JP2001002738A - Anion exchanger and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anion exchanger excellent in physical properties, easy to mold into a shape suitable for use, excellent in characteristics, excellent in heat resistance, and less dissolved, and a method for producing the same. provide. An anion exchanger obtained by graft-polymerizing at least a structural unit represented by the following general formula (1) or (2) on a polymer substrate. Embedded image (In the above formula, A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, and R ₁ , R ₂ ,
R ₃ each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or an alkanol group, and X represents a counter ion of an ammonium salt. Rings a and b may be further substituted. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a new anion exchanger utilizing a graft polymerization technique and a method for producing the same.

[0002]

2. Description of the Related Art It is well known that a trimethylammonium group introduced into a styrene polymer, which is best known as a functional group of an anion exchanger, is easily desorbed at high temperatures. On the other hand, Japanese Patent Application Laid-Open Nos.
JP-289921 discloses that between a benzene ring and an amino group or an ammonium group instead of an amino group or an ammonium group bonded to a benzene ring via a methylene group which is a functional group of a conventional styrene-based anion exchanger. It is disclosed that a styrene-based polymer into which a spacer group consisting of an alkylene group having 3 or more carbon atoms or an alkyleneoxymethylene group has been introduced is a heat-resistant ion exchanger in which functional groups are hardly eliminated even at a high temperature. Although the above-mentioned publication states that the heat-resistant ion exchanger can be in various shapes such as fibers or membranes, the specific disclosure is only a granular ion-exchange resin. There is no description about the ion exchanger in the form.

[0003] Conventionally, as a method for producing ion exchange fibers,
Several methods are known. One of them is a method of polymerizing a monomer having an ion-exchange group to form a fiber or a method of polymerizing the monomer and introducing a functional group after the formation of a fiber, and a polymer of an aromatic monovinyl compound represented by polystyrene is, When used alone, the workability (spinnability) during fiberization is extremely poor, and the strength of the obtained fiber is low, resulting in poor moldability. Polystyrene is a matrix (matrix) or sea, and polyethylene is a filamentous multifilament or multifilamentary fiber in the substrate. There are also known ion-exchange fibers in which an ion-exchange group has been introduced, but these polymers have the property that the polymer used as the base material can be processed into fibers, and that the ion-exchange group can be introduced. And the polymers that can be used are limited.

A functional material obtained by polymerizing a polymerizable monomer on a polymer base material by graft polymerization has been manufactured and used in many fields. The advantage of graft polymerization is that there is no restriction on the type and shape of the polymer base material used, so that the molding process is relatively easy. A functional material having both characteristics of a polymer base material and a polymerizable monomer can be processed. Among functional materials, separation functional materials such as ion-exchange materials and adsorbents are generally said to have greater exchange rate and adsorption speed as the surface area is larger. Therefore, the frequency of using a fibrous base material having a large surface area as an ion exchange material or an adsorbent is increasing, and these ion exchangers by graft polymerization,
The production of the adsorbent is suitable for utilizing the characteristics of the fibrous base material (JP-A-5-64726, JP-A-6-142).
439).

However, the production by the graft polymerization method also has disadvantages. When styrene is graft-polymerized as a polymerizable monomer into ion-exchange fibers, sulfuric acid and chlorosulfonic acid require a long-term and severe reaction under long-term conditions for the introduction of cation exchange groups. Accompanying damage and deterioration of the substrate. This damage causes a reduction in strength and a generation of dust.
In addition, the introduction of an anion exchange group requires chloromethylation using chloromethyl methyl ether as a carcinogenic substance. Since the introduction reaction of a quaternary ammonium group is performed after the chloromethylation, the reaction becomes two-stage and complicated. Becomes When the number of reaction steps increases, a step of removing the solvent used after the reaction, the reaction aid, etc. is also indispensable.
These substances that could not be removed also cause the performance of the functional material to deteriorate. That is, the reactivity of the graft-polymerized polymerizable monomer greatly affects the performance as a functional material.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a material having excellent physical properties such as strength and easy to form into a shape suitable for use. Another object of the present invention is to provide a new anion exchanger having excellent properties, excellent heat resistance, and low elution, and a method for producing the same.

