JP4316973B2 - Organic-inorganic hybrid proton conducting material and fuel cell - Google Patents

Description

  The present invention relates to an organic-inorganic hybrid material used as an optically anisotropic material, a proton conductive material used in an energy device or an electrochemical sensor, and a fuel cell.

  In recent years, a direct methanol fuel cell (DMFC) using methanol instead of hydrogen as a fuel has been proposed, and it is expected and actively researched as a high-capacity battery for portable devices replacing a lithium secondary battery.

  The important functions of the electrolyte membrane (proton conducting membrane) for polymer electrolyte fuel cells are the physical function of the fuel (hydrogen, methanol aqueous solution, etc.) supplied to the positive electrode and the oxidant gas (oxygen, etc.) supplied to the negative electrode. Electrically insulating, electrically insulating the positive electrode and the negative electrode, and transmitting protons generated on the positive electrode to the negative electrode. In order to satisfy these functions, a certain degree of mechanical strength and high proton conductivity are required.

  As the electrolyte membrane for a polymer electrolyte fuel cell, a sulfonic acid group-containing perfluorocarbon polymer typically represented by Nafion (registered trademark) is used. These electrolyte membranes have excellent ionic conductivity and relatively high mechanical strength, but further improvements are desired in the following respects. That is, in these electrolyte membranes, protons conduct through water in the cluster channels formed by the water and sulfonic acid groups contained in the membrane, so that the ionic conductivity depends greatly on the moisture content of the membrane due to the humidity of the battery usage environment. To do. The polymer electrolyte fuel cell is preferably operated in a temperature range of 100 to 150 ° C. from the viewpoint of reducing poisoning of the catalyst electrode by CO and increasing the activation of the catalyst electrode. However, in such an intermediate temperature range, the ionic conductivity decreases with a decrease in the water content of the electrolyte membrane, so that expected battery characteristics cannot be obtained. Also, the softening point of the electrolyte membrane is around 120 ° C., and the mechanical strength of the electrolyte membrane cannot be obtained when operated in this temperature range.

  On the other hand, when these electrolyte membranes are used for DMFC, the following phenomenon occurs. That is, these membranes that are inherently water-containing have a low barrier property against methanol of fuel, so that methanol supplied to the positive electrode permeates the electrolyte membrane and reaches the negative electrode. This causes a methanol crossover phenomenon in which the battery output decreases. This is one of the important issues to be solved for the practical application of DMFC.

  Under such circumstances, the momentum for developing proton conductive membranes to replace Nafion has increased, and several promising electrolyte materials have been proposed. For example, proton conductive glass is known as an inorganic proton conductive material. These are obtained by polymerizing tetraalkoxysilane in the presence of an acid by a sol-gel method, and are known to have low humidity dependency at high temperatures. However, since the material is inflexible and extremely fragile, it is difficult to produce a film with a large area, and it is not suitable as an electrolyte for a fuel cell.

  In order to facilitate film formation while taking advantage of the properties of inorganic materials, nanocomposite materials combined with polymer materials have been proposed. For example, a method for producing a proton conductive membrane by complexing with a polymer compound having a sulfonic acid group in the side chain, silicon oxide, and protonic acid is disclosed (for example, see Patent Documents 1 to 3). In addition, an organic-inorganic nano-hybrid type proton conductive material which has an organosilicon compound as a precursor and is generated by a sol-gel reaction in the presence of a protonic acid has been proposed (for example, see Patent Document 4).

  These organic-inorganic composite and hybrid proton conductive materials are composed of an inorganic component that is a proton conducting site and composed of silicic acid and protonic acid, and an organic component that imparts flexibility to the material, but the proton conductivity of the membrane. If the inorganic component is increased to increase the membrane strength, the mechanical strength of the membrane will decrease, and if the organic component is increased to increase the membrane flexibility, the proton conductivity will decrease. Is difficult. Moreover, there is no sufficient description regarding methanol permeability, which is an important characteristic for DMFC applications.

  Patent Documents 5 and 6 disclose proton conductive membranes in which a carbon atom-containing compound having a hydrolyzable silyl group is represented by the following general formula.

（式中、Ｒ³はＣＨ₃、Ｃ₂Ｈ₅またはＣ₆Ｈ₅から選ばれるいずれかの基、ＸはＣｌ、ＯＣＨ₃、ＯＣ₂Ｈ₅またはＯＣ₆Ｈ₅から選ばれるいずれかの基、ｍは３以下の自然数である。）
さらに、特許文献７には、界面活性剤を含有させた溶液中でテトラアルコキシシランやテトラクロロシラン等のシリカ（ＳＯ₂二酸化ケイ素）前駆体を用いたゾル−ゲル反応により、膜面に配向したシリカメソ構造体を形成させる方法が記載されている。しかし、無機成分（シリカ）が集合するため柔軟な膜にすることが困難である。

Wherein R ³ is any group selected from CH ₃ , C ₂ H ₅ or C ₆ H ₅ , and X is any group selected from Cl, OCH ₃ , OC ₂ H ₅ or OC ₆ H ₅ , M is a natural number of 3 or less.)
Further, Patent Document 7 discloses a silica meso that is oriented on the film surface by a sol-gel reaction using a silica (SO ₂ silicon dioxide) precursor such as tetraalkoxysilane or tetrachlorosilane in a solution containing a surfactant. A method for forming a structure is described. However, since inorganic components (silica) are aggregated, it is difficult to form a flexible film.

Furthermore, Non-Patent Document 1 discloses a liquid crystal organopolysiloxane in which mesogenic units are bonded from the side to the main chain.
Japanese Patent Laid-Open No. 10-69817, page 4-7 JP-A-11-203936, page 6-10 Page 6-7 of JP 2001-307752 A Japanese Patent No. 3103888, pages 4-7 JP 2003-157863 A European Patent Application No. 1223632 A2 JP 2002-42550 A Liquid Crystals, 2002, 29, 9, 1247-1250

  The present invention aims to solve the above problems. That is, the first object of the present invention is to provide a novel organic-inorganic hybrid material, and the second object is to obtain a proton conductive membrane having high heat resistance suitable for a fuel cell. The third object is to provide a proton conductive membrane suitable for DMFC, having resistance to high concentration of methanol and having low methanol permeability, and a fuel cell using the same.

（一般式（１−１）中、Ａ¹は下記一般式（１−２）で表されるメソゲン基と炭素数4以上のアルキレン基を含む有機原子団を表し、Ｒ¹¹はアルキル基、アリール基又はヘテロ環基を表し、Ｘ¹はハロゲン原子又はＯＲ¹⁴を表し、Ｒ¹⁴は水素原子、アルキル基、アリール基又はシリル基を表し、ｍ１１は０を表し、ｎ１１は１を表す。Ｘ¹はそれぞれ同一でも異なっていてもよい。）

（一般式（１−２）中、Ｑ¹¹及びＱ¹²はそれぞれ２価の連結基又は単結合を表し、Ｙ¹¹は２価の４、５、６又は７員環の置換基、又はそれらから構成される縮合環の置換基を表し、ｍ１２は１〜３の整数を表す。）

（一般式（１−３）中、Ｒ¹²は置換又は無置換のアルキル基、アリール基又はヘテロ環基を表し、Ｚ¹はハロゲン原子又はＯＲ¹⁵を表し、Ｒ¹⁵は水素原子、アルキル基、アリール基又はシリル基を表し、ｍ１３は０または１を表す。Ｚ ¹はそれぞれ同一でも異なっても良い。また、Ｒ¹²又はＲ¹²の置換基により互いに連結し、多量体を形成していてもよい。）
（２）前記一般式（１−３）で表される化合物が、テトラメトキシシランおよび／またはテトラエトキシシランである、（１）に記載の有機−無機ハイブリッド型プロトン伝導材料。
（３）下記一般式（２−１）で表される化合物、下記（Ｓ−２−１５）、（Ｓ−２−１６）、（Ｓ−２−１７）、（Ｓ−２−１８）、（Ｓ−２−１９）、（Ｓ−２−２０）、（Ｓ−２−２１）、（Ｓ−２−２２）、（Ｓ−２−２８）、（Ｓ−２−２９）または（Ｓ−２−３０）を前駆体とし、前記前駆体のゾル−ゲル反応によって形成されるＳｉ−Ｏ−Ｓｉの３次元架橋構造と、エポキシ基またはオキセタン基を有する基の重合反応によってエポキシ基またはオキセタン基を有する基を開環重合させることにより得られる主鎖構造とを有する有機−無機ハイブリッド材料に、プロトン伝導性付与剤として、リン化合物、有機スルホン酸類及びパーフルオロカーボンスルホン酸ポリマーの少なくとも一種が保持されていることを特徴とする有機−無機ハイブリッド型プロトン伝導材料。

（一般式（２−１）中、Ａ²は下記一般式（１−２）で表されるメソゲン基を含む有機原子団を表し、Ｒ²¹はアルキル基を表し、Ｒ²²はアルキル基、アリール基又はヘテロ環基を表し、Ｒ²³はエポキシ基またはオキセタン基を有する基を表し、ｍ２１は０を表し、ｎ２１は１を表し、ｎ２２は１を表す。Ｒ ²¹ は、それぞれ同一でも異なってもよい。）

（一般式（１−２）中、Ｑ¹¹及びＱ¹²はそれぞれ２価の連結基又は単結合を表し、Ｙ¹¹は２価の４、５、６又は７員環の置換基、又はそれらから構成される縮合環の置換基を表し、ｍ１２は１〜３の整数を表す。）

（４）下記一般式（３−１）で表される繰り返し単位を有する高分子化合物、（Ｓ−３−１３）、（Ｓ−３−１４）、（Ｓ−３−１５）、（Ｓ−３−１６）、（Ｓ−３−１７）または（Ｓ−３−２０）を前駆体として架橋重合してなることを特徴とする有機−無機ハイブリッド材料に、プロトン伝導性付与剤として、リン化合物、有機スルホン酸類及びパーフルオロカーボンスルホン酸ポリマーの少なくとも一種が保持されていることを特徴とする有機−無機ハイブリッド型プロトン伝導材料。

（一般式（３−１）中、Ａ³は下記一般式（１−２）で表されるメソゲン基及びアルキレン基を含む有機原子団を表し、Ｒ³¹はアルキル基を表し、Ｒ³²はアルキル基、アリール基、又はヘテロ環基を表し、Ｅ³はアルキレンオキシ基、アルキレン基、又はシロキシ基を表し、Ｌ³は連結基を表し、ｍ３１は０〜２の整数を表し、ｎ３１は１を表し、ｎ３２は１〜５の整数を表す。ｍ３１が０または１のときＲ ³¹ はそれぞれ同一でも異なってもよく、又、ｍ３１が２のときＲ ³² はそれぞれ同一でも異なってもよい）

（一般式（１−２）中、Ｑ¹¹及びＱ¹²はそれぞれ２価の連結基又は単結合を表し、Ｙ¹¹は２価の４、５、６又は７員環の置換基、又はそれらから構成される縮合環の置換基を表し、ｍ１２は１〜３の整数を表す。）

（５）前記有機−無機ハイブリッド材料が、下記一般式(１−４)で表される化合物、下記一般式（１−５）で表される化合物、下記（Ｋ−１）、（Ｋ−２）、（Ｋ−３）、（Ｋ−４）、（Ｋ−１８）または（Ｋ−１９）を、前記前駆体のモル数に対し１〜５０モル%添加してなることを特徴とする有機−無機ハイブリッド材料である、（１）〜（４）のいずれか１項に記載の有機−無機ハイブリッド型プロトン伝導材料。

（一般式(１−４)中、Ａ¹⁴は、前記一般式（１−２）で表されるメソゲン基及び炭素数４以上のアルキレン基を含む有機原子団を表し、Ｚ¹⁴は水素原子、水酸基、カルボキシル基、スルホ基、スルフィノ基、ホスホノ基、またはビニル基を表し、ｎ１３は１を表し、ｎ１４は１を表し、Ｙ¹⁴ はエポキシ基またはオキセタン基を有する基を表す。
一般式(１−５)中、Ａ¹⁵は、前記一般式（１−２）で表されるメソゲン及び炭素数４以上のアルキレン基を含む有機原子団を表し、Ｚ¹⁵は水素原子、水酸基、カルボキシル基、スルホ基、スルフィノ基、ホスホノ基、またはビニル基を表し、ｎ１５は１を表し、ｎ１６は１〜５の整数を表し、L¹⁵は**−ＣＯＯ−、**−ＯＣＯ−、**−（ＣＨ₂）_nn3−、**−（ＣＨ₂）_nn3Ｏ−、**−Ｏ（ＣＨ₂）_nn3−、**−ＣＯＮ（Ｒ³⁴’）−またはフェニレン基（**はＥ¹⁵と結合する位置を表し、Ｒ³⁴’はアルキル基であり、ｎｎ３は１〜６の整数を表す）を表し、Ｅ¹⁵はアルキレンオキシ基、アルキレン基又はシロキシ基を表す。ｎ１６が２以上の場合、それぞれの単位は同一でも異なっていてもよい。）

（６）（１）〜（５）のいずれか１項に記載の有機−無機ハイブリッド型プロトン伝導材料を用いることを特徴とする燃料電池。
As a result of intensive studies in view of the above object, the present inventor has found that the above problems can be solved by the following means.
(1) A compound represented by the following general formula (1-1), the following (S-1-1), (S-1-2), (S-1-3), (S-1-6), (S-1-17), (S-1-18), (S-1-21), (S-1-22), (S-1-23), (S-1-24) or (S −1-25) as a precursor, and adding a compound represented by the following general formula (1-3 ) to the precursor and polymerizing the three-dimensional crosslinked structure of Si—O—Si. An organic-inorganic hybrid proton conductive material, wherein the organic-inorganic hybrid material has at least one of a phosphorus compound, an organic sulfonic acid, and a perfluorocarbon sulfonic acid polymer as a proton conductivity-imparting agent.

(In the general formula (1-1), A ¹ represents an organic atomic group containing a mesogenic group represented by the following general formula (1-2) and an alkylene group having 4 or more carbon atoms, and R ¹¹ represents an alkyl group or an aryl group. represents a group or a heterocyclic group, X ¹ represents a halogen atom or oR ^14, R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group or a silyl group, m11 represents 0, n11 represents 1 .X ¹ May be the same or different.)

(In General Formula (1-2), Q ¹¹ and Q ¹² each represent a divalent linking group or a single bond, and Y ¹¹ represents a divalent 4-, 5-, 6- or 7-membered ring substituent, or from them The substituent of the condensed ring comprised is represented, m12 represents the integer of 1-3.)

(In General Formula (1-3), R ¹² represents a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, Z ¹ represents a halogen atom or OR ¹⁵ , R ¹⁵ represents a hydrogen atom, an alkyl group, Represents an aryl group or a silyl group, and m13 represents 0 or 1. Z ¹ may be the same or different from each other, and may be linked to each other by a substituent of R ¹² or R ¹² to form a multimer. Good.)
(2) The organic-inorganic hybrid proton conductive material according to (1), wherein the compound represented by the general formula (1-3) is tetramethoxysilane and / or tetraethoxysilane.
(3) A compound represented by the following general formula (2-1), the following (S-2-15), (S-2-16), (S-2-17), (S-2-18), (S-2-19), (S-2-20), (S-2-21), (S-2-22), (S-2-28), (S-2-29) or (S 2-30) as a precursor, and an epoxy group or oxetane by a polymerization reaction of a three-dimensional crosslinked structure of Si-O-Si formed by a sol-gel reaction of the precursor and a group having an epoxy group or an oxetane group An organic-inorganic hybrid material having a main chain structure obtained by ring-opening polymerization of a group having a group has at least one of a phosphorus compound, an organic sulfonic acid, and a perfluorocarbon sulfonic acid polymer as a proton conductivity imparting agent. Organic characterized by being Inorganic hybrid proton conducting material.

