JP4131216B2 - Polyarylene, production method thereof, solid polymer electrolyte and proton conducting membrane - Google Patents

Description

  The present invention relates to a polyarylene having a sulfonic acid group, a method for producing the same, a polymer solid electrolyte, and a proton conductive membrane.

  The electrolyte is usually used in a (water) solution. However, in recent years, there is an increasing tendency to replace this with a solid system. The first reason is, for example, the ease of processing when applied to the above-mentioned electric / electronic materials, and the second reason is the shift to light, thin, small and labor saving. Conventionally, both proton-conducting materials made of inorganic substances and organic substances are known. Examples of inorganic substances include uranyl phosphate, which is a hydrated compound, but these inorganic compounds do not have sufficient contact at the interface, and there are many problems in forming a conductive layer on a substrate or electrode.

  On the other hand, examples of organic compounds include polymers belonging to so-called cation exchange resins, for example, sulfonated vinyl polymers such as polystyrene sulfonic acid, perfluoroalkyl sulfonic acid polymers represented by Nafion (manufactured by DuPont), perfluoro Organic polymers such as alkylcarboxylic acid polymers and polymers in which sulfonic acid groups or phosphoric acid groups are introduced into heat-resistant polymers such as polybenzimidazole and polyetheretherketone (for example, see Non-Patent Documents 1 to 3) It is done.

  These organic polymers are usually used in the form of a film, but a conductive film can be bonded on the electrode by utilizing the solubility in a solvent or thermoplasticity. However, in many of these organic polymers, proton conductivity is not yet sufficient, proton conductivity decreases at durability and high temperature (100 ° C or higher), and mechanical properties, particularly elastic modulus. Is greatly reduced, is highly dependent on humidity conditions, or is not sufficiently satisfactory in adhesion to the electrode, or the strength due to excessive swelling during operation due to the water-containing polymer structure. There is a problem that it leads to a drop and collapse of the shape. Therefore, these organic polymers have various problems when applied to the above electric / electronic materials.

Furthermore, Patent Document 1 proposes a solid polymer electrolyte made of sulfonated rigid polyphenylene. This polymer is mainly composed of a polymer obtained by polymerizing an aromatic compound composed of a phenylene chain (structure described in the column 9 of Patent Document 1), and this is reacted with a sulfonating agent to introduce a sulfonic acid group. ing. However, although the proton conductivity is improved by increasing the amount of sulfonic acid groups introduced, the mechanical properties of the sulfonated polymer obtained at the same time, such as toughness such as elongation at break and bending resistance, and hot water resistance are significantly impaired.
US Pat. No. 5,403,675 Polymer Preprints Japan, 1993, Vol. 42, No. 7, p. 2490-2492 (Polymer Preprints, Japan, 2490-2942, Vol.42, No.7, 1993) Polymer Preprints Japan, 1994, Vol. 43, No. 3, p. 735-736 (Polymer Preprints, Japan, 735-736, Vol.43, No.3, 1994) Polymer Preprints Japan, 1993, Vol. 42, No. 3, p. 730 (Polymer Preprints, Japan, 730, Vol.42, No.3, 1993)

The present invention solves the problems in the prior art as described above. By having an aliphatic sulfonic acid group, it has high proton conductivity over a wide range of temperature and humidity, as well as hot water resistance and chemical properties. Provided are a polyarylene-based copolymer capable of obtaining a proton conductive membrane excellent in stability, a method for producing the same, and a proton conductive membrane comprising the copolymer.

  The polyarylene of the present invention includes a structural unit represented by the following general formula (1).

[Wherein X and Y represent a divalent organic group or a direct bond, Z represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom, a fluorine atom, an alkyl group, or a fluorine-substituted alkyl group. And a represents an integer of 1 to 20, n represents an integer of 1 to 5, and p represents an integer of 0 to 10. ]
Here, in the polyarylene, 0.5 to 100 mol% of the structural unit represented by the general formula (1) and 0 to 99.5 mol% of the structural unit represented by the following general formula (2) Can be included.

[Wherein, R ^{1 to} R ⁸ may be the same as or different from each other, and are at least one atom selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluorine-substituted alkyl group, an allyl group, and an aryl group; Represents a group, W represents a divalent electron-withdrawing group, T represents a divalent organic group, and m represents 0 or a positive integer. ]
The method for producing polyarylene of the present invention includes a compound (A) containing a structural unit represented by the following general formula (3), a compound (B) represented by the following general formula (4), or the following general formula (5). And the compound (C) represented by formula (I).

  [Wherein, X, Y, Z, n, and p are as defined in the general formula (1), and M represents a hydrogen atom or an alkali metal atom. ]

  [Wherein, R and a are as defined in the general formula (1). ]

[Wherein, R and a are as defined in the general formula (1), M is as defined in the general formula (3), and L is any one of a chlorine atom, a bromine atom and an iodine atom. Indicates. ]
Here, in the method for producing polyarylene, the compound (A) may further include a structural unit represented by the general formula (2).

  The solid polymer electrolyte of the present invention contains the polyarylene. The proton conducting membrane of the present invention contains the polyarylene.

  According to the polyarylene of the present invention, by having an aliphatic sulfonic acid group, it is possible to obtain a proton conductive membrane having high proton conductivity over a wide range of temperature and humidity, and excellent in hot water resistance and chemical stability. A polyarylene-based copolymer, a method for producing the same, and a proton conductive membrane made of the copolymer can be provided.

  Further, according to the present invention, a sulfonic acid group can be introduced without using a large amount of a sulfonating agent. Furthermore, the processing load when collecting the polyarylene of the present invention is small. Furthermore, according to the present invention, it is easy to control the introduction position and introduction amount of the sulfonic acid group. Therefore, the proton conductivity of the polyarylene of the present invention is well adjusted as a solid electrolyte or a conductive membrane.

  Therefore, the polymer solid electrolyte of the present invention can be used as, for example, a polymer solid electrolyte for a fuel cell. The proton conductive membrane of the present invention is used as a conductive membrane for primary battery electrolytes, secondary battery electrolytes, polymer solid electrolytes for fuel cells, display elements, various sensors, signal transmission media, solid capacitors, ion exchange membranes, and the like. The industrial significance is extremely large.

[Detailed Description of the Invention]
Hereinafter, the polyarylene of the present invention and the production method thereof will be specifically described.

(Polyarylene)
The polyarylene of the present invention includes a structural unit represented by the following general formula (1).

Wherein, X, Y is a direct bond, or, for example, -CO -, - CONH -, - (CF 2) q - ( wherein, q is an integer of 1 to 10), - C _(CF 3) _2- , —COO—, —SO—, —SO ₂ — and other electron withdrawing groups, —O—, —S—, —CH═CH—, —C═C— and the following formulae

And an electron donating group such as a group represented by

X is preferably an electron-withdrawing group, particularly preferably —CO— or —SO ₂ — because the polymerization activity during production of the polyarylene of the present invention is high. On the other hand, Y may or may not be electron withdrawing.

  The electron-withdrawing group means a group having a Hammett substituent constant of 0.06 or more when the phenyl group is in the m-position and 0.01 or more when the p-position is p-position.

  Z represents an oxygen atom or a sulfur atom.

  R represents at least one atom or group selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, and a fluorine-substituted alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group, and a methyl group and an ethyl group are preferable. Examples of the fluorine-substituted alkyl group include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, trifluoromethyl group, pentafluoroethyl group, and the like. Etc. are preferable.

  a represents an integer of 1 to 20, n represents an integer of 1 to 5, and p represents an integer of 0 to 10.

