JP2000080166A - Polyelectrolyte and ion exchanger - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyelectrolytes excellent in resistance to acids and alkalis and oxidation resistance, heat resistance and solvent resistance, a method for preparing the same and further, ion exchangers using the same. SOLUTION: Ion-exchange groups are introduced into a polyarylene sulfide sulfone and/or polyarylene sulfone. Further, polyelectrolytes containing a base polymer and a polyarylene sulfide sulfone and/or polyarylene sulfone and ion- exchange groups are introduced into the base polymer. Further, when the average degree X of oxidation of the sulfur atom in the sulfide group (-S-), the sulfoxide group (-SO-) and the sulfone group (-SO2-) which are contained in the polyarylene sulfide sulfone and/or polyarylene sulfone is represented in the form of (-SOx-), x is set in the range of 0.8-2.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer electrolyte which can be suitably used for a water treatment device, an electrolytic cell, a dialysis device, a fuel cell and the like, a method for producing the same, and an ion exchanger using the same.

[0002]

2. Description of the Related Art Polymer electrolytes have attracted attention as polymers containing ion exchange groups in terms of their physical properties and functions. For example, they have functions of surface modification, surface activation, water solubilization, and ion exchange. It is used for pre-coating treatment such as surface treatment and hydrophilic treatment of resin, and for applications such as surfactants and thickeners, ion exchange resins, ion exchange membranes and ion exchange fibers. ing.

In particular, various attempts have been made for use as an ion exchanger focusing on the ion exchange function, and styrene-divinylbenzene copolymer and styrene-divinylbenzene- (meth) acrylate copolymer have been used. Polymer, phenolic resin, perfluorovinylether-tetrafluoroethylene copolymer, polyethersulfone (PES), polyetheretherketone (PEE)
K) and examples using polymers such as polyphenylene sulfide (PPS) have been reported.

[0004] Among them, an ion exchanger using a styrene-divinylbenzene copolymer is inexpensive, and is used for water production for salt production by electrolyte concentration, separation and recovery of ionic substances such as acids, and desalination. Used in processing and food production. Further, an ion exchanger using a fluororesin such as a perfluorovinyl ether-tetrafluoroethylene copolymer is expensive, but is excellent in acid / alkali resistance, oxidation resistance, heat resistance, and solvent resistance. It has been used under severe conditions such as high-concentration chlorine, alkali, and high-temperature oxidizing atmosphere, such as caustic soda production by salt electrolysis and a cation exchange membrane of a polymer electrolyte fuel cell.

However, when the above-mentioned fluororesins are used, there is a problem that the water content at a high temperature is lowered and the ionic conductivity is lowered, and a polymer electrolyte fuel cell using these is used in automobiles. In order to be used for applications, it must be inexpensive.

Therefore, it is inexpensive, has excellent resistance to acids, alkalis, and solvents, and can withstand high temperatures and oxidizing atmospheres.
As an ion exchange membrane that can be used for fuel cells, P
The use of ion exchange membranes in which ion exchange groups are introduced into heat-resistant engineering plastics such as ES, polysulfone (PSF), polyetherimide (PEI), PPS, PEEK, and polyphenylene oxide (PPO) has been studied. Of these, PES, PSF, PPS
Such aromatic sulfur-containing polymers are preferably used as a film material because they have excellent mechanical strength in addition to heat resistance, chemical resistance, and moldability. The introduction of ion exchange groups into PES, PSF, etc. is described in “Advanced Polymer Materials Series 2 High Performance Aromatic Polymer Materials” (edited by The Society of Polymer Science, Maruzen Co., Ltd.) WO 97/05191 discloses an example in which a sulfonic acid group is introduced.

[0007] However, the above-mentioned conventional polymer electrolytes obtained by introducing an ion exchange group into an aromatic sulfur-containing polymer are inexpensive, but insufficient in acid / alkali resistance, oxidation resistance, heat resistance and solvent resistance. There is a problem that sufficient performance cannot be obtained under severe conditions such as high-concentration chlorine, alkali, and high-temperature oxidizing atmosphere.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and to provide a polymer electrolyte excellent in acid / alkali resistance, oxidation resistance, heat resistance and solvent resistance, and a method for producing the same. An object of the present invention is to provide an ion exchanger using the same.

[0009]

According to the present invention, there is provided a polymer electrolyte having an ion exchange group introduced into polyarylene sulfide sulfone and / or polyarylene sulfone.

[0010] The present invention is also characterized by a polymer electrolyte containing a base polymer and polyarylene sulfide sulfone and / or polyarylene sulfone, and having an ion exchange group introduced into the base polymer.

Here, it is preferable that the base polymer is a fluorine-based polymer, and it is also preferable that the base polymer contains a structural unit represented by the following structural formula (A) and / or (B). .

[0012]

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[0013]

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M, n: integers of 0 to 10 When the base polymer is used, the content of polyarylene sulfide sulfone and / or polyarylene sulfone is 10 to 10
It is also preferred that it is in the range of 80% by weight.

Further, it is also preferable that the polyarylene sulfide sulfone and / or the polyarylene sulfone has a porous membrane shape having pores, and the base polymer is present inside the pores.

Further, the average degree of oxidation of sulfur atoms of the sulfide group (-S-), sulfoxide group (-SO-) and sulfone group (-SO _2- ) contained in polyarylene sulfide sulfone and / or polyarylene sulfone. When X is represented in the form of (-SO _X- ), X is 0.8 to
It is also preferred that it be in the range of 2.0.

