JP2002114854A - Anion exchange membrane, method for producing the same and apparatus for treating solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anion exchange membrane excellent in alkali resistance and heat resistance and a processing apparatus for membrane separation which has hither to been difficult to apply by using the aforesaid anion exchange membrane and provide a method for using the same. SOLUTION: This anion exchange membrane has a homogeneously mixed resin phase of a polymer containing a repeating unit expressed by general formula (1) (A expresses a 2-8C straight chain, branched alkylene or a 4-8C alkyleneoxyalkyl; R1, R2 and R3 express each H, a 1-6C alkyl or a hydroxyalkyl; X- expresses an anion; the hydrogen atom bonded to the benzene ring may be substituted with an alkyl or a halogen) with a thermoplastic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an anion exchange membrane,
The present invention relates to a manufacturing method and a solution processing apparatus.

[0002]

2. Description of the Related Art As an anion exchange membrane, there are many documents,
Patents have been reported, but the most practical and useful are those obtained by introducing an anion exchange group into a styrene-divinylbenzene copolymer or a vinylpyridine-divinylbenzene copolymer having a chloromethyl group on the aromatic ring. There is an ion exchange membrane. In addition to their chemical resistance and heat resistance, they can control ion exchange characteristics and permselectivity by changing the content of divinylbenzene as a cross-linking agent. Was. In particular, in the field of seawater concentration by electrodialysis relating to salt production, a membrane having a low resistance, a high transport number, and an advanced function of selectively transmitting monovalent ions has been developed.

However, an anion exchange membrane based on this styrene-divinylbenzene copolymer or vinylpyridine-divinylbenzene copolymer has difficulty in controlling heat generation and dimensional change during polymerization or ion exchange group introduction reaction. There is a disadvantage that the yield is not always high. In addition, because it is composed of a styrene-based resin that is relatively brittle mechanically, the membrane may excessively swell due to the use at high temperatures or depending on the components in the treated water, resulting in reduced ion selective permeability and reduced membrane strength. There was a problem in durability, such as the possibility of inviting.

[0004] In particular, in a solution having a high pH, an anion exchange group is decomposed at an accelerated rate as the temperature increases, which may cause an increase in membrane resistance and a decrease in ion selective permeability.
For this reason, there have been many restrictions on the use conditions, such as the need to lower the alkali concentration or the temperature.

On the other hand, as for an anion exchange resin having good durability, an anion exchange resin in which a specific substituent A is introduced between a benzene ring and an anion exchange group is disclosed in JP-A-4-334.
Numerous proposals such as No. 491 and Japanese Patent Application Laid-Open No. 7-289921. However, the properties and durability of such an ion exchange membrane having an anion exchange group, such as anion selective permeability, and a new application method using the same are not known.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an anion exchange membrane excellent in permselectivity and durability and to provide a new use method using the membrane. And

[0007]

The present invention provides a compound represented by the following general formula (1) (where A represents an alkylene group having 3 to 8 carbon atoms or an alkyleneoxyalkyl group having 4 to 9 carbon atoms in total. R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group.
^- represents an anion. The hydrogen atom bonded to the benzene ring may be substituted with an alkyl group or a halogen atom. 2) a polymer containing a repeating unit represented by
An anion exchange membrane containing a resin phase in which 0 to 96% by mass and 4 to 80% by mass of a thermoplastic polymer having no ion exchange group are substantially uniformly provided.

[0008]

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The present invention further relates to a thermoplastic polymer having no ion-exchange group, and a compound represented by the following general formula (2): wherein A is an alkylene group having 3 to 8 carbon atoms or an alkyleneoxyalkyl having 4 to 9 carbon atoms in total. Z represents chlorine, bromine, iodine, a hydroxyl group, a tosyl group, a primary to tertiary amine, or -NR.
¹ represents a R ² R ³ group. Here, R ¹ , R ² and R ³ each represent a hydrogen atom or a group selected from an alkyl group having 1 to 6 carbon atoms and a hydroxyalkyl group. The hydrogen atom bonded to the benzene ring may be substituted with an alkyl group or a halogen atom. ), Or a polymerization component comprising a mixture of a monomer of the general formula (2) and a monomer copolymerizable therewith, and then polymerizing the polymerization component, wherein Z is chlorine or bromine. A method for producing an anion exchange membrane, which further carries out a reaction for substituting Z with an ion exchange group in the case of iodine, hydroxyl group or tosyl group.