(In the general formula (2-1), A ² represents an organic atomic group containing a mesogenic group represented by the following general formula (1-2), R ²¹ represents an alkyl group, R ²² represents an alkyl group, aryl represents a group or a heterocyclic group, R ²³ represents a group having an epoxy group or an oxetane group, m21 represents 0, n21 represents 1,. R ²¹ representing a 1 n22 are each Re their Re are identical May be different.)

(In General Formula (1-2), Q ¹¹ and Q ¹² each represent a divalent linking group or a single bond, and Y ¹¹ represents a divalent 4-, 5-, 6- or 7-membered ring substituent, or from them The substituent of the condensed ring comprised is represented, m12 represents the integer of 1-3.)

(4) a polymer compound having a repeating unit represented by the following general formula (3-1) , (S-3-13), (S-3-14), (S-3-15), (S- 3-16) An organic-inorganic hybrid material obtained by crosslinking polymerization using (S-3-17) or (S-3-20) as a precursor, and a phosphorus compound as a proton conductivity-imparting agent An organic-inorganic hybrid proton conductive material, wherein at least one of organic sulfonic acids and perfluorocarbon sulfonic acid polymer is retained.

(In General Formula (3-1), A ³ represents an organic atomic group containing a mesogenic group and an alkylene group represented by the following General Formula (1-2), R ³¹ represents an alkyl group, and R ³² represents an alkyl group. A group, an aryl group, or a heterocyclic group, E ³ represents an alkyleneoxy group, an alkylene group, or a siloxy group, L ³ represents a linking group, m31 represents an integer of 0 to 2, and n31 represents 1 . N32 represents an integer of 1 to 5. When m31 is 0 or 1, R ³¹ may be the same or different, and when m31 is 2, R ³² may be the same or different.

(In General Formula (1-2), Q ¹¹ and Q ¹² each represent a divalent linking group or a single bond, and Y ¹¹ represents a divalent 4-, 5-, 6- or 7-membered ring substituent, or from them The substituent of the condensed ring comprised is represented, m12 represents the integer of 1-3.)

(5) The organic-inorganic hybrid material is a compound represented by the following general formula (1-4) , a compound represented by the following general formula (1-5), the following (K-1), (K-2) ), (K-3), (K-4), (K-18) or (K-19) is added in an amount of 1 to 50 mol% based on the number of moles of the precursor, The organic-inorganic hybrid proton conductive material according to any one of (1) to (4), which is an inorganic hybrid material.

(In the general formula (1-4), A ¹⁴ represents an organic atomic group containing the formula (1-2) mesogenic groups and having 4 or more alkylene group having a carbon represented by, Z ¹⁴ is a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a sulfino group, a phosphono group or a vinyl group,, n13 represents 1, n14 represents 1, Y ¹⁴ represents a group having a d epoxy group or an oxetane group.
In the general formula (1-5), A ¹⁵ represents an organic atomic group containing a mesogen represented by the general formula (1-2) and an alkylene group having 4 or more carbon atoms, Z ¹⁵ represents a hydrogen atom, a hydroxyl group, represents a carboxyl group, a sulfo group, a sulfino group, a phosphono group or a vinyl group,, n15 represents 1, n16 represents an integer of 1 to 5, L ¹⁵ is ** - COO -, ** - OCO -, * * — (CH ₂ ) _nn3 —, ** — (CH ₂ ) _nn3 O—, ** — O (CH ₂ ) _nn3 —, ** — CON (R ³⁴ ′) — or a phenylene group (** is E ¹⁵ represents the position which binds to, R ³⁴ 'is an alkyl group, NN3 represents represents) an integer from 1 to 6, E ¹⁵ is to Table alkyleneoxy group, an alkylene group or a siloxy group. When n16 is 2 or more, each unit may be the same or different. )

(6) A fuel cell using the organic-inorganic hybrid proton conductive material described in any one of (1) to (5).

  The organic-inorganic hybrid proton conductive material of the present invention is formed by holding a proton source as a proton conductivity-imparting agent in the organic-inorganic hybrid material. The proton source is preferably at least one of a phosphorus compound, an organic sulfonic acid, and a perfluorocarbon sulfonic acid polymer. Such an organic-inorganic hybrid proton conductive material is suitable as an electrolyte membrane for a fuel cell.

BEST MODE FOR CARRYING OUT THE INVENTION

[1] Organosilicon compound precursor Hereinafter, the organic-inorganic hybrid material, the organic-inorganic hybrid proton conductive material, and the fuel cell of the present invention will be described in detail. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. In the present invention, the “organic-inorganic hybrid material” is a material containing an organic part (atomic group) and an inorganic part (atomic group), and the organic part and the inorganic part are bonded by a covalent bond. Say.

  The first organic-inorganic hybrid material of the present invention is a material which is obtained by three-dimensionally cross-linking an organosilicon compound having a mesogenic group and includes at least one organic and inorganic ptron source. In particular, those having a structure in which an aggregate in which at least a part of the organic molecular chain in the proton conducting material is oriented in one direction are formed are preferable.

  More specifically, in the above, the organic-inorganic hybrid material is an organic-inorganic hybrid material obtained by polymerizing an organosilicon compound represented by the formula (1-1).

一般式（１−１）において、Ｒ¹¹は、アルキル基、アリール基又はヘテロ環基を表す。アルキル基の好ましい例としては、直鎖、分岐鎖又は環状アルキル基（炭素数１〜２０のアルキル基であり、例えばメチル基、エチル基、イソプロピル基、ｎ−ブチル基、２−エチルヘキシル基、ｎ−デシル基、シクロプロピル基、シクロヘキシル基、シクロドデシル基等）が挙げられ、アリール基の好ましい例としては、炭素数６〜２０の置換又は無置換のフェニル基、炭素数１０〜２０の置換又は無置換のナフチル基等が挙げられる。ヘテロ環基の好ましい例としては、置換又は無置換のへテロ６員環（ピリジル基、モルホリノ基等）、置換又は無置換のヘテロ５員環（フリル基、チオフェン基等）等が挙げられる。

In General Formula (1-1), R ¹¹ represents an alkyl group, an aryl group, or a heterocyclic group. Preferable examples of the alkyl group include linear, branched or cyclic alkyl groups (C1-C20 alkyl groups such as methyl, ethyl, isopropyl, n-butyl, 2-ethylhexyl, n -Decyl group, cyclopropyl group, cyclohexyl group, cyclododecyl group, etc.), and preferred examples of the aryl group include substituted or unsubstituted phenyl groups having 6 to 20 carbon atoms, substituted or unsubstituted carbon atoms having 10 to 20 carbon atoms, and the like. An unsubstituted naphthyl group etc. are mentioned. Preferable examples of the heterocyclic group include a substituted or unsubstituted hetero 6-membered ring (pyridyl group, morpholino group, etc.), a substituted or unsubstituted hetero 5-membered ring (furyl group, thiophene group, etc.) and the like.

X ¹ represents a halogen atom (chlorine, bromine, iodine or the like) or OR ¹⁴ , and R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group or a silyl group. Preferred examples of the alkyl group and aryl group for R ¹⁴ are the same as those exemplified for the preferred examples of the alkyl group and aryl group for R ¹¹ . Preferable examples of the silyl group include a silyl group (trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, etc.) substituted with three groups selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, or polysiloxane Group (— (Me ₂ SiO) _n H (n = 10 to 100) or the like). m11 represents an integer of 0 to 2, and n11 represents an integer of 1 to 10. When m11 or 3-m11 is 2 or more, R ¹¹ or X ¹ may be the same or different.

In general formula (1-1), X ¹ is preferably an alkoxy group (OR ¹⁴ : R ¹⁴ is an alkyl group), m11 is preferably 0, and n11 is an integer of 1 to 4. preferable. A ¹ is an organic atomic group containing a mesogen and an alkylene group having 4 or more carbon atoms, and preferred examples of the mesogen group include “Frequency Kristall in Tablen II” by Dietrich Demus and Horst Zashke, 1984, What is described in p.7-18 is mentioned. Among these, the following general formula (1-2) is preferable.

一般式（１−２）中、Ｑ¹¹及びＱ¹²は２価の連結基又は単結合を表す。２価の連結基としては、−ＣＨ=ＣＨ−、−ＣＨ=Ｎ−、−Ｎ=Ｎ−、−Ｎ（Ｏ）=Ｎ−、−ＣＯＯ−、−ＣＯＳ−、−ＣＯＮＨ−、−ＣＯＣＨ₂−、−ＣＨ₂ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＮＨ−、−ＣＨ₂−、−ＣＯ−、−Ｏ−、−Ｓ−、−ＮＨ−、−（ＣＨ₂）₁〜₃−、−ＣＨ=ＣＨ−ＣＯＯ−、−ＣＨ=ＣＨ−ＣＯ−、−（Ｃ≡Ｃ）₁〜₃−、又は、これらの組合せ等が好ましく、−ＣＨ₂−、−ＣＯ−、−Ｏ−、−ＣＨ=ＣＨ−、−ＣＨ=Ｎ−、−Ｎ=Ｎ−、又は、これらの組合せ等がより好ましい。これらの２価の連結基は水素原子が他の置換基で置換された基であってもよい。Ｑ¹¹及びＱ¹²は、−ＣＯ−、−Ｏ−、又は単結合及びそれらの組み合わせが好ましい。

In the general formula (1-2), Q ¹¹ and Q ¹² represents a divalent linking group or a single bond. Examples of the divalent linking group include —CH═CH—, —CH═N—, —N═N—, —N (O) ═N—, —COO—, —COS—, —CONH—, —COCH _2. —, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ NH—, —CH ₂ —, —CO—, —O—, —S—, —NH—, — (CH ₂ ) ₁ to ₃ — , —CH═CH—COO—, —CH═CH—CO—, — (C≡C) ₁ to ₃ —, or combinations thereof are preferred, —CH ₂ —, —CO—, —O—, -CH = CH-, -CH = N-, -N = N-, or a combination thereof is more preferred. These divalent linking groups may be groups in which a hydrogen atom is substituted with another substituent. Q ¹¹ and Q ¹² are preferably —CO—, —O—, or a single bond and a combination thereof.

Y ¹¹ represents a divalent 4-, 5-, 6- or 7-membered ring substituent, or a condensed ring substituent composed thereof, and m12 represents an integer of 1 to 3. Y ¹¹ is preferably a 6-membered aromatic group, a 4- to 6-membered saturated or unsaturated aliphatic group, a 5- or 6-membered heterocyclic group, or a condensed ring thereof. Preferable specific examples of Y ¹¹ include substituents represented by (Y-1) to (Y-28) shown below, and combinations thereof. Among these substituents, (Y-1), (Y-2), (Y-18), (Y-19), (Y-21) and (Y-22) are more preferable, and more preferable. Are (Y-1), (Y-2) and (Y-21).

  The organosilicon compound preferably contains an alkyl group or alkylene group having 5 or more carbon atoms together with a mesogenic group in order to enhance molecular orientation. 5-25 are preferable and, as for carbon number of an alkyl group or an alkylene group, 6-18 are more preferable. The alkyl group or alkylene group may have a substituent. Preferred groups include the following groups.

(1) Alkyl group The alkyl group may have a substituent, more preferably an alkyl group having 1 to 24 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms. It may be a shape. For example, methyl group, ethyl group, propyl group, butyl group, i-propyl group, i-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, t-octyl group, decyl group, dodecyl group, tetradecyl group 2-hexyldecyl group, hexadecyl group, octadecyl group, cyclohexylmethyl group, octylcyclohexyl group and the like.
(2) Aryl group The aryl group may have a substituent or a condensed ring, and more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group, a 4-methylphenyl group, a 3- A cyanophenyl group, a 2-chlorophenyl group, a 2-naphthyl group, and the like.
(3) Heterocyclic group The heterocyclic group may have a substituent or may be condensed, and in the case of a nitrogen-containing heterocyclic group, the nitrogen in the ring may be quaternized. More preferably, it is a C2-C24 heterocyclic group, for example, 4-pyridyl group, 2-pyridyl group, 1-octylpyridinium-4-yl group, 2-pyrimidyl group, 2-imidazolyl group, 2-thiazolyl group. Etc.
(4) Alkoxy group More preferably, it is an alkoxy group having 1 to 24 carbon atoms. For example, methoxy group, ethoxy group, butoxy group, octyloxy group, methoxyethoxy group, methoxypenta (ethyloxy) group, acryloyloxyethoxy group, penta And a fluoropropoxy group.
(5) Acyloxy group More preferably, it is an acyloxy group having 1 to 24 carbon atoms, such as an acetyloxy group and a benzoyloxy group.
(6) Alkoxycarbonyl group More preferably, it is a C2-C24 alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.
(7) Cyano group (8) Fluoro group (9) Alkoxycarbonyl group (10) Polymerizable group Preferably, a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a cinnamic acid residue are exemplified. The alkyl group or alkylene group is particularly preferably unsubstituted or has a polymerizable group at the terminal. The silyl group (—Si (X ¹ ) _3-m11 (R ¹¹ ) _m11 ) is directly bonded to the mesogenic group, alkyl group or alkenyl group constituting the organic atomic group A ¹ or bonded through a linking group. The linking group is preferably an alkylene group having 1 to 15 carbon atoms or a combination with a mesogenic group linking group Q ¹¹ or Q ¹² . The silyl group is preferably bonded to the alkylene group.

In the general formula (1-1), X ¹ is preferably an alkoxy group (OR ¹⁴ : R ¹⁴ is an alkyl group), m11 is 0, and n is an integer of 1 to 4. Specific examples of the organosilicon compound are shown below in (S-1-1) to (S-1-29), but are not limited thereto. In addition, these compounds are not limited to any liquid, liquid crystal, or crystal at room temperature.

  Next, the second organic-inorganic hybrid material of the present invention uses as an precursor an organosilicon compound having an alkoxysilyl group, a mesogenic group and a substituent capable of forming a carbon-carbon bond or a carbon-oxygen bond by polymerization, The precursor is three-dimensionally crosslinked. The precursor is preferably a compound represented by the following general formula (2-1).

