JP2003272695A - Alkoxysulfonic acid group contained polyarylene ether, and composite containing the same, ion conductive membrane using the same, adhesive, compound, and fuel cell and their manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polymer material that is superior in heat resistance, processing, and ion conductivity and is especially useful for an ion conductive membrane by polyarylene ether introducing alkoxysulfonic acid group that is useful for a polymer electrolyte membrane. <P>SOLUTION: A polymer material for achieving the above objective is obtained by composing polyarylene ether that has introduced alkoxysulfonic acid group having the carbon number of 1-8 in an aromatic ring. This alkoxysulfonic acid contained aromatic group ring unit can be introduced at monomer stage, thereby, the introducing quantity of the sulfonic acid group can be controlled at polymerization. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an alkoxy sulfonic acid group-containing aromatic polyarylene ether compound useful as a polymer electrolyte membrane.

[0002]

2. Description of the Related Art As an example of an electrochemical device using a solid polymer electrolyte as an ionic conductor instead of a liquid electrolyte, a water electrolysis cell or a fuel cell can be mentioned. The polymer membranes used for these must be sufficiently stable chemically, thermally, electrochemically and mechanically as a cation exchange membrane together with proton conductivity. Therefore, as a material that can be used for a long period of time, a perfluorocarbon sulfonic acid membrane typified by "Nafion (registered trademark)" manufactured by DuPont, USA has been mainly used. However, if the Nafion membrane is operated at a temperature higher than 100 ° C., the water content of the membrane drops sharply and the membrane softens significantly. Therefore, in a fuel cell that uses methanol as a fuel, which is expected in the future, the performance of the fuel cell deteriorates due to the permeation of methanol in the membrane, and it is not possible to exhibit sufficient performance. Further, even in a fuel cell currently operated mainly with hydrogen as a fuel and operated at around 80 ° C., it is pointed out that the cost of the membrane is too high as an obstacle to establishment of the fuel cell technology.

In order to overcome such drawbacks, various studies have been made on polymer electrolyte membranes in which a sulfonic acid group is introduced into a non-fluorine-containing aromatic ring-containing polymer. As the polymer skeleton, considering heat resistance and chemical stability, aromatic polyarylene ether compounds such as aromatic polyarylene ether ketones and aromatic polyarylene ether sulfones can be regarded as a promising structure, For example, sulfonation of polyarylethersulfone (Journal of MembraneScie)
nce, 83 , P.N. 211 (1993)), sulfonated polyetheretherketone (JP-A-6-9)
3114), sulfonated polystyrene and the like have been reported. However, it has been pointed out that a polymer electrolyte membrane in which a sulfonic acid group is directly introduced onto an aromatic ring is unlikely to form a large ion channel that contributes to proton conductivity like the above-mentioned perfluorocarbon sulfonic acid membrane (Journal of Membrane Sci
ence, 185 , p. 29 (2001)). For this reason, it is considered to introduce a sulfonic acid group into the aromatic polyarylene ether compound via a side chain, but JP-A-60-195130 and JP-A-62-26970.
In the case of introducing an alkylsulfonic acid into the polymer by using the Friedel-Crafts reaction in the polymer disclosed in Japanese Patent Publication No. 4, it is difficult to sufficiently control the amount of the alkylsulfonic acid group introduced, and sufficient performance as an ion conductive membrane is exhibited. It wasn't something to do.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a polyarylene ether compound having an alkoxy sulfonic acid group introduced therein, which is useful as a polymer electrolyte membrane, to obtain heat resistance,
The object is to obtain a polymer material having excellent processability and ion conductivity, which is particularly useful as an ion conductive film.

[0005]

As a result of intensive studies, the present inventors have found that the above-mentioned object can be achieved by a polyarylene ether compound in which a specific alkoxysulfonic acid is introduced on an aromatic ring. I arrived.

That is, the present invention provides the following (1) to (11):
Achieved by

(1) Having an alkoxyl sulfonic acid group having 1 to 8 carbon atoms on the aromatic ring, together with the general formula (1),

[0008]

[Chemical 5] (However, n is an integer of 1 to 8, X is hydrogen or fluorine, Y is hydrogen, a monovalent metal atom, or a nitrogen-containing organic group.) General formula (2) and / or general formula (3) Including components

[0009]

[Chemical 6]

[0010]

[Chemical 7] (However, Z represents a direct bond, a sulfone group, a ketone group, or an organic group having 1 to 20 carbon atoms.), And a reduced specific viscosity of 0.1 or more, a polyarylene ether.

