JPH07289921A - Anion exchanger - Google Patents

Abstract

PURPOSE:To obtain an anion exchanger high in heat resistance and easy to produce by adding a constitutional unit represented by the specific general formula and a constitutional unit derived from an unsaturated hydrocarbon group-containing crosslinkable monomer to a crosslinkable anion exchanger. CONSTITUTION:A constitutional unit represented by the formula (wherein A is a direct bond or a l-4C straight chain or branched chain alkylene group, B is a 4-8C straight chain, branched chain or cyclic alkylene group, R1-R3 may be same or different and a 1-4C alkyl group or a 1-4C alkanol group, X is a pair ion coordinated with an ammonium group and a benzene ring D may be substituted with an alkyl group or a halogen atom) and a constitutional unit derived from an unsaturated hydrocarbon group-containing crosslinkable monomer are added to a crosslinkable anion exchanger. By this constitution, an anion exchanger high in heat resistance and easy to produce is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel anion exchanger, particularly a crosslinked anion exchanger having excellent heat resistance.

[0002]

2. Description of the Related Art Conventionally, as anion exchangers, for example, various ion exchange groups having nitrogen and phosphorus compounds such as quaternary ammonium groups and phosphonium groups as anion exchange groups, polystyrene, poly (meth) and the like. Strongly basic anion exchangers comprising a combination with structural units such as acrylate, polyvinyl alcohol, polyvinyl / allylamine, etc. are known. Of these, anion exchangers having trimethylaminomethylstyrene as a repeating unit are widely used because they have excellent chemical stability and are extremely inexpensive.

However, in a styrene-based anion exchanger having trimethylaminomethylstyrene as a constituent unit, trimethylamine is easily eliminated (reduction of neutral salt decomposing capacity) and methyl group is easily eliminated under a temperature higher than room temperature. It cannot be said to be chemically stable due to (weak base), and when used at high temperatures, the resin has a short life or there is a limit on the upper limit of the use temperature, and trimethylamine elutes to give off an amine odor. However, there were many problems such as a large amount of eluate from the anion exchanger.

In addition to the trimethylammonium group, there is also a styrene-based anion exchange resin having an ω-hydroxyalkyldimethylammonium group as an ion exchange group, but it has been reported that it is further inferior in heat resistance (48th Inte.
national Water Conference
e (1992) IWC-87-9). In addition, anion exchangers and the like having a constitutional unit of triethylaminoethyl (meth) acrylate having a trimethylamino group at the terminal are known, but it is also known that they have poor heat resistance (IWC-87-9). .

As a method for improving the heat resistance of the anion exchange group, a strongly basic anion exchanger in which a benzene ring and an ion exchange group are bonded by a polyalkylene chain has been proposed (JP-A-4-349941). However, when the polyalkylene chain is an ethylene chain, there is a problem that Hofmann decomposition (E2 elimination reaction) is likely to occur and heat resistance is poor. An anion exchanger having a 1,1-dimethylethylene chain having a dimethyl group at the β-position of the ion-exchange group has been reported in order to remove desorbable hydrogen. However, it is known that the thermal stability of the trimethylammonium group is poor due to the steric hindrance of the methyl group (J. App.
l. Polym. Sci. , 8.1659 (196
4)). Therefore, in order to suppress the elimination reaction of trimethylamine, at least the alkylene chain must be a propylene chain or more. However, in order to produce this anion exchanger, the Grignard reaction was used to introduce alkylene chains (J. Amer. Chem. S.
oc. , 96.7101, (1974), Synth.
Comm. , 20 (15) 2349 (1990)), which is difficult and industrially expensive to manufacture. Furthermore, since it is composed of an alkylene group,
The resulting anion exchanger becomes a hydrophobic resin. As a result, the water content and the degree of swelling of the resin are lowered, which is disadvantageous in manufacturing.

Japanese Unexamined Patent Publication No. 3-35010 discloses a functional group
-(CH₂)_nX (CH₂)_mNR ₁R₂R₃Y (X is
O, S, SO₂, R₁~ R₃Is an alkyl group, n is 0
Or 1, m is 1 to 20, and Y is a physiologically acceptable pair.
Polystyrene polymer with (ion)
It discloses that it is effective in lowering sterol levels.
It However, this polystyrene polymer is anion exchanged.
No mention is made of its use as a resin in water treatment.
No, and there is no description regarding heat resistance. This special release
The resin described in Xu Example 1 is subject to our investigation.
If so, the heat resistance is extremely poor. Similarly, N, N-dimethyl
Minoethyl (or propyl) oxymethylstyrene and di
A weakly basic aniline composed of a spherical copolymer with vinylbenzene.
On-exchanger or its quaternary ammonium salt, amine
The side in cyanide displacemen
used as a catalyst for ton 1-bromooctate
Studies have been reported (Chem. Lett., 6
77-678 (1980)), but regarding water treatment,
Not listed.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an anion exchanger which has extremely high heat resistance and is easy to manufacture.

[0008]

The present invention has been made to solve the above problems, and its gist is to provide a crosslinkable anion exchanger having the following general formula (I):

[0009]

[Chemical 3]

(In the general formula (I), A has 1 to 4 carbon atoms.
Represents a linear (or branched) alkylene group, and B is carbon
Represents a straight-chain alkylene group of the formulas 4 to 8, R₁ , R
₂ , R ₃ Are from 1 to 1 carbon atoms which may be the same or different
4 is an alkyl group or an alkanol group, and X is
It shows a counter ion coordinated to the ammonium group, and the benzene ring D
Is substituted with an alkyl group or a halogen atom
Good. ) Containing a structural unit represented by) and an unsaturated hydrocarbon group
Containing a structural unit derived from a crosslinkable monomer
Exists in an anion exchanger characterized by. Used in the method of the present invention
The anion exchanger used is preferably of the general formula (II)
Crosslinked polymer composed of P, Q and R units
Is.

[0011]

[Chemical 4]

In the formula (II), n is an integer of 4 to 8, R ₁ and R
₂ , R ₃ represents an alkyl group or an alkanol group having 1 to 4 carbon atoms which may be the same or different, and X represents an ion coordinated with an ammonium group. The benzene rings E and D may be substituted with an alkyl group or a halogen atom.

[0013]

[Chemical 5]

Is a third polymerizable monomer residue. The structural unit Q is 5 to 99.9 mol%, the structural unit P derived from the crosslinking agent is 50 to 0.1 mol%, and the structural unit R derived from the third polymerizable monomer is 0 to 50 mol%. % (All are based on crosslinked polymer). Hereinafter, the present invention will be described in detail. The anion exchanger in the present invention has the general formula (I)
A water-insoluble cross-linked copolymer containing a structural unit represented by:

The carbon number of the alkylene chain B is preferably at least a butylene chain or more in order to develop the heat resistance of the ion exchange group. However, when the chain length of the alkylene chain B becomes long, the molecular weight of the structural unit (I) becomes large, so that the ion exchange capacity per unit weight of the anion exchanger is decreased, leading to a decrease in the exchange capacity. Therefore, the alkylene chain B preferably has 8 or less carbon atoms. Particularly preferably, the alkylene chain B has 6 or less carbon atoms.

