JPH0735443B2 - Anion exchange membrane and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel anion exchange membrane and a method for producing the same, and particularly provides an anion exchange membrane having excellent flexibility and mechanical strength and low electric resistance. Is.

[Conventional technology]

Anion exchange membranes are currently used in electrodialysis for desalting and concentrating salt water (brine or seawater), desalting foods, desalting and refining amino acids, refining pharmaceuticals, physiologically active substances, etc. It is used for the recovery of wastewater, the synthesis of various compounds, and the recovery of waste acid by diffusion dialysis. As a typical production method of these films, a paste prepared by adding polyvinyl chloride powder to a mixed solution of styrene monomer, divinylbenzene, a plasticizer (dioctyl phthalate etc.) and a polymerization catalyst (benzoyl peroxide etc.) is used as a core. Applied to the cloth of the material, polymerized and cross-linked by heating and pressurization to obtain a base film, and then chloromethylated and aminated, or after applying the styrene-butadiene copolymer latex to the core material. , Cross-linking, chloromethylation, amination, etc. in sequence, or by mixing partially polymerized styrene, divinylbenzene and a polymerization catalyst, polymerization and cross-linking are performed to obtain a bulk polymer, which is cut flat to form a base film. There is known a method of producing and then chloromethylation and amination.

However, the anion exchange membranes produced by these conventional methods are crosslinked at a considerably high density in order to increase the dimensional stability and mechanical strength of the membrane or to prevent the membrane from being damaged by the chloromethylation reaction, Further, in the production of the membrane, a portion having an ion-exchange group is inevitably mixed with a portion contributing to crosslinking. Thus, the conventional anion exchange membrane is hard,
It is weak against bending, making it difficult to lower the film resistance. Furthermore, it is extremely difficult to mold because the film thickness is thinned and the flexibility of the film is lost when it is molded into a tube or tube. I have to. These cause various inconveniences when using the membrane, and are also a cause of narrowing the application of the membrane.

Further, recently, anion exchange membranes having fluorocarbon as a skeleton are also known, but these membranes are excellent in mechanical strength and flexibility, but their cost is a problem.

[Problems to be solved by the invention]

The present invention improves the problems of the conventional anion exchange membranes described above, and provides an anion exchange membrane having excellent mechanical strength, flexibility and moldability, and low electric resistance, and a method for producing the same. .

[Means for solving problems]

The gist of the present invention is to use a linear block copolymer as a raw material for an anion exchange membrane, and to separate a part having an anion exchange group and a part not having an ion exchange group of its constituent polymer into microscopic regions. The details will be described below.

TECHNICAL FIELD The present invention relates to an anion exchange membrane composed of a block copolymer in which a polymer having an anion exchange group and a polymer not having an ion exchange group are linearly bonded, and a method for producing the same.

The region constituting the anion exchange membrane in the present invention means an assembly of molecules or polymers, and the region having anion exchange groups means the polymer having anion exchange groups of the program copolymer. And the region having no ion-exchange group means a polymer aggregate having no ion-exchange group of the block copolymer.

The anion exchange membrane of the present invention has a heterogeneous structure composed of a region having an anion exchange group and a region having no ion exchange group, and its morphology (morphology) and the size of each region are as follows. Two cases are preferred.

a) Both the region having an anion exchange group and the region not having an ion exchange group have a lamellar structure (layered), and the thickness of each layer is 50 to 500 angstroms.

b) The region having anion exchange groups is columnar, the region not having ion exchange groups is the matrix phase, and the region having anion exchange groups has a diameter of 50 to 500 angstroms.

c) The region having anion-exchange groups is the matrix phase, the region having no ion-exchange groups is island-shaped or column-shaped, and the diameter of the region having no ion-exchange groups is 50 to 500.
Angstrom. The above morphology is
The content of the block copolymer of the membrane (the portion excluding the support and the reinforcing material) may be 50% or more by volume, and more preferably 70% or more. In the present invention, partial morphological disorder is unavoidable. Further, the effect of the present invention is not significantly impaired even if the columnar or layered regions meander.

