JPH0160296B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a porous anion exchange resin and a method for producing the same. Specifically, the present invention relates to a porous anion exchange resin having a crosslinked polyvinyl alcohol skeleton and a method for producing the same. The anion exchange resins currently widely used are
Since it has a crosslinked polyethylene skeleton, it exhibits specific interactions with compounds having aromatic rings. Crosslinked polyethyleneimine is known as an anion exchange resin without an aromatic ring, but this resin is a polyfunctional type containing from primary amino groups to quaternary ammonium groups. Also, an anion exchange resin having a polyvinyl alcohol skeleton has been proposed, but this resin is a gel type resin due to its manufacturing method. The present inventors have studied porous anion exchange resins having a polyvinyl alcohol skeleton because porous resins having physical pores have many advantages over gel-type resins. The invention has been completed. In the porous anion exchange resin according to the present invention, the exchange groups are substantially

[expression] or

[Formula] (In the formula, R ¹ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, R ² , R ³ and R ⁴ represent an alkyl group or a hydroxyalkyl group, and Y represents an alkylene group.) It has a structure characterized by at least one of a specific surface area of 0.5 m ² /g or more and a pore volume of 0.1 ml/g or more. In addition, the present invention provides for reacting an aminoaldehyde or its acetal with porous crosslinked polyvinyl alcohol characterized by at least one of a specific surface area of 0.5 m ² /g or more and a pore volume of 0.1 ml/g or more, or Alternatively, the present invention provides a method for producing a porous anion exchange resin by reacting haloaldehyde or its acetal and then reacting with an amine. Furthermore, the present invention involves suspension polymerization of an aqueous salt solution containing polyvinyl alcohol, a crosslinking agent, and an acetal of an aminoaldehyde or an acetal of a haloaldehyde (if an acetal of a haloaldehyde is used, then reacting with an amine) to form a porous material. A method of manufacturing an anion exchange resin is provided. To explain the present invention in detail, the porous anion exchange resin according to the present invention has a structure in which aminoaldehyde is acetal bonded to porous crosslinked polyvinyl alcohol, and its porosity is 0.5.
It is characterized by at least one of a specific surface area of m ² /g or more and a pore volume of 0.1 ml/g or more. Preferably, the porous anion exchange resin according to the invention is characterized by both a specific surface area of 0.5 m ² /g or more, in particular 5 m ² /g or more, and a pore volume of 0.1 ml/g or more. The porous anion exchange resin according to the present invention uses porous crosslinked polyvinyl alcohol as a raw material, reacts it with amino acetal, or reacts it with haloaldehyde or its acetal,
It can then be easily produced by amination with an amine. Porous crosslinked polyvinyl alcohol is produced by reacting polyvinyl alcohol and a crosslinking agent in water in which a salt is dissolved or suspended. Preferably,
An aqueous solution or aqueous suspension containing a salt, polyvinyl alcohol, and a crosslinking agent is dispersed in an oil-based dispersion medium, and a reaction is carried out in a suspended state to produce spherical crosslinked polyvinyl alcohol. As the salt, both water-soluble salts and insoluble salts can be used. As water-soluble salts, usually used are chlorides such as sodium chloride, potassium chloride, and calcium chloride, nitrates such as sodium nitrate, potassium nitrate, and calcium nitrate, sulfates such as magnesium sulfate, and phosphates such as sodium phosphate. These water-soluble salts are thought to have the effect of precipitating the polyvinyl alcohol from the reaction medium through a salting-out effect when the molecular weight of the polyvinyl alcohol reacts with the crosslinking agent. The formation of a precipitate is estimated from the fact that the reaction medium turns cloudy shortly after the start of the reaction). Therefore, it is necessary to use these water-soluble salts at a concentration sufficient to exhibit the above-mentioned salting-out effect. The concentration varies depending on the type of salt, and is preferably 5 to 12% for sodium chloride, but 20% or more for calcium chloride.
Generally speaking, salt concentrations used range from 1 to 40%. As water-insoluble salts, sulfates such as calcium nitrate, barium nitrate, and lead nitrate are usually used. The amount used is usually 5 to 70 g, preferably 20 to 60 g, per 100 g of polyvinyl alcohol aqueous solution.
