon, and may be linear, branched, or cyclic. Furthermore, the hydrogen atom may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention. 1-24 are preferable and, as for carbon number of an aliphatic hydrocarbon group, 1-6 are more preferable.
Preferred examples of R ¹ and R ² include methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, decylene group, isobutylene group, —CH ₂ —O— (CH ₂ ) _n — (n is , An integer of 0 or more, preferably an integer of 1 to 6), —CH ₂ CH ₂ OCH ₂ CH ₂ —, — (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ —, C ((CH ₂ ) _n −) ₄ (n is an integer of 0 or more, preferably each of 0 to 6), CH ((CH ₂ ) _n −) ₃ (n is an integer of 0 or more, respectively) Each is preferably an integer of 0 to 6), CH ₃ C ((CH ₂ ) _n —) ₃ (n is an integer of 0 or more, and preferably an integer of 0 to 6). EtC ((CH ₂ ) _n —) ₃ (n is an integer of 0 or more, preferably 0 to 0, respectively. 6 is an integer _{of), - C ((CH 2} ) n -) 3 (n are each integer of 0 or greater, each an integer of preferably 0~6), - CH ((CH 2) n -) ₂ (n is an integer of 0 or more, preferably an integer of 0 to 6, respectively), and these (including groups in which two or more of the above groups are combined), -O-, -CO -, - SO -, - CS -, - SO 2 -,

の１つ以上との組み合わせが挙げられる。
Ｒ¹およびＲ²は特に好ましくは、−Ｏ−、−ＣＨ₂−、−Ｏ（ＣＨ₂）_n−、−Ｏ（ＣＨ₂）_nＯ−、−ＳＯ₂−、−ＣＯ−または、これらの２以上の組み合わせからなる基である。

And a combination with one or more of the above.
R ¹ and R ² are particularly preferably —O—, —CH ₂ —, —O (CH ₂ ) _n —, —O (CH ₂ ) _n O—, —SO ₂ —, —CO— or these A group consisting of two or more combinations.

In the formula (1), Ar ¹ is preferably an aromatic hydrocarbon group or a heterocyclic group, and these, —O—, —CO—, —S—, —SO—, —CS—, —SO _2. A group composed of one or more combinations of-.
Here, 6-25 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-16 are more preferable, and 6-12 are more preferable. The hydrogen atom on the ring of the aromatic hydrocarbon group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention.
The heterocyclic group preferably contains any of a sulfur atom, a nitrogen atom and an oxygen atom, and preferably contains a sulfur atom or a nitrogen atom. Moreover, 2-12 are preferable and, as for carbon number which a heterocyclic group has, 3-8 are more preferable. The hydrogen atom on the ring of the heterocyclic group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention.
Specific examples of Ar ¹ include a triphenylene ring, a pyrene ring, an anthracene ring, a naphthalene ring, a biphenylene ring, a group having a benzene ring, and these, and —O—, —CO—, —S—, —SO—. , —CS—, —SO ₂ — or a combination of one or more, or a group having a group having a pyridine ring, a furan ring, a thiophene ring or a triazine ring, and these, and —O—, —CO—, — S -, - SO -, - CS -, - SO 2 - is a combination of one or more preferred.

In the formula (1), n ₁ , n ₂ and n ₃ are each preferably an integer of 0 to 5, and more preferably 0 or 1, respectively. The sum of n ₁ , n ₂ and n ₃ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. When n ₁ , n ₂ or n ₃ is 2 or more, two or more of R ¹ , Ar ¹ and R ² may be the same or different.

Wherein (1), n ₄ is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. When n ₄ is 2 or more, two or more R ^{2 s} may be the same or different.
n ₅ is preferably 1 or 3. When n ₅ is 2 or more, two or more of R ¹ , Ar ¹ and R ² may be the same or different.
In addition, Lc is a symbol representing a connection portion between the linking group and the carbon material, and no specific group exists. Similarly, Lp is a symbol that represents the connection point between the linking group and the polymer, and no specific group exists.

The connecting part between the linking group and the carbon material is preferably connected via a carbon atom, oxygen atom or sulfur atom, and is preferably constituted by a chemical bond having solvolysis resistance and heat resistance. . As the chemical bond having solvolysis resistance and heat resistance, a carbon-carbon single bond, an ether bond, a carbon-SO ₂ bond, a carbon-carbon double bond, a carbon-carbon triple bond, and a thioether bond are preferable. A carbon single bond, an ether bond and a carbon-SO ₂ bond are more preferable.
More specifically, when the carbon material used in the present invention is carbon black, it is formed of an oxygen atom derived from a phenolic hydroxyl group present on the carbon black surface and a carbon atom derived from R ¹ in the formula (1). An ether bond, a single bond formed by the carbon atom at the ortho position of the phenolic hydroxyl group and the carbon atom of R ¹ , an oxygen atom derived from a hydroxymethyl group obtained by reducing a carboxyl group on carbon black, An ether bond formed with the carbon atom of R ¹ , an ether bond formed with the quinone carbonyl oxygen atom present on the carbon black surface and the carbon atom derived from R ¹ in formula (1), on the carbon black A single bond formed by a carbon atom and a carbon atom of R ¹ is particularly preferable. When the carbon material is a carbon nanotube, an ether bond formed by an oxygen atom derived from a hydroxymethyl group obtained by reducing a carboxyl group on the carbon nanotube and a carbon atom of R ¹ is particularly preferable.

Further, when connecting the carbon material and R ¹ is 2 ways of connecting the R ¹ via the method of connecting the R ¹ via a carbon atom present in the carbon material, the oxygen atoms present in the carbon material Although there are various methods, any method can be preferably used in the present invention.

0-60 are preferable, as for the total carbon number of the coupling group represented by Formula (1), 0-50 are more preferable, and 0-40 are more preferable.
Further, in the fuel cell catalyst material of the present invention, only one type of linking group represented by the formula (1) may be included, or two or more types may be included.

  Although the coupling group represented by Formula (1) is illustrated below, this invention is not limited to these.

(5) Method of connecting polymer (X) to carbon material When connecting polymer (X) to a carbon material, the following three reactions are roughly used.
(1) Nucleophilic substitution reaction A method in which a phenolic hydroxyl group present on the surface of a carbon material is reacted under basic conditions and the polymer (X) is introduced into the carbon material via an ether bond can be employed.
(2) Electrophilic aromatic nucleus substitution reaction A site having an aromatic C—H bond existing on the surface of a carbon material is reacted under a Lewis acid catalyst, and the polymer (X) is introduced into the carbon material through various bonding modes. Can be used.
(3) Radical trapping reaction Carbon materials such as carbon black and carbon nanotubes are known to act as powerful radical scavengers (for example, a report by N. Tsubawa et al., J. Polym. Sci., Part). A: Polym. Chem., 36, 3165 (1998), etc.), which can be used for the ligation reaction. That is, a site having an aromatic C—H bond and a quinone carbonyl site existing on the surface of the carbon material are reacted with radicals generated on the polymer (X), and the polymer (X) is bonded through various bonding modes. Can be introduced into the carbon material. It is known that the unpaired electron density of the carbon material increases after the reaction, and the ESR spectrum area increases compared to that before the reaction (for example, Chemistry and Industry, 1961, 1532-1533). Progress can be confirmed.

（上式中、ＣＢはカーボン材料の一部を表す。）

(In the above formula, CB represents a part of the carbon material.)

  Any of the above reactions can be preferably used. In particular, when a plurality of connection points are formed between the polymer (X) and the carbon material by a single reaction, a radical trapping reaction with a large number of reaction sites on the surface of the carbon material and a small activation energy of the reaction is preferable. Used.

Specifically, there are the following two methods for connecting the polymer (X) to the surface of the carbon material through a plurality of connection points.
(Method α)
In this method, after introducing a plurality of linking sites into the polymer (X), it is reacted with a carbon material and linked to the carbon material via a plurality of linking groups at once.
(Method β)
A method in which a polymer (X) and a carbon material are linked via one linking group, a plurality of linking sites are further introduced into the linked polymer (X), and a plurality of linking points are formed by a second-stage reaction. It is.

  By using the method α, the polymer (X) can be easily introduced into the carbon material via a plurality of linking groups. In addition, although the number of reaction steps is increased by using the method β, the polymer (X) can be reliably connected at more connection points. Each of these methods has advantages and disadvantages, and it is preferable to use them appropriately according to the situation. In the method β, the first-stage reaction and the second-stage reaction may be performed using the same kind of ligation reaction or different kinds of reactions. The number of reaction sites on the carbon material used for the eye reaction is large and more preferable.

(6) Polymer (X)
The polymer (X) of the present invention has a group having solvolysis resistance and heat resistance and an ionic functional group. The solvolysis resistance and heat resistance are the same as those in the above linking group, and the same applies to specific examples and the like.
The polymer skeleton excluding the ionic functional group site of the present invention has an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-,

からなる基から選ばれる１つ以上の組み合わせから構成されることが好ましい。

It is preferably composed of one or more combinations selected from the group consisting of

Here, the aliphatic hydrocarbon group may be a saturated hydrocarbon or an unsaturated hydrocarbon, and may be linear, branched, or cyclic. Furthermore, the hydrogen atom may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention. 1-24 are preferable and, as for carbon number of an aliphatic hydrocarbon group, 1-6 are more preferable.
6-25 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-16 are more preferable, and 6-12 are more preferable. The hydrogen atom on the ring of the aromatic hydrocarbon group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention. Group, fluorenyl group and phenanthronyl group are preferable, naphthyl group and biphenyl group are more preferable, and phenyl group is most preferable.
The heterocyclic group preferably contains any of a sulfur atom, a nitrogen atom and an oxygen atom, and preferably contains a sulfur atom or a nitrogen atom. Moreover, 2-12 are preferable and, as for carbon number which a heterocyclic group has, 3-8 are more preferable. The hydrogen atom on the ring of the heterocyclic group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom) without departing from the spirit of the present invention.
The heterocyclic group is preferably a pyridyl group, a furyl group, or a thienyl group, and more preferably a triazinyl group.

The ionic functional group in the polymer (X) used in the present invention may be either cationic or anionic, but is preferably an anionic ionic functional group.
As the cationic ionic functional group, a sulfonium group, an iodonium group, a thioronium group, a phosphonium group, a pyridyl group, and an ammonium group are preferable, and a pyridyl group and an ammonium group are more preferable. Specific examples of pyridyl group and ammonium group include-(dimethylcetyl) ammonium group,-(benzyldibutyl) ammonium group,-(benzyldiethyl) ammonium group,-(dimethyldodecyl) ammonium group, and-(didecylmethyl) ammonium. Group,-(stearyldimethyl) ammonium group,-(lauryldimethyl) ammonium group,-(trimethyl) ammonium group,-(triethyl) ammonium group,-(trin-butyl) ammonium group,-(triheptyl) ammonium group,- (Butyldiethyl) ammonium group,-(phenyldiethyl) ammonium group,-(2-methyl) pyridyl group,-(3-methyl) pyridyl group,-(4-methyl) pyridyl group are preferred,-(stearyldimethyl) ammonium Group,-(lauryldimethyl) ammonium group,-(trimethyl) ammonium Group,-(triethyl) ammonium group,-(trin-butyl) ammonium group,-(triheptyl) ammonium group,-(butyldiethyl) ammonium group,-(phenyldiethyl) ammonium group,-(2-methyl) pyridyl Group,-(3-methyl) pyridyl group and-(4-methyl) pyridyl group are more preferable,-(trimethyl) ammonium group,-(triethyl) ammonium group and-(tri-n-butyl) ammonium group are particularly preferable.
Moreover, as a counter anion, a chloride ion, a bromide ion, an iodide ion, and a hydroxide ion are preferable, and a hydroxide ion is particularly preferable.
As the anionic ionic functional group, a perfluorosulfo group, a sulfo group, a phosphonic acid group, and a carboxylic acid group are preferable, and a sulfo group and a phosphonic acid group are more preferable.
Further, as the counter cation, calcium ion, barium ion, quaternary ammonium ion, lithium ion, sodium ion, potassium ion and proton are preferable, lithium ion, sodium ion, potassium ion and proton are more preferable, and proton is particularly preferable.

 It is preferable that at least one ionic functional group exists per one repeating unit of the polymer (X), and it is more preferable that two or more ionic functional groups exist per one repeating unit.

 The weight average molecular weight of the polymer (X) is preferably 500 to 1,000,000, more preferably 1000 to 200,000, and particularly preferably 3000 to 100,000.

 The ion functional group concentration in the polymer (X) can be measured as an ion exchange capacity, preferably 0.1 to 7 meq / g, more preferably 0.5 to 5 meq / g, and still more preferably 1 to 3 meq / g. . Proton conductivity can be further increased by setting the ionic functional group concentration to 0.1 meq / g or more, and durability and mechanical strength can be further increased by setting the ion functional group concentration to 7 meq / g or less.

In the polymer (X) employed in the present invention, the main chain portion includes a repeating unit represented by the formula (2), and at least one partial structure selected from the formulas (3) to (5) is the main chain. It is preferably bonded to an aromatic ring. Hereinafter, such a polymer is referred to as a polymer series A.
Here, in the polymer series A, the repeating unit represented by the formula (2) may contain only one type or two or more types. Each of the partial structures of Formula (3), Formula (4), and Formula (5) may include only one type, or may include two or more types.