  The polyarylene of the present invention further comprises 0.5 to 100 mol% of the structural unit represented by the general formula (1) and 0 to 99.5 mol% of the structural unit represented by the following general formula (2). Can be included.

In the general formula (2), R ^{1 to} R ⁸ may be the same as or different from each other, and at least 1 selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluorine-substituted alkyl group, an allyl group, and an aryl group. Indicates an atom or group of species. Here, as the alkyl group and the fluorine-substituted alkyl group, those exemplified as the alkyl group and fluorine-substituted alkyl group used for R in the general formula (1) can be used. Examples of the allyl group include a propenyl group, and examples of the aryl group include a phenyl group and a pentafluorophenyl group.

W is a divalent electron-withdrawing group, the electron withdrawing group, e.g. -CO -, - CONH -, - (CF 2) q - ( wherein, q is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—, —SO—, —SO ₂ — and the like can be mentioned.

  T may be an electron-withdrawing group or an electron-donating group. As the electron-withdrawing group, the groups exemplified as the aforementioned W can be used. Examples of the electron donating group include —O—, —S—, —CH═CH—, —C═C—, and the following formulae.

Group represented by these.

  m is 0 or a positive integer, and the upper limit is usually 100, preferably 80.

  The molecular weight of the polyarylene of the present invention is 10,000 to 1,000,000, preferably 20,000 to 800,000 in terms of polystyrene by gel permeation chromatography (GPC), and preferably in terms of polystyrene by GPC. 0.5 to 200,000, preferably 1 to 160,000. If it is less than 10,000, the coating film properties are insufficient, such as cracking in the molded film, and the strength properties are also problematic. On the other hand, when it exceeds 1,000,000, there are problems such as insufficient solubility, high solution viscosity, and poor workability.

  The amount of sulfonic acid group in the polyarylene of the present invention is 0.5 to 3 meq / g, preferably 0.8 to 2.8 meq / g. If it is less than 0.5 meq / g, proton conductivity may not be improved. On the other hand, if it exceeds 3 meq / g, the hydrophilicity is improved and it becomes soluble in hot water even if it is not water-soluble polymer or water-soluble. In addition, durability may be reduced even if water solubility is not reached.

Structure of the polyarylene of the invention, for example, by an infrared absorption ^{spectrum, 1,030~1,045cm -1,} S = O absorption at 1,160~1,190cm ^-1, 1,130~1,250cm ^-1 C—O—C absorption, 1,640 to 1,660 cm ⁻¹ C═O absorption, and the like, and the composition ratio thereof can be known by neutralization titration of sulfonic acid or elemental analysis. Moreover, the structure can be confirmed from the peak of aromatic protons at 6.8 to 8.0 ppm by nuclear magnetic resonance spectrum ( ¹ H-NMR).

(Polyarylene production method)
The polyarylene of the present invention is produced by reacting the compound (A) with the compound (B) or the compound (C). Hereinafter, the compound (A), the compound (B) and the compound (C) used for producing the polyarylene of the present invention will be described in order.

{Compound (A)}
The compound (A) has a structural unit represented by the following general formula (3).

  In the general formula (3), X, Y, Z, n, and p are as defined in the general formula (1), and M represents a hydrogen atom or an alkali metal atom.

  Examples of the alkali metal atom represented by M include sodium, potassium, lithium and the like.

Further, the compound (A) can further contain a structural unit represented by the general formula (2). More specifically, the compound (A) is polymerized alone using at least one compound (A ₁ ) represented by the following general formula (6) as a monomer, or represented by the following general formula (6). By copolymerizing at least one compound (A ₁ ) and another aromatic compound (preferably at least one compound (A ₂ ) represented by the following general formula (7)) as monomers, respectively. Obtainable. Specifically, as shown in equation (10) described later, when ^{R 9} in the compound _{(A 1)} in (see below general formula (6)) is a hydrocarbon group, the compound _(A 1) (or, After compound (A ₁ ) and compound (A ₂ ) and other aromatic compounds are polymerized to obtain compound (A ′), the hydrocarbon group represented by R ⁹ is removed to obtain compound (A). Obtainable.

In the general formula (6), X, Y, Z, n, and p are as defined in the general formula (1), and A and A ′ may be the same as or different from each other, and are halogen atoms other than fluorine atoms. atom (chlorine, bromine, iodine) or -OSO 2 Q _(here, Q is an alkyl group, fluorine-substituted alkyl group or an aryl group.) shows a group represented by.

  Examples of the alkyl group represented by Q include a methyl group and an ethyl group, examples of the fluorine-substituted alkyl group include a trifluoromethyl group, and examples of the aryl group include a phenyl group and a p-tolyl group.

R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, iso-propyl, tert-butyl, iso-butyl, n-butyl, sec-butyl, neopentyl, Cyclopentyl group, hexyl group, cyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, adamantyl group, adamantylmethyl group, 2-ethylhexyl group, bicyclo [2.2.1] heptyl group, bicyclo [2.2.1] heptylmethyl Group, tetrahydrofurfuryl group, 2-methylbutyl group, 3,3-dimethyl-2,4-dioxolane methyl group and other linear hydrocarbon groups, branched hydrocarbon groups, alicyclic hydrocarbon groups, 5-membered Examples thereof include a hydrocarbon group having a heterocyclic ring. The hydrocarbon group may contain an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the hydrocarbon group containing an oxygen atom include a tetrahydro-2-pyranyl group, a methoxymethyl group, an ethoxyethyl group, and a propoxymethyl group. Of these, a tetrahydro-2-pyranyl group and a methoxymethyl group are preferred.

In the general formula (7), R ^{1 to} R ⁸ , W, T, and m are as defined in the general formula (2), and B and B ′ may be the same or different from each other. A halogen atom excluding an atom or a group represented by —OSO ₂ Q (where Q represents an alkyl group, a fluorine-substituted alkyl group or an aryl group). Examples of Q include the groups exemplified in the general formula (6).

Next, the compound (A ₁ ) and the compound (A ₂ ) will be described respectively.

"Compound _(A 1)"
Compound (A ₁ ) can be synthesized, for example, by the following method. In this case, an aromatic acid halogen compound is used as a starting material (compound (I)), and the compound (A ₁ ′) obtained by reacting the aromatic acid halogen compound with anisole contains a hydroxyl group. Although the case where the protecting group of the hydroxyl group is a tetrahydro-2-pyranyl group has been shown, the compound (A ₁ ′), the reactant, and the protecting group are not limited thereto. For example, instead of anisole, an aromatic acid halogen compound and other reactants (for example, 1,4-dimethoxybenzene, 1,3-dimethoxybenzene, 1,2-dimethoxybenzene, 1,2,3-trimethoxybenzene) Or methylthiobenzene) can be reacted.

(I) Friedel-Crafts acylation
For example, after adding aluminum chloride to a dichloromethane solution of anisole in an ice bath (−10 ° C.), the compound (I) is dropped and stirred at room temperature for 1 to 12 hours. Next, the reaction solution is poured into ice water containing concentrated hydrochloric acid, and the separated organic layer is extracted with a 10% aqueous sodium hydroxide solution. The aqueous layer is neutralized with hydrochloric acid, and the precipitated solid is converted into an organic solvent (for example, ethyl acetate). Then, the extract is concentrated and then recrystallized as necessary to obtain a compound (A ₁ ′) containing an acyl group and a hydroxyl group. In the above process, when using a methylthio benzene in place of anisole, Compound (A ₁ ') thio - having Le group.