(2) The above-mentioned (1), wherein the ion exchange capacity by the sulfonic acid group is 0.1 to 2.5.
The polyarylene ether described in 1.

(3) A composition comprising 50 to 100% by mass of the polyarylene ether compound according to any one of (1) to (2) above.

(4) An ion-conducting membrane containing the compound described in any one of (1) to (3) above.

(5) A composite containing the ion-conducting membrane described in (4) above and an electrode.

(6) A fuel cell containing the composite according to (5) above.

(7) An adhesive containing the polyarylene ether described in (1) or (2) above.

(8) In any one of the above (1) to (2), the polymerization is carried out by an aromatic nucleophilic substitution reaction containing a compound represented by the general formula (4) and a bisphenol compound as a monomer. A method for producing the described polyarylene ether.

[0018]

[Chemical 8] However, n is an integer of 1 to 8, X is hydrogen or fluorine,
Y represents a monovalent metal atom, a nitrogen-containing organic group, and W represents chlorine or fluorine.

(9) A step of casting the solution containing the compound according to any one of the above (1) and (2) and a solvent so that the cast thickness is in the range of 10 to 1000 μm, and casting is performed. The method for producing an ion-conducting membrane according to (4) above, which comprises a step of drying the solution.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The present invention provides a polymer material having excellent heat resistance, processability, and ion conductivity, which is particularly useful as an ion conductive film, by using a polyarylene ether compound having a specific alkoxysulfonic acid introduced on the aromatic ring. It is provided. That is, a polyarylene having an alkoxyl sulfonic acid group having 1 to 8 carbon atoms on an aromatic ring and containing a constituent represented by the general formula (2) and / or the general formula (3) together with the following general formula (1). It is ether.

[0022]

[Chemical 9] Here, n is an integer of 1 to 8, X is hydrogen or fluorine,
Y represents hydrogen, a monovalent metal atom, or a nitrogen-containing organic group. 1
Examples of the valent metal atom include lithium, sodium and potassium. As the nitrogen-containing organic group, ammonia, triethylamine, aniline, N, N
-Diethylaniline, pyridine, N-methylmorpholine and the like can be mentioned, but the invention is not limited thereto.

[0023]

[Chemical 10]

[0024]

[Chemical 11] Here, Z is selected from a direct bond, a sulfone group, a ketone group, or an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include, but are not limited to, methylene, ethylene, ethylidene, isopropylidene, hexafluoroisopropylidene, phenylmethylene, diphenylmethylene and fluorenylidene. The abundance ratio of the constituent components represented by the general formula (2) and / or the general formula (3) together with the general formula (1) is not particularly limited, but the constituent component represented by the general formula (1) is 20% by weight. The above content is preferable, and the one containing 30% by weight or more is particularly preferable.

The polyarylene ether compound in the present invention is an aromatic polymer in which a polymer chain is formed by various bonds connecting aromatic rings, and one of the main bonds contributing to the connection is an ether bond. Say. The polymer need not be linked only by ether bonds, but may be sulfones, ketones, alkylenes, sulfides,
Sulfoxide, direct bond and the like can also be mentioned as an example of the main bond that exists together with the ether bond. The above-mentioned alkoxy sulfonic acid group means a sulfonic acid group bonded to a part of the alkoxy group. The alkoxy group may be not only a straight-chain one but also a branched one, and a part or all of hydrogen atoms of the alkoxy group may be replaced with halogen atoms such as fluorine and chlorine. The sulfonic acid group is present as a free sulfonic acid group,
Derivatives such as metal salts and nitrogen-containing organic compound salts including ammonia salts may be used.

In the present invention, the above general formula (1)
Since it is important that the structure of exists in the polymer chain,
Structural units other than those represented by the general formula (2) or the general formula (3) may be contained. At this time, the structural unit other than those represented by the general formula (2) or the general formula (3) is preferably 50% by weight or less of the polyarylene ether introduced with the alkoxysulfonic acid of the present invention.

As the alkoxy sulfonic acid group-containing polyarylene ether compound of the present invention, a compound containing a constituent represented by the following general formula (5) is particularly preferable.