In the polymer series A, for example, after forming a main chain containing a repeating unit represented by the formula (2), at least one partial structure selected from the formulas (3) to (5) is introduced into the aromatic ring of the main chain. Alternatively, it is obtained by polymerizing at least one of a compound represented by the following formula (13), a compound represented by the following formula (14), and a compound represented by the following formula (15).
Formula (13)

（式（１３）中、Ｘ⁴は単結合または２価の連結基であり、Ｒ⁶およびＲ⁷はそれぞれ芳香環を含む基を表す。Ｂ⁶およびＢ⁷はそれぞれ単結合または２〜６価の連結基を表す。Ａ⁵およびＡ⁶はそれぞれイオン性官能基である。ｎ₁₉およびｎ₂₀はそれぞれ１〜５の整数を表し、ｎ₂₁およびｎ₂₂はそれぞれ０〜４の整数を表し、ｎ₂₁とｎ₂₂の和は２以上の整数である。Ｚ¹およびＺ²は、それぞれ、水酸基、ハロゲン基、アルキルスルホネート基またはニトロ基を表す。）
式（１４）

(In formula (13), X ⁴ is a single bond or a divalent linking group, and R ⁶ and R ⁷ each represent a group containing an aromatic ring. B ⁶ and B ⁷ are each a single bond or 2-6 valent groups. A ⁵ and A ⁶ are each an ionic functional group, n ₁₉ and n ₂₀ each represent an integer of 1 to 5, n ₂₁ and n ₂₂ each represent an integer of 0 to 4, The sum of n ₂₁ and n ₂₂ is an integer equal to or greater than 2. Z ¹ and Z ² each represent a hydroxyl group, a halogen group, an alkyl sulfonate group, or a nitro group.
Formula (14)

（式（１４）中、Ｚ³およびＺ⁴は、それぞれ、水酸基、ハロゲン基、アルキルスルホネート基またはニトロ基を表し、Ｒ⁸は芳香環を含む基を表す。）
式（１５）

(In formula (14), Z ³ and Z ⁴ each represent a hydroxyl group, a halogen group, an alkyl sulfonate group or a nitro group, and R ⁸ represents a group containing an aromatic ring.)
Formula (15)

（式（１５）中、Ｘ⁵は単結合または２価の連結基であり、Ｒ⁹およびＲ¹⁰はそれぞれ芳香環を含む基を表す。Ｅ⁶、Ｅ⁷およびＥ⁸はそれぞれ酸素透過性の高い置換基を表す。ｎ₂₃、ｎ₂₄およびｎ₂₅はそれぞれ０〜４の整数を表し、ｎ₂₃とｎ₂₄とｎ₂₅の和は１以上である。Ｚ⁵およびＺ⁶は、それぞれ、水酸基、ハロゲン基、アルキルスルホネート基またはニトロ基を表す。）

(In Formula (15), X ⁵ is a single bond or a divalent linking group, and R ⁹ and R ¹⁰ each represent a group containing an aromatic ring. E ⁶ , E ⁷ and E ⁸ are each oxygen-permeable. N ₂₃ , n ₂₄ and n ₂₅ each represents an integer of 0 to 4, and the sum of n ₂₃ , n ₂₄ and n ₂₅ is at least 1. Z ⁵ and Z ⁶ are each a hydroxyl group Represents a halogen group, an alkyl sulfonate group or a nitro group.)

Further, the polymer (X) preferably has a main chain portion having a repeating unit represented by the formula (6), and the formula (7) or the formula (8) is bonded to the aromatic ring of the main chain. . Hereinafter, such a polymer is referred to as a polymer series B.
In the polymer series B, for example, after forming a main chain containing a repeating unit represented by the formula (6), at least one partial structure represented by the formula (7) or the formula (8) is converted into an aromatic ring of the main chain. It is obtained by introducing or polymerizing a compound represented by the following formula (16) and a compound represented by the following formula (17).

（式（１６）および（１７）中、Ｗ²¹、Ｗ²²、Ｗ²³、Ｗ²⁴、Ｗ²⁵およびＷ²⁶はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表し、Ｂ⁸は単結合または２〜６価の連結基を表し、Ａ⁷はイオン性官能基を表し、ｎ₂₆は１〜５の整数を表し、ｎ₂₇は１〜５の整数を表す。Ｅ¹⁰は酸素透過性の高い置換基を表し、ｎ₂₈は１〜５の整数を表す。）

(Expressed in the formula (16) and ^{(17), W 21, W} 22, W 23, W 24, W 25 and W ²⁶ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, B ⁸ Represents a single bond or a bivalent to hexavalent linking group, A ⁷ represents an ionic functional group, n ₂₆ represents an integer of 1 to 5, n ₂₇ represents an integer of 1 to 5. E ¹⁰ represents oxygen Represents a highly permeable substituent, and n ₂₈ represents an integer of 1 to 5.)

  Hereinafter, the repeating units of both polymer series and the compounds for forming them will be described in detail.

Structure of polymer series A

（上記式（２）中、Ｒ³は芳香環を含む２価の基であり、Ｘ¹は２価の連結基である。式（３）中、Ｂ¹は単結合または２〜６価の連結基、Ａ¹はイオン性官能基を表し、ｎ₆は１〜５の整数を表す。式（４）中、Ｂ²は単結合または２〜６価の連結基を、Ｄは少なくとも１つのイオン性官能基を有するラジカル重合性モノマーの重合物を表す。式（５）においてＥ¹は酸素透過性の高い置換基を表す。）

(In the above formula (2), R ³ is a divalent group containing an aromatic ring, and X ¹ is a divalent linking group. In formula (3), B ¹ is a single bond or a 2-6 valent group. A linking group, A ¹ represents an ionic functional group, n ₆ represents an integer of 1 to 5. In formula (4), B ² represents a single bond or a bivalent to hexavalent linking group, and D represents at least one This represents a polymer of a radically polymerizable monomer having an ionic functional group.In formula (5), E ¹ represents a substituent having high oxygen permeability.

In the formula (2), R ³ is preferably 1 to 50, more preferably 1 to 30, and still more preferably 1 to 15 as the total number of carbon atoms constituting the aromatic ring. Further, the hydrogen atom on the aromatic ring may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention. The aromatic ring of R ³ is preferably composed of a benzene ring and a condensed benzene ring.
The preferred structure of R ³ is illustrated below. Among these, (C-1), (C-2), (C-4), (C-5), (C-8), and (C-12) are preferable, and (C-1), ( C-4) is more preferable.

In the formula (2), X ¹ is ^one of groups selected from the group consisting of —C (R ⁹¹ R ¹⁰¹ ) —, —O—, —S—, —CO—, —SO—, —SO ₂ —. The divalent group consisting of the above is represented. Here, R ⁹¹ and R ¹⁰¹ are each a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20, for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, tert-butyl group, isopropyl group) Group, n-pentyl group, neopentyl group, methoxyethyl group), alkenyl group (preferably having 2 to 20 carbon atoms, such as vinyl group, allyl group), aryl group (preferably having 6 to 26 carbon atoms, such as phenyl group, 2-naphthyl group), and a hydrogen atom contained therein may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention.
R ⁹¹ and R ¹⁰¹ are preferably a methyl group, an ethyl group, an isopropyl group, a neopentyl group, a trifluoromethyl group, a tert-butyl group, a propyl group, an n-butyl group, an n-pentyl group, or a phenyl group, An ethyl group, an isopropyl group, a neopentyl group, a trifluoromethyl group, a tert-butyl group, and a phenyl group are more preferable, and a methyl group, a trifluoromethyl group, and a tert-butyl group are more preferable.
Preferred examples of X ¹ include —C (tert-Bu) ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—, —S—, —CO—, —SO. _2- .

  As the repeating unit represented by the formula (2), a polyethersulfone compound, a polyetherethersulfone compound, a polyetheretherketone compound, a polyphenylenesulfide compound, a polyphenyleneether compound, a polysulfone compound, or a polyetherketone It is preferable that it is comprised from a system compound. Among these, it is particularly preferable to be derived from a polyethersulfone compound, a polyetherethersulfone compound, or a polysulfone compound that has excellent oxidation resistance.

  In the main chain containing the repeating unit represented by the formula (2), the total number of repeating units represented by the repeating unit represented by the formula (2) is preferably 2 to 1000, more preferably 10 to 500, and more preferably 10 To 200 is particularly preferable (hereinafter, sometimes referred to as condition “A”).

  Although the preferable example of the repeating unit represented by Formula (2) below is illustrated below, this invention is not limited to these. In the compound group, n represents the number of repeating units of each compound, and a preferable range of n is appropriately determined so as to correspond to the preferable range described in the condition “A”.

In Formula (3), B ¹ is a single bond, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, —O—,

からなる群から選ばれる１つ以上の組み合わせからなる基が好ましい。

A group consisting of one or more combinations selected from the group consisting of

Here, the aliphatic hydrocarbon group may be a saturated hydrocarbon or an unsaturated hydrocarbon, and the hydrogen atom is a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention. May be substituted. 1-12 are preferable and, as for carbon number of an aliphatic hydrocarbon group, 1-6 are more preferable.
The aromatic hydrocarbon group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) within the range in which the hydrogen atom on the ring does not depart from the spirit of the present invention. Group, naphthyl group, biphenyl group and phenyl group are preferred, naphthyl group, biphenyl group and phenyl group are more preferred, and phenyl group is most preferred.
The heterocyclic group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) within the range in which the hydrogen atom on the ring does not depart from the spirit of the present invention, a pyridyl group, a furyl group, A thienyl group and a triazinyl group are preferable, and a triazinyl group is more preferable.
When B ¹ is a single bond, from the viewpoint of heat resistance, it is necessary to satisfy the preferable conditions described in the condition “B” described above.
Preferred examples of B ¹ include a single bond, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, a decylene group, a phenylene (—Ph—) group, —CH ₂ —O— (CH ₂ ). n-(n is an integer, preferably an integer from 1 to _{6), - CH 2 -Ph -,} - CH 2 CH 2 OCH 2 CH 2 -, - (CH 2 CH 2 O) 2 CH ₂ CH ₂ —, —CH ₂ CH═CH—, —CH ₂ CH ₂ CH═CH—, C ((CH ₂ ) _n —) ₄ (n is an integer of 0 or more, preferably 0 to 0, respectively. 6), CH ((CH ₂ ) _n −) ₃ (n is an integer of 0 or more, preferably each an integer of 0 to 6), CH ₃ C ((CH ₂ ) _n -) ₃ (n are each an integer of 0 or more, each an integer of preferably 0~6), EtC ((C _{2) n} -) _{3 (n} is an integers of 0 or more, preferably an integer of 0~6), - C ((CH 2) n -) 3 (n is integers of 0 or more Each of which is preferably an integer of 0 to 6), —CH ((CH ₂ ) _n —) ₂ (n is an integer of 0 or more, preferably each of 0 to 6), In addition, these (including a group in which two or more of the above groups are combined) and —CO—, —SO—, —CS—, —SO ₂ —, —O—,

の１つ以上との組み合わせが挙げられる。

And a combination with one or more of the above.

In formula (3), A ¹ has the same meaning as the description of the ionic functional group described above, and the preferred range is also the same.
Wherein (3), n ₆ is 1-3 are preferable. When n ₆ is 2 or more, each A ¹ may be the same or different.
The amount introduced into the polymer main chain of formula (3) is preferably such that the content of the introduced ionic functional group is 0.1 meq / g to 7 meq / g, and 0.5 meq / g to 4 meq. The amount is more preferably 1 g / g, particularly preferably 1 meq / g to 3 meq / g.
Although the preferable example of Formula (3) is illustrated below, this invention is not limited to these.

In formula (4), B ² has the same meaning as B ^{1 in} formula (3), and the preferred range is also the same.
In Formula (4), the ionic functional group which D has is synonymous with the above-mentioned ionic functional group, and a preferable range is also synonymous. The polymer of radical polymerizable monomers refers to a polymer obtained by polymerizing two or more radical polymerizable monomers. As a preferred example of D, a polymer having a main chain having a repeating unit represented by the formula (6), wherein the formula (7) or the formula (8) is bonded to an aromatic ring of the main chain as a side chain. (Y). When B ² is a trivalent or higher linking group, D may be bonded to B ^{2 at a} plurality of positions, or a plurality of D may be present.
The amount of D introduced into the main chain is preferably such that the content of the introduced ionic functional group is 0.1 meq / g to 7 meq / g, and 0.5 meq / g to 4 meq / g. More preferably, the amount is 1 meq / g to 3 meq / g.