Further, the polyarylene sulfide sulfone and / or the polyarylene sulfone contains a structural unit represented by at least one selected from the group consisting of the following structural formulas (C), (D) and (E). It is also preferred.

[0018]

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[0019]

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[0020]

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Ar ¹ , Ar ² , Ar ³ : an arylene group having 6 to 24 carbon atoms, wherein the ion exchange group is at least selected from the group consisting of an acidic cation exchange group, a basic anion exchange group and a chelate-forming group. It is also preferred that it is one group.

Further, a solution obtained by dissolving polyarylene sulfide sulfone and / or polyarylene sulfone in a first solvent is brought into contact with a second solvent capable of coagulating polyarylene sulfide sulfone and / or polyarylene sulfone. The above-described method for producing a polymer electrolyte, in which polyarylene sulfide sulfone and / or polyarylene sulfone is formed into a porous film, is also preferable.

In this case, the first solvent is at least one selected from the group consisting of dimethylformamide, N-methylpyrrolidone, p-chlorophenol, hexamethylphosphoric triamide, m-cresol, dichloroacetic acid and dimethylimidazolidinone. It is also preferred to include one solvent, wherein the second solvent is water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and acetic acid. It is also preferable to include at least one solvent selected from the group consisting of isobutyl.

It is also preferable to oxidize a sulfide group of polyarylene sulfide sulfone containing a structural unit represented by the following structural formula (F).

[0025]

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Ar ⁴ , Ar ⁵ : an arylene group having 6 to 24 carbon atoms In this case, peracetic acid, perbenzoic acid, perpropionic acid, perbutylic acid, hydrogen peroxide, sodium hypochlorite, chlorine, bromine, nitric acid It is also preferable to oxidize using at least one substance selected from the group consisting of peroxymonosulfuric acid and peroxymonosulfuric acid.

Further, an ion exchanger containing the above-mentioned polymer electrolyte is also preferable, and the ion exchanger may have any one shape selected from the group consisting of granular, fibrous and membrane-like. preferable.

Further, a fuel cell having the above-mentioned ion exchanger is preferable, and an automobile having this fuel cell is also preferable.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer electrolyte of the present invention is characterized in that an ion exchange group is introduced into polyarylene sulfide sulfone and / or polyarylene sulfone. In the present invention, since polyarylene sulfide sulfone and / or polyarylene sulfone is used, a polymer electrolyte having improved acid / alkali resistance, oxidation resistance, heat resistance, and solvent resistance can be obtained.

Further, even if a base polymer and a polyarylene sulfide sulfone and / or a polyarylene sulfone are contained and an ion-exchange group is introduced into the base polymer, a polymer electrolyte having the above-mentioned properties is obtained. be able to.

The above-mentioned ion-exchange group is preferably at least one group selected from the group consisting of an acidic cation-exchange group, a basic anion-exchange group and a chelate-forming group. The acidic cation exchange group is preferably a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a carboxylic acid group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a phosphonic acid group, or a phenol group. The basic anion exchange group is preferably a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group. The chelating group is preferably an iminodiacetic acid group. In particular, when a polymer electrolyte is used for an ion exchange membrane, an ion exchange fiber, or an ion exchange resin, if the above ion exchange group is a sulfonic acid group or a carboxylic acid group, the ion exchange performance is improved, It is preferable because the properties and oxidation resistance are also improved.

The ion exchange group contained in the polymer electrolyte is
The necessary amount may be appropriately introduced, but when the polymer electrolyte is used as an ion exchange resin, an ion exchange fiber, or an ion exchange membrane, the ion exchange capacity (meq / g: milliequivalent of ion exchange group / weight of polymer electrolyte) ) Is 0.05-20m
eq / g, preferably 0.1 to 10 eq / g.
It is more preferably in the range of meq / g, 0.3
More preferably, it is in the range of 5 to 5 meq / g.
If the ion exchange amount is less than 0.05 meq / g, the ion exchange capacity tends to be insufficient, and if it exceeds 20 meq / g, the hydrophilicity is increased and the polymer electrolyte tends to be in a gel state, and the form of the membrane or fiber is increased. Is difficult to impart.

Here, the ion exchange capacity means a value calculated by the following method.

Weigh 1-2 g of the polymer electrolyte (mass:
wg).

100 ml of 0.1N NaOH is added to the polymer electrolyte and stirred for 24 hours.

Next, the polymer electrolyte was taken out, and
Titrate with N-HCl (Titration: aml) Calculate ion exchange capacity (meq / g): 1,000 ×
It is calculated by (0.01-0.001 × a) / w.

The average oxidation of the sulfur atoms of the sulfide group (—S—), sulfoxide group (—SO—) and sulfone group (—SO ₂ —) contained in the polyarylene sulfide sulfone and / or polyarylene sulfone described above. the degree (-SO _X -) _X when expressed in the form of, 0.8
It is preferably in the range of 2.0, more preferably in the range of 1.2 to 2.0, and even more preferably in the range of 1.6 to 2.0. When X is less than 0.8, acid-alkali resistance, oxidation resistance, heat resistance, and solvent resistance tend to be insufficient. Further, considering the degree of oxidation of the sulfur atom, it is considered that X does not exceed 2.0.

Here, the oxidation degree X refers to a value calculated by the following method.

[0039] Elemental analysis determining the content of sulfur and oxygen polyelectrolyte (respectively, and S _W, O _W).

Using the value of the ion exchange capacity of the polymer electrolyte, the contents of sulfur and oxygen derived from the sulfonic acid group in the polymer electrolyte are determined (S _S and O _S respectively).