[0010]

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[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The anion exchange membrane of the present invention comprises a polymer containing a repeating unit represented by the general formula (1) (hereinafter referred to as a polymer).
It is called a polymer of the general formula (1). A) A film-like resin phase in which 20 to 96% by mass and 4 to 80% by mass of a thermoplastic polymer having no ion exchange group are substantially uniformly mixed.
The substantially homogeneously mixed film-like resin phase in the present invention refers to a polymer of the general formula (1) and a thermoplastic polymer having no ion exchange group when the resin phase is observed with an optical microscope. However, it is in a state where it cannot be separately observed and the phase size is 1
A state in which a phase separation structure having a size of μm or more cannot be observed.

For example, an inhomogeneously mixed ion exchange membrane obtained by mechanically mixing a powdery polymer of the general formula (1) and a thermoplastic polymer and forming the mixture into a membrane by a hot press or the like has an electrolyte concentration of The decrease in the ion selective permeability is large due to the increase in the amount, and when used for a long time at a high temperature or in a solution composition that swells the resin, the ion selective permeability and the membrane strength are undesirably reduced. When the amount of the polymer represented by the general formula (1) is 20% by mass or less, the electric resistance of the membrane increases and the ion selective permeability decreases. When the amount is 96% by mass or more, the resin phase has insufficient strength or durability during use. Is inferior. It is more preferable that the content of the polymer of the general formula (1) in the resin phase is 40 to 94% by mass.

A in the general formula (1) represents an alkylene group having 3 to 8 carbon atoms or an alkyleneoxyalkyl group having 4 to 9 carbon atoms in total. Here, the alkyleneoxyalkyl group is an alkylene group containing an etheric oxygen atom. The alkylene group may be linear or branched. In the case of an alkylene group having 1 or 2 carbon atoms, a positively charged ammonium group is easily affected by a benzene ring through the alkylene group, and the anion exchange group has poor heat resistance. On the other hand, when the number of carbon atoms is 9 or more, the ion exchange capacity per mass decreases, resulting in an increase in electric resistance of the membrane and a decrease in ion selective permeability.

In the case of an alkyleneoxyalkyl group, when the range of the number of carbons is out of the above range, it is the same as in the case of the alkylene group. _{Specifically, - (CH 2) n -} (n is an integer from 1 to _{6), - (CH 2) 4} -O-CH 2 - ( those tetramethylene group side is bonded to the nitrogen), - (CH ₂ ) ₅ −
O-CH _2- (the pentamethylene group side is bonded to nitrogen) is exemplified.

R ¹ , R ² and R ^{3 each} represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group.
These may be the same or different from each other. As these alkyl groups or hydroxyalkyl groups, methyl, ethyl, propyl, butyl, hydroxyethyl and hydroxypropyl groups are preferably used.

[0016] X ^- represents an anion which is a counter ion coordinated to an ammonium group. Specifically, Cl ⁻ , Br ⁻ , I
^{And the} like, HCO ₃ ⁻ , CO ₃ ²⁻ , acetate ion, NO ₃ ⁻ , OH ⁻ , p-toluenesulfonic acid ion and the like. Here, X ⁻ may be a polyvalent anion such as SO ₄ ²⁻ ion, in which case X ⁻ represents a polyvalent anion equivalent to monovalent.

The hydrogen atom bonded to the benzene ring in the general formula (1) may be substituted with an alkyl group or a halogen atom. As the alkyl group, a methyl group or an ethyl group is preferable, and as the halogen atom, chlorine or bromine is preferable.