In formula (5), E ¹ represents a substituent having high oxygen permeability. Here, the substituent having a high oxygen permeability means a substituent having a negative permacol value. For permacall values of substituents, see M.M. By Salame, ACS Polymer Preprints 8, 137 (1967). The permacol value of E ¹ is preferably −10 / N or less, more preferably −20 / N or less, and particularly preferably −50 / N or less. Here, N represents the total number of structural units constituting the polymer main chain, and is synonymous with N described in the above document. More specifically, E ¹ is preferably composed of 3 or more carbon atoms. E ¹ is preferably a low-polarity substituent, and particularly preferably contains a silicon atom or a fluorine atom. The total number of carbon atoms in E ¹ present on two repeating units, preferably from 3 to 60, more preferably 5 to 40, 6 to 30 are particularly preferred.
E ¹ is, for example, an alkyl group (n-propyl group, isopropyl group, n-butyl group, n-pentyl group, benzyl group, 3-sulfopropyl group, 4-sulfobutyl group, carboxymethyl group, carboxypentyl group), Alkoxy groups (ethoxy group, n-propoxy group, n-butoxy group, tert-butoxy group, pentyloxy group, neopentyloxy group), alkenyl group (allyl group, 2-butenyl group, 1,3-butadienyl group), A cycloalkyl group (cyclopentyl group, cyclohexyl group), aryl group (phenyl group, 2-chlorophenyl group, 4-methoxyphenyl group, 3-methylphenyl group, 1-naphthyl group, 2-nitrophenyl group), heterocyclic group ( Pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino , Piperidino group, morpholino group), alkynyl group (2-propynyl group, 1,3-butadiynyl group, 2-phenylethynyl group), and a combination of these and a methylol group, preferably an alkyl group, alkenyl group Group, cycloalkyl group, methyloxyalkyl group, methyloxyalkenyl group, methyloxycycloalkyl group, alkyl group, cycloalkyl group, methyloxyalkyl group, and methyloxycycloalkyl group are particularly preferable. Compounds having an ether structure or silicon atom in the methylene chain (ethoxymethyl group, propoxymethyl group, butoxymethyl group, hexyloxymethyl group, trimethylsilyl group, triethylsilyl group, tributylsilyl group, 3-trimethylsilylpropyl group, 2- Trimethi Rusilylethyl group, 6-triethylsilylhexyl group, triethylsilylpropyl group) are particularly preferred.
These substituents may have a substituent without departing from the gist of the present invention. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an amino group (preferably having 0 to 20 carbon atoms, for example, an amino group, a dimethylamino group, a diethylamino group, a dibutylamino group, Anilino group), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, phosphonic acid group, acyl group (preferably having 1 to 20 carbon atoms, for example, alkoxy group (preferably having 1 to 20 carbon atoms, For example, methoxy group, butoxy group, cyclohexyloxy group), aryloxy group (preferably having 6 to 26 carbon atoms, such as phenoxy group, 1-naphthoxy group), alkylthio group (preferably having 1 to 20 carbon atoms, such as methylthio group) Group, ethylthio group), arylthio group (preferably having 6 to 20 carbon atoms, such as phenylthio group) 4-chlorophenylthio group), alkylsulfonyl group (preferably having 1 to 20 carbon atoms, such as methanesulfonyl group, butanesulfonyl group), arylsulfonyl group (preferably having 6 to 20 carbon atoms, such as benzenesulfonyl group, para Toluenesulfonyl group).

  The weight average molecular weight of the polymer of the polymer series A is preferably 500 to 200,000, more preferably 1000 to 100,000, and particularly preferably 1500 to 50,000.

Production method of polymer series A and introduction method to carbon material After forming the main chain containing the repeating unit represented by formula (2), the partial structure represented by formula (3), formula (4) and / or formula (5) is introduced into the aromatic ring of the main chain. 1. Method (hereinafter, this method is referred to as Method A-1), and 2. A method comprising polymerizing at least one of a compound represented by formula (13), a compound represented by formula (14) and a compound represented by formula (15) (hereinafter, this method is referred to as method A-2). Is preferred). In addition, the method of linking the polymer series A to the carbon material is different between the case where A-1 is used as the production method of the polymer series A and the case where A-2 is used. Hereinafter, the production method A-1 and the production method A-2 of the polymer series A and the method of linking the polymer series A to the carbon material when using the respective production methods will be described in detail.

Method A-1
Method A-1 introduces at least one partial structure selected from formulas (3) to (5) into the aromatic ring of the main chain after forming a main chain containing the repeating unit represented by formula (2). Is the method. Here, as a method for forming the main chain portion, it is preferable to use a known method as described in "Fourth Edition Experimental Chemistry Course, Vol. 29, 4.1 Heat resistant material". Commercially available polymers can also be used as the main chain.

As a method for introducing the partial structure represented by the formula (3) into the main chain, for example, when the ionic functional group is a sulfo group, a halogenomethylating agent such as chloromethylmethyl ether described below is used by using a halogenomethylating agent. Examples thereof include a method in which a halogenated polymer is converted into a sulfo group after the halogen moiety is acetylthiolated, or a method in which a halogenomethylated polymer and sodium sulfite are reacted to form a sulfo group. In the case of a sulfoalkyl group having a larger number of carbon atoms, for example, a chloro-substituted acid chloride represented by Cl— (CH ₂ ) _n —COCl (n is, for example, 2 to 6), for example, aluminum chloride, iron chloride, etc. A method in which a chloro-substituted acyl group is introduced by a Friedel-Crafts reaction using a Lewis acid, and then the chloro atom is converted to a sulfo group with dimethylthioether and sodium thiosulfate, and then the carbonyl group is reduced with hydrazine. Org. Chem. 45.2717 (1980), a method in which hydrogen of an aromatic ring is lithiated, then halogenoalkylated with a dihalogenoalkane, and then a chloro atom is converted to a sulfo group by the above method. Can be mentioned.

  In order to introduce a preferred halogenomethyl group in the present invention into an aromatic ring (halogenomethylation reaction of an aromatic ring), known reactions can be widely used. For example, chloromethyl methyl ether, 1,4-bis (chloromethoxy) butane, 1-chloromethoxy-4-chlorobutane, etc. are used as chloromethylating agents, and tin chloride, zinc chloride, aluminum chloride, titanium chloride, etc. are used as catalysts. A chloromethyl group can be introduced into an aromatic ring by carrying out a chloromethylation reaction using a Lewis acid or hydrofluoric acid. The solvent is preferably dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, nitrobenzene, etc., and the reaction is preferably carried out in a homogeneous system. Alternatively, the halogenomethylation reaction can be performed using paraformaldehyde and hydrogen chloride or hydrogen bromide.

Furthermore, as a method for introducing a sulfo group, as a general method, for example, a Friedel-Crafts reaction using a sultone as shown below and a Lewis acid (for example, AlCl ₃ ) (Journal of Applied Polymer Science, Vol. 36). , 1753-1767, 1988) can also be used.

  When performing the Friedel-Crafts reaction, the solvents are hydrocarbons (benzene, toluene, nitrobenzene, acetophenone, etc.), alkyl halides (methylene chloride, chloroform, dichloroethane, carbon tetrachloride, trichloroethane, dichloroethane, tetrachloroethane, chlorobenzene, Chlorobenzene etc.) can be used. The reaction temperature may be selected in the range of room temperature (for example, 18 ° C.) to 250 ° C. In these reactions, a mixture of two or more solvents may be used.

In addition, when the main chain is polysulfone, the structure of the sulfone group-containing polymer compound of the present invention has S = ⁰ of 1,030 to 1,045 cm ⁻¹ and 1,160 to 1,190 cm ⁻¹ according to the infrared absorption spectrum. Absorption, 1,130 to 1,250 cm ⁻¹ C—O—C absorption, 1,640 to 1,660 cm ⁻¹ C═O absorption, and the like. These composition ratios are determined by neutralization titration of sulfonic acid. Or by elemental analysis. Moreover, the structure can be confirmed from the peak of aromatic protons at 6.8 to 8.0 ppm by nuclear magnetic resonance spectrum ( ¹ H-NMR).

  In the method of introducing the partial structure represented by the formula (4) into the main chain, when the ionic functional group is other than a sulfo group, a halogenomethylated polymer using a halogenomethylating agent such as chloromethylmethyl ether is used. A known method of introducing each ionic functional group-containing component via an ether bond using Williamson ether synthesis is preferably used.

  As a method for introducing the partial structure represented by the formula (4) into the main chain, a radical polymerization starting point is formed in the main chain via a linking group, and using the starting point, the formula (16) and / or Alternatively, a method of performing atom transfer radical polymerization or stable free radical polymerization using a styrene derivative represented by the formula (17) as a monomer is preferably used. The linking group and the radical polymerization initiation point can be formed by a known method such as halogenoalkylation of the main chain aromatic ring described above.

  Examples of the starting point of atom transfer radical polymerization include halogenoalkyl, halogenobenzyl, α-haloketone, α-halonitrile, sulfonyl halide and the like, and sulfonyl halide and halogenobenzyl are particularly preferable. “Starting point of stable free radical polymerization” includes 2,2,6,6-tetramethylpiperidinyloxyalkyl, 4-oxo-2,2,6,6-tetramethylpiperidinyloxyalkyl, 4- Hydroxy-2,2,6,6-tetramethylpiperidinyloxyalkyl, 4-amino-2,2,6,6-tetramethylpiperidinyloxyalkyl, 2,2,5,5-tetramethylpyrrolidini Ruoxyalkyl, N, N-di-tert-butylaminooxyalkyl, 1,1,3,3-tetramethylisoindoline-oxyalkyl, N-tert-butyl-N- (2-methyl-1-phenylpropyl) Aminooxyalkyl and the like, and 2,2,6,6-tetramethylpiperidinyloxyalkyl and 4-oxo-2,2,6,6-tetramethylpiperidinyloxyalkyl are particularly preferred. Arbitrariness.

Although the preferable example of this coupling group and radical polymerization starting point is illustrated below, this invention is not limited to these. Incidentally, L _p in compound represents a connecting portion between the polymer backbone.

The following are mentioned as a solvent at the time of performing radical polymerization.
1) 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.
2) Aprotic amide solvents N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N -Methylcaprolactam, hexamethylphosphorotriamide and the like.
3) Amine solvents pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine etc.
4) Other solvents: dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole and the like.

  Among the above-mentioned solvents, particularly preferred solvents include the aprotic amide solvent described in the above item 2) and the dimethyl sulfoxide and sulfolane described in the item 4). N, N-dimethylacetamide, N, N-diethylacetamide, N -Methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane are particularly preferred. These solvents may be used alone or in combination of two or more.

  Nitrogen, helium, neon, and argon are used as the reaction atmosphere, and there is no particular limitation, but an inert gas such as nitrogen or argon is particularly preferable.

  As a method for introducing the partial structure represented by the formula (5) into the main chain, a known method using Williamson ether synthesis after halomethylation of the main chain aromatic ring can be used.

  In the case of synthesizing the polymer series A using the method A-1, examples of the polymer linking method to the carbon material include three methods represented by (Method A1-1) to (Method A1-3). Any of these methods can be preferably used. Hereinafter, (Method A1-1) to (Method A1-3) will be described in detail.

(Method A1-1)
Method A1-1 introduces the polymer main chain formation and at least one partial structure selected from the formulas (3) to (5) and a connecting portion with the carbon material by the above method, and the polymer is converted into the carbon material. It is a method of connecting.
(Method A1-2)
In method A1-2, the main chain of the polymer is formed by the above method, the main chain of the polymer is connected to the carbon material by one connection point, and then a connection site with the carbon material is further introduced to perform the second-stage connection reaction. And then introducing at least one partial structure selected from the formulas (3) to (5).
(Method A1-3)
In the method A1-3, by forming the polymer main chain by the above method in the presence of the carbon material, the formation of the polymer main chain and the connection to the carbon material by one connection point are simultaneously performed, and then the formula ( In this method, at least one partial structure selected from 3) to (5) and a connecting portion with a carbon material are introduced to perform a second-stage connecting reaction.

Method A-2
Method A-2 includes a step of polymerizing one or more compounds selected from the compound represented by Formula (13), the compound represented by Formula (14), and the compound represented by Formula (15). It is. Here, each of the compound represented by the formula (13), the compound represented by the formula (14), and the compound represented by the formula (15) may be used alone, or two or more of them may be used. It may be used. These compounds will be described.

Formula (13)

（式（１３）中、Ｘ⁴は単結合または２価の連結基であり、Ｒ⁶およびＲ⁷はそれぞれ芳香環を含む２〜６価の連結基を表す。Ｂ⁶およびＢ⁷はそれぞれ単結合または２〜６価の連結基を表す。Ａ⁵およびＡ⁶はそれぞれイオン性官能基である。ｎ₁₉およびｎ₂₀はそれぞれ１〜５の整数を表し、ｎ₂₁およびｎ₂₂はそれぞれ０〜４の整数を表し、ｎ₂₁とｎ₂₂の和は２以上の整数である。Ｚ¹およびＺ²は、それぞれ、水酸基、ハロゲン基、アルキルスルホネート基またはニトロ基を表す。）

(In Formula (13), X ⁴ is a single bond or a divalent linking group, and R ⁶ and R ⁷ each represent a divalent to hexavalent linking group containing an aromatic ring. B ⁶ and B ⁷ are each a single bond. Represents a bond or a bivalent to hexavalent linking group, A ⁵ and A ⁶ each represent an ionic functional group, n ₁₉ and n ₂₀ each represent an integer of 1 to 5, and n ₂₁ and n ₂₂ each represents 0 to 4 represents an integer of 4, and the sum of n ₂₁ and n ₂₂ is an integer of 2 or more, and Z ¹ and Z ² each represent a hydroxyl group, a halogen group, an alkyl sulfonate group, or a nitro group.