However, if the membrane does not satisfy the above-mentioned morphology, there is a great risk that the performance as an ion exchange membrane will be impaired, and the mechanical strength and flexibility will be impaired.

In the anion exchange membrane of the present invention, the proportion of the polymer having anion exchange groups in the block copolymer is 25 to 75 by weight.
Must be a percentage. If you are not satisfied with this,
It is not possible to obtain the required film morphology in the present invention,
The effect of the present invention is impaired. More preferably, the proportion of the polymer having anion exchange groups is 30 to 70 percent by weight (however, this weight ratio is the value when the block copolymer is dried).

The anion exchange membrane of the present invention is a block copolymer formed by linearly bonding a polymer (polyA) into which an anion exchange group can be introduced and a polymer (polyB) into which an ion exchange group cannot be introduced. After molding, an anion exchange group may be introduced into the polyA portion, and this may be obtained as a polymer (polyA ⁺ ) having an anion exchange group.

Here, the binding mode of the block copolymer is such that polyA and polyB are (polyA-polyB) n, polyBpolyA-polyB) n, polyApo
Any of lyB-polyA) n may be used. However, n is an integer, preferably 1 to 10, and more preferably 1 to 3. Further, when polyB polyA-polyB) n is 1 or 2 among these binding modes, a particularly excellent anion exchange membrane can be obtained.

Further, the block copolymer is preferably composed of a polymer capable of introducing an anion exchange group (polyA) and at least two types of polymers not introducing an ion exchange group (polyB ₁ and polyB ₂ ). In this case, the binding mode is polyB ₁ −
polyA−polyB ₂ , polyB ₁ −polyA−polyB ₂ −polyA, polyB ₁
−polyA−polyB ₂ −polyA−polyB ₁ , polyA−polyB ₁ −poly
It is desirable that the A-polyB ₂ -polyA. By using these block copolymers, it becomes easy to obtain an anion exchange membrane with less disorder in morphology.

Polymers that make up block copolymers polyA, polyB, poly
The number average molecular weight of B ₁ and polyB ₂ is 10 ³ to 10 ⁶ g / mol, respectively.
And more preferably 5 × 10 ^{3 to} 5
× 10 ⁵ g / mol. If the molecular weight of these polymer blocks is lower than this, a definite microphase separation structure is not formed in the finally obtained anion exchange membrane, and the effect of the present invention is impaired. Also, if the molecular weight is higher than this,
It is difficult to obtain a block copolymer having a controlled molecular structure, and it is difficult to form the block copolymer into a film.

In the present invention, the polymer (polyA) capable of introducing the anion exchange membrane constituting the block copolymer is preferably a polymer of a monomer having a tertiary amino group. Examples of such monomers include vinyl pyridines (2-vinyl pyridine, 4-vinyl pyridine, 2-methyl-5-vinyl pyridine, etc.), vinyl pyrimidines, vinyl quinolines, vinyl carbazoles or general formulas. (A is an integer of 0 to 3, R ₇ and R ₈ each have 1 to 12 carbon atoms
Styrene derivatives such as o, m, p-vinylbenzyldialkylamines represented by (R ₉ is hydrogen or an alkyl group having 1 to 12 carbon atoms) alkylamino acrylates represented by the general formula The dialkyl acryl amines represented by

The polymer with these tertiary amino groups (polyA) is (R ₁₀ , R ₁₁ , R ₁₂ is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 11 carbon atoms, X is a bromine or iodine atom), or XCH ₂ bX (b is 1 to 10) A compound represented by X'-CH ₂ -Ar (X 'is a halogen atom, Ar is an aromatic ring) or an acid halide group (-CO
1 to 6 carbon atoms having 1 to 6 X'or -SO ₂ X'groups)
A polymer polyA ⁺ having an anion exchange group can be easily obtained by quaternization using the compound of 0. Further, among the above compounds, a halogen group or an acid halide group is
The use of a compound having two or more compounds is preferable because the polyA portion is cross-linked at the same time as quaternization and an anion exchange membrane having a low water content is produced.

