Method for producing anion exchange resin and method for producing electrolyte membrane
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.
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.