Further, when a base polymer is used,
(And O _E) determining the content of the polymer electrolyte of the oxygen derived from ether groups using NMR technique.

[0042] From the values of above, determine the atomic ratio of sulfur and oxygen derived from the sulfide group, a sulfoxide group and sulfone group, calculates the _{X (((O W -O S} -O E) / 1
_{6) / ((S W -S} S) / 32) to calculate a).

In addition, the polyarylene sulfide sulfone and / or the polyarylene sulfone contains a structural unit represented by at least one selected from the group consisting of the following structural formulas (C), (D) and (E). Is preferred.

[0044]

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[0045]

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[0046]

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Ar ¹ , Ar ² , Ar ³ : Among the arylene groups having 6 to 24 carbon atoms, the arylene group preferably contains a structural unit represented by the following structural formula.

[0048]

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In the above, (1), (4),
(5) and (7) are particularly preferred.

Further, polyphenylene sulfide sulfone (PPS) containing a structural unit represented by the following structural formula
S) and polyphenylene sulfone (PPSO) are also preferred.

[0051]

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Unlike conventional polysulfones such as PES and PSF, these polymers do not contain an ether bond in the main chain.
Heat resistance and solvent resistance are particularly excellent and are preferred.

When a base polymer is used as described above, it is preferable that the base polymer is a fluorine-based polymer because acid resistance, alkali resistance, oxidation resistance, heat resistance and solvent resistance are improved. In particular, it is preferable that the base polymer contains a structural unit represented by the following structural formula (A) and / or (B).

[0054]

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[0055]

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M, n: an integer of 0 to 10 Among them, m is in the range of 0 to 3, and n is 1 to 5
Within this range, ion exchange performance can be improved, which is preferable.

Further, the number of the structural units represented by the structural formula (A) is set at 0. 0 to the number of the structural units represented by the structural formula (B).
It is preferably in the range of 1 to 1,000, and 1 to 500
More preferably, it is within the range. If the above value is less than 0.1, the ion exchange capacity tends to be insufficient, and
If it exceeds 1,000, the hydrophilicity is increased and the polymer electrolyte tends to be in a gel state, and it is difficult to give a form such as a membrane or a fiber.

Further, it is preferable that the base polymer contains an aromatic ring or a crosslinked structure in the molecule, because acid resistance, alkali resistance, oxidation resistance, heat resistance and solvent resistance are improved.

Further, when a base polymer is used, the content of polyarylene sulfide sulfone and / or polyarylene sulfone is preferably in the range of 10 to 80% by weight based on the whole polymer electrolyte.
More preferably, it is in the range of 20 to 60% by weight. When the content is less than 10% by weight, it is difficult to obtain sufficient acid / alkali resistance, oxidation resistance, heat resistance, and solvent resistance.
If it exceeds 80% by weight, the ion exchange capacity tends to be insufficient.

The form of the polymer electrolyte may be selected according to the intended use, such as a granular form, a membrane form, or a fibrous form. However, it is particularly preferable to adopt a membrane form in which the surface area is increased and the ion exchange capacity is easily increased.

When a polymer electrolyte is obtained using the base polymer, it is preferable that the polyarylene sulfide sulfone and / or the polyarylene sulfone and the base polymer have a layered structure. It is also preferable that the sulfone and / or the polyarylene sulfone form a sea component and the base polymer has a sea-island structure forming an island component. Further, it is also preferable that the polyarylene sulfide sulfone and / or the polyarylene sulfone have a network structure, and the base polymer is present inside the network.

If the polyarylene sulfide sulfone and / or the polyarylene sulfone has a porous membrane shape having pores, and the base polymer is present inside the pores, the surface area of the membrane is increased. It is preferable because the ion exchange capacity can be increased. In this case, it is also preferable to have an asymmetric structure in which the base polymer exists only near one surface of the porous film.

The number average molecular weight of the polymer used in the polymer electrolyte of the present invention is preferably in the range of 5,000 to 1,000,000, and is preferably in the range of 10,000 to 200,000.
More preferably, it is in the range of 000. When the number average molecular weight is less than 5,000, the acid resistance, alkali resistance and oxidation resistance,
Heat resistance and solvent resistance tend to be insufficient,
If it exceeds 000, it becomes difficult to dissolve in a solvent and the like, so that it becomes difficult to produce a polymer electrolyte.

The polymer electrolyte of the present invention has excellent solvent resistance, but it is particularly preferable that the polymer electrolyte does not substantially dissolve in a polar aprotic solvent.

Next, a method for producing the polymer electrolyte of the present invention will be described.

The polymer electrolyte of the present invention is produced by a method including a step of introducing an ion exchange group. In addition, a step of imparting a form, a step of performing an oxidation reaction, a step of adding a base polymer, and the like are performed. It can be appropriately selected and manufactured as needed. These steps can be performed in various combinations depending on the required form, the characteristics of the ion-exchange group to be introduced, the properties of the base polymer to be used, and the like, and the order can be arbitrarily determined.

First, the step of introducing an ion exchange group may be carried out on polyarylene sulfide sulfone and / or polyarylene sulfone, or on a base polymer. For example,
When a sulfonic acid group is introduced, it is preferable to use a sulfonic acid group-introducing agent such as concentrated sulfuric acid, chlorosulfonic acid, sulfur trioxide-triethyl phosphate, or trimethylsilyl chlorosulfate.