[0007]

The gist of the present invention is to provide an anion exchanger obtained by graft-polymerizing at least a structural unit represented by the following general formula (1) or (2) on a polymer substrate. In the production method and production intermediate.

[0008]

Embedded image

(In the above formula, A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms;
R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkanol group, and X represents a counter ion of an ammonium salt. Rings a and b may be further substituted. )

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The anion exchanger of the present invention is obtained by graft-polymerizing at least one of the structural units represented by the general formula (1) or (2) on a polymer substrate. The general formula (1)
Alternatively, in (2), A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms. Examples of the alkylene group include linear, branched, and cyclic propylene groups, butylene groups, pentylene groups, hexylene groups, heptylene groups, and the like.Alkoxymethylene groups include the corresponding alkyleneoxymethylene groups. Is preferably a linear alkylene group.
Particularly, a linear alkylene group having 3 to 4 carbon atoms is preferable. A
In the case where is a methylene or ethylene chain, the ammonium group is chemically unstable because it is easily decomposed and desorbed by Hoffman decomposition, and when A has more than 8 carbon atoms, the molecular weight per structural unit increases, and anion exchange occurs. This is not preferred because the exchange capacity per unit weight of the body is reduced.

A in the general formula (1) or (2) may be located at any of the styrene residue substitution positions, o-, m- and p-positions. Position is preferred. R ₁ , R ₂ and R ₃ of the anion exchange group are a hydrogen atom,
An alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, or a hydroxyethyl group, a hydroxypropyl group, etc. Is an alkanol group having 1 to 6, preferably 1 to 4 carbon atoms. R ₁ , R ₂ , R ₃
May be the same. However, if the ion exchange capacity per unit weight is increased or heat resistance is taken into consideration, R
₁ , R ₂ and R ₃ are preferably a methyl group, and particularly preferably the structural unit of the general formula (2) has a trimethylammonium group.

[0012] As X ^over a counterion of the ammonium salt, for _{^{example, OH -, HCO 3 -,}} CO 3 2-, C
_{^{l -, Br -, SO 4}} 2-, CH 3 COO - , and the like. Rings a and b may be further substituted with an alkyl group, a halogen atom, or the like. Examples of the alkyl group include lower alkyl groups such as a methyl group and an ethyl group, and examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

The material of the polymer substrate on which the above-mentioned structural units are graft-polymerized is not particularly limited, but polyolefin and halogenated polyolefin-based materials are preferred. Specifically, ethylene, propylene,
Polymers or copolymers such as butene, hexene, tetrafluoroethylene, chlorotrifluoroethylene and the like, more specifically, polyethylene, polybutene, polystyrene, polytetrafluoroethylene, ethylene-propylene copolymer, ethylene-propylene -Butene three-dimensional copolymer, propylene-butylene copolymer, tetrafluoroethylene-chlorotrifluoroethylene copolymer and the like. Also, polymers or copolymers composed of various vinyl monomers, such as polystyrene, polyvinyl toluene, styrene-vinyl toluene copolymer, styrene-acrylonitrile copolymer, styrene butadiene-acrylonitrile copolymer, polyacrylate, polymethacrylate, etc. Is mentioned.

Polycondensates such as polyesters, polyamides and polyurethanes, and polymers such as polysaccharides, proteins and polypeptides can also be used as the base material. These may not only be used alone, but also be a blend of two or more polymers, or they may be various polymers which are interconnected by adhesion, fusion or fusion. The shape of the substrate can be selected from a wide range depending on the application. Preferred shapes of the substrate include a single fiber, a woven or non-woven fabric, or a single fiber or a woven fabric, a processed product of a non-woven fabric, a hollow fiber and a processed product thereof, a film material and a processed product thereof, a plate-like material and Processed goods. The method for producing the anion exchanger according to the present invention is not particularly limited, but any of the following methods is preferable. General formula (3) below for polymer base

[0015]

Embedded image

Wherein A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, and Z represents a halogen atom or a hydroxyl group. Ring c may be further substituted. A) graft-polymerizing the polymerizable monomer represented by the formula (1), and then introducing an anion exchange group into the graft polymer. The polymer represented by the following general formula (4) or (5)

[0017]

Embedded image

[0018] (In the formulas, A represents an alkylene group or an alkoxy methylene group having 4 to 8 carbon atoms having 3 to 8 carbon atoms, R _1, R
₂ and R ₃ each independently represent a hydrogen atom, a carbon number of 1 to 6;
X represents a counter ion of an ammonium salt. Rings d and e may be further substituted. A) a method of graft-polymerizing the polymerizable monomer represented by the formula (1).