Further, the above-mentioned tertiary amino group can be converted to a strong acid by dissolving in water, for example, can be converted to a tertiary ammonium group by treating with steam or an aqueous solution of hydrogen chloride, hydrogen bromide, sulfuric acid, etc. A polymer polyA having a primary amino group can be a polymer polyA ⁺ having an anion exchange group.

Here, the introduction rate of the anion exchange group is 50 per monomer unit constituting the polymer polyA capable of introducing the anion exchange group.
% Or more, and more preferably 75% or more.

The polymer having no ion exchange group (polyB, polyB ₁ , polyB ₂ ) of the block copolymer constituting the anion exchange membrane of the present invention
Etc.) is hydrophobic, and it is desirable that the homopolymer has a glass transition point of 20 ° C. or lower, and more desirably
It is below 10 ℃. If its glass transition point is above 20 ℃,
The flexibility of the finally obtained anion exchange membrane is impaired and hardened, and it becomes weak against bending.

Examples of such polymers in the present invention include polyethylene, polypropylene, polyisoprene, polybutadiene, polyisobutylene, polyvinylidene chloride, polytetrafluoroethylene, polydimethylsiloxane, poly (n).
-Butyl methacrylate), polymethyl acrylate, etc., and polydiene-based polymers are particularly desirable. This is because such a polymer has rubber elasticity, and thus the obtained anion exchange membrane becomes even stronger against bending and vibration. The diene monomer that constitutes this polymer has the general formula (Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are represented by hydrogen atom, alkyl group having 1 to 12 carbon atoms, aromatic ring, fluorine atom or chlorine atom) .

Representative examples of the method for obtaining the polymer forming the block copolymer according to the present invention include the commonly known stepwise polymerization method and coupling method. Among these, in the sequential polymerization method, for example, butyl lithium (n-, sec-, tert-, etc.), 2
-Methylbutyllithium, sodium naphthalene, sodium anthracene, α-methylstyrene tetramer sodium, sodium biphenyl as a polymerization initiator, aromatic hydrocarbons, cyclic ethers, aliphatic hydrocarbons and the like as a solvent, vacuum Alternatively, polymerization may be carried out by introducing the required monomer into a solvent containing a polymerization initiator at an appropriate time interval in an inert gas atmosphere. On the other hand, in the coupling method, the above-mentioned polymer capable of introducing an anion exchange group and the polymer not introducing an ion exchange group are separately polymerized by a usual method, and then bonded to one end or both ends of each polymer. Introducing an active group suitable for the above, mixing both, and performing a usual binding reaction.

In the present invention, an ordinary method may be used as an example of the method for molding the block copolymer into a film shape, for example, a flat film, a tube, a hollow fiber, etc., and a solvent evaporation method is representative. In this case, the block copolymer is volatilely dissolved in a solvent (at this time, the polymer concentration is preferably 5 to 40% by weight), the solution is evenly adhered to the support, and the solvent is slowly evaporated. Just do it. The support may be a net, a hollow braid, a non-woven fabric, a porous sheet, a tube or a hollow fiber. Here, it is desirable that the net and the braid be made of yarn or fiber having a thickness of 200 μm or less. Further, the above block copolymer solution is applied onto a porous support surface or an object having a smooth surface, and the solvent is evaporated as it is, or after a suitable time has passed, a coagulant (of the original block copolymer is (Non-solvent), or using a composite spinneret arranged concentrically as a block copolymer solution as a sheath component, a coagulant or a suitable gas as a core component, after allowing the space to fall naturally, Film formation is also possible by introducing into a coagulant.