In the polyarylene of the present invention finally obtained by adjusting the substitution position and the number of substitutions of the hydroxyl group (or thiol group) on the aromatic ring in the compound (A ₁ ′), the introduction position of the sulfonic acid group and The amount introduced can be controlled. That is, in this step (Friedel-Crafts acylation reaction), a predetermined position is substituted with an OR group or an SR group (for example, R = hydrogen atom, methyl group, ethyl group, t-butyl group alkyl group, etc.). By using benzene, the introduction position and introduction amount of the sulfonic acid group in the finally obtained polyarylene of the present invention can be controlled.

(Ii) Introduction of protecting group For example, the compound (A ₁ ') and 1 to 20-fold molar amount of 2H-dihydropyran are dissolved in toluene in the presence of an acid catalyst (for example, a cation exchange resin). Allow to stir at room temperature for 1-24 hours. Next, after removing the acid catalyst, the toluene solution is concentrated, and then recrystallized as necessary to obtain a compound (A ₁ ) having a tetrahydro-2-pyranyl group introduced as a protecting group. In the above step, when methylthiobenzene is used instead of anisole, the tetrahydro-2-pyranyl group functions as a thiol protecting group.

Examples of the compound (A ₁ ) represented by the general formula (6) include the following compounds.

Examples of the compound (A ₁ ) represented by the general formula (6) include a compound in which a chlorine atom is replaced with a bromine atom or an iodine atom in the above compound, and a compound in which —CO— is replaced with —SO ₂ — in the above compound. And compounds in which the chlorine atom is replaced by a bromine atom or an iodine atom and -CO- is replaced by -SO ₂ -in the above compound.

"Compound _(A 2)"
The compound represented by the above general formula (7) as _{(A 2)} is specifically the case of m = 0, for example, 4,4'-dichlorobenzophenone, 4,4'-dichloro-benzanilide, bis (chlorophenyl ) Difluoromethane, 2,2-bis (4-chlorophenyl) hexafluoropropane, 4-chlorobenzoic acid-4-chlorophenyl, bis (4-chlorophenyl) sulfoxide, bis (4-chlorophenyl) sulfone, chlorine atoms in these compounds In which at least one of the halogen atoms substituted at the 4-position in these compounds is substituted at the 3-position, and the like.

When m = 1, the specific compound (A ₂ ) represented by the general formula (7) includes, for example, 4,4′-bis (4-chlorobenzoyl) diphenyl ether, 4,4′-bis ( 4-chlorobenzoylamino) diphenyl ether, 4,4′-bis (4-chlorophenylsulfonyl) diphenyl ether, 4,4′-bis (4-chlorophenyl) diphenyl ether dicarboxylate, 4,4′-bis [(4-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4′-bis [(4-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-chlorophenyl) tetrafluoroethyl] diphenyl ether, in these compounds the chlorine atom is placed on the bromine or iodine atom Compounds obtained by substitution, compounds in which the halogen atom substituted in the 4-position in these compounds is substituted in the 3-position, compounds in which at least one of the groups substituted in the 4-position of diphenyl ether in these compounds is substituted in the 3-position, etc. It is done.

Further, the compound (A ₂ ) represented by the general formula (7) is 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3. , 3-hexafluoropropane, bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] sulfone, and a compound represented by the following formula.

The compound (A ₂ ) represented by the general formula (7) can be synthesized, for example, by the method shown below.

  First, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, dimethylsulfoxide, etc., in order to convert the bisphenol linked with an electron-withdrawing group to the corresponding alkali metal salt of bisphenol In a polar solvent having a high dielectric constant, an alkali metal such as lithium, sodium or potassium, an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate or the like is added.

  Usually, the alkali metal is reacted in excess with respect to the hydroxyl group of phenol, and usually 1.1 to 2 times equivalent is used. Preferably, 1.2 to 1.5 times equivalent is used. In this case, fluorine, chlorine, etc. activated with an electron-withdrawing group in the presence of azeotropic solvent such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, phenetole, etc. Aromatic dihalide compounds substituted by halogen atoms of, for example, 4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-chlorofluorobenzophenone, bis (4-chlorophenyl) sulfone, bis (4 -Fluorophenyl) sulfone, 4-fluorophenyl-4'-chlorophenylsulfone, bis (3-nitro-4-chlorophenyl) sulfone, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, hexafluorobenzene, deca Fluorobiphenyl, , 5-difluorobenzophenone, 1,3-bis (4-chlorobenzoyl) reacting benzene. In terms of reactivity, a fluorine compound is preferable, but in consideration of the following aromatic coupling reaction, it is necessary to assemble an aromatic nucleophilic substitution reaction so that the terminal is a chlorine atom. The active aromatic dihalide is used in an amount of 2 to 4 times mol, preferably 2.2 to 2.8 times mol, of bisphenol. Prior to the aromatic nucleophilic substitution reaction, an alkali metal salt of bisphenol may be used. The reaction temperature is 60 to 300 ° C, preferably 80 to 250 ° C. The reaction time ranges from 15 minutes to 100 hours, preferably from 1 hour to 24 hours. The most preferable method is to use a chlorofluoro compound having one halogen atom having a different reactivity as the active aromatic dihalide represented by the following formula, and a nucleophilic substitution reaction with phenoxide occurs preferentially by the fluorine atom. It is convenient to obtain the desired activated terminal chloro form.

(Wherein, W is as defined in the general formula (2).)
Alternatively, as described in JP-A-2-159, a flexible compound composed of a target electron-withdrawing group and electron-donating group is synthesized by combining a nucleophilic substitution reaction and an electrophilic substitution reaction. By using the method, compound (A ₂ ) can be obtained.

  Specifically, an aromatic bishalide activated with an electron-withdrawing group, for example, bis (4-chlorophenyl) sulfone is subjected to a nucleophilic substitution reaction with phenol to obtain a bisphenoxy-substituted product. Subsequently, the compound of interest can be obtained, for example, by performing a Friedel-Crafts reaction with 4-chlorobenzoic acid chloride using this substituted product. As the aromatic bishalide activated with the electron-withdrawing group used here, the compounds exemplified above can be applied. The phenol compound may be substituted, but an unsubstituted compound is preferable from the viewpoint of heat resistance and flexibility. In addition, it is preferable to use an alkali metal salt for the substitution reaction of phenol, and as the usable alkali metal compound, the compounds exemplified above can be used. The amount used is 1.2 to 2 moles per mole of phenol. In the reaction, the polar solvent described above or an azeotropic solvent with water can be used. The bisphenoxy compound is reacted with chlorobenzoic acid chloride as an acylating agent in the presence of an activator for the Friedel-Crafts reaction of Lewis acids such as aluminum chloride, boron trifluoride, and zinc chloride. Chlorobenzoic acid chloride can be used in an amount of 2 to 4 times mol, preferably 2.2 to 3 times mol, of the bisphenoxy compound. The Friedel-Crafts activator is used in an amount of 1.1 to 2 times the amount of an active halide compound such as chlorobenzoic acid as an acylating agent. The reaction time is in the range of 15 minutes to 10 hours, and the reaction temperature is in the range of -20 to 80 ° C. As the solvent used, a solvent inert to the Friedel-Crafts reaction (for example, chlorobenzene, nitrobenzene, etc.) can be used.