Examples of the alkylene chain B include linear alkylene groups such as n-butylene, n-pentylene, n-hexylene, n-heptylene and n-octylene. Among them, n-butylene chain, pentene chain and hexene chain are particularly preferable. On the other hand, it is considered that the alkylene chain A bonded to the benzene ring has an action of suppressing the oxidation reaction of the benzene ring. In the case of a phenoxy group in which the carbon number of A is 0 (direct bond), the benzene ring is easily oxidized, and the ion exchange group is likely to be removed. Therefore, the chain length of the alkylene chain A bonded to the benzene ring has 1 or more carbon atoms. As in B, when the chain length of A is increased, the number of ion-exchange groups per unit weight is reduced, so that the alkylene chain A preferably has 4 or less carbon atoms. For example, methylene chain, ethylene chain,
A linear alkylene group such as an isopropylene chain and a butylene chain, a branched alkylene group and the like can be mentioned (the alkyl group of the branched alkylene group may be located anywhere).
Among them, the alkylene chain A is particularly preferably a methylene chain in view of manufacturing advantages.

From the viewpoint of the production method and production cost, it is particularly preferable that the alkylene chain A and the alkylene chain B are combined such that the alkylene chain A is a methylene chain and the alkylene chain B is a butylene chain. It is presumed that the alkylene chain B bonded to the ion exchange group contributes to improving heat resistance, and the alkylene chain A bonded to the benzene ring contributes to suppressing the oxidation reaction of the benzene ring. Therefore, what is particularly important for expressing the heat resistance of the ion exchanger is the chain length of the alkylene chain B bonded to the ion exchange group.

Alkoxyalkylene groups having an ion-exchange group are mostly introduced at the p-position of styrene residues during production. Even if this alkoxyalkylene group is introduced at the m-position or the o-position, the distance between the ammonium group and the benzene ring is several Å or more, so that the benzene ring and the polyethylene chain have little steric effect. Therefore, the alkoxyalkylene group having an ion exchange group may be substituted at any position on the benzene ring.

The anion exchanger according to the present invention can be produced by various production methods. For example, the following general formula (III-1) (A and B are synonymous with the above formula (I).
Y represents a functional group that can be converted into an ion exchange group. Examples thereof include halogen atoms such as chlorine, bromine, iodine, etc., or tosyl groups. ) Synthesize a precursor monomer represented by
A method of performing copolymerization with a crosslinking agent and, if necessary, a third monomer component, and then reacting with an amine to convert into an ion exchange group,

[0020]

[Chemical 6]

A method of polymerizing a monomer having a structural unit represented by the general formula (III-2) together with a crosslinking agent and the like can be mentioned. In the general formula (III-2), A, B, R _{1 to} R
₃ , D and X have the same meanings as in formula (I). X is a counterion coordinated to an ion exchange group,
For example, chloride ion, bromide ion, iodide ion,
Examples thereof include sulfate ion, nitrate ion, and hydroxyl group. When it is a divalent anion such as sulfate ion,
One counter ion is coordinated with two molecules of the repeating unit of the general formula (I).

The polymerizable monomer as the precursor represented by the general formula (III-1) can be synthesized by various methods depending on the number of methylene chains and the substituent X as described below. (1) When the alkylene chain A is a methylene chain; ω-hydroxyalkoxymethylstyrene is converted to ω-hydroxyalkoxymethylstyrene by a reaction of chloromethylstyrene and (excess) 1, ω-alkanediol (Williamson ether synthesis) under basic conditions. Can be generated. The ω-hydroxyalkoxyalkylstyrene can be replaced with halogen by a reagent described later.

Alternatively, under basic conditions, vinylbenzyl alcohol (Polymer, 1973, 14, 330) is used.
-332, Makromol. Chem. Rapid
Commun. , 7, 143 (1986)) and 1, ω-
By reacting with a dihalogenoalkane, ω-halogenoalkoxymethylstyrene can be synthesized. As dihalogenoalkane, 1,4-dichlorobutane, 1,
4-dibromobutane, 1,4-diiodobutane, 1,5
-Dichloropentane, 1,5-dibromopentane, 1,
Examples thereof include 6-dichlorohexane and 1,6-dibromohexane.

As another method for synthesizing halogenoalkoxymethylstyrene, there is a known document (Bull. Chem. So.
c. Jpn. , 1976, 49, 2500) (method in which chloromethylstyrene is reacted with tetrahydrofuran in the presence of mercury chloride) is also known. However, this reaction has a very low yield. General formula (III −
The polymerizable monomer represented by 1) is prepared by synthesizing vinylbenzyl alcohol using halogenoethylchloromethylbenzene as a raw material and then reacting it with 1, ω-dihalogenoalkane to give the polymerizable monomer 2 It can be manufactured in stages. Examples of the benzene derivative that can be the starting material include α-chloroethylchloromethylbenzene and β-chloroethylchloromethylbenzene.
Many synthetic methods of chloroethyl chloromethylbenzene have been reported.

These benzene derivatives are respectively o,
There are three types of nuclear isomers, m and p, but any nuclear isomer may be used. In addition, although there are two types of positional isomers in the chloroethyl group, any of the α-position and β-positional isomers may be present. However, in order to make the dehydrochlorination reaction efficient (the difference in reactivity with the chloromethyl group is remarkable), the β-chloroethyl group is preferable.

(2) When the alkylene chain A is an ethylene chain: First, 2-hydroxyethylstyrene is synthesized as follows. After preparing a Grignard reagent of halogenostyrene, a method of reacting with ethylene oxide (Industrial Chemistry Journal, 64, 932 (1961)), after preparing a Grignard reagent of chloromethylstyrene,
Method of reacting trioxane or paraformaldehyde, or G of 2-hydroxyethyl bromobenzene
2-Hydroxyethylstyrene can be synthesized by a method such as preparing a lignard reagent and reacting it with vinyl bromide. The obtained 2-hydroxyethylstyrene can be reacted with 1, ω-dihalogenoalkane to obtain ω-halogenoalkoxyethylstyrene.

(3) When the alkylene chain A is a trimethylene chain or a tetramethylene chain; first, a Grignard reagent of halogenostyrene is prepared and then reacted with oxetane / tetrahydrofuran to synthesize an ω-hydroxyalkylstyrene, and then a basic By reacting with 1, ω-dihalogenoalkane under the conditions, a ω-halogenoalkoxyalkylstyrene having a halogen at the terminal can be synthesized. Alternatively, halogenostyrene Grignard reagent has 1, ω-
After reacting a dihalogenoalkane to synthesize a ω-halogenoalkylstyrene having a halogen at the terminal, 1, ω
-A dihydroxyalkane can be reacted to synthesize ω-hydroxyalkoxyalkylstyrene having a hydroxyl group at the terminal.

With respect to the ω-hydroxyalkoxyalkylstyrene having a hydroxyl group at the terminal, the hydroxyl group at the terminal can be converted into a halogen atom by a halogenating reagent having a halogen atom. In the case of chlorination as these reagents, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosgene, triphosgene can be used. In the case of bromination, bromine-Ph
Bromine can be replaced by reaction with ₃ P, thionyl bromide, phosphorus tribromide. Toluenesulfonic acid can be used when converting the terminal hydroxyl group to a tosyl group.

