JP5973861B2 - Anion exchange resin, electrolyte layer for fuel cell, binder for forming electrode catalyst layer, battery electrode catalyst layer and fuel cell - Google Patents

Description

  The present invention relates to an anion exchange resin, an electrolyte layer for a fuel cell, a binder for forming an electrode catalyst layer, a battery electrode catalyst layer, and a fuel cell.

  To date, various types of fuel cells such as alkaline type (AFC), solid polymer type (PEFC), phosphoric acid type (PAFC), molten carbonate type (MCFC), and solid electrolyte type (SOFC) are known. It has been. Among these, since the polymer electrolyte fuel cell can be operated at a relatively low temperature, use in various applications such as an automobile application has been studied.

  Such a polymer electrolyte fuel cell includes, for example, an electrolyte layer made of an anion exchange membrane, and a fuel side electrode and an oxygen side electrode that are arranged to face each other with the electrolyte layer interposed therebetween. There has been proposed a fuel cell in which a gas containing oxygen and water are supplied and a catalyst is supported on a fuel side electrode and a fuel such as hydrazine is supplied (see, for example, Patent Document 1). .)

  In addition, as an electrolyte forming an electrolyte layer used in such a fuel cell, for example, an aromatic compound having a structure in which a super strong acid group is introduced into a polymer fluorenyl group represented by the following formula (25): Group polymer electrolytes have been proposed (see, for example, Patent Document 2).

(In the formula, n and m represent proportions in the polymer, and 0 ≦ n ≦ 100, 0 ≦ m ≦ 100, and n + m = 100. The benzene ring constituting the fluorenyl group and the benzene ring constituting the main chain are May be substituted.)
By using such an electrolyte, durability of the electrolyte layer, specifically, mechanical strength at high temperature can be improved, and further, proton conductivity at high temperature and low humidity can be improved.

JP 2006-244960 A JP 2010-229352 A

  However, in the electrolyte described in Patent Document 2, since the aromatic polymer electrolyte contains a sulfonyl group, a carbonyl group, and the like as shown in the above formula (25), it is inferior in durability. For example, a sulfonyl group is inferior in hydrazine resistance and alkali resistance, and a carbonyl group may react with hydrazines. For example, when the aromatic polymer electrolyte contains an imide group, the durability may be inferior.

  Therefore, an electrolyte layer is formed from an electrolyte containing such a group, and the electrolyte layer is used as the fuel cell described in Patent Document 1, specifically, a fuel cell to which hydrazines (alkaline fuel) are supplied as fuel. In some cases, the electrolyte layer may be decomposed by hydrazines.

  Therefore, further improvement in durability is required as an electrolyte in a fuel cell.

  In the fuel cell, when the catalyst is supported on the fuel side electrode and / or the oxygen side electrode, a binder resin is used. Since this binder resin is used as a path for ions generated by the catalyst, it needs to be an electrolyte resin. And durability is requested | required also as such binder resin.

  An object of the present invention is to provide a fuel cell electrolyte layer having excellent durability, an electrode catalyst layer-forming binder, an anion exchange resin capable of producing a battery electrode catalyst layer, a fuel cell electrolyte layer formed from the anion exchange resin, and An object of the present invention is to provide an electrode catalyst layer-forming binder, a battery electrode catalyst layer formed from the electrode catalyst layer-forming binder, and a fuel cell comprising the fuel cell electrolyte layer or battery electrode catalyst layer.

  In order to achieve the above object, the anion exchange resin of the present invention comprises a divalent hydrophobic group comprising a plurality of aromatic rings bonded to each other via a divalent saturated hydrocarbon group, and a single aromatic ring. Or a divalent linking group composed of a plurality of aromatic rings bonded to each other via a carbon-carbon bond and a plurality of aromatic rings bonded to each other via an oxygen atom or a sulfur atom and having an anion exchange group A hydrophobic unit in which the hydrophobic group and the binding group are repeated through an ether bond, and a hydrophilic unit in which the hydrophilic group and the binding group are repeated through an ether bond. And the hydrophobic unit and the hydrophilic unit are bonded via an ether bond.

  In the anion exchange resin of the present invention, the hydrophobic group is preferably a bisphenol residue which is represented by the following formula (1) and may be substituted with a halogen atom.

(In the formula, R represents —CH ₂ — or —C (CH ₃ ) ₂ — which may be substituted with a halogen atom, X represents the same or different from each other, and represents a halogen atom; Are the same or different from each other and represent an integer of 0 to 4.)
In the anion exchange resin of the present invention, the binding group is preferably a biphenylene group represented by the following formula (2), which may be substituted with a halogen atom.

(In the formula, X is the same or different from each other and represents a halogen atom, and c and d are the same or different from each other and represent an integer of 0 to 4.)
In the anion exchange resin of the present invention, the hydrophilic group is represented by the following formula (3a) and is substituted with the anion exchange group, and / or the following bis (hydroxyphenyl) oxide residue: A bis (hydroxyphenyl) sulfide residue substituted with the anion exchange group represented by formula (3b) is preferred.

Wherein A is the same or different from each other and represents an anion exchange group, e and f are the same or different from each other and represent an integer of 0 to 4, and at least one of e and f is 1 or more.)

(In the formula, A, e and f are as defined above.)
In addition, an electrolyte layer for a fuel cell according to the present invention includes the above anion exchange resin.

  Moreover, the binder for electrode catalyst layer formation of this invention is characterized by including said anion exchange resin.

  Moreover, the battery electrode catalyst layer of the present invention is characterized by including the above-mentioned binder for forming an electrode catalyst layer.

  Further, the fuel cell of the present invention is a fuel cell comprising an electrolyte layer, a fuel-side electrode that is disposed to face the electrolyte layer, to which fuel is supplied, and an oxygen-side electrode to which oxygen is supplied. The electrolyte layer is the fuel cell electrolyte layer described above, and the fuel is a hydrogen-containing liquid fuel.

  In the fuel cell of the present invention, it is preferable that the hydrogen-containing liquid fuel is hydrazines.

  Further, the fuel cell of the present invention is a fuel cell comprising an electrolyte layer, a fuel-side electrode that is disposed to face the electrolyte layer, to which fuel is supplied, and an oxygen-side electrode to which oxygen is supplied. The fuel-side electrode and / or the oxygen-side electrode includes a catalyst layer, the catalyst layer is the battery electrode catalyst layer, and the fuel is a hydrogen-containing liquid fuel.

  In the fuel cell of the present invention, it is preferable that the hydrogen-containing liquid fuel is hydrazines.

  The anion exchange resin of the present invention comprises a divalent hydrophobic group consisting of a plurality of aromatic rings bonded to each other via a divalent saturated hydrocarbon group, a single aromatic ring, or a carbon-carbon bond. A divalent linking group composed of a plurality of aromatic rings bonded to each other via a divalent hydrophilic group composed of a plurality of aromatic rings bonded to each other via an oxygen atom or a sulfur atom and having an anion exchange group; A hydrophobic unit in which the hydrophobic group and the binding group are repeated through an ether bond, and a hydrophilic unit in which the hydrophilic group and the binding group are repeated through an ether bond. The unit and the hydrophilic unit are bonded through an ether bond.

  That is, the anion exchange resin of the present invention does not contain a sulfonyl group, a carbonyl group, an imide group or the like, and therefore has excellent durability such as alkali resistance.

  Therefore, the fuel cell electrolyte layer and electrode catalyst layer forming binder of the present invention obtained using such an anion exchange resin, and the battery electrode catalyst layer obtained using the electrode catalyst layer forming binder, Excellent durability.

  As a result, the fuel cell including such an electrolyte layer for a fuel cell and the fuel cell including the cell electrode catalyst layer are excellent in durability.

It is a schematic block diagram which shows one Embodiment of the fuel cell of this invention. The evaluation result of the fuel cell of the comparative example 2 is shown. The evaluation result of the fuel cell of Reference Example 2 is shown.

  The anion exchange resin of the present invention comprises a divalent hydrophobic group, a divalent binding group, and a divalent hydrophilic group.

  In the anion exchange resin of the present invention, the divalent hydrophobic group is composed of a plurality (two or more, preferably two) aromatic rings bonded to each other via a divalent saturated hydrocarbon group.

Examples of the divalent saturated hydrocarbon group include methylene (—CH ₂ —), ethylene, propylene, isopropylene (—C (CH ₃ ) ₂ —), butylene, isobutylene, sec-butylene, pentylene (pentene), 2 having 1 to 20 carbon atoms, such as isopentylene, sec-pentylene, hexylene (hexamethylene), 3-methylpentene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, isodecylene, dodecylene, tetradecylene, hexadecylene, octadecylene, etc. Valent saturated hydrocarbon group.

The divalent saturated hydrocarbon group is preferably a divalent saturated hydrocarbon group having 1 to 3 carbon atoms, specifically methylene (—CH ₂ —), ethylene, propylene, isopropylene (—C (CH _{3) 2} -) and the like, more preferably methylene _(-CH 2 -), isopropylene (-C _{(CH 3) 2} -) and the like, especially preferably isopropylene (-C _(CH 3) _2- ).

  The divalent saturated hydrocarbon group may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine. As the halogen atom, preferably, fluorine is used.

  When the divalent saturated hydrocarbon group is substituted with a halogen atom, the number of substitutions and the substitution position of the halogen atom are appropriately set according to the purpose and application.

  More specific examples of the divalent saturated hydrocarbon group substituted with a halogen atom include, for example, methylene substituted with a halogen atom (eg, fluoromethylene, difluoromethylene, chloromethylene, dichloromethylene, bromomethylene, dibromomethylene). , Iodomethylene, iodomethylene, etc.), isopropylene substituted with a halogen atom (eg, fluoroisopropylene, difluoroisopropylene, trifluoroisopropylene, tetrafluoroisopropylene, pentafluoroisopropylene, hexafluoroisopropylene, chloroisopropylene) Propylene, dichloroisopropylene, trichloroisopropylene, tetrachloroisopropylene, pentachloroisopropylene, hexachloroisopropylene, bromoisopropylene, dibromo Propylene, tribromoisopropylene, tetrabromoisopropylene, pentabromoisopropylene, hexabromoisopropylene, iodoisopropylene, diiodoisopropylene, triiodoisopropylene, tetraiodoisopropylene, pentaiodoisopropylene, hexaiodoisopropylene Etc.).

  The divalent saturated hydrocarbon group substituted with a halogen atom is preferably isopropylene substituted with a halogen atom, and more preferably hexafluoroisopropylene.