In formula (13), X ⁴ is preferably composed of a single bond or —C (Q ¹⁰¹ Q ²⁰² ) —, —O—, —CO—, —S—, —SO— and —SO ₂ —. It is a divalent group consisting of one or a combination of two or more selected from the group. Q ¹⁰¹ and Q ²⁰² each represent a hydrogen atom or a substituent, and preferred examples of the substituent include a fluorine atom, a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, and a phenyl group. Q ¹⁰¹ and Q ²⁰² are preferably the same.
R ⁶ and R ⁷ are divalent to hexavalent linking groups containing an aromatic ring, and the total number of carbon atoms constituting the aromatic ring is preferably 1-50, more preferably 1-30, and even more preferably 1-15. . Further, the hydrogen atom on the aromatic ring may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention.
Examples of preferred structures of R ⁶ and R ⁷ are shown below. ^{Here, -B 6 - (A 5)} n 19 and -B ⁷ - although not specifically described in the structural formulas for the connecting portion between (A ⁶⁾ n _20, at any position on the aromatic ring A desired number may be linked, and in the following structural formula, it is shown as a divalent linking group structure. ^{Here, -B 6 - (A 5)} n 19 or ^{-B 7 - (A 6) n} 20 is preferably linked 1-4 respectively, more preferably are you 1-2 linked It is particularly preferable that one is connected.
Among these, (A-2), (A-5), (A-8), and (A-12) are more preferable, and (A-1) and (A-4) are particularly preferable.

Z ¹ and Z ² are each preferably a hydroxyl group, a fluorine atom, a chlorine atom, a methanesulfonate group, or a p-toluenesulfonate group.
B ⁶ and B ⁷ each have the same meaning as B ¹ in formula (3), and the preferred range is also the same.
A ⁵ and A ⁶ have the same meaning as A ¹ in formula (3), and the preferred range is also the same.
n ₁₉ and n ₂₀ are preferably each an integer of 1 to 4, n ₂₁ and n ₂₂ are preferably each represent an integer of 1-3. The sum of n ₂₁ and n ₂₂ is preferably 2 to 4. When n _{19 to} n ₂₂ is 2 or more and B ⁶ , B ⁷ , A ⁵ and / or A ⁶ is 2 or more, these B ⁶ , B ⁷ , A ⁵ and / or A ⁶ are respectively May be the same or different.
Although the preferable example of Formula (13) is illustrated below, this invention is not limited to these.

Formula (14)

（式（１４）中、Ｚ³およびＺ⁴は、それぞれ、水酸基、ハロゲン基、アルキルスルホネート基またはニトロ基を表し、Ｒ⁸は芳香環を含む基を表す。）

(In formula (14), Z ³ and Z ⁴ each represent a hydroxyl group, a halogen group, an alkyl sulfonate group or a nitro group, and R ⁸ represents a group containing an aromatic ring.)

In formula (14), R ⁸ is preferably a divalent linking group containing an aromatic ring, has the same definition as R ³ in formula (2), and the preferred range is also the same.
Z ³ and Z ⁴ are each preferably a hydroxyl group, a fluorine atom, a chlorine atom, a methanesulfonate group, or a p-toluenesulfonate group.

  Specific examples of the compound represented by the formula (14) include hydroquinone, resorcin, 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-hexylhydroquinone, 2-octylhydroquinone, 2 -Decanyl hydroquinone, 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'-dihydride Roxybiphenyl, 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'-tetra Fluoro-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, '-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'-dihi Roxydiphenyl 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'-dihydroxy Diphenyl 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′-dihydroxydiphenylsulfone, 2,2′-dihydroxydiphenylsulfone, 3,3′-dimethyl-4,4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4,4 '-Dihydroxydiphenylsulfone, 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone, 3,3', 5,5'-tetrachloro-4,4'-dihydroxydiphenylsulfone, 3,3'-dibromo -4,4'-dihydroxydiphenylsulfone, 3,3 ', 5,5'-tetrabromo-4,4'-dihydroxydiphenyls Hong, 3,3′-difluoro-4,4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetrafluoro-4,4′-dihydroxydiphenylsulfone, 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-hydroxy Phenyl) -1,3-diisopropylbenzene, 4,4′-dichlorodiphenylsulfone, 2,2′-dichlorodiphenylsulfone, 3,3′-dimethyl-4,4′-dichlorodiphenylsulfone, 3,3 ′, 5 , 5′-tetramethyl-4,4′-dichlorodiphenyl sulfone, 3,3′-dihydroxy-4,4′-dichlorodiphenyl sulfone, 3,3′-dibromo-4,4′-dichlorodiphenyl sulfone, 3, 3'-difluoro-4,4'-dichlorodiphenyl sulfone, 3,3 ', 5,5'-tetrafluoro-4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 2,2'- Difluorodiphenyl sulfone, 3,3′-dimethyl-4,4′-fluorodiphenyl sulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-difluoro Diphenylsulfone, 3,3′-dihydroxy-4,4′-difluorophenylsulfone, 3,3′-dibromo-4,4′-difluorodiphenylsulfone, 3,3′-difluoro-4,4′-difluorodiphenylsulfone 3,3 ′, 5,5′-tetrafluoro-4,4′-difluorodiphenyl sulfone, perfluorobiphenyl, 4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-dihydroxybenzophenone 3,3′-difluorobenzophenone, 3,3′-dichlorobenzophenone, 3,3′-dihydroxybenzophenone, 4,4′-difluoro-3,3′-dimethylbenzophenone, 4,4′-dichloro-3,3 Examples include '-dimethylbenzophenone.

Formula (15)

（式（１５）中、Ｘ⁵は単結合または２価の連結基であり、Ｒ⁹およびＲ¹⁰はそれぞれ芳香環を含む基を表す。Ｅ⁶、Ｅ⁷およびＥ⁸はそれぞれ酸素透過性の高い置換基を表す。ｎ₂₃、ｎ₂₄およびｎ₂₅はそれぞれ０〜４の整数を表し、ｎ₂₃とｎ₂₄とｎ₂₅の和は１以上である。Ｚ⁵およびＺ⁶は、それぞれ、水酸基、ハロゲン基、アルキルスルホネート基またはニトロ基を表す。）

(In Formula (15), X ⁵ is a single bond or a divalent linking group, and R ⁹ and R ¹⁰ each represent a group containing an aromatic ring. E ⁶ , E ⁷ and E ⁸ are each oxygen-permeable. N ₂₃ , n ₂₄ and n ₂₅ each represents an integer of 0 to 4, and the sum of n ₂₃ , n ₂₄ and n ₂₅ is at least 1. Z ⁵ and Z ⁶ are each a hydroxyl group Represents a halogen group, an alkyl sulfonate group or a nitro group.)

In formula (15), X ⁵ has the same meaning as X ^{1 in} formula (2), and the preferred range is also the same.
R ⁹ and R ¹⁰ are preferably divalent to hexavalent linking groups containing an aromatic ring, and have the same meanings as R ⁶ and R ^{7 in} formula (13), and B ^6- (A ⁵ ) _n19 and B ^The preferred range is the same as R ⁶ and R ⁷ _except that the linking site with _7- (A ⁶ ) _n20 is _replaced with the linking site with E ⁶ and E ⁸ .
Z ⁵ and Z ⁶ are each preferably a hydroxyl group, a fluorine atom, a chlorine atom, a methanesulfonate group, or a p-toluenesulfonate group.
n ₂₃ , n ₂₄ and n ₂₅ each represent an integer of 0 to 4, and the sum of n ₂₃ , n ₂₄ and n ₂₅ is 1 or more.
E ⁶ , E ⁷ and E ⁸ each represent a substituent having high oxygen permeability, each having the same meaning as E ¹ in formula (5), and the preferred range is also the same.
When n ₂₃ , n ₂₄ or n ₂₅ is 2 or more, each E ⁶ , E ⁷ or E ⁸ may be the same or different.
Although the preferable example of Formula (15) is illustrated below, this invention is not limited to these.

  When synthesizing the polymer series A using the method A-2, as the polymer series A linking method to the carbon material, for example, two methods represented by (Method A2-1) and (Method A2-2) Any of these methods can be preferably used. Hereinafter, (Method A2-1) and (Method A2-2) will be described in detail.

(Method A2-1)
In method A2-1, after the formation of the polymer main chain by the above-described method, a plurality of connecting parts with the carbon material are introduced into the polymer series A, and the polymer series A is connected to the carbon material via a plurality of connecting points. It is a method of connecting.
(Method A2-2)
In the method A2-2, the polymer main chain is formed by the above-described method in the presence of the carbon material, so that the formation of the polymer main chain and the connection to the carbon material at one connection point are simultaneously performed, and then the polymer series In this method, a plurality of connecting portions with a carbon material are introduced into A, and the polymer series A is connected to the carbon material through a plurality of connecting points in the second-stage reaction.

The connecting part with the carbon material in the polymer series A, and the method of introducing the connecting part into the polymer series A The connecting part with the carbon material in the polymer series A and the introducing method of the connecting part into the polymer series A include: Broadly divided as follows.
(1) Halogenobenzyl moiety The halogenobenzyl moiety reacts with a hydroxyl group in the carbon material by nucleophilic substitution and is linked to the carbon material. Further, the halogenobenzyl moiety is present in a catalyst used for atom transfer radical polymerization (for example, the catalyst described in Chem. Rev. 2001, 101, 2921-2990) such as a 2,2′-bipyridine complex of copper (I) halide. In order to generate carbon radicals underneath, it is linked to the carbon material by a radical trapping reaction.
The halogenobenzyl moiety is obtained by halogenomethylating the aromatic ring of the main chain of the polymer series A using a halogenomethylating agent such as chloromethylmethyl ether.
(2) Sulfonyl halide moiety The sulfonyl halide moiety is a catalyst used for atom transfer radical polymerization such as 2,2′-bipyridine complex of copper (I) halide (for example, described in Chem. Rev. 2001, 101, 2921-2990). In order to generate radicals in the presence of a catalyst, it is linked to a carbon material by a radical trapping reaction.
The method for introducing a sulfonyl halide moiety can be obtained by allowing chlorosulfonic acid or the like to act on the aromatic ring of the main chain of the polymer series A.
(3) 2,2,6,6-tetramethylpiperidinyloxyalkyl derivative moiety Introduced an initiator for stable free radical polymerization such as 2,2,6,6-tetramethylpiperidinyloxyalkyl derivative Then, carbon radicals are generated by heating and are linked to the carbon material by radical trapping reaction. Preferred examples of the derivative are the same as the preferred examples of the “starting point of stable free radical polymerization” described above.
As for the method of introducing the derivative moiety, the aromatic ring of the main chain of the polymer series A can be halogenomethylated using a halogenomethylating agent such as chloromethylmethyl ether, and the derivative can be introduced by a nucleophilic substitution reaction. .
(4) Diazonium salt site When a diazonium salt is formed from an aniline derivative in the presence of a carbon material, radicals generated by the decomposition of the diazonium salt are trapped in the carbon material and linked to the carbon material. As a method for introducing the diazonium salt, the aromatic ring of the main chain of the polymer series A is halogenomethylated using a halogenomethylating agent such as chloromethylmethyl ether, and an aniline derivative is introduced by a nucleophilic substitution reaction, followed by sodium nitrite. Or a method of forming a main chain of the polymer series A using a monomer having a nitro group, reducing the nitro group to aniline with iron under acidic conditions, and reacting with sodium nitrite.
(5) Peracid ester site When the peracid ester is heated, a carbon radical is generated together with a decarboxylation reaction, and is linked to a carbon material by a radical trapping reaction. Examples of the method for introducing a peracid ester include a method in which a carboxylic acid is introduced into the main chain of the polymer series A, an acid chloride is formed with thionyl chloride, and then reacted with a peroxide such as tert-butyl hydroperoxide. .
(6) Azo compound derivative site An azo compound is also decomposed by heating to generate a carbon radical, and is linked to a carbon material by a radical trapping reaction. Examples of the method for introducing the azo compound include a method in which the main chain of the polymer series A is halogenomethylated and reacted with an azo compound derivative such as 4,4′-azobis (4-cyanopentanol).
(7) Hydroxyl group-containing site The hydroxyl group-containing site reacts with tetravalent cerium ions under acidic conditions to generate carbon radicals or oxygen radicals, and is linked to the carbon material by radical trapping reaction. Examples of the method for introducing a hydroxyl group-containing site include a method in which the main chain of the polymer series A is hydroxymethylated.

  When the above linking groups are classified according to the reaction format, the linking site by nucleophilic substitution reaction is (1) a halogenobenzyl site, the linking site by radical trapping is (1) a halogenobenzyl site, (2) a sulfonyl halide site, (3) 2, 2,6,6-tetramethylpiperidinyloxyalkyl derivative moiety, (4) diazonium salt, (5) peracid ester, (6) azo compound derivative, (7) hydroxyl group-containing moiety, It can be preferably used. In addition, any of the sites (1) to (7) can easily generate radicals, and the sites (1) to (7) may be referred to as radical generating groups hereinafter. As the amount of introduction of the sites (1) to (7), it is preferable that one or more is introduced with respect to eight repeating units represented by the formula (2). The repeating unit 4 represented by the formula (2) It is more preferable that one or more is introduced per one, and it is particularly preferable that one or more is introduced for two repeating units represented by the formula (2).

Structure of polymer series B

（式(６)中、Ｗ¹¹、Ｗ¹²およびＷ¹³はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表す。式(７)中、Ｂ³は単結合または２〜６価の連結基を表し、Ａ²はイオン性官能基を表し、ｎ₇は１〜５の整数である。式(８)中、Ｅ²は酸素透過性の高い置換基を表す。）

(In the formula (6), W ¹¹ , W ¹² and W ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. In the formula (7), B ³ is a single bond or 2-6. Represents a valent linking group, A ² represents an ionic functional group, and n ₇ represents an integer of 1 to 5. In formula (8), E ² represents a substituent having high oxygen permeability.