In general formula (7) compound represented by the (A _2), m is larger than 2, polymers, for example, a source of ethereal oxygen as an electron-donating group T in the general formula (7) A compound in which bisphenol is combined with> C═O, —SO ₂ —, and / or> C (CF ₃ ) ₂ that are electron-withdrawing groups W, specifically 2,2-bis (4-hydroxy) Alkali metals of bisphenol such as phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxyphenyl) sulfone A substitution reaction of a salt with an excess of an active aromatic halogen compound such as 4,4-dichlorobenzophenone or bis (4-chlorophenyl) sulfone is carried out using N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfora Obtained by sequentially polymerizing the synthesis method of the monomer in the presence a polar solvent such as.

  Examples of such compounds include compounds represented by the following formulas.

  In the above compound, l is 2 or more, preferably 2 to 100.

《Catalyst and others》
The catalyst used when polymerizing the compound (A ₁ ) as a monomer, or when polymerizing the compound (A ₁ ) and the compound (A ₂ ) as a monomer, respectively, is a catalyst system containing a transition metal compound. As the system, (i) a transition metal salt and a compound to be a ligand (hereinafter referred to as “ligand component”), or a transition metal complex in which a ligand is coordinated (including a copper salt), and (Ii) A reducing agent is an essential component, and a “salt” may be added to increase the polymerization rate.

  Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate; palladium compounds such as palladium chloride, palladium bromide and palladium iodide; iron chloride and iron bromide And iron compounds such as iron iodide; cobalt compounds such as cobalt chloride, cobalt bromide, and cobalt iodide. Of these, nickel chloride, nickel bromide and the like are particularly preferable.

  Examples of the ligand component include triphenylphosphine, 2,2′-bipyridine, 1,5-cyclooctadiene, 1,3-bis (diphenylphosphino) propane, and the like. Of these, triphenylphosphine and 2,2′-bipyridine are preferred. The compound which is the said ligand component can be used individually by 1 type or in combination of 2 or more types.

  Furthermore, as the transition metal complex in which the ligand is coordinated, for example, nickel chloride bis (triphenylphosphine), nickel bromide bis (triphenylphosphine), nickel iodide bis (triphenylphosphine), nickel nitrate bis (Triphenylphosphine), nickel chloride (2,2'-bipyridine), nickel bromide (2,2'-bipyridine), nickel iodide (2,2'-bipyridine), nickel nitrate (2,2'-bipyridine) ), Bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like. Of these, nickel chloride bis (triphenylphosphine) and nickel chloride (2,2′-bipyridine) are preferred.

  Examples of the reducing agent that can be used in the catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium, and the like. Of these, zinc, magnesium and manganese are preferred. These reducing agents can be used after being more activated by bringing them into contact with an acid such as an organic acid.

  Examples of the “salt” that can be used in the above catalyst system include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, potassium fluoride, potassium chloride, potassium bromide, Examples include potassium compounds such as potassium iodide and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate. Of these, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide, and tetraethylammonium iodide are preferred.

  The proportion of each component used is usually 0.0001 to 10 mol, preferably 0.01 to 0.5 mol, per 1 mol of the total amount of the above monomers of the transition metal salt or transition metal complex. When the amount is less than 0.0001 mol, the polymerization reaction may not proceed sufficiently. On the other hand, when the amount exceeds 10 mol, the molecular weight may decrease.

  When a transition metal salt and a ligand component are used in the catalyst system, the ratio of the ligand component used is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the transition metal salt. is there. When the amount is less than 0.1 mol, the catalytic activity may be insufficient. On the other hand, when the amount exceeds 100 mol, the molecular weight may decrease.

  Moreover, the usage-amount of a reducing agent is 0.1-100 mol normally with respect to the total of 1 mol of the said monomer, Preferably it is 1-10 mol. If the amount is less than 0.1 mol, polymerization may not proceed sufficiently. If the amount exceeds 100 mol, purification of the resulting polymer may be difficult.

  Furthermore, when using "salt", the usage-ratio is 0.001-100 mol normally with respect to the total of 1 mol of the said monomer, Preferably it is 0.01-1 mol. If it is less than 0.001 mol, the effect of increasing the polymerization rate may be insufficient, and if it exceeds 100 mol, purification of the resulting polymer may be difficult.

  Examples of polymerization solvents that can be used include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, γ-butyrolactam, Examples thereof include dimethylimidazolidinone and tetramethylurea. Of these, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable. These polymerization solvents are preferably used after sufficiently dried.

  The total concentration of the monomers in the polymerization solvent is usually 1 to 90% by weight, preferably 5 to 40% by weight.

  Moreover, the superposition | polymerization temperature at the time of superposing | polymerizing is 0-200 degreeC normally, Preferably it is 50-120 degreeC. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

One example of a reaction formula for obtaining the compound (A) by reacting the compound (A ₁ ) with the compound (A ₂ ) is shown in the following formula (10). In the following formula, x and y are positive integers. As shown in the following formula (10), the compound (A ₁ ) and the compound (A ₂ ) first react to produce the compound (A ′). Subsequently, R ⁹ in this compound (A ′) is removed to produce compound (A).

Specifically, at least one compound (A ₁ ) represented by the general formula (6) 0.5 to 100 mol% (preferably 10 to 99.999 mol%), other aromatic monomers, Preferably, at least one compound (A ₂ ) represented by the general formula (7) is reacted with 0 to 99.5 mol% (preferably 0.001 to 90 mol%) in the presence of a catalyst, It is preferable to obtain compound (A).

{Compound (B)}
The compound (B) has a structural unit represented by the following general formula (4).

  In the general formula (4), R and a are as defined in the general formula (1).

  Examples of the compound (B) include compounds represented by the following formula.

  In producing the polyarylene of the present invention, by adjusting the number of carbon atoms of the compound (B), that is, the number of “a” in the above general formula (4), The introduction position and introduction amount of the acid group can be adjusted.

{Synthesis Example of Compound (A) and Compound (B)}
By reacting the compound (A) containing the structural unit represented by the general formula (3) with the compound (B) represented by the general formula (4), the polysiloxane of the present invention having a sulfonic acid group is reacted. Arylene is obtained.

  Next, synthesis examples of the compound (A) and the compound (B) are shown. The reaction of the compound (A) and the compound (B) can be carried out by dissolving the compound (A) and the compound (B) in a solvent under basic conditions as shown in the following formula (11), for example.

  For example, when M is a hydrogen atom in the compound (A) (see general formula (3)), N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, dimethylsulfoxide, etc. The compound (A) can be converted to an alkali metal salt by adding an alkali metal, an alkali metal hydride, an alkali metal carbonate, or the like as required in a polar solvent having a high dielectric constant.

  Examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkali metal hydride, alkali metal hydroxide, and alkali metal carbonate include the alkali metal hydride, hydroxide, and carbonate, respectively. .

  Usually, the alkali metal is reacted in excess with respect to the sulfonic acid group in the compound (A), and usually 1.1 to 4 times the equivalent amount of the sulfonic acid group is used. Preferably, 1.2 to 3 times equivalent is used.

  In the reaction between the compound (A) and the compound (B), under basic conditions, the oxygen atom or sulfur atom represented by Z in the compound (A) is changed to a carbon atom adjacent to the oxygen atom of the compound (B). On the other hand, a nucleophilic substitution reaction occurs, and the compound (B) opens. A specific example of the above reaction is shown in the following formula (12). Here, the compound (A) and the compound (B) and the alkaline reagent used are not limited to these.

{Compound (C)}
The compound (C) has a structural unit represented by the following general formula (5).

  In the general formula (5), R and a are as defined in the general formula (1), and L represents any one of a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the compound (C) include compounds represented by the following formulas. In the following compounds, K, Li or H may be used instead of Na. Further, Br or I may be used instead of Cl.