[0028]

[Chemical 12] Here, n is an integer of 1 to 8, X is hydrogen or fluorine,
Y represents hydrogen, a monovalent metal atom, or a nitrogen-containing organic group. 1
Examples of the valent metal atom include lithium, sodium and potassium. As the nitrogen-containing organic group, ammonia, triethylamine, aniline, N, N
-Diethylaniline, pyridine, N-methylmorpholine and the like can be mentioned, but the invention is not limited thereto. Ar represents a divalent aromatic group.

The alkoxy sulfonic acid group-containing polyarylene ether compound containing the constituent component represented by the general formula (5) is an aromatic nucleophilic substitution reaction containing a compound represented by the following general formula (4) as a monomer. Can be polymerized.

[0030]

[Chemical 13] Here, n is an integer of 1 to 8, X is hydrogen or fluorine,
Y represents a monovalent metal atom, a nitrogen-containing organic group, and W represents chlorine or fluorine.

In the above-mentioned aromatic nucleophilic substitution reaction, various activated difluoroaromatic compounds and dichloroaromatic compounds can be used as a monomer together with the compound represented by the general formula (4). Examples of these compounds include 4,4′-dichlorodiphenyl sulfone, 4,4 ′
-Difluorodiphenyl sulfone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone and the like.

Ar in the component represented by the above general formula (5) is generally a structure introduced by polymerizing an aromatic diol component as a monomer. Examples of such aromatic diol monomers include 4,
4'-biphenol, bis (4-hydroxyphenyl)
Sulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 2,2-
Bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxy-3,5) -Dimethylphenyl) methane, bis (4-hydroxy-2,5-dimethylphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) )
Examples thereof include fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, hydroquinone and resorcin. It is also possible to use various aromatic diols that can be used for the polymerization of the polyarylene ether compound by the nuclear substitution reaction. These aromatic diols can be used alone, but it is also possible to use a plurality of aromatic diols in combination.

When a polyarylene ether compound containing an alkoxysulfonic acid group of the present invention is polymerized by an aromatic nucleophilic substitution reaction, an activated difluoroaromatic compound and / or dichloroaromatic containing a compound represented by the above general formula (4). A polymer can be obtained by reacting a group compound with an aromatic diol in the presence of a basic compound. The polymerization can be carried out in the temperature range of 0 to 350 ° C., but 5
The temperature is preferably 0 to 250 ° C. If the temperature is lower than 0 ° C, the reaction tends not to proceed sufficiently.
If it is higher than 0 ° C, decomposition of the polymer also tends to start. Although the reaction can be carried out without a solvent, it is preferably carried out in a solvent. Solvents that can be used include
Examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, diphenylsulfone, and sulfolane, but are not limited thereto, and aromatic nucleophilic Any solvent can be used as long as it can be used as a stable solvent in the substitution reaction. These organic solvents may be used alone or as a mixture of two or more kinds. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate and the like. It can be used without limitation. Water may be produced as a by-product in the aromatic nucleophilic substitution reaction. At this time, regardless of the polymerization solvent, toluene or the like can be allowed to coexist in the reaction system to remove water as an azeotrope out of the system. When the aromatic nucleophilic substitution reaction is carried out in a solvent, it is preferable to charge the monomer so that the obtained polymer concentration is 5 to 50% by weight. If it is less than 5% by weight, the degree of polymerization tends to be difficult to increase. On the other hand, when it is more than 50% by weight, the viscosity of the reaction system becomes too high,
Post-treatment of reactants tends to be difficult. After the completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation, and the residue is washed if necessary to obtain the desired polymer. It is also possible to precipitate the polymer as a solid by adding the reaction solution to a solvent in which the polymer has low solubility, and obtain the polymer by filtering the precipitate.

The amount of the sulfonic acid group present in the alkoxy sulfonic acid group-containing polyarylene ether compound of the present invention is such that the ion exchange capacity expressed as the equivalent amount of the sulfonic acid group present in 1 kg of the polymer is 0.1. ~
A value of 2.5 is preferable, and a value of 0.5 to 2.4 is more preferable. When the ion exchange capacity is smaller than 0.1, it becomes difficult to exhibit the excellent ionic conductivity which is a feature of the present invention. On the other hand, the ion exchange capacity is 2.
When it is larger than 5, the hydrophilicity of the polymer becomes too high, and when it is used for the ion conductive membrane, swelling due to water becomes remarkable and the shape retention as the ion conductive membrane is deteriorated.