Further, the monomer component represented by the general formula (III-2) can be synthesized by aminating the monomer represented by the general formula (III-1) with alkylamines. Of course, the benzene ring D of the formula (III-1) may be substituted with an alkyl group or halogen. Specifically, by reacting an ω-halogenoalkoxyalkylstyrene having a halogen atom with ammonia and a primary to tertiary amine, an ω- (alkyl) aminoalkoxyalkylstyrene having a primary to tertiary amine at the terminal is obtained. Alternatively, a vinylbenzyloxyalkyltrialkylammonium salt having an ammonium group at the terminal can be obtained. In this case, the amine used is preferably an amine whose alkyl group has 4 or less carbon atoms, and examples thereof include ammonia, dimethylamine, trimethylamine and triethylamine. In addition, alkanolamines such as dimethylhydroxyethylamine can be used.

The above are the general formulas (III-1) and (III
The method of using the polymerizable monomer of -2) is as follows.
The ion exchanger of the present invention having the structural unit of can be produced. The chloroalkylated polystyrene or its cross-linked polymer obtained according to the known technique has 1, ω-
By subjecting dihydroxyalkane to an etherification reaction under basic conditions, a polymer having a ω-hydroxyalkoxyalkylene chain is obtained. There is a method of converting a hydroxyl group into a halogen atom and then converting it into an ion exchange group by reacting with the above-mentioned amine.

Further, a hydroxyalkylated polystyrene or a crosslinked copolymer thereof obtained according to a known technique is reacted with 1, ω-dihalogenoalkane under a basic condition to give a ω-halogenoalkoxyalkylene having a halogen atom. There is a method of obtaining a polymer having a chain and reacting it with the above-mentioned amine to convert it into an ion exchange group. In these methods, in imparting water insolubility to the ion exchanger, unsaturated hydrocarbon-containing cross-linking which will be described later when polymerizing a styrene derivative such as styrene or chloroalkylstyrene, hydroxyalkylstyrene as a precursor polymerizable monomer A monomer may be used, or the intermediate in the above nuclear reaction step may be crosslinked by a known method. It can also be crosslinked by alkylene chains, for example by the Friedel-Crafts reaction. Further, when the chloroalkylated polystyrene is reacted with 1, ω-dihydroxyalkane, it can be crosslinked by reacting both hydroxyl groups to form a diether. Similarly, when the hydroxyalkylated polystyrene is reacted with 1, ω-dihalogenoalkane, both halogeno groups may be reacted to dietherify to crosslink.

The copolymer component in the anion exchanger of the present invention is an unsaturated hydrocarbon-containing crosslinkable monomer, and a third unsaturated hydrocarbon-containing monomer which can be used if necessary. This unsaturated hydrocarbon-containing crosslinkable monomer is necessary for producing a water-insoluble crosslinked copolymer. This monomer includes divinylbenzene, polyvinylbenzene, alkyldivinylbenzene, dialkyldivinylbenzene, ethylene glycol (poly) (meth)
Acrylate, polyethylene glycol di (meth) acrylate, (poly) ethylenebis (meth) acrylamide and the like can be mentioned, with preference given to divinylbenzene.

Further, a crosslinking component having an ether group, which is a by-product when a polymerizable monomer as a precursor represented by the general formula (III-1) is synthesized according to the method described above or in the examples, It is contained in the above-mentioned unsaturated hydrocarbon-containing crosslinkable monomer and can be used without purification and isolation. These components include, for example, when chloromethylstyrene is used, bisvinylbenzyl ether which is an ether compound of chloromethylstyrene and its hydrolyzate, vinylbenzyl alcohol, and 1, ω used as a raw material. -Alkanediol or 1, ω
-Diether compounds with dihalogenoalkanes. For example, when using chloromethylstyrene,
1, ω-bisvinylbenzyloxyalkane may be mentioned. If necessary, these by-produced ether crosslinking component and diether crosslinking component should be isolated as by-products when synthesizing the polymerizable monomer as the precursor represented by the general formula (III-1). Although it is also possible, it can be used without isolation within the range of the content rate shown below.

When the content of the unsaturated hydrocarbon-containing crosslinkable monomer in the anion exchanger is low, the obtained anion exchanger is a highly swelling polymer. On the other hand, when the content is high, the content of the constituent component (I) having an ion exchange group is low, and the ion exchange capacity is reduced. Therefore, the amount of the unsaturated hydrocarbon-containing crosslinkable monomer used in the production of the anion exchanger of the present invention is such that the constitutional unit derived from the unsaturated hydrocarbon-containing crosslinkable monomer in the anion exchanger is 0. 0.1% to 50 mol%, preferably 0.1.
It is used so as to be 2% to 25 mol%.

The third unsaturated hydrocarbon-containing monomer can be used in a range that does not reduce the function of the anion exchanger in the present invention. Examples of the polymerizable monomer include styrene, alkylstyrene, polyalkylstyrene, (meth) acrylic acid ester, (meth) acrylic acid and acrylonitrile. The amount of the third unsaturated hydrocarbon-containing monomer used is such that the constituent unit derived from the third unsaturated hydrocarbon-containing monomer in the anion exchanger is 0% to 50 mol%, preferably 0% to It is used so as to be 20 mol%.

The amount of the polymerizable monomer capable of deriving the structural unit of the general formula (I) is 5% to 99.9 mol% of the structural unit represented by the general formula (I) in the anion exchanger, preferably It is used so as to be 10 to 99 mol%. In this case, in order to increase the ion exchange capacity, the content of the general formula (I) is preferably as high as possible. The exchange capacity per unit weight (neutral salt exchange capacity) of the anion exchanger of the present invention varies depending on the molecular weight of the constituent element represented by the general formula (I). That is, although it varies depending on the alkylene chains A and B and the substituent R of the ion exchange group, it is generally in the range of 0.2 meq / g to 5 meq / g. (Meq / g represents a milliequivalent per dry resin weight.) More preferably, 1.5 meq / g to 4.5.
It is in the range of meq / g. The ion exchange capacity per volume depends on the degree of swelling, but is usually 0.3 meq / ml.
It is about 1.5 meq / ml.

The anion exchanger of the present invention has the general formula (I)
It is produced by polymerizing a polymerizable monomer capable of deriving the structural unit (1), a crosslinkable monomer and, if necessary, a third monomer in the presence of a polymerization initiator. As the polymerization initiator, a peroxide type polymerization initiator such as benzoyl peroxide (BPO), lauroyl peroxide, and t-butyl hydroperoxide,
Azobisisobutyronitrile (AIBN), 2,2'-
Azobis (2,4-dimethylvaleronitrile) (trade name; V-65 (Wako Pure Chemical Industries)) 2,2'-azobis (2-
Methylpropionamidine) dihydrochloride (trade name; V-
Azo-based polymerization initiators such as 50 Wako Pure Chemical Industries, water-soluble polymerization initiators) are used. The content thereof is usually 0.1% to 5% by weight with respect to all the monomers. The polymerization temperature varies depending on the half-life temperature of the polymerization initiator, the content rate, the type of monomer, etc., but is usually 40 ° C to 150 ° C, preferably 50 ° C to
Used at 100 ° C. The initiation of polymerization is 1 hour to 30 hours, preferably 1 hour to 15 hours.