The polymer of the general formula (1) may have another repeating unit. For example, a repeating unit containing an ion exchange group other than the ion exchange group included in the repeating unit represented by the general formula (1), for example, a repeating unit based on vinylpyridine, chloromethylstyrene, or the like can be used. In that case, 90 mol of all ion exchange groups
% Or more is an ion exchange group contained in the repeating unit represented by the general formula (1), from the viewpoint of heat resistance and durability. Further, as a repeating unit that does not contribute to crosslinking or ion exchange, a repeating unit based on styrene, vinyltoluene, ethylene, propylene, acrylonitrile, or the like may be included.

The preferred method for producing the resin phase is to uniformly mix 25 to 2500 parts by mass of the monomer of the formula (2) with 100 parts by mass of the thermoplastic polymer having no ion exchange group. A method of polymerizing the monomer is preferred. In the monomer of the general formula (2), A is the same as that of the general formula (1).

In the monomer of the general formula (2), Z is the first
-In the case of a tertiary amine or -NR ¹ R ² R ³ group, when the monomer is copolymerized with another monomer due to hydrophilicity, when mixed with a thermoplastic polymer having no ion exchange group Mixing is not easy. Therefore, for example, by immersing a polyethylene film or polypropylene film irradiated with an electron beam or γ-ray in an aqueous solution of the monomer, dissolving the monomer in the thermoplastic polymer and polymerizing, An anion exchange membrane comprising a uniform mixed resin phase of the polymer of the formula (1) and the thermoplastic polymer can be obtained.
In other words, the term “dissolve” means that the monomer is diffused into the thermoplastic polymer by diffusion.

On the other hand, Z is chlorine, bromine, iodine, a hydroxyl group,
In the case of a tosyl group, after polymerization, ammonia or primary
It is necessary to react with a tertiary amine to convert to a primary to tertiary amine or a quaternary ammonium base, and an ion exchange group is formed by performing this reaction. As described above, the above-mentioned Z is preferably used because of good modification by copolymerization with other monomers and good mixing or solubility with a thermoplastic polymer. Especially monomer stability,
From the viewpoint of polymerizability and conversion to an anion exchange group, a monomer in which Z is bromine is preferably used.

Further, by copolymerizing the monomer of the general formula (2) with another monomer, ion selectivity and mechanical strength can be controlled to desired characteristics. In this case, the other monomer is preferably a monomer containing a hydrocarbon group having an unsaturated bond. Specific examples include those having two or more vinyl groups, such as divinylbenzene, trivinylbenzene, divinyltoluene, divinylnaphthalene, and ethylene glycol dimethacrylate. Styrene, vinyltoluene, ethylene, propylene, acrylonitrile, or the like may be used as a monomer that does not contribute to crosslinking or ion exchange.

The thermoplastic polymer constituting the resin phase of the anion exchange membrane has a main chain unsaturated bond ratio of 3% or less;
A thermoplastic polymer in which 25 parts by mass or more of the monomer of the general formula (2) is dissolved per 100 parts by mass of the thermoplastic polymer is preferable. Here, the unsaturated bond ratio of the main chain is the percentage of the number of double bonds or triple bonds in the total number of carbon bonds constituting the main chain, and for example, the polybutadiene polymer has an unsaturated bond ratio of Is 25.0%, and the copolymer having a styrene-butadiene mass ratio of 1: 1 has an unsaturated bond ratio of 16.7%.
It is.

When the unsaturated bond of the main chain exceeds 3%,
Even if the initial performance of the obtained anion exchange membrane is good, it is not preferable because the unsaturated bonds are broken during long-term use, and the long-term durability of heat resistance and chemical resistance is reduced. As the thermoplastic polymer having an unsaturated bond ratio of 3% or less and dissolving the monomer of the general formula (2) in an amount of 25 parts by mass or more per 100 parts by mass of the thermoplastic polymer, thermoplastic olefins, thermoplastic elastomers, Thermoplastic plastomers and the like are preferred.

Specifically, polyvinyl chloride, chlorinated polyvinyl chloride, a copolymer of ethylene and vinyl chloride, polyethylene, chlorinated polyethylene, chlorosulfonated polyethylene, styrene-based thermoplastic elastomer, or hydrogenated styrene and Examples thereof include a copolymer with butadiene, a hydrogenated nitrile rubber, a hydrogenated pyridine rubber, and a mixture thereof.