On the anion exchanger obtained by graft-polymerizing the structural unit of the general formula (2), a polymerizable monomer represented by the general formula (4) is graft-polymerized on a polymer substrate. It can also be obtained by a method of quaternizing the ion exchange group. In the general formulas (3), (4) and (5), A and R
Specific examples of the substituents of ₁ , R ₂ , R _3, X and rings c to e are the same as those shown in formulas (1) and (2). When Z is a halogen atom, a chlorine atom, a bromine atom and an iodine atom are used, and a bromine atom is particularly preferable.

The polymerizable monomer as the precursor represented by the general formula (3) can be synthesized by several methods.
For example, Grignard reagent of chlorostyrene and 1, ω-
It can be synthesized by reacting a dihalogenoalkane. Alternatively, the method described in JP-A-4-34991 or JP-A-7-289921 may be used.
When a monomer represented by the general formula (3) is used as the polymerizable monomer, a graft having a structural unit represented by the following general formula (6) is formed on a polymer substrate.

[0021]

Embedded image

Wherein A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, Z represents a halogen atom or a hydroxyl group, and the ring f may be further substituted. The graft polymer is reacted with ammonia or an amine according to a known method and, if necessary, further reacted with an alkylating agent to convert the terminal functional group Z into an amino group or an ammonium group, thereby obtaining the anion exchanger of the present invention. Can be

The polymerizable monomers of the general formulas (4) and (5) are
It is obtained by reacting ammonia or an amine with the monomer of the general formula (3) to convert Z into an amino group or an ammonium group. Further, the monomer of the general formula (5) can be obtained by treating the monomer of the general formula (4) with an alkylating agent such as an alkyl halide. In the general formula (3) or (6), the method of converting the functional group Z into an amino group or an ammonium group can be performed according to a known method. That is, when Z is a halogen atom, ammonia,
What is necessary is just to make it react with alkylamines, such as methylamine, dimethylamine, triethylamine, and dimethylethanolamine. When Z is a hydroxyl group, it may be once converted into a halogen atom and then reacted with the above-mentioned ammonia or alkylamines.

In introducing the amino group and the ammonium group, a solvent is generally used. In particular,
Water, methanol, acetone, 1,2-dichloroethane,
Examples include dioxane, dioxane, and toluene. The reaction temperature varies depending on the reaction mode, the type of the functional group, and the type of the solvent, but is generally 20 to 100 ° C. Examples of the polymer base material on which the polymerizable monomers represented by the general formulas (3) to (5) are graft-polymerized include the above-described various base materials.

Various known methods can be used for the graft polymerization. For example, a method in which an active site is introduced onto a polymer trunk by bringing a peroxide initiator into contact with a polymer base material, and these are grafted as a polymerization start point (chemical grafting method); Ozone treatment to generate active sites on the polymer trunk and grafting the active sites as polymerization initiation points (ozone grafting method). A plasma method (high-temperature plasma graft method) in which the polymer is formed on the substrate and grafted with the polymerization start point is used.

The chemical grafting method in which a polymerization initiator is brought into contact with a polymer substrate is industrially useful because it can be applied to various materials in combination of the material of the polymer substrate and the initiator. In the method in which the polymerization initiator is brought into contact with the polymer base material, the polymerization initiator is added to the polymer base material according to the general formulas (3) to (3).
After impregnating the polymerizable monomer represented by (5), the polymerization is started by heating. The heating temperature varies depending on the decomposition temperature of the polymerization initiator, the type of the polymerizable monomer, particularly the boiling point of the polymerizable monomer, but is preferably 15 to 100 ° C, more preferably 25 to 90 ° C. As the polymerization initiator,
Peroxides, azo compounds and the like, specifically, benzoyl peroxide and azobisisobutyronitrile are preferred.