Next, in the step of imparting a form, in this step, a granular, fibrous, or film-like shape is imparted according to the purpose. In any case, a polyarylene sulfide sulfone and / or a polyarylene sulfone in a molten state or a solution state can be molded into a granular form, a fibrous form, or a film form by intermittently or continuously extruding from a die. In the case of forming a film, it is preferable to form a porous film, and it is preferable to use a wet film forming method because the production is simple and easy. That is, a solution obtained by dissolving polyarylene sulfide sulfone and / or polyarylene sulfone in a first solvent and a second solvent capable of coagulating polyarylene sulfide sulfone and / or polyarylene sulfone are brought into contact with each other, A method in which polyarylene sulfide sulfone and / or polyarylene sulfone is formed into a porous film is preferable.

In this case, as a method of bringing the solution obtained by dissolving in the first solvent into contact with the second solvent, for example, the solution obtained by dissolving in the first solvent is placed on a substrate. After the application, a method in which the second solvent is brought into contact with the solution on the substrate by application or the like can be used. When the method of forming a porous film on a substrate in this manner is used, the thickness of the porous film, the density and size of pores, the porosity, etc. are adjusted, and the mechanical strength of the porous film is increased. This is preferable.

Further, the solution obtained by dissolving in the first solvent is directly discharged into the second solvent, or the substrate coated with the solution obtained by dissolving in the first solvent is coated in the second solvent. Or a solution obtained by dissolving in a first solvent is applied on a substrate, and then a second solvent is applied by spraying.

As the first solvent, any solvent capable of dissolving polyarylene sulfide sulfone and / or polyarylene sulfone can be used, but dimethylformamide, N-methylpyrrolidone,
at least one selected from the group consisting of p-chlorophenol, hexamethylphosphoric triamide, m-cresol, dichloroacetic acid and dimethylimidazolidinone
A solvent containing a kind of solvent is preferable because solubility is increased.

As the substrate, any material can be preferably used as long as it can maintain the membrane shape. In particular, when the substrate is used for a water treatment device, an electrode reaction device, a dialysis device, a battery, a fuel cell, an electrolytic cell and the like. Is required to have high electric conductivity and high permeability to ions, gases, and electrolytes. Therefore, it is preferable to use a conductive porous body in a sheet shape, and a conductive carbon fiber sheet. It is particularly preferred to use

When calculating the content of polyarylene sulfide sulfone and / or polyarylene sulfone or measuring the physical properties of the polymer electrolyte such as ion exchange capacity, the base material is not included in the polymer electrolyte. Absent.

As the second solvent, any solvent can be used as long as it can coagulate polyarylene sulfide sulfone and / or polyarylene sulfone. However, any solvent which can be substantially miscible with the first solvent can be used. preferable. In particular, it contains at least one solvent selected from the group consisting of water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate. This is preferable because solidification can be performed efficiently.

The second solvent is appropriately selected in accordance with the first solvent. When N-methylpyrrolidone is used as the first solvent, water is used as the second solvent. It is particularly preferred to use.

Next, regarding the oxidation step, this step is performed as necessary. That is, when polyarylene sulfone or polyarylene sulfide sulfone having a large content of sulfone groups is used, it is difficult to dissolve in a solvent or the like, and it is difficult to impart a form such as a film shape. It is preferable to obtain polyarylene sulfide sulfone and / or polyarylene sulfone by oxidizing a sulfide group contained in a molecule after forming the polyarylene sulfide sulfone having a relatively small amount into a desired shape.

In particular, it is preferable to use a method of oxidizing a sulfide group of polyarylene sulfide sulfone containing a structural unit represented by the following structural formula (F).

[0078]

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Ar ⁴ , Ar ⁵ : arylene group having 6 to 24 carbon atoms In this case, if the arylene group is a phenylene group, it is inexpensive and has excellent acid / alkali resistance, oxidation resistance, heat resistance and solvent resistance. Particularly preferred.

The oxidation is at least one selected from the group consisting of peracetic acid, perbenzoic acid, perpropionic acid, perbutylic acid, hydrogen peroxide, sodium hypochlorite, chlorine, bromine, nitric acid and peroxymonosulfuric acid. Preference is given to using certain substances as oxidizing agents. Among them, peroxymonosulfuric acid is preferable because the oxidation reaction can be efficiently performed.

Next, a step of adding a base polymer to polyarylene sulfide sulfone and / or polyarylene sulfone is performed. This step is performed, for example, when the above-mentioned wet film forming method is used. It can be carried out by dissolving the base polymer in a solution obtained by dissolving the polyarylene sulfone in the first solvent, or by mixing a dispersion in which fine particles of the base polymer are dispersed. Alternatively, it can be performed by dissolving the base polymer in the second solvent or dispersing fine particles of the base polymer in contact with the solution obtained by dissolving in the first solvent. . Furthermore, after forming a polyarylene sulfide sulfone and / or a polyarylene sulfone in the form of a porous membrane, a solution of a base polymer or a liquid in which fine particles of a base polymer are dispersed may be applied or impregnated.

Of the above steps, the steps other than the step of introducing an ion-exchange group are steps that are performed as necessary.
It can be used as a polymer electrolyte in the form of a solution.

The order in which the above steps are performed can be arbitrarily set in order to achieve ease of manufacture and improvement in performance.

For example, an ion-exchange group is introduced in advance into a polyarylene sulfide sulfone containing a structural unit represented by the above structural formula (F), and then a film-like or fibrous form is added thereto. By oxidizing the sulfide group to be obtained, a polymer electrolyte can be obtained.