一般式（２−１）において、Ｒ²¹はアルキル基を表し、Ｒ²²はアルキル基、アリール基、ヘテロ環基を表す。Ｒ²¹及びＲ²²で表されるアルキル基の好ましい例としては、直鎖、分岐鎖又は環状アルキル基（例えば炭素数１〜２０のアルキル基であり、メチル基、エチル基、イソプロピル基、ｎ−ブチル基、２−エチルヘキシル基、ｎ−デシル基、シクロプロピル基、シクロヘキシル基、シクロドデシル基等）が挙げられ、アリール基の好ましい例としては、炭素数６〜２０の置換又は無置換のフェニル基、炭素数１０〜２０の置換又は無置換のナフチル基等が挙げられ、ヘテロ環基の好ましい例としては、置換又は無置換のへテロ６員環（ピリジル基、モルホリノ基等）、置換又は無置換のヘテロ５員環（フリル基、チオフェン基等）等が挙げられる。Ａ²は、上記一般式（１−１）における、Ａ¹と同義である。Ｒ²³は、炭素−炭素結合又は炭素−酸素結合を新たに生成し、重合体を形成しうる置換基であり、好ましくはアクリロイル基、メタクリロイル基、ビニル基、エチニル基及びアルキレンオキシド基（エチレンオキシド、トリメチレンオキシド等）からなる群から選ばれる置換基である。中でもアクリロイル基、メタクリロイル基、エチレンオキシド基、及びトリメチレンオキシド基が好ましい。Ｒ²³の存在は、プロトン伝導膜の強度を向上し、ゾル−ゲル法の後で重合することにより製膜が容易になる等の有利な効果を有する。

In General Formula (2-1), R ²¹ represents an alkyl group, and R ²² represents an alkyl group, an aryl group, or a heterocyclic group. Preferable examples of the alkyl group represented by R ²¹ and R ²² include a linear, branched or cyclic alkyl group (for example, an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, n- Butyl group, 2-ethylhexyl group, n-decyl group, cyclopropyl group, cyclohexyl group, cyclododecyl group, etc.), and preferred examples of the aryl group include substituted or unsubstituted phenyl groups having 6 to 20 carbon atoms. A substituted or unsubstituted naphthyl group having 10 to 20 carbon atoms and the like. Preferred examples of the heterocyclic group include a substituted or unsubstituted hetero 6-membered ring (pyridyl group, morpholino group, etc.), substituted or unsubstituted. Substituted hetero 5-membered rings (furyl group, thiophene group, etc.) and the like can be mentioned. A ² has the same meaning as A ¹ in the general formula (1-1). R ²³ is a substituent capable of newly forming a carbon-carbon bond or a carbon-oxygen bond to form a polymer, and preferably an acryloyl group, a methacryloyl group, a vinyl group, an ethynyl group, and an alkylene oxide group (ethylene oxide, A substituent selected from the group consisting of trimethylene oxide and the like. Of these, an acryloyl group, a methacryloyl group, an ethylene oxide group, and a trimethylene oxide group are preferable. The presence of R ²³ has advantageous effects such as improving the strength of the proton conducting membrane and facilitating membrane formation by polymerization after the sol-gel method.

The silyl group (—Si (OR ²¹ ) _3-m21 (R ²² ) _m21 ) has the same _{meaning as} the silyl group in the general formula (1-1). In addition, like the first organosilicon compound of the present invention, the organosilicon compound preferably contains an alkyl group or alkylene group having 5 or more carbon atoms together with a mesogenic group in order to enhance molecular orientation. .

  Specific examples of the second organosilicon compound of the present invention are shown below in (S-2-1) to (S-2-30), but are not limited thereto.

  Furthermore, the third organic-inorganic hybrid material of the present invention is formed by cross-linking polymerization using a polymer compound having an atomic group containing an alkoxysilyl group, a mesogenic group and an alkylene group in the side chain as a precursor. The precursor is preferably a polymer compound having a repeating unit represented by the following general formula (3-1).

一般式（３−１）において、Ｒ³¹はアルキル基を表し、Ｒ³²はアルキル基、アリール基、又はヘテロ環基を表す。Ｒ³¹及びＲ³²で表されるアルキル基の好ましい例としては、直鎖、分岐鎖、又は環状アルキル基（例えば炭素数１〜２０のアルキル基であり、メチル基、エチル基、イソプロピル基、ｎ−ブチル基、２−エチルヘキシル基、ｎ−デシル基、シクロプロピル基、シクロヘキシル基、シクロドデシル基等）が挙げられる。アリール基の好ましい例としては、炭素数６〜２０の置換又は無置換のフェニル基、炭素数１０〜２０の置換又は無置換のナフチル基等が挙げられ、ヘテロ環基の好ましい例としては、置換又は無置換のへテロ６員環（ピリジル基、モルホリノ基等）、置換又は無置換のヘテロ５員環（フリル基、チオフェン基等）等が挙げられる。Ａ³は、上記一般式（１−１）におけるＡ¹と同義である。

In General Formula (3-1), R ³¹ represents an alkyl group, and R ³² represents an alkyl group, an aryl group, or a heterocyclic group. Preferable examples of the alkyl group represented by R ³¹ and R ³² include a linear, branched, or cyclic alkyl group (for example, an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, n -Butyl group, 2-ethylhexyl group, n-decyl group, cyclopropyl group, cyclohexyl group, cyclododecyl group, etc.). Preferred examples of the aryl group include substituted or unsubstituted phenyl groups having 6 to 20 carbon atoms, substituted or unsubstituted naphthyl groups having 10 to 20 carbon atoms, and preferred examples of the heterocyclic group include substituted Alternatively, an unsubstituted hetero 6-membered ring (pyridyl group, morpholino group, etc.), a substituted or unsubstituted hetero 5-membered ring (furyl group, thiophene group, etc.) and the like can be mentioned. A ³ is synonymous with A ¹ in the general formula (1-1).

E ³ represents an alkylene group, an alkyleneoxy group or a siloxy group. When E ³ is an alkylene group, an ethylene group represented by the following general formula (3-a) is preferable, and when it is an alkyleneoxy group, an ethyleneoxy group represented by the following general formula (3-b) or the following general formula A trimethyleneoxy group represented by (3-c) is preferred, and in the case of a siloxy group, a group represented by the following general formula (3-d) is preferred. These groups represented by the general formulas (3-a) to (3-c) may be further substituted.

一般式（３−ａ）〜（３−ｄ）中、Ｒ³⁴はアルキル基（好ましくは炭素数１〜１２のアルキル基であり、例えばメチル基、エチル基、プロピル基、ヘキシル基、ドデシル基等）又は水素原子を表し、＊は連結基Ｌ³と結合する位置を表し、Ｒ³⁵はＲ³⁴又は単結合（−＊）を表す。

In the general formulas (3-a) to (3-d), R ³⁴ is an alkyl group (preferably an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a hexyl group, a dodecyl group, etc. ) Or a hydrogen atom, * represents a position bonded to the linking group L ^3, and R ³⁵ represents R ³⁴ or a single bond (— *).

L ³ is a linking group, and preferred examples include ** — _COO— , ** — _OCO— , ** — (CH ₂ ) _nn3 —, ** — (CH ₂ ) _nn3 O—, ** — O. (CH ₂ ) _nn3 —, ** — CON (R ³⁴ ′) —, phenylene group, etc. (** represents the position bonded to E ³ , R ³⁴ ′ is synonymous with R ³⁴ , nn3 is 1-6 Divalent linking group). L ³ may be the same linking group as Q ¹¹ or Q ¹² .

The combination of E ³ and L ³ is preferably a combination represented by the following general formulas (3-e) to (3-h).

一般式（３−ｅ）〜（３−ｈ）中、***はＡ³と結合する位置を表す。中でもより好ましい組合せは、一般式（３−ｆ）においてＲ³⁴＝Ｈとき、一般式（３−ｇ）においてＲ³⁵＝Ｈ、ＣＨ₃、又はＣＨ₂ＣＨ₃のとき、及び一般式（３−ｈ）である。

In the general formulas (3-e) to (3-h), *** represents a position bonded to A ³ . Among these, a more preferable combination is when R ³⁴ = H in the general formula (3-f), when R ³⁵ = H, CH ₃ , or CH ₂ CH _{3 in} the general formula (3-g), and the general formula (3- h).

The silyl group (—Si (OR ³¹ ) _3-m31 (R ³² ) _m31 ) has the same _{meaning as} the silyl group in the general formula (1-1).

  In General Formula (3-1), m31 represents an integer of 0 to 2, and is preferably 0, n31 represents an integer of 1 to 10, preferably an integer of 1 to 3, and n32 represents 1 Represents an integer of ˜5, preferably 1 or 2. The molecular weight of the third organosilicon polymer compound of the present invention varies depending on the polymerization conditions and may be arbitrary, but the number average molecular weight is preferably 5,000 to 500,000, more preferably 5,000 to 50,000. . In addition, like the first organosilicon compound of the present invention, the organosilicon compound preferably contains an alkyl group or alkylene group having 5 or more carbon atoms together with a mesogenic group in order to enhance molecular orientation. .

  Specific examples of the organosilicon polymer compound as a precursor are shown below in (S-3-1) to (S-3-20), but the present invention is not limited to these.

[2] Organic-inorganic hybrid material [2-1] Method for producing organic-inorganic hybrid material In the present invention, hydrolysis, dehydration condensation, and polymerization of metal alkoxide, generally referred to as sol-gel method, using an organosilicon compound as a precursor. A method of obtaining a solid by drying, (possibly firing) or the like is used (see, for example, “Electrochimica Acta”). Alternatively, the obtained solid is newly formed with a carbon-carbon bond or a carbon-oxygen bond by polymerization of a polymerizable group (for example, R ²³ ) introduced into the organosilicon compound precursor to form a polymer. obtain. At that time, acid or alkali is used as a catalyst for controlling hydrolysis and polymerization. As the alkali, it is common to use hydroxides of alkali metals such as NaOH and KOH, ammonia and the like. Specifically, the following method can be employed.

  Examples of the sol-gel method include, for example, JP 2000-272932 A, JP 2000-256007 A, JP 2000-357524 A, JP 2001-93543 A, “Electrochimica Acta”, 1998. 43, No. 10-11, p.1301, Japanese Patent No. 3103888, and the like. Here, a typical method will be described as an example. By dissolving the first organosilicon compound of the present invention in an arbitrary solvent and adding water and acid thereto, hydrolysis of the alkoxysilyl group and polycondensation reaction (sol-gel reaction) proceed. At that time, the viscosity of the reaction mixture (sol) gradually increases, and the solvent is distilled off and dried to obtain a solid (gel). If the sol is poured into a desired container or applied at a stage where the fluidity exists, the solvent can be distilled off and dried to obtain a solid having a desired shape such as a plate or film. Further, the obtained solid can be pulverized and then compressed into a plate shape. In order to make the generated silica network more dense, it may be further heated after drying, if necessary.

  The solvent used in the sol-gel reaction is not particularly limited as long as it dissolves the precursor organosilicon compound, but is preferably a carbonate compound (ethylene carbonate, propylene carbonate, etc.), a heterocyclic compound (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 mono Alkyl ether, polypropylene glycol monoalkyl ether, etc.), polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, etc.), nitrile compounds (acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile) Etc.), esters (carboxylic acid esters, phosphoric acid esters, phosphonic acid esters, etc.), aprotic polar substances (dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide, etc.), nonpolar solvents (toluene, xylene, etc.), chlorine-based A solvent (methylene chloride, ethylene chloride, etc.), water or the like can be used. Of these, alcohols such as ethanol and isopropanol, nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile, and cyclic ethers such as dioxane and tetrahydrofuran are particularly preferable. These may be used alone or in combination of two or more.

  For the purpose of controlling the drying rate, a solvent having a boiling point of 100 ° C. or higher, such as N-methylpyrrolidone, dimethylacetamide, sulfolane, dioxane, or the like may be added to the solvent. The total amount of the solvent is preferably 0.1 to 100 g, more preferably 1 to 10 g, with respect to 1 g of the precursor compound.

The acid catalyst for the sol-gel reaction is preferably an inorganic or organic proton acid. Examples of inorganic protonic acids include hydrochloric acid, sulfuric acid, phosphoric acids (H ₃ PO ₄ , H ₃ PO ₃ , H ₄ P ₂ O ₇ , H ₅ P ₃ O ₁₀ , metaphosphoric acid, hexafluorophosphoric acid, etc.), boric acid, nitric acid Perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid, solid acids (tungstophosphoric acid, tungsten peroxo complex, etc.), and the like. Examples of organic protonic acids include phosphoric acid esters (for example, phosphoric acid esters having 1 to 30 carbon atoms, phosphoric acid methyl ester, phosphoric acid propyl ester, phosphoric acid dodecyl ester, phosphoric acid phenyl ester, phosphoric acid dimethyl ester, Phosphorous acid dododecyl ester, etc.), phosphorous acid esters (for example, phosphorous acid esters having 1 to 30 carbon atoms, phosphorous acid methyl ester, phosphorous acid dodecyl ester, phosphorous acid diethyl ester, phosphorous acid Diisopropyl, phosphorous acid dododecyl ester, etc.), sulfonic acids (for example, sulfonic acids having 1 to 15 carbon atoms, such as benzenesulfonic acid, toluenesulfonic acid, hexafluorobenzenesulfonic acid, trifluoromethanesulfonic acid, dodecylsulfonic acid, etc.) Carboxylic acids (for example, carboxylic acids having 1 to 15 carbon atoms) Acetic acid, trifluoroacetic acid, benzoic acid, substituted benzoic acid, etc.), imides (bis (trifluoromethanesulfonyl) imidic acid, trifluoromethanesulfonyl trifluoroacetamide, etc.), phosphonic acids (for example, phosphones having 1 to 30 carbon atoms) Low molecular weight compounds such as methylphosphonic acid, ethylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, 1,5-naphthalene bisphosphonic acid, etc., or perfluorocarbon sulfonic acid polymers represented by Nafion, phosphorus in the side chain Poly (meth) acrylate having an acid group (Japanese Patent Laid-Open No. 2001-114844), sulfonated polyether ether ketone (Japanese Patent Laid-Open No. 6-93111), sulfonated polyether sulfone (Japanese Patent Laid-Open No. 10-45913), Sulfonated polysulfone Polymer having a Putoron acid sites, such as sulfonated heat resistant aromatic polymer of JP-A-9-245818 JP), and the like. Two or more of these may be used in combination. As solid acids, α-Zr (HPO ₄ ) ₂ .nH ₂ O, γ-Zr (PO ₄ ) (H ₂ PO ₄ ) · 2H ₂ O, α-Zr sulfophenyl phosphate, γ-Zr sulfophenyl Layered compounds such as phosphates, hydrated oxides such as SnO ₂ .2H ₂ O, Sb ₂ O ₅ .5.4H ₂ O, H ₄ SiW ₁₂ O ₄₀ .nH ₂ O, H ₃ PW ₁₂ O _40. Heteropolyacids such as nH ₂ O are particularly preferred.

The above protonic acid acts as a catalyst for the sol-gel reaction, and at the same time remains in the solid produced after the reaction. In the case of an organic-inorganic hybrid material, it is possible to wash away the protonic acid in the solid and use it as a liquid crystal material, etc., but in the case of an organic-inorganic hybrid type proton conductive material, the proton acid functions as a proton conductivity-imparting agent. Therefore, it is desirable that a large amount be retained in the solid. Therefore, a proton source other than the proton acid used as a catalyst for the sol-gel reaction may be further added as a proton source. As proton sources, phosphorus compounds (preferably phosphoric acids, phosphate esters, etc.) that form chemical bonds (Si-OP) in the silicate network, organic sulfonic acids with low solubility in water, and difficult to elute It is preferable to use a polymer compound having a proton acid site, or a solid acid that physically interacts and is retained on silica, and among them, H ₃ PO ₄ , H ₃ PO ₃ , phosphate esters, phosphites It is particularly preferable to use phosphorus compounds such as organic sulfonic acids and perfluorocarbon sulfonic acid polymers. The amount of the acid is preferably 0.1 to 10 molar equivalents, more preferably 0.5 to 5 molar equivalents relative to Si of the precursor silicon compound.