In formula (6), W ¹¹ , W ¹² and W ¹³ are each preferably a hydrogen atom, a halogen atom or an alkyl group.
When W ¹¹ , W ¹² and W ¹³ are halogen atoms, each is preferably a chlorine atom or a fluorine atom, more preferably a fluorine atom.
When W ¹¹ , W ¹² and W ¹³ are alkyl groups, each may be a linear, branched or cyclic alkyl group, and the carbon number thereof is preferably 1-20, more preferably 1-6. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group, a decyl group, a cyclopropyl group, a cyclohexyl group, and a cyclododecyl group.
When W ¹¹ , W ¹² and W ¹³ are aryl groups, examples thereof include a substituted or unsubstituted phenyl group and naphthyl group having 6 to 20 carbon atoms.
When W ¹¹ , W ¹² and W ¹³ are heterocyclic groups, each is a substituted or unsubstituted hetero 6-membered ring (eg, pyridyl group, morpholino group, etc.), substituted or unsubstituted hetero 5-membered ring (furyl group, A preferred example is a thiophene group.
The repeating unit represented by formula (10) may contain only one type, or may contain two or more types.

  The number of repeating units of the formula (6) is preferably 2 to 2000, more preferably 5 to 1000, and particularly preferably 10 to 400.

In formula (7), B ³ has the same meaning as B ^{1 in} formula (3), and the preferred range is also the same.
A ² represents an ionic functional group and has the same meaning as A ^{1 in} formula (3), and the preferred range is also the same. When n ₆ is 2 or more, two or more A ^{2 s} may be the same or different.

  The amount introduced into the polymer main chain of the formula (7) is preferably such that the content of the introduced ionic functional group is 0.1 meq / g to 7 meq / g, 0.5 meq / g to 4 meq. / G is more preferable, and an amount of 1 meq / g to 3 meq / g is particularly preferable.

Wherein (8), E ² is a substituent of high oxygen permeability, has the same meanings as E ¹ of the formula (5), and the preferred range is also the same.

  The weight average molecular weight of the polymer of the polymer series B is preferably 500 to 200,000, more preferably 1000 to 100,000, and particularly preferably 1500 to 50,000.

Production method of polymer series B and introduction method to carbon material Examples of the production method of polymer series B include: A method of introducing a partial structure represented by formula (7) or formula (8) into an aromatic ring of the main chain after forming a main chain containing a repeating unit of formula (6) (hereinafter, this method is referred to as method B- 1), and 2. And a method comprising polymerizing the compound represented by formula (16) and the compound represented by formula (17) (hereinafter, this method is referred to as method B-2), and any of these methods is preferably used. be able to. In addition, the method of introducing the polymer series B into the carbon material differs depending on whether B-1 is used or B-2 is used as the production method of the polymer series B. Hereinafter, the production methods B-1 and B-2 of the polymer series B and the method of introducing the polymer series B into the carbon material when using the respective production methods will be described in detail.

Method B-1
Method B-1 is a method of introducing a partial structure represented by formula (7) or formula (8) into an aromatic ring of the main chain after forming a main chain containing a repeating unit of formula (6). is there. Here, as a method for forming the main chain portion, a known method such as radical polymerization, cation polymerization or anion polymerization using a styrene derivative as a monomer can be used.

  For introducing the partial structure represented by formula (7) into the main chain, Friedel-Crafts reaction of sultones, halomethylation of the main chain aromatic ring, sulfonation reaction with sodium sulfite, main chain aromatic ring After halomethylation, a known method such as introduction of a sulfo group by Williamson ether synthesis can be used.

  As a method for introducing the partial structure represented by the formula (8) into the main chain, a known method using Williamson ether synthesis after halomethylation of the main chain aromatic ring can be used.

  When synthesizing the polymer series B using the method B-1, examples of the polymer linking method to the carbon material include two methods represented by (Method B1-1) and (Method B1-2). Any of these methods can be preferably used. Hereinafter, (Method B1-1) and (Method B1-2) will be described in detail.

(Method B1-1)
In the method B1-1, when a polymer main chain is formed, for example, 4-chloromethylstyrene is copolymerized to introduce a plurality of linking sites, and after connecting the polymer series B to a carbon material via a plurality of linking points, the formula (7 ) Or a partial structure represented by the formula (8).
(Method B1-2)
Method B1-2 is a method in which a radical polymerization initiation point is formed in a carbon material, and atom transfer radical polymerization or stable free radical polymerization is performed using a styrene derivative as a monomer using the initiation point.・ Connecting to a carbon material at one connection point ・ Introducing a connection site used for the second-stage connection reaction at the same time, and connecting to the carbon material through a plurality of connection points by the second-stage connection reaction, In this method, a partial structure represented by the formula (7) or the formula (8) is introduced into the polymer main chain grafted to the carbon material.

Although the preferable example of the starting point of the radical polymerization formed in a carbon material below and a coupling group with a carbon material is illustrated below, this invention is not limited to these. In addition, L _C in the compound represents a connecting portion with the carbon material.

Method B-2
Method B-2 is a method including a step of polymerizing the compound represented by formula (16) and the compound represented by formula (17). As for the compound represented by Formula (16) and the compound represented by Formula (17), only 1 type may respectively be used, and 2 or more types may be used. Hereinafter, these compounds will be described.

（式（１６）および（１７）中、Ｗ²¹、Ｗ²²、Ｗ²³、Ｗ²⁴、Ｗ²⁵およびＷ²⁶はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表し、Ｂ⁸は単結合または２〜６価の連結基を表し、Ａ⁷はイオン性官能基を表し、ｎ₂₆は１〜５の整数を表し、ｎ₂₇は１〜５の整数を表す。Ｅ¹⁰は酸素透過性の高い置換基を表し、ｎ₂₈は１〜５の整数を表す。）

(Expressed in the formula (16) and ^{(17), W 21, W} 22, W 23, W 24, W 25 and W ²⁶ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, B ⁸ Represents a single bond or a bivalent to hexavalent linking group, A ⁷ represents an ionic functional group, n ₂₆ represents an integer of 1 to 5, n ₂₇ represents an integer of 1 to 5. E ¹⁰ represents oxygen Represents a highly permeable substituent, and n ₂₈ represents an integer of 1 to 5.)

In formula (16) and formula (17), W ²¹ , W ²² , W ²³ , W ²⁴ , W ²⁵ and W ²⁶ are respectively synonymous with W ¹¹ in formula (6), and the preferred range is also synonymous. .
B ⁸ has the same meaning as B ^{1 in} formula (3), and the preferred range is also the same.
A ⁷ represents an ionic functional group and has the same meaning as A ¹ in formula (3), and the preferred range is also the same.
E ¹⁰ represents a substituent having high oxygen permeability, and has the same meaning as E ¹ in formula (5), and the preferred range is also the same.
n ₂₆ is preferably an integer of 1 to 4. n ₂₇ and n ₂₈ are preferably each an integer of 1 to 3.
When n ₂₆ , n ₂₇ and n ₂₈ are 2 or more and A ⁷ , B ⁸ and / or E ¹⁰ are 2 or more, each A ⁷ , B ⁸ and / or E ¹⁰ may be the same Good or different,
Although the preferable example of Formula (16) and Formula (17) is illustrated below, this invention is not limited to these.

  For the polymerization of the compounds represented by the formulas (16) and (17), radical polymerization, cationic polymerization, anionic polymerization, and coordination polymerization are preferably used, radical polymerization or cationic polymerization is more preferable, and radical polymerization is more preferable. Among radical polymerizations, living radical polymerization such as atom transfer radical polymerization and stable free radical polymerization is most preferable. The polymerization is preferably used for random copolymerization or block copolymerization. The composition ratio X of the component derived from the compound represented by formula (16) and the component derived from the compound represented by formula (17) contained in the produced polymer is preferably 0 to 10, preferably 0 to 5. More preferably, it is particularly preferably 0-2.

  When the polymer series B is synthesized using the method B-2, there are (Method B2-1) and (Method B2-2) as a method for introducing a polymer into the carbon material. Hereinafter, these will be described.

(Method B2-1)
Method B2-1 forms a starting point of radical polymerization in the carbon material, and using the starting point, the compound represented by formula (16), the compound represented by formula (17), and 4-chloromethylstyrene Performs atom transfer radical polymerization or stable free radical polymerization using as a monomer to form the main chain of the polymer series B, to connect to a carbon material at one point, and to introduce a connecting site used for the second-stage connecting reaction Is performed at the same time, and is connected to the carbon material through a plurality of connection points by a second-stage connection reaction. Here, it is preferable to use the compound shown above as the starting point of radical polymerization formed in the carbon material and the linking group with the carbon material.

(Method B2-2)
Method B2-2 copolymerizes the compound represented by formula (16), the compound represented by formula (17) and 4-chloromethylstyrene to form a polymer main chain and introduce a plurality of linking sites. The polymer series B is connected to the carbon material through a plurality of connection points.

The connecting part with the carbon material in the polymer series B, and the method of introducing the connecting part into the polymer series B. The connecting part with the carbon material in the polymer series B and the introducing method of the connecting part into the polymer series B include: Broadly divided as follows.
(1) Halogenobenzyl moiety The halogenobenzyl moiety reacts with a hydroxyl group in the carbon material by nucleophilic substitution and is linked to the carbon material. Further, the halogenobenzyl moiety is present in a catalyst used for atom transfer radical polymerization such as a 2,2′-bipyridine complex of copper (I) halide (for example, a catalyst described in Chem. Rev. 2001, 101, 2921-2990). In order to generate carbon radicals underneath, it is linked to the carbon material by a radical trapping reaction. Examples of the method for introducing the halogenobenzyl moiety include a method of copolymerizing 4-chloromethylstyrene.
(2) Sulfonyl halide moiety The sulfonyl halide moiety is a catalyst used for atom transfer radical polymerization such as 2,2′-bipyridine complex of copper (I) halide (for example, described in Chem. Rev. 2001, 101, 2921-2990). In order to generate radicals in the presence of a catalyst, it is linked to a carbon material by a radical trapping reaction.
Examples of the method for introducing a sulfonyl halide moiety include a method in which p-styrenesulfonic acid is copolymerized and treated with thionyl chloride.
(3) 2,2,6,6-tetramethylpiperidinyloxyalkyl derivative moiety Introduced an initiator for stable free radical polymerization such as 2,2,6,6-tetramethylpiperidinyloxyalkyl derivative Then, carbon radicals are generated by heating and are linked to the carbon material by radical trapping reaction. Preferred examples of the derivative are the same as the preferred examples of the “starting point of stable free radical polymerization” described above.
As for the method of introducing the derivative site, for example, 4-chloromethylstyrene can be copolymerized and the derivative can be introduced by a nucleophilic substitution reaction.
(4) Diazonium salt site When a diazonium salt is formed from an aniline derivative in the presence of a carbon material, radicals generated by the decomposition of the diazonium salt are trapped in the carbon material and linked to the carbon material. Examples of the method for introducing a diazonium salt include a method in which 4-chloromethylstyrene is copolymerized, an aniline derivative is introduced by a nucleophilic substitution reaction, and then reacted with sodium nitrite.
(5) Peracid ester site When the peracid ester is heated, a carbon radical is generated together with a decarboxylation reaction, and is linked to a carbon material by a radical trapping reaction. Examples of the method for introducing the peracid ester include a method in which 4-vinylbenzoic acid is copolymerized, an acid chloride is formed with thionyl chloride, and then reacted with a peroxide such as tert-butyl hydroperoxide.
(6) Azo compound derivative site An azo compound is also decomposed by heating to generate a carbon radical, and is linked to a carbon material by a radical trapping reaction. Examples of the method for introducing the azo compound include a method in which 4-chloromethylstyrene is copolymerized and reacted with an azo compound derivative such as 4,4′-azobis (4-cyanopentanol).
(7) Hydroxyl group-containing site The hydroxyl group-containing site reacts with tetravalent cerium ions under acidic conditions to generate carbon radicals or oxygen radicals, and is linked to the carbon material by radical trapping reaction. Examples of the method for introducing a hydroxyl group-containing site include a method in which the main chain of the polymer series A is hydroxymethylated.

  When the above linking groups are classified by reaction type, the linking site by nucleophilic substitution reaction is (1) a halogenobenzyl moiety, the linkage by radical trapping is (1) a halogenobenzyl moiety, (2) a sulfonyl halide moiety, (3) 2, 2 , 6,6-tetramethylpiperidinyloxyalkyl derivative site, (4) diazonium salt site, (5) peracid ester site, (6) azo compound derivative site, (7) hydroxyl group-containing site, Either can be preferably used. In addition, any of the sites (1) to (7) can easily generate radicals, and the sites (1) to (7) may be referred to as radical generating groups hereinafter. As the amount of introduction of the sites of (1) to (7), it is preferable to introduce at least one repeating unit represented by the formula (6), and the repeating unit represented by the formula (6) 10 It is more preferable to introduce one or more per one, and it is particularly preferable to introduce one or more to five repeating units represented by the formula (2).

(7) Method for supporting catalyst particles The catalyst material for a fuel cell of the present invention is preferably used as a carrier for a catalyst metal (electrode catalyst) such as platinum particles. Examples of the method for supporting the catalytic metal include a thermal reduction method, a sputtering method, a pulse laser deposition method, a vacuum deposition method, and the like (for example, International Publication No. WO2002 / 0545414).