Here, the styrene-based thermoplastic elastomer is a copolymer having a hard segment made of polystyrene and a soft segment. As the soft segment, those composed of polybutadiene, polyisoprene, poly (ethylene / butylene) (hereinafter referred to as an ethylene-butylene alternating copolymer, the same applies hereinafter), poly (ethylene / propylene) and the like are preferably used.

As the styrene thermoplastic elastomer, polystyrene-hydrogenated polybutadiene-polystyrene block polymer (H-SBS), polystyrene-
(Polyethylene / butylene rubber) -polystyrene block polymer (SEBS), polystyrene-hydrogenated polyisoprene rubber-polystyrene block polymer (H-
SIS), polystyrene- (polyethylene / propylene rubber) -polystyrene block polymer (SEPS),
Polystyrene-polyethylene- (polyethylene / propylene rubber) -polystyrene block polymer (SEEP
S), polystyrene-vinylpolyisoprene (poly (propenylethylene))-polystyrene block polymer and the like are preferable because of good compatibility with the monomer of the general formula (2).

In the method for producing an ion-exchange membrane of the present invention, 25 parts by mass or more of the monomer represented by the general formula (2) is uniformly mixed with 100 parts by mass of the above-mentioned thermoplastic polymer having no ion-exchange group. It is mixed and then polymerized to form a film-like resin phase.If the film is used in small dimensions or is not required for mechanical strength or dimensional stability, it is composed of the resin phase obtained by polymerization alone An anion exchange membrane is used.

In this case, 25 to 2500 parts by mass of the monomer of the general formula (2) is added to 100 parts by mass of the thermoplastic polymer.
Preferably, 50 to 500 parts by mass, particularly 70 to 200 parts by mass, is dissolved and polymerized. Above all, a method having no ion-exchange group, after impregnating a thermoplastic polymer film-shaped molded product with a polymerizable component comprising a monomer, and then polymerizing the polymerizable component, is preferable in terms of mass productivity. Illustrated as a method.

On the other hand, in the case where the membrane is used in large dimensions or in applications where mechanical strength and dimensional stability are required, an anion exchange membrane in which a resin phase obtained by polymerization is reinforced with a porous membrane support material. It is desirable to use As a method of reinforcing, a composite membrane in which a porous membrane support material having a lower solubility with a monomer than the thermoplastic polymer, such as cloth or nonwoven fabric, is embedded in the thermoplastic polymer membrane in advance by hot pressing or the like. And a method of dissolving the monomer in the polymer and polymerizing the same.

As another preferable method of reinforcing the membrane, a monomer of the general formula (2) or a mixture of the monomer of the general formula (2) and another monomer copolymerizable therewith is used. A method is used in which a polymerizable component consisting of the above and a thermoplastic polymer are mixed, the resulting viscous liquid is impregnated into a porous membrane supporting material, and then the above polymerizable component is polymerized. At this time, although it varies depending on the structure and molecular weight of the thermoplastic polymer, the monomer is 25 to 2500 parts by mass, preferably 100 to 2,000 parts by mass, particularly 200 to 150 parts by mass with respect to 100 parts by mass of the thermoplastic resin polymer.
It is preferred to add 0 parts by weight.

As the porous membrane support material used in the reinforced anion exchange membrane of the present invention, polyvinyl chloride, polyvinylidene chloride woven fabric, nonwoven fabric, microporous membrane, etc. can be used. From the viewpoint of long-term durability at high temperatures and high temperatures, a woven fabric or a microporous membrane of polyethylene, polypropylene, or a fluorine-containing olefin is preferred.

When a porous membrane support material is used, the membrane support material is irradiated with an electron beam or γ-ray before contacting the monomer containing the general formula (2), Irradiating the immersed membrane support material with an electron beam or γ-ray to make the porous substrate and the membrane adhere to each other, the electrical resistance of the obtained reinforcing membrane,
It is preferable in terms of mechanical strength and long-term durability. For the same purpose, the porous substrate is preferably subjected to a chemical treatment such as sulfonation or halogenation in advance.