Further, a redox initiator can be used, and ceric ammonium nitrate, H ₂ O ₂ / Fe
It is possible to use a Fenton's reagent such as a system, a manganese salt-based compound, a vanadium salt-based compound, a cobalt complex and the like, and various compounds such as an acid may be added in combination therewith. When impregnating the polymer base material with the polymerization initiator, it is also possible to use a solvent for dissolving the polymerization initiator and the polymerizable monomer, and a solvent for suspending or emulsifying these. Specifically, water and various solvents such as alcohols, ethers, aromatics, aliphatics, esters, and halogens can be used as organic solvents, and these can be used alone or as a mixture. Can be either. Specific examples include methanol, ethanol, isopropyl alcohol, toluene, benzene, xylene, hexane, cyclohexane, ethyl acetate, butyl acetate, and methylene chloride. Preferably, the organic solvent does not dissolve the base material during the graft polymerization.

The substrate to be graft-polymerized by contacting the polymerization initiator with the polymer substrate is capable of polymerizing a reducing group such as a hydroxy group, an aldehyde group or an amino group or an unsaturated double bond in the molecule or on the surface of the substrate. When the compound has a suitable group, graft polymerization occurs more efficiently, which is preferable. Particularly, in a system using a redox polymerization initiator, a hydroxy group,
Materials having a reducing group such as an aldehyde group or an amino group are preferred.

In the production of the anion exchanger by graft polymerization in the present invention, the general formulas (3) to (5)
A polymerizable monomer other than the monomer represented by may be present. The second polymerizable monomer is selected from a crosslinkable monomer having two or more unsaturated hydrocarbons and a polymerizable monomer having one unsaturated hydrocarbon. Specifically, divinylbenzene, polyvinylbenzene, polyvinylbenzene, alkyldivinylbenzene, dialkyldivinylbenzene, bis (alkylstyrene), ethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polyethylene bis ( Examples thereof include (meth) acrylamide, styrene, alkylstyrene, (meth) acrylate, (meth) acrylic acid, acrylonitrile, hydroxyethyl (meth) acrylate, vinylpyrrolidone, and dimethylacrylamide.

These second polymerizable monomers can be added as long as the function of the ion exchanger is not reduced. The content is 0 to 50 relative to the polymerizable monomer.
%, Preferably 0-20% by weight. In the anion exchanger of the present invention thus obtained, since a spacer having 3 or more carbon atoms exists between the benzene ring and the amino group or the ammonium group, elimination of the ion exchange group at high temperatures is small. Also, as compared with the conventional styrene-based anion exchanger grafted product, an ion-exchange group can be introduced under mild conditions, or a monomer having an ion-exchange group introduced can be grafted, so elution of amines and the like can be prevented. Less damage and deterioration of the polymer substrate. Further, by selecting a polymer base material to be used, it is possible to obtain ion exchangers of various shapes, and it is also possible to select a base material having properties suitable for the intended use, or to perform a molding process. Have various advantages. Therefore, the anion exchanger of the present invention can be used for a wide range of applications.

For example, the ion exchanger of the present invention can be used for removing ions from a liquid as in general water treatment. Specifically, it can be used for pure water production in electric power / nuclear power generation, electronics industry, pharmaceutical manufacturing industry, etc., and desalination in processes in food manufacturing industry and chemical manufacturing industry. The ion exchanger of the present invention can also be used for adsorbing gas components in air. Specific examples include a filter for the purpose of deodorization, a filter for purifying a small amount of pollutants in a clean room, and the like.

The ion exchanger of the present invention can also be used for an ion exchanger packed in an electric regeneration type desalination apparatus, a battery separator, and the like. In addition, instead of introducing the above-mentioned anion exchange group into the grafted product having the structural unit represented by the general formula (6), if a chelate-forming group such as an iminodiphosphate group or an aminophosphate group is introduced, a heavy metal can be obtained. An adsorbent is obtained. Alternatively, a carrier for affinity chromatography can be obtained by introducing an active terminal such as an epoxy group, an amino group, or a carbonyl group to which a ligand such as an antibody or a substrate can be easily bound.

[0033]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following Examples and Comparative Examples, meq / g indicates a milliequivalent per dry ion exchanger weight. The exchange capacity of the anion exchanger was measured according to Diaion Manual (issued by Mitsubishi Chemical Corporation). In addition, ¹ H-NMR and ¹³ C-NMR
The measurement of the monomer was performed using Varian Unity-300
₃ and dissolved in δ / ppm based on TMS. In addition, the manufacturing method of the monomer was shown as a reference example.

