Anion exchange resin, electrolyte membrane, binder for forming electrode catalyst layer, fuel cell electrode catalyst layer and fuel cell
Provided are an anion exchange resin being capable of producing an electrolyte membrane and the like, which have improved chemical properties (durability). For example, used is an anion exchange resin comprising a hydrophobic unit being composed of a plurality of divalent hydrophobic groups repeated via carbon-carbon bond, the divalent hydrophobic group having a plurality of aromatic rings which are connected to each other via a divalent fluorine-containing group; and a hydrophilic unit being composed of a plurality of hydrophilic groups repeated via carbon-carbon bond, the hydrophilic groups being composed of a plurality of aromatic rings which are connected to each other via a divalent hydrocarbon group and/or carbon-carbon bond, and the hydrophilic groups containing an anion exchange group-containing group including a quaternary ammonium salt having a piperidine ring, and wherein the hydrophobic unit and the hydrophilic unit are connected via carbon-carbon bond.
1. An anion exchange resin, comprising:
a hydrophobic unit being composed of a divalent hydrophobic group alone, or being composed of a plurality of divalent hydrophobic groups repeated via ether bond, thioether bond, or carbon-carbon bond; and
a hydrophilic unit being composed of a divalent hydrophilic group alone containing an anion exchange group-containing group, or being composed of a plurality of divalent hydrophilic groups containing an anion exchange group-containing group repeated via ether bond, thioether bond, or carbon-carbon bond;
wherein the anion exchange group-containing group is represented by the following formula (A) or (B); and
wherein the hydrophobic unit and the hydrophilic unit are connected via ether bond, thioether bond, or carbon-carbon bond;
(In the formula (A), R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different and represent carbon atom or silicon atom connected with hydrogen atom, a halogen atom, or a pseudohalide; Q represents nitrogen atom or phosphorus atom; and n 1 , n 2 , and n 5 are the same or different and represent an integer of 0 or more)
(In the formula (B), R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , and R 8 are the same or different and represent carbon atom or silicon atom connected with hydrogen atom, a halogen atom, or a pseudohalide; R 9 represents carbon atom or silicon atom; Q represents nitrogen atom or phosphorus atom; T represents hydrogen atom, a halogen atom, or a pseudohalide; and n 1 , n 2 , n 5 , n 7 , and n 8 are the same or different and represent an integer of 0 or more).
2. The anion exchange resin according to claim 1 , wherein the anion exchange group-containing group is represented by the following formula (A2) or (B2)
(In the formula, Q represents nitrogen atom or phosphorus atom; and n 1 and n 5 are the same or different and represent an integer of 0 or more)
(In the formula, Q represents nitrogen atom or phosphorus atom; and n 1 and n 5 are the same or different and represent an integer of 0 or more).
3. The anion exchange resin according to claim 1 ,
wherein the hydrophobic group is composed of one aromatic ring, or is composed of a plurality of aromatic rings which are connected to each other by a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, a divalent sulfur-containing group, or carbon-carbon bond; and
wherein the hydrophilic group is composed of one aromatic ring, or being composed of a plurality of aromatic rings which are connected to each other via a linking group and/or carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group, and at least one of the linking group or the aromatic ring is connected to the anion exchange group-containing group.
4. The anion exchange resin according to claim 3 , wherein the hydrophobic group comprises a bisphenol residue which is substituted with a halogen atom, a pseudohalide, an alkyl group, or an aryl group, as shown in the following formula (2)
(In the formula, R represents a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, an aromatic group, or direct bond, each of which may be substituted with a halogen atom or a pseudohalide; each Alk is the same or different and represents an alkyl group or an aryl group; each X is the same or different and represents a halogen atom or a pseudohalide; and a, b, c, and d are the same or different and represent an integer of 0 to 4).
5. The anion exchange resin according to claim 4 , wherein the hydrophobic group comprises a bisphenol residue which is substituted with a halogen atom, a pseudohalide, an alkyl group, or an aryl group, as shown in the following formula (1)
(In the formula, Alk, X, a, b, c, and d have the same meaning as Alk, X, a, b, c, and d in the formula (2); each Z is the same or different and represents carbon atom or silicon atom; each R is the same or different and represents a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, or direct bond; I represents an integer of 1 or more; h, h′, h″, i, i′, i″, j, and k are the same or different and represent an integer of 0 or more).