Further, after a polyarylene sulfide sulfone containing the structural unit represented by the above structural formula (F) is imparted with a membrane or fibrous form, an ion exchange group is introduced, and then the compound is contained in the molecule. By oxidizing the sulfide group to be obtained, a polymer electrolyte can be obtained.

Further, the sulfide group contained in the polyarylene sulfide sulfone containing the structural unit represented by the above structural formula (F) is oxidized to polyarylene sulfide sulfone and / or polyarylene sulfone, and then the ion exchange group By introducing the above, a polymer electrolyte can be obtained.

Further, after a polyarylene sulfide sulfone containing a structural unit represented by the above structural formula (F) is given a film-like or fibrous form, a sulfide group contained in the molecule is oxidized to give a polyarylene sulfide. A polymer electrolyte can be obtained by using sulfide sulfone and / or polyarylene sulfone and then introducing an ion exchange group.

Further, after introducing an ion exchange group into the polyarylene sulfide containing the structural unit represented by the structural formula (C), the sulfide group contained in the molecule is oxidized to convert the polymer electrolyte. Obtainable.

Further, a polymer electrolyte can be obtained by previously oxidizing a sulfide group contained in a polyarylene sulfide containing a structural unit represented by the above structural formula (C) and then introducing an ion exchange group. .

Further, after a polyarylene sulfide sulfone containing a structural unit represented by the above structural formula (C) or (F) is given a film-like or fibrous form, a sulfide group contained in the molecule is oxidized. Then, a polyarylene sulfide sulfone and / or polyarylene sulfone is obtained, and then a base polymer is added to obtain a polymer electrolyte.

Further, the above structural formula (C) or (F)
After imparting a membrane-like or fibrous form to the polyarylene sulfide sulfone containing the structural unit represented by the formula, a base polymer is added, and then sulfide groups contained in the molecule are oxidized to polyarylene sulfide sulfone and / or By using polyarylene sulfone, a polymer electrolyte can be obtained.

Further, after a polyarylene sulfide sulfone containing a structural unit represented by the above structural formula (C) or (F) is given a film-like or fibrous form, a sulfide group contained in the molecule is oxidized. Thus, a polyarylene sulfide sulfone and / or polyarylene sulfone is obtained, and then a polymer electrolyte can be obtained by introducing an ion exchange group and then adding a base polymer.

Further, the above structural formula (C) or (F)
After imparting a membrane-like or fibrous form to the polyarylene sulfide sulfone containing the structural unit represented by the formula, the sulfide group contained in the molecule is oxidized to obtain polyarylene sulfide sulfone and / or polyarylene sulfone, and then the base A polymer electrolyte can be obtained by adding a polymer and then introducing an ion exchange group.

Further, after a polyarylene sulfide sulfone containing a structural unit represented by the above structural formula (C) or (F) is imparted with a membrane or fibrous form, an ion exchange group is introduced, and then the molecule is added. A polymer electrolyte can be obtained by oxidizing a sulfide group contained therein to obtain a polyarylene sulfide sulfone and / or a polyarylene sulfone, and then adding a base polymer.

Further, the above structural formula (C) or (F)
After imparting a membrane or fibrous form to the polyarylene sulfide sulfone containing the structural unit represented by, an ion exchange group is introduced, and then a base polymer is added, and then the sulfide group contained in the molecule is removed. A polymer electrolyte can be obtained by oxidizing to polyarylene sulfide sulfone and / or polyarylene sulfone.

Further, a polyarylene sulfide sulfone containing a structural unit represented by the above structural formula (C) or (F) is given a membrane or fibrous form, and then a base polymer is added thereto. Is oxidized to polyarylene sulfide sulfone and / or polyarylene sulfone, and then a polymer electrolyte can be obtained by introducing an ion exchange group.

Further, the above structural formula (C) or (F)
After imparting a membrane or fibrous form to the polyarylene sulfide sulfone containing the structural unit represented by, a base polymer is added, and then an ion exchange group is introduced, and then the sulfide group contained in the molecule is removed. A polymer electrolyte can be obtained by oxidizing to polyarylene sulfide sulfone and / or polyarylene sulfone.

The polymer electrolyte of the present invention is excellent in acid / alkali resistance, oxidation resistance, heat resistance, solvent resistance, etc., is inexpensive, and can be suitably used as an ion exchanger. Further, it is preferable to give the ion exchanger a form such as a granular form, a fibrous form, and a film form, and thereby, it is possible to suitably use the ion exchanger as an ion exchange resin, an ion exchange fiber, or an ion exchange membrane. This ion exchanger can be suitably used, for example, as an ion exchange resin or an ion exchange membrane of a water treatment apparatus, and is also suitably used as an ion exchange membrane of an electrode reaction apparatus, a dialysis apparatus, a battery, or the like. Can be. In particular, it is preferable to use it as an ion exchange membrane for an electrolytic cell, an ion exchange resin or an ion exchange membrane for a fuel cell. Further, for example, when the fuel cell is a solid polymer fuel cell including an anode gas diffusion layer, an anode catalyst layer, an ion exchange membrane, a cathode catalyst layer, and a cathode gas diffusion layer, as the ion exchange membrane, Further, it can be suitably used as an ion exchange resin added to the anode catalyst layer or the cathode catalyst layer. Further, it is particularly preferable to use this fuel cell in an automobile.