  Examples of the aromatic ring include monocyclic or polycyclic aromatic hydrocarbons having 6 to 14 carbon atoms such as a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, and phenanthrene ring.

  As an aromatic ring, Preferably, C6-C14 monocyclic aromatic hydrocarbon is mentioned, More preferably, a benzene ring is mentioned.

  In addition, the aromatic ring may be substituted with a halogen atom as necessary.

  When the aromatic ring is substituted with a halogen atom, the number of substitutions and the substitution position of the halogen atom are appropriately set according to the purpose and application.

  More specifically, examples of the aromatic ring substituted with a halogen atom include a benzene ring substituted with 1 to 4 halogen atoms (for example, a benzene ring substituted with 1 to 4 fluorine atoms, and 1 to 4 chlorine atoms). Benzene ring substituted with 1 to 4 bromine, benzene ring substituted with 1 to 4 iodine, and the like.

Such a hydrophobic group is preferably a bisphenol residue (methylene (—CH ₂ —) or isopropylene (—C (CH ₃ )) optionally substituted with a halogen atom represented by the following formula (1). ₂ ), a divalent hydrophobic group composed of two benzene rings bonded to each other via.

(In the formula, R represents —CH ₂ — or —C (CH ₃ ) ₂ — which may be substituted with a halogen atom, X represents the same or different from each other, and represents a halogen atom; Are the same or different from each other and represent an integer of 0 to 4.)
In the above formula (1), R represents methylene (—CH ₂ —) or isopropylene (—C (CH ₃ ) ₂ —) optionally substituted with a halogen atom, preferably substituted with a halogen atom. Isopropylene (—C (CH ₃ ) ₂ —) that may be present is shown.

  In the above formula (1), Xs are the same or different from each other and represent the above-described halogen atom.

  In the above formula (1), a and b are the same or different and each represents an integer of 0 to 4, preferably 0 to 2, and more preferably a and b both represent 0.

  As such a hydrophobic group, a bisphenol residue (bisphenol A residue) represented by the following formula (4) is particularly preferable.

  In the anion exchange resin of the present invention, the binding group is composed of a single aromatic ring or a plurality of (two or more, preferably two) aromatic rings that are bonded to each other via a carbon-carbon bond. .

  As an aromatic ring, the above-mentioned aromatic ring is mentioned, for example, Preferably, a C6-C14 monocyclic aromatic hydrocarbon is mentioned, More preferably, a benzene ring is mentioned.

  Moreover, the aromatic ring may be substituted with a substituent such as a halogen atom or a cyano group, if necessary.

  When the aromatic ring is substituted with a substituent such as a halogen atom or a cyano group, the number of substitutions and the substitution position of the substituent are appropriately set according to the purpose and application.

  As such a binding group, a biphenylene group which may be substituted with a halogen atom, represented by the following formula (2), or a halogen atom which is represented by the following formula (2 ′) Good o-, m-, or p-phenylene groups, and o-, m-, or p-phenylene groups that are optionally substituted with a cyano group, represented by the following formula (2 ″) are mentioned.

(In the formula, X is the same or different from each other and represents a halogen atom, and c and d are the same or different from each other and represent an integer of 0 to 4.)

(In the formula, X represents a halogen atom, and c 'represents an integer of 0 to 4.)

(In the formula, c ″ represents an integer of 0 to 4.)
In the above formula (2), Xs are the same or different from each other and represent the halogen atom described above.

  In the above formula (2), c and d are the same or different and each represents an integer of 0 to 4, and from the viewpoint of radical resistance, preferably, at least one of c and d represents 1 to 4, Particularly preferably, c and d both represent 4.

  In the above formula (2 '), X represents the above-described halogen atom, and c' represents an integer of 0 to 4, preferably 4.

  In the above formula (2 ″), c ″ represents an integer of 0 to 4, preferably 1.

  As such a binding group, particularly preferably, a biphenylene group represented by the following formula (5) (a biphenylene group in which four fluorines are substituted on each benzene ring), a perfluoro group represented by the following formula (5 ′): p-phenylene group (p-phenylene group in which four fluorine atoms are substituted on the benzene ring), 2-cyano-1,3-phenylene group (one cyano group in the benzene ring) represented by the following formula (5 ″) M-phenylene group in which is substituted.

  In the anion exchange resin, the hydrophilic group is composed of a plurality of aromatic rings having an anion exchange group bonded to each other via an oxygen atom or a sulfur atom.

  In the hydrophilic group, examples of the plural (two or more, preferably two) aromatic rings include the above-described aromatic rings, and preferably include a benzene ring.

  Moreover, an anion exchange group is introduce | transduced into a side chain in a hydrophilic group. The anion exchange group is not particularly limited, and examples thereof include a quaternary ammonium group, a tertiary amino group, a secondary amino group, a primary amino group, a phosphine, a phosphazene, a tertiary sulfonium group, and a quaternary boronium group. Any known anion exchange group such as a quaternary phosphonium group can be employed. From the viewpoint of anion conductivity, preferably, a quaternary ammonium salt is used.

  The number of substitutions and substitution positions of such anion exchange groups are appropriately set according to the purpose and application. That is, the anion exchange group may be substituted with at least one aromatic ring of a plurality of aromatic rings, or may be substituted with all aromatic rings. One anion exchange group may be substituted for one aromatic ring, or a plurality (two or more) may be substituted.

  Such a hydrophilic group is preferably a bis (hydroxyphenyl) oxide residue substituted with an anion exchange group represented by the following formula (3a), an anion exchange represented by the following formula (3b). And bis (hydroxyphenyl) sulfide residues substituted with groups.

Wherein A is the same or different from each other and represents an anion exchange group, e and f are the same or different from each other and represent an integer of 0 to 4, and at least one of e and f is 1 or more.)

(In the formula, A, e and f are as defined above.)
In the above formula (3a) and the above formula (3b), A is the same or different from each other and represents the anion exchange group described above, preferably the quaternary ammonium group described above.

  In the above formula (3a) and the above formula (3b), e and f are the same or different from each other and represent an integer of 0 to 4, and at least one of e and f represents 1 or more.

  In the above formula (3a) and the above formula (3b), when e and / or f is in the range of 1 to 3, the substitution position of the anion exchange group is appropriately determined according to the purpose and application. Is set.

  Particularly preferable examples of such a hydrophilic group include a bis (hydroxyphenyl) oxide residue represented by the following formula (6a) and a bis (hydroxyphenyl) sulfide residue represented by the following formula (6b).

(In the formula, at least one of A ′ and A ″ represents CH ₂ N ⁺ (CH ₃ ) ₃ OH ⁻ , and the other represents CH ₂ N ⁺ (CH ₃ ) ₃ OH ⁻ or a hydrogen atom. )

(In the formula, A ′ is as defined above.)
In addition, as the hydrophilic group, for example, the above-described bis (hydroxyphenyl) oxide residue, bis (hydroxyphenyl) sulfide residue and the like can be used alone, or they can be used in combination. In addition, in the case of using together, those ratios are not restrict | limited, It sets suitably according to the objective and a use. The hydrophilic group is preferably a single use of a bis (hydroxyphenyl) oxide residue or a single use of a bis (hydroxyphenyl) sulfide residue, more preferably a single use of a bis (hydroxyphenyl) oxide residue. Is mentioned.

  Such a hydrophilic group has a smaller molecular weight than a hydrophilic group of a resin (such as the above formula (25)) contained in a conventional aromatic polymer electrolyte, that is, a bisphenolfluorene residue. Therefore, if such a hydrophilic group is used, the molecular weight of the entire resin can be reduced. As a result, the content of anion exchange groups in the resin can be improved, and the ion exchange capacity can be improved. Can be achieved.

  In this anion exchange resin, the hydrophobic unit and the binding group described above are repeated via an ether bond, and the hydrophilic group and the binding group described above are repeated via an ether bond. And a hydrophilic unit.

  The binding group in the hydrophobic unit and the binding group in the hydrophilic unit may be the same or different from each other. The unit corresponds to a block of a generally used block copolymer.

  The hydrophobic unit is preferably a bisphenol residue (hydrophobic group) optionally substituted with a halogen atom represented by the above formula (1) and a halogen atom substituted by the above formula (2). Examples thereof include a unit formed by repeating a good biphenylene group (bonding group) through an ether bond.

  Such a hydrophobic unit is represented by, for example, the following formula (7).

(Wherein X is the same or different from each other and represents a halogen atom, a and b are the same as a and b in the above formula (1), and c and d are those in the above formula (2). The same meaning as c and d is shown, and n is a numerical value of 1 to 200.)
In said Formula (7), n is the number of repeating units of the hydrophobic unit in an anion exchange resin, Comprising: For example, 1-200, Preferably it is 4-40, More preferably, it shows 4-20.

  As such a hydrophobic unit, particularly preferably, a bisphenol residue (bisphenol A residue) represented by the above formula (4) and a biphenylene group represented by the above formula (5) (four fluorines are substituted on each benzene ring) And a unit formed by repeating a biphenylene group) via an ether bond.

  Such a hydrophobic unit is represented by, for example, the following formula (8).

(In the formula, n has the same meaning as n in the above formula (7).)
The hydrophilic unit is preferably a bis (hydroxyphenyl) oxide residue substituted with an anion exchange group represented by the above formula (3a) or an anion exchange group represented by the above formula (3b). The substituted bis (hydroxyphenyl) sulfide residue (hydrophilic group) and the biphenylene group (bonding group) optionally substituted with a halogen atom as shown in the above formula (2) form an ether bond. And a unit formed repeatedly.

  Such a hydrophilic unit is represented, for example, by the following formula (9a) when a bis (hydroxyphenyl) oxide residue (the above formula (3a)) is employed as the hydrophilic group. When a bis (hydroxyphenyl) sulfide residue (the above formula (3b)) is employed as the hydrophilic group, it is represented by the following formula (9b).

Wherein X is the same as or different from each other and represents a halogen atom, A represents the same meaning as A in the above formula (3a), c and d represent c and d in the above formula (2), The same meaning is shown, e and f are the same meaning as e and f in the above formula (3a), and m is a numerical value of 1 to 200.)

Wherein X is the same as or different from each other and represents a halogen atom, A is the same as A in the above formula (3b), c and d are c and d in the above formula (2), The same meaning is shown, e and f are the same meaning as e and f in the above formula (3b), and m is a numerical value of 1 to 200.)
In the above formula (9a) and the above formula (9b), m is the number of repeating units of the hydrophilic unit in the anion exchange resin, and is, for example, 1 to 200, preferably 4 to 40, more preferably 4 to 20 is shown.