  The reaction temperature of the sol-gel reaction is related to the reaction rate, and can be selected depending on the reactivity of the precursor and the kind and amount of the acid. Preferably it is -20-150 degreeC, More preferably, it is 0-80 degreeC, More preferably, it is 20-60 degreeC.

[2-2] Addition of plastic compound In the proton conducting membrane of the present invention, a compound represented by the following general formula (1-4) and / or (1-5) that does not change in the sol-gel reaction is used as a plasticizer. By adding, flexibility can be imparted to the film. The addition amount is from 1 mol% to 50 mol%, and preferably from 5 mol% to 20 mol%, based on the number of moles of the aforementioned organosilicon compound.

一般式（１−４）及び（１−５）中、Ａ¹⁴及びＡ¹⁵は、それぞれ、メソゲン及び炭素数４以上のアルキレン基を含む有機原子団を表し、メソゲンは、前述のメソゲン含有有機ケイ素化合物中のＡ¹とそれぞれ同義であり、本発明のプロトン伝導膜作成時に用いるメソゲン含有有機ケイ素化合物中のメゾゲンと同一のものが特に好ましい。

In the general formulas (1-4) and (1-5), A ¹⁴ and A ¹⁵ each represent an organic atomic group containing a mesogen and an alkylene group having 4 or more carbon atoms, and the mesogen is the mesogen-containing organosilicon described above. Each of them is synonymous with A ¹ in the compound, and is particularly preferably the same as the mesogen in the mesogen-containing organosilicon compound used for producing the proton conducting membrane of the present invention.

Z ¹⁴ and Z ¹⁵ each represent a substituent or a hydrogen atom that does not change in the sol-gel reaction, and examples of preferred substituents include 1. alkyl group, 2 described above with respect to the substituent in formula (1-1), Aryl group, 3. Heterocyclic group, 4. Alkoxy group, 5. Acyloxy group, 6. Alkoxycarbonyl group, 7. Cyano group, 8. Fluoro group, 9. Alkoxycarbonyl group, hydroxyl group, and carboxyl group , Sulfo groups, sulfino groups, phosphono groups and other acid residues, vinyl groups and the like. Among these, hydrogen atoms, hydroxyl groups, acid residues and vinyl groups are particularly preferable.

n13 and n15 each represent an integer of 1 to 8, and 1 or 2 is particularly preferable. n14 represents an integer of 0 to 4, and 1 or 2 is particularly preferable. n16 represents an integer of 1 to 5, and 1 or 2 is particularly preferable. When n13 or n15 is 2 or more, Z ¹⁴ or Z ¹⁵ may be the same or different. When n16 is 2 or more, each unit may be the same or different.

Y ¹⁴ represents a polymerizable group capable of forming a carbon-carbon bond or a carbon-oxygen bond by polymerization, and is synonymous with Y ¹¹ in the organosilicon compound represented by the above formula (1-1). The same as Y ¹¹ of the mesogen-containing organosilicon compound used for producing the proton conducting membrane of the present invention is preferable. When n15 is 2 or more, Z ¹⁵ may be the same or different.

E ¹⁵ and L ¹⁵ are synonymous with E ³ and L ³ in the general formula (3-1). The molecular weight of the compound having the structure represented by the formulas (3-e) to (3-h) is arbitrary depending on the polymerization conditions, and the number average molecular weight is preferably 5,000 to 500,000, preferably 5,000 to 50, 000 is more preferable.

  Specific examples of the compounds represented by the formulas (1-4) and (1-5) are shown below, but are not limited thereto.

[2-3] Addition of other organosilicon compounds Other metal alkoxides or silicon compounds may be added as necessary to improve the properties of the material. These function as, for example, a crosslinking agent and can retain a large amount of acid. Further, it can be combined with a precursor organosilicon compound to impart flexibility and strength. Preferred metal alkoxides include alkoxides such as Al, Ti and Zr. As an example of a preferable silicon compound, the organosilicon compound represented by the following general formula (1-3), or a polymer using them as a monomer can be given.

一般式（１−３）中、Ｒ¹²は置換又は無置換のアルキル基、アリール基又はヘテロ環基を表し、Ｚ¹はハロゲン原子（塩素、臭素、ヨウ素等）又はＯＲ¹⁵を表し、Ｒ¹⁵は水素原子、アルキル基、アリール基又はシリル基を表し、ｍ１３は０〜４の整数を表す。ｍ１３及び／又は４−ｍ１３が２以上のときＲ¹²及びＺ¹はそれぞれ同一でも異なっても良い。また、Ｒ¹²又はＲ¹²の置換基により互いに連結し、多量体を形成していてもよい。

In the general formula (1-3), R ¹² represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, Z ¹ represents a halogen atom (chlorine, bromine, iodine, etc.) or OR ¹⁵ , and R ¹⁵ Represents a hydrogen atom, an alkyl group, an aryl group or a silyl group, and m13 represents an integer of 0 to 4. When m13 and / or 4-m13 is 2 or more, R ¹² and Z ¹ may be the same or different. Further, they may be linked to each other by a substituent of R ¹² or R ¹² to form a multimer.

R ¹² and Z ^{1 in} the general formula (1-3) have the same meanings as R ¹¹ and X ^{1 in} the general formula (1-1), respectively. m13 is preferably 0 or 1, Z ¹ is preferably OR ¹⁵ , and R ¹⁵ is preferably an alkyl group. Examples of preferable compounds when m13 is 0 include tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and the like, and preferable examples of compounds when m13 is 1 include the following compounds.

  When the compound represented by the general formula (1-3) is used in combination, it is preferably used in the range of 1 to 50 mol%, and more preferably in the range of 10 to 25 mol%, relative to the precursor organosilicon compound. More preferred.

[2-4] Film-forming method In the present invention, the support for applying the sol-gel reaction mixture is not particularly limited. Preferred examples include a glass substrate, a metal substrate, a polymer film, and a reflector. Can do. Polymer films include cellulose polymer films such as TAC (triacetyl cellulose), ester polymer films such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate), and fluorine such as PTFE (polytrifluoroethylene). Based polymers and the like. The coating method may be a known method, for example, 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. it can.

  A film may be formed by applying a sol-gel reaction solution on a substrate having pores, or the substrate is immersed in the sol-gel reaction solution, and the pores are filled with a proton conductive material. May be formed. Preferable examples of the substrate having pores include porous polypropylene, porous polytetrafluoroethylene, porous cross-linked heat-resistant polyethylene, and porous polyimide film.

  The sol-gel reaction using the organosilicon compound as a precursor proceeds while applying the sol-gel reaction solution while the organic sites of the organosilicon compound are oriented. Various techniques can be employed to promote the orientation of the sol-gel composition. For example, the above-described support or the like can be subjected to an orientation treatment in advance. Various general methods can be adopted as the alignment treatment, but preferably a method for performing alignment treatment such as rubbing by providing a liquid crystal alignment layer such as various polyimide alignment films and polyvinyl alcohol alignment films on a support, etc. A method of applying a magnetic field or an electric field to the sol-gel composition on the support, a method of heating, or the like can be used.

  The orientation state of the organic-inorganic hybrid proton conductive membrane can be confirmed by observing optical anisotropy with a polarizing microscope. The observation direction may be arbitrary, but it can be said that there is anisotropy if there is a portion where the light and darkness are switched by rotating the sample under crossed Nicols. The orientation state is not particularly limited as long as it exhibits anisotropy. When a texture that can be recognized as a liquid crystal phase is observed, the phase can be specified. In this case, it may be a lyotropic liquid crystal phase, a thermotropic liquid crystal phase, or another phase. In the case of a lyotropic liquid crystal phase, the alignment state is preferably a hexagonal phase, a cubic phase, a lamellar phase, a sponge phase, or a micelle phase, and particularly preferably exhibits a lamellar phase or a sponge phase at room temperature. In the case of the thermotropic liquid crystal phase, a nematic phase, a smectic phase, a crystal phase, a columnar phase and a cholesteric phase are preferable, and a smectic phase and a crystal phase are particularly preferable at room temperature. An orientation state in which the orientation in these phases is maintained in a solid state is also preferable. The anisotropy referred to in the present invention means a state where the direction vector of the molecule is not isotropic.

  The thickness of the proton conducting membrane of the present invention is preferably 10 to 500 μm, particularly preferably 25 to 100 μm.

[2-5] Addition of inorganic filler In the present invention, inorganic fine particles (inorganic filler) may be added in order to improve the film properties (mechanical strength, ion conductivity, etc.). The inorganic fine particles are preferably inorganic oxides such as silica (silicon oxide), aluminum oxide, zinc oxide, magnesium oxide, and titanium oxide, and two or more kinds may be mixed and used. As for the particle size of the inorganic fine particles, the average diameter of the primary particles is preferably 500 nm or less, more preferably 200 nm or less, and particularly preferably 2 to 200 nm. The inorganic fine particles may be crystalline or amorphous, or a mixture thereof.

  As the inorganic fine particles, those treated with dimethyl silicone oil, a silane coupling agent or the like may be used. For example, in the case of silica, it is possible to use a hydrated amorphous silica obtained by treating an amorphous silica surface mainly composed of powdered silicon dioxide with a methyl group, an octylsilyl group, or a trimethylsilyl group.

[2-6] Polymerizable group (for example, polymerization of R ²³ above)
When the polymerizable group R ²³ is a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a vinyl group, an ethynyl group, etc., Takayuki Otsu and Masaaki Kinoshita, “Experimental Methods for Polymer Synthesis”, Kagaku Dojin and Otsu The radical polymerization method, which is a general polymer synthesis method described in Takayuki's "Lecture Polymerization Reaction Theory 1 Radical Polymerization (I)", Chemistry Dojin, can be used. As the radical polymerization method, a thermal polymerization method using a thermal polymerization initiator and a photopolymerization method using a photopolymerization initiator can be used. Preferred examples of the thermal polymerization initiator include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methyl). Azo initiators such as propionate) and peroxide initiators such as benzoyl peroxide. Preferred examples of the photopolymerization initiator include α-carbonyl compounds (US Pat. Nos. 2,367,661 and 2,367,670). ), Acyloin ether, α-hydrocarbon substituted aromatic acyloin compound (US Pat. No. 2,722,512), polynuclear quinone compound (US Pat. Nos. 3,046,127 and 2,951,758), triarylimidazole dimer And a combination of p-aminophenylketone, acridine and phenazine compounds (JP 60-105667 A) Publications and U.S. Patent 4239850 Pat) and oxadiazole compounds (U.S. Patent 4,212,970 No. herein).

  The polymerization initiator may be added to the reaction solution before the sol-gel reaction or may be added immediately before the reaction solution is applied. The addition amount of the polymerization initiator is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of monomers.

When R ²³ is an alkylene oxide group such as an ethylene oxide group or a trimethylene oxide group, the polymerization catalyst is a protonic acid (as mentioned in (2-1) above) or a Lewis acid (preferably boron trifluoride (ether complex). Zinc chloride, aluminum chloride, etc.). In the case of using a sol-gel reaction proton acid as the proton acid, it is not particularly necessary to add a proton acid for the polymerization of R ²³ , but when it is added, it is preferably added to the reaction solution immediately before coating. . Polymerization usually proceeds in the film by heating or light irradiation after coating. As a result, the molecular orientation is fixed and the strength of the film is improved.

[2-7] Addition of polymer compound The proton conducting membrane of the present invention contains various polymer compounds for the purpose of (1) increasing the mechanical strength of the membrane and (2) increasing the acid concentration in the membrane. You may make it contain.

  (1) In order to increase the mechanical strength, it is preferable to add a polymer compound having a molecular weight of 10,000 to 1,000,000 and having good compatibility with the proton conducting material of the present invention. Examples thereof include perfluorinated polymers, polystyrene, polyethylene glycol, polyoxetane, poly (meth) acrylate, polyether ketone, polyether sulfone, and copolymers thereof. The content of the polymer compound is preferably in the range of 1 to 30% by mass.

  (2) In order to increase the acid concentration, a perfluorocarbon sulfonic acid polymer represented by Nafion, poly (meth) acrylate having a phosphate group in the side chain, sulfonated polyetheretherketone, sulfonated polyethersulfone, sulfone It is preferable to use a polymer compound having a ptronic acid moiety such as a sulfonated product of a heat-resistant aromatic polymer such as sulfonated polysulfone or sulfonated polybenzimidazole. The content of the polymer compound is preferably in the range of 1 to 30% by mass.

[2-8] Addition of Catalytic Metal to Proton Conducting Membrane An active metal catalyst that promotes the redox reaction of the anode fuel and / or the cathode fuel may be added to the proton conducting membrane of the present invention. As a result, the fuel that has penetrated into the proton conducting membrane can be consumed in the proton conducting membrane without reaching the other electrode, and crossover can be prevented. The active metal species to be used is not limited as long as it functions as an electrode catalyst, but platinum or an alloy based on platinum is preferable.

[3] Fuel Cell A fuel cell using the organic-inorganic hybrid material of the present invention as a proton conductive material will be described.

[3-1] Structure of Battery FIG. 1 shows a catalyst electrode assembly (hereinafter referred to as “MEA”) 10 used in a fuel cell. The MEA 10 includes a proton conducting membrane 11 and a cathode side electrode 12 and an anode side electrode 13 which are opposed to each other with the proton conducting membrane 11 interposed therebetween.

The cathode side electrode 12 and the anode side electrode 13 have porous conductive materials (for example, carbon paper) 12a and 13a and catalyst layers 12b and 13b. The catalyst layer is made of a dispersion in which carbon particles (for example, ketjen black, acetylene black, carbon nanotubes, etc.) carrying a catalyst metal such as platinum particles are dispersed in a proton conductive material (for example, Nafion). In order to bring the catalyst layers 12b and 13b into close contact with the proton conductive membrane 11, the porous conductive materials 12a and 13a coated with the catalyst layers 12b and 13b are applied to the proton conductive membrane 11 by a hot press method (preferably 120 to 130 ° C. , 2-100 kg / cm ² ), or after pressure-bonding an appropriate support coated with the catalyst layers 12b, 13b while being transferred to the proton conductive membrane 11, the porous conductive materials 12a, 13a A sandwiching method is generally used.

  FIG. 2 shows an example of a single fuel cell. 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 that are stainless steel nets attached to the separators 21 and 22. The cathode electrode side separator 15 is provided with a cathode electrode side opening 15, and the anode electrode side separator 22 is provided with an anode electrode side opening 16. A gas fuel such as hydrogen and alcohols (such as methanol) or a liquid fuel such as an aqueous alcohol solution is supplied from the cathode electrode side opening 15, and an oxidant gas such as oxygen gas and air is supplied from the anode electrode side opening 16. Is supplied.

[3-2] Catalyst Material For the anode electrode and the cathode electrode, for example, a catalyst in which active metal particles such as platinum are supported on a carbon material can be used. The particle diameter of the normally used active metal is preferably in the range of 2 to 10 nm. When the particle diameter is 10 nm or less, the surface area per unit mass is increased, and the activity can be enhanced. On the other hand, when the particle diameter is 2 nm or more, it becomes easy to disperse without aggregation.

  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 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-based ternary metals such as Pt—Ru—Fe, Pt—Ru—Ni, Pt—Ru—Cu, Pt—Ru—Sn, and Pt—Ru—Au can be used.

  As the carbon material for supporting the active metal, acetylene black, Vulcan XC-72, ketjen black, carbon nanohorn (CNH), and carbon nanotube (CNT) are preferably used.