  In producing the polyarylene of the present invention, by adjusting the number of carbon atoms of the compound (C), that is, the number of “a” in the general formula (5), The introduction position and introduction amount of the acid group can be adjusted.

{Synthesis Example of Compound (A) and Compound (C)}
By reacting the compound (A) containing the structural unit represented by the general formula (3) with the compound (C) represented by the general formula (5), the polysiloxane of the present invention having a sulfonic acid group is reacted. Arylene is obtained.

  Next, synthesis examples of the compound (A) and the compound (C) are shown. The reaction between the compound (A) and the compound (C) can be carried out by dissolving the compound (A) and the compound (C) in a solvent under basic conditions, for example, as shown in the following formula (13).

  In the reaction between the compound (A) and the compound (C), for example, the polar solvent and the alkali reagent exemplified in the reaction between the compound (A) and the compound (B) described above can be used.

  In the reaction between the compound (A) and the compound (C), under basic conditions, the oxygen atom or sulfur atom represented by Z in the compound (A) is changed to a carbon atom adjacent to the oxygen atom of the compound (B). In contrast, a nucleophilic substitution reaction occurs. A specific example of the above reaction is shown in the following formula (14). Here, the compound (A) and the compound (C) and the alkaline reagent used are not limited to these.

(Polymer solid electrolyte and proton conducting membrane)
The solid polymer electrolyte and proton conductive membrane of the present invention are composed of the polyarylene of the present invention having a sulfonic acid group. When preparing a proton conductive membrane from the polyarylene of the present invention, in addition to the polyarylene of the present invention, an inorganic acid such as sulfuric acid and phosphoric acid, an organic acid containing a carboxylic acid, an appropriate amount of water, etc. may be used in combination. Good.

  In the proton conducting membrane of the present invention, the polyarylene of the present invention is dissolved in a solvent to form a solution, and then cast on a substrate by casting to form a film (casting method). It can manufacture by shape | molding in a shape. Here, the substrate is not particularly limited as long as it is a substrate used in an ordinary solution casting method. For example, a substrate made of plastic, metal, or the like is used. Preferably, for example, a polyethylene terephthalate (PET) film or the like is used. A substrate made of a thermoplastic resin is used.

  Examples of the solvent for dissolving the polyarylene of the present invention include N-methyl-2-pyrrolidone, N, N-dimethylformamide, 縺 | butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, dimethylurea, dimethylimidazolidinone and the like. Among these, N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) is preferable from the viewpoint of solubility and solution viscosity. The aprotic polar solvent can be used alone or in combination of two or more.

  In addition, as a solvent for dissolving the polyarylene of the present invention, a mixture of the above aprotic polar solvent and alcohol can also be used. Examples of the alcohol include methanol, ethanol, propyl alcohol, iso-propyl alcohol, sec-butyl alcohol, tert-butyl alcohol and the like, and methanol is particularly preferable because it has an effect of lowering the solution viscosity in a wide composition range. Alcohol can be used alone or in combination of two or more.

  When a mixture of an aprotic polar solvent and an alcohol is used as the solvent, the aprotic polar solvent is 95 to 25% by weight, preferably 90 to 25% by weight, and the alcohol is 5 to 75% by weight, preferably 10 to 10%. 75% by weight (however, the total is 100% by weight). When the amount of alcohol is within the above range, the effect of lowering the solution viscosity is excellent.

  The polymer concentration of the solution in which the polyarylene of the present invention is dissolved is usually 5 to 40% by weight, preferably 7 to 25% by weight, although it depends on the molecular weight of the polyarylene. If it is less than 5% by weight, it is difficult to form a thick film, and pinholes are easily generated. On the other hand, if it exceeds 40% by weight, the solution viscosity is so high that it is difficult to form a film, and surface smoothness may be lacking.

  The solution viscosity is usually 2,000 to 100,000 mPa · s, preferably 3,000 to 50,000 mPa · s, although it depends on the molecular weight of the polyarylene of the present invention and the polymer concentration. If it is less than 2,000 mPa · s, the retention of the solution during film formation is poor, and it may flow from the substrate. On the other hand, if it exceeds 100,000 mPa · s, the viscosity is too high to be extruded from the die and it may be difficult to form a film by the casting method.

  After film formation as described above, by immersing the obtained undried film in water, the organic solvent in the undried film can be replaced with water, and the residual solvent amount of the resulting proton conducting membrane can be reduced. Can be reduced.

  In addition, after film formation, before immersing an undried film in water, you may predry an undried film. The preliminary drying is performed by holding the undried film at a temperature of usually 50 to 150 ° C. for 0.1 to 10 hours.

  When immersing an undried film in water, it may be a batch system in which a single wafer is immersed in water, or a laminated film in a state of being formed on a substrate film (for example, PET) that is usually obtained, Alternatively, a continuous method in which a film separated from a substrate is dipped in water and wound is also applicable.

  In the case of the batch method, a method of placing the treated film in a frame is advantageous in that wrinkle formation on the surface of the treated film is suppressed.

  When the undried film is immersed in water, the contact ratio of water is 10 parts by weight or more, preferably 30 parts by weight or more with respect to 1 part by weight of the undried film. In order to minimize the amount of residual solvent in the resulting proton conducting membrane, it is preferable to maintain a contact ratio as large as possible. It is also effective to reduce the amount of residual solvent in the resulting proton conducting membrane by changing the water used for immersion or allowing it to overflow so that the organic solvent concentration in the water is always kept below a certain level. is there. In order to suppress the in-plane distribution of the amount of the organic solvent remaining in the proton conducting membrane, it is effective to homogenize the concentration of the organic solvent in water by stirring or the like.

  The temperature of water when the undried film is immersed in water is preferably in the range of 5 to 80 ° C. The higher the temperature, the faster the replacement rate of the organic solvent and water, but the greater the amount of water absorbed by the film, so there is a concern that the surface state of the proton conducting membrane obtained after drying will be rough. Usually, a temperature range of 10 to 60 ° C. is convenient because of the replacement speed and ease of handling.

  The immersion time is usually in the range of 10 minutes to 240 hours, although depending on the initial residual solvent amount, contact ratio, and treatment temperature. Preferably, it is in the range of 30 minutes to 100 hours.

  When the undried film is immersed in water and dried as described above, a proton conductive membrane with a reduced amount of residual solvent is obtained. The residual amount of the proton conductive membrane thus obtained is usually 5% by weight or less. It is.

  Further, depending on the immersion conditions, the amount of residual solvent in the obtained proton conducting membrane can be set to 1% by weight or less. As such conditions, for example, the contact ratio between the undried film and water is 50 parts by weight or more with respect to 1 part by weight of the undried film. There is a method of setting 10 minutes to 10 hours.

  After immersing the undried film in water as described above, the film is dried at 30-100 ° C, preferably 50-80 ° C, for 10-180 minutes, preferably 15-60 minutes, and then at 50-150 ° C. The proton conducting membrane of the present invention can be obtained by vacuum drying under reduced pressure of 500 mmHg to 0.1 mmHg for 0.5 to 24 hours.

  The proton conductive membrane of the present invention obtained by the above production method has a dry film thickness of usually 10 to 100 · fragrance A, preferably 20 to 80 · high.

  The proton conductive membrane of the present invention may contain an anti-aging agent, preferably a hindered phenol compound having a molecular weight of 500 or more. By containing an anti-aging agent, the durability of the proton conductive membrane can be further improved. it can.