The alkoxy sulfonic acid group-containing polyarylene ether compound of the present invention preferably has a polymer reduced specific viscosity of 0.1 or more as measured by the method described later. When the reduced specific viscosity is less than 0.1,
When molded as an ion-conducting membrane, the membrane tends to become brittle. The reduced specific viscosity is more preferably 0.3 or more. On the other hand, if the reduced specific viscosity exceeds 5, it is not preferable because it causes problems in processability such as difficulty in dissolving the polymer. In addition, as a solvent for measuring the reduced specific viscosity, a polar organic solvent such as N-methylpyrrolidone or N, N-dimethylacetamide can be generally used, but concentrated sulfuric acid is used when the solubility thereof is low. Can also be measured.

The alkoxy sulfonic acid group-containing polyarylene ether compound of the present invention can be used as a simple substance, but can also be used as a resin composition in combination with another polymer. Examples of these polymers include polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyamides such as nylon 6, nylon 6,6, nylon 6,10 and nylon 12, polymethylmethacrylate, polymethacrylic acid ester. Kind,
Acrylate resin such as polymethyl acrylate and polyacrylic acid ester, polyacrylic acid resin, polymethacrylic acid resin, polyethylene, polypropylene,
Various polyolefins including polystyrene and diene polymers, polyurethane resins, cellulose acetate, cellulose resins such as ethyl cellulose, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyether sulfone, polyether ether ketone, polyether There is no particular limitation on aromatic polymers such as imide, polyimide, polyamideimide, polybenzimidazole, polybenzoxazole, and polybenzthiazole, and thermosetting resins such as epoxy resin, phenol resin, novolac resin, and benzoxazine resin. A resin composition with a basic polymer such as polybenzimidazole or polyvinyl pyridine can be said to be a preferable combination for improving the polymer dimensional property, and if a sulfonic acid group is further introduced into these basic polymers, The processability of the composition becomes more preferable. When used as these resin compositions, the alkoxy sulfonic acid group-containing polyarylene ether compound of the present invention is preferably contained in an amount of 50% by weight or more and less than 100% by weight of the entire resin composition. It is more preferably 70% by weight or more and less than 100% by weight. When the content of the alkoxy sulfonic acid group-containing polyarylene ether compound of the present invention is less than 50% by weight of the entire resin composition, the sulfonic acid group concentration of the ion conductive membrane containing this resin composition becomes low, which is favorable. Ion conductivity tends not to be obtained, and the unit containing a sulfonic acid group becomes a discontinuous phase, and the mobility of conductive ions tends to decrease. The composition of the present invention, if necessary, for example, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a viscosity modifier, an antistatic agent, an antibacterial agent, an antifoaming agent, It may contain various additives such as a dispersant and a polymerization inhibitor.

The alkoxy sulfonic acid group-containing polyarylene ether compound and the resin composition thereof of the present invention are
A molded body such as a fiber or a film can be formed by any method such as extrusion, spinning, rolling or casting. Above all, it is preferable to mold from a solution dissolved in a suitable solvent. Examples of the solvent include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and hexamethylphosphonamide, and alcohols such as methanol and ethanol. Appropriate ones can be selected, but are not limited to these. A plurality of these solvents may be mixed and used within a possible range. The compound concentration in the solution is preferably in the range of 0.1 to 50% by weight. If the compound concentration in the solution is less than 0.1% by weight, it tends to be difficult to obtain a good molded product, and if it exceeds 50% by weight, the processability tends to deteriorate. As a method for obtaining a molded product from a solution, a conventionally known method can be used. For example, the molded product can be obtained by removing the solvent by heating, drying under reduced pressure, immersion in a compound non-solvent that can be mixed with a solvent that dissolves the compound, and the like. When the solvent is an organic solvent, it is preferable to distill off the solvent by heating or drying under reduced pressure.
At this time, in the form of being compounded with other compounds as necessary, fibrous, film-like, pellet-like, plate-like, rod-like,
It can also be formed into various shapes such as a pipe shape, a ball shape, and a block shape. The combination with a compound having a similar dissolution behavior is preferable because good molding can be achieved.