[0099]

[Example] (Example 1) Toray Philippe Sptrolley
Polyphenylene sulfide sulfone (P
PSS) dissolved in N-methylpyrrolidone (NMP)
Was. This solution is supplied to a carbon paper TGP manufactured by Toray Industries, Inc.
-Apply on H-060 (0.2mm thickness) and immediately
Immersed in water to form a wet film to create a porous PPSS film
Was. Aldrich, an ion exchange resin solution, is applied to this porous membrane.
Impregnated with 5% by weight solution of Nafion manufactured by Ji Co., Ltd. and dried
An ion exchange membrane was prepared. The sulfone of this ion exchange membrane
The average degree of oxidation of sulfur atoms other than acid groups is 1.0,
When the exchange capacity was measured, it was 0.5 meq / g.
Was. In addition, this ion exchange membrane was prepared using Fenton's reagent (H _Two
O_Two-FeCl_Two), But the film has no abnormality
It was an ion exchange membrane with excellent properties. (Example 2) A porous membrane of PPSS was prepared in the same manner as in Example 1.
Oxon manufactured by DuPont Co., Ltd.
After oxidizing the sulfide group to a sulfone group,
Impregnated with 5% by weight of Fion solution, dried and ion exchange membrane
It was created. Sulfur other than sulfonic acid groups of this ion exchange membrane
The average degree of yellow atom oxidation is 1.8, and the ion exchange capacity is
The measured value was 0.5 meq / g. Also,
Fenton's reagent, hydrochloric acid, sodium hydroxide
Immersion in lithium etc., but there is no abnormality in the film, oxidation resistance,
Io with excellent acid / alkali properties, heat resistance and solvent resistance
An exchange membrane was obtained. (Example 3) A porous membrane of PPSS was prepared in the same manner as in Example 1.
Then, the porous membrane is sulfided with oxone to sulfide groups.
After performing the oxidation reaction twice as a hon group, Nafion 5
Impregnated with a weight percent solution and dried to form an ion exchange membrane
Was. Sulfur atoms other than sulfonic acid groups in this ion exchange membrane
The degree of soaking was 2.0, and the ion exchange capacity was measured.
At this time, it was 0.5 meq / g. Also, this ion exchange
Replacement membrane with Fenton reagent, hydrochloric acid, sodium hydroxide, etc.
Immersed in water, but there was no abnormality in the film.
Ion-exchange membranes with excellent resilience, heat resistance and solvent resistance
Obtained. (Example 4) In addition to immersion in methanol to form a wet film
Prepared a porous membrane of PPSS in the same manner as in Example 1,
This porous membrane is impregnated with a 5% by weight solution of Nafion and dried.
To prepare an ion exchange membrane. Sulfo of this ion exchange membrane
The average degree of oxidation of sulfur atoms other than acid groups is 1.0,
When the exchange capacity was measured, it was 0.5 meq / g.
Was. This ion exchange membrane was immersed in Fenton's reagent
However, there is no abnormality in the membrane and it is an ion exchange membrane with excellent oxidation resistance.
Was. (Example 5) Immersion in i-propyl alcohol and wet
Except that the film was formed, the same as in Example 1
A membrane was prepared and a 5% by weight solution of Nafion was added to the porous membrane.
It was immersed and dried to form an ion exchange membrane. This ion exchange
The average degree of oxidation of sulfur atoms other than sulfonic acid groups in the exchange membrane is 1.0.
When the ion exchange capacity was measured, it was 0.4 me.
q / g. This ion exchange membrane is
Immersion in water
It was an exchange membrane. (Example 6) PPSS was dissolved in dimethylformamide
Otherwise, an ion exchange membrane was prepared in the same manner as in Example 1.
Was. Sulfur atoms other than sulfonic acid groups in this ion exchange membrane
The degree of soaking was 1.0, and the ion exchange capacity was measured.
At this time, it was 0.4 meq / g. This ion exchange membrane
I was immersed in Fenton's reagent.
It was an ion exchange membrane with excellent properties. (Example 7) A 5% by weight solution of Nafion was applied by spraying.
Ion-exchanged in the same manner as in Example 1, except that
An exchange membrane was prepared. Other than sulfonic acid groups of this ion exchange membrane
Has an average degree of sulfur atom oxidation of 1.0 and an ion exchange capacity of
Was 0.4 meq / g. This
The on-exchange membrane was immersed in Fenton reagent, but the membrane was abnormal.
However, it was an ion exchange membrane having excellent oxidation resistance. (Example 8) The same weight of NMP was added to a Nafion 5% by weight solution.
And heat to evaporate the solvent until the weight is reduced by half.
Then, an NMP solution of Nafion was prepared. This NMP solution
Liquid and PPSS NMP solution, and mix with carbon paper.
And immediately immersed in water to form a wet film.
An on-exchange membrane was prepared. Sulfonic acid of this ion exchange membrane
The average degree of oxidation of sulfur atoms other than the group is 1.0,
When the exchange capacity was measured, it was 0.4 meq / g.
This ion exchange membrane was immersed in Fenton's reagent.
There was no abnormality and the ion exchange membrane was excellent in oxidation resistance. (Example 9) In addition to immersion in butyl acetate to form a wet film
Prepared an ion exchange membrane in the same manner as in Example 8. This
Average oxidation of sulfur atoms other than sulfonic acid groups in ion exchange membranes
The degree was 1.0, and when the ion exchange capacity was measured,
0.4 meq / g. This ion exchange membrane is
Immersion in ton reagent
It was an ion-exchange membrane obtained. (Embodiment 10) As in Embodiment 1, PPSS is changed to NMP.
Dissolved. This solution was prepared with an outer diameter of 1.18 mm and an inner diameter of 0.8.
mm into the water to form a wet film,
A porous hollow fiber membrane was prepared. This porous hollow fiber membrane
Ion-exchange membrane by impregnating and drying 5% by weight solution
did. Sulfur atoms other than sulfonic acid groups of this ion exchange membrane