In these polymerization reactions, a solvent which dissolves in each of the above-mentioned monomer components may be added, if necessary. Toluene, which is a poor solvent for these monomers,
When a non-polar organic solvent such as hexane is added and copolymerized, an anion exchanger having a porous structure is obtained.
On the other hand, when a good solvent such as tetrahydrofuran or 1,4-dioxane is added, a swelling anion exchanger is obtained. The physical structure of the produced porous exchanger varies depending on the type and amount of the solvent added, and the desired porous exchanger can be obtained by controlling these solvents. Others, for example, as a solvent, water, methanol,
A solvent such as ethanol or acetone, or a mixed solution of these solvents is used. The amount added is in the range of 0% to 100% by weight based on the total monomer components.

Polymers derived from the general formula (III-1)
Y in is an ammonium group -NR ₁R₂R₃Convert to
The method can be performed according to a known method. Y
Is a halogen atom, in the presence of a suitable solvent, a tertiary amine
Can react with the min to convert it to an ammonium group
It Similarly, when Y is a tosyl group, it is
It can be converted to an ammonium group. Ammoni above
When introducing the um group, it is derived from the general formula (III-1)
A solvent is generally added to swell the polymer.
Is. Examples of the solvent used include water and methano
Alcohol, alcohols such as ethanol, toluene, hexa
Hydrocarbons such as benzene, dichloromethane, 1,2-dichloro
Chlorine hydrocarbons such as ethane, diethyl ether, geo
Ethers such as xane and tetrahydrofuran, and other diethers
A solvent such as methylformamide or acetonitrile is used alone,
Alternatively, it is used as a mixed solution. The reaction temperature depends on the reaction
Although it depends on the formula, the type of sensitive group, the solvent, etc., it is usually 2
It is 0 ° C to 100 ° C. Represented by the general formula (III-2)
By polymerizing a polymerizable monomer with a crosslinking agent
It is also possible to obtain anion exchangers.

The monomer (III-2) has the general formula (III
It can be copolymerized with the above-mentioned crosslinkable monomer in the same manner as the polymerizable monomer represented by -1). In this case, since the monomer having the ion exchange copolymer is copolymerized with the crosslinking agent, it is not necessary to carry out the amination reaction or the like after the polymerization as described above. Then, the counterion is converted into various anion forms by a known method to obtain the anion exchanger of the present invention.

The anion exchanger of the present invention can be molded into various shapes according to known methods. Spherical anion exchangers are produced by water / oil or oil / water suspension polymerizations. It is preferable to carry out suspension polymerization using the monomer components shown above in the presence of a polymerization initiator. The average particle size of the anion exchanger in the present invention is 100 μm to
The range is 2 mm. After that, if necessary, it can be used after being subjected to suspension polymerization and pulverized into a powder form. It is also possible to mold it into various shapes such as lumps or powders, other fibers, films by solution polymerization.

The anion exchanger of the present invention has various uses. Particularly, it is preferably used for desalting water. The desalting method is performed by bringing an anion exchanger composed of a crosslinked polymer having a structural unit represented by the general formula (I) into contact with water or an aqueous solution. As a contact method, a conventional water treatment method is adopted. It can be carried out, for example, in batch, semi-batch, continuous or semi-continuous processes using fluidized beds, stirred tanks, batch tanks, cocurrent or countercurrent columns.

The contact time between the water to be treated and the anion exchanger depends on the exchange capacity of the anion exchanger and the amount of the ion exchanger used.
A wide range is selected depending on the amount of anionic substance in the water to be treated and the contact temperature. The temperature of the water to be treated is from 10 ° C to 12
It is selected from a wide range of 0 ° C., but in particular, the anion exchanger used in the method of the present invention has excellent heat resistance and easily deteriorates the conventional anion exchanger having trimethylammonium methylstyrene as a structural unit. It is stable in hot water and can exhibit its performance for a long time without deteriorating the ion exchange capacity. Therefore, the method of the present invention is particularly suitable for treating hot water at 60 ° C. or higher.

[0044]

[Production Example-1]

(Synthesis 1 of 4-bromobutoxymethylstyrene 1) 300
20 g of sodium hydroxide (0.
5 mol) and 20 ml of water were added and stirred to form a uniform solution. After the solution temperature was returned to room temperature, 13.42 g of vinylbenzyl alcohol (mixture of m-form and p-form) (0.1
mol), 32.39 g of 1,4-dibromobutane (0.
15 mol) and 3.22 g (0.01 mol) of tetrabutylammonium bromide were dissolved in 100 ml of toluene and added. This mixed solution was reacted at 40 ° C. for 6 hours while vigorously stirring. After the reaction, the solution was separated and thoroughly washed with water. Magnesium sulfate was added to this organic phase and dried, and then toluene was distilled off under reduced pressure to obtain a solution, which was DPPH (diphenylpicryl-2-hydrazyl).
Vacuum distillation in the presence (bp 125-128 ° C / 16P
a) to obtain a colorless transparent solution. The structure of 4-bromobutoxymethylstyrene was confirmed by the obtained solution having the following NMR and IR absorptions. Yield is 1
The amount was 5.0 g and the yield was 56%.

¹ H-NMR is EX-270 manufactured by JEOL Ltd.
(270 MHz, all solvents were measured by using CDCl _3. TMS standard δ; ppm. This compound is m-form and p-form.
Since it is a mixture of bodies, the binding constant cannot be calculated. ),
As the infrared absorption spectrum (IR spectrum), FT-IR 4000 manufactured by Shimadzu Corporation was used. (In (), b
r. Has a wide line width. Is a sharp Str. Is a large absorption med. Indicates moderate absorption. )

¹ H-NMR; 7.15-7.36 (m:
Aromatic hydrogen), 6.61-6.73 (m: α of vinyl group)
Position hydrogen), 5.67-5.76 (m: hydrogen at β position of vinyl group), 5.17-5.23 (m: hydrogen at β position of vinyl group), 4.42 and 4.41 (s: (Benzylic methylene chain), 3.33-3.45 (m: α- and δ-methylene chains of Br), 1.85-1.96 (m: β-methylene chain of Br), 1. 64-1.74 (m: methylene chain at γ position of Br).

IR spectrum (NaCl method) 2950
(Sh.), 2860 (sh.), 1630 (s
h. ), 1440 (med.), 1360 (me)
d. ), 1250 (med.), 1110 (st.
r. ), 990 (str.), 910 (str.), 8
30 (med.), 800 (med.), 720 (me
d. ).