An ion-conducting membrane can also be prepared from the alkoxy sulfonic acid group-containing polyarylene ether compound of the present invention and the resin composition thereof. The most preferable method for molding the ion conductive membrane is casting from a solution, and the solvent can be removed from the cast solution as described above to obtain an ion conductive membrane. It is preferable to remove the solvent by drying in terms of uniformity of the ion conductive membrane. In addition, in order to avoid decomposition or alteration of the compound or solvent,
It is also possible to dry under reduced pressure at the lowest temperature possible.
Further, when the viscosity of the solution is high, heating the substrate or the solution and casting at a high temperature lowers the viscosity of the solution, so that the solution can be easily cast. The thickness of the solution used for casting is not particularly limited, but is preferably 10 to 1000 μm. More preferably, it is 50 to 500 μm.
If the thickness of the solution is thinner than 10 μm, the form of the ion conductive membrane cannot be maintained, and if it is thicker than 1000 μm, a non-uniform polymer electrolyte membrane tends to be easily formed. A known method can be used for controlling the cast thickness of the solution. For example, an applicator, a doctor blade, or the like may be used to make the thickness constant, or a glass petri dish or the like may be used to make the casting area constant to control the thickness by the amount or concentration of the solution. A more uniform film can be obtained from the cast solution by adjusting the removal rate of the solvent. For example, when heating, the evaporation rate can be lowered by lowering the temperature in the first step. When immersed in a non-solvent such as water, the coagulation rate of the compound can be adjusted by leaving the solution in air or an inert gas for an appropriate time. The ion conductive film of the present invention can have an arbitrary film thickness according to the purpose, but it is preferably as thin as possible from the viewpoint of ion conductivity. Specifically, it is preferably 5 to 200 μm, more preferably 5 to 50 μm, and 5 to
Most preferably, it is 20 μm. If the thickness of the ion conductive film is less than 5 μm, it is difficult to handle the ion conductive film, and a short circuit or the like tends to occur when a fuel cell is manufactured.
If it is thicker than 200 μm, the electric resistance value of the ion conductive membrane increases, and the power generation performance of the fuel cell tends to decrease. The ionic conductivity of the ion conductive membrane is 1.0 × 10 ⁻⁵ S /
It is preferably at least cm. Ionic conductivity is 1.0
When it is 10 × 10 ⁻⁵ S / cm or more, good output tends to be obtained in the fuel cell using the ion conductive membrane, and when it is less than 1.0 × 10 ⁻⁵ S / cm, The output tends to decrease.

By arranging the above-described ion-conducting membrane or film of the present invention on an electrode, a bonded body of the ion-conducting membrane or film of the present invention and an electrode can be obtained. As a method for producing this bonded body, a conventionally known method can be used, and for example, a method of applying an adhesive to the electrode surface to bond the ion conductive film and the electrode or an ion conductive film and the electrode can be used. There is a method of heating and pressing. Among these, the method of applying and adhering the adhesive having the alkoxy sulfonic acid group-containing polyarylene ether compound of the present invention and the resin composition thereof as the main component to the electrode surface is preferable. This is because it is considered that the adhesion between the ion conductive film and the electrode is improved, and that the ion conductivity of the ion conductive film is less likely to be impaired.

A fuel cell can also be manufactured by using the above-mentioned bonded body of the ion conductive membrane or film and the electrode. The ion-conducting membrane or film of the present invention is excellent in heat resistance, processability, and ion conductivity, so that it can withstand operation at high temperatures, is easy to manufacture, and has a good output. Can be provided.