  In the present invention, as a method for producing a catalyst material for a fuel cell, there are a method of supporting a catalytic metal after introducing an ionic functional group into the carbon material, and a method of introducing an ionic functional group after supporting the catalytic metal on the carbon material. However, either method is preferably used. Alternatively, by introducing an ionic functional group into a commercially available catalyst-supported carbon material (for example, platinum-supported ketjen black, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., or platinum-supported XC-72, manufactured by E-TEK). can get.

  When an ionic functional group is introduced after a catalytic metal is supported on a catalyst material for fuel cells, or when an ionic functional group is introduced into a commercially available catalyst-supporting carbon material, a method of performing the reaction under an oxygen-free condition or the reaction is difficult. A method of performing in a flammable solvent or a method of adding a flame retardant to the reaction system is preferable for safety. Examples of the method for carrying out the reaction under an oxygen-free condition include a method for carrying out the reaction in an inert gas atmosphere. Examples of the inert gas include helium, argon, neon, nitrogen, and the like, and argon and nitrogen are particularly preferable.

  Nonflammable solvents include dichloromethane, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetra. Examples include chloroethane and water. These are appropriately selected and used in consideration of the solubility of the reaction reagent, the reaction temperature, the boiling point of the solvent, and the like. In addition, these solvents may be used alone or in combination.

 Flame retardants include hexamethylphosphoramide, trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, bisphenol A bis (diphenyl) phosphate, hydroquinol bis (diphenyl) phosphate, phenyl dialkyl. Examples include phosphoric acid ester-based flame retardants such as silenyl phosphate, xylenyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, and 2-ethylhexyl diphenyl phosphate. These may be used alone or in combination. The proportion of these flame retardants added is preferably 5% or more, more preferably 10% or more, and particularly preferably 15% or more with respect to the reaction solvent. Moreover, you may use as a reaction solvent about the liquid thing in the said flame retardant.

  Further, the fuel cell catalyst material of the present invention is only a catalyst material in which the polymer (X) is introduced to the surface of the carbon material through a plurality of connection points (hereinafter, such a catalyst material is referred to as catalyst material A). Alternatively, a mixture of the catalyst material A and a catalyst material having no polymer (X) on the surface (hereinafter, such a catalyst material will be referred to as catalyst material B) may be used. When the mixture of the catalyst material A and the catalyst material B is used, the catalyst material A is prevented from being corroded by sacrificial corrosion of the catalyst material B, and a material superior in durability can be obtained. When the mixture of the catalyst material A and the catalyst material B is used, the content of the catalyst material A is preferably 50 to 95% by weight, more preferably 70 to 95% by weight, and particularly preferably 80 to 95% by weight.

(8) Fuel cell The fuel cell catalyst material of the present invention is applied to a fuel cell electrode, an electrode membrane assembly (hereinafter referred to as “MEA”), and a fuel cell using the electrode membrane assembly. Can be used.
FIG. 1 shows an example of a schematic cross-sectional view of the electrode membrane assembly of the present invention. The MEA 10 includes a solid electrolyte membrane 11 and an anode electrode 12 and a cathode electrode 13 that are opposed to each other with the solid electrolyte membrane 11 interposed therebetween. The solid electrolyte membrane 11 referred to here is a perfluorocarbon sulfonic acid polymer represented by Nafion (registered trademark), poly (meth) acrylate having a phosphate group in the side chain, sulfonated polyether ether ketone, sulfonated polyether ketone, Heat-resistant aromatic polymers such as sulfonated polyethersulfone, sulfonated polysulfone, and sulfonated polybenzimidazole, sulfonated polystyrene, sulfonated polyoxetane, sulfonated polyimide, sulfonated polyphenylene sulfide, sulfonated polyphenylene oxide, and sulfonated polyphenylene. Specific examples include membranes, and specifically, JP-A No. 2002-110174, JP-A No. 2002-105200, JP-A No. 2004-10777, JP-A No. 2003-132908, and JP-A No. 200. JP-A-179154, JP-A-2004-175997, JP-A-2004-247182, JP-A-2003-147074, JP-A-2004-234931, JP-A-2002-289222, JP-A-2003-208816. And the membrane described in the publication No .. Among these, the membrane described in Nafion 112, Nafion 1135, Nafion 115, Nafion 117, JP-A-2002-110174, and the repeating unit represented by the formula (2) are included as a main chain structure, and The aromatic ring of the main chain is particularly preferably a film made of a polymer in which at least one partial structure selected from the above formulas (3) to (5) is bonded.

  The anode electrode 12 and the cathode electrode 13 are composed of porous conductive sheets (for example, carbon paper) 12a and 13a and catalyst layers 12b and 13b. As the catalyst layers 12b and 13b, the catalyst film of the present invention can be used. Here, the catalyst membrane of the present invention is made of, for example, a dispersion in which the fuel cell catalyst material of the present invention carrying a catalyst metal such as platinum particles is dispersed in a solid electrolyte.

  A method for manufacturing the electrode will be described. A solid electrolyte typified by Nafion is dissolved in a solvent, and a dispersion mixed with the catalyst material for a fuel cell of the present invention carrying a catalyst metal is dispersed. Solvents of the dispersion are heterocyclic compounds (3-methyl-2-oxazolidinone, N-methylpyrrolidone, etc.), cyclic ethers (dioxane, tetrahydrofuran, etc.), chain ethers (diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl) Ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, isopropanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.), many Polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol, poly Pyrene glycol, glycerin, etc.), nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc.), nonpolar solvents (toluene, xylene, etc.), chlorinated solvents (methylene chloride, ethylene chloride, etc.), Amides (N, N-dimethylformamide, N, N-dimethylacetamide, acetamide and the like), water and the like are preferably used, and among these, heterocyclic compounds, alcohols, polyhydric alcohols and amides are preferably used.

  The dispersion method may be a method using stirring, but ultrasonic dispersion, ball mill, or the like can also be used. The resulting dispersion is applied using a coating method such as curtain coating, extrusion coating, roll coating, spin coating, dip coating, bar coating, spray coating, slide coating, or print coating. be able to.

  Application of the dispersion will be described. In the coating step, the dispersion may be used to form a film by extrusion molding, or these dispersions may be cast or applied to form a film. The support in this case is not particularly limited, but preferred examples include a glass substrate, a metal substrate, a polymer film, a reflector and the like. Examples of polymer films include cellulose polymer films such as triacetylcellulose (TAC), ester polymer films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and fluorine such as polytrifluoroethylene (PTFE). Examples thereof include a polymer film and a polyimide film. The coating method may be a known method, for example, using curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, etc. Can do. In particular, when a conductive porous body (carbon paper, carbon cloth) is used as a support, a catalyst electrode can be directly produced.

 These operations can be performed by a film forming machine using a roll such as a calendar roll or a cast roll or a T die, or can be a press forming using a press machine. Further, a stretching process may be added to control film thickness and improve film characteristics.

  The drying temperature of the coating process is related to the drying speed and can be selected according to the properties of the material. Preferably it is -20 degreeC-150 degreeC, More preferably, it is 20 degreeC-120 degreeC, More preferably, it is 50 degreeC-100 degreeC. A short drying time is preferable from the viewpoint of productivity. However, if the drying time is too short, defects such as bubbles and surface irregularities are caused. For this reason, the drying time is preferably 1 minute to 48 hours, more preferably 5 minutes to 10 hours, and further preferably 10 minutes to 5 hours. Control of humidity is also important, and is preferably 25 to 100% RH, more preferably 50 to 95% RH.

  A coating liquid (dispersion) in the coating step preferably has a low content of metal ions, and particularly preferably has a low transition metal ion content, especially iron ions, nickel ions, and cobalt ions. The content of transition metal ions is preferably 500 ppm or less, and more preferably 100 ppm or less. Therefore, the solvent used in the above-mentioned process is also preferably a solvent having a low content of these ions.

  Further, the surface treatment may be performed after the coating process. As the surface treatment, rough surface treatment, surface cutting treatment, removal treatment, and coating treatment may be performed, which may improve the adhesion with the solid electrolyte membrane or the porous conductor.

  The thickness of the catalyst layer of the electrode membrane assembly of the present invention is preferably 5 to 200 μm, particularly preferably 10 to 100 μm.

In order to bring the catalyst layers 12b and 13b into close contact with the solid electrolyte membrane 11, the porous conductive sheets 12a and 13a coated (coated) with the catalyst layers 12b and 13b are applied to the solid electrolyte membrane 11 with a hot press method (preferably Pressure bonding at 120 to 130 ° C. and 2 to 100 kg / cm ² ), or after applying the catalyst layers 12b and 13b coated on a suitable support to the solid electrolyte membrane 11 while being transferred, In general, a method of sandwiching between the sheets 12a and 13a is preferably used.

  FIG. 2 shows an example of a fuel cell structure. The fuel cell includes an MEA 10, a pair of separators 21 and 22 that sandwich the MEA 10, and a current collector 17 and a packing 14 made of a stainless steel net attached to the separators 21 and 22. An anode pole side opening 15 is provided in the anode pole side separator 21, and a cathode pole side opening 16 is provided in the cathode pole side separator 22. Gas fuel such as hydrogen and alcohols (such as methanol) or liquid fuel such as an alcohol aqueous solution is supplied from the anode electrode side opening 15, and oxidant gas such as oxygen gas and air is supplied from the cathode electrode side opening 16. Is supplied.

  The fuel cell catalyst material of the present invention is used for the anode electrode and the cathode electrode. The particle size of the normally used active metal is preferably in the range of 2 to 10 nm. By reducing the particle size, the surface area per unit mass can be increased, and the activity is advantageously increased. By doing so, it is possible to more effectively suppress aggregation and difficulty in dispersion.

  The active polarization in the hydrogen-oxygen fuel cell is larger in the cathode electrode (air electrode) than in the anode electrode (hydrogen electrode). This is because the cathode electrode reaction (oxygen reduction) is slower than the anode electrode. For the purpose of improving the activity of the oxygen electrode, various platinum-based binary metals such as Pt—Cr, Pt—Ni, Pt—Co, Pt—Cu, and Pt—Fe can be preferably used. In a direct methanol fuel cell using an aqueous methanol solution as an anode fuel, it is important to suppress catalyst poisoning due to CO that occurs during the oxidation process of methanol. For this purpose, platinum-based binary metals such as Pt—Ru, Pt—Fe, Pt—Ni, Pt—Co, Pt—Mo, Pt—Ru—Mo, Pt—Ru—W, Pt—Ru—Co Platinum group ternary metals such as Pt—Ru—Fe, Pt—Ru—Ni, Pt—Ru—Cu, Pt—Ru—Sn, Pt—Ru—Au can be preferably used.

  As the carbon material for supporting the active metal, the fuel cell catalyst material of the present invention is preferably used.

  The function of the catalyst layer was caused by (1) transporting the fuel to the active metal, (2) providing a field for the oxidation (anode electrode) and reduction (cathode electrode) reaction of the fuel, and (3) redox. (4) transporting protons generated by the reaction to the solid electrolyte. For (1), the catalyst layer needs to be porous so that liquid and gaseous fuel can permeate deeply. (2) is responsible for the active metal catalyst described above, and (3) is also responsible for the fuel cell catalyst material of the present invention. The function (4) is performed by the fuel cell catalyst material of the present invention, but in order to perform a sufficient function, it is preferable to mix a solid electrolyte in the catalyst layer.

  The solid electrolyte of the catalyst layer is not limited as long as it is a solid having a proton donating group, but is a perfluorocarbon sulfonic acid polymer represented by Nafion (registered trademark), and a poly (meth) having a phosphate group in the side chain. Heat-resistant aromatic polymers such as acrylate, sulfonated polyetheretherketone, sulfonated polyetherketone, sulfonated polyethersulfone, sulfonated polysulfone, sulfonated polybenzimidazole, sulfonated polystyrene, sulfonated polyoxetane, sulfonated polyimide Sulfonated polyphenylene sulfide, sulfonated polyphenylene oxide, sulfonated polyphenylene, and the like. Specific examples include JP-A No. 2002-110174, JP-A No. 2002-105200, JP-A No. 2004-10777. JP-A 2003-132908, JP-A 2004-179154, JP-A 2004-175997, JP-A 2004-247182, JP-A 2003-147074, JP-A 2004-234931, Examples thereof include the polymers described in JP-A No. 2002-289222 and JP-A No. 2003-208816. Among these, Nafion, the polymer described in JP-A-2002-110174, and the repeating unit represented by the formula (2) as a main chain structure, and the aromatic ring of the main chain include A polymer in which at least one partial structure selected from the formulas (3) to (5) is bonded is particularly preferable. Use of the same type of material as the solid electrolyte membrane 11 is more advantageous because the electrochemical adhesion between the solid electrolyte membrane 11 and the catalyst layer is increased.

The amount of active metal used is suitably in the range of 0.03 to 10 mg / cm ² from the viewpoint of battery output and economy. The amount of the catalyst material for the fuel cell supporting the active metal is suitably 1 to 10 times the mass of the active metal. 0.1-0.7 times is preferable with respect to the mass of the catalyst material for fuel cells of this invention, and, as for the quantity of the solid electrolyte of a catalyst layer, 0.3-3 times is more preferable.