  As such a hydrophilic unit, the bis (hydroxyphenyl) oxide residue represented by the above formula (6a) or the bis (hydroxyphenyl) sulfide residue represented by the above formula (6b) and the above formula are particularly preferable. Examples thereof include a unit formed by repeating the biphenylene group represented by (5) (biphenylene group in which four fluorine atoms are substituted on each benzene ring) through an ether bond.

  For example, when the bis (hydroxyphenyl) oxide residue represented by the above formula (6a) is employed, such a hydrophilic unit is represented by the following formula (10a) and represented by the above formula (6b). When a bis (hydroxyphenyl) sulfide residue is employed, it is represented by the following formula (10b).

(In the formula, A ′ and A ″ have the same meaning as A ′ and A ″ in the formula (6a), and m has the same meaning as m in the formula (9a).)

(In the formula, A ′ and A ″ are the same as A ′ and A ″ in the above formula (6b), and m is the same as m in the above formula (9b).)
And in this anion exchange resin, the above-mentioned hydrophobic unit and the above-mentioned hydrophilic unit are couple | bonded through the ether bond.

  As the anion exchange resin, preferably, as shown by the following formula (11a), the hydrophobic unit shown by the above formula (7), the hydrophilic unit shown by the above formula (9a), and the following formula (11b): As shown, an anion exchange resin in which a hydrophobic unit represented by the above formula (7) and a hydrophilic unit represented by the above formula (9b) are bonded via an ether bond can be mentioned.

(Wherein R represents the same meaning as R in the above formula (1), X represents the same or different from each other and represents a halogen atom, and A represents the same meaning as A in the above formula (3a). , A and b are the same as a and b in the above formula (1), c and d are the same as c and d in the above formula (2), and e and f are the same as those in the above formula (3a ) Have the same meaning as e and f, n has the same meaning as n in the above formula (7), m has the same meaning as m in the above formula (9a), and l represents 1-100 Indicates a numerical value.)

Wherein R represents the same meaning as R in the above formula (1), X represents the same or different from each other, represents a halogen atom, and A represents the same meaning as A in the above formula (3b). , A and b are the same as a and b in the above formula (1), c and d are the same as c and d in the above formula (2), and e and f are the same as those in the above formula (3b). ) Is the same as e and f in the formula (7), n is the same as n in the formula (7), m is the same as m in the formula (9b), and l is 1-100. Indicates a numerical value.)
In the above formula (11a) and the above formula (11b), l is the number of repeating units of a unit composed of a hydrophobic unit and a hydrophilic unit bonded by an ether bond, and is, for example, 1 to 100, preferably 1 to 80 More preferably, it shows 1-50, More preferably, it is 1-20, Most preferably, it shows 1-5.

  In addition, as l, it adjusts so that the number average molecular weight of an anion exchange resin may be 10-300 kDa, Preferably, it is 30-150 kDa.

  As such an anion exchange resin, particularly preferably, as shown by the following formula (12a), the hydrophobic unit represented by the above formula (8) and the hydrophilic unit represented by the above formula (10a) are ether-bonded. An anion exchange resin bonded via the above, or a hydrophobic unit represented by the above formula (8) and a hydrophilic unit represented by the above formula (10b) as shown by the following formula (12b). And anion exchange resin bonded through the above.

(In the formula, A ′ and A ″ are the same as A ′ and A ″ in the above formula (6a), n is the same as n in the above formula (7), m Represents the same meaning as m in the above formula (9a), and l represents the same meaning as l in the above formula (11a).

(In the formula, A ′ and A ″ are the same as A ′ and A ″ in the formula (6b), n is the same as n in the formula (7), and m Represents the same meaning as m in the above formula (9b), and l represents the same meaning as l in the above formula (11a).
Moreover, the number average molecular weight of such an anion exchange resin is, for example, 10 to 300 kDa, preferably 30 to 150 kDa, as described above.

  It does not restrict | limit especially as a method of manufacturing an anion exchange resin, A well-known method is employable. Preferably, a method using a polycondensation reaction is employed.

  In the case of producing an anion exchange resin by this method, for example, first, a first oligomer for forming a hydrophobic unit and a second oligomer for forming a hydrophilic unit are each produced by a polycondensation reaction. Then, after performing a polycondensation reaction on them, an anion exchange group is introduced into the resulting anion exchange resin precursor polymer.

  As for the polycondensation reaction, a conventionally known general method (“New Polymer Experiment 3 Polymer Synthesis Method / Reaction (2) Synthesis of Condensation Polymer” p.7-57, p.399-401, ( (1996) Kyoritsu Publishing Co., Ltd.), (J. Am. Chem. Soc., 129, 3879-3887 (2007)), (Eur. Polym. J., 44, 4054-4062 (2008)). Can do. Preferably, a method of reacting a dihalogenated compound and a diol compound is employed.

  In order to produce the first oligomer, first, a diol compound or dihalogenated compound for forming a hydrophobic group and a dihalogenated compound for forming a binding group (a diol compound for forming a hydrophobic group A polycondensation reaction with a diol compound for forming a binding group (when a dihalogenated compound for forming a hydrophobic group is used).

  Examples of the diol compound for forming a hydrophobic group include a plurality of (preferably two) aromatic rings that are bonded to each other via the above-described divalent saturated hydrocarbon group and bonded to the aromatic ring. And a compound containing the two hydroxyl groups formed.

  Preferred examples of the diol compound for forming a hydrophobic group include compounds represented by the following formula (13) corresponding to the above formula (1).

(Wherein R represents the same meaning as R in formula (1), X represents the same meaning as X in formula (1), and a and b represent a and b in formula (1). It shows the same meaning as
The diol compound for forming a hydrophobic group is particularly preferably a compound (2,2-bis (4-hydroxyphenyl) hexafluoro represented by the following formula (14) corresponding to the above formula (4). Propane).

  On the other hand, examples of the dihalogenated compound for forming a hydrophobic group include a plurality of (preferably two) aromatic rings bonded to each other via the above-described divalent saturated hydrocarbon group, and the aromatic group. And compounds containing two of the above-described halogen atoms bonded to the ring.

  Preferred examples of the dihalogenated compound for forming a hydrophobic group include compounds represented by the following formula (13 ′) corresponding to the above formula (1).

(Wherein R represents the same meaning as R in formula (1), X represents the same meaning as X in formula (1), and a and b represent a and b in formula (1). It shows the same meaning as
Examples of the dihalogenated compound for forming a bonding group include, for example, one or a plurality (preferably two) of the aromatic rings bonded to each other via a carbon-carbon bond, and bonded to the aromatic ring. And the above-mentioned compounds containing the above-mentioned two halogen atoms.

  Preferred examples of the dihalogenated compound for forming a binding group include compounds represented by the following formula (15) corresponding to the above formula (2).

(In the formula, X has the same meaning as X in the formula (2), and c and d have the same meaning as c and d in the formula (2).)
Moreover, as a dihalogenated compound for forming a bonding group, a compound (decafluorobiphenyl) represented by the following formula (16) corresponding to the above formula (5) is particularly preferable.

  On the other hand, as a diol compound for forming a bonding group, for example, a single or a plurality of (preferably two) aromatic rings bonded to each other via a carbon-carbon bond, and the aromatic ring Examples thereof include compounds containing two bonded hydroxyl groups.

  Preferred examples of the diol compound for forming a binding group include compounds represented by the following formula (15 ′) corresponding to the above formula (2).

(In the formula, X has the same meaning as X in the formula (2), and c and d have the same meaning as c and d in the formula (2).)
In the polycondensation reaction, the blending amount of the diol compound or dihalogenated compound for forming these hydrophobic groups and the dihalogenated compound or diol compound for forming the binding group is the repeating unit in the obtained first oligomer. The number is adjusted to be n in the above equation (7).

  Such a first oligomer is formed as a dihalogenated compound or a diol compound, and is preferably formed as a dihalogenated compound in order to cause a polycondensation reaction with a second oligomer described later.

  When the first oligomer is formed as a dihalogenated compound, a diol compound (preferably a diol compound for forming a hydrophobic group) and a dihalogenated compound (preferably dihalogenated to form a binding group) The compounding ratio with the compound) is adjusted so that the dihalogenated compound becomes excessive. Specifically, the dihalogenated compound is preferably (n + 1) / n mol or more in relation to n in the above formula (7) with respect to 1 mol of the diol compound.

  On the other hand, when forming the first oligomer as a diol compound, a diol compound (preferably a diol compound for forming a hydrophobic group) and a dihalogenated compound (preferably a dihalogen for forming a binding group). Compounding compound) is adjusted so that the diol compound becomes excessive. Specifically, the diol compound is preferably (n + 1) / n mol or more in relation to n in the above formula (7) with respect to 1 mol of the dihalogenated compound.

  In this method, the diol compound or dihalogenated compound for forming these hydrophobic groups and the dihalogenated compound or diol compound for forming the binding group are subjected to a polycondensation reaction in an organic solvent.

  Examples of the organic solvent include polar aprotic solvents.

  Examples of the polar aprotic solvent include dimethyl sulfoxide, sulfolane, pyridine, N-methylpyrrolidone, N-cyclohexylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide (DMAc) and the like.

  These polar aprotic solvents can be used alone or in combination of two or more.

  Preferred polar aprotic solvents include N, N-dimethylacetamide and dimethyl sulfoxide.

  Further, as the organic solvent, other solvents can be used in combination.

  Other solvents are not particularly limited and are known nonpolar solvents (for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons (for example, chloroform)), alicyclic hydrocarbons (for example, cyclohexane). Aromatic hydrocarbons) and known polar aprotic solvents (for example, toluene, xylene, chlorobenzene or o-dichlorobenzene).

  In addition, when using together a polar aprotic solvent and another solvent, those compounding ratios are suitably set according to the objective and the use.

  The mixing ratio of the organic solvent to the diol compound or dihalogen compound for forming the hydrophobic group and the dihalogen compound or diol compound for forming the binding group is appropriately determined according to the purpose and application. Is set.

  Moreover, a basic compound can be mix | blended in a polycondensation reaction.

  Examples of the basic compound include lithium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, and the like carbonates such as lithium hydroxide, sodium hydroxide, water Examples thereof include metal hydroxides such as potassium oxide, for example, phosphates such as sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, and the like.

  These basic compounds can be used alone or in combination of two or more.

  The basic compound is preferably a metal hydroxide, more preferably potassium carbonate.