6. The anion exchange resin according to claim 5 , wherein, in the formula (1), Z is carbon atom; R is direct bond; X is fluorine atom; and h, h′, h″, i, i′, i″, j, and k are 0.
7. The anion on exchange resin according to claim 2 ,
wherein the hydrophobic group is composed of one aromatic ring, or is composed of a plurality of aromatic rings which are connected to each other by a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, a divalent sulfur-containing group, or carbon-carbon bond; and
wherein the hydrophilic group is composed of one aromatic ring, or being composed of a plurality of aromatic rings which are connected to each other via a linking group and/or carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group, and at least one of the linking group or the aromatic ring is connected to the anion exchange group-containing group.
8. The anion exchange resin according to claim 7 , wherein the hydrophobic group comprises a bisphenol residue which is substituted with a halogen atom, a pseudohalide, an alkyl group, or an aryl group, as shown in the following formula (2)
(In the formula, R represents a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, an aromatic group, or direct bond, each of which may be substituted with a halogen atom or a pseudohalide; each Alk is the same or different and represents an alkyl group or an aryl group; each X is the same or different and represents a halogen atom or a pseudohalide; and a, b, c, and d are the same or different and represent an integer of 0 to 4).
9. The anion exchange resin according to claim 8 , wherein the hydrophobic group comprises a bisphenol residue which is substituted with a halogen atom, a pseudohalide, an alkyl group, or an aryl group, as shown in the following formula (1)
(In the formula, Alk, X, a, b, c, and d have the same meaning as Alk, X, a, b, c, and d in the formula (2); each Z is the same or different and represents carbon atom or silicon atom; each R is the same or different and represents a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, or direct bond; I represents an integer of 1 or more; h, h′, h″, i, i′, i″, j, and k are the same or different and represent an integer of 0 or more).
10. The anion exchange resin according to claim 9 , wherein, in the formula (1), Z is carbon atom; R is direct bond; X is fluorine atom; and h, h′, h″, i, i′, i″, j, and k are 0.
11. The anion exchange resin according to claim 1 , wherein the hydrophilic group is composed of one polycyclic compound, or is composed of a plurality of polycyclic compounds which are connected to each other via a linking group and/or carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group.
12. The anion exchange resin according to claim 11 , wherein the hydrophilic group comprises a fluorene residue as shown in the following formula (3)
(In the formula, Ion and Ion′ are the same or different and represent an anion exchange group-containing group).
13. The anion exchange resin according to claim 2 , wherein the hydrophilic group is composed of one polycyclic compound, or is composed of a plurality of polycyclic compounds which are connected to each other via a linking group and/or carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group.
14. The anion exchange resin according to claim 13 , wherein the hydrophilic group comprises a fluorene residue as shown in the following formula (3)
(In the formula, Ion and Ion′ are the same or different and represent an anion exchange group-containing group).
15. The anion exchange resin according to claim 3 , wherein the hydrophilic group is composed of one polycyclic compound, or is composed of a plurality of polycyclic compounds which are connected to each other via a linking group and/or carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group.
16. The anion exchange resin according to claim 15 , wherein the hydrophilic group comprises a fluorene residue as shown in the following formula (3)
(In the formula, Ion and Ion′ are the same or different and represent an anion exchange group-containing group).
17. The anion exchange resin according to claim 7 , wherein the hydrophilic group is composed of one polycyclic compound, or is composed of a plurality of polycyclic compounds which are connected to each other via a linking group and/or carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group.
18. The anion exchange resin according to claim 17 , wherein the hydrophilic group comprises a fluorene residue as shown in the following formula (3)
(In the formula, Ion and Ion′ are the same or different and represent an anion exchange group-containing group).
19. An electrolyte membrane, comprising the anion exchange resin according to claim 1 .
20. A binder for forming an electrode catalyst layer, comprising the anion exchange resin according to claim 1 .