  As a hindered phenol compound having a molecular weight of 500 or more that can be used in the present invention, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) proonate] (trade name: IRGANOX 245) 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 259), 2,4-bis- (n- Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -3,5-triazine (trade name: IRGANOX 565), pentaerythrityl-tetrakis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ] (Trade name: IRGANOX 1035), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (trade name: IRGANOX 1076), N, N-hexamethylene bis (3.5 -Di-t-butyl-4-hydroxy-hydrocinnamamide) (IRGAONOX 1098) 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) ) Benzene (trade name: IRGANOX 1330), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (trade name: IRGANOX 3114), 3,9-bis [2- [3 -(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: Sumilizer GA-80).

  In the present invention, the hindered phenol compound having a molecular weight of 500 or more with respect to 100 parts by weight of polyarylene is preferably used in an amount of 0.01 to 10 parts by weight.

  The proton conductive membrane of the present invention is a proton that can be used for, for example, an electrolyte for a primary battery, an electrolyte for a secondary battery, a polymer solid electrolyte for a fuel cell, a display element, various sensors, a signal transmission medium, a solid capacitor, an ion exchange membrane, and the like. It can be used for a conductive film.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Various measurement items in the examples were determined as follows. In this example, the polymer film (film sample) used for various measurements is a film having a thickness of 40 μm. This film was produced by dissolving the polyarylene having a sulfonic acid group obtained in each example in N-methylpyrrolidone at a concentration of 18%, and then by a casting method.

(Equivalent of sulfonic acid group)
The obtained polyarylene was washed with distilled water until it was neutralized, sufficiently washed with water except for the remaining free acid, and then dried. Thereafter, a predetermined amount is weighed and dissolved in a THF / water mixed solvent, titrated with a standard solution of NaOH using phenolphthalein as an indicator, and an equivalent amount of sulfonic acid groups (ion exchange capacity) from the neutralization point. (Meq / g) was determined.

(Proton conductivity)
For AC resistance, the membrane sample is formed into a strip shape having a width of 5 mm, a platinum wire (φ = 0.5 mm) is pressed against the surface of the membrane sample, the membrane sample is held in a constant temperature and humidity apparatus, and a platinum wire It was calculated from the AC impedance measurement. The impedance at an AC of 10 kHz was measured in an environment of 85 ° C. and a relative humidity of 90%. A chemical impedance measurement system manufactured by NF Circuit Design Block Co., Ltd. was used as the resistance measurement device, and JW241 manufactured by Yamato Scientific Co., Ltd. was used as the constant temperature and humidity device. Five platinum wires were pressed at intervals of 5 mm, the distance between the wires was changed to 5 to 20 mm, and the AC resistance was measured. The specific resistance of the membrane was calculated from the line-to-line distance and the resistance gradient, the AC impedance was calculated from the reciprocal of the specific resistance, and the proton conductivity was determined from this impedance.

Specific resistance R [Ω · cm] = 0.5 [cm] × film thickness [cm] × resistance line gradient [Ω / cm]
(Thermal properties)
Thermal decomposition start temperature;
The temperature at which decomposition of the sulfonated polyarylene started from TGA (temperature increase rate of 20 ° C./min under a nitrogen atmosphere) was defined as the thermal decomposition start temperature (° C.).

Hot water resistance;
A membrane sample (sulfonated polymer film) having a thickness of 40 μm was immersed in hot water at 95 ° C. for 48 hours, and the ratio of the weight of the film after immersion to the weight of the film before immersion was expressed as weight retention (%). did.

(Fenton reagent resistance)
Hydrogen peroxide water was diluted with pure water to a concentration of 3%, and iron sulfate was dissolved therein so that the iron ion (Fe ²⁺ ) concentration was 20 ppm. A fixed-size membrane sample (sulfonated polymer film) was immersed in this solution and allowed to stand at 45 ° C. for 20 hours. The ratio of the weight of the film after immersion to the weight of the film before immersion was defined as the weight retention rate (%).

(Molecular weight measurement)
The weight average molecular weight and number average molecular weight of the polyarylene of the present example are molecular weights in terms of polystyrene measured by GPC using tetrahydrofuran (THF) as a solvent.

(I) Synthesis of benzophenone derivative (compound (A ₁ '-1)) (i) Synthesis of 2,5-dichloro-4'-hydroxybenzophenone 64.9 g (600 mmol) of anisole and 480 mL of dichloromethane were added to a stirring apparatus and nitrogen was introduced. The flask was placed in a 2 L 3-neck flask equipped with a dropping funnel and cooled to 10 ° C. in an ice bath, and then 80 g (600 mmol) of aluminum chloride was added. Next, 125.7 g (600 mmol) of 2,5-dichlorobenzoyl chloride was slowly dropped from the dropping funnel. After completion of dropping, 80 g (600 mmol) of aluminum chloride was added. Thereafter, the temperature was returned to room temperature and stirring was continued for 12 hours.

Thereafter, the reaction solution was poured into 2 L of ice water containing 300 mL of concentrated hydrochloric acid, and the separated organic layer was extracted with a 10% aqueous sodium hydroxide solution. On the other hand, the aqueous layer was neutralized with hydrochloric acid, and the precipitated solid was extracted with 2 L of ethyl acetate. The solvent was evaporated, and the obtained solid with ethyl acetate: recrystallized from n- hexane, 136.3 g (85% yield) of 2,5-dichloro-4'-hydroxybenzophenone (Compound _{(A 1} '- 1)) was obtained. The ¹ H-NMR spectrum of this compound _{(A 1} '-1) in FIG.

(Ii) Synthesis of 2,5-dichloro-4 ′-(tetrahydro-2-pyranyloxy) benzophenone (compound (A ₁ -1)) 2,5-dichloro-4′- which is compound (A ₁ -1) Hydroxybenzophenone 26.7 g (100 mmol), 2H-dihydropyran 100 g (1200 mmol) and toluene 100 mL were placed in a flask, and 1.5 g of cation exchange resin (Amberlyst 15) was added to the flask while stirring. After continuing the stirring, the cation exchange resin was removed by filtration. Subsequently, the obtained filtrate was washed with an aqueous sodium hydroxide solution and brine, dried over magnesium sulfate, and then the solvent was distilled off. The obtained solid was recrystallized from toluene to obtain 16.4 g (yield 47%) of 2,5-dichloro-4 ′-(tetrahydro-2-pyranyloxy) benzophenone (compound (A ₁ -1)). It was. The ¹ H-NMR spectrum of this compound _(A 1 -1) in FIG. Moreover, the said process (i) and (ii) in Example 1 is shown in following formula (15).

(II) Synthesis of Compound (A-1) 15.6 g (44.4 mmol) of 2,5-dichloro-4 ′-(tetrahydro-2-pyranyloxy) benzophenone which is Compound (A ₁ -1), Compound (A ₂₎ 4,4′-dichlorobenzophenone · 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane polycondensate (number average molecular weight 11,200) 6 .55 g (0.585 mmol), bis (triphenylphosphine) nickel dichloride 0.883 g (1.35 mmol), sodium iodide 0.877 g (5.85 mmol), triphenylphosphine 4.72 g (18 mmol), zinc 7. 06 g (108 mmol) was taken in a 500 mL flask equipped with a stirring blade, a thermometer, and a nitrogen introducing tube, and dried in a vacuum. After replacing the inside of the flask with dry nitrogen, 52 mL of N, N-dimethylacetamide (DMAc) was added to initiate polymerization. During the polymerization, the temperature of the reaction solution was controlled to be in the range of 70 to 90 ° C. Three hours later, DMAc (200 mL) was added for dilution, and the insoluble portion was filtered to obtain a polymer solution filtrate.