In the reinforced anion exchange membrane, it is preferable that the polymer of the general formula (1) is present in the porous membrane support material. For example, when reinforced with a cloth, it is preferable that the polymer of the general formula (1) penetrates and exists inside the fibers constituting the cloth. At this time, when the content of the repeating unit represented by the general formula (1) in the porous membrane supporting material is compared with the intensity of the fluorescent X-ray caused by X in the general formula (1), Of its content in
It is preferably from 0.5 to 0.7 times.

The state was determined by a scanning electron microscope-X-ray fluorescence (SEM-ED) on a section of the reinforced anion exchange membrane.
This can be observed by performing AX) analysis and determining the intensity of the element contained in X in the general formula (1). From the observation, it is preferable that the ratio of the strength of the supporting material portion to the strength of the resin phase portion is 0.05 to 0.7. When the strength ratio is 0.05 or less, the electrical resistance of the film is high, and the long-term durability decreases. When the strength ratio is 0.7 or more, the mechanical strength decreases. The electron beam or γ-ray is preferably obtained by selecting an irradiation level and polymerization conditions so as to be preferably 0.1 to 0.6.

When the polymer film obtained in this manner is the same as the chloromethylstyrene polymer film, when Z in the general formula (2) is a halogen atom, for example, a weak base reacted with ammonia, methylamine or dimethylamine. A strong basic anion exchange membrane reacted with anionic anion exchange membrane, trimethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, etc., ethylenediamine, tetramethyldiaminopropane, etc. to bind ion exchange groups Anion exchange membrane.

The anion exchange membrane of the present invention obtained by the above method varies depending on the purpose of use, but the ion exchange capacity of the resin phase is 0.5-4 meme when the counter ion is Cl.
q / g dry resin is preferred. Hereinafter, in this specification, the ion exchange capacity indicates a value when the counter ion is Cl. When the ion exchange capacity is smaller than this, the electrical resistance of the obtained anion exchange membrane increases, and when it is larger than this, the mechanical strength and long-term durability of the membrane decrease.

The anion exchange membrane of the present invention is an electrodialysis mechanism for concentrating seawater, desalinating brackish water, concentrating or recovering acid, recovering valuable metals, and a diffusion mechanism for recovering acid. It can be used for a dialysis mechanism. In addition, it is also useful for separators such as fuel cells and secondary batteries. In particular, because of its excellent alkali resistance and heat resistance, a solution processing device that concentrates, desalinates, and purifies hydroxide ions by electrodialysis or diffusion dialysis from a solution with a pH of 10 or more, or a solution process that requires high-temperature sterilization It is useful for equipment and self-regenerating type deionized water production equipment. It is also preferable as a base membrane of a composite membrane with a cation exchange membrane (a so-called bipolar membrane).

[0039]

EXAMPLES Examples of the present invention (Examples 1, 4 to 7) and comparative examples (Examples 2 and 3) will be described below. [Example 1] As a monomer represented by the general formula (2), 4- (4-bromobutyl) styrene in which A is a tetramethylene group and Z is bromine (colorless and transparent solution, boiling point 115 ° C / 0.2 m
mHg). A monomer mixture of 45% by mass of this monomer, 35% by mass of styrene, and 20% by mass of divinylbenzene (purity: 57% by mass, the balance being ethylbenzene) was obtained.

A styrene-based thermoplastic elastomer having 100 parts by mass of the monomer mixture and having a polystyrene as a hard segment and a poly (ethylene / propylene) as a soft segment as a thermoplastic polymer (manufactured by Shell Japan Co., Ltd. Clayton 1730, unsaturated bond ratio 0%) 15 parts by mass, benzoyl peroxide as a polymerization initiator (trade name Niiper B, manufactured by NOF Corporation)
O) 4 parts by mass were mixed to obtain a 1500 cps viscous liquid.