  It is also called an electrode base material, a permeable layer, or a backing material, and plays a role of collecting current and preventing water from accumulating and deteriorating gas permeation. Usually, carbon paper or carbon cloth is used, and PTFE treatment for water repellency can also be used.

The following four methods are preferable for the production of MEA.
(1) Catalyst layer coating method: a catalyst material for fuel cell of the present invention, a catalyst layer coating liquid (ink) containing a solid electrolyte for a catalyst layer and a solvent is directly applied to both sides of the solid electrolyte membrane 11, and a porous conductive sheet (Thermal) is bonded to produce a 5-layer MEA.
(2) Porous conductive sheet coating method: After a catalyst layer coating solution is applied to the surface of the porous conductive sheet to form a catalyst layer, it is pressure-bonded to the solid electrolyte membrane 11 to produce a MEA having a five-layer structure.
(3) Decal method: After a catalyst layer coating solution is applied onto PTFE to form a catalyst layer, only the catalyst layer is transferred to the solid electrolyte membrane 11 to form a three-layer MEA, and the porous conductive sheet is pressure-bonded. Then, an MEA having a five-layer structure is manufactured.
(4) Post-catalyst loading method: A catalyst layer coating solution obtained by mixing the catalyst material for fuel cells of the present invention not loaded with platinum together with a solid electrolyte for the catalyst layer is applied onto the solid electrolyte membrane 11, the porous conductive sheet or PTFE. After film formation, the solid electrolyte membrane is impregnated with platinum ions, and platinum particles are reduced and precipitated in the membrane to form a catalyst layer. After forming the catalyst layer, the MEA is produced by the above methods (1) to (3).

  The anode fuel that can be used as fuel for the fuel cell using the fuel cell catalyst material of the present invention is hydrogen, alcohols (methanol, ethanol, isopropanol, ethylene glycol, etc.), ethers (dimethyl ether, dimethoxymethane). , Trimethoxymethane, etc.), formic acid, borohydride complexes, ascorbic acid and the like, and hydrogen and methanol are particularly preferred. Examples of the cathode fuel include oxygen (including oxygen in the atmosphere) and hydrogen peroxide.

  The methods for supplying the anode fuel and the cathode fuel to the respective catalyst layers include (1) a method of forced circulation using an auxiliary device such as a pump (active type), and (2) a method not using an auxiliary device ( For example, in the case of a liquid, there are two types, ie, a passive type in which a catalyst layer is exposed to the atmosphere and supplied to the atmosphere in the case of a gas due to capillary action or natural fall, and these can be combined. An active type capable of obtaining a high output is preferable.

  Since the single cell voltage of the fuel cell is generally 1 V or less, the single cells are used by stacking in series according to the required voltage of the load. As the stacking method, “planar stacking” in which single cells are arranged on a plane and “bipolar stacking” in which single cells are stacked via separators having fuel flow paths formed on both sides thereof are used. The latter is suitable for a fuel cell because of its high thermal efficiency and a compact battery. In addition to this, a method of applying MEMS technology, performing fine processing on a silicon wafer, and stacking has been proposed.

  The fuel cell is considered for various uses such as transportation, home use, and portable equipment. For example, preferable transportation applications include automobiles (passenger cars, freight cars, motorcycles, personal beagles), ships, For home use, cogeneration systems, vacuum cleaners, robots, and portable devices include mobile phones, notebook computers, electronic still cameras, PDAs, video cameras, and portable game machines. Furthermore, it can be used for portable generators, outdoor lighting devices, and the like. It can also be preferably used as a power source for industrial or household robots or other toys. Furthermore, it is also useful as a power source for charging secondary batteries and capacitors mounted on these devices.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1 Production of catalyst material for fuel cell (1)
[Production of carbon material M-1]
(Modification of carbon material)
Carbon black (trade name: Carbon ECP, manufactured by Ketjen Black International Co., Ltd.) was used as the carbon material, and the reaction was performed according to the following scheme 1. (In the scheme 1 below, CB indicates a part of carbon black, and two arbitrary points on the surface of one carbon black are noted. The same applies to CB.)

所定量の上記カーボンブラック、Ｎ，Ｎ−ジメチルホルムアミド、ジブロモペンタン、炭酸カリウムを加え、窒素気流下で攪拌しながら１１０℃で２４時間反応した。反応後、生成物を水、次いでアセトンで洗浄し、減圧乾燥して、ブロモペンチル基を導入したカーボン材料ｃ−１を得た。

A predetermined amount of the carbon black, N, N-dimethylformamide, dibromopentane, and potassium carbonate were added, and the reaction was performed at 110 ° C. for 24 hours with stirring under a nitrogen stream. After the reaction, the product was washed with water and then with acetone and dried under reduced pressure to obtain a carbon material c-1 having a bromopentyl group introduced.

(Synthesis of ionic functional group-containing polymer)
According to a known method, a predetermined amount of potassium carbonate, N-methyl-2-pyrrolidone, toluene and bisphenol A and 3,3′-disulfo-4,4′-dichlorodiphenylsulfone disodium salt in a ratio of 20:19 And stirred for 8 hours in an oil bath at 200 ° C. under a nitrogen stream. After the reaction, the reaction solution was poured into a large excess of acetonitrile to obtain a precipitate. The supernatant was removed, and the precipitate was washed with acetonitrile and then dried under reduced pressure to obtain a sulfo group-containing polymer p-1 having a phenol group at the polymer terminal.

(Introduction of ionic functional group-containing polymers into carbon materials)
Reacted according to scheme (2). That is, a predetermined amount of the carbon material c-1, sulfo group-containing polymer p-1, N, N-dimethylacetamide and potassium carbonate were added, and the mixture was stirred at 110 ° C. for 36 hours under a nitrogen stream. After the reaction, the product was washed with water and dried under reduced pressure to obtain a carbon material c-2 into which a sulfo group-containing polymer was introduced via the linking group represented by (B-9).

(Polymer multi-point connection formation)
Performed according to Scheme (3). That is, thionyl chloride was added to a predetermined amount of the carbon material c-2 and refluxed for 24 hours under a nitrogen stream. After the reaction, the pressure is reduced to remove thionyl chloride, and then a predetermined amount of N-methyl-2-pyrrolidone, copper (I) chloride and 2,2′-bipyridine are added, and in an oil bath at 150 ° C. under a nitrogen stream. Reacted for 15 hours. After the reaction, water was added to the system, and the mixture was further stirred for 2 hours in an oil bath at 100 ° C., and then the product was separated by filtration. The obtained solid was washed with water and then acetonitrile and dried under reduced pressure. Next, the obtained solid was immersed in an aqueous hexaamine platinum (IV) chloride solution at room temperature for 1 hour, washed and dried, then reduced at 180 ° C. in a hydrogen stream, and platinum was supported on the carbon material. By the above, the catalyst-supporting carbon material (fuel cell catalyst material) M-1 in which the sulfo group-containing polymer is linked by the linking group represented by (B-9) and the linking group represented by (B-70). Got. In addition, when the ESR spectrum of M-1 and c-2 was measured, since the spectrum area of M-1 is larger, the radical trapping reaction proceeds and the linking group represented by (B-70) is linked. Was confirmed to have progressed.

 In scheme (3), the graft chain of M-1 is described as if it has one carbon attachment point for each repeating unit of the graft chain. It was not possible to specify how much and where in the graft chain the linkage by the linking group represented by 70) was present. However, it was confirmed by ESR measurement that at least one linking point represented by (B-70) was present.

[Production of carbon material M-2]
Performed according to Scheme (4). That is, a predetermined amount of carbon material c-2, tin chloride, chloromethyl methyl ether, and 1,1,2,2-tetrachloroethane were added and stirred at 110 ° C. for 24 hours under a nitrogen stream. After the reaction, the product was filtered off, and the resulting powder was washed with chloroform and acetonitrile and dried under reduced pressure. To the obtained powder, copper (I) chloride, 2,2′-bipyridine and N-methyl-2-pyrrolidone were added and stirred in a 160 ° C. oil bath for 10 hours under a nitrogen stream. Thereafter, hydroquinone was added to the reaction system and further stirred for 2 hours. After the reaction, the product was washed with N, N-dimethylacetamide, acetonitrile and water, and then immersed in 1N aqueous sulfuric acid solution at room temperature for 30 minutes. Thereafter, the product was washed with water and dried under reduced pressure. Next, the obtained solid was immersed in an aqueous hexaamine platinum (IV) chloride solution at room temperature for 1 hour, washed and dried, then reduced at 180 ° C. in a hydrogen stream, and platinum was supported on the carbon material. As described above, the sulfo group-containing polymer is a linking group represented by (B-9) and a catalyst-supported carbon material (fuel cell catalyst material) M-2 linked by a linking group represented by (B-43). Got.
In addition, when the ESR spectrum of M-2 and c-2 was measured, since the spectrum area of M-2 was larger, the radical trapping reaction proceeded and the linking group represented by (B-43) was linked. Was confirmed to have progressed.

 In the scheme (4), the graft chain of M-2 is described as if it has one carbon linking point for each repeating unit of the graft chain. 43) It was not possible to specify how much and at what position in the graft chain the linkage by the linking group was present. However, it was confirmed by ESR measurement that at least one or more linking points represented by (B-43) are present.

[Production of carbon material M-3]
(Synthesis of graft polymer)
According to a known method, bisphenol A and 4,4′-dichlorodiphenylsulfone are added at a ratio of 20:19 to a predetermined amount of potassium carbonate, N-methyl-2-pyrrolidone, and toluene, and an oil at 200 ° C. under a nitrogen stream is added. Stir in the bath for 8 hours. After the reaction, the reaction solution was poured into a large excess of acetonitrile to obtain a precipitate. The supernatant was removed and the precipitate was washed with water and then dried under reduced pressure to obtain a polymer main chain p-2.
Next, a carbon material into which a predetermined amount of polymer p-2 was introduced, tin chloride, chloromethyl methyl ether, and 1,1,2,2-tetrachloroethane were added, and the mixture was stirred at 110 ° C. for 6 hours in a nitrogen stream. After the reaction, the product was washed with chloroform and acetonitrile to obtain a polymer p-3 having a chloromethyl group in the side chain.
(Introduction of graft polymer to carbon surface and introduction of sulfo group)
Reaction was performed according to scheme (5) using platinum-supported carbon black (trade name: TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.) (a) as the catalyst-supported carbon material. That is, a predetermined amount of carbon black (a), copper (I) chloride, 2,2′-bipyridine, polymer p-3, N-methyl-2-pyrrolidone was added, and a 150 ° C. hot water bath in a nitrogen stream. Stir for 6 hours. After returning the reaction solution to room temperature, the reaction solution was separated by filtration, and the obtained powder was washed with acetonitrile to obtain a carbon material c-3.
Next, 3-hydroxypropanesulfonic acid sodium salt and sodium hydride were added to N, N-dimethylformamide, and after stirring at room temperature for 30 minutes, carbon material c-3 was added and stirred at 80 ° C. for 12 hours. Thereafter, the reaction solution was separated by filtration, the obtained powder was washed with water, and then immersed in a 1 N aqueous sulfuric acid solution at room temperature for 30 minutes. Thereafter, the product is washed with water, dried under reduced pressure, and a catalyst-carrying carbon material (fuel cell catalyst material) M-3 in which the sulfo group-containing polymer is linked by a linking group represented by (B-43) is obtained. Obtained. In addition, when the ESR spectrum of M-3 and carbon black (a) was measured, since the spectrum area of M-3 is larger, the radical trapping reaction proceeds, and the linking group represented by (B-43) It was confirmed that the connection by

 In the scheme (5), the graft chain of M-3 is described as if it has two carbon connection points for every two repeating units of the graft chain. It was not possible to specify how much and where in the graft chain the linkage by the linking group represented by 43) was present. However, it was confirmed by ESR measurement that at least two or more connecting points by the connecting group represented by (B-43) exist.

[Production of carbon material M-4]
(Synthesis of graft polymer)
Polymer p-4 was obtained in the same manner except that 4,4′-dichlorodiphenylsulfone was replaced with 4,4′-difluorobenzophenone during the synthesis of the graft polymer in the production of carbon material M-3.
(Introduction of graft polymer to carbon surface and introduction of sulfo group)
The carbon material M-4 was obtained in the same manner except that the polymer p-3 was replaced with the polymer p-4 during the introduction of the graft polymer onto the carbon surface and the introduction of the sulfo group in the production of the carbon material M-3. In addition, when the ESR spectrum of M-4 and carbon black (a) was measured, since M-4 has a larger spectrum area, the radical trapping reaction proceeds, and the linking group represented by (B-43) It was confirmed that the connection by

 The graft chain of M-4 is described as if it has two carbon linking points for every two repeating units of the graft chain, but the linking group represented by (B-43) is actually used. It was not possible to specify how much and where the ligation was due to in the graft chain. However, it was confirmed by ESR measurement that at least two or more connecting points by the connecting group represented by (B-43) exist.

[Production of carbon material M-5]
(Synthesis of ionic functional group-containing polymer)
A sulfo group-containing polymer p-5 was obtained in the same manner except that bisphenol A was replaced with 4,4′-dihydroxybiphenyl during the synthesis of the ionic functional group-containing polymer in the production of the carbon material M-1.
(Introduction of ionic functional group-containing polymers into carbon materials)
A carbon material c-4 into which an ion functional group-containing polymer was introduced was obtained in the same manner except that p-1 was replaced with p-5 during the production of the carbon material M-1.
(Polymer multi-point connection formation)
A carbon material M-5 was obtained in the same manner except that c-2 was replaced with c-4 during the production of the carbon material M-1. In addition, when the ESR spectrum of M-5 and c-4 was measured, since the spectrum area of M-5 is larger, the radical trapping reaction proceeds and the linking group represented by (B-70) is linked. Was confirmed to have progressed.

