Anion exchange resin, electrolyte membrane for fuel cell, binder for forming electrode catalyst layer, battery electrode catalyst layer and fuel cell

Patent metadata

Field	Value
Publication number	US-10287409-B2
Application number	US-201515505606-A
Country	US
Kind code	B2
Filing date	Aug 22, 2015
Priority date	Aug 22, 2014
Publication date	May 14, 2019
Grant date	May 14, 2019

Abstract

The present invention provides an anion exchange resin capable of producing an electrolyte membrane for a fuel cell, a binder for forming an electrode catalyst layer and a battery electrode catalyst layer. The anion exchange resin of the present invention has a hydrophobic unit, a hydrophilic unit and divalent fluorine-containing groups. The hydrophobic unit has divalent hydrophobic groups composed of one aromatic ring or a plurality of aromatic rings that are repeated via carbon-carbon bond. The hydrophilic unit has divalent hydrophilic groups composed of one aromatic ring or a plurality of aromatic rings, at least one of which has an anion exchange group, that are repeated via carbon-carbon bond. The divalent fluorine-containing groups have a specific structure and are bonded via carbon-carbon bond to the hydrophobic unit and/or the hydrophilic unit and/or a moiety other than these units.

First claim

What is claimed is:

1. An anion exchange resin, comprising:
divalent hydrophobic groups being composed of one aromatic ring, or being composed of a plurality of aromatic rings which are bonded to each other via 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;
divalent hydrophilic groups being composed of one aromatic ring, or being composed of a plurality of aromatic rings which are bonded to each other via 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, the aromatic ring or at least one of the aromatic rings having an anion exchange group; and
divalent fluorine-containing groups as shown in formula (11′);
wherein the divalent hydrophobic groups are repeated via ether bond, thioether bond, or carbon-carbon bond to form a hydrophobic unit;
wherein the divalent hydrophilic groups are repeated via ether bond, thioether bond, or carbon-carbon bond to form a hydrophilic unit;
wherein the hydrophobic unit and the hydrophilic unit are bonded via ether bond, thioether bond, or carbon-carbon bond; and
wherein the divalent fluorine-containing group as shown in formula (11′) is bonded via ether bond, thioether bond, a carbon-silicon bond, or carbon-carbon bond in the main chain or main chains of the hydrophobic unit and/or the hydrophilic unit

wherein, I is an integer of 2 to 12.

2. The anion exchange resin according to claim 1 , wherein each of the hydrophilic groups comprises a bisphenol residue which may be substituted with a halogen atom, a pseudohalide, or an alkyl group, as shown in formula (2)

wherein, R is a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, which may be substituted with a halogen atom or a pseudohalide, or direct bond; each Alk is the same or different and is an alkyl group; each X is the same or different and is a halogen atom or a pseudohalide; and a, b, c, and d are the same or different and is an integer of 0 to 4.

3. The anion exchange resin according to claim 1 , wherein each of the hydrophilic groups is:
a bisphenol residue substituted with a substituent group having the anion exchange group, as shown in formula (3),

wherein, R is 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, which may be substituted with a substituent group having the anion exchange group, or direct bond; each Alk is the same or different and is an alkyl group; each A is the same or different and is a substituent group having an anion exchange group; a and b are the same or different and is an integer of 0 to 4; and s, t, and u are the same or different and is an integer of 0 to 4, and at least one of s, t, and u is 1 or more and/or
an o-, m- or p-phenylene group substituted with a substituent group having the anion exchange group, as shown in formula (3′),

wherein, Alk is an alkyl group; A is a substituent group having an anion exchange group; a is an integer of 0 to 4; and s is an integer of 1 to 4.

4. The anion exchange resin according to claim 1 , wherein I in the divalent fluorine-containing groups as shown in formula (11′) ranges from 2 to 6.

5. An electrolyte membrane for a fuel cell, comprising the anion exchange resin according to claim 1 .

6. A binder for forming an electrode catalyst layer, comprising the anion exchange resin according to claim 1 .

7. The anion exchange resin according to claim 2 , wherein each of the hydrophilic groups is:
a bisphenol residue substituted with a substituent group having the anion exchange group, as shown in formula (3),

wherein, R is 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, which may be substituted with a substituent group having the anion exchange group, or direct bond; each Alk is the same or different and is an alkyl group; each A is the same or different and is a substituent group having an anion exchange group; a and b are the same or different and is an integer of 0 to 4; and s, t, and u are the same or different and is an integer of 0 to 4, and at least one of s, t, and u is 1 or more and/or
an o-, m- or p-phenylene group substituted with a substituent group having the anion exchange group, as shown in formula (3′),

wherein, Alk is an alkyl group; A is a substituent group having an anion exchange group; a is an integer of 0 to 4; and s is an integer of 1 to 4.

8. The anion exchange resin according to claim 2 , wherein I in the divalent fluorine-containing groups in formula (11′) ranges from 2 to 6.

9. The anion exchange resin according to claim 3 , wherein I in the divalent fluorine-containing groups in formula (11′) ranges from 2 to 6.

10. The electrolyte membrane for a fuel cell according to claim 5 , wherein each of the hydrophilic groups comprises a bisphenol residue which may be substituted with a halogen atom, a pseudohalide, or an alkyl group, as shown in formula (2)

wherein, R is a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, which may be substituted with a halogen atom or a pseudohalide, or direct bond; each Alk is the same or different and is an alkyl group; each X is the same or different and is a halogen atom or a pseudohalide; and a, b, c, and d are the same or different and is an integer of 0 to 4.

11. The electrolyte membrane for a fuel cell according to claim 5 , wherein each of the hydrophilic groups is:
a bisphenol residue substituted with a substituent group having the anion exchange group, as shown in following formula (3),

wherein, R is 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, which may be substituted with a substituent group having the anion exchange group, or direct bond; each Alk is the same or different and is an alkyl group; each A is the same or different and is a substituent group having an anion exchange group; a and b are the same or different and is an integer of 0 to 4; and s, t, and u are the same or different and is an integer of 0 to 4, and at least one of s, t, and u is 1 or more and/or
an o-, m- or p-phenylene group substituted wit

Assignees

• Takahata Prec Japan Co Ltd
• Univ Yamanashi

Inventors

• Shimada Manai
• Yokota Naoki
• Miyatake Kenji
• Watanabe Masahiro
• Miyake Junpei
• Ono Hideaki
• Nishino Eriko
• Asazawa Koichiro

Classifications

• H01M8/1034

  having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh] · CPC title

• C08G65/40

  from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group · CPC title

• H01M2004/026

  characterised by the polarity · CPC title

• C08G2261/344

  containing heteroatoms · CPC title

• H01M8/1032

  having sulfur, e.g. sulfonated-polyethersulfones [S-PES] · CPC title