Next, 300 kGy of γ-ray was irradiated.
After impregnating the above viscous liquid into a membrane support material made of polypropylene cloth having a thickness of 300 μm and a basis weight of 100 g / m 2, the monomer mixture was polymerized to form a 320 μm thick film. This film-like molded product was immersed in a 1 mol / L methanol solution of trimethylamine at 40 ° C. for 16 hours,
The repeating unit Z based on the monomer represented by the general formula (2) was converted to a quaternary ammonium salt type, which was further exchanged for a Cl type. Thus, the structural unit represented by the general formula (1) (where A is a tetramethylene group, R ¹ , R ² , R ³
Methyl Both, X ^- is Cl ^- is. ) Was obtained.

The resulting anion exchange membrane had an ion exchange capacity of 1.8 meq / g resin phase. When the specific resistance of the film was measured at an alternating current of 1000 Hz in a 0.5 mol / L saline solution, it was 600 Ω · cm. The static transfusion number (0.5 mol / L saline) / (1.0 mol / L saline) measured at 25 ° C. was 0.97.
The anion exchange membrane was dried, and its cross section was SEM-E
The strength ratio of the Cl element in the portion of the polypropylene fiber of the cloth to the strength of the Cl element in the resin phase was determined by DAX measurement, and the ratio was 0.4. The specific resistance, static transport number, and intensity ratio of Cl element were measured in the same manner in the following examples.

This anion exchange membrane was immersed in a 0.1 mol / L aqueous solution of sodium hydroxide to reduce the anion exchange groups to O.
After conversion to H-type, excess sodium hydroxide was removed by washing with water, and then immersed in ion-exchanged water at 80 ° C. for 6 months. The ion exchange capacity of the anion exchange membrane after immersion is 1.76 meq.
/ G resin phase, the specific resistance was 630 Ω · cm, and the static transport number was 0.97.

Example 2 (Comparative Example) An anion exchange membrane was obtained in the same manner as in Example 1 except that the styrenic thermoplastic elastomer in Example 1 was not used. The specific resistance of this anion exchange membrane is 400 to 500 Ω · cm, and the static transport number is 0.90 to
A variation of 0.97 was observed in properties. Also SEM-EDA
The intensity ratio of the Cl element in the cloth portion to the resin phase by X was 0.4. This anion exchange membrane was converted to the OH type in the same manner as in Example 1 and was placed in 80 ° C. ion-exchanged water.
Soaked for months. After immersion, cracks occurred in the resin phase. The static transport number of the anion exchange membrane after immersion was 0.88.

Example 3 (Comparative Example) 4- (4-
An anion exchange membrane was obtained in the same manner as in Example 1, except that chloromethylstyrene (45% by mass in the monomer mixture) was used instead of 45% by mass of (bromobutyl) styrene. The ion exchange capacity of this anion exchange membrane is 1.9 meq / g resin phase, the specific resistance is 500 Ω · cm, and the static transport number is 0.97.
Met. Further, the intensity ratio of the Cl element in the cloth portion to the resin phase by SEM-EDAX was 0.4. This anion exchange membrane was converted to OH type in the same manner as in Example 1, and immersed in ion exchange water at 80 ° C. for 6 months. The ion exchange capacity of the membrane after immersion was 1.5 meq / g resin phase, the specific resistance was 1000 Ω · cm, and the static transport number was 0.92.

Example 4 A γ-ray irradiated at 300 kGy in place of the polypropylene cloth in Example 1 has a thickness of 260 μm.
m, a polyethylene cloth having a basis weight of 70 g / m ² , and 10 parts by mass of a hydrogenated nitrile rubber (trade name: Zetpol 2000, manufactured by Zeon Corporation) instead of 15 parts by mass of a styrene-based thermoplastic elastomer An anion exchange membrane was obtained in the same manner as in Example 1 except that the above procedure was followed.

The specific resistance of this anion exchange membrane is 500Ω.
cm, and the static transference number was 0.97. Also SEM-ED
The intensity ratio of the Cl element in the cloth portion to the resin phase by AX was 0.35. This anion exchange membrane was converted to OH type in the same manner as in Example 1, and immersed in ion exchange water at 80 ° C. for 6 months. The specific resistance of the film after immersion is 550Ω
cm, and the static transference number was 0.97.