[3-3] Structure and material of catalyst layer The function of the catalyst layer provides (1) transport of fuel to active metal (2) oxidation (anode) and reduction (cathode) reaction fields of fuel (3) transferring electrons generated by redox to the current collector, and (4) transporting protons generated by the reaction to the proton conducting membrane. For (1), the catalyst layer needs to be porous so that liquid and gaseous fuel can permeate deeply. (2) is the active metal catalyst described in [3-2], and (3) is the same as the carbon material described in [3-2]. In order to fulfill the function (4), a proton conductive material is mixed in the catalyst layer.

  The proton conductive material of the catalyst layer is not limited as long as it is a solid having a proton donating group, but a polymer compound having an acid residue used for the proton conductive membrane (for example, perfluorocarbon sulfonic acid represented by Nafion, side Sulfonated products of heat-resistant aromatic polymers such as chain phosphate group poly (meth) acrylate, sulfonated polyetheretherketone, sulfonated polybenzimidazole, etc.), organic-inorganic hybrid proton conducting material with fixed acid ( For example, proton conductive materials described in JP-A-10-69817, JP-A-11-203936, JP-A-2001-307752, JP-A-3103888 and the like are preferably used. Moreover, it is also possible to use the proton conductive material obtained by carrying out the sol-gel reaction of the precursor used for the proton conductive film of this invention for a catalyst layer. In this case, since the same material as the proton conducting membrane is used, the adhesion between the proton conducting membrane and the catalyst layer is advantageously increased.

The amount of active metal used is preferably in the range of 0.03 to 10 mg / cm ² from the viewpoint of battery output and economy. The amount of the carbon material supporting the active metal is preferably 1 to 10 times the mass of the active metal. The amount of the proton conductive material is preferably 0.1 to 0.7 times the mass of the active metal-carrying carbon.

[3-4] Porous conductive sheet (electrode substrate)
The porous conductive sheet is also called an electrode base material, a diffusion layer, or a backing material, and plays a role of preventing current collection and water accumulation and gas diffusion from deteriorating. Usually, carbon paper or carbon cloth is used. Moreover, what gave PTFE process for water repellency can also be used.

[3-5] Preparation of MEA (Electrode Membrane Complex) Examples of the preparation of MEA include the following methods.
(1) Proton conductive membrane coating method: A catalyst paste (ink) based on active metal-carrying carbon, putron conductive material, and solvent is applied directly to both sides of the proton conductive membrane, and a porous conductive sheet is (thermally) pressed. A five-layer MEA is manufactured.
(2) Porous conductive sheet coating method: After a catalyst paste is coated on the surface of the porous conductive sheet to form a catalyst layer, it is pressure-bonded to a proton conductive membrane to produce a 5-layer MEA.
(3) Decal method: After applying a catalyst paste on PTFE to form a catalyst layer, only the catalyst layer is transferred to the proton conductive membrane to form a three-layer MEA, and a porous conductive sheet is pressure-bonded. A MEA having a layer structure is manufactured.
(4) Post-catalyst support method: After applying and forming an ink in which a platinum unsupported carbon material is mixed with a proton conductive material on a proton conductive membrane, a porous conductive sheet or PTFE, the membrane is impregnated with platinum ions, Platinum particles are reduced and deposited in the film to form a catalyst layer. After the formation of the catalyst layer, the MEA is produced by the methods (1) to (3) above.

[3-6] Fuel and Supply Method As fuel for a fuel cell using a solid polymer membrane, as anode fuel, hydrogen, alcohols (methanol, isopropanol, ethylene glycol, etc.), ethers (dimethyl ether) can be used. , Dimethoxymethane, trimethoxymethane, etc.), formic acid, borohydride complexes, ascorbic acid and the like. Examples of the cathode fuel include oxygen (including oxygen in the atmosphere) and hydrogen peroxide.

In the direct methanol fuel cell, a methanol aqueous solution having a methanol concentration of 3 to 64% by mass is used as the anode fuel. According to the anode reaction formula (CH ₃ OH + H ₂ O → CO ₂ + 6H ⁺ + 6e), 1 mol of water is required for 1 mol of methanol, and the methanol concentration at this time corresponds to 64% by mass. The higher the methanol concentration, the smaller the mass and volume of the battery including the fuel tank with the same energy capacity. On the other hand, the lower the methanol concentration, the more the so-called crossover phenomenon that methanol permeates through the proton conducting membrane and reacts with oxygen on the cathode side to lower the voltage, and the output can be prevented from lowering. That is, the optimum concentration is determined by the methanol permeability of the proton conducting membrane used. The cathode reaction formula of the direct methanol fuel cell is (3 / 2O ₂ + 6H ⁺ + 6e → H ₂ O), and oxygen (for example, oxygen in the air) is used as the fuel.

  For the method of supplying the anode fuel and the cathode fuel to the respective catalyst layers, for example, (1) a method of forced circulation using an auxiliary device such as a pump (active type) and (2) an auxiliary device are used. There are two types of methods (for example, a passive type in the case of liquid due to capillary action or natural fall, and in the case of gas, a passive type in which the catalyst layer is exposed and supplied to the atmosphere). In (1) above, by circulating the water produced by the cathode fuel, high-concentration methanol can be used as the fuel, and high output by air supply is possible. However, it may be difficult to reduce the size by providing the fuel supply system. On the other hand, the above (2) can be reduced in size, but the fuel supply is likely to be rate-determined and there is a case where high output is difficult to be output. Therefore, a method of combining the above methods (1) and (2) with respect to the anode fuel and the cathode fuel is preferably employed.

[3-7] Cell Stacking Since the single cell voltage of the fuel cell is generally 1 V or less, it is preferable to stack the single cells in series according to the required voltage of the load. Examples of stacking methods include (1) “planar stacking” in which single cells are arranged on a plane, and (2) “bipolar stacking” in which single cells are stacked via separators having fuel flow paths formed on both sides. Used. Planar stacking is more suitable for a small fuel cell because the cathode electrode (air electrode) comes out on the surface and air can be easily taken in and can be made thin. In addition, it is also possible to adopt a method of stacking by applying a fine processing on a silicon wafer by applying MEMS technology.

[4] Applications of fuel cells Fuel cells are considered for various uses such as automobiles, homes, portable devices, and portable devices. In particular, direct methanol fuel cells are expected to be used as various energy sources by taking advantage of the fact that they can be reduced in size and weight and do not require charging. For example, mobile phones, mobile notebook computers, electronic still cameras, PDAs, video cameras, portable game machines, mobile servers, wearable personal computers, mobile displays, portable generators, outdoor lighting equipment, flashlights, electric (assist) bicycles, etc. Can be mentioned. Moreover, it can 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 mounted on these devices.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Synthesis Example 1-1]
The precursor (S-1-1) was synthesized by the following synthesis route.

(1) Synthesis of Intermediate (M-1-2) p- (trans-4-pentylcyclohexyl) phenol (M-1-1, manufactured by Kanto Chemical Co., Inc.) (24.6 g, 100 mmol) was dissolved in 100 ml of DMF. Then, 25 g of potassium carbonate was added, and 11-bromo-1-undecene (24.5 g, 105 mmol) was added dropwise over 10 minutes while heating and stirring at 80 ° C. After stirring with heating for 3 hours, the reaction mixture was poured into 300 ml of water to collect crystals. The obtained crude crystals were recrystallized from methanol to obtain 36.4 g of an intermediate (M-1-2).

(2) Synthesis of (S-1-1) (M-1-2) (3.9 g, 10 mmol) and triethoxysilane (1.8 g, 11 mmol) were dissolved in toluene, and the inside of the reaction vessel was purged with nitrogen. . The reaction solution was kept at 80 ° C., chloroplatinic acid (5 mg) was added, and the mixture was heated for 3 hours. The reaction mixture was concentrated and purified by silica gel column chromatography to obtain 1.1 g of (S-1-1) as a colorless oil.

[Synthesis Example 1-2]
The precursor (S-1-4) was synthesized by the following synthesis route.

(1) Synthesis of Intermediate (M-1-7) 1,1,1-Tris-hydroxymethylethane (M-1-4) (100 g, 833 mmol) and 2,2-dimethoxypropane (100 g, 917 mmol) It melt | dissolved in 750 ml of chloroform, 1 g of p-toluenesulfonic acid hydrate was added, and it heated and refluxed for 7 hours using the Soxhlet extractor equipped with the molecular sieve 3A. After adding 4 g of potassium carbonate to the reaction mixture and stirring at room temperature for 20 minutes, the reaction mixture was filtered and concentrated to obtain 136 g of (M-1-5) as a colorless oil. The obtained (M-1-5) (135 g, 833 mmol) was dissolved in 400 ml of THF, 143 ml of triethylamine and 5 g of dimethylaminopyridine were added, and paratoluenesulfonyl chloride (178 g, 916 mmol) was added at room temperature. The reaction mixture was heated to reflux for 6 hours, water was added to the reaction solution, extracted with ethyl acetate, and the residue obtained after concentration was crystallized with normal hexane to obtain 225 g of (M-1-6). The obtained (M-1-6) (201 g, 639 mmol) was dissolved in 700 ml of acetonitrile, sodium iodide (290 g) was added, and the mixture was heated to reflux for 2 hours. The reaction mixture was filtered to remove inorganic substances, water was added, and the mixture was extracted with ethyl acetate. The extract was concentrated, the residue was distilled under reduced pressure, and a fraction of 0.5 mmHg and 75 to 85 ° C. was collected to obtain 129 g of (M-1-7).

(2) Synthesis of Intermediate (M-1-8) p- (trans-4-pentylcyclohexyl) phenol (M-1-1, manufactured by Kanto Chemical Co., Inc.) (12.3 g, 50 mmol) was dissolved in 50 ml of DMF. Then, 10 g of potassium carbonate was added, and 8-bromo-octanol (8.6 g, 52.5 mmol) was added dropwise over 5 minutes while heating and stirring at 80 ° C. After stirring with heating for 3 hours, the reaction mixture was poured into 100 ml of water to collect crystals. The obtained crude crystals were recrystallized with cold methanol to obtain 14.4 g of (M-1-8).

(3) Synthesis of intermediate (M-1-11) (M-1-8) (25 g, 66.7 mmol) was dissolved in 100 ml of DMSO, and sodium hydride (30% liquid paraffin added) (3.5 g) After stirring at room temperature for 20 minutes, (M-1-7) (19.8 g, 73.4 mmol) was added dropwise. After dropping, the mixture was stirred at 60 ° C. for 4 hours, and then the reaction solution was poured into ice water, extracted with ethyl acetate, and the concentrated residue was purified by silica gel column chromatography to obtain 26.7 g of (M-1-9). It was. 26.7 g of the obtained (M-1-9) was dispersed in a mixed solution of 70 ml of ethanol and 50 ml of concentrated hydrochloric acid, heated and refluxed for 30 minutes, poured into 500 ml of water, and the precipitated crystals were collected and dried. As a result, 24 g of (M-1-10) was obtained. Next, (M-1-10) (20.4 g, 428 mmol) was dissolved in 100 ml of DMF, sodium hydride (30% liquid paraffin added) (5.16 g, 1284 mmol) was added, and allyl iodide ( 21.4 g, 1284 mmol) was added dropwise. The reaction solution was heated at 60 ° C. for 5 hours, poured into ice water, and extracted with ethyl acetate. The concentrated residue of the extract was purified by silica gel column chromatography to obtain 20.3 g of (M-1-11).

(4) Synthesis of (S-1-4) The obtained (M-1-11) (14.5 g, 26 mmol) and triethoxysilane (12.8 g, 78 mmol) were dissolved in toluene. 10 mg of chloroplatinic acid was added at 80 ° C. After reacting at 85 ° C. for 3 hours, the reaction mixture was concentrated and purified by silica gel column chromatography to obtain 5.6 g of (S-1-4) as a colorless oil.

[Synthesis Example 1-3]
A precursor (S-1-12) was synthesized by the following synthesis route.

(1) Synthesis of (M-1-15) 4,4′-dihydroxy-biphenyl monoacetyl (M-1-13) (22.8 g, 100 mmol) was dissolved in 100 ml of DMF, and 25 g of potassium carbonate was added. The dichloride body (M-1-18) (10.85 g, 50 mmol) was dripped over 10 minutes when heated and stirred at 80 degreeC. After stirring at 80 ° C. for 5 hours, the reaction mixture was poured into 200 ml of water, and the precipitated crystals were collected by filtration. After recrystallization from acetonitrile / ethyl acetate, 58 g of (M-1-14) was obtained. (M-1-14) (31.4 g, 50 mmol) was dispersed in a solution containing 100 ml of methanol, 50 ml of water and 8 g of sodium hydroxide, heated under reflux for 2 hours, poured into 100 ml of water and neutralized with hydrochloric acid. The precipitated crystals were filtered and dried to obtain 26 g of (M-1-15).

(2) Synthesis of (M-1-17) The obtained (M-1-15) (13.3 g, 25 mmol) was dissolved in 40 ml of DMF, 12 g of potassium carbonate was added, and then 8-chloro-1-octanol was added. (8.23 g, 50 mmol) was added, and the mixture was heated with stirring at 80 ° C. for 6 hours. The reaction solution was poured into 100 ml of water, and the crystals were collected by filtration and recrystallized from methanol to obtain 15.7 g of (M-1-16). (M-1-16) (10 g, 12.7 mmol) was dissolved in 30 ml of DMSO, sodium hydride (liquid paraffin added 30%) (1 g) was added, and at room temperature, allyl iodide (4.7 g, 28 mmol) was added. ) Was added dropwise, and the mixture was heated and stirred at 50 ° C. for 3 hours. The reaction solution was poured into water and extracted with ethyl acetate, and the concentrate was purified by silica gel column chromatography to obtain 7 g of (M-1-17).

(3) Synthesis of (S-1-12) The obtained (M-1-17) (5 g, 5.8 mmol) and tetraethoxysilane (2.3 g, 14 mmol) were dissolved in toluene. Under a nitrogen atmosphere, When heated to 80 ° C., 10 mg of chloroplatinic acid was added. After stirring with heating at 80 to 90 ° C. for 4 hours, the reaction solution was concentrated and purified by silica gel column chromatography to obtain 2.1 g of (S-1-12).

[Synthesis Example 2-1]
A precursor (S-2-1) was synthesized by the following synthesis route.

(1) Synthesis of Intermediate (M-2-3) 4,4′-Dihydroxy-biphenyl monoacetyl (M-2-1) (45.6 g, 200 mmol) was dissolved in 1000 ml of DMF, and 20 g of potassium carbonate was added. Then, 11-bromo-1-undecene (47.2 g, 200 mmol) was added dropwise thereto. The reaction solution was heated at 80 ° C. for 5 hours, cooled to room temperature, poured into water, and the precipitated crystals were collected by filtration. The crude crystal was washed with heated methanol and dried to obtain 72 g of (M-2-2). (M-2-2) (50.8 g, 133.5 mmol) was dispersed in 100 ml of methanol, an aqueous potassium hydroxide solution (12 g of KOH / 10 ml of water) was added, and the mixture was heated at 40 ° C. for 1 hour and at 80 ° C. for 20 minutes. Thereafter, the reaction solution was poured into water, and the precipitated crystals were filtered, washed with heated methanol, and dried to obtain 44 g of (M-2-3).