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Various measurements were performed as follows. Solution viscosity: N, polymer powder at a concentration of 0.5 g / dl,
The product was dissolved in N-dimethylacetamide, the viscosity was measured using an Ostwald viscometer in a thermostat at 25 ° C., and the reduced specific viscosity [(ta-tb)] / (tb · c) was evaluated (ta
Is the number of seconds of dropping the sample solution, tb is the number of seconds of dropping only the solvent, and c
Is the polymer concentration). TGA: Shimadzu thermogravimetry (TGA-50)
The measurement was performed at a temperature rising rate of 10 ° C./min in an argon atmosphere.
The temperature at which a weight loss of 5% was reached was measured based on the weight of the sample in the stable region of 150 to 200 ° C. where it was confirmed that the evaporation of water was completed. DSC: Perkin Elmer differential scanning calorimeter (DSC-7) was used and the temperature rising rate was 2 in a nitrogen atmosphere.
The measurement was performed at 0 ° C / min. Ion conductivity measurement: A platinum wire (diameter: 0.2 mm) was pressed onto the surface of a strip-shaped membrane sample on a self-made measurement probe (made of polytetrafluoroethylene), and a constant temperature and constant humidity oven at 80 ° C and 95% RH ( Nagano Scientific Machinery Works, LH
-20-01), hold the sample in place, and measure the impedance between the platinum wires by SOLARTRON 1250FREQUEN.
It was measured by CY RESPONSE ANALYSER.
Measurement was performed by changing the distance between the electrodes, and the electrical conductivity in which the contact resistance between the membrane and the platinum wire was canceled was calculated from the gradient in which the distance between the electrodes and the measured resistance value estimated from the CC plot were plotted by the following formula. Conductivity [S / cm] = 1 / film width [cm] x film thickness [cm]
x Resistance Electrode Gradient [Ω / cm] Durability: A film sample was immersed in water at 80 ° C. in a sealed ampoule and left for 3 days. The longitudinal and lateral dimensions of the film before and after the treatment were compared, and the durability was evaluated depending on whether the morphology before the treatment was maintained without dissolution or swelling.

Example 1 3,5-bis (4-fluorobenzoyl) phenoxy-
Synthesis of 3-propylsulfonic acid sodium salt (BFSB) (1): 5-hydroxyisophthalic acid (3.85 × 10 ^-2 mo
l), 3.5 times mol potassium hydroxide (13.5 × 10 ^-2 mol),
Also, distilled water (50 ml) was placed in a 200 ml three-necked flask and dissolved. After cooling the solution to below 0 ° C with ice cooling, under vigorous stirring, add 1.25-fold molar acetic anhydride (4.81 × 10 ^-2
mol) was added, and immediately after that, crushed ice was added. After stirring at 0 ° C for 15 minutes, the mixture was stirred at room temperature for 5 minutes. The potassium salt was converted to a carboxylic acid with dilute hydrochloric acid, and the precipitate was filtered off and washed with water to obtain a crude product. By recrystallizing from ethyl acetate, white crystals of the desired product, 5-acetoxyisophthalic acid, were obtained. The yield was 77.8%. 5-acetoxyisophthalic acid (2.6
× 10 ^-2 mol), thionyl chloride (40 ml), and N, N-
Dimethylformamide (a few drops) was placed in an eggplant-shaped flask, heated in a water bath at about human skin temperature to dissolve, and stirred overnight at room temperature. After the thionyl chloride was distilled off, it was recrystallized from dehydrated hexane to obtain the desired product, 5-acetoxyisophthalic acid chloride white crystals. The yield was 82.0%. Aluminum chloride (6.1 × 10 ^-2 mol), fluorobenzene (50 ml)
Was placed in an absolutely dried 200 ml three-necked flask. Add 5-acetoxyisophthalic acid chloride (1.71 × 10 ^-2) to the dropping funnel.
mol) was added to a solution of fluorobenzene (20 ml), and the solution was slowly added dropwise with stirring under a nitrogen stream. After the dropwise addition was completed, the mixture was stirred at room temperature for 6 hours and then refluxed overnight. After distilling off excess fluorobenzene, a small amount of ethyl acetate was added and stirred, and crushed ice and water were added little by little to hydrolyze the remaining aluminum chloride. Then, the mixture was extracted with ethyl acetate, dried over sodium sulfate, and the ethyl acetate was evaporated to obtain a crude product. By recrystallizing from a mixed solvent of toluene and hexane, the target product, 1,3-bis (4-fluorobenzoyl) -5-hydroxybenzene
White crystals of (BFHB) were obtained. The yield was 47.5%. BFHB
And equimolar sodium bromopropane sulfonate, KO
Refluxed in H / ethanol for 48 hours. After refluxing, ethanol was evaporated and dried under reduced pressure. After that, it was purified by reprecipitation with ethyl acetate / n-hexane to obtain the desired product, BFS.
A yellow powder of B was obtained. The IR spectrum is shown in FIG.