[Production Example-2] (Synthesis 2 of 4-bromobutoxymethylstyrene 2) 145 g (3.63) of sodium hydroxide was placed in a 2 L 4-necked flask.
mol) and 140 g of demineralized water were added and the solution was stirred to form a uniform solution. After the solution was brought to room temperature, it was placed in a 4-necked flask containing 608.2 g (6.75 mol) of 1,4-butanediol, and chloromethylstyrene (hereinafter abbreviated as CMS, m).
Mixture of body and p-body) 387.6 g (2.54 mo)
l) was dropped using a dropping funnel. The solution was reacted at 60 ° C. for 6 hours with vigorous stirring. After the reaction, the organic phase was separated and washed thoroughly with water. The obtained organic matter was subjected to silica gel column chromatography (Wako Gel C-20.
Purified in 0). First, the mixture was developed with n-hexane (n-Hex) to remove the remaining CMS, and further remove by-produced 1,4-bisvinylbenzyloxybutane.
Further, it was developed with an eluent of n-Hex: THF = 85: 15 to obtain the target product hydroxybutoxymethylstyrene. Alternatively, vacuum distillation in the presence of DPPH (bp 15
A colorless transparent liquid was obtained at 6 ° C./40 Pa). The yield of 4-hydroxybutoxymethylstyrene was 413 g, and the yield was 79%.

¹ H-NMR; 7.20-7.39 (m:
Aromatic hydrogen), 6.64-6.76 (m: α of vinyl group)
Hydrogen), 5.69-5.78 (m: hydrogen at β position of vinyl group), 5.20-5.26 (m: hydrogen at β position of vinyl group), 4.49 and 4.48 (s: Methylene hydrogen at benzyl position), 3.60-3.63 (m: methylene hydrogen at α position of OH group), 3.47-3.58 (m: methylene hydrogen at δ position of OH group), 2.57 (S: broad, hydrogen of OH group), 1.66-1.73 (m: methylene hydrogen at β-position and γ-position of OH group).

¹³ C-NMR; 138.6, 137.9,
137.8, 170.0, 136.8, 136.6 (above, quaternary carbon of benzene ring), 128.6, 128.0,
127.2, 126.3, 125.6 (above, tertiary carbon of benzene ring), 114.0, 113.8 (above, carbon at vinyl group β-position), 72.9 (carbon at benzyl position), 7
2.7 (benzylic carbon), 70.4, 70.3 (B
r methylene carbon at δ position), 62.4 (methylene carbon at α position of OH group), 29.9, 29.8 (methylene carbon at γ position of OH group), 26.5, 26.4 (OH Methylene carbon at the β-position of the group)

IR spectrum (NaCl method) 3400
(Br.), 2950 (sh.), 2880 (s)
h. ), 1630 (sh.), 1480 (med.),
1450 (med.), 1410 (med.), 136
0 (med.), 1090 (br.str.), 106
5 (br.str.), 990 (med.), 910.
(Med.), 800 (med.), 715 (me
d. ).

26 g (0.126 mol) of the obtained 4-hydroxybutoxymethylstyrene was placed in a 300 ml four-necked flask, 80 ml of benzene was added, and 38.8 g (0.148 mol) of triphenylphosphine was added and dissolved. Bromine 23.9g (0.150mol)
Was added and reacted at 80 ° C. for 6 hours. After the reaction, the reaction solution was poured into water and extracted with methylene chloride. After magnesium sulfate was added to this solution and dried, the solvent was distilled off under reduced pressure, and the mixture was subjected to vacuum distillation (bp 13) in the presence of DPPH.
0 to 135 ° C./50 Pa) to obtain a colorless transparent liquid. The structure was confirmed by NMR. The yield of 4-bromobutoxymethylstyrene was 67%.

[Production Example-3] (Synthesis of 3-bromopropoxymethylstyrene) 100
80 g sodium hydroxide in a 0 ml 4-necked flask
(2.0 mol), 1,3-propanediol 500 g
(6.5 mol), charged with 1.5 g of hydroquinone 8
The reaction was carried out at 0 ° C for 2 hours. Subsequently, 250 g (1.5 mo of chloromethylstyrene (mixture of m-form and p-form))
1) was added dropwise in 30 minutes. After further reacting this mixed solution, it was cooled to room temperature in a water bath and brine (20 wt.
%) 300 ml. The organic phase was separated and the aqueous phase was extracted with toluene. The organic phase and toluene were combined, magnesium sulfate was added and dried, and then toluene was distilled off under reduced pressure to obtain a solution, and DPPH (diphenylpicryl-2-
Hydrazyl) in the presence of vacuum distillation (bp 101-3 ° C /
56 Pa) to obtain the desired 3-hydroxypropoxymethylstyrene. The yield was 60%.

192 g (1.0 mol) of the obtained 3-hydroxypropoxymethylstyrene and 55 ml of dehydrated and purified pyridine were charged into a 300 ml four-necked flask, and 108 g of phosphorus tribromide (0 0.4 mol) was added dropwise. After the dropping is completed,
It was stirred at room temperature for 15 h. The reaction mixture is brine (20 wt
%) 250 ml and extracted with toluene. The organic phase was washed with water-8% aqueous sodium hydrogen carbonate solution, added with magnesium sulfate and dried, and then toluene was distilled off under reduced pressure to obtain a solution, which was vacuum distilled in the presence of DPPH (bp 9
0-91 ° C./45 Pa) to obtain the desired 3-bromopropoxymethylstyrene. The yield was 35%. The obtained solution was confirmed by ¹ H-NMR and IR spectrum.

¹ H-NMR; 7.18-7.40 (m:
Aromatic hydrogen), 6.64-6.76 (m: α of vinyl group)
Position hydrogen), 5.70-5.79 (m: β-position hydrogen of vinyl group), 5.20-5.28 (m: β-position hydrogen of vinyl group), 4.50 and 4.49 (s: Benzyl methylene hydrogen), 3.48-3.62 (m: methylene hydrogen adjacent to ether oxygen and m-hydrogen adjacent α position of terminal Br), 2.06-2.16 (m: β position of Br). Methylene hydrogen).

IR spectrum (NaCl method) 2950
(Sh.), 2850 (sh.), 1440 (we
k. ), 1360 (med.), 1250 (me)
d. ), 1110 (str.), 990 (med.),
910 (str.), 800 (sh.), 720 (me
d. ).

[Production Example-4] (Synthesis of 5-bromopentoxymethylstyrene) 57 g of sodium hydroxide was placed in a 1 L 4-necked flask under ice cooling.
(1.425 mol) and 57 ml of demineralized water were added, and 1,5
-98.33 g of dibromopentane (0.428 mo
l), tetrabutylammonium bromide 9.19 g
A solution of (0.0285 mol) in 285 ml of toluene was added. The solution was set at 50 ° C., and 38.25 g (0.285 g) of vinylbenzyl alcohol (mixture of m-form and p-form)
70 ml of a toluene solution containing 30 mg of DPPH and DPPH was added dropwise over 1 hour. Most of the raw material disappeared during the dropping. The mixture was reacted at 60 ° C. for 8 hours with vigorous stirring. After the reaction, the organic phase was separated and washed thoroughly with water. After adding magnesium sulfate to this organic phase and drying, toluene was distilled off under reduced pressure, and the resulting mixture was mixed with DPPH.
Vacuum distillation in the presence (bp 107-108 ° C / 40P
After a), a colorless transparent liquid was obtained. The resulting solution is N
The structure was confirmed by MR. The yield of 5-bromopentoxymethylstyrene was 40.8 g, and the yield was 51%.