In the present invention, a polymer polyB having no ion exchange group,
PolyB ₁ and polyB ₂ do not necessarily have to be homopolymers, and even if they are copolymers with other monomers that do not have an ion exchange group (are not introduced), they do not deviate from the spirit of the present invention. In this case, if the homopolymers of polyB, polyB ₁ or polyB ₂ are copolymers of monomers with glass transition points of 20 ° C or lower and 50 ° C or higher, the anion exchange finally obtained by adjusting the composition. It is possible to control the hardness of the membrane.

Here, the content ratio of Tg of the monomer at 50 ° C. or higher may be 50 wt% or less of the polymer portion not crossing the ion exchange group. In addition, _one of polyB ₁ and polyB ₂ has a glass transition point of 20.
A polymer having a glass transition point of 50 ° C. or higher may be used as the polymer having a temperature of not higher than 0 ° C., and the film finally obtained can be adjusted to have an appropriate hardness.

〔The invention's effect〕

As described above, according to the present invention, a block copolymer is first prepared and anionized to form an anion membrane, so that not only an anion exchange membrane having excellent mechanical strength and flexibility and low electric resistance can be obtained, With respect to the molding, it is possible to easily obtain various anion exchange membranes such as a tubular shape and a cylindrical shape as well as a flat shape. These are expected to expand the applications of anion exchange membranes.

〔Example〕

Hereinafter, the present invention will be described with reference to Example 1, but the present invention is not limited to these Examples.

Example 1 Benzene 2 purified through a sodium mirror as a solvent, n
-Butyllithium 2.2 x 10 ^-3 mol as a polymerization initiator, isoprene 55 g, 4-vinylbenzylmethylamine (4-VBD
MA) 130g, butadiene 55g in this order every 20 hours into the polymerization tank to carry out ordinary sequential polymerization to obtain polyB ₁ -polyA-pol.
235 g of a yB ₂ type original block copolymer was obtained.

This raw block copolymer was dissolved in xylene to a polymer concentration of 20 weight percent, which was applied to a cylindrical rotor made of tetrafluoroethylone, and the solvent was naturally evaporated while rotating the rotor horizontally. The obtained original block copolymer film was peeled off from the rotor and the thickness was measured.
It was 0 μm. The membrane was allowed to stand in vapor of methyl iodide for 10 hours to quaternize the amine portion, and vacuum dried to obtain an anion exchange membrane. The anion exchange capacity of this membrane is determined by the conventional method. The membrane is immersed in 1N sodium chloride solution for one day and then washed with water, immersed in 1N sodium nitrate for one day and one day, and the liberated Cl ⁻ ion is quantified by ion chromatography. The conversion rate of the quaternization reaction was 95%.
Met. This was dyed with a 2% osmium tetroxide aqueous solution and observed with a transmission electron microscope.
A lamella structure in which VBIMA) layers (white portions) and polyisobrene or polybutadiene layers (black portions) were alternately arranged was observed. Although these layers were tortuous and tortuous, the thickness of one layer was on the order of 100-200 Angstroms. In addition, the obtained anion exchange membrane
After soaking in 1 mol / KCl aqueous solution for 50 hours, 0.02 mol / and 0.01
The static anion transference number was 0.97 when the mol / KCl aqueous solution was brought into contact with each surface of the membrane, and the static anion transport number was 0.97. When the film resistance was measured using an alternating current, it was a small value of 1 Ω · cm ² or less. Also, 0.5 mol /
When electrolysis was performed using a NaCl solution at a current density of ² A / dm ² , the current efficiency of chloride ions was calculated to be 90%.

Moreover, the obtained anion exchange membrane was flexible in both a dry state and a state containing water, and no whiskers or tears were formed even when it was bent.

Examples 2 to 4 Anion exchange membranes were obtained in the same manner as in Example 1 except that the weight ratio of the monomers used in Example 1 was changed. The weight of these monomers and the properties of the film are shown in Table 1. However, in Example 3, since the quaternization of the amine moiety was performed using 1,3-dipromopropane, the amine moiety was crosslinked. It can be seen that all the membranes have good properties as anion exchange membranes. The lower the 4-VBDMA content of these membranes, the more flexible they were.