Example 2 3,5-bis (4-fluorobenzoyl) phenoxy-
Synthesis of 3-propylsulfonic acid sodium salt (BFSB) (2): dimethyl 5-hydroxyisophthalate (2.85)
× 10 ^-2 mol), 5-fold moles of 1-bromo-hexane (14.2 × 10 ^-2
mol), 5-fold molar potassium carbonate (14.2 × 10 ^-2 mol), and acetone (200 ml) were placed in a 500 ml three-necked flask equipped with a mantle heater and a slider, and refluxed for 4 days with stirring. After the reaction was completed, suction filtration was performed to remove inorganic salts and unreacted potassium carbonate, and the filtrate was evaporated to remove acetone. After that, 1-bromohexane was distilled off and recrystallized from petroleum ether to obtain white crystals of the target dimethyl 5-hexyloxyisophthalate. The yield was 76.9% and the melting point was 49.0 ° C. Dimethyl 5-hexyloxyisophthalate (2.19 x 1
0 ^-2 mol), 10 times molar potassium hydroxide (2.19 × 10 ^-3 mol),
Also, put distilled water (200 ml) in a 500 ml eggplant-shaped flask,
Refluxed. After that, ethanol (6
0 ml) and 2-propanol (20 ml) were added, and the mixture was refluxed overnight.
After completion of the reaction, dilute hydrochloric acid was added to remove the potassium salt, and the precipitate was filtered and washed with water to obtain a crude product. By recrystallizing from methanol, white crystals of 5-hexyloxyisophthalic acid, which was a target substance, were obtained. Yield 85.5%, melting point
It was 240 ° C. 5-hexyloxyisophthalic acid (1.43
X10 ^-2 mol), thionyl chloride (20 ml), and N, N-dimethylformamide (a few drops) were placed in a 50 ml eggplant-shaped flask,
Stir overnight at room temperature. After the thionyl chloride was distilled off, the product was recrystallized from dehydrated hexane to obtain white crystals of the desired product, 5-hexyloxyisophthalic acid chloride. Yield 86.2
%Met. Aluminum chloride (3.2 × 10 ^-2 mol) and dehydrated fluorobenzene (27 ml) were placed in an absolutely dried 100 ml three-necked flask. Add 5-hexyloxyisophthalic acid chloride (1.23 × 10 ^-2 mol) and fluorobenzene (10
(ml) was added and slowly added dropwise with stirring under a nitrogen stream. After the dropping was completed, the mixture was refluxed overnight. At this time, the color of the solution changed to yellow, orange, and brown. After completion of the reaction, excess fluorobenzene was distilled off, and crushed ice and water were added little by little to hydrolyze the remaining aluminum chloride. Extraction with dichloromethane, drying over sodium sulphate and evaporation of the dichloromethane gave the crude product. Recrystallization from toluene gave white crystals. The yield was 35.1%. The white crystals, acetic acid (2.4 ml) and hydrogen bromide (1.8 ml) were placed in an eggplant-shaped flask and refluxed overnight. After completion of the reaction, water was added and the precipitate was filtered off and washed with water to obtain a crude product. Recrystallized from toluene and the desired product, BF
White crystals of HB were obtained. The yield was 76.7% and the melting point was 152 ° C. BFHB is the target product B in the same manner as in Example 1.
A yellow powder of FSB was obtained.

Example 3 9,9-bis (4-hydroxyphenyl) fluorene
(HF) (5.21 × 10^-Fourmol), potassium carbonate (5.21 × 10^-Fourm
ol), sulfolane (1.5 ml) and toluene (1.5 ml)
A 10 ml flask equipped with a reflux tube and a Dean Stark trap.
I put it in Sco. Heat to 170 ° C with stirring under nitrogen stream
And azeotropic dehydration for 3 hours to synthesize the potassium salt of HF.
It was When the theoretical amount of water comes out, toluene is distilled and removed.
I slowly cooled it a little. BFSB (2.61 x 10^-Fourmol), 4,4
‘-Difluorobenzophenone (DFBP) (2.61 × 10
^-Fourmol) and stirred for 5 hours at 230 ° C under a nitrogen stream.
It was made to react. After the reaction is complete, vigorously stir with a household mixer
The polymer was precipitated by pouring into running water. like this
50 mol% of the sulfonic acid group-containing unit obtained in
Including PEK (HF) -SO₃Na0.5 polymer is filtered off
And dried under reduced pressure. The yield was 70.3%. The obtained po
Limer solution viscosity is 1.16 dl / g, glass transition temperature
(Tg) was 265 ° C. Polymer 20 wt% N, N
-A dimethylacetamide solution that is held horizontally
The thickness of 25 μm
I got a film. Film is 1N sulfuric acid aqueous solution at 60 ℃
After soaking for 2 hours, soak in 1N sulfuric acid solution at room temperature for 1 day.
After soaking and washing with water, soak in pure water at 80 ° C for 1 hour, then at room temperature
Free sulfonic acid type polymer after immersion in pure water for 2 days
did. The IR spectrum is shown in FIG. Ion of this film
When the conductivity was measured, it was 5 × 10 ^-FourShows the value of S / cm
did. 5% weight loss temperature by thermogravimetric measurement of this film
Was 407 ° C. Also, in the durability evaluation
The elongation of the horizontal dimension is 10% or less in both length and width,
No change was observed.