  In addition, the compounding quantity of a basic compound is equimolar or more with respect to the hydroxyl group which exists in a reaction mixture, for example in the case of a carbonate catalyst, Preferably it is 1.2 times mole or more.

  The reaction temperature in the polycondensation reaction is, for example, 50 to 300 ° C., preferably 50 to 200 ° C., and the reaction time is, for example, 1 to 20 hours, preferably 2 to 5 hours.

  Such a first oligomer is preferably a dihalogenated compound or a diol compound by a reaction between the diol compound represented by the above formula (13) and the dihalogenated compound represented by the above formula (15) as described above. Preferably, it is obtained as a dihalogenated compound.

  Such a dihalogenated compound is specifically represented by the following formula (17).

(Wherein R represents the same meaning as R in the above formula (1), X represents the same or different from each other, represents a halogen atom, and a and b represent the same as a and b in the above formula (1), respectively. (C and d have the same meaning as c and d in the above formula (2), and n has the same meaning as n in the above formula (7).)
In addition, the first oligomer is particularly preferably a dihalogen compound or a diol compound, preferably a dihalogen by reaction of the diol compound represented by the above formula (14) with the dihalogen compound represented by the above formula (16). As a compound.

  Such a dihalogenated compound is specifically represented by the following formula (18).

(In the formula, n has the same meaning as n in the above formula (7).)
In addition, for example, as described above, the first oligomer is obtained by reacting the dihalogenated compound represented by the above formula (13 ′) with the diol compound represented by the above formula (15 ′). Preferably, it can also be obtained as a diol compound.

  Such a diol compound is specifically represented by the following formula (17 ′).

(Wherein R represents the same meaning as R in the above formula (1), X represents the same or different from each other and represents a halogen atom, and a and b are the same as a and b in the above formula (1) (C and d have the same meaning as c and d in the above formula (2), and n has the same meaning as n in the above formula (7).)
In order to produce the second oligomer, first, a diol compound or dihalogenated compound for forming a hydrophilic group and the above-described dihalogenated compound for forming a binding group (diol for forming a hydrophilic group). When a compound is used) or the above-described diol compound for forming a binding group (when a dihalogenated compound for forming a hydrophilic group is used) is subjected to a polycondensation reaction.

  Examples of the diol compound for forming a hydrophilic group include a compound having a plurality of aromatic rings bonded to each other via an oxygen atom or a sulfur atom and having two hydroxyl groups.

  As a diol compound for forming such a hydrophilic group, preferably, a compound (bis (hydroxyphenyl) oxide (dihydroxydiphenyl ether)) represented by the following formula (19a) corresponding to the above formula (3a), A compound (bis (hydroxyphenyl) sulfide) represented by the following formula (19b) corresponding to the above formula (3b) may be mentioned.

  On the other hand, examples of the dihalogenated compound for forming a hydrophilic group include a compound having a plurality of aromatic rings bonded to each other via an oxygen atom or a sulfur atom and having two halogen atoms as described above. It is done.

  The dihalogenated compound for forming such a hydrophilic group is preferably a compound represented by the following formula (19a ′) corresponding to the above formula (3a), or a compound represented by the following formula (3b), The compound shown by a formula (19b ') is mentioned.

(In formula, X is mutually the same or different, and shows a halogen atom.)

(In formula, X is mutually the same or different, and shows a halogen atom.)
In the polycondensation reaction, the blending amount of the diol compound or dihalogenated compound for forming these hydrophilic groups and the above dihalogenated compound or the above diol compound for forming the binding group is obtained as the second obtained. The number of repeating units in the oligomer is adjusted to be m in the above formula (9a) and the above formula (9b).

  Further, the second oligomer is formed as a dihalogenated compound or a diol compound, and is preferably formed as a diol compound in order to cause a polycondensation reaction with the first oligomer formed as a dihalogenated compound as described above. .

  When forming the second oligomer as a diol compound, a diol compound (preferably a diol compound for forming a hydrophilic group) and a dihalogenated compound (preferably a dihalogenated compound for forming a binding group) ) Is adjusted so that the diol compound becomes excessive. Specifically, the diol compound is preferably (m + 1) / mmol or more in relation to m in the above formula (9a) and the above formula (9b) with respect to 1 mol of the dihalogenated compound.

  On the other hand, when forming the second oligomer as a dihalogenated compound, a diol compound (preferably a diol compound for forming a hydrophilic group) and a dihalogenated compound (preferably for forming a binding group). The mixing ratio with the dihalogenated compound is adjusted so that the dihalogenated compound becomes excessive. Specifically, the dihalogenated compound is preferably (m + 1) / mmol or more in relation to m in the formula (9a) and the formula (9b) with respect to 1 mol of the diol compound.

  In this method, the diol compound or dihalogenated compound for forming the hydrophilic group and the dihalogenated compound or diol compound for forming the binding group are subjected to a polycondensation reaction in the organic solvent described above. .

  The mixing ratio of the organic solvent to the diol compound or dihalogenated compound for forming the hydrophilic group and the dihalogenated compound or diol compound for forming the binding group is appropriately determined depending on the purpose and application. Is set.

  In the polycondensation reaction, the basic compound described above can be blended in the above-described ratio.

  The reaction temperature in the polycondensation reaction is, for example, 50 to 300 ° C., preferably 50 to 150 ° C., and the reaction time is, for example, 1 to 20 hours, preferably 2 to 5 hours.

  Such a second oligomer is preferably obtained by reacting the diol compound represented by the above formula (19a) with the dihalogenated compound represented by the above formula (15) as described above. Preferably, it is obtained as a diol compound.

  Such a diol compound is specifically represented by the following formula (20a).

Wherein X is the same as or different from each other and represents a halogen atom, c and d are the same as c and d in the above formula (2), and m is the same as m in the above formula (9a). It shows the same significance.)
The second oligomer is particularly preferably a diol compound or a dihalogenated compound, preferably a diol, by a reaction between the diol compound represented by the above formula (19a) and the dihalogenated compound represented by the above formula (16). It is obtained as a compound, and specifically represented by the following formula (21a).

(In the formula, m has the same meaning as m in the above formula (9a).)
The second oligomer is preferably a diol compound or a dihalogenated compound obtained by reacting the diol compound represented by the formula (19b) with the dihalogenated compound represented by the formula (15), as described above. Preferably, it is obtained as a diol compound.

  Such a diol compound is specifically represented by the following formula (20b).

(Wherein X is the same as or different from each other and represents a halogen atom, c and d are the same as c and d in the above formula (2), and m is the same as m in the above formula (9b)). It shows the same significance.)
The second oligomer is particularly preferably a diol compound or a dihalogenated compound, preferably a diol, by a reaction between the diol compound represented by the above formula (19b) and the dihalogenated compound represented by the above formula (16). Obtained as a compound, specifically, represented by the following formula (21b).

(In the formula, m has the same meaning as m in the above formula (9b).)
In addition, for example, as described above, the second oligomer is obtained by reacting the dihalogenated compound represented by the above formula (19a ′) with the diol compound represented by the above formula (15 ′). Preferably, it can also be obtained as a dihalogenated compound.

  Such a dihalogenated compound is specifically represented by the following formula (20a ′).

Wherein X is the same as or different from each other and represents a halogen atom, c and d are the same as c and d in the above formula (2), and m is the same as m in the above formula (9a). It shows the same significance.)
In addition, for example, as described above, the second oligomer can be obtained by reacting the dihalogenated compound represented by the above formula (19b ′) with the diol compound represented by the above formula (15 ′). Preferably, it can also be obtained as a dihalogenated compound.

  Such a dihalogenated compound is specifically represented by the following formula (20b ′).

(Wherein X is the same as or different from each other and represents a halogen atom, c and d are the same as c and d in the above formula (2), and m is the same as m in the above formula (9b)). It shows the same significance.)
In this method, the first oligomer and the second oligomer obtained as described above are subjected to a polycondensation reaction in, for example, the organic solvent described above.

  Specifically, as the first oligomer, a dihalogenated compound represented by the above formula (17), the above formula (18), or a diol compound represented by the above formula (17 ′) is used. Further, as the second oligomer, the above formula (20a), the above formula (20b), the above formula (21a), the diol compound represented by the above formula (21b), or the above formula (20a ′), the above formula (20b ′). ) Is used.

  Preferably, a dihalogenated compound represented by the above formula (17) and the above formula (18) is used as the first oligomer, and the above formula (20a), the above formula (20b), and the above formula (21a) are used as the second oligomer. ), A diol compound represented by the above formula (21b) is used.

  In addition, the mixture ratio of the organic solvent with respect to the 1st oligomer and the 2nd oligomer is suitably set according to the objective and the use.

  In the polycondensation reaction, the basic compound described above can be blended in the above-described ratio.

  The reaction temperature in the polycondensation reaction is, for example, 50 to 300 ° C., preferably 50 to 100 ° C., and the reaction time is, for example, 1 to 20 hours, preferably 2 to 5 hours.

  Thereby, an anion exchange resin precursor polymer, preferably an anion exchange resin precursor polymer represented by the following formula (22a) and the following formula (22b) is obtained.

(Wherein R represents the same meaning as R in the above formula (1), X represents the same or different from each other, represents a halogen atom, and a and b represent the same as a and b in the above formula (1), respectively. C and d are the same as c and d in the above formula (2), n is the same as n in the above formula (7), and m is the same as in the above formula (9a). m represents the same meaning, and l represents the same meaning as l in the formula (11a).

(Wherein R represents the same meaning as R in the above formula (1), X represents the same or different from each other and represents a halogen atom, and a and b are the same as a and b in the above formula (1) C and d are the same as c and d in the above formula (2), n is the same as n in the above formula (7), and m is the same as in the above formula (9b). m represents the same meaning, and l represents the same meaning as l in the above formula (11b).
Further, as the anion exchange resin precursor polymer, an anion exchange resin precursor polymer represented by the following formula (23a) and the following formula (23b) is particularly preferable.

(In the formula, n represents the same meaning as n in the formula (7), m represents the same meaning as m in the formula (9a), and l represents the same as the l in the formula (11a). It shows the same significance.)

(In the formula, n represents the same meaning as n in the formula (7), m represents the same meaning as m in the formula (9b), and l represents the same as the l in the formula (11b). It shows the same significance.)
Next, in this method, an anion exchange group is introduced into the anion exchange resin precursor polymer.

  The method for introducing an anion exchange group is not particularly limited, and a known method can be adopted.

  For example, after an anion exchange resin precursor polymer is chloromethylated by a chloromethylation reaction, the chloromethylated anion exchange resin precursor polymer is quaternized (for example, an ammonium reaction). To introduce an anion exchange group.