Comparative Examples 1 and 2 An attempt was made to prepare an anion exchange membrane by the same method except that the weight ratio of the monomers used in Example 1 was changed. Table 1
As shown in FIG. 5, the content of 4-VBDMA was reduced by about 20% in Comparative Example 1, and was increased to about 80% in Comparative Example 2.
As a result, in Comparative Example 1, the film was too soft, and in Comparative Example 2
On the contrary, the film was too hard to maintain the shape of the film.

COMPARATIVE EXAMPLE 3 The film obtained in Comparative Example 1 was treated with stannic chloride vapor.
By the time treatment, the polyisoprene and polybutadiene portions of the membrane were crosslinked to fix the shape of the membrane. When the electric resistance of this film was measured under the same conditions as in Example 1, it was found that
It was a large value of 18 Ω · cm ² .

Comparative Example 4 Paste prepared by mixing styrene (230 parts), divinylbenzene (30 parts), plasticizer (dioctyl phthalate 30 parts), catalyst (benzoyl peroxide 2.5 parts) and polyvinyl chloride fine powder (100 parts). Is applied to the cloth of the core material (Teijin Co., Ltd., PVC screen), which is sandwiched between two polytetrafluoroethylene plates and heated to 100 ° C in a closed container and left to stand for 12 hours for polymerization. I went. The obtained membranous polymer (thickness 200 μm) was treated with anhydrous aluminum chloride catalyst, treated with chloromethyl ether to chloromethylate (reaction time 40 minutes, temperature 20 ° C.), and then trimethylamine was used. A quaternary ammonium group was introduced by a conventional method.

The obtained anion-exchange membrane had a high anion transport number of 0.97 with respect to KCl aqueous solution, but the electrical resistance in 0.5 mol / NaCl aqueous solution was 4.2 Ωcm ^2, which was quite large, and this membrane lacked flexibility. When it was bent, it cracked.

Example 5 Using benzene 1 purified in the same manner as in Example 1 as a solvent, se
c-butyllithium 1.1 × 10 ^-3 mol as a polymerization initiator,
56 g of butadiene and 81 g of 2-vinylpyridine were placed in a polymerization tank to carry out polymerization to obtain 135 g of a polyB-polyA type original block copolymer.

This raw block copolymer was dissolved in xylene to a polymer concentration of 5 weight percent and spread on the mercury surface,
The solvent was evaporated to form a film having a thickness of 130 μm. The membrane was allowed to stand in vapor of ethyl iodide for 20 hours at 60 ° C. to quaternize the pyridine ring and vacuum dried to obtain an anion exchange membrane. The conversion rate of the quaternization reaction at this time is 94%
Met. This was stained with a 2% osmium tetroxide aqueous solution and observed with a transmission electron microscope.
A lamella structure in which vinyl pyridine) layers (white portions) and polybutadiene layers (black portions) were alternately arranged was observed. The thickness of each layer was about 150 Å. The obtained anion exchange membrane was dissolved in 1 mol / KCl aqueous solution.
After 50 hours of immersion, 0.02 mol / and 0.01 mol / KCl aqueous solutions were separated by a membrane, and the static anion transport number was calculated from the potential generated between these solutions to be 0.95, which was 1000 Hz in a 0.5 mol / NaCl aqueous solution. When the film resistance was measured using an alternating current, it was a very small value of 1 Ω · cm ² or less. Also,
When electrolysis was carried out at a current density of ² A / dm ² using 0.5 mol / NaCl, the current efficiency of chloride ion was 86%.

Further, the obtained anion exchange membrane was flexible in both a dry state and a state containing water, and did not crack or tear even when bent.