¹ H-NMR; 7.36-7.40 (m:
Aromatic hydrogen), 7.22-7.31 (m: aromatic hydrogen), 6.65-6.76 (m: α-position hydrogen of vinyl group), 5.70-5.78 (m: vinyl group) Β-position hydrogen), 5.20-5.26 (m: β-position hydrogen of vinyl group), 4.48 and 4.47 (s: methylene hydrogen at benzyl position), 3.44-3.48 (m Is a methylene hydrogen at the α and ε positions of Br), 3.36-3.41 (m: methylene hydrogen at the α position of oxygen), 1.80-1.91 (m: β of oxygen)
Position methylene hydrogen), 1.59-1.68 (m: Br methylene hydrogen at β position), 1.47-1.54 (m: Br
Methylene hydrogen at the γ position).

IR spectrum (NaCl method) 2940
(Sh.), 2860 (sh.), 1630 (s
h. ), 1455 (med.), 1360 (st)
r. ), 1245 (med.), 1105 (st
r. ), 990 (med.), 910 (str.), 8
30 (med.), 800 (med.), 715 (me
d. ), 645 (med.), 560 (med.).

[Production Example-5] (Synthesis of 6-bromohexoxymethylstyrene) In a 1 L 4-necked flask equipped with a cooling tube and an isobaric dropping funnel,
Under ice cooling, 100 g (2.5 mol) of sodium hydroxide and 100 ml of demineralized water were added to make a homogeneous solution. The solution temperature was returned to room temperature, and 331 g (1.3 g of 1,6-dibromohexane) was added.
6 mol), tetra-n-butylammonium bromide 16.2 g (50.2 mol) of toluene 500 ml
The solution was added. The solution was set at 50 ° C., and 49.7 g (3 parts of a mixture of vinylbenzyl alcohol (m-form and p-form)).
66 mmol), DPPH 50 mg THF solution 100
ml was added dropwise over 90 minutes. The reaction was carried out at 55 ° C. for 5 hours with vigorous stirring so as to obtain a suspended state. After the reaction
The organic phase was separated and washed thoroughly with water. The mixture obtained by distilling toluene off under reduced pressure was subjected to vacuum distillation in the presence of DPPH (b.
p. At 88 to 92 ° C./200 Pa), 1,6-dibromohexane was removed. Then, it refine | purified using the silica gel column (Wako gel C-200) chromatography. 6-Bromohexoxymethylstyrene was a pale yellow transparent viscous solution. ^The structure was confirmed by ¹ H-NMR. The yield of 6-bromohexoxymethylstyrene was 70%.

¹ H-NMR; 7.20-7.41 (m:
Aromatic hydrogen), 6.64-6.76 (m: α of vinyl group)
Position hydrogen), 5.70-5.79 (m: β-position hydrogen of vinyl group), 5.20-5.27 (m: β-position hydrogen of vinyl group), 4.48 and 4.47 (s: Methylene hydrogen at benzyl position), 3.41 to 3.47 (m: methylene hydrogen adjacent to ether oxygen), 3.34 to 3.41 (m: terminal B)
r adjacent methylene hydrogens), 1.82-1.92 (b
r. m: methylene hydrogen at position ε of Br), 1.57-1.
65 (br.m: methylene hydrogen at β-position of Br), 1.3
6-1.47 (br.m: methylene hydrogen at γ position and δ position of Br).

IR spectrum (KBr method); 2950
(Sh.), 2850 (sh.), 1440 (we
k), 1360 (med.), 1250 (med.),
1110 (str.), 990 (med.), 910
(Str.), 800 (sh.), 720 (me
d. ).

Example 1 A 500 ml four-necked flask equipped with a nitrogen gas inlet tube and a cooling tube was charged with 200 m of demineralized water.
l, add 2% polyvinyl alcohol aqueous solution 50 ml,
Nitrogen was introduced to remove dissolved oxygen. On the other hand, 4-bromobutoxymethylstyrene 46.4 g, divinylbenzene 1.72 g (for industrial use; purity 56%), and AIBN0.
A monomer phase having 4 g dissolved therein was prepared, and dissolved oxygen was removed in the same manner as the aqueous phase. Put the monomer solution in the flask and
Stirred at 0 rpm to form monomer droplets. After stirring at room temperature for 30 minutes, the temperature was raised to 70 ° C, and the mixture was stirred at 70 ° C for 18 hours. After the polymerization, the polymer was taken out and the resin was washed with water and then with methanol three times. The polymerization yield was 93%, and a light yellow transparent spherical resin having a charge crosslinking degree of 4 mol% was obtained.

The above resin was placed in a 500 ml four-necked flask equipped with a cooling tube, and 1,4-dioxane (500 ml) was added.
Was added and stirred at room temperature. To this solution, 200 ml of a 30% trimethylamine aqueous solution was added, and the reaction was carried out at 50 ° C. for 10 hours to introduce a trimethylammonium group. After the reaction, the polymer was taken out and thoroughly washed with water. In order to convert the counter ion of the anion exchange resin from bromide ion to chloride ion (Cl type), a 4 wt% sodium chloride aqueous solution was passed in an amount 10 times the amount of the resin. The following performances of the Cl type resin were measured. The average particle size is 750 μm
Met.

[0065]

[Table 1] Neutral salt decomposition capacity 3.42 meq / g Neutral salt decomposition capacity 0.832 meq / ml Water content 57.0% Swelling degree 4.11 ml / g

The IR spectrum of the anion exchange resin obtained in Example-1 was as follows. (KBr method) (counterion X is Cl type) 3450
(Br.), 2950 (sh.), 2870 (s)
h. ), 1640 (br.), 1480 (str.),
1360 (med.), 1110 (str.), 970
(Med.), 910 (med.), 800 (me
d. ). (KBr method) (counterion X is OH type) 3400
(Br.), 2950 (sh.), 2870 (s)
h. ), 1650 (br.), 1480 (str.),
1450 (str.), 1370 (med.), 109
0 (str.), 970 (med.), 910 (me
d. ), 790 (med.).

[Example-2] The reaction was performed in the same manner as in Example-1 except that 44.7 g of 4-bromobutoxymethylstyrene and 2.60 g of divinylbenzene (for industrial use) were used, and the degree of crosslinking was 6 mol. %, An anion exchange resin having an average particle diameter of 730 μm was obtained. The polymerization yield was 91%.

[0068]

[Table 2] Neutral salt decomposition capacity 3.21 meq / g Neutral salt decomposition capacity 0.919 meq / ml Moisture content 51.0% Swelling degree 3.49 ml / g

Example 3 The reaction was performed in the same manner as in Example 1 except that 42.9 g of 4-bromobutoxymethylstyrene and 3.46 g of divinylbenzene (for industrial use) were used, and the degree of crosslinking was 8 mol. %, And an anion exchange resin having an average particle diameter of 750 μm was obtained. The polymerization yield was 93%.

[0070]

[Table 3] Neutral salt decomposition capacity 3.32 meq / g Neutral salt decomposition capacity 1.02 meq / ml Moisture content 44.5% Swelling degree 3.25 ml / g

[Example-4] A chloromethylstyrene-divinylbenzene copolymer was prepared according to the method described in the literature (Polymer, 1).
4, July 1973 330-332),
Polymerization was carried out using a monomer solution prepared so that the divinylbenzene content was 4 mol%, and the polymerization was performed. Further, according to the above-mentioned literature, after converting the chloromethyl group into an acetic acid ester derivative, it was hydrolyzed with a sodium hydroxide solution to obtain a vinylbenzyl alcohol-divinylbenzene copolymer.