  The chloromethylation reaction is not particularly limited. For example, an anion exchange resin precursor polymer is dissolved in a solvent such as tetrachloroethane (1,1,2,2-tetrachloroethane, etc.), and iron chloride, A known method such as a method of immersing in chloromethyl methyl ether can be employed using a Lewis acid such as zinc chloride as a catalyst.

  The reaction temperature in the chloromethylation reaction is, for example, 20 to 120 ° C., preferably 35 to 100 ° C., and the reaction time is, for example, 24 to 168 hours, preferably 36 to 72 hours.

  Thereby, a chloromethylated anion exchange resin precursor polymer can be obtained.

  In the quaternization reaction, a chloromethylated anion exchange resin precursor polymer is formed into a film by a known method if necessary, and for example, amine, phosphine, phosphazene, sulfide, boron compound, etc. are added at an appropriate ratio. Then, an anion exchange group is introduced by substituting the chlorine atom of the chloromethyl group with them.

  Examples of the amine include secondary amines such as dimethylamine, diethylamine, diallylamine, di-n-propylamine, di-n-butylamine, and di-n-pentylamine, such as trimethylamine, N, N-dimethylethanolamine, triethylamine, triethylamine, and the like. Examples include tertiary amines such as allylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, and tri-n-hexylamine, for example, cyclic amines such as pyridine, quinoline, and imidazole, for example, guanidine.

  These amines can be used alone or in combination of two or more.

  The reaction temperature in the quaternization reaction is, for example, 15 to 40 ° C., preferably 20 to 30 ° C., and the reaction time is, for example, 24 to 72 hours, preferably 48 to 72 hours.

  In this method, the quaternization reaction can be performed, for example, in a solution state without forming the anion exchange resin precursor polymer.

  In this method, if necessary, the amine, phosphine, phosphazene, sulfide, boron compound and the like are removed by a known method.

  Thereby, an anion exchange group is introduced into the anion exchange resin precursor polymer, and the anion exchange resin, preferably the anion exchange resin represented by the above formula (11a) or the above formula (11b), particularly preferably The anion exchange resin represented by the above formula (12a) and the above formula (12b) is obtained.

  The ion exchange group capacity of the anion exchange resin is, for example, 0.5 to 2.3 meq. / G, preferably 0.6 to 1.2 meq. / G.

The ion exchange group capacity can be obtained by the following formula (24).
[Ion exchange group capacity (meq./g)]=ion exchange group introduction amount × m × 1000 / (molecular weight of first oligomer × n + molecular weight of second oligomer × m + molecular weight of ion exchange group × m) − (24)
(In the formula, n has the same meaning as n in the above formula (7), and m has the same meaning as m in the above formula (9a) or the above formula (9b).)
The ion exchange group introduction amount is defined as the number of chloromethyl groups per unit hydrophilic group.

  Such an anion exchange resin is composed of a divalent hydrophobic group composed of a plurality of aromatic rings bonded to each other via a divalent saturated hydrocarbon group, a single aromatic ring, or a carbon-carbon A divalent hydrophilic group composed of a plurality of aromatic rings bonded to each other via a bond and a divalent hydrophilic group composed of a plurality of aromatic rings bonded to each other via an oxygen atom or a sulfur atom and having an anion exchange group A hydrophobic unit in which the hydrophobic group and the binding group are repeated via an ether bond, and a hydrophilic unit in which the hydrophilic group and the binding group are repeated via an ether bond, The hydrophobic unit and the hydrophilic unit are bonded through an ether bond.

  That is, this anion exchange resin does not contain a sulfonyl group, a carbonyl group, an imide group or the like, and therefore has excellent durability such as alkali resistance.

  The hydrophilic group contained in such an anion exchange resin has a lower molecular weight than a hydrophilic group contained in a conventional aromatic polymer electrolyte (formula (25), etc.), that is, a bisphenolfluorene residue. . Therefore, by using such a hydrophilic group, the molecular weight of the entire electrolyte can be reduced. As a result, the content of anion exchange groups in the electrolyte can be improved, and the ion exchange capacity can be improved. Can be achieved.

  As such a hydrophilic group, preferably, a bis (hydroxyphenyl) oxide residue is used alone or a bis (hydroxyphenyl) sulfide residue is used alone, more preferably a bis (hydroxyphenyl) oxide residue. Is used alone.

  The present invention further includes a fuel cell electrolyte layer (fuel cell electrolyte membrane) obtained by using such an anion exchange resin, and further includes a fuel cell comprising the fuel cell electrolyte layer as an electrolyte layer. It is out.

  FIG. 1 is a schematic configuration diagram showing an embodiment of a fuel cell of the present invention. In FIG. 1, the fuel cell 1 includes a fuel cell S, and the fuel cell S includes a fuel side electrode 2, an oxygen side electrode 3, and an electrolyte layer 4, and the fuel side electrode 2 and the oxygen side electrode 3. However, they are opposed to each other with the electrolyte layer 4 sandwiched therebetween.

As the electrolyte layer 4, the above-described anion exchange resin can be used (that is, the electrolyte layer 4 includes the above-described anion exchange resin).
The electrolyte layer 4 can be reinforced with, for example, a known reinforcing material such as a porous substrate, and further, for example, biaxial stretching treatment for controlling molecular orientation or the like, Various treatments such as heat treatment for controlling the residual stress can be performed. In addition, a known filler can be added to the electrolyte layer 4 in order to increase its mechanical strength, and the electrolyte layer 4 and a reinforcing agent such as a glass nonwoven fabric can be combined by pressing.

  Further, in the electrolyte layer 4, various commonly used additives, for example, compatibilizers for improving compatibility, for example, antioxidants for preventing resin deterioration, for example, handling properties in molding as a film An antistatic agent, a lubricant, and the like for improving the viscosity can be appropriately contained within a range that does not affect the processing and performance of the electrolyte layer 4.

  The thickness of the electrolyte layer 4 is not particularly limited, and is appropriately set according to the purpose and application.

  The thickness of the electrolyte layer 4 is, for example, 1.2 to 350 μm, preferably 5 to 200 μm.

  The fuel side electrode 2 is in opposed contact with one surface of the electrolyte layer 4. The fuel side electrode 2 includes, for example, a catalyst layer (battery electrode catalyst layer) in which a catalyst is supported on a porous carrier.

  The porous carrier is not particularly limited and includes a water-repellent carrier such as carbon.

  The catalyst is not particularly limited, and examples thereof include periodic table elements 8 to 10 (IUPAC Periodic Table) of platinum group elements (Ru, Rh, Pd, Os, Ir, Pt), iron group elements (Fe, Co, Ni), and the like. of the Elements (version date 19 February 2010). The same shall apply hereinafter.) Group elements, Group 11 elements of the periodic table such as Cu, Ag, Au, and the like, and combinations thereof, preferably, Pt (platinum) is mentioned.

  For example, the fuel-side electrode 2 is obtained by dissolving the porous simple substance and the catalyst in a known electrolyte solution (for example, a fluorine resin having a quaternary ammonium group in the side chain in the organic solvent (for electrode catalyst layer formation). The electrode ink is prepared by dispersing in a binder)). Then, if necessary, the viscosity of the electrode ink is adjusted by blending an appropriate amount of an organic solvent such as alcohols, and then the electrode ink is prepared by a known method (for example, spray method, die coater method, etc.) as an electrolyte layer. 4 is applied to one surface of the electrode 4 and dried at a predetermined temperature, whereby the electrode layer is bonded to the one surface of the electrolyte layer 4 as a thin film electrode film.

Amount of catalyst supported in the fuel-side electrode 2 is not particularly limited, for example, 0.1 to 10.0 mg / cm ^2, preferably from 0.5 to 5.0 / cm ^2.

In the fuel side electrode 2, as will be described later, the supplied fuel and the hydroxide ions (OH ⁻ ) that have passed through the electrolyte layer 4 are reacted to generate electrons (e ⁻ ) and water (H ₂ O). Generate. For example, when the fuel is hydrogen (H ₂ ), only electrons (e ⁻ ) and water (H ₂ O) are generated, and when the fuel is hydrazine (NH ₂ NH ₂ ), electrons are generated. (E ⁻ ), water (H ₂ O) and nitrogen (N ₂ ) are produced.

  The oxygen side electrode 3 is in opposed contact with the other surface of the electrolyte layer 4. The oxygen side electrode 3 includes, for example, a catalyst layer (battery electrode catalyst layer) in which a catalyst is supported on a porous carrier.

  The oxygen-side electrode 3 includes, for example, the above porous simple substance and a catalyst prepared by dissolving a known electrolyte solution (for example, a fluorine-based resin having a quaternary ammonium group in the side chain in the above organic solvent (for electrode catalyst layer formation). The electrode ink is prepared by dispersing in a binder)). Then, if necessary, the viscosity of the electrode ink is adjusted by blending an appropriate amount of an organic solvent such as alcohols, and then the electrode ink is prepared by a known method (for example, spray method, die coater method, etc.) as an electrolyte layer. 4 is applied to the other surface of the electrode 4 and dried at a predetermined temperature to be bonded to the other surface of the electrolyte layer 4 as a thin electrode film.

  Thus, the electrolyte layer 4, the fuel side electrode 2, and the oxygen side electrode 3 are joined to the thin film fuel side electrode 2 on one surface of the electrolyte layer 4, and the thin film oxygen side electrode 3 on the other surface of the electrolyte layer 4. A membrane / electrode assembly is formed by bonding.

Amount of catalyst supported in the oxygen-side electrode 3 is not particularly limited, for example, 0.1 to 10.0 mg / cm ^2, preferably from 0.5 to 5.0 / cm ^2.

In the oxygen side electrode 3, as will be described later, oxygen (O ₂ ) supplied, water (H ₂ O) that has passed through the electrolyte layer 4, and electrons (e ⁻ ) that have passed through the external circuit 13 are reacted. Thus, hydroxide ions (OH ⁻ ) are generated.

  The fuel cell S further includes a fuel supply member 5 and an oxygen supply member 6. The fuel supply member 5 is made of a gas-impermeable conductive member, and one surface thereof is in opposed contact with the fuel-side electrode 2. The fuel supply member 5 is formed with a fuel-side flow path 7 for bringing fuel into contact with the entire fuel-side electrode 2 as a distorted groove recessed from one surface. The fuel-side flow path 7 is formed with a supply port 8 and a discharge port 9 passing through the fuel supply member 5 at the upstream end and the downstream end, respectively.