(2) Synthesis of intermediate (M-2-5) (M-2-3) (20.3 g, 60 mmol) was dissolved in 400 ml of methylene chloride, 120 ml of 0.5 M aqueous sodium hydrogen carbonate solution was added and stirred. While adding m-chloroperbenzoic acid (purity 69%, 16.5 g, 66 mmol) over 10 minutes. After stirring for 7 hours, water and a small amount of sodium bisulfite were added to the reaction solution, washed with water, and methylene chloride was distilled off to obtain crude crystals. The crude crystals were washed with heated acetonitrile to obtain 12 g of (M-2-4). Next, (M-2-4) (11 g, 31 mmol) was dissolved in 50 ml of dimethylformamide, 10 g of potassium carbonate was added, and allyl iodide (5.2 g, 31 mmol) was added dropwise with stirring. After stirring at room temperature for 2 hours, the mixture was stirred at 50 ° C. for 1 hour. The reaction solution was poured into water, and the precipitated crystals were recrystallized from methanol to obtain 12.1 g of (M-2-5).

(3) Synthesis of (S-2-1)
(M-2-5) (5 g, 12.7 mmol) and triethoxysilane (3.13 g, 19.05 mmol) were dissolved in 50 ml of toluene and 5 ml of isopropanol, and 10 mg of chloroplatinic acid was added at 80 ° C. under a nitrogen stream. did. The reaction solution was kept at 80 to 90 ° C. and reacted for 1 hour, then the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 3.2 g of (S-2-1).

[Synthesis Example 2-2]
A precursor (S-2-4) was synthesized by the following synthesis route.

(1) Synthesis of Intermediate (M-2-8) 4,4′-Dihydroxybiphenyl (M-2-6) (76.2 g, 410 mmol) was dissolved in 400 ml of dimethylacetamide and potassium carbonate (42.2 g). And potassium iodide (24.1 g) were added, and 8-chlorooctanol (47.2 g, 287 mmol) was added. The reaction solution was stirred at 110 ° C. for 5 hours and returned to room temperature, and then the reaction solution was poured into water, and the precipitated crystals were filtered. The obtained crude crystals were recrystallized from acetonitrile to obtain 63.8 g of (M-2-7). The obtained (M-2-7) (10 g, 31.8 mmol) was dissolved in 40 ml of dimethylacetamide, potassium carbonate (3.3 g) was added, and epichlorohydrin (3. 24 g, 35 mmol) was added dropwise. After reacting at 80 ° C. for 3 hours, the reaction mixture was poured into water, and the resulting crude crystals were recrystallized twice with acetonitrile to obtain 8.2 g of (M-2-8).

(2) Synthesis of (S-2-4) (M-2-8) (10 g, 27 mmol) and 3- (triethoxysilyl) propyl isocyanate (M-2-9) (6.7 g, 27 mmol) Was dissolved in ethyl acetate, dibutyltin (IV) dilaurate (10 mg) was added, and the mixture was heated to reflux for 4 hours. The reaction mixture was concentrated and purified by silica gel column chromatography to obtain 6.4 g of a white solid (S-2-4).

[Synthesis Example 2-3]
A precursor (S-2-23) was synthesized by the following synthesis route.

(1) Synthesis of Intermediate M-2-17 4,4′-Dihydroxynaphthalene M-14 (23.5 g, 143 mmol) was dissolved in 8 ml of dimethylacetamide, and potassium carbonate (11.1 g, 80 mmol) and potassium iodide were dissolved. When (6.7 g) was added, 8-chlorooctanol (71.8 g, 72 mmol) was added. The reaction solution was stirred at 110 ° C. for 9 hours and returned to room temperature, and then the reaction solution was poured into water and the precipitated crystals were filtered. The obtained crude crystals were recrystallized from acetonitrile to obtain 16.3 g of M-2-15. The obtained M-2-15 (10 g, 34.7 mmol) was dissolved in 40 ml of dimethylacetamide, potassium carbonate (9.6 g) was added, and iodide M-2-16 (9. 4 g, 41.6 mmol) was added dropwise. After reacting at 100 ° C. for 4 hours, the reaction mixture was poured into water, and the resulting crude crystals were recrystallized from acetonitrile to obtain 4.2 g of M-2-17.

(2) Synthesis of Intermediate M-2-18 M-2-17 (3.6 g, 9.4 mmol) was dissolved in dehydrated tetrahydrofuran, heated to 60 ° C. and stirred with sodium hydride (60% in oil). ) (0.5 g, 12.2 mmol) was added little by little to foam. After foaming subsided, allyl iodide (2.4 g, 14.1 mmol) was added dropwise. The reaction mixture was stirred at 60 ° C. for 3 hours, poured into water, extracted with ethyl acetate, and purified by column chromatography to obtain 2.1 g of M-2-18.

(3) Synthesis of S-2-23 M-2-18 (1.5 g, 3.4 mmol) and triethoxysilane (2.4 g, 14.3 mmol) were dissolved in 10 ml of toluene, and at 80 ° C. in a nitrogen stream. Then, a solution of 10 mg of chloroplatinic acid dissolved in 0.5 ml of benzonitrile was added dropwise. After the reaction solution was reacted at 80 ° C. for 1 hour, the reaction mixture was concentrated and purified by silica gel column chromatography to obtain 0.76 g of S-2-23.

[Synthesis Example 2-4]
A precursor (S-2-24) was synthesized by the following synthesis route.

(1) Synthesis of Intermediate M-2-24 Tetrabutylammonium bromide (3.0 g) was dissolved in 50% aqueous sodium hydroxide solution, and 3-ethyl-3-oxetanemethanol M-2-19 (19 g, 0.2 g) was dissolved. 16 mol) and 1,8-dibromooctane M-2-20 (136 g, 0.5 mol) were added. The reaction mixture was stirred for 3.5 hours under heating to reflux, then the reaction mixture was ice-cooled, 600 ml of water was added, and the mixture was extracted with ethyl acetate. Excess bromide M-2-20 was removed by distillation under reduced pressure, followed by purification by column chromatography to obtain 36 g of M-2-21. The obtained M-2-21 (33 g, 0.107 mol) was dissolved in 120 ml of dimethylacetamide, and ethyl 4-hydroxybenzoate M-2-22 (17 g, 0.102 mol) and potassium carbonate (23 g) were added. . After stirring at 80 ° C. for 8 hours, the mixture was poured into water, extracted with ethyl acetate, and purified by column chromatography to obtain 35 g of M-2-23. The obtained M-2-23 (35.4 g, 90.2 mmol) was dissolved in 60 ml of ethanol, sodium hydroxide (7.2 g, 180 mmol) and 20 ml of water were added, and the mixture was stirred at 60 ° C. for 3 hours. The reaction mixture was neutralized with concentrated hydrochloric acid (15.4 ml, 85.8 ml / mol), extracted with ethyl acetate, and purified by column chromatography to obtain 33 g of M-2-24.

(2) Synthesis of Intermediate M-2-26 Dihydroxybiphenyl M-2-25 (25 g, 134 mmol) was dissolved in 100 ml of acetone, potassium carbonate (20 g, 145 mmol) was added, and allyl bromide ( A solution of 16.2 g, 134 mmol) dissolved in 100 ml of acetone was added dropwise. After stirring at 60 ° C. for 7 hours, the deposited salt was removed by filtration. Water, dilute hydrochloric acid and sodium chloride were added to the filtrate, and the mixture was extracted with ethyl acetate. The concentrated crude crystals were recrystallized from ethanol to obtain 6 g of M-2-26.

(3) Synthesis of Intermediate M-2-27 M-2-24 (10.5 g, 31.2 mmol) was dissolved in 100 ml of chloroform, M-2-26 (6.4 g, 28.4 mmol) and dimethylamino were dissolved. Pyridine (5.2 g, 42.6 mmol) was added. After cooling the reaction solution to 0 ° C., a solution of dicyclohexylcarbodiimide (5.8 g, 45.4 mmol) dissolved in 20 ml of chloroform was added dropwise, and the mixture was stirred at 0 ° C. for 1 hour. The precipitated salt was filtered, concentrated, and purified by column chromatography to obtain 11.9 g of M-2-27.

(4) Synthesis of S-2-24 M-2-27 (5.7 g, 10 mmol) and triethoxysilane (5.0 g, 30 mmol) were dissolved in 25 ml of toluene and chloroplatinic acid in a nitrogen stream at 80 ° C. A solution in which 17 mg was dissolved in 0.5 ml of benzonitrile was added dropwise. After reacting the reaction solution at 80 ° C. for 1 hour, the reaction mixture was concentrated and purified by silica gel column chromatography to obtain 3.2 g of S-2-24.

[Synthesis Example 3-1]
A precursor (S-3-1) was synthesized by the following synthesis route.

(1) Synthesis of intermediate (M-3-3) 4,4′-dihydroxy-biphenyl monoacetyl (M-3-1) (45.6 g, 200 mmol) was dissolved in 1000 ml of DMF, and 20 g of potassium carbonate was added. After that, 11-bromo-1-undecene (47.2 g, 200 mmol) was added dropwise. The reaction solution was heated at 80 ° C. for 5 hours, cooled to room temperature, poured into water, and the precipitated crystals were collected by filtration. The crude crystals were washed with heated methanol and dried to obtain 72 g of (M-3-2).

  (M-3-2) (50.8 g, 133.5 mmol) was dispersed in 100 ml of methanol, an aqueous potassium hydroxide solution (KOH 12 g / water 10 ml) was added, and the mixture was heated at 40 ° C. for 1 hour and further at 80 ° C. for 20 minutes. After that, the reaction solution was poured into water, and the precipitated crystals were filtered. The obtained crystal was washed with heated methanol and dried to obtain 44 g of (M-3-3).

(2) Synthesis of intermediate (M-3-5) (M-3-3) (20.3 g, 60 mmol) was dissolved in 400 ml of methylene chloride, 120 ml of 0.5 M aqueous sodium hydrogen carbonate solution was added and stirred. While adding m-chloroperbenzoic acid (purity 69%, 16.5 g, 66 mmol) over 10 minutes. After further stirring for 7 hours, water and a small amount of sodium bisulfite were added to the reaction solution, washed with water, and methylene chloride was distilled off to obtain crude crystals. This crude crystal was washed with heated acetonitrile to obtain 12 g of (M-3-4).

  (M-3-4) (11 g, 31 mmol) was dissolved in 50 ml of dimethylformamide, 10 g of potassium carbonate was added, and allyl iodide (5.2 g, 31 mmol) was added dropwise with stirring. After stirring at room temperature for 2 hours, the mixture was stirred at 50 ° C. for 1 hour. The reaction solution was poured into water, and the precipitated crystals were recrystallized from methanol to obtain 12.1 g of (M-3-5).

(3) Synthesis of intermediate (M-3-6) (M-3-5) (5 g, 12.7 mmol) and triethoxysilane (3.13 g, 19.05 mmol) in a mixed solvent of 50 ml of toluene and 5 ml of isopropanol Then, the mixture was heated to 80 ° C. and 10 mg of chloroplatinic acid hexahydrate was added under a nitrogen stream. After the reaction solution was reacted at 80 to 90 ° C. for 1 hour, the solvent was distilled off, and the residue was purified by column chromatography using silica gel to obtain 3.2 g of (M-3-6).

(4) Synthesis of (S-3-1) (M-3-6) (5 g, 8.94 mmol) was dissolved in 20 ml of methylene chloride, and boron trifluoride diethyl ether complex (0.02 ml, 1.63 ×). 10 ⁻² mmol) was added, and the mixture was allowed to react at room temperature for 24 hours under a nitrogen stream. The obtained reaction solution was poured into 400 ml of methanol, and the precipitated solid was filtered to obtain 3.8 g of a waxy solid (S-3-1).

[Synthesis Example 3-2]
The precursor (S-3-7) was synthesized by the following synthesis route.

(1) Synthesis of Intermediate (M-3-9) 3-Ethyl-3-hydroxymethyloxetane (50 g, 430 mmol) and 2-g of 4- (N, N-dimethylamino) pyridine were mixed with 200 ml of tetrahydrofuran and 72 ml of triethylamine. After dissolving in a solvent and further adding p-toluenesulfonic acid (90.3 g, 473 mmol), the mixture was heated to reflux for 24 hours. The reaction solution was extracted with ethyl acetate, the residue obtained after concentration was dissolved in 300 ml of acetonitrile, 100 g of sodium iodide was further added, and the mixture was heated to reflux for 5 hours. An organic substance was extracted from the reaction solution, and the obtained organic substance was purified by column chromatography using silica gel to obtain 38 g of a colorless oily iodide (M-3-9).

(2) Synthesis of Intermediate (M-3-12) (M-3-10) (76.2 g, 410 mmol) was dissolved in 400 ml of dimethylacetamide, and 42.2 g of potassium carbonate and 24.1 g of potassium iodide were dissolved. In addition, 8-chlorooctanol (47.2 g, 287 mmol) was added. The reaction solution was stirred at 110 ° C. for 5 hours, cooled to room temperature, poured into water, and the precipitated crystals were filtered. The obtained crude crystals were recrystallized from acetonitrile to obtain 63.8 g of (M-3-11).

  (M-3-11) (10 g, 31.8 mmol) was dissolved in 40 ml of dimethylacetamide, 3.3 g of potassium carbonate was added, and (M-3-9) (8 g, 35. 4 mmol) was added dropwise. The reaction solution was heated to 85 ° C. and reacted for 5 hours. The reaction mixture was poured into water, and the resulting crude crystals were recrystallized twice with acetonitrile to obtain 10 g of (M-3-12). .

(3) Synthesis of Intermediate (M-3-14) (M-3-12) (5.71 g, 13.8 mmol) was dissolved in dimethyl sulfoxide (50 ml) heated to 60 ° C., and sodium hydride (30 ˜40% oil content, 0.83 g) was added. Allyl bromide (2.5 g, 20.7 mmol) was added dropwise to the reaction solution, and the mixture was reacted at 70 ° C. for 5 hours. The obtained reaction solution was poured into water, and organic substances were extracted with ethyl acetate. The extracted solution was concentrated and then washed with acetonitrile to obtain 4.1 g of a white solid (M-3-13).

  (M-3-13) (4.0 g, 8.84 mmol) and triethoxysilane (1.74 g, 10.6 mmol) were dissolved in 20 ml of toluene, heated to 80 ° C., and subjected to platinum chloride under a nitrogen stream. 10 mg of acid hexahydrate was added. The reaction solution was heated to 80 to 90 ° C. and reacted for 2 hours, and then the reaction solution was filtered through a filter paper and concentrated. The concentrated reaction mixture was purified by column chromatography using silica gel to obtain 2.1 g of a colorless oil (M-3-14).

(4) Synthesis of (S-3-7) (M-3-14) (2 g, 3.24 mmol) was dissolved in 10 ml of methylene chloride, and further boron trifluoride diethyl ether complex (0.01 ml, 8.13). × 10 ⁻³ mmol) was added, and the mixture was allowed to react at room temperature for 24 hours under a nitrogen stream. The reaction solution was poured into 200 ml of methanol, and the precipitated solid was filtered to obtain 1.3 g of a waxy solid (S-3-7).

