US-12624157-B2 - Method for producing anion exchange resin and method for producing electrolyte membrane

US12624157B2US 12624157 B2US12624157 B2US 12624157B2US-12624157-B2

Abstract

Provided are a method for producing an anion exchange resin which is capable of producing an electrolyte membrane with excellent mechanical property (strength). A monomer for forming a hydrophobic group is reacted with a monomer for forming a hydrophilic group in the presence of bis(1,5-cyclooctadiene)nickel(0) as a catalyst, 2,2′-bipyridine as a co-ligand, a bromide or an iodide as a co-catalyst, and a reducing agent to produce an anion exchange resin where the hydrophobic group is connected to the hydrophilic group via direct bond, in which a mole number of bis(1,5-cyclooctadiene)nickel(0) is 0.3 to 1.8 times a total mole number of the monomer for forming a hydrophobic group and the monomer for forming a hydrophilic group.

Inventors

Kenji Miyatake
Yosuke Konno
Naoki Yokota
Katsuya Nagase

Assignees

UNIVERSITY OF YAMANASHI
Takahata Precision Co., Ltd.

Dates

Publication Date: 20260512
Application Date: 20210702
Priority Date: 20200716

Claims (11)

1 . A method for producing an anion exchange resin, comprising: (A) preparing a monomer for forming a hydrophobic group, being composed of a single aromatic ring or being composed of a plurality of aromatic rings which are connected 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 direct bond, wherein two chlorine atoms are bonded to the single aromatic ring, or to each of two terminal aromatic rings of the plurality of aromatic rings; (B) preparing a monomer for forming a hydrophilic group, being composed of a single aromatic ring or being composed of a plurality of aromatic rings which are connected to each other via a linking group and/or via direct 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; two chlorine atoms are bonded to the single aromatic ring or to each of the two terminal aromatic rings of the plurality of aromatic rings; and at least one of the linking group or the aromatic ring of the single aromatic ring or the plurality of aromatic rings is connected to a precursor functional group for an anion exchange group via a divalent saturated hydrocarbon group or direct bond; (C) reacting the monomer for forming a hydrophobic group with the monomer for forming a hydrophilic group in the presence of bis(1,5-cyclooctadiene)nickel(0) as a catalyst, 2,2′-bipyridine as a co-ligand, a bromide or an iodide as a co-catalyst, and a reducing agent to synthesize a polymer; and (D) producing an anion exchange group by ionizing the precursor functional group to form the anion exchange resin; wherein a mole number of bis(1,5-cyclooctadiene)nickel(0) used in the step (C) is 0.3 to 1.8 times a total mole number of the monomer for forming a hydrophobic group and the monomer for forming a hydrophilic group; and wherein, in the anion exchange resin, a residue of the monomer for forming a hydrophobic group forms a divalent hydrophobic group; a residue of the monomer for forming a hydrophilic group having the anion exchange group forms a divalent hydrophilic group; and the hydrophobic group is connected to the hydrophilic group via direct bond.
2 . The method for producing an anion exchange resin according to claim 1 , wherein the co-catalyst is a quaternary ammonium bromide or a quaternary ammonium iodide.
3 . The method for producing an anion exchange resin according to claim 1 , wherein a mole number of the co-catalyst used in the step (C) is 1.0 to 3.0 times a mole number of bis(1,5-cyclooctadiene)nickel(0).
4 . The method for producing an anion exchange resin according to claim 1 , wherein the reducing agent is metallic zinc or metallic magnesium.
5 . The method for producing an anion exchange resin according to claim 1 , wherein a mole number of 2,2′-bipyridine used in the step (C) is 1.5 to 2.5 times the mole number of bis(1,5-cyclooctadiene)nickel(0).
6 . The method for producing an anion exchange resin according to claim 1 , wherein the hydrophobic group comprises a bisphenol residue which may be substituted with a halogen atom, a pseudohalide, an alkyl group, or an aryl group, represented by the following formula (2): wherein, in the formula, R represents 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 direct bond, which may be substituted with a halogen atom or a pseudohalide; Alk are the same or different from each other and each represents an alkyl group or an aryl group; X are the same or different from each other and each represents a halogen atom or a pseudohalide; and a, b, c, and d are the same or different from each other and each represents an integer of 0 to 4.
7 . The method for producing an anion exchange resin according to claim 6 , wherein the hydrophobic group comprises a bisphenol residue which may be substituted with a halogen atom, a pseudohalide, an alkyl group, or an aryl group, represented by the following formula (1): wherein, in formula (1), Alk, X, a, b, c, and d have the same meaning as Alk, X, a, b, c, and d, respectively, in the formula (2); Z are the same or different from each other and each represents carbon atom or silicon atom; R are the same or different from each other and each represents 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 direct bond; l represents an integer of 1 or more; and h, h′, h″, i, i′, i″, j, and k are the same or different from each other and each represents an integer of 0 or more.
8 . The method for producing an anion exchange resin according to claim 7 , wherein, in the above formula (1), Z is a carbon atom, R is a direct bond, X is fluorine atom, and h, h′, h″, i, i′, i″, j, and k are 0.
9 . The method for producing an anion exchange resin according to claim 1 , wherein the hydrophilic group is a divalent hydrophilic group, being composed of a single polycyclic compound or being composed of a plurality of polycyclic compounds which are connected to each other via a linking group and/or via direct 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 polycyclic compound is connected to an anion exchange group via a divalent saturated hydrocarbon group with a carbon number of 2 or more.
10 . The method for producing an anion exchange resin according to claim 9 , wherein the hydrophilic group comprises a fluorene residue represented by the following formula (3): wherein, in the formula, Ion and Ion′ are the same or different from each other and each represents an anion exchange group, and y and z are the same or different from each other and each represents an integer of 2 to 20.
11 . A method for producing an electrolyte membrane, comprising: obtaining an anion exchange resin produced by the method of claim 1 ; casting the anion exchange resin to form a membrane thereof; and immersing the membrane in an aqueous solution of potassium hydroxide to convert the anion exchange resin into a hydroxide form to obtain an electrolyte membrane.