  Similarly to the fuel supply member 5, the oxygen supply member 6 is made of a gas-impermeable conductive member, and one surface thereof is opposed to the oxygen side electrode 3. The oxygen supply member 6 is also formed with an oxygen-side flow channel 10 for contacting oxygen (air) with the entire oxygen-side electrode 3 as a distorted groove recessed from one surface. The oxygen-side flow path 10 also has a supply port 11 and a discharge port 12 that pass through the oxygen supply member 6 continuously formed at the upstream end portion and the downstream end portion thereof.

  The fuel cell 1 is actually formed as a stack structure in which a plurality of the fuel cells S described above are stacked. Therefore, the fuel supply member 5 and the oxygen supply member 6 are actually configured as separators in which the fuel side flow path 7 and the oxygen side flow path 10 are formed on both surfaces.

  Although not shown, the fuel cell 1 is provided with a current collector plate formed of a conductive material, and an electromotive force generated in the fuel cell 1 is taken out from a terminal provided on the current collector plate. It is configured to be able to.

  In FIG. 1, the fuel supply member 5 and the oxygen supply member 6 of the fuel cell S are connected by an external circuit 13, and a voltage meter 14 is interposed in the external circuit 13 to measure the generated voltage. I am doing so.

  In the fuel cell 1, the fuel is supplied to the fuel side electrode 2 directly without going through reforming or the like or after going through reforming or the like.

  An example of the fuel is a hydrogen-containing liquid fuel.

  The hydrogen-containing liquid fuel is a liquid fuel containing hydrogen atoms in the molecule, and examples thereof include alcohols and hydrazines, and preferably hydrazines.

Specific examples of hydrazines include hydrazine (NH ₂ NH ₂ ), hydrated hydrazine (NH ₂ NH ₂ .H ₂ O), hydrazine carbonate ((NH ₂ NH ₂ ) ₂ CO ₂ ), hydrazine hydrochloride ( NH ₂ NH ₂ · HCl), hydrazine sulfate _{(NH 2 NH 2 · H 2} SO 4), monomethyl hydrazine _(CH 3 NHNH _2), dimethylhydrazine _{((CH 3) 2 NNH 2} , CH 3 NHNHCH 3), a carboxylic hydrazide ((NHNH ₂ ) ₂ CO) and the like. The fuels illustrated above can be used alone or in combination of two or more.

Among the above fuel compounds, compounds that do not contain carbon, that is, hydrazine, hydrated hydrazine, hydrazine sulfate, etc., do not generate CO and CO ₂ , and do not cause catalyst poisoning. Can be achieved, and substantially zero emission can be realized.

  Further, as the above exemplified fuel, the above fuel compound may be used as it is. However, the above exemplified fuel compound may be water and / or alcohol (for example, lower alcohol such as methanol, ethanol, propanol, isopropanol, etc.) ) And the like. In this case, the concentration of the fuel compound in the solution varies depending on the type of the fuel compound, but is, for example, 1 to 90% by mass, preferably 1 to 30% by mass.

  Further, as the fuel, the above-described fuel compound can be used as a gas (for example, vapor).

Then, if the above-described fuel is supplied to the fuel-side channel 7 of the fuel supply member 5 while supplying oxygen (air) to the oxygen-side channel 10 of the oxygen supply member 6, As described, electrons (e ⁻ ) generated at the fuel side electrode 2 and moving via the external circuit 13 react with water (H ₂ O) and oxygen (O ₂ ) generated at the fuel side electrode 2. Thus, hydroxide ions (OH ⁻ ) are generated. The generated hydroxide ions (OH ⁻ ) move from the oxygen side electrode 3 to the fuel side electrode 2 through the electrolyte layer 4 made of an anion exchange membrane. In the fuel side electrode 2, the hydroxide ions (OH ⁻ ) that have passed through the electrolyte layer 4 react with the fuel to generate electrons (e ⁻ ) and water (H ₂ O). The generated electrons (e ⁻ ) are moved from the fuel supply member 5 to the oxygen supply member 6 via the external circuit 13 and supplied to the oxygen side electrode 3. The generated water (H ₂ O) moves the electrolyte layer 4 from the fuel side electrode 2 to the oxygen side electrode 3. An electromotive force is generated by such an electrochemical reaction in the fuel side electrode 2 and the oxygen side electrode 3, and power generation is performed.

  The operating conditions of the fuel cell 1 are not particularly limited. For example, the pressure on the fuel side electrode 2 side is 200 kPa or less, preferably 100 kPa or less, and the pressure on the oxygen side electrode 3 side is 200 kPa or less. Preferably, it is 100 kPa or less, and the temperature of the fuel cell S is set to 0 to 120 ° C., preferably 20 to 80 ° C.

  And in such a fuel cell 1, the electrolyte layer for fuel cells containing the anion exchange resin which is excellent in said durability for the electrolyte layer 4 is used.

  Therefore, the fuel cell electrolyte layer of the present invention obtained by using the anion exchange resin of the present invention, and the fuel cell including such a fuel cell electrolyte layer are excellent in durability.

  The present invention also includes an electrode catalyst layer forming binder containing the anion exchange resin described above, a battery electrode catalyst layer containing the electrode catalyst layer forming binder, and a fuel cell comprising the battery electrode catalyst layer. Yes.

  That is, in the fuel cell 1, an anion exchange resin can be contained in the electrode catalyst layer forming binder when the fuel side electrode 2 and / or the oxygen side electrode 3 are formed.

  As a method for incorporating the anion exchange resin into the binder for forming an electrode catalyst layer, specifically, for example, the anion exchange resin is shredded and dissolved in the organic solvent described above to obtain the binder for forming an electrode catalyst layer. Prepare.

  In the electrode catalyst layer forming binder, the content ratio of the anion exchange resin is, for example, 2 to 10 parts by mass, or preferably 2 to 5 parts by mass with respect to 100 parts by mass of the electrode catalyst layer forming binder.

  Further, by using the electrode catalyst layer forming binder in the formation of the catalyst layer (battery electrode catalyst layer) of the fuel side electrode 2 and / or the oxygen side electrode 3 described above, the anion exchange resin is used as the catalyst layer (battery). Thus, the fuel cell 1 having a catalyst layer (battery electrode catalyst layer) containing an anion exchange resin can be obtained.

  And in such a fuel cell 1, in formation of a battery electrode catalyst layer, the binder for electrode catalyst layer formation containing the anion exchange resin excellent in said durability is used.

  Therefore, the electrode catalyst layer-forming binder of the present invention obtained using the anion exchange resin of the present invention, and the battery electrode catalyst layer obtained using the electrode catalyst layer-forming binder have durability and ion The exchange capacity is excellent, and excellent anion conductivity can be ensured.

  As a result, a fuel cell including such a battery electrode catalyst layer is excellent in durability and ion exchange capacity, and can ensure excellent anion conductivity.

  As mentioned above, although embodiment of this invention was described, embodiment of this invention is not limited to this, A design can be suitably changed in the range which does not change the summary of this invention.

  Applications of the fuel cell of the present invention include, for example, power sources for driving motors in automobiles, ships, airplanes, etc., and power sources in communication terminals such as mobile phones.

  Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example.

Example 1
<Synthesis of first oligomer>
A 100 ml round bottom three-necked flask equipped with a nitrogen inlet and a Dean stack trap was charged with hexafluorobisphenol A (2,2-bis (4-hydroxyphenyl) hexafluoropropane) (2.50 g, 7.44 mmol), potassium carbonate ( 1.54 g, 11.15 mmol), N, N-dimethylacetamide (16 ml) and toluene (8 ml) were added. The mixture was stirred to dissolve hexafluorobisphenol A, then heated to 150 ° C. and dehydrated for 3 hours while azeotroping with toluene.

  After dehydration, toluene in the Dean stack trap was removed, and toluene was removed from the mixture by trapping the refluxed toluene. Then, it stood to cool to normal temperature, decafluorobiphenyl (2.98 g, 8.92 mmol) was added, and it heated up at 60 degreeC, and was made to react for 2 hours.

  Here, decafluorobiphenyl (0.30 g, 0.89 mmol) was added as an end cap agent, and the reaction was continued for another hour.

  The reaction mixture was dropped into hot water to stop the reaction and precipitate the product. The product was collected by filtration, washed several times with hot water and hot methanol, and then vacuum dried at 60 ° C. overnight.

As a result, a white first oligomer (n = 5) represented by the above formula (18) was obtained in a yield of 84%.
<Synthesis of second oligomer>
In a 100 ml round bottom three-necked flask equipped with a nitrogen inlet and a Dean stack trap, 4,4′-bis (hydroxyphenyl) sulfide (3.68 g, 16.84 mmol), potassium carbonate (3.49 g, 25.25 mmol), N, N-dimethylacetamide (30 ml) and toluene (15 ml) were added. The mixture was stirred to dissolve 4,4′-bis (hydroxyphenyl) sulfide, then heated to 150 ° C. and dehydrated for 3 hours while azeotroping with toluene.

  After dehydration, toluene in the trap was removed, and toluene was removed from the mixture by trapping the refluxed toluene. Then, it stood to cool to normal temperature, decafluorobiphenyl (4.50 g, 13.47 mmol) was added, and it heated up at 60 degreeC, and was made to react for 1.5 hours.

  Here, 4,4'-bis (hydroxyphenyl) sulfide (0.37 g, 1.68 mmol) was added as an end cap agent, and the reaction was continued for another hour.

  The reaction mixture was dropped into hot water to stop the reaction and precipitate the product. The product was collected by filtration, washed several times with hot water and hot methanol, and then vacuum dried at 60 ° C. overnight.

As a result, a white second oligomer (m = 4) represented by the above formula (21b) was obtained in a yield of 80%.
<Synthesis of anion exchange resin precursor polymer>
To a 100 ml round bottom three-necked flask equipped with a nitrogen inlet, a mechanical stirrer and a condenser tube, a first oligomer 1 (2.08 g, 0.45 mmol), a second oligomer (2.00 g, 0.45 mmol), potassium carbonate (0 0.09 g, 0.68 mmol) and N, N-dimethylacetamide (14 ml) were added. The mixture was stirred to dissolve the oligomers 1 and 2, and then heated to 60 ° C. and reacted for 8 hours.

  The reaction mixture was dropped into hot water to stop the reaction and precipitate the product. The product was collected by filtration, washed several times with hot water and several times with hot methanol, and then vacuum dried at 60 ° C. overnight.

