JP5827077B2 - 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 a divalent saturated hydrocarbon group, the saturated An aromatic ring having an anion exchange group on a hydrocarbon group is composed of a divalent hydrophilic group bonded via a carbon-carbon bond, and the hydrophobic group and the binding group are repeated via an ether bond. A hydrophobic unit 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 through an ether bond. As That.

  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, it is preferable that the hydrophilic group is a bisphenolfluorene residue substituted with the anion exchange group represented by the following formula (3).

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 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.

  The battery electrode catalyst layer of the present invention is characterized by including the above-mentioned binder for forming a fuel cell 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 fuel cell 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. Having a divalent linking group composed of a plurality of aromatic rings bonded to each other via a divalent saturated hydrocarbon group and having a plurality of aromatic rings bonded to each other via a divalent saturated hydrocarbon group A hydrophobic unit comprising an aromatic ring having a divalent hydrophilic group bonded via a carbon-carbon bond, wherein the hydrophobic group and the binding group are repeated via an ether bond, and the hydrophilic group and the bond The hydrophobic group and the hydrophilic unit are bonded to each other through the 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 Example 2 is shown. The evaluation result of the fuel cell of the comparative 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 has a plurality of aromatic rings bonded to each other via a divalent saturated hydrocarbon group, and an anion exchange group is added to the divalent saturated hydrocarbon group. The aromatic ring it has is connected through a carbon-carbon bond.

In the hydrophilic group, examples of the divalent saturated hydrocarbon group include the divalent saturated hydrocarbon group which may be substituted with the above-described halogen atom, preferably methylene which may be substituted with a halogen atom. (-CH ₂ -) and the like, more preferably methylene which is not substituted with a halogen atom - include (-CH _2).

  In addition, examples of the plural (two or more, preferably two) aromatic rings bonded to each other via the divalent saturated hydrocarbon group include the aromatic rings described above. Preferably, the benzene ring is Can be mentioned.

  The anion exchange group is introduced into the side chain in the hydrophilic group, and is not particularly limited, and is a quaternary ammonium group, tertiary amino group, secondary amino group, primary amino group, phosphine, phosphazene, three Any known anion exchange group such as a quaternary sulfonium group, a quaternary boronium group, or a quaternary phosphonium group can be employed. From the viewpoint of anion conductivity, preferably, a quaternary ammonium salt is used.

  Moreover, as an aromatic ring which has such an anion exchange group, the above-mentioned aromatic ring is mentioned, Preferably, a benzene ring is mentioned.

  The number of aromatic rings bonded to the divalent saturated hydrocarbon group is one or two, and preferably two.

  In addition, when one aromatic ring is bonded to a divalent saturated hydrocarbon group, the saturated hydrocarbon group is trivalent, and when two aromatic rings are bonded, The saturated hydrocarbon group is tetravalent (a carbon atom when the number of carbon atoms is 1).

  In the case where two aromatic rings are bonded to a divalent saturated hydrocarbon group, the anion exchange group may be substituted on at least one of the aromatic rings, and may be substituted on both. Good.

  Moreover, when two aromatic rings couple | bond with respect to a bivalent saturated hydrocarbon group, these aromatic rings may couple | bond together through the carbon-carbon bond, for example.

  As such a hydrophilic group, Preferably, the bisphenol fluorene residue substituted by the anion exchange group shown by following formula (3) is mentioned.

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 above formula (3), 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 (3), 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 addition, in the said Formula (3), when e and / or f are the range of 1-3, the substitution position of an anion exchange group is suitably set according to the objective and use.

  As such a hydrophilic group, a bisphenolfluorene residue represented by the following formula (6) is particularly preferable.

(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 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 shows 4-50.

  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).)
Moreover, as a hydrophilic unit, Preferably, it replaces with the bisphenol fluorene residue (hydrophilic group) substituted by the anion exchange group shown by the said Formula (3), and a halogen atom when shown by the said Formula (2). And a unit formed by repeating a biphenylene group (bonding group) which may be formed via an ether bond.

  Such a hydrophilic unit is represented by, for example, the following formula (9).

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 (3), and c and d are the same as 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 (3), and m is a numerical value of 1 to 200.)
In said formula (9), m is the repeating unit number of the hydrophilic unit in anion exchange resin, Comprising: For example, 1-200, Preferably it shows 4-50.

  As such a hydrophilic unit, particularly preferably, a bisphenolfluorene residue represented by the above formula (6) and a biphenylene group represented by the above formula (5) (biphenylene group in which four fluorines are substituted on each benzene ring). And a unit formed by repeating an ether bond.

  Such a hydrophilic unit is represented by, for example, the following formula (10).

(In the formula, A ′ and A ″ have the same meaning as A ′ and A ″ in the above formula (6), and m has the same meaning as m in the above formula (9).)
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 (11), the hydrophobic unit represented by the above formula (7) and the hydrophilic unit represented by the above formula (9) are bonded via an ether bond. Anion exchange resin made.