Reference Example 1: Synthesis of trimethylvinylphenylbutylammonium bromide In a 1 L four-necked flask equipped with a cooling tube and stirring blades, 200 ml of methanol, 40 g (0.167 mol) of 4- (4-bromobutyl) styrene, 39 g (0.20 mol) of a 30% aqueous solution of trimethylamine was added and dissolved, and reacted at 30 ° C. for 5 hours in the presence of 100 ppm of diphenylpicrylhydrazyl (polymerization inhibitor). After the completion, methanol and water were distilled off under reduced pressure, whereby white crystals were deposited. A mixed solvent of ethanol and 2-propanol was added to the white crystals and recrystallized to obtain colorless scaly crystals. The powder was identified as trimethylvinylphenylbutylammonium bromide from the following analysis results.

¹ H-NMR measurement: methyl group 3.42 (S) of ammonium group, methylene chain at α-position 3.65 (t), β adjacent to ammonium group, hydrogen 1.74 (m) at methylene chain at γ-position, methylene chain at benzyl position Hydrogen 2.69 (t), vinyl group β-position trans hydrogen 5.22 (dd), vinyl group β-cis hydrogen 5.70 (dd), vinyl group α-position hydrogen 6.68 (dd), aromatic hydrogen (2,6-position hydrogen) 7.14
(d), 3,5-position hydrogen 7.3 (d)

Reference Example 2: Synthesis of N, N-dimethylaminobutylstyrene In a 1 L four-necked flask equipped with a cooling tube and stirring blades, 500 ml of methanol and 40 g of 4- (4-bromobutyl) styrene (0.167 mol) were added. ) And 0.75 mol of a 50% aqueous dimethylamine solution were dissolved and reacted at 50 ° C. for 5 hours. After completion, methanol and water were distilled off under reduced pressure. The reaction solution was made weakly basic with 300 ml of a 0.1 N NaOH aqueous solution, separated, and bisdimethylvinylphenylbutylammonium bromide in the aqueous phase was extracted. This operation was repeated twice to remove by-product ammonium salts. The oil phase was recovered. Diphenylpicrylhydrazyl (polymerization inhibitor) 100 ppm was added and distilled under reduced pressure (97 ° C / 0.4mm
Hg). Immediately after vacuum distillation, it was a pale yellow transparent solution,
Exposure to air resulted in a clear orange solution.

¹ H-NMR analysis: methyl hydrogen of amino group 2.20 (S), hydrogen hydrogen of methylene chain adjacent to amino group 2.26
(t), β, γ position methylene chain hydrogen 1.63 (m), 1.49 (m), benzyl position methylene chain hydrogen 2.62 (t), vinyl group β trans position hydrogen 5.19 (dd), vinyl group β cis position hydrogen 5.70 ( dd), vinyl group α-position hydrogen 6.69 (dd), aromatic hydrogen (2,6-position hydrogen) 7.13
(d), hydrogen at 3,5-position 7.31 (d) ¹³ C-NMR measurement: methyl group carbon 45.2, methylene chain carbon adjacent to amino group 59.4, β, γ-position methylene chain carbon 27.1, 28.
8, methylene chain carbon at benzyl position 35.2, β-position carbon at vinyl group
112.2, vinyl group α-position carbon 141.8, aromatic hydrogen carbon 125.
8,128.2,136.4, 1st (vinyl group ipso position) carbon 134.8