As a result, a white anion exchange resin precursor polymer (n = 5, m = 4, l = 2.32) represented by the above formula (23b) was obtained in a yield of 91%.
<Introducing anion exchange groups>
(Chloromethylation reaction)
An anion exchange resin precursor polymer (1.00 g) and 1,1,2,2-tetrachloroethane (22 ml) were added to a 100 ml glass reaction vessel. This mixture was stirred to dissolve the anion exchange resin precursor polymer, and then chloromethyl methyl ether (13.27 ml) and zinc chloride (0.5 mol / L tetrahydrofuran solution) (2.06 ml) were added, and argon was added. And allowed to react at 80 ° C. for 5 days.

  The reaction mixture was dropped into methanol to stop the reaction, and the product was precipitated. The product was collected by filtration, washed several times with methanol, and then vacuum dried at 60 ° C. overnight.

Thereby, the anion exchange resin precursor polymer was chloromethylated.
(Film formation)
A chloromethylated anion exchange resin precursor polymer was formed by a solution casting method.

That is, a chloromethylated anion exchange resin precursor polymer (0.2 g) was dissolved in 1,1,2,2-tetrachloroethane (2.7 ml) and filtered through a glass filter (G3). The filtrate is poured into a 3 × 9 cm rimmed glass plate with silicon rubber, left on a horizontally adjusted hot plate at 50 ° C., and dried to obtain a transparent film having a thickness of about 50 μm. It was.
(Quaternization reaction)
The membrane of the chloromethylated anion exchange resin precursor polymer was immersed in a 45% by mass trimethylamine aqueous solution at room temperature for 2 days to be quaternized.

  The membrane was washed several times with pure water and vacuum dried at 60 ° C. overnight. The dried membrane (0.2 g) was dissolved in dimethyl sulfoxide (2.7 ml) and cast into a membrane as described above to obtain a transparent anion exchange resin membrane.

In this membrane, since the counter ion of the ion exchange group (ammonio group) is chloride, it is immersed in a 1 mol / L sodium hydroxide aqueous solution for 2 days and washed with deaerated pure water to obtain a hydroxide type. Converted.
<Solution>
0.04 g of the anion exchange resin membrane was weighed and finely chopped, and a solvent (DMF: chloroform = 1: 4) was added so as to be 5% by mass. At this time, the anion exchange resin was first dissolved in DMF and then diluted with chloroform.

  Then, the solution of the anion exchange resin was obtained by stirring and dissolving.

Example 2
In the synthesis of the second oligomer, instead of 4,4′-bis (hydroxyphenyl) sulfide (3.68 g, 16.84 mmol), 4,4′-bis (hydroxyphenyl) oxide (4,4′-dihydroxydiphenyl ether) ) (3.41 g, 16.84 mmol) was used in the same manner as in Example 1 to obtain an anion exchange resin membrane and an anion exchange resin solution.

  In Example 2, as the second oligomer, a white second oligomer (m = 4) represented by the above formula (21a) was obtained in a yield of 80%.

  Further, as the anion exchange resin precursor polymer, a white anion exchange resin precursor polymer represented by the above formula (23a) (n = 5, m = 4, l = 2.14) was obtained in a yield of 91%. It was.

Comparative Example 1
<Synthesis of first oligomer>
Bis (4-fluorophenyl) sulfone (hereinafter referred to as FPS) 10.000 g (molecular weight 254.2, 39.331 mmol), 4,4′-dihydroxybenzophenone (hereinafter referred to as DHBP) 7.9300 g (molecular weight 214.2, 37. 018 mmol) and 13.589 g of potassium carbonate (molecular weights 138.21, 98.328 mmol) were weighed and placed in a 300 mL three-necked eggplant flask. Next, 160 ml of DMAc was added while washing the wall surface of the three-necked eggplant flask, and a forced-stirrer and a Dean stack trap containing 40 mL of toluene were attached to the three-necked eggplant flask. The mixture was heated to 150 ° C., and after 3 hours, the Dean stack trap was removed and reacted at 170 ° C. for 3 hours. Next, 0.5000 g (1.9666 mmol) of FPS as an end cap agent was added, and the mixture was further stirred for 1 hour. Subsequently, it was dripped so that it might disperse | distribute to the whole in the hot water in the beaker set | placed on the stirrer using the Pasteur pipette in the form of a fine film. Next, the solution was suction filtered using a membrane filter and washed with hot water. Thereafter, the solution was suction filtered with a membrane filter, washed with hot methanol, suction filtered again, and vacuum dried at 80 ° C. As a result, an oligomer of n = 16 represented by the following formula (26) was obtained.

<Synthesis of second oligomer>
BHF 7.7524 g (22.124 mmol), FPS 5.000 g (19.666 mmol) and potassium carbonate 7.6444 g (55.310 mmol) were weighed and placed in a 300 mL three-necked eggplant flask. Next, 80 ml of DMAc was added while washing the wall surface of the three-necked eggplant flask, and a forced-stirrer and a Dean stack trap containing 20 mL of toluene were attached to the three-necked eggplant flask. After heating to 140 ° C. and stirring for 2 hours, the Dean stack trap was removed and the reaction was carried out at 165 ° C. for 2 hours. Next, 0.3876 g (1.1062 mmol) of BHF as an end cap agent was added, and the mixture was further stirred for 1 hour. The obtained polymer was purified in the same manner as the first oligomer. This obtained the oligomer of m = 11 shown by following formula (27).

<Synthesis of anion exchange resin precursor polymer>
7.4300 g ([-F] = 20.000 mmol) of the first oligomer, 6.7817 g ([-OH] = 20.000 mmol) of the second oligomer, 3.4553 g (25.000 mmol) of potassium carbonate, 25.048 g of calcium carbonate (Molecular weight 100.2, 250.00 mmol), DMAc 100 mL, and toluene 25 mL were placed in a 300 mL three-necked eggplant flask. Forced agitation was installed, the oil bath was heated to 145 ° C., and after 3 hours, the Dean stack trap was removed and reacted at 160 ° C. for 5 hours. After diluting with 100 mL of DMAc, it was dropped into hot water in a beaker placed on a stirrer using a Pasteur pipette. Next, the solution was suction filtered using a membrane filter and washed with hot water. Thereafter, the solution was suction filtered with a membrane filter, washed with hot methanol, suction filtered again, and vacuum dried at 80 ° C. This obtained the anion exchange resin precursor polymer (n = 16, m = 11) shown by following formula (28).

<Introducing anion exchange groups>
(Chloromethylation reaction)
1.0000 g of anion exchange resin precursor polymer (1.0374 mmol in terms of second oligomer) was weighed and placed in a reaction vessel, and 20 mL (1.000 mmol) of a 0.05 mol / L aqueous solution of tetrachloroethane (hereinafter TCE) was added. And stirred at 35 ° C. for 30 minutes to dissolve.

Next, the resulting solution was added to a solution of 0.1414 g (1.0374 mmol) of zinc chloride in 1.0 mL of tetrahydrofuran and 40 times mol of anion exchange resin precursor polymer (based on the fluorene group) chloromethyl methyl ether (based on fluorene groups). (Molecular weight 80.51, 41.696 mmol) was added and the mixture was stirred at 35 ° C. for 120 hours. The obtained mixed solution was dropped into methanol using a Pasteur pipette and stirred and washed. Thereafter, the supernatant was discarded, methanol was further added for further washing, suction filtration with a membrane filter, and vacuum drying at 50 ° C.
(Film formation)
1.000 g of the chloromethylated polymer was dissolved in 25 mL of TCE, filtered through a 0.45 μm PTFE membrane filter, and then the obtained filtrate was poured into a container and dried at 60 ° C. Thereby, a film of 50 ± 5 μm was produced.
(Quaternization reaction)
The chloromethylated anion exchange resin precursor polymer membrane was placed in a container, and an aqueous trimethylamine solution (concentration: 30% by mass) was placed until the membrane was immersed.

  Next, the container was covered and stored at room temperature for 2 days, and then the membrane was stirred and washed several times with ultrapure water and then dried.

  Next, the membrane was immersed in an aqueous potassium hydroxide solution (concentration: 1 mol / L), supplemented at room temperature for 2 nights, then stirred and washed several times with ultrapure water, and then dried.

  Thereby, an anion exchange resin membrane was obtained.

Reference example 1
<Synthesis of first oligomer>
2,2-bis (4-hydroxyphenyl) hexafluoropropane (= hexafluorobisphenol) 2.5000 g (molecular weight 336.23, 7.435 mmol), potassium carbonate 2.0502 g (molecular weight 138.21, 14.87 mmol), 15.24 mL of dimethylacetamide (hereinafter referred to as DMAc) and 5 mL of toluene were placed in a 100 mL three-necked eggplant flask.

Next, a three-necked eggplant flask was equipped with a forced stirrer, a Dean stack trap with toluene and an N ₂ gas tube, heated to 160 ° C. in an oil bath, and stirred, whereby the terminal hydroxyl group and potassium carbonate in the above compound were mixed. Water generated by the reaction was removed.

  Then, the oil bath was cooled to 80 ° C., and 2.6084 g (molecular weight 334.1, 7.807 mmol) of decafluorobiphenyl was added and stirred, and after 2.5 hours, 0.2608 g (0 7807 mmol) and stirred for another 0.5 hours.

  Next, the eggplant flask is lifted from the oil bath, diluted with DMAc, and the resulting diluted solution is dispersed in the form of a fine film into hot water in a beaker placed on a stirrer using a Pasteur pipette. It was dripped so that.

  Next, the solution was suction filtered using a membrane filter and washed with hot methanol. Thereafter, the solution was suction filtered with a membrane filter, washed again with hot methanol, suction filtered again, and vacuum dried at 50 ° C.

This obtained the 1st oligomer (n = 30) shown by the said Formula (18).
<Synthesis of second oligomer>
9,9-bis (4-hydroxyphenyl) fluorene (hereinafter referred to as BHF) 2.9498 g (molecular weight 350.4, 8.4184 mmol), decafluorobiphenyl 2.5000 g (molecular weight 334.1, 7.483 mmol) and potassium carbonate 2.9088 g (molecular weight 138.21, 21.0459 mmol) was weighed and placed in a 100 mL three-necked eggplant flask.

Next, 20 mL of DMAc was added while washing the wall surface of the three-necked eggplant flask, and a forced-stirrer, a Dean stack trap containing cyclohexane, a condenser tube and an N ₂ gas tube were attached to the three-necked eggplant flask, and ₂ mL of cyclohexane was added.

  Next, the oil bath was heated to 85 ° C., and the stirring was started so that the oil level and the liquid level in the flask were the same level. After 1.5 hours, 0.2812 g (0.8418 mmol) of BHF as an end cap agent was used. ) And stirred for another hour.