Example 6 A toluene solution of the raw block copolymer obtained in Example 1 (polymer concentration: 20% by weight) was added to a polyethylene net (manufactured by NBC Industry Co., Ltd., trade name “Nip Strength Steel” 120 × 1).
(02 mesh) was dipped and wound on a rotor made of tetrafluoroethylene, and the solvent was dried to obtain a raw block copolymer film backed with polyethylene net. This was left in the vapor of ethyl iodide for 10 hours, and the
Anion exchange membrane was obtained by performing grading and vacuum drying.
At this time, the conversion rate of the quaternization reaction was 96%. Example 1
Observation with an electron microscope in the same manner as in Example 1 revealed the same lamella structure as in Example 1. The static anion transport number determined in the same manner as in Example 1 was 0.96 and the membrane resistance was 1 Ω · cm ² or less.

This membrane was attached to a two-chamber type dialysis cell, one chamber was filled with 1N hydrochloric acid and the other chamber was filled with pure water, and dialysis was performed while stirring both solutions with a magnetic stirrer. At this time, the diffusion rate obtained from the membrane permeation rate of hydrochloric acid was 18 mol / m ² · hr · (mol /
) And a value more than twice as large as that of the conventional anion exchange membrane.

Example 7 Benzene 1 purified through a sodium mirror as solvent, n
-Butyllithium 8 x 10 ^-4 mol was used as a polymerization initiator to polymerize 70 g of butadiene for 20 hours, and then 4
-Vinylbenzyldiethylamine (4-VBDEA) (105 g) was added and the mixture was polymerized for 20 hours to obtain 170 g of a polyA-polyB type original block copolymer.

This raw block copolymer was dissolved in toluene to a polymer concentration of 18 weight percent, which was applied to a tetrafluoroethylene columnar rotor, and the solvent was allowed to spontaneously evaporate while rotating the rotor horizontally to a thickness of 140 μm. A film of The membrane was left in vapor of diiodobutane at 35 ° C for 10 days to quaternize and crosslink the amine moiety, and then in methyl vapor iodide vapor at 25 ° C for 10 hours.
Vacuum drying was performed to produce an anion exchange membrane. The quaternization rate is
It was 95%.

The obtained anion exchange membrane was dyed with a 2% osmium tetroxide aqueous solution and observed with a transmission electron microscope. As a result, a quaternized poly (4-VBDEA) layer (white portion) and a polybutadiene layer (black portion) were formed. An alternating lamella structure was observed. These layers are quite disorderly and winding,
The thickness of one layer was on the order of 100-250 Angstroms. In addition, this anion exchange membrane was added to a 1 mol / KCl aqueous solution.
After 50 hours of immersion, when 0.02 mol / and 0.01 mol / KCl aqueous solutions were contacted with the respective surfaces of the membrane, the static anion transport number was calculated from the potential generated between both solutions to be 0.98, which was 0.5 mol. When the membrane resistance was measured in a NaCl aqueous solution of / using 1000 Hz alternating current, it was about 1.5 Ω · cm ² . Also,
When electrolysis was carried out at a current density of ² A / dm ² using a 0.5 mol / NaCl aqueous solution, the current efficiency of chloride ions was determined to be 95%.
Met. Further, the obtained anion exchange membrane was flexible in both a dry state and a state containing water, and did not crack or tear even when bent.

Claims (17)