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 (3). , 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 (3). ) 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 (9), and l is 1-100. Indicates a numerical value.)
In the above formula (11), 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 1 -50, more preferably 1-20, particularly preferably 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 (12), a hydrophobic unit represented by the above formula (8) and a hydrophilic unit represented by the above formula (10) are ether-bonded. And anion exchange resins bonded via the.

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

  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 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 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, 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 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 the hydrophilic group include a plurality of (preferably two) aromatic rings bonded to each other via the above-described divalent saturated hydrocarbon group, and the divalent saturation thereof. Examples include compounds in which the above-described aromatic ring having an anion exchange group on a hydrocarbon group is bonded via a carbon-carbon bond, and which has two hydroxyl groups.

  As the diol compound for forming such a hydrophilic group, a compound (bisphenolfluorene) represented by the following formula (19) corresponding to the above formula (3) is preferably exemplified.

On the other hand, the dihalogenated compound for forming the hydrophilic group has, for example, a plurality of (preferably two) aromatic rings that are bonded to each other via the above-described divalent saturated hydrocarbon group. Examples include compounds in which the above-described aromatic ring having an anion exchange group is bonded to a valent saturated hydrocarbon group via a carbon-carbon bond, and the above-described two halogen atoms are included.

  Preferred examples of the dihalogenated compound for forming such a hydrophilic group include a compound (bishalogenophenylfluorene) represented by the following formula (19 ′) corresponding to the above formula (3).

(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 so as to be m in the above formula (11).

  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 (9) 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 above formula (9) 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 (19) 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 (20).

(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 (9)). 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 (19) and the dihalogenated compound represented by the above formula (16). It is obtained as a compound, and specifically represented by the following formula (21).

(In the formula, m has the same meaning as m in the above formula (9).)
In addition, for example, as described above, the second oligomer is obtained by reacting the dihalogenated compound represented by the above formula (19 ′) 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 (20 ').

(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 (9)). It shows the same significance.)
In this method, the first oligomer obtained above (the dihalogenated compound represented by the above formula (17), the above formula (18), or the diol compound represented by the above formula (17 ′)), and the above The second oligomer obtained by the above (the diol compound represented by the above formula (20), the above formula (21), or the dihalogenated compound represented by the above formula (20 ′)), for example, in the above organic solvent And polycondensation reaction.

  Preferably, a dihalogenated compound represented by the above formula (17) or the above formula (18) is used as the first oligomer, and a diol compound represented by the above formula (20) or the above formula (21) is used as the second oligomer. 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, the anion exchange resin precursor polymer, Preferably, the anion exchange resin precursor polymer shown by following formula (22) 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 (9). m represents the same meaning, and l represents the same meaning as l in the formula (11).
As the anion exchange resin precursor polymer, an anion exchange resin precursor polymer represented by the following formula (23) is particularly preferably obtained.

(In the formula, n represents the same meaning as n in the formula (7), m represents the same meaning as m in the formula (9), and l represents the same as the l in the formula (11). 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, and a Lewis acid such as iron chloride or zinc chloride is used as a catalyst to prepare chloromethylmethyl. A known method such as a method of immersing in ether can be employed.

  The reaction temperature in the chloromethylation reaction is, for example, 20 to 60 ° C., preferably 35 to 50 ° 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. For example, amine, phosphine, phosphazene, tertiary sulfonium salt, quaternary boronium salt, etc. An anion exchange group is introduced by adding at an appropriate ratio and 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 above-mentioned catalyst 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 (11), particularly preferably the above formula (12). ) 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 formula (7), and m has the same meaning as m in the formula (9).)
The ion exchange group introduction amount is defined as the number of chloromethyl groups per unit hydrophilic group.

  Such an anion exchange resin includes a divalent hydrophobic group composed of a plurality of (preferably two) aromatic rings bonded to each other via a divalent saturated hydrocarbon group, and a single aromatic ring. Or a plurality of (preferably two) divalent linking groups composed of aromatic rings bonded to each other through a carbon-carbon bond and a plurality of (bonded to each other through a divalent saturated hydrocarbon group Preferably, it is composed of a divalent hydrophilic group having 2) aromatic rings and an aromatic ring having an anion exchange group attached to the saturated hydrocarbon group via a carbon-carbon bond, Having a hydrophobic unit in which a functional group and a binding group are repeated through an ether bond, and a hydrophilic unit in which a hydrophilic group and a binding group are repeated through an ether bond. The hydrophobic unit and the hydrophilic unit have an ether bond. Coupled through That. 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 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 provides an electrode catalyst layer-forming binder containing the anion exchange resin described above, a battery electrode catalyst layer containing the fuel cell electrode catalyst layer-forming binder, and a fuel cell comprising the battery electrode catalyst layer. Contains.