A very small amount of the filtrate of the polymer solution is collected, poured into methanol, the polymer is precipitated, the precipitate is separated by filtration, and the precipitate is dried, and the solid ¹ H-NMR obtained is dried. The spectrum is shown in FIG. From the ¹ H-NMR spectrum shown in FIG. 3, it was confirmed that this solid had a tetrahydro-2-pyranyl group, and the structure thereof was presumed to be the compound (A′-1). Moreover, the number average molecular weight calculated | required by GPC about this solid was 28,000, and the weight average molecular weight was 103,000.

On the other hand, the remaining polymer solution filtrate was poured into 1.5 L of methanol containing 10 vol% concentrated hydrochloric acid to precipitate the polymer. Next, after separating the precipitate by filtration, the obtained solid was dried to obtain 14.3 g of a polymer (compound (A-1)) having a hydroxyl group. The ¹ H-NMR spectrum of this compound (A-1) is shown in FIG. From the spectrum shown in FIG. 4, it was confirmed that this polymer had a hydroxyl group. In addition, the said process (II) in Example 1 is shown to following formula (16). In Expression (16), d, e, and f are positive integers.

(III) Synthesis of polyarylene (1) having a sulfonic acid group 15.2 g of the compound (A-1) was added to 250 mL of N, N-dimethylacetamide (DMAc), and dissolved by stirring while heating to 100 ° C. . Next, 1.06 g (133 mmol) of lithium hydride was added and stirred for 2 hours. Subsequently, 16.2 g (133 mmol) of propane sultone (B-1) was added and reacted for 8 hours. Next, the insoluble part of the reaction solution was filtered, and then poured into 1N hydrochloric acid to precipitate the polymer. The precipitated polymer was washed with 1N hydrochloric acid and then washed with distilled water until the pH became neutral. This polymer was dried at 75 ° C. to obtain 19.2 g of a polyarylene (compound (1)) having a powdered sulfonic acid group. The ¹ H-NMR spectrum of this compound (1) is shown in FIG. Moreover, the said process (III) in Example 1 is shown in following formula (17). In Expression (17), d, e, and f are positive integers.

  Example 1 (III) was the same as Example 1 except that 18.1 g (133 mmol) of butane sultone (B-2) was used instead of 16.2 g (133 mmol) of propane sultone (B-1). The reaction was performed to obtain 20.8 g of a polyarylene (compound (2)) having a powdered sulfonic acid group. Moreover, the said process (III) in Example 2 is shown to following formula (18). In Expression (18), d, e, and f are positive integers.

(I) Synthesis of benzophenone derivative (compound (A ₁ '-2)) (i) Synthesis of 2,5-dichloro-2', 4'-dihydroxybenzophenone 1,3-dimethoxybenzene 33.2 g (240 mmol), dichloromethane 300 mL was placed in a 2 L three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel, cooled to 10 ° C. in an ice bath, and 32 g (240 mmol) of aluminum chloride was added. Next, 50.3 g (240 mmol) of 2,5-dichlorobenzoic acid chloride was slowly dropped from the dropping funnel. After completion of the dropwise addition, 32 g (240 mmol) of aluminum chloride was added. Thereafter, the temperature was returned to room temperature and stirring was continued for 12 hours.

Thereafter, the reaction solution was poured into 1 L of ice water containing 150 mL of concentrated hydrochloric acid, and the separated organic layer was extracted with a 10% aqueous sodium hydroxide solution. On the other hand, the aqueous layer was neutralized with hydrochloric acid, and the precipitated solid was extracted with 1 L of ethyl acetate. The solvent was evaporated, and the obtained solid with ethyl acetate: recrystallized from n- hexane, 57 g (76% yield) of 2,5-dichloro-2 ', 4'-dihydroxybenzophenone (Compound _{A 1'} - 2) was obtained.

(Ii) Synthesis of 2,5-dichloro-2 ′, 4′-di (tetrahydro-2-pyranyloxy) benzophenone (compound (A ₁ -2)) 2,5-dichloro which is the compound (A ₁ ′ -2) -2 ′, 4′-dihydroxybenzophenone 28.3 g (100 mmol), 2H-dihydropyran 200 g (2400 mmol) and toluene 100 mL were placed in a flask, and while stirring, 3.0 g of cation exchange resin (Amberlyst 15) And the stirring was continued at room temperature for 5 hours, and then the cation exchange resin was removed by filtration. Subsequently, the obtained filtrate was washed with an aqueous sodium hydroxide solution and brine, dried over magnesium sulfate, and then the solvent was distilled off. The resulting solid was recrystallized from toluene, 21.2 g (47% yield) of 2,5-dichloro-2 ', 4'-di (tetrahydro-2-pyranyloxy) benzophenone (Compound _(A 1 -2 )). Moreover, the said process (i) and (ii) in Example 3 is shown to following formula (19).

(II) polyarylene (Compound (A-2)) A solution of compound _(A 1 -2) 2,5-dichloro-2 ', 4'-di (tetrahydro-2-pyranyloxy) benzophenone 19.45 g (43 .1 mmol), 4,4′-dichlorobenzophenone · 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane polycondensation which is the compound (A ₂ -2) Product (number average molecular weight 11,200) 20.12 g (1.80 mmol), bis (triphenylphosphine) nickel dichloride 0.883 g (1.35 mmol), sodium iodide 0.877 g (5.85 mmol), triphenylphosphine 4.72 g (18 mmol), 7.06 g (108 mmol) of zinc, 500 mL with a stirring blade, a thermometer, and a nitrogen introduction tube It took to the flask and vacuum-dried. After replacing the inside of the flask with dry nitrogen, 87 mL of N, N-dimethylacetamide (DMAc) was added to initiate polymerization. During the polymerization, the temperature of the reaction solution was controlled to be in the range of 70 to 90 ° C. Three hours later, DMAc (200 mL) was added for dilution, and the insoluble portion was filtered to obtain a polymer solution filtrate. The filtrate of this polymer solution contains a compound (A′-2), and this compound (A′-2) is presumed to have a tetrahydro-2-pyranyl group. Next, the filtrate of this polymer solution was poured into 1.5 L of methanol containing 10 vol% of concentrated hydrochloric acid to precipitate the polymer. Next, after separating the precipitate by filtration, the obtained solid was dried to obtain 28.5 g of a polymer (compound (A-2)) having a hydroxyl group. The above step (II) in Example 3 is shown in the following formula (20). In Expression (20), d, e, and f are positive integers.

(III) Synthesis of polyarylene (3) having a sulfonic acid group 29.1 g of compound (A-2) was converted to N, N-dimethylacetamide (DMAc).
The solution was added to 500 mL and dissolved by stirring while heating to 100 ° C. Next, 2.06 g (258 mmol) of lithium hydride was added and stirred for 2 hours. Subsequently, 31.6 g (258 mmol) of propane sultone (B-1) was added and reacted for 8 hours. Next, the insoluble part of the reaction solution was filtered, and then poured into 1N hydrochloric acid to precipitate the polymer. The precipitated polymer was washed with 1N hydrochloric acid and then washed with distilled water until the pH became neutral. This polymer was dried at 75 ° C. to obtain 38.2 g of a polyarylene (compound (3)) having a powdered sulfonic acid group. Moreover, the said process (III) in Example 3 is shown to following formula (21). In the formula (21), d, e, and f are positive integers.