Example 1 Cellophane film pieces (thickness: about 25 μm, size: 1 cm)
× 1 cm, specific gravity about 1.2) 100 g was placed in a reaction vessel equipped with a stirrer, and 350 ml of toluene as an organic solvent was added thereto.
Was added. The inside of the reaction vessel was replaced with nitrogen, and the subsequent steps were performed under nitrogen. 1.35 g of ceric ammonium nitrate as a polymerization initiator, 6 ml of a 2N-nitric acid aqueous solution (about 7.2 ml as a combined initiator solution), and Sorgen 50 (sorbitan monostearate: Daiichi Kogyo Co., Ltd.) as a surfactant 0.4 g of a pharmaceutical solution was dissolved in 50 ml of a toluene solution in which nitrogen was dissolved, and the mixture was stirred to form a suspension. After that, the suspension was added to the reaction vessel, stirred for 2 minutes, and allowed to contact and react with a piece of cellophane film. Thereafter, the reaction vessel was placed in a thermostatic bath set at 25 ° C., and 100 g of 4-bromobutylstyrene was added, and graft polymerization was performed for 5 hours. After completion of the polymerization, the sample was washed with distilled water and dried. After the completion of the reaction, the grafting ratio was 70%. The grafted cellophane film was reacted in a 30% aqueous solution of trimethylamine at 50 ° C. for 5 hours to obtain a quaternary ammonium ion exchanger. The obtained ion exchanger was treated with an aqueous solution of sodium hydroxide and then with an aqueous solution of sodium chloride to convert the counter ion of the ion exchange group into Cl ion, and the ion exchange capacity was measured. The ion exchange capacity was 1.6.
It was 5 meq / g.

Comparative Example 1 A grafted product of CMS was obtained in the same manner as in Example 1 except that chloromethylstyrene (CMS) was used instead of 4-bromobutylstyrene used in Example 1. After completion of the polymerization, the sample was washed with distilled water and dried. After the completion of the reaction, the grafting ratio was 68%. The grafted cellophane film was reacted in a 30% aqueous solution of trimethylamine at 50 ° C. for 5 hours to obtain a quaternary ammonium ion exchanger. The obtained ion exchanger was treated with an aqueous solution of sodium hydroxide and then with an aqueous solution of sodium chloride to convert the counter ion of the ion exchange group into Cl ion. Then, the ion exchange capacity was measured. The ion exchange capacity was 2.30 meq. / G.

Example 2 The ion exchanger obtained in Example 1 and Comparative Example 1 was
After conversion to the OH form with aqueous sodium hydroxide, 125
ml. Ultrapure water (total organic carbon content TOC = 0.3 ppb) was added to this column at room temperature by SV30 for 24 hours.
After passing water for an hour, warm ultrapure water at 80 ° C. was passed through SV30. The results of measuring the TOC by sampling the passed water are shown in Table 1 below, and the ion exchanger of the present invention showed very little elution.

[0041]

Table 1 Dissolution properties of anion exchanger Ion exchanger TOC (ppb) Example 1 100 Comparative Example 1 1000

The anion exchanger of Comparative Example 1 is a general-purpose anion exchanger in which a trimethylammonium methylene group is bonded to a benzene ring, and has a smaller weight per unit weight than the anion exchanger of the present invention of Example 1. Although the ion exchange capacity is large, the amount of organic carbon eluted is also extremely large.

Example 3 100 g of cellophane film pieces as in Example 1 were placed in a reaction vessel equipped with a stirrer, and 350 ml of water was added thereto. The inside of the reaction vessel was replaced with nitrogen, and the subsequent steps were performed under nitrogen. 1.35 g of ceric ammonium nitrate as a polymerization initiator, 50 ml of an aqueous solution of 6 ml of a 2N-nitric acid aqueous solution (about 7.2 ml as an initiator solution) were mixed under nitrogen, and then added to the reaction vessel. Stir,
It was reacted with a piece of cellophane film. Thereafter, the reaction vessel was placed in a thermostatic bath set at 25 ° C., and 100 g of trimethylvinylphenylbutylammonium bromide obtained in Reference Example 1 was added, and graft polymerization was performed for 5 hours. After completion of the polymerization, the sample was washed with distilled water and dried. After the completion of the reaction, the grafting ratio was 40%. The obtained ion exchanger was treated with an aqueous solution of sodium hydroxide and subsequently with an aqueous solution of sodium chloride to convert the counter ion of the ion exchange group into Cl ion, and then the ion exchange capacity was measured. The ion exchange capacity was 0.93 meq /. g.

Example 4 The same cellophane film piece as in Example 1 was graft-polymerized with the N, N-dimethylaminobutylstyrene obtained in Reference Example 2 in the same manner as in Example 1. However, the organic solvent used was methanol. After performing the graft polymerization at 25 ° C. for 5 hours, the sample was washed with distilled water and dried. After the completion of the reaction, the graft ratio was 50%. The weak base exchange capacity of this ion exchanger was 1.60 meq / g.