Description

RELATED APPLICATIONS This application is the U.S. National Phase of and claims priority to International Patent Application No. PCT/JP2021/025062, International Filing Date Jul. 2, 2021, entitled Method For Producing Anion Exchange Resin And Method For Producing Electrolyte Membrane; which claims priority to Japan Application No. 2020-121967 filed Jul. 16, 2020, both of which are incorporated herein by reference in their entireties. TECHNICAL FIELD The present invention relates to a method for producing an anion exchange resin and a method for producing an electrolyte membrane. BACKGROUND ART The anion exchange resin is known, in which the anion exchange resin comprises a divalent hydrophobic group being composed of a single aromatic ring, or being composed of a plurality of aromatic rings which are connected 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; and a divalent hydrophilic group being composed of a single polycyclic compound, or being 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; and at least one of the linking group or the polycyclic compound is connected to an anion exchange group via a divalent saturated hydrocarbon group with a carbon number of 2 or more; wherein the anion exchange resin comprises a hydrophobic unit being composed of the hydrophobic group alone, or being composed of a plurality of hydrophobic groups repeated via ether bond, thioether bond, or carbon-carbon bond; wherein the anion exchange resin comprises a hydrophilic unit being composed of the hydrophilic group alone, or being composed of a plurality of hydrophilic groups repeated via ether bond, thioether bond, or carbon-carbon bond; and wherein the hydrophobic unit and the hydrophilic unit are connected via ether bond, thioether bond, or carbon-carbon bond. PRIOR ART DOCUMENT Patent Document Patent Document 1: JP 2019-23258 A SUMMARY OF THE INVENTION Problem to be Solved by the Invention However, in the patent document 1, a large amount of bis(1,5-cyclooctadiene)nickel(0) which is very expensive is used as a catalyst the polymerization reaction (cross-coupling) of monomers to produce an anion exchange resin in which a hydrophobic unit and a hydrophilic unit are connected via carbon-carbon bond, which makes it difficult to reduce production cost. When the amount of the catalyst used is reduced, there is a problem that the molecular weight (in particular, weight average molecular weight) of the polymer obtained becomes lowered, which results in lowered mechanical property (strength) of the anion exchange resin. Accordingly, an object of the present invention is to provide a method for producing an anion exchange resin which is capable of producing an electrolyte membrane with excellent mechanical property (strength) and a method for producing an electrolyte membrane formed from the anion exchange resin. Means of Solving the Problem In order to solve the above problem, a method for producing an anion exchange resin according to the present invention comprises: (A) preparing a monomer for forming a hydrophobic group, being composed of a single aromatic ring or being composed of a plurality of aromatic rings which are connected 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 direct bond, wherein two chlorine atoms are bonded to the aromatic ring;(B) preparing a monomer for forming a hydrophilic group, being composed of a single aromatic ring or being composed of a plurality of aromatic rings which are connected to each other via a linking group and/or via direct 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; two chlorine atoms are bonded to the aromatic ring; and at least one of the linking group or the aromatic ring is connected to a precursor functional group for an anion exchange group via a divalent saturated hydrocarbon group or direct bond;(C) reacting the monomer for forming a hydrophobic group with the monomer for forming a hydrophilic group in the presence of bis(1,5-cyclooctadiene)nickel(0) as a catalyst, 2,2′-bipyridine as a co-ligand, a bromide or an iodide as a co-catalyst, and a reducing agent