Example 4 PEK (HF) -SO ₃ Na0.1, PEK (HF)-was prepared by changing the ratio of BFSB and DFBP so that the ratio of sulfonic acid group-containing units was 10, 30, 40 and 100 mol%.
SO ₃ Na0.3, PEK (HF) except that the polymer composition of -SO ₃ Na0.4 and PEK (HF) -SO ₃ Na1.0 performed a polymer synthesis and evaluated in the same manner as in Example 3. The results are shown in Table 1.

[0046]

[Table 1]

[0047]

The sulfonic acid group-containing aromatic polyarylene ether-based compound of the present invention capable of highly controlling the introduction amount of the sulfonic acid group provides not only ionic conductivity but also heat resistance,
It is possible to provide a material having excellent durability and processability, which exhibits outstanding performance as a polymer electrolyte for fuel cells and the like.

[Brief description of drawings]

FIG. 1 IR spectrum of BFSB

FIG. 2 IR spectrum after neutralization of PEK (HF) -SO ₃ Na0.1 polymer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 171/00 C09J 171/00 5H026 H01B 1/06 H01B 1/06 A H01M 8/02 H01M 8/02 P // B29K 71:00 B29K 71:00 B29L 7:00 B29L 7:00 31:00 31:00 (72) Inventor Satoshi Takase 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Term (reference) 4F071 AA51 AA86 AF61 AH15 FA05 FB01 FB07 FC01 4F205 AA32 AG01 AH33 GA06 GB01 GW31 4J005 AA24 BA00 4J040 EE061 GA06 GA25 LA08 LA09 5G301 CA30 CD01 5H026 AA06 BB00 BB03 H00H00 EE00H18 BB00 BB10 HO00 BB10 HO00 BB00

Claims (9)

[Claims] 1. Having an alkoxyl sulfonic acid group having 1 to 8 carbon atoms on the aromatic ring, and together with the general formula (1): (However, n is an integer of 1 to 8, X is hydrogen or fluorine, Y is hydrogen, a monovalent metal atom, or a nitrogen-containing organic group.) General formula (2) and / or general formula (3) Including the components [Chemical 3] (However, Z represents a direct bond, a sulfone group, a ketone group, or an organic group having 1 to 20 carbon atoms.) A polyarylene ether having a reduced specific viscosity of 0.1 or more. 2. The ion exchange capacity of the sulfonic acid group is 0.
It is 1-2.5, The polyarylene ether of Claim 1 characterized by the above-mentioned. 3. A composition comprising the polyarylene ether compound according to claim 1 in an amount of 50 to 100% by mass. 4. An ion conductive membrane comprising the compound according to any one of claims 1 to 3. 5. A composite containing the ion conductive membrane according to claim 4 and an electrode. 6. A fuel cell containing the composite according to claim 5. 7. An adhesive containing the polyarylene ether according to claim 1. 8. The polyarylene according to claim 1, wherein the polymerization is carried out by an aromatic nucleophilic substitution reaction containing a compound represented by the general formula (4) and a bisphenol compound as a monomer. Method for producing ether. [Chemical 4] However, n is an integer of 1 to 8, X is hydrogen or fluorine,
Y represents a monovalent metal atom, a nitrogen-containing organic group, and W represents chlorine or fluorine. 9. A solution containing the compound according to claim 1 and a solvent is cast to a thickness of 10 to 1.
The method for producing an ion-conducting membrane according to claim 4, comprising a step of casting to a range of 000 μm and a step of drying the cast solution.