Example 5 An anion exchange membrane was obtained in the same manner as in Example 4, except that a polyvinyl chloride cloth having a thickness of 160 μm and a basis weight of 80 g / m 2 was used instead of the polyethylene cloth in Example 4. The specific resistance of this anion exchange membrane is 40
0 Ω · cm and the static transport number were 0.98. After converting the anion exchange group of this anion exchange membrane to SO ₄ type,
When the intensity ratio of the S element in the cloth portion to the resin phase was determined by EM-EDAX, it was 0.6. This anion exchange membrane was converted to OH type in the same manner as in Example 1, and 8
It was immersed in ion exchange water at 0 ° C. for 6 months. The specific resistance of the membrane after immersion was 650 Ω · cm, and the static transport number was 0.97.

[Example 6] Thickness 5 irradiated with 300 kGy of γ-rays
A 0 μm polyethylene film is immersed in a mixture of 100% by mass of 4- (4-bromobutyl) styrene and 1 part by mass of an initiator benzoyl peroxide (trade name: Nipper BO, manufactured by NOF Corporation). The body was allowed to penetrate and simultaneously polymerize.

The resulting film-like molded product contained 50 parts by mass of a polymer of 4- (4-bromobutyl) styrene with respect to 100 parts by mass of polyethylene. The formed film was aminated with trimethylamine in the same manner as in Example 1 to obtain an anion exchange membrane. This anion exchange membrane
The membrane had an ion exchange capacity of 1.3 meq / g, the specific resistance of the membrane was 200 Ω · cm, and the static transport number was 0.98.

Example 7 260 μm thick as a membrane support material
Apply γ-rays to a polyethylene cloth with a basis weight of 70 g / m ^2.
A styrene-vinyl polyisoprene copolymer (manufactured by Kuraray Co., Ltd., trade name: Hibra-2751) was used after irradiation with 00 kGy, and instead of 10 parts by mass of hydrogenated nitrile rubber.
An anion exchange membrane was obtained in the same manner as in Example 4, except that 18 parts by mass was used.

The specific resistance of this anion exchange membrane is 370 Ω ·
cm and the static transference number was 0.98. In addition, SEM-E
The intensity ratio of the Cl element in the cloth portion to the resin phase by DAX was 0.20. This anion exchange membrane was converted to the OH ion type in the same manner as in Example 1, and was immersed in ion exchange water at 80 ° C. for 6 months. The specific resistance of the film after immersion is 4
20 Ω · cm and the static transport number were 0.97.

[0053]

The anion exchange membrane of the present invention is excellent in alkali resistance and heat resistance and has high mechanical strength. For this reason, the conventional anion exchange membrane can be suitably used for applications having a problem in durability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 41/14 B01J 41/14 F 47/12 47/12 D C02F 1/469 C08F 2/00 C C08F 2 / 00 C08L 25/18 C08L 25/18 101/00 101/00 C02F 1/46 103 (72) Inventor Hiroshi Toda 10 Goi Kaigan, Ichihara-shi, Chiba Asahi Glass Co., Ltd. (72) Inventor Yukio Matsumura Chiba-shi 10 Asahi Glass Co., Ltd., Goi Kaigan, Hara-shi (72) Inventor Hirohisa Kubota 1-1 Kurosaki Shiroishi, Yawatanishi-ku, Kitakyushu-shi, Fukuoka F-term in the Kurosaki Office of Mitsubishi Chemical Corporation 4D006 GA13 GA17 MA03 MA06 MA14 MB07 MB12 MB15 MB16 MB16 MB18 MC22X MC23X MC24X MC27X MC39X MC77 MC78X NA42 NA46 NA49 NA54 PA01 PA03 PA04 PB03 PB12 4D061 DA04 DB18 EA09 EB04 EB13 4F071 AA02 AA22 FA01 FA10 FB02 FC04 FD01 FD02 4J002 BB02X BB24X BB27X BC02X BC05X BC10W BC11W BC12W BD03X BG10X BP01X GD01 4J011 CA01 CA08 CB00