[0045]

The ion exchanger of the present invention has an anion-exchange group having excellent thermal stability. The amount of by-products generated due to the introduction of ion-exchange groups is minimized, and damage and deterioration of the polymer substrate are small. It is a very clean anion exchanger because it has a great feature that, when used, water to be treated,
There is an advantage that contamination such as air can be minimized. In addition, the ion exchanger of the present invention can be used in a high-temperature environment, and can be easily molded by utilizing graft polymerization. Therefore, the industrial value is remarkable.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Junya Watanabe 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Yokohama Research Laboratory (72) Inventor Naoko Honda 1000-Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Co., Ltd. Yokohama Research Laboratory F-term (reference) 4F071 AA09C AA14C AA22 AA33C AA43C AA53C AA54C AA77 FA01 FA10 FB02 FC06 FD02 4J026 AA02 AA11 AA12 AA13 AA14 AA17 AA26 AA55 DB02 AC01 DB02 AC02 FA01 GA01 GA08

Claims (13)

[Claims] 1. An anion exchanger obtained by graft-polymerizing at least a structural unit represented by the following general formula (1) or (2) on a polymer substrate. Embedded image (In the above formula, A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, and R ₁ , R ₂ ,
R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkanol group, and X represents a counter ion of an ammonium salt. Rings a and b may be further substituted. ) 2. The anion exchanger according to claim 1, wherein in the general formula (1) or (2), A is a linear alkylene group having 3 to 8 carbon atoms. 3. In the general formula (1) or (2), R
_3. The anion exchanger according to claim ₁ , wherein each of ₁ , R ₂ and R ₃ is a methyl group. 4. The anion exchanger according to claim 1, wherein a polymer of trimethylvinylphenylbutylammonium bromide is formed on the polymer substrate by graft polymerization. 5. The polymer substrate is selected from a single fiber, a woven fabric or a nonwoven fabric, or a processed product thereof, a film material and a processed product thereof, a plate-shaped material and a processed product thereof. Item 5. The anion exchanger according to any one of Items 1 to 4. 6. A polymer base material represented by the following general formula (3): (In the formula, A is an alkylene group having 3 to 8 carbon atoms or 4 carbon atoms.
And Z represents an alkoxymethylene group, and Z represents a halogen atom or a hydroxyl group. Ring c may be further substituted. The method for producing an anion exchanger according to any one of claims 1 to 5, wherein the polymerizable monomer represented by the formula) is graft-polymerized, and then an anion exchange group is introduced into the graft polymer. 7. A polymer substrate, which is represented by the following general formula (4) or (5): (In the formula, A is an alkylene group having 3 to 8 carbon atoms or 4 carbon atoms.
~ 8 alkoxymethylene groups, R ₁ , R ₂ , R ₃
Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanol group. X represents a counter ion of an ammonium salt. Rings d and e may be further substituted. 6. The method for producing an anion exchanger according to claim 1, wherein the polymerizable monomer represented by the formula) is graft-polymerized. 8. The method for producing an anion exchanger according to claim 6, wherein the polymerizable monomer represented by the general formula (3) is 4-bromobutylstyrene. 9. The method for producing an anion exchanger according to claim 6, wherein the polymerizable monomer represented by the general formula (5) is trimethylvinylphenylbutylammonium bromide. 10. The polymer base material is selected from a single fiber, a woven fabric or a nonwoven fabric, or a processed product thereof, a film material and its processed product, a plate-shaped material and a processed product thereof. Item 10. The method for producing an anion exchanger according to any one of Items 6 to 9. 11. The method according to claim 1, wherein the grafting method is a chemical grafting method.
The method for producing an anion exchanger according to any one of claims 6 to 10, wherein the method is selected from a grafting method using an ozone treatment and a grafting method using a high-temperature plasma treatment. 12. A graft product obtained by graft-polymerizing a structural unit represented by the following general formula (6) on a polymer base material. Embedded image (In the formula, A is an alkylene group having 3 to 8 carbon atoms or 4 carbon atoms.
And Z represents an alkoxymethylene group, and Z represents a halogen atom or a hydroxyl group. Ring f may be further substituted. ) 13. The grafted product according to claim 12, which is obtained by graft polymerization of 4-bromobutylstyrene on a polymer substrate.