In a 1-liter 4-necked flask, 50 g of the above copolymer, 500 ml of 1,4-dioxane, and 1,4-
200 g (0.926 mol) of dibromobutane was added,
The polymer was swollen by stirring at 50 ° C. for 30 minutes. Into this, sodium methoxide 31 g (0.574 mol)
Was added and reacted at 70 ° C. for 10 hours. After the reaction, the polymer was taken out, thoroughly washed with methanol, and then washed with water.

The above resin and 500 ml of methanol were added to a 500 ml four-necked flask and stirred at room temperature. To this solution, 200 ml of a 30% trimethylamine aqueous solution was added, and an amination reaction was carried out at 50 ° C. for 10 hours. After the reaction
The polymer was taken out and washed thoroughly with water. In order to convert the counter ion into Cl form, 10 times amount of 4% aqueous sodium chloride solution was passed through with respect to the amount of resin. The average particle size of the obtained resin was 560 μm.

[0074]

[Table 4] Neutral salt decomposition capacity 2.32 meq / g Neutral salt decomposition capacity 0.71 meq / ml Moisture content 44.5% Swelling degree 3.25 ml / g

Example-5 46.4 g of 5-bromopentoxymethylstyrene, divinylbenzene (for industrial use)
Was reacted in the same manner as in Example 1 except that the amount was 1.64 g to obtain an anion exchange resin having a charged crosslinking degree of 4 mol% and an average particle diameter of 700 μm. The polymerization yield was 90%.

[0076]

[Table 5] Neutral salt decomposition capacity 2.61 meq / g Neutral salt decomposition capacity 0.74 meq / ml Moisture content 51.5% Swelling degree 3.54 ml / g

Example 6 44.7 g of 5-bromopentoxymethylstyrene, divinylbenzene (for industrial use)
Was reacted in the same manner as in Example 1 except that the amount was 2.47 g to obtain an anion exchange resin having a charged crosslinking degree of 6 mol% and an average particle diameter of 720 μm. The polymerization yield was 91%.

[0078]

[Table 6] Neutral salt decomposition capacity 3.00 meq / g Neutral salt decomposition capacity 0.93 meq / ml Moisture content 51.7% Swelling degree 3.25 ml / g

Example-7 46.4 g of 6-bromohexoxymethylstyrene and divinylbenzene (for industrial use)
Was reacted in the same manner as in Example 1 except that the amount was 1.56 g to obtain an anion exchange resin having a charged crosslinking degree of 4 mol% and an average particle diameter of 680 μm. The polymerization yield was 89%.

[0080]

Table 7 Neutral salt decomposition capacity 3.00 meq / g Neutral salt decomposition capacity 0.87 meq / ml Moisture content 57.5% Swelling degree 3.47 ml / g

Example-8 A chloromethylstyrene-divinylbenzene copolymer was produced using a monomer solution prepared so that the divinylbenzene content was 3.2 mol%. The yield of the obtained copolymer was 83%. In addition, dimethylformamide (DMF)
Degree of swelling against 6.90 ml / g (dry copolymer)
Met.

In a 300 ml four-necked flask, 20 ml of dimethylformamide and 17.4-butanediol.
64 g (0.195 mol) and 60% pure sodium hydride 2.61 g (0.065 mol) were added, and the mixture was stirred at room temperature for 1 hour, and then 10 g of the above copolymer swollen with 80 ml of dimethylformamide was added. The mixture was reacted at 60 ° C. for 25 hours under a stream of dry nitrogen. After the reaction, the hydroxybutoxylated copolymer was taken out, washed with water, thoroughly washed with acetone, washed again with water, and vacuum dried.

In a 300 ml four-necked flask, 5 g of the hydroxybutoxylated copolymer was swollen with 30 ml of dimethylformamide at room temperature, and then 5.75 g of pyridine was added.
Was added and ice-cooled. 8.70 g (0.073 mol) of thionyl chloride was added dropwise over 30 minutes while stirring under ice cooling, and then reacted at 70 ° C. for 5 hours. After the reaction, the copolymer having chlorinated hydroxyl groups was taken out, washed with water, thoroughly washed with acetone, and further washed with water.

5 g of the chlorinated copolymer was placed in a stainless steel closed container, 25 ml of a 30% aqueous solution of trimethylamine and 10 ml of methanol were added, and the mixture was heated to 80 ° C. under pressure.
The amination reaction was carried out for 6 hours. After the reaction, the polymer was taken out and thoroughly washed with water. In order to convert the counter ion to the Cl form, a 10-fold amount of 4% aqueous sodium chloride solution was passed through the polymer. The performance of the obtained resin is as follows.

[0085]

Table 8 Neutral salt decomposition capacity 2.46 meq / g Neutral salt decomposition capacity 0.58 meq / ml Water content 63.3%

Comparative Example A styrene-based cross-linked copolymer having a trimethylaminoalkylene chain or a trimethylaminopropoxy chain as an ion exchange group was produced. [Comparative Example-1] (4 mol% crosslinked type I gel-type anion exchange resin having a methylene chain); Example-except that chloromethylstyrene was used in place of 4-bromobutoxymethylstyrene in Example-1. The same procedure as 1 was performed.

[Comparative Example-2] (4 mol% crosslinked type I gel-type anion exchange resin having an ethylene chain); 2-bromoethylstyrene (known method) in Example 1 instead of 4-bromobutoxymethylstyrene. Was synthesized using bromoethylbenzene as a raw material in accordance with the procedure of Example 1.).

[Comparative Example-3] (4 mol% crosslinked type I anion exchange resin having a butylene chain); except that 4-bromobutylstyrene was used in place of 4-bromobutoxymethylstyrene in Example-1. , Done exactly the same.

[Comparative Example-4] (6 mol% crosslinked I-type anion exchange resin having a butylene chain); except that 4-bromobutylstyrene was used in place of 4-bromobutoxymethylstyrene in Example-2. , Done exactly the same.

[Comparative Example-5] (4 mol% crosslinked type I anion exchange resin having a heptylene chain); except that 7-bromoheptylstyrene was used in place of 4-bromobutoxymethylstyrene in Example-1. , Done exactly the same.

[Comparative Example-6] 46.4 g of 3-bromopropoxymethylstyrene and divinylbenzene (for industrial use)
Was reacted in the same manner as in Example 1 except that the amount was 1.83 g to obtain an anion exchange resin having a charged crosslinking degree of 4 mol% and an average particle diameter of 610 μm. The polymerization yield was 86%.

[0092]

[Table 9] Neutral salt decomposition capacity 3.38 meq / g Neutral salt decomposition capacity 0.74 meq / ml Moisture content 60.8% Swelling degree 4.57 ml / g

Comparative Example-7 44.7 g of 3-bromopropoxymethylstyrene, divinylbenzene (for industrial use)
Was reacted in the same manner as in Example-2 except that the amount was 2.74 g to obtain an anion exchange resin having a charged crosslinking degree of 6 mol% and an average particle diameter of 650 μm. The polymerization yield was 83%.