The average degree of oxidation was 1.0, and the ion exchange capacity was measured.
However, it was 0.5 meq / g. Also, this ion
The exchange membrane was immersed in Fenton's reagent.
It was an ion exchange membrane having excellent oxidation resistance. (Example 11) A porous hollow of PPSS in the same manner as in Example 10.
A thread membrane was prepared. This porous hollow fiber membrane is
After oxidizing the sulfide group to a sulfone group,
Impregnated with 5% by weight solution and dried to form an ion exchange membrane
Done. Sulfur source other than sulfonic acid group of this ion exchange membrane
The average degree of oxidation is 1.8, and the ion exchange capacity is measured.
As a result, it was 0.5 meq / g. This Io
Exchange membrane with Fenton's reagent, hydrochloric acid, sodium hydroxide
Immersion, etc., but there is no abnormality in the film, oxidation resistance, acid resistance
Ion exchange with excellent lubricity, heat resistance and solvent resistance
A film was obtained. (Example 12) Toray Philippe Sporolurium
Polyphenylene sulfide sulfone (PPS)
S) was dissolved in N-methylpyrrolidone (NMP).
Then, using concentrated sulfuric acid as a sulfonic acid group-introducing agent,
A phonic acid group introduction reaction was performed. The obtained sulfonic acid introduction port
The phenylene sulfide sulfone was purified, and NMP was again purified.
And made into a cast film to form an ion-exchange membrane.
Sulfur atom average acid other than sulfonic acid group of this ion exchange membrane
The degree of conversion X was 1.0, and the ion exchange capacity was measured.
The filtration yield was 1.0 meq / g. Also, this ion exchange membrane
Was immersed in Fenton's reagent.
An ion-exchange membrane excellent in the conversion property was obtained. (Example 13) Ion exchange obtained in Example 12
Oxidation treatment of the membrane with Oxone manufactured by DuPont
To obtain an ion-exchange membrane with sulfide groups as sulfone groups.
Was. Sulfur atoms other than sulfonic acid groups in this ion exchange membrane
The degree of soaking X was 1.8, and the ion exchange capacity was measured.
However, it was 1.0 meq / g. Also, this ion exchange
Replace the membrane with hydrochloric acid, sodium hydroxide and Fenton's reagent.
Although immersed, there is no abnormality in the film, oxidation resistance, acid resistance, alkali
Ion exchange membrane with excellent heat resistance, heat resistance and solvent resistance
Was. Example 14 As a sulfonic acid group-introducing agent, chlorosulfur
The same procedure as in Example 12 was carried out except that folic acid was used.
On-exchange membrane and Oxon manufactured by DuPont
The oxidation reaction was performed twice to obtain an ion exchange membrane. This ion exchange
The average degree of oxidation X of sulfur atoms other than sulfonic acid groups of the exchange membrane is 2.
0 and the ion exchange capacity was measured to be 1.0 me
q / g. In addition, this ion exchange membrane is
immersed in n-reagent, but with no abnormality in the film and excellent oxidation resistance
An ion exchange membrane was obtained. (Example 15) After dissolving PPSS in NMP, cast
Film formation was performed. The resulting membrane is used as a sulfonic acid group-introducing agent.
With sulfur trioxide-triethyl phosphate
A phonic acid group introduction reaction was performed. In addition, DuPont
An oxidation reaction was performed using oxone to obtain an ion exchange membrane.
Sulfur atom average acid other than sulfonic acid group of this ion exchange membrane
The degree of chemical conversion X was 1.9, indicating that the ion exchange capacity was measured.
The filtration yield was 0.8 meq / g. Also, this ion exchange membrane
Was immersed in Fenton's reagent.
An ion-exchange membrane excellent in the conversion property was obtained. (Example 16) PPSS is dissolved in NMP to form a wet film
Thus, a porous film having pores was prepared. In this porous membrane,
Oxidation reaction was performed using Oxone manufactured by DuPont.
After that, trimethylsilylchloro
A sulfonic acid group introduction reaction is performed using sulfate
An exchange membrane was obtained. Other than sulfonic acid groups of this ion exchange membrane
Has an average sulfur atom oxidation degree X of 2.0,
When the amount was measured, it was 1.2 meq / g. Also,
This ion exchange membrane was immersed in Fenton's reagent.
An ion exchange membrane with excellent resistance to oxidation without any abnormalities
Was. (Comparative Example 1) Polyphenylene sulfide (PPS) was converted to N
Except for dissolving in MP, ion exchange was performed in the same manner as in Example 1.
An exchange membrane was prepared. Other than sulfonic acid groups of this ion exchange membrane
Has a sulfur atom average oxidation degree X of 0 and an ion exchange capacity of 0.3
Meq / g, an ion exchange membrane with poor oxidation resistance
Was. (Comparative Example 2) U manufactured by Amoco Corporation, which is a polysulfone
Except that del was dissolved in NMP,
To prepare an ion exchange membrane. Sulfo of this ion exchange membrane
The average degree of oxidation X of sulfur atoms other than acid groups is 2.0,
The exchange capacity was 0.4 meq / g, and
It was an on-exchange membrane. (Comparative Example 3) Example except that PPS was dissolved in NMP
An ion exchange membrane was prepared in the same manner as in No. 12. This ion
The average oxidation degree X of sulfur atoms other than sulfonic acid groups of the exchange membrane is
0, ion exchange capacity is 1.1 meq / g, oxidation resistant
It was an ion exchange membrane with poor properties. (Comparative Example 4) U which is a polysulfone manufactured by Amoco Corporation
Except that del was dissolved in NMP, the same as in Example 13
As a result, an ion exchange membrane was prepared. The ion exchange membrane
Sulfur atom average oxidation degree X other than phonic acid group is 2.0, ion
The exchange capacity was 1.1 meq / g, but Fenton
When immersed in reagent, the membrane is damaged and has poor oxidation resistance
Was an ion exchange membrane.