[Example 1-1]
(1) Preparation of proton conducting membrane (E-1-1) As a precursor, 500 mg of (S-1-1) and tetraethoxysilane (TEOS, 185 mg) were dissolved in 5 ml of ethanol, and 1% hydrochloric acid water was added at 25 ° C. .4 ml was added. After stirring at 25 ° C. for 20 minutes, a phosphoric acid ethanol solution (phosphoric acid (H ₃ PO ₄ , 174 mg) / ethanol 3 ml) was added dropwise. The reaction solution was applied onto a Teflon (registered trademark) sheet using an applicator, allowed to stand at room temperature for 2 hours, heated at 50 ° C. for 2 hours, and further heated at 120 ° C. for 3 hours. Then, it peeled off from the Teflon sheet | seat and white sheet-like solid (E-1-1) with a thickness of 82 micrometers was obtained. When observed with a polarizing microscope, a texture showing a smectic A phase was observed in the temperature range of 25 to 160 ° C.

(2) Production of proton conducting membrane (E-1-2) A white sheet solid (E-) having a thickness of 88 μm was obtained in the same manner as (1) except that 185 mg of TEOS was replaced with 250 mg of silicon compound (X-6). 1-2) was obtained.

(3) Production of proton conducting membrane (E-1-3) A white sheet-like solid (E-75 μm) having a thickness of 75 μm was obtained in the same manner as (1) except that 185 mg of TEOS was replaced with 250 mg of silicon compound (X-11). 1-3) was obtained.

(4) Production of proton conducting membrane (E-1-4) 880 mg of (S-1-4) as a precursor was dissolved in isopropanol, and 36 μl of 2% hydrochloric acid water was added at 25 ° C., followed by stirring for 20 minutes. When an isopropanol phosphate solution (phosphoric acid (H ₃ PO ₄ , 192 mg) / isopropanol 1 ml) was added to this solution, the reaction solution became cloudy. When 2 ml of toluene was added and the reaction liquid became transparent, it was applied to a Teflon sheet using an applicator. The mixture was allowed to stand at room temperature for 2 hours, then heated at 50 ° C. for 2 hours, and further heated at 80 ° C. for 3 hours. Thereafter, it was peeled off from the Teflon sheet to obtain a white sheet-like solid (E-1-4) having a thickness of 50 μm. When observed with a polarizing microscope, a texture showing a smectic A phase was observed in the temperature range of 25 to 130 ° C.

(5) Production of proton conducting membrane (E-1-5) As precursor, (S-1-4) 700 mg and silicon compound (X-6) 176 mg were dissolved in isopropanol, and 2% hydrochloric acid water 36 μl was added at 25 ° C. Added and stirred for 20 minutes. When an isopropanol phosphate solution (phosphoric acid (H ₃ PO ₄ , 192 mg) / isopropanol 1 ml) was added to this solution, the reaction solution became cloudy. When 2 ml of toluene was added and the reaction liquid became transparent, it was applied to a Teflon sheet using an applicator. The mixture was allowed to stand at room temperature for 2 hours, then heated at 50 ° C. for 2 hours, and further heated at 80 ° C. for 3 hours. Thereafter, it was peeled off from the Teflon sheet to obtain a white sheet-like solid (E-1-5) having a thickness of 58 μm.

(6) Preparation of proton conducting membrane (E-1-6) A white sheet-like solid having a thickness of 62 μm (similar to (5) except that the silicon compound (X-6) was replaced with the silicon compound (X-11)) E-1-6) was obtained.

(7) Production of proton conducting membrane (E-1-7) S-1-4 (680 mg) and K-10 (200 mg) were dissolved in isopropanol, and 36 μl of 2% hydrochloric acid water was added at 25 ° C. and stirred for 5 minutes. did. An isopropanol phosphate solution (phosphoric acid (H ₃ PO ₄ , 192 mg) / isopropanol 1 ml) and 3 ml of xylene were added to cast a polyimide film. The mixture was allowed to stand at room temperature for 2 hours, then heated at 50 ° C. for 2 hours, and further heated at 80 ° C. for 3 hours. Thereafter, it was peeled off from the polyimide film to obtain a sheet-like solid (E-1-7) showing a milky white color having a thickness of 100 μm. When observed with a polarizing microscope, an aggregate of domains exhibiting optical anisotropy was observed.

(8) Production of proton conductive membrane (E-1-8) A translucent membrane (E-1-) having a thickness of 110 μm was obtained in the same manner except that K-10 in (7) was changed to K-14. 8) was obtained. When observed with a polarizing microscope, an aggregate of domains exhibiting optical anisotropy was observed.

[Example 1-2]
(1) Preparation of proton conductive membrane (E-2-1) 500 mg of (S-2-1) as a precursor was dissolved in 5 ml of ethanol, and 0.4 ml of 1% hydrochloric acid water was added at 25 ° C. After stirring at 25 ° C. for 20 minutes, a phosphoric acid ethanol solution (phosphoric acid (H ₃ PO ₄ , 85 mg) / ethanol 3 ml) was added dropwise. The reaction solution was poured onto a Teflon petri dish, blown and dried at room temperature for 2 hours, heated at 50 ° C. for 2 hours, and further heated at 120 ° C. for 3 hours. Thereafter, it was peeled off from the Teflon petri dish to obtain a 111 μm thick white sheet solid (E-2-1). When observed with a polarizing microscope, a texture showing a smectic A phase was observed.

(2) Preparation of proton conducting membrane (E-2-2) 500 mg of (S-2-7) and tetraethoxysilane (TEOS, 185 mg) as a precursor were dissolved in 5 ml of ethanol, and 1% hydrochloric acid solution was added at 25 ° C. .4 ml was added. After stirring at 25 ° C. for 20 minutes, a phosphoric acid ethanol solution (phosphoric acid (H ₃ PO ₄ , 174 mg) / ethanol 3 ml) was added dropwise. The reaction solution was poured onto a Teflon petri dish, allowed to stand at room temperature for 2 hours, heated at 50 ° C. for 2 hours, and further heated at 120 ° C. for 6 hours. Thereafter, it was peeled from the Teflon petri dish to obtain a white sheet-like solid (E-2-2) having a thickness of 124 μm.

(3) Production of proton conducting membrane (E-2-3) A white sheet-like solid (E-2-3) having a thickness of 124 μm was obtained in the same manner as (2) except that 185 mg of TEOS was replaced with 250 mg of (X-11). ) When observed with a polarizing microscope, a texture showing a smectic A phase was observed.

(4) Production of proton conducting membrane (E-2-4) (S-2-1) A white sheet having a thickness of 108 μm in the same manner as (1) except that 500 mg was replaced with 500 mg of (S-2-4) A solid (E-2-4) was obtained. When observed with a polarizing microscope, a texture showing a smectic A phase was observed.

(5) Production of proton conducting membrane (E-2-5) (S-2-7) White sheet having a thickness of 126 μm in the same manner as (2) except that 500 mg was replaced with 500 mg of (S-2-4) A solid (E-2-5) was obtained. When observed with a polarizing microscope, a texture showing a smectic A phase was observed.

(6) Production of proton conducting membrane (E-2-6) (S-2-7) White sheet with a thickness of 133 μm in the same manner as (3) except that 500 mg was replaced with 500 mg of (S-2-4) A solid (E-2-6) was obtained.

(7) Production of Proton Conducting Membrane (E-2-7) S-2-7 (880 mg) was dissolved in isopropanol, and 36 μl of 2% aqueous hydrochloric acid was added at 25 ° C. and stirred for 5 minutes. To this solution, an isopropanol phosphate solution (phosphoric acid (H ₃ PO ₄ , 192 mg) / isopropanol 1 ml) and 3 ml of xylene were added and cast onto a polyimide film. The mixture was allowed to stand at room temperature for 8 hours and then heated at 50 ° C. for 2 hours. Thereafter, it was peeled off from the polyimide film to obtain a sheet-like solid (E-2-7) having a thickness of 110 μm and showing milky white. When observed with a polarizing microscope, an aggregate of domains exhibiting optical anisotropy was observed.

(8) Preparation of proton conducting membrane (E-2-8) S-2-7 (680 mg) and K-10 (200 mg) were dissolved in isopropanol, and 36 μl of 2% hydrochloric acid water was added at 25 ° C. for 5 minutes. Stir. To this solution, an isopropanol phosphate solution (phosphoric acid (H ₃ PO ₄ , 192 mg) / isopropanol 1 ml) and 3 ml of xylene were added and cast onto a polyimide film. The mixture was allowed to stand at room temperature for 8 hours and then heated at 50 ° C. for 2 hours. Thereafter, it was peeled off from the polyimide film to obtain a translucent sheet-like solid (E-2-8) having a thickness of 115 μm. When observed with a polarizing microscope, an aggregate of domains exhibiting optical anisotropy was observed.

(9) Production of proton conducting membrane (E-2-9) A thickness of 105 μm, milky white sheet, except that S-2-7 in (7) above was replaced with S-2-23 A solid (E-2-9) was obtained. When observed with a polarizing microscope, an aggregate of domains exhibiting optical anisotropy was observed.

(10) Production of proton conducting membrane (E-2-10) A thickness of 105 μm, milky white sheet, except that S-2-7 in (8) above was replaced with S-2-23 A solid (E-2-10) was obtained. When observed with a polarizing microscope, an aggregate of domains exhibiting optical anisotropy was observed.

[Example 1-3]
(1) Production of proton conducting membrane (E-3-1) (S-3-1) (500 mg) as a precursor was dissolved in a mixed solvent consisting of 5 ml of isopropanol and 5 ml of toluene, and 1% hydrochloric acid water was added at 25 ° C. 0.5 ml was added. Next, after stirring at 25 ° C. for 20 minutes, a phosphoric acid ethanol solution (phosphoric acid (H ₃ PO ₄ , 85 mg) / ethanol 3 ml) was added dropwise. The reaction solution was poured onto a Teflon petri dish, blown and dried at room temperature for 2 hours, heated at 50 ° C. for 2 hours, and further heated at 120 ° C. for 5 hours. Then, it peeled from the Teflon petri dish and obtained the white sheet-like solid (E-3-1) of thickness 50 micrometers.

(2) Production of proton conducting membrane (E-3-2) (S-3-1) (500 mg) and tetraethoxysilane (TEOS, 185 mg) as a precursor were dissolved in a mixed solvent consisting of 5 ml of isopropanol and 5 ml of toluene. Then, 0.5 ml of 1% aqueous hydrochloric acid was added at 25 ° C. Subsequently, after stirring at 25 ° C. for 20 minutes, a phosphoric acid ethanol solution (phosphoric acid (H ₃ PO ₄ , 174 mg) / ethanol 3 ml) was added dropwise. The reaction solution was poured onto a Teflon petri dish, allowed to stand at room temperature for 2 hours, heated at 50 ° C. for 2 hours, and further heated at 120 ° C. for 6 hours. Thereafter, it was peeled from the Teflon petri dish to obtain a white sheet-like solid (E-3-2) having a thickness of 78 μm. When observed with a polarizing microscope, a texture showing a smectic A phase was observed.

(3) Production of proton conducting membrane (E-3-3) White sheet-like solid having a thickness of 98 μm in the same manner as (2) except that TEOS (185 mg) was replaced with silicon compound (X-11) (250 mg) (E-3-3) was obtained.

(4) Production of proton conducting membrane (E-3-4) (S-3-1) (500 mg) was replaced by (S-3-7) (500 mg), and the thickness was determined in the same manner as (1). A 92 μm white sheet-like solid (E-3-4) was obtained.

(5) Preparation of proton conducting membrane (E-3-5) Thickness is the same as (2) except that (S-3-1) (500 mg) is replaced with (S-3-7) (500 mg). A white sheet-like solid (E-3-5) of 98 μm was obtained.

(6) Fabrication of proton conducting membrane (E-3-6) (S-3-1) (500 mg) was replaced with (S-3-7) (500 mg) in the same manner as (3), with the same thickness. A white sheet-like solid (E-3-6) of 101 μm was obtained. When observed with a polarizing microscope, a texture showing a smectic A phase was observed.

(7) Production of proton conducting membrane (E-3-7) S-3-1 (500 mg) and K-10 (50 mg) were dissolved in a mixed solvent consisting of 5 ml of isopropanol and 5 ml of toluene, and 1% hydrochloric acid at 25 ° C. 0.5 ml of water was added. Next, after stirring at 25 ° C. for 20 minutes, a phosphoric acid ethanol solution (phosphoric acid (H ₃ PO ₄ , 85 mg) / ethanol 3 ml) was added dropwise. The reaction solution was poured into a Teflon petri dish, blown and dried at room temperature for 2 hours, heated at 50 ° C. for 2 hours, and further heated at 120 ° C. for 5 hours. Then, it peeled from the Teflon petri dish and the sheet-like solid (E-3-7) which shows the milky white of thickness 70 micrometers was obtained. When observed with a polarizing microscope, an aggregate of domains exhibiting optical anisotropy was observed.

(8) Production of proton conducting membrane (E-3-8) A semi-transparent membrane (E-3-8) having a thickness of 65 μm was obtained in the same manner except that K-10 in (7) was changed to K-14. 8) was obtained. When observed with a polarizing microscope, an aggregate of domains exhibiting optical anisotropy was observed.

[Comparative Example 1]
(1) Production of proton conducting membrane (R-1-1) 1 g of silicon compound (X-6) as a precursor was dissolved in ethanol, 50 μl of 2% hydrochloric acid water was added at 25 ° C., and the mixture was stirred for 20 minutes. To this solution was added an isopropanol phosphate solution (phosphoric acid (H ₃ PO ₄ , 500 mg) / isopropanol 1 ml), and the mixture was stirred at 25 ° C. for 30 minutes, and then applied onto a Teflon sheet using an applicator. The mixture was allowed to stand at room temperature for 2 hours, then heated at 50 ° C. for 2 hours, and further heated at 80 ° C. for 3 hours. Thereafter, it was peeled off from the Teflon sheet to obtain a transparent sheet-like solid (R-1-1) having a thickness of 95 μm.

(2) Production of proton conducting membrane (R-1-2) Transparent sheet-like solid (R) having a thickness of 92 μm in the same manner as (1) except that 800 mg of silicon compound (X-6) and 200 mg of TEOS were used as precursors. -1-2) was obtained.

(3) Production of proton conducting membrane (R-1-3) Transparent sheet-like solid (R) having a thickness of 95 μm in the same manner as (1) except that 800 mg of silicon compound (X-11) and 200 mg of TEOS were used as precursors. 1-3) was obtained.

[Comparative Example 2]
(1) Preparation of proton conducting membrane (R-2-1) As a precursor, 800 mg of (X-11) and 200 mg of TEOS were dissolved in ethanol, 50 μl of 2% hydrochloric acid water was added at 25 ° C., and the mixture was stirred for 20 minutes. To this solution, an isopropanol phosphate solution (phosphoric acid (H ₃ PO ₄ , 500 mg) / isopropanol 1 ml) was added, stirred at 25 ° C. for 30 minutes, and then applied onto a Teflon sheet using an applicator. The mixture was allowed to stand at room temperature for 2 hours, then heated at 50 ° C. for 2 hours, and further heated at 80 ° C. for 3 hours. Then, it peeled from the Teflon sheet | seat and obtained the transparent sheet-like solid (R-2-1) of thickness 85micrometer.

[Comparative Example 3]
(1) Production of proton conducting membrane (R-3-1) Silicon compound (X-11) (800 mg) and TEOS (200 mg) were dissolved in ethanol as a precursor, and 50 μl of 2% hydrochloric acid water was added at 25 ° C. For 20 minutes. To this solution, an isopropanol phosphate solution (phosphoric acid (H ₃ PO ₄ , 500 mg) / isopropanol 1 ml) was added and stirred at 25 ° C. for 30 minutes, and then applied to a Teflon sheet using an applicator. After leaving still for 2 hours, it heated at 50 degreeC for 2 hours, and also heated at 80 degreeC for 3 hours. Subsequently, it peeled from the Teflon sheet | seat and obtained the transparent sheet-like solid (R-3-1) with a thickness of 85 micrometers.