[0094]

Table 10 Neutral salt decomposition capacity 3.33 meq / g Neutral salt decomposition capacity 0.88 meq / ml Moisture content 52.6% Swelling degree 3.80 ml / g

[Test Example-1] (Heat resistance test of anion exchange resin) Examples-1, 2, 5 and 5
The anion exchanger produced in 7 and the anion exchange resins of Comparative Examples 1 to 7 were used. A 10-fold amount of a 4% sodium chloride aqueous solution was passed through the anion exchange resin to change the counter ion to Cl type. Weigh 50 ml of these resins, 500 m
l of 2N-sodium hydroxide aqueous solution was passed through to regenerate into OH form, and the volume was measured.

The obtained resin was put into a glass autoclave tube, and demineralized water in an amount 0.8 times the volume of the OH type resin was added. In order to remove the dissolved oxygen in the tube, nitrogen gas was passed through for 1 hour while being heated to 50 ° C. Immerse this autoclave tube in an oil bath and keep it at 100 ° C for 30 days or 9
After standing for 0 days, take out the resin and remove 500 ml of 2N.
-Sodium hydroxide aqueous solution was passed through to regenerate into OH form.
The volume of the resin after regeneration was measured. Further, a 5-fold amount of 4% sodium chloride aqueous solution was passed through to convert the counter ion into Cl form. At this time, the volume of the resin and the neutral salt decomposition capacity of the resin were measured, and the residual ratio of ion-exchange groups was calculated. The heat resistance test results are shown in Table 1.

[0097]

[Table 11]

(1) The ion exchange groups of the anion exchange resin are all trimethylammonium groups. (2) Spacer: A functional group that bonds the anion exchange group and the benzene ring. (3) Residual rate: The residual rate is expressed by the following formula. Residual rate (%) = (Neutral salt decomposition capacity meq / after heat resistance test)
ml × Cl type resin volume after the test) / (neutral salt decomposition capacity meq / ml before heat resistance test × Cl type resin volume before the test) × 100 From Table 1, the anion exchanger of the present invention is heat resistant. It can be seen that it has excellent properties.

Similarly, the heat resistance at 120 ° C. and 140 ° C. was tested. The results are shown in Table-2 and Table-3, respectively.

[0100]

[Table 12]

[0101]

[Table 13]

That is, each of the anion exchangers of the present invention has excellent heat resistance as compared with the resin of Comparative Example 1 which is the most widely used type I gel resin at present. Further, even when compared with the resin of Comparative Example 1-5 having an alkylene group as a spacer, it is clear that the resin of the present invention has excellent heat resistance in consideration of the degree of crosslinking and the carbon number of the spacer. Further, the resin of the present invention has much higher heat resistance than the resins of Comparative Examples 6 and 7 having spacers having a similar structure.

Test Example 2 (Desalination Test) A test was performed using the crosslinked anion exchanger produced in Example 2. 10 in the anion exchanger of Example 2
Double the volume of 4% sodium chloride solution to pass counterion C
After forming the l-shape, 450 ml was weighed. This was packed in a cylindrical column having an inner diameter of 30 mm and a length of 1000 mm,
1350 ml of 1N-sodium hydroxide aqueous solution was passed through. Then, 2700 ml of demineralized water was passed through for 50 minutes, and an aqueous solution having the following composition was added to the regenerated cation exchange resin 100.
After contacting with 0 ml, the solution was passed and the electrical conductivity was measured at the column outlet. Test water Sodium ion 210ppm Calcium ion 140ppm Silica 87.5ppm Sulfuric acid ion 210ppm Chlorine ion 140ppm (each concentration is calculated as calcium carbonate) Result Electric conductivity of treated water is 0.3 μS /
cm, and 103 liters of test water could be desalted per 1000 ml of the ion exchanger of Example 2 until reaching 1.0 μS / cm.

[0104]

INDUSTRIAL APPLICABILITY The anion exchanger of the present invention is extremely excellent in heat resistance and can be used in a wide range of temperatures. The anion exchanger of the present invention is used as an anion exchange resin, anion exchange fiber, anion exchange membrane for various uses, and further for an anion exchanger for humidifiers, pharmaceuticals, for the production of lotion, an anion exchanger gas adsorbent, a low amine odor anion. Exchange,
It can be used as a desalting resin or the like.

Claims (8)

[Claims] 1. A crosslinkable anion exchanger having the following general formula (I): (In the general formula (I), A represents a linear or branched alkylene group having 1 to 4 carbon atoms, B represents a linear alkylene group having 4 to 8 carbon atoms, R ₁ , R ₂ , R ₃ is an alkyl group having 1 to 4 carbon atoms, which may be the same or different,
Alternatively, it represents an alkanol group, X represents a counter ion coordinated to an ammonium group, and the benzene ring D may be substituted with an alkyl group or a halogen atom. An anion exchanger comprising a structural unit represented by the formula (1) and a structural unit derived from an unsaturated hydrocarbon group-containing crosslinkable monomer. 2. The constitutional unit represented by the general formula (I) is 5 to
99.9 mol%, 50 to 0.1 mol% of a structural unit derived from an unsaturated hydrocarbon group-containing crosslinkable monomer, and 0 to an unsaturated hydrocarbon group-containing monomer different from the above structural unit. 5
The anion exchanger according to claim 1, which contains 0 mol%. 3. A crosslinkable anion exchanger having the following general formula (II): (In the general formula (II), A represents a linear or branched alkylene group having 1 to 4 carbon atoms, B represents a linear alkylene group having 4 to 8 carbon atoms, R ₁ , R ₂ , R ₃ is an alkyl group having 1 to 4 carbon atoms, which may be the same or different,
Alternatively, it represents an alkanol group, X represents a counter ion coordinated to an ammonium group, and the benzene ring D may be substituted with an alkyl group or a halogen atom. -CH
(Z) -CH ₂ - represents a third polymerizable monomer residue. )
And the structural unit Q is 5 to 99.9 mol%, the structural unit P is 50 to 0.1 mol%, and the structural unit R is 0 to 5
Anion exchanger characterized in that it is 0 mol% (based on the crosslinkable anion exchanger). 4. In the structural units represented by the general formulas (I) and (II), A is a linear alkylene group having 1 to 2 carbon atoms and B is an alkylene group having 4 to 6 carbon atoms. The anion exchanger according to any one of claims 1 to 3, which is characterized. 5. In the structural units represented by the general formulas (I) and (II), A is a methylene group, B is an alkylene group having 4 to 6 carbon atoms, and R ₁ , R ₂ and R ₃ are It is a methyl group, The anion exchanger of Claim 4 characterized by the above-mentioned. 6. The anion exchanger according to claim 5, wherein A is a methylene group and B is an n-butylene group in the structural units represented by the general formulas (I) and (II). . 7. The anion exchanger according to claim 4, wherein A is an ethylene group and B is an n-butylene group in the structural units represented by the general formulas (I) and (II). . 8. A method for desalinating water, which comprises contacting the anion exchanger according to claim 1 with water or an aqueous solution to be desalted.