  Then, lift the eggplant flask from the oil bath, dilute with DMAc, and then use the Pasteur pipette to disperse the diluted solution as a fine film into hot water in a beaker placed on a stirrer. It was dripped so that.

  Next, the solution was suction filtered using a membrane filter and washed with hot water. Thereafter, the solution was suction filtered with a membrane filter, washed with hot methanol, suction filtered again, and vacuum dried at 50 ° C.

  This obtained the 2nd oligomer (m = 8) shown by following formula (29).

<Synthesis of anion exchange resin precursor polymer>
0.5000 g ([-F] = 0.0528 mmol) of the first oligomer, 0.1610 g ([-OH] = 0.0528 mmol) of the second oligomer and 0.0091 g of potassium carbonate (molecular weight 138.21, 0.066 mmol). Weighed and placed in a 100 mL three-necked eggplant flask.

  Next, 2 mL of DMAc was added to the three-necked eggplant flask, a forced stirrer and a condenser tube were attached, and the mixture was heated to 80 ° C. with an oil bath and stirred. When the stirring bar became difficult to rotate, a small amount of DMAc was added and stirred.

  After 2.5 hours, lift the eggplant flask from the oil bath and dilute with DMAc. Then, dilute the obtained diluted solution into hot water in a beaker placed on a stirrer using a Pasteur pipette. The solution was added dropwise so as to be dispersed throughout.

  Then, after suction filtration using a membrane filter, the membrane was washed with hot water. Thereafter, the solution was suction filtered with a membrane filter, washed with hot methanol, suction filtered again, and vacuum dried at 50 ° C.

  This obtained the anion exchange resin precursor polymer (n = 30, m = 8, l = 1.06) shown by following formula (30).

<Introducing anion exchange groups>
(Chloromethylation reaction)
1.0000 g of an anion exchange resin precursor polymer (0.362 mmol in terms of second oligomer) was weighed and placed in a reaction vessel, and dissolved in 7.91 mL (0.362 mmol) of a 0.04574 mol / L aqueous solution of tetrachloroethane.

  Next, 0.724 mL (0.362 mmol) of 0.5 mol / L tetrahydrofuran solution of zinc chloride and 80 times mol (based on fluorene group) of chloromethylmethyl anion exchange resin precursor polymer were added to the obtained solution. Ether (molecular weight 80.51, 28.96 mmol) was added, and the mixture was stirred at 50 ° C.

  Two days later, the obtained mixed solution was dropped into methanol using a Pasteur pipette, and stirred and washed. Thereafter, the supernatant was discarded, methanol was further added for further washing, suction filtration with a membrane filter, and vacuum drying at 50 ° C.

Thereby, the anion exchange resin precursor polymer was chloromethylated.
(Film formation)
The chloromethylated anion exchange resin precursor polymer was placed in a screw tube and dissolved in DMAc.

The amount of the anion exchange resin precursor polymer was calculated by the following formula.
Required mass (g) = Cast container area (cm ² ) × film thickness (cm) × 1.5 (g / cm ³ )
Next, after the solution was filtered using a Kiriyama funnel and Kiriyama filter paper, the obtained filtrate was poured into a container and dried at 45 ° C. After confirming that it was completely dried, pure water was poured into the container, and carefully peeled off with a spatula to obtain a chloromethylated anion exchange resin precursor polymer membrane.
(Quaternization reaction)
The chloromethylated anion exchange resin precursor polymer membrane was placed in a container, and an aqueous trimethylamine solution (concentration: 30% by mass) was placed until the membrane was immersed.

  Next, the container was covered and stored at room temperature for 2 days, and then the membrane was stirred and washed several times with ultrapure water and then dried.

  Next, the membrane was immersed in an aqueous potassium hydroxide solution (concentration: 1 mol / L), supplemented at room temperature for 2 nights, then stirred and washed several times with ultrapure water, and then dried.

  This obtained the film | membrane of the anion exchange resin (n = 30, m = 8, l = 1.06) shown by following formula (31).

(In the formula, at least one of A ′ and A ″ represents CH ₂ N ⁺ (CH ₃ ) ₃ OH ⁻ , and the other represents CH ₂ N ⁺ (CH ₃ ) ₃ OH ⁻ or a hydrogen atom. )
<Solution>
0.04 g of the anion exchange resin membrane was weighed and finely chopped, and a solvent (DMF: chloroform = 1: 4) was added so as to be 5% by mass. At this time, the anion exchange resin was first dissolved in DMF and then diluted with chloroform.

  Then, the solution of the anion exchange resin was obtained by stirring and dissolving.

Comparative Example 2
A cell unit of an anion exchange membrane-electrode assembly was produced.

  Specifically, in the production of the anion exchange membrane-electrode assembly, first, a cobalt catalyst and a solution of an anion exchange resin (electrode catalyst layer forming binder, commercially available hydrocarbon anion exchange resin) are mixed, The obtained mixture was appropriately dispersed in an organic solvent such as alcohol to prepare an ink.

  Thereafter, the obtained ink was directly applied to one side surface of the anion exchange membrane (fuel cell electrolyte layer) obtained in Comparative Example 1, and a cathode side electrode (Co-based battery electrode catalyst) was formed on the one side surface. Layer) were integrally formed.

  Next, the nickel-based catalyst and the above anion exchange resin were mixed, and the obtained mixture was dispersed in an organic solvent such as alcohol as appropriate to prepare an ink. The anode side electrode (Ni-based battery electrode catalyst layer) was integrally formed on the other surface of the anion exchange membrane obtained in the above.

  This produced the anion exchange membrane-electrode assembly.

  The carbon sheet of the electroconductive porous body used as a gas diffusion layer was joined to both surfaces of the obtained anion exchange membrane-electrode assembly, and the single cell unit of the fuel cell was produced.

Reference example 2
The anion exchange resin solution obtained in Reference Example 1 was used as the electrode catalyst layer-forming binder, and the anion exchange resin membrane obtained in Reference Example 1 was used as the fuel cell electrolyte layer. Produced an anion exchange membrane-electrode assembly and a single cell unit of a fuel cell in the same manner as in Comparative Example 2.
(Evaluation of anion exchange resin)
The ion exchange group capacity of the anion exchange resin obtained in each example and reference example was calculated according to the above formula (24).

  Moreover, the ionic conductivity and moisture content of the anion exchange resin obtained in each Example and Reference Example were evaluated according to the following methods.

  That is, a beaker containing pure water was immersed in a water bath, and the temperature of the water bath was set to 60 ° C. In the beaker, an anion exchange resin film cut out in a size of 2 cm × 2 cm was put and immersed in pure water to absorb water.

  At this time, the mass of the membrane of the anion exchange resin before and after water absorption was measured, the amount of mass increase before and after water absorption (mass after water absorption-mass before water absorption) was calculated as the mass of water, and the water content was measured.

  Then, the test cell was produced by pinching | interposing a film | membrane so that an electrode might become inside and it might become 1 cm between two glass cells with a platinum electrode, and it may be fastened with a double clip.

  Next, the test cell was placed in the beaker again, the electrode was sandwiched between alligator clips of an LCR HiTester (Hioki Electric Co., Ltd.), adjusted so that the frequency θ of the LCR HiTester was small, and the resistance value was read when stable.

Thereafter, the test cell was taken out from the beaker, the length of contact between the electrode and the membrane (electrode length) and the film thickness were measured, and the ionic conductivity (OH ^- conductivity) was calculated by the following formula.
Ionic conductivity (mS / cm) = 1000 × distance between electrodes (cm) / resistance value (Ω) × electrode length (cm) × film thickness (cm)
The ion conductivity was measured at 30 ° C., 40 ° C., 60 ° C. and 80 ° C.

  The measurement results are shown in Table 1.

(Evaluation of electrical characteristics of fuel cells)
On the fuel electrode side of the single cell unit of the fuel cell obtained in Comparative Example 2 and Reference Example 2, a mixed solution of hydrazine hydrate (concentration 5 mass% to 20 mass%) and aqueous potassium hydroxide solution (concentration 1 mol / L). Was fed at 2 mL / min and humidified oxygen at 500 mL / min and operated at 80 ° C. The results for the fuel cell (single cell unit) of Comparative Example 2 are shown in FIG. 2, and the results for the fuel cell (single cell unit) of Reference Example 2 are shown in FIG.
(Discussion)
2 and 3, it was confirmed that the fuel cell using the anion exchange resin of Reference Example 1 was superior in electric characteristics as compared with the fuel cell using the anion exchange resin of Comparative Example 1.

  In addition, from Table 1, it was confirmed that the anion exchange resin of each example was superior in moisture content and electrical characteristics as compared to the anion exchange resin of Reference Example 1.

DESCRIPTION OF SYMBOLS 1 Fuel cell 2 Fuel side electrode 3 Oxygen side electrode 4 Electrolyte layer S Fuel cell

Claims (8)

Chloromethylation and quaternization of an anion exchange resin precursor polymer represented by the following formula (23a), or
An anion exchange resin characterized by being a chloromethylated and quaternized product of an anion exchange resin precursor polymer represented by the following formula (23b) .

(In the formula, n represents 4 to 20, m represents 4 to 20, and l represents 1 to 20.)

(In the formula, n represents 4 to 20, m represents 4 to 20, and l represents 1 to 20.) A fuel cell electrolyte layer comprising the anion exchange resin according to claim 1 . The binder for electrode catalyst layer formation characterized by including the anion exchange resin of Claim 1 . A battery electrode catalyst layer comprising the binder for forming an electrode catalyst layer according to claim 3 . In a fuel cell comprising an electrolyte layer, a fuel-side electrode that is disposed to face the electrolyte layer and is supplied with fuel, and an oxygen-side electrode that is supplied with oxygen,
The electrolyte layer is a fuel cell electrolyte layer according to claim 2 ,
A fuel cell, wherein the fuel is a hydrogen-containing liquid fuel. The fuel cell according to claim 5 , wherein the hydrogen-containing liquid fuel is hydrazines. In a fuel cell comprising an electrolyte layer, a fuel-side electrode that is disposed to face the electrolyte layer and is supplied with fuel, and an oxygen-side electrode that is supplied with oxygen,
The fuel side electrode and / or the oxygen side electrode includes a catalyst layer;
The catalyst layer is a battery electrode catalyst layer according to claim 4 ,
A fuel cell, wherein the fuel is a hydrogen-containing liquid fuel. The fuel cell according to claim 7 , wherein the hydrogen-containing liquid fuel is hydrazines.