Claims (13)

[Claims] 1. The following general formula (1) (where A is carbon
An alkylene group having 3 to 8 carbon atoms or an alkyl having 4 to 9 carbon atoms in total
Represents a renoxyalkyl group. R¹, R^Two, R ^ThreeEach
A hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
Represents a silalkyl group. X^-Represents an anion. Benze
The hydrogen atom bonded to the ring is an alkyl group or halogen
And it may be substituted by a substituent atom. )
20 to 96% by mass of a polymer containing units and ion exchange
4 to 80% by mass of a thermoplastic polymer having no group is substantially
Anion exchange membrane containing a resin phase uniformly contained. Embedded image 2. The anion exchange membrane according to claim 1, comprising the resin phase and a porous membrane support material. 3. The method according to claim 1, wherein the porous membrane supporting material has a general formula (1)
3. The polymer according to claim 2, wherein the polymer has a repeating unit represented by the formula: and the content of the repeating unit represented by the general formula (1) is 0.05 to 0.7 times the resin phase. 4. Anion exchange membrane. 4. A thermoplastic polymer having no ion-exchange group and a general formula (2) wherein A represents an alkylene group having 3 to 8 carbon atoms or an alkyleneoxyalkyl group having 4 to 9 carbon atoms in total. Z represents chlorine, bromine, iodine, a hydroxyl group, a tosyl group, a tertiary to tertiary amine or a —NR ¹ R ² R ³ group, wherein R ¹ , R ² and R ³ are each a hydrogen atom, or Represents a group selected from an alkyl group and a hydroxyalkyl group having 1 to 6 carbon atoms, and the hydrogen atom bonded to the benzene ring may be substituted with an alkyl group or a halogen atom. A polymerization component comprising a mixture of a monomer of formula (2) and a monomer copolymerizable therewith is mixed, and then the polymerization component is polymerized so that Z is chlorine, bromine, iodine, hydroxyl, or tosyl. In the case of a group, Z is replaced with an ion exchange group Method of manufacturing a anion-exchange membrane and performing the reaction. Embedded image 5. The anion exchange according to claim 4, wherein the monomer of the general formula (2) is used in an amount of 20 to 96% by mass based on the total amount of the thermoplastic polymer having no ion exchange group and the polymerization component. Manufacturing method of membrane. 6. The shade according to claim 4, wherein the thermoplastic polymer and the polymer component are mixed by impregnating the polymer component into a film-shaped thermoplastic polymer having no ion exchange group. A method for producing an ion exchange membrane. 7. The method according to claim 4, wherein after a solution obtained by mixing a thermoplastic polymer having no ion exchange group with the polymer component is formed into a film, the polymer component is polymerized. A method for producing an ion exchange membrane. 8. The polymerizable component is polymerized after impregnating a solution obtained by mixing a thermoplastic polymer having no ion exchange group with the polymerizable component into a porous membrane supporting material. A method for producing the anion exchange membrane according to the above. 9. The method for producing an anion exchange membrane according to claim 8, wherein the porous membrane support material is irradiated with an electron beam or a γ-ray before or during the contact with the polymerization component. 10. The thermoplastic polymer having no ion-exchange group is a thermoplastic polymer having an unsaturated bond ratio of a main chain of 3% or less, and 100 parts by mass of the thermoplastic polymer has the general formula (2) The method for producing an anion exchange membrane according to any one of claims 4 to 9, wherein at least 25 parts by mass of the monomer of (1) is dissolved. 11. A solution processing apparatus comprising an electrodialysis mechanism or a diffusion dialysis mechanism using the anion exchange membrane according to any one of claims 1 to 3. 12. A unit represented by the general formula (2) used for obtaining the repeating unit represented by the general formula (1) in the anion exchange membrane according to any one of claims 1 to 3. Mers. 13. A monomer represented by the general formula (2) used in the method for producing an anion exchange membrane according to any one of claims 4 to 10.