[0100]

According to the present invention, as compared with a conventional polymer electrolyte in which an ion exchange group is introduced into an aromatic sulfur-containing polymer or an ion exchange membrane using the same, acid resistance, alkali resistance, heat resistance and oxidation resistance are improved. Polymer electrolyte, which has excellent ion exchange performance under severe conditions such as high-concentration chlorine, alkali, and high-temperature oxidizing atmosphere, and is less expensive than conventional fluorine-based ion exchange membranes. An ion exchanger using the same can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 47/12 B01J 47/12 BE EC08G 75/18 C08G 75/18 75/20 75/20 C08J 5 / 22 CEZ C08J 5/22 CEZ C08L 71/02 C08L 71/02 81/02 81/02 C25B 13/08 301 C25B 13/08 301 H01B 1/06 H01B 1/06 A H01M 8/02 H01M 8/02 P

Claims (18)

[Claims] 1. A polymer electrolyte wherein an ion exchange group is introduced into polyarylene sulfide sulfone and / or polyarylene sulfone. 2. A polymer electrolyte comprising a base polymer and polyarylene sulfide sulfone and / or polyarylene sulfone, wherein an ion exchange group is introduced into the base polymer. 3. The base polymer is a fluoropolymer,
The polymer electrolyte according to claim 2. 4. The polymer electrolyte according to claim 3, wherein the base polymer contains a structural unit represented by the following structural formula (A) and / or (B). Embedded image Embedded image m, n: integers from 0 to 10 5. The method according to claim 2, wherein the content of the polyarylene sulfide sulfone and / or the polyarylene sulfone is in the range of 10 to 80% by weight based on the whole polymer electrolyte. Molecular electrolyte. 6. The method according to claim 2, wherein the polyarylene sulfide sulfone and / or the polyarylene sulfone has a porous membrane shape having pores, and a base polymer is present inside the pores. Polyelectrolyte. 7. A polyarylene sulfide sulfone and / or sulfide groups contained in the polyarylene sulfones (-S-), sulfoxide group (-SO-) and a sulfone group (-SO ₂ -) oxidation degree of the average of the sulfur atom of the When X is represented in the form of (-SO _X- ), X is 0.8 to 2.
The polymer electrolyte according to any one of claims 1 to 6, which is within a range of 0. 8. The polyarylene sulfide sulfone and / or polyarylene sulfone contains a structural unit represented by at least one selected from the group consisting of the following structural formulas (C), (D) and (E). The polymer electrolyte according to any one of claims 1 to 7. Embedded image Embedded image Embedded image Ar ¹ , Ar ² , Ar ³ : an arylene group having 6 to 24 carbon atoms 9. The method according to claim 1, wherein the ion exchange group is at least one group selected from the group consisting of an acidic cation exchange group, a basic anion exchange group and a chelate-forming group. Polymer electrolyte. 10. A solution obtained by dissolving polyarylene sulfide sulfone and / or polyarylene sulfone in a first solvent, and a second solution capable of coagulating polyarylene sulfide sulfone and / or polyarylene sulfone.
The method for producing a polymer electrolyte according to claim 6, wherein the polyarylene sulfide sulfone and / or polyarylene sulfone is formed into a porous film by contacting the solvent with the solvent. 11. The method according to claim 11, wherein the first solvent is dimethylformamide,
The method according to claim 10, comprising at least one solvent selected from the group consisting of N-methylpyrrolidone, p-chlorophenol, hexamethylphosphoric triamide, m-cresol, dichloroacetic acid and dimethylimidazolidinone. A method for producing a polymer electrolyte. 12. The second solvent is selected from the group consisting of water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate. The method for producing a polymer electrolyte according to claim 10, wherein the method comprises at least one solvent. 13. The method for producing a polymer electrolyte according to claim 9, wherein a sulfide group of polyarylene sulfide sulfone containing a structural unit represented by the following structural formula (F) is oxidized. Embedded image Ar ^4, Ar ^5: arylene group having 6 to 24 carbon atoms 14. Peracetic acid, perbenzoic acid, perpropionic acid,
Perbutylic acid, hydrogen peroxide, sodium hypochlorite,
14. The method for producing a polymer electrolyte according to claim 13, wherein the oxidation is performed using at least one substance selected from the group consisting of chlorine, bromine, nitric acid, and peroxymonosulfuric acid. 15. An ion exchanger comprising the polymer electrolyte according to any one of claims 1 to 9. 16. The sheet according to claim 15, wherein the sheet has any one shape selected from the group consisting of granular, fibrous, and film-shaped.
The ion exchanger according to the above. 17. A fuel cell comprising the ion exchanger according to claim 15 or 16. 18. An automobile having the fuel cell according to claim 17.