(I) Synthesis of benzophenone derivative (compound (A ₁ '-3)) (i) Synthesis of 2,5-dichloro-4'-hydrothiobenzophenone 74.5 g (600 mmol) of methylthiobenzene and 480 mL of dichloromethane were added to a stirrer, The flask was placed in a 2 L three-necked flask equipped with a nitrogen inlet tube and a dropping funnel, cooled to 10 ° C. with an ice bath, and then 80 g (600 mmol) of aluminum chloride was added. Next, 125.7 g (600 mmol) of 2,5-dichlorobenzoyl chloride was slowly dropped from the dropping funnel. After completion of dropping, 80 g (600 mmol) of aluminum chloride was added. Thereafter, the temperature was returned to room temperature and stirring was continued for 12 hours.

Thereafter, the reaction solution was poured into 2 L of ice water containing 300 mL of concentrated hydrochloric acid, and the separated organic layer was extracted with a 10% aqueous sodium hydroxide solution. On the other hand, the aqueous layer was neutralized with hydrochloric acid, and the precipitated solid was extracted with 2 L of ethyl acetate. The solvent was evaporated, and the obtained solid with ethyl acetate: n-was recrystallized from hexane, 150 g 2,5-dichloro-4'-hydro-thiobenzophenone (compound (88% yield) _{(A 1} '-3 )).

(Ii) 2,5-dichloro-4 - a '(tetrahydro-2-Piraniruchio) benzophenone (Compound _(A 1 -3)) Compound of _{(A 1'} -3) 2,5-dichloro-4'- 28.3 g (100 mmol) of hydrothiobenzophenone, 100 g (1200 mmol) of 2H-dihydropyran and 100 mL of toluene were placed in a flask, and 1.5 g of cation exchange resin (Amberlyst 15) was added to the flask while stirring. After stirring for an hour, the cation exchange resin was removed by filtration. Subsequently, the obtained filtrate was washed with an aqueous sodium hydroxide solution and brine, dried over magnesium sulfate, and then the solvent was distilled off. The obtained solid was recrystallized from toluene to obtain 19.5 g (yield 53%) of 2,5-dichloro-4 ′-(tetrahydro-2-pyranylthio) benzophenone (compound (A ₁ -3)). It was. Moreover, the said process (i) and (ii) in Example 4 is shown to following formula (22).

(II) Synthesis of polyarylene (compound (A-3)) 16.3 g (44.4 mmol) of 2,5-dichloro-4 ′-(tetrahydro-2-pyranylthio) benzophenone which is compound (A ₁ -3), compound _(a 2 -3) is 4,4'-dichlorobenzophenone-2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane polycondensate (number average Molecular weight 11,200) 6.55 g (0.585 mmol), bis (triphenylphosphine) nickel dichloride 0.883 g (1.35 mmol), sodium iodide 0.877 g (5.85 mmol), triphenylphosphine 4.72 g ( 18 mmol) and 7.06 g (108 mmol) of zinc in a 500 mL flask equipped with a stirring blade, a thermometer, and a nitrogen introduction tube. Ri, and dried under vacuum. After replacing the inside of the flask with dry nitrogen, 52 mL of N, N-dimethylacetamide (DMAc) was added to initiate polymerization. During the polymerization, the temperature of the reaction solution was controlled to be in the range of 70 to 90 ° C. Three hours later, DMAc (200 mL) was added for dilution, and the insoluble portion was filtered to obtain a polymer solution filtrate. The filtrate of this polymer solution contains a compound (A′-3), and this compound (A′-3) is presumed to have a tetrahydro-2-pyranyl group. The filtrate of this polymer solution was poured into 1.5 L of methanol containing 10 vol% concentrated hydrochloric acid to precipitate the polymer. Next, after separating the precipitate by filtration, the obtained solid was dried to obtain 15.2 g of a polymer (compound (A-3)) having a thiol group. The above step (II) in Example 4 is represented by the following formula (23). In Expression (23), d, e, and f are positive integers.

(III) Synthesis of polyarylene (4) having a sulfonic acid group 15.2 g of compound (A-3) was converted to N, N-dimethylacetamide (DMAc).
The solution was added to 250 mL and stirred and dissolved while heating to 100 ° C. Next, 1.06 g (133 mmol) of lithium hydride was added and stirred for 2 hours. Subsequently, 16.2 g (133 mmol) of propane sultone (B-1) was added and reacted for 8 hours. Next, the insoluble part of the reaction solution was filtered, and then poured into 1N hydrochloric acid to precipitate the polymer. The precipitated polymer was washed with 1N hydrochloric acid and then washed with distilled water until the pH became neutral. This polymer was dried at 75 ° C. to obtain 19.9 g of a polyarylene (compound (4)) having a powdered sulfonic acid group. Moreover, the said process (III) in Example 4 is shown to following formula (24). In Expression (24), d, e, and f are positive integers.

  Table 1 shows the characteristics of the polyarylenes of the present invention obtained in Examples 1 to 4, respectively.

1 is a ¹ H-NMR spectrum of a compound (A ₁ '-1) obtained in Example 1. 1 is a ¹ H-NMR spectrum of a compound (A ₁ -1) obtained in Example 1. 2 is a ¹ H-NMR spectrum of the compound (A′-1) obtained in Example 1. 1 is a ¹ H-NMR spectrum of the compound (A-1) obtained in Example 1. 1 is a ¹ H-NMR spectrum of the compound (1) obtained in Example 1.

Claims (6)

A polyarylene containing a structural unit represented by the following general formula (1).

Wherein, X, Y is -CO -, - CONH -, - (CF 2) q - ( wherein, q is an integer of 1 to _{10), - C (CF 3)} 2 -, - COO- , —SO—, —SO ₂ —, —O—, —S—, —CH═CH—, —C≡C—,

In represented by a group or a direct bond, Z is an oxygen atom or a sulfur atom, R represents a hydrogen atom, a fluorine atom, an alkyl group, and at least one atom or group chosen from the group consisting of fluorine-substituted alkyl group A is an integer of 1 to 20, n is an integer of 1 to 5, and p is an integer of 0 to 10. ] In claim 1,
The polyarylene containing 0.5-100 mol% of structural units represented by the general formula (1) and 0-99.5 mol% of structural units represented by the following general formula (2).

[Wherein, R ^{1 to} R ⁸ may be the same as or different from each other, and are at least one atom selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluorine-substituted alkyl group, an allyl group, and an aryl group; W represents a divalent electron-withdrawing group, T represents —CO—, —CONH—, — (CF ₂ ) _q — (where q is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—, —SO—, —SO ₂ —, —O—, —S—, —CH═CH—, —C≡C— or the following formula

And m represents 0 or a positive integer. ] A compound (A) containing a structural unit represented by the following general formula (3), a compound (B) represented by the following general formula (4) or a compound (C) represented by the following general formula (5); A process for producing polyarylene, which comprises reacting

[Wherein, X, Y, Z, n, and p are as defined in the general formula (1), and M represents a hydrogen atom or an alkali metal atom. ]

[Wherein, R and a are as defined in the general formula (1). ]

[Wherein, R and a are as defined in the general formula (1), M is as defined in the general formula (3), and L is any one of a chlorine atom, a bromine atom and an iodine atom. Indicates. ] In claim 3,
The said compound (A) is a manufacturing method of polyarylene further including the structural unit represented by the said General formula (2).   A polymer solid electrolyte comprising the polyarylene according to claim 1.   A proton conducting membrane comprising the polyarylene according to claim 1.

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