[Claims] 1. A block copolymer having a heterogeneous structure in which a polymer having an anion exchange group and a polymer not having an ion exchange group are linearly bonded to each other, and a polymer portion having the anion exchange group An anion exchange membrane, characterized in that the ratio to the copolymer is 25 to 75% by weight. 2. The anion exchange membrane according to claim 1, wherein the anion exchange region and the region having no ion exchange group are layered and each has a thickness of 50 to 500 angstroms. 3. The anion according to claim 1, wherein the anion exchange region is columnar, the region having no ion exchange group is the matrix phase, and the diameter of the anion exchange region is 50 to 500 angstrom. Exchange membrane. 4. The anion exchange region is a matrix phase, the region without ion exchange groups is island-like or columnar, and the diameter of the region without ion exchange groups is 50 to 500.
The anion exchange membrane according to claim 1, which is angstrom. 5. A block copolymer having a polymer having an anion exchange group (polyA ⁺ ) and a polymer having no ion exchange group (po).
lyB) and its binding mode is (polyA ⁺ −polyB) n, po
The anion exchange membrane according to claim 1, which is any one of lyBpolyA ⁺ -polyB) n and polyA ⁺ polyB-polyA ⁺ ) n (n is an integer). 6. A block copolymer comprising a polymer having an anion exchange group (polyA ⁺ ) and at least two types of polymers (polyB ₁ and poly) composed of different monomers having no ion exchange group.
B ₂ ) and its binding mode is polyB ₁ −polyA ⁺ −
polyB ₂ , polyB ₁ −polyA ⁺ −polyB ₂ −polyA ⁺ , polyB ₁ −poly
A ⁺ −polyB ₂ −polyA ⁺ −polyB ₁ , polyA ⁺ −polyB ₁ −polyA ⁺
Claim 1 which is any one of -polyB ₂ -polyA ⁺
Anion exchange membrane according to item. 7. A poly (A ⁺ , poly) constituting a block copolymer
The polymer represented by B, polyB ₁ and polyB ₂ has a molecular weight of 10 ³ to 10 ⁶ g / mol, respectively.
Anion exchange membrane according to item. 8. The anion exchange membrane according to claim 1, wherein the polymer having no ion exchange group is hydrophobic, and the homopolymer has a glass transition point of 20 ° C. or lower. . 9. A polymer having no ion exchange group is represented by the general formula: (Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aromatic ring, a fluorine atom, or a chlorine atom). The anion exchange membrane according to any one of claims 1 to 8, which is obtained by polymerizing the represented diene monomer. 10. The anion exchange membrane according to any one of claims 1 to 9, wherein either or both of the anion exchange region and the region having no ion exchange group are crosslinked. 11. A polymer having a tertiary nitrogen atom and a polymer not having an ion exchange group introduced therein are subjected to a sequential reaction or a coupling reaction so that the proportion of the polymer portion having a tertiary nitrogen atom is 25 to 50 by weight. A linearly bonded block copolymer was produced to be 75%, and after being molded into a film,
A method for producing an anion exchange membrane, which comprises introducing an anion exchange group by making the polymer having a tertiary nitrogen atom a tertiary base or a quaternary ammonium base. 12. The block copolymer is composed of a polymer having a tertiary nitrogen atom (polyA) and a polymer having no ion exchange group introduced (polyB), and its binding mode is (polyA-polyB).
n, polyB polyA-polyB) n, polyA polyB-polyA) n
Claim 11 being any one of (n is an integer)
The manufacturing method according to the item. 13. A block copolymer is composed of a polymer having a tertiary nitrogen atom (polyA) and a polymer having no ion exchange group introduced (polyB ₁ and polyB ₂ ), and its binding mode is po.
lyB ₁ −polyA−polyB ₂ , polyB ₁ −polyA−polyB ₂ −polyA, p
olyB ₁ −polyA−polyB ₂ −polyA−polyB ₁ , polyA−polyB ₁
-PolyA-polyB ₂ manufacturing method of the claims claim 11 wherein either of -polyA. 14. PolyA, poly constituting a block copolymer
The polymer represented by B, polyB ₁ and polyB ₂ has a molecular weight of 10 ³ to 10 ⁶ g / mol, respectively.
The manufacturing method according to the item. 15. The production method according to claim 11, wherein the polymer having no ion exchange group introduced therein is hydrophobic and the homopolymer has a glass transition point of 20 ° C. or lower. 16. A polymer having no ion exchange group is represented by the general formula: (Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aromatic ring, a fluorine atom, or a chlorine atom.). 16. The production method according to claim 11, which is obtained by polymerizing a diene monomer. 17. The method according to claim 11, wherein one or both of a polymer having an anion exchange group and a polymer not having an ion exchange group are crosslinked. .