  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.

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

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

  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 are excellent in durability.

  As a result, a fuel cell provided with such a battery electrode catalyst layer is excellent in durability.

  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>
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 the said Formula (20).
<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, m8, l = 1.06) shown by the said Formula (23).
<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.

Thereby, an anion exchange resin membrane was obtained.
<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 1 (Production of anion exchange resin)
<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 by the fine film form. 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.

Example 2 (Manufacture of fuel cell)
<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.

Example 2 (Manufacture of fuel cell)
A cell unit of an anion exchange membrane-electrode assembly was prepared, and its cell power generation characteristics were measured.

  In the production of the anion exchange membrane-electrode assembly, specifically, first, the cobalt-based catalyst and the anion exchange resin obtained in Example 1 are mixed, and the resulting mixture is used as an organic solvent such as alcohols. After the ink was appropriately dispersed, the obtained ink was directly applied to one side surface of the anion exchange membrane obtained in Example 1, and the cathode side electrode (Co-based electrode) was applied to the one side surface. ) Were integrally formed.

  Next, the nickel-based catalyst and the anion exchange resin described above were mixed, and the resulting mixture was appropriately dispersed in an organic solvent such as alcohols to prepare an ink. The anode side electrode (Ni system) was integrally formed on the other side 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.

Comparative Example 2 (Manufacture of fuel cell)
In the same manner as in Example 2, using the anion exchange membrane obtained in Comparative Example 1, an anion exchange membrane-electrode assembly and a single cell unit of a fuel cell were produced.

  At this time, a commercially available hydrocarbon anion exchange resin solution was used as the binder for forming the catalyst layer.

Evaluation (Fuel resistance evaluation of anion exchange membrane)
Example 1 and Comparative Example 1 The obtained anion exchange resin membrane was cut into a size of 2 × 3 cm and immersed in 30 mL of hydrazine hydrate (concentration: 10 wt%) at 80 ° C. for 500 hours.

As a result, the membrane shape was maintained, the weight retention of the anion exchange resin membrane of Example 1 was 100%, and the weight retention of the anion exchange resin membrane of Comparative Example 1 was 93%. (Performance evaluation)
A mixed solution of hydrazine hydrate (concentration 5 mass% to 20 mass%) and aqueous potassium hydroxide (concentration 1 mol / L) is formed on the fuel electrode side of the single cell unit of the fuel cell obtained in Example 2 and Comparative Example 2. Was fed at 2 mL / min and humidified oxygen at 500 mL / min and operated at 80 ° C. FIG. 2 shows the results of the fuel cell (single cell unit) of Example 2, and FIG. 3 shows the results of the fuel cell (single cell unit) of Comparative Example 2.

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

Claims (11)

And divalent hydrophobic group composed of two aromatic rings linked to each other through a divalent saturated hydrocarbon group,
A divalent linking group consisting of a single aromatic ring or consisting of a plurality of aromatic rings bonded to each other via a carbon-carbon bond;
An aromatic ring having two aromatic rings bonded to each other via a divalent saturated hydrocarbon group and having an anion exchange group different from the aromatic ring has a carbon-carbon bond to the saturated hydrocarbon group. Consisting of a divalent hydrophilic group bonded via
A hydrophobic unit in which the hydrophobic group and the binding group are repeated via an ether bond;
The hydrophilic group and the binding group have a hydrophilic unit repeated through an ether bond,
An anion exchange resin, wherein the hydrophobic unit and the hydrophilic unit are bonded through an ether bond. The anion exchange resin according to claim 1, wherein the hydrophobic group is a bisphenol residue optionally substituted with a halogen atom represented by the following formula (1).

(In the formula, R represents —CH 2 — or —C (CH 3) 2 — optionally substituted with a halogen atom, X represents the same or different from each other, represents a halogen atom, and a and b are And are the same or different from each other and represent an integer of 0 to 4.) The anion exchange resin according to claim 1, wherein the binding group is 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.) The hydrophilic group is a bisphenolfluorene residue substituted with the anion exchange group represented by the following formula (3), according to any one of claims 1 to 3. Anion exchange resin.

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.)   An electrolyte layer for a fuel cell, comprising the anion exchange resin according to any one of claims 1 to 4.   The binder for electrode catalyst layer formation characterized by including the anion exchange resin as described in any one of Claims 1-4.   A battery electrode catalyst layer comprising the binder for forming a fuel cell electrode catalyst layer according to claim 6. 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 5,
A fuel cell, wherein the fuel is a hydrogen-containing liquid fuel.   The fuel cell according to claim 8, 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 fuel cell electrode catalyst layer according to claim 7,
A fuel cell, wherein the fuel is a hydrogen-containing liquid fuel.   The fuel cell according to claim 10, wherein the hydrogen-containing liquid fuel is hydrazines.