 In addition, although the graft chain of M-5 is described as if it has one connection point with carbon for each repeating unit of the graft chain, it is actually represented by (B-70). It was not possible to determine how much and where in the graft chain the linkage by the linking group was present. However, it was confirmed by ESR measurement that at least one linking point represented by (B-70) was present.

[Production of carbon material M-6]
Carbon material M-6 was obtained by mixing 80% by weight of carbon material M-2 and 20% by weight of commercially available platinum-supported carbon black (trade name: TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.).

[Production of carbon material M-7]
90% by weight of carbon material M-2 and commercially available platinum-supported carbon black (trade name: TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.) were mixed at a ratio of 10% by weight to obtain carbon material M-7.

[Production of carbon material M-8]
(Synthesis of ionic functional group-containing polymer)
A predetermined amount of benzoyl peroxide, 2,2,6,6-tetramethylpiperidine-N-oxyl, N-methyl-2-pyrrolidone, 4-sulfopropyloxystyrene lithium salt, 4-chloromethylstyrene 15: 1 And stirred for 24 hours in a 150 ° C. hot water bath under a nitrogen stream. After returning to room temperature, the reaction solution was poured into a large amount of acetonitrile, and the resulting precipitate was filtered off. This precipitate was washed with acetonitrile and dried under reduced pressure to obtain an ion functional group-containing polymer p-6.

(Introduction of ion functional group-containing polymer onto carbon surface)
Reaction was performed according to Scheme 6 using carbon black (trade name: Carbon ECP, manufactured by Ketjen Black International) as the carbon material. That is, a predetermined amount of carbon black, polymer p-6, and N-methyl-2-pyrrolidone were added and stirred for 6 hours in an oil bath at 150 ° C. under a nitrogen stream. After returning to room temperature, the reaction solution was filtered off, and the resulting powder was washed with N, N-dimethylacetamide and then dried under reduced pressure to obtain carbon material c-5.
Next, copper (I) chloride, 2,2′-bipyridine, and N-methyl-2-pyrrolidone were added to a predetermined amount of the carbon material c-5, and the mixture was stirred at 150 ° C. for 8 hours under a nitrogen stream. The reaction solution was filtered off, and the resulting powder was washed with acetonitrile and water, and then immersed in a 1N aqueous sulfuric acid solution at room temperature for 30 minutes. Thereafter, the product was washed with water and dried under reduced pressure. Next, the obtained solid was immersed in an aqueous hexaamine platinum (IV) chloride solution at room temperature for 1 hour, washed and dried, then reduced at 180 ° C. in a hydrogen stream, and platinum was supported on the carbon material. As described above, the catalyst-supporting carbon material (fuel cell catalyst material) M-8 in which the sulfo group-containing polymer is linked by the linking group represented by (B-69) and the linking group represented by (B-43). Got. In addition, when the ESR spectrum of M-8 and c-5 was measured, since the spectrum area of M-8 is larger, the radical trapping reaction proceeds and the linking group represented by (B-43) is linked. Was confirmed to have progressed.

 Although the graft chain of M-8 is described as if it were a block copolymer, it was actually specified whether it was a random copolymer, block copolymer or alternating copolymer. Not. In addition, each graft chain repeating unit is described as if it has one carbon linking point. Actually, however, linking by the linking group represented by (B-43) is not present in the graft chain. It is not possible to specify how much and where it exists. However, it was confirmed by ESR measurement that at least one or more linking points represented by (B-43) are present.

Comparative Example 1 Carbon material in which a sulfo group-containing polymer is connected by a single connection point
[Production of carbon material R-1]
The carbon material c-2 was impregnated in a 1N sulfuric acid aqueous solution at room temperature for 30 minutes, washed with water, and dried under reduced pressure. Next, the obtained solid was immersed in an aqueous hexaamine platinum (IV) chloride solution at room temperature for 1 hour, washed and dried, then reduced at 180 ° C. in a hydrogen stream, and platinum was supported on the carbon material. The carbon material R-1 was obtained by the above.

Example 2 Fabrication of a fuel cell
[Production Method 1]
A fuel cell was prepared using the catalyst-supported carbon of Example 1. 2 g of each catalyst-supporting carbon material and 15 g of a Nafion solution (5% alcohol aqueous solution) as a binder were mixed and dispersed for 30 minutes with an ultrasonic disperser. The obtained dispersion was coated on carbon paper (thickness 350 μm), dried, and then punched out into a circle having a diameter of 9 mm to produce a catalyst film.
A Nafion 117 membrane was used as the solid electrolyte membrane, and the catalyst membrane obtained above was bonded to both sides of the Nafion 117 membrane so that the coated surface was in contact with the Nafion 117 membrane, and thermocompression bonded by hot pressing to prepare an MEA.

[Production Method 2]
An MEA was produced in the same manner as in Production Method 1, except that the solid electrolyte membrane and the binder were produced from the polymer E-1 composed of the following repeating units. When the polymer E-1 was used as a binder, a polymer having a weight average molecular weight of 30,000 to 100,000 was used. When the polymer E-1 was used as a solid electrolyte membrane, a polymer having a weight average molecular weight of 100,000 to 300,000 was used.

Polymer E-1

[Production Method 3]
An MEA was produced in the same manner as in Production Method 1, except that the solid electrolyte membrane was produced from Polymer E-1, and the binder was produced from Polymer E-2 composed of the following repeating units. Here, the polymer E-1 has a weight average molecular weight of 100,000 to 300,000, and the polymer E-2 has a weight average molecular weight of 30,000 to 100,000.

Polymer E-2

Example 3 Fuel Cell Evaluation The MEA obtained in Example 2 was set in the fuel cell shown in FIG. 2, and hydrogen gas was flowed into the anode side opening 15. At this time, the cathode side opening 16 flowed air. A potentiostat was connected between the anode electrode 12 and the cathode electrode 13, and the current value at 400 mV was recorded. The results are shown in Table 1.

  It was confirmed that the fuel cell catalyst material of the present invention has durability even under the conditions of strong acid and high temperature assumed at the start of the fuel cell and can maintain a high output even in a high current density region. In particular, it was confirmed that the fuel cell catalyst material of the present invention is more effective by adopting a solid electrolyte as a binder having the same main chain as the polymer main chain of the present invention.

  It was confirmed that the fuel cell catalyst material of the present invention has high proton conductivity while maintaining gas permeability into the pores, and can maintain high output even in a high current density region.

It is a schematic sectional drawing which shows the structure of the catalyst electrode bonding film using the polymer electrolyte of this invention. It is a schematic sectional drawing which shows an example of the structure of the fuel cell of this invention.

Explanation of symbols

10 ... Fuel cell electrode membrane composite (MEA)
11 ... Solid electrolyte membrane
12 ... Anode electrode
12a ... Anode porous conductive sheet
12b ... Anode electrode catalyst layer
13 ... Cathode electrode
13a ... Cathode porous conductive sheet
13b ... Cathode electrode catalyst layer
14 ... Packing
15 ... Anode pole side opening
16 ... Cathode pole side opening
17 ... current collector
21,22 ... Separator

Claims (17)

Solvolysis resistance having an ionic functional group, which is connected to the carbon material via a linking group having solvolysis resistance and heat resistance at least at two or more points on the surface of the carbon material, and A fuel cell catalyst material comprising a heat-resistant polymer (X). The catalyst material for a fuel cell according to claim 1, wherein the polymer (X) is connected to the surface of the carbon material at at least two points via a connecting group having the same structure. 2. The catalyst material for a fuel cell according to claim 1, wherein the polymer (X) is connected to the surface of the carbon material at at least two points via connecting groups having different structures. The fuel cell catalyst material according to claim 1, wherein the carbon material contains an electrode catalyst. The catalyst material for fuel cells according to any one of claims 1 to 4, wherein the carbon material is carbon black or carbon nanotubes. The fuel cell catalyst material according to any one of claims 1 to 5, wherein at least one of the linking groups is a linking group represented by the following formula (1).
Formula (1)

(In formula (1), R ¹ and R ² each represent a divalent to tetravalent linking group, Ar ¹ represents a divalent to hexavalent linking group containing an aromatic hydrocarbon and / or a heterocycle, and n ₁ , N ₂ and n ₃ are each an integer of 0 or more, and the sum of n ₁ , n ₂ and n ₃ is an integer of 1 or more, n ₄ is an integer of 1 to 10, and n ₅ is 1 to (It is an integer of 3. Lc represents a connection point connected to the carbon material side, and Lp represents a connection point connected to the polymer (X) side.) The polymer (X) includes a repeating unit represented by the following formula (2) as a main chain structure, and the aromatic ring of the main chain is at least selected from the following formulas (3) to (5) The fuel cell catalyst material according to any one of claims 1 to 6, wherein one partial structure is bonded.

(In the above formula (2), R ³ is a divalent group containing an aromatic ring, and X ¹ is a divalent linking group. In formula (3), B ¹ is a single bond or a 2-6 valent group. A linking group, A ¹ represents an ionic functional group, n ₆ represents an integer of 1 to 5. In formula (4), B ² represents a single bond or a bivalent to hexavalent linking group, and D represents at least one This represents a polymer of a radically polymerizable monomer having an ionic functional group.In formula (5), E ¹ represents a substituent having high oxygen permeability. The main chain portion of the polymer (X) is a polyether sulfone compound, a polyether ether sulfone compound, a polyether ether ketone compound, a polyphenylene sulfide compound, a polyphenylene ether compound, a polysulfone compound or a polyether ketone compound. The catalyst material for fuel cells according to any one of claims 1 to 7, wherein The main chain portion of the polymer (X) contains a repeating unit represented by the following formula (6), and the aromatic ring of the main chain has a partial structure represented by the following formula (7) and / or The fuel cell catalyst material according to any one of claims 1 to 6, wherein a partial structure represented by the following formula (8) is bonded.

(In the formula (6), W ¹¹ , W ¹² and W ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. In the formula (7), B ³ is a single bond or 2-6. Represents a valent linking group, A ² represents an ionic functional group, and n ₇ represents an integer of 1 to 5. In formula (8), E ² represents a substituent having high oxygen permeability. The method includes generating a radical from a polymer having at least two radical generating groups and capturing the radical in a carbon material, thereby connecting the polymer and the carbon material at at least two points. The manufacturing method of the catalyst material for fuel cells of any one of these. A polymer having a linking group having solvolysis resistance and heat resistance is linked to a carbon material through the linking group, and at least one radical generating group is introduced into the polymer to generate a radical, The method for producing a catalyst material for a fuel cell according to any one of claims 1 to 9, comprising connecting the polymer and the carbon material at at least two points by capturing the radicals in the carbon material. The catalyst film containing the catalyst material for fuel cells of any one of Claims 1-9, and a solid electrolyte. A catalyst film comprising a first fuel cell catalyst material, a second fuel cell catalyst material, and a solid electrolyte, wherein the first fuel cell catalyst material is any one of claims 1 to 9. The fuel cell catalyst material according to item 2, wherein the second fuel cell catalyst material has no solvolysis-resistant and heat-resistant polymer having an ionic functional group on the carbon surface. The catalyst membrane that is the material. The solid electrolyte includes a repeating unit represented by the following formula (2) as a main chain structure, and the aromatic ring included in the main chain includes at least one selected from the following formulas (3) to (5). The catalyst membrane of Claim 12 or 13 containing the polymer which the partial structure has couple | bonded.

(In the above formula (2), R ³ is a divalent group containing an aromatic ring, and X ¹ is a divalent linking group. In formula (3), B ¹ is a single bond or a 2-6 valent group. A linking group, A ¹ represents an ionic functional group, n ₆ represents an integer of 1 to 5. In formula (4), B ² represents a single bond or a bivalent to hexavalent linking group, and D represents at least one This represents a polymer of a radically polymerizable monomer having an ionic functional group.In formula (5), E ¹ represents a substituent having high oxygen permeability. It has a porous conductive sheet, a catalyst film provided in contact with the porous conductive sheet, and a solid electrolyte film provided in contact with the catalyst film, and the catalyst film comprises claims 12 to 14. An electrode membrane assembly, which is the catalyst membrane according to any one of the above. The solid electrolyte membrane includes a repeating unit represented by the following formula (2) as a main chain structure, and the aromatic ring included in the main chain is at least one selected from the following formulas (3) to (5). The electrode membrane assembly according to claim 15, comprising a polymer having two partial structures bonded thereto.

(In the above formula (2), R ³ is a divalent group containing an aromatic ring, and X ¹ is a divalent linking group. In formula (3), B ¹ is a single bond or a 2-6 valent group. A linking group, A ¹ represents an ionic functional group, n ₆ represents an integer of 1 to 5. In formula (4), B ² represents a single bond or a bivalent to hexavalent linking group, and D represents at least one This represents a polymer of a radically polymerizable monomer having an ionic functional group.In formula (5), E ¹ represents a substituent having high oxygen permeability. A fuel cell comprising the electrode membrane assembly according to claim 15 or 16.

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