[Example 2-1]
Proton conducting membranes (E-1-1) to (E-1-8) of the present invention obtained in Example 1-1 and comparative samples (R-1-1) to (R) obtained in Comparative Example 1 1-3) and Nafion 117 (manufactured by DuPont) were punched into a circle having a diameter of 13 mm, sandwiched between two stainless steel plates, and measured for ion conductivity at 25 ° C. and a relative humidity of 60% by the AC impedance method. The results are shown in Table 1.

  Although the proton conducting membrane of the present invention does not reach Nafion 117, it exhibits higher ionic conductivity than the non-oriented comparative hybrid membranes (R-1-1) to (R-1-3). all right. In addition, the membrane (E-1-7) and the membrane (E-1-8) containing the compounds K-10 and K-14 that impart plasticity to the membrane showed high ionic conductivity.

[Example 2-2]
The proton conductors (E-2-1) to (E-2-10) of the present invention obtained in Example 2-1 and the sample (R-2-1) obtained in Comparative Example 2 and Nafion 117 ( For DuPont), the ionic conductivity was measured in the same manner as in Example 1-2 above. The results are shown in Table 2.

  Although the proton conducting membrane of the present invention did not reach Nafion 117, it was found that the proton conducting membrane showed higher ionic conductivity than the hybrid membrane (R-2-1) of Comparative Example 2-1, which did not show liquid crystallinity. Moreover, the film | membrane (E-2-8) and the film | membrane (E-2-10) containing the compound K-10 and K-14 which provide a plasticizer with respect to a film | membrane showed high ionic conductivity.

[Example 2-3]
The proton conductor ((E-3-1) to (E-3-8)) obtained in Example 1-3, the sample (R-3-1) obtained in Comparative Example 3, and Nafion 117 ( (Made by DuPont) was made into an outer shape with a diameter of 13 mm, sandwiched between two stainless steel plates, and the ionic conductivity of each sample was measured by an AC impedance method at 25 ° C. and a relative humidity of 60%. The results are shown in Table 3.

  Although the proton conducting membrane of the present invention does not reach Nafion 117, it can be seen that the proton conducting membrane exhibits higher ionic conductivity than the comparative hybrid membrane (R-3-1) that does not exhibit liquid crystallinity. Further, the membranes (E-7) and (E-8) to which the compounds K-10 and K-14 imparting a plasticizer were added showed higher ionic conductivity than the membrane to which no plasticizer was added.

[Example 3-1]
(1) Production of catalyst film 2 g of platinum-supporting carbon (supporting 50% by mass of platinum on Vulcan XC72) and 15 g of Nafion solution (5% alcohol aqueous solution) were mixed and dispersed with an ultrasonic disperser for 30 minutes. The average particle size of the dispersion was about 500 nm. The obtained dispersion was coated on carbon paper (thickness 350 μm), dried, and then punched into a circle having a diameter of 9 mm.

(2) Production of MEA The catalyst membrane obtained in (1) was bonded to both sides of the proton conducting membrane produced in Example 1-1 and Comparative Example 1-1 so that the coated surface was in contact with the proton conducting membrane. Hot pressing was performed at 120 ° C. and 50 kg / cm ² to prepare an MEA.

(3) Fuel Cell Characteristics The MEA obtained in (2) was set in the fuel cell shown in FIG. 2, and a 10% by mass methanol aqueous solution was injected into the cathode side opening 15. At this time, the anode side opening portion 16 was in contact with the atmosphere. A constant current of 5 mA / cm ² was passed between the cathode electrode 12 and the anode electrode 13 with a galvanostat, and the cell voltage at this time was measured. The results are shown in Table 4.

  Although the initial voltage of the battery C-1-12 produced by MEA-1-12 using a Nafion membrane was high, the voltage decreased with time. This voltage drop with time is due to a so-called methanol crossover phenomenon in which methanol of fuel supplied on the cathode electrode side leaks to the anode electrode side through the Nafion membrane. On the other hand, the voltages of the batteries C-1-1 to C-1-1 configured by the MEA-1-1 to MEA-1-1 using the organic-inorganic hybrid film are stable. In particular, it was found that higher voltages could be maintained in the batteries C-1-1 to C-1-8 of the present invention constituted by MEA-1-1 to MEA-1-8.

[Example 3-2]
Proton conducting membranes produced in Example 2-1 and Comparative Example 2 ((E-2-1), (E-2-3), (E-2-6), (E-2-6)) 7), (E-2-8), (E-2-9), (E-2-10), (R-2-1)) The voltage was measured. The results are shown in Table 5.

  Battery C-2-9 produced by MEA-2-9 using a Nafion membrane had a high initial voltage, but the voltage decreased over time. This voltage drop with time is due to a so-called methanol crossover phenomenon in which methanol of fuel supplied on the cathode electrode side leaks to the anode electrode side through the Nafion membrane. On the other hand, the voltages of the batteries C-2-1 to C-2-8 produced by the MEA-2-1 to MEA-2-8 using the organic-inorganic hybrid film are stable. In particular, it was found that batteries C-2-1 to C-2-7 produced by MEA-2-1 to MEA-2-7 of the present invention can maintain a higher voltage.

[Example 3-3]
Proton conducting membranes ((E-3-3), (E-3-4), (E-3-6), and (R-3) produced in Example 3-1 and Comparative Example 3 were used as proton conducting membranes. The cell voltage was measured in the same manner as in Example 3-1, except that -1)) was used. The results are shown in Table 6.

  Although the initial voltage of the battery C-3-7 produced by MEA-3-7 using a Nafion membrane was high, the voltage decreased with time. This decrease in voltage over time is due to a so-called methanol crossover phenomenon in which methanol of fuel supplied to the cathode electrode side leaks to the anode electrode side through the Nafion membrane. On the other hand, the voltages of the batteries C-3-1 to C-3-6 produced by MEA-3-1 to MEA-3-6 using the organic-inorganic hybrid film are stable. In particular, it was found that the batteries C-3-1 to C-3-5 of the present invention produced by MEA-3-1 to MEA-3-5 can maintain a higher voltage.

[Example 4-1]
Proton conducting membranes (E-1-1) to (E-1-8) of the present invention used in Example 2-1 and comparative samples (R-1-1)-(R-1-3) Was immersed in a 50% by mass aqueous methanol solution and allowed to stand for 18 hours, and changes in the film shape were observed. The proton conducting membranes (E-1-1) to (E-1-6) and the comparative sample (R-1-1)-(R-1-3) of the present invention were all cracked, but K-10 And the film | membrane (E-1-7) and (E-1-8) of this invention which added K-14 kept the original shape. This shows that the methanol resistance of the membrane is improved by adding the compounds (K-10) and (K-14).

[Example 4-2]
The proton conductive membranes (E-2-1) to (E-2-10) of the present invention and the comparative sample (R-2-1) used in Example 2-2 were mixed with a 50% by mass methanol aqueous solution. The film was immersed in and allowed to stand for 18 hours, and the change in the film shape was observed. The proton conducting membranes (E-2-1) to (E-2-7), (E-2-9) and the comparative sample (R-2-1) of the present invention all had cracks, but K-10 And the film | membrane (E-2-8) and (E-2-10) of this invention which added K-14 kept the original shape. This shows that the methanol resistance of the membrane is improved by adding the compounds (K-10) and (K-14).

[Example 4-3]
The proton conductive membranes (E-3-1) to (E-3-8) of the present invention and the comparative sample (R-3-1) used in Example 2-3 were placed in a 50% by mass methanol aqueous solution. Immersion was allowed to stand for 18 hours, and changes in the film shape were observed. The proton conducting membranes (E-3-1) to (E-3-6) and the comparative sample (R-3-1) of the present invention were all cracked, but K-10 and K-14 were added. The films (E-7) and (E-3-8) of the present invention maintained their original shapes. This shows that the methanol resistance of the membrane is improved by adding the compounds (K-10) and (K-14).

  As described above, the organic-inorganic hybrid proton conductive material of the present invention obtained by a sol-gel reaction using an organosilicon compound having a mesogen group as a precursor has high ionic conductivity at room temperature and reduces methanol crossover. can do. Therefore, when used in a direct methanol fuel cell, it is possible to obtain a higher output than a conventional proton conducting membrane.

It is sectional drawing which shows the catalyst electrode joining film | membrane using the organic-inorganic hybrid type proton conductive material of this invention. It is an exploded sectional view showing an example of the structure of the fuel cell of the present invention.

Explanation of symbols

10 Catalytic electrode assembly (MEA)
DESCRIPTION OF SYMBOLS 11 Proton conductive film 12 Cathode side electrode 13 Anode side electrode 12a, 13a Porous conductive material 12b, 13b Catalyst layer 14 Packing 15 Cathode pole side opening 16 Anode pole side opening 17 Current collector 21, 22 Separator

Claims (6)

Compounds represented by the following general formula (1-1), the following (S-1-1), (S-1-2), (S-1-3), (S-1-6), (S- 1-17), (S-1-18), (S-1-21), (S-1-22), (S-1-23), (S-1-24) or (S-1- 25) as a precursor, and an organic compound having a three-dimensional crosslinked structure of Si—O—Si formed by adding a compound represented by the following general formula (1-3 ) to the precursor and polymerizing the compound: An organic-inorganic hybrid proton conductive material, wherein at least one of a phosphorus compound, an organic sulfonic acid, and a perfluorocarbon sulfonic acid polymer is retained in the inorganic hybrid material as a proton conductivity imparting agent.

(In the general formula (1-1), A ¹ represents an organic atomic group containing a mesogenic group represented by the following general formula (1-2) and an alkylene group having 4 or more carbon atoms, and R ¹¹ is an alkyl group or aryl. represents a group or a heterocyclic group, X ¹ represents a halogen atom or oR ^14, R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group or a silyl group, m11 represents 0, n11 represents 2 .X ¹ May be the same or different.)

(In General Formula (1-2), Q ¹¹ and Q ¹² each represent a divalent linking group or a single bond, and Y ¹¹ represents a divalent 4-, 5-, 6- or 7-membered ring substituent, or from them The substituent of the condensed ring comprised is represented, m12 represents the integer of 1-3.)

(In General Formula (1-3), R ¹² represents a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, Z ¹ represents a halogen atom or OR ¹⁵ , R ¹⁵ represents a hydrogen atom, an alkyl group, Represents an aryl group or a silyl group, and m13 represents 0 or 1. Z ¹ may be the same or different from each other, and may be linked to each other by a substituent of R ¹² or R ¹² to form a multimer. Good.) The organic-inorganic hybrid proton conductive material according to claim 1, wherein the compound represented by the general formula (1-3) is tetramethoxysilane and / or tetraethoxysilane. Compounds represented by the following general formula (2-1), the following (S-2-15), (S-2-16), (S-2-17), (S-2-18), (S- 2-19), (S-2-20), (S-2-21), (S-2-22), (S-2-28), (S-2-29) or (S-2- 30) as a precursor, and having an epoxy group or an oxetane group by a polymerization reaction of a three-dimensional crosslinked structure of Si-O-Si formed by a sol-gel reaction of the precursor and a group having an epoxy group or an oxetane group An organic-inorganic hybrid material having a main chain structure obtained by ring-opening polymerization of a group retains at least one of a phosphorus compound, an organic sulfonic acid, and a perfluorocarbon sulfonic acid polymer as a proton conductivity imparting agent. Organic-inorganic Hybrid type proton conductive material.

(In the general formula (2-1), A ² represents an organic atomic group containing a mesogenic group represented by the following general formula (1-2), R ²¹ represents an alkyl group, R ²² represents an alkyl group, aryl represents a group or a heterocyclic group, R ²³ represents a group having an epoxy group or an oxetane group, m21 represents 0, n21 represents 1,. R ²¹ representing a 1 n22 are each Re their Re are identical May be different.)

(In General Formula (1-2), Q ¹¹ and Q ¹² each represent a divalent linking group or a single bond, and Y ¹¹ represents a divalent 4-, 5-, 6- or 7-membered ring substituent, or from them The substituent of the condensed ring comprised is represented, m12 represents the integer of 1-3.)

Polymer compound having a repeating unit represented by the following general formula (3-1) , (S-3-13), (S-3-14), (S-3-15), (S-3-16) ), (S-3-17) or (S-3-20) as a precursor, and an organic-inorganic hybrid material characterized by comprising a phosphorus compound, an organic sulfone as a proton conductivity-imparting agent. An organic-inorganic hybrid proton conductive material, wherein at least one of acids and perfluorocarbon sulfonic acid polymer is retained.

(In General Formula (3-1), A ³ represents an organic atomic group containing a mesogenic group and an alkylene group represented by the following General Formula (1-2), R ³¹ represents an alkyl group, and R ³² represents an alkyl group. A group, an aryl group, or a heterocyclic group, E ³ represents an alkyleneoxy group, an alkylene group, or a siloxy group, L ³ represents a linking group, m31 represents an integer of 0 to 2, and n31 represents 1 . N32 represents an integer of 1 to 5. When m31 is 0 or 1, R ³¹ may be the same or different, and when m31 is 2, R ³² may be the same or different.

(In General Formula (1-2), Q ¹¹ and Q ¹² each represent a divalent linking group or a single bond, and Y ¹¹ represents a divalent 4-, 5-, 6- or 7-membered ring substituent, or from them The substituent of the condensed ring comprised is represented, m12 represents the integer of 1-3.)

The organic-inorganic hybrid material is a compound represented by the following general formula (1-4) , a compound represented by the following general formula (1-5), the following (K-1), (K-2), ( An organic-inorganic hybrid comprising K-3), (K-4), (K-18) or (K-19) added in an amount of 1 to 50 mol% based on the number of moles of the precursor. The organic-inorganic hybrid proton conductive material according to any one of claims 1 to 4, which is a material.

(In the general formula (1-4), A ¹⁴ represents an organic atomic group containing the formula (1-2) mesogenic groups and having 4 or more alkylene group having a carbon represented by, Z ¹⁴ is a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a sulfino group, a phosphono group or a vinyl group,, n13 represents 1, n14 represents 1, Y ¹⁴ represents a group having a d epoxy group or an oxetane group.
In the general formula (1-5), A ¹⁵ represents an organic atomic group containing a mesogen represented by the general formula (1-2) and an alkylene group having 4 or more carbon atoms, Z ¹⁵ represents a hydrogen atom, a hydroxyl group, represents a carboxyl group, a sulfo group, a sulfino group, a phosphono group or a vinyl group,, n15 represents 1, n16 represents an integer of 1 to 5, L ¹⁵ is ** - COO -, ** - OCO -, * * — (CH ₂ ) _nn3 —, ** — (CH ₂ ) _nn3 O—, ** — O (CH ₂ ) _nn3 —, ** — CON (R ³⁴ ′) — or a phenylene group (** is E ¹⁵ represents the position which binds to, R ³⁴ 'is an alkyl group, NN3 represents represents) an integer from 1 to 6, E ¹⁵ is to Table alkyleneoxy group, an alkylene group or a siloxy group. When n16 is 2 or more, each unit may be the same or different. )

A fuel cell using the organic-inorganic hybrid proton conductive material according to any one of claims 1 to 5.

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