It is g. These insoluble salts, unlike the water-soluble salts mentioned above, are included in the crosslinked polyvinyl alcohol during the crosslinking reaction. When these insoluble salts are then extracted from the resulting crosslinked product with an aqueous acid solution, the residue remains in the crosslinked product in the form of pores. Therefore, it is preferable to use as fine an insoluble salt as possible. Polyvinyl alcohol has a degree of polymerization of several dozen to
The saponification degree is several thousand, preferably 200 to 2000, and the degree of saponification is 50 mol or more, preferably 85 mol% or more. Polyvinyl alcohol is dissolved in water to a concentration of 2 to 30%, preferably 5 to 15%, and used for the crosslinking reaction. Examples of crosslinking agents include dialdehydes such as glyoxal, glutaraldehyde, and terephthalaldehyde; diepoxy compounds such as 1,2-3,4-diepoxybutane; bisepoxypropyl ether, ethylene glycol bisepoxypropyl ether, 1,4- Glycidyl ethers such as butanediol bisepoxypropyl ether; epihalohydrins such as epichlorohydrin and epibromohydrin; and those capable of forming a crosslinking moiety having two or more carbon atoms between polyvinyl alcohol molecules are used. The crosslinking agent is usually used in an amount of 0.01 to 0.15 mol per mol of hydroxyl group of polyvinyl alcohol. The preferred amount of the crosslinking agent used is 0.02 to 0.1 mole per mole of hydroxyl group of polyvinyl alcohol. If the amount of crosslinking agent is large, only a resin with a small exchange capacity can be obtained in the end. Moreover, when the amount of crosslinking agent is small, the degree of swelling of the resulting resin becomes large. The crosslinking reaction is preferably carried out by dissolving or suspending a salt in an aqueous polyvinyl alcohol solution, adding a crosslinking agent thereto, and suspending the mixture in an oily dispersion medium. The dispersion medium usually includes aromatic hydrocarbons and their halogen derivatives such as toluene, benzene, chlorobenzene, and dichlorobenzene; aliphatic hydrocarbons such as n-heptane, n-hexane, liquid paraffin, cyclohexane, dichloromethane, and dichloroethane; Alicyclic hydrocarbons and their halogen derivatives are used. These dispersion measures are usually used alone, but two or more types may be used in combination. The amount of the dispersion solution used is at least 2 (volume) times, preferably 3 to 6 (volume) times that of the polyvinyl alcohol aqueous solution. In addition, the dispersion medium contains dispersion stabilizers such as oil-soluble cellulose such as ethyl cellulose, cellulose acetate butyrate, and ethyl hydroxyethyl cellulose, and oil-soluble dispersion stabilizers such as gum arabic, sorbitan sesquioleate, sorbitan monooleate, and sorbitan monostearate. It is preferable to add an agent. The amount is usually 0.05~ for diversification strategies
10%, preferably 0.1-5%. The crosslinking reaction is carried out at 0°C to 100°C, preferably
It is carried out at 20°C to 80°C for 1 hour to 20 hours, preferably 2 hours to 8 hours. During the crosslinking reaction, an acid such as hydrochloric acid or nitric acid or an alkali such as sodium hydroxide or potassium hydroxide is used as necessary. The crosslinked polyvinyl alcohol thus obtained is separated from the dispersion medium by sieving. Next, it is washed with a hydrophilic organic solvent such as acetone, and then with water, and used for the next acetalization reaction. When a water-soluble salt is dissolved in an aqueous polyvinyl alcohol solution during the crosslinking reaction, the amount of crosslinked polyvinyl alcohol used for acetalization is 0.5 m ² /
It is necessary to have a specific surface area of at least 55 m ² /g, preferably at least 55 m 2 /g. This specific surface area can be easily changed by adjusting the degree of salting-out effect of the salt. When an insoluble salt is suspended in an aqueous polyvinyl alcohol solution during the crosslinking reaction, the insoluble salt may be extracted from the crosslinked polyvinyl alcohol with hydrochloric acid or the like and then subjected to the next acetalization reaction. The acetalization reaction may be carried out as is, and then insoluble salts may be removed from the acetalized product using hydrochloric acid or the like. In either case, the crosslinked polyvinyl alcohol must have a pore volume of 0.1 ml/g or more when the insoluble salt contained therein is extracted and removed. The pore volume can be easily varied by adjusting the suspension concentration of the insoluble salt. In addition, as crosslinked polyvinyl alcohol,
As long as it has a specific surface area of 0.5 m ² /g or more, preferably 5 m ² /g or more and/or a pore volume of 0.1 ml/g or more, it can be used in the following acetalization even if it is obtained by a method other than the above. Can be used for reactions. The porous crosslinked polyvinyl alcohol thus obtained is then reacted with haloaldehyde or its acetal to form a haloacetal of crosslinked polyvinyl alcohol. Examples of the haloaldehyde include chloracetaldehyde, bromoacetaldehyde, α-chloropropionaldehyde, α-bromopropionaldehyde, β-
Any haloaliphatic aldehyde represented by the general formula: can. Moreover, these haloaldehydes can also be subjected to a reaction as an acetal with methanol, ethanol, or other alcohol. The reaction between crosslinked polyvinyl alcohol and haloaldehyde or its aldehyde is carried out using an acid as a catalyst. Water is usually used as the reaction medium, but an organic solvent can also be used if desired. A mixed solvent of water and a hydrophilic organic solvent such as dioxane or dimethylformamide is generally advantageous in terms of reaction progress. When water is used as a reaction medium, the crosslinked polyvinyl alcohol shrinks and the specific surface area of the finally obtained anion exchange resin tends to decrease, but when a mixed solvent such as water and dioxane is used, the specific surface area decreases little. The reaction temperature is 40-100℃, preferably 60-90℃
C. for 2 to 30 hours, preferably 5 to 15 hours. The haloaldehyde or its acetal is usually used in an amount of 0.4 mole or more, preferably 0.9 to 3 moles, per mole of hydroxyl group in the crosslinked polyvinyl alcohol. The concentration of haloaldehyde or its acetal in the reaction medium is usually 5-60%, preferably
It is 10-40%. As the acid, in addition to mineral acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid can also be used. The acid is generally used in a reaction medium such that the concentration is 10 ^-2 normal or more, preferably 10 ^-1 to 1 normal. The haloacetalized crosslinked polyvinyl alcohol is then reacted with an amine to form an anion exchange resin. This reaction is also generally carried out using water as a solvent. Further, if a solvent that swells the haloacetalized crosslinked polyvinyl alcohol, such as dioxane or dimethylformamide, is used, the reaction tends to proceed. The reaction is carried out at 30-150°C, preferably 50-100°C for 3-30 hours, preferably 5-15
Time is done. The amines generally include primary amines such as methylamine, ethylamine, ethanolamine, and propanolamine, secondary amines such as dimethylamine, diethylamine, diethanolamine, and dipropanolamine, and trimethylamine, triethylamine, triethanolamine, and dimethylethanolamine. Although tertiary amines are used, other amines can also be used. Amine is 10% as an aqueous solution in the reaction medium
It is preferable to use the concentration above. The amount of amine to be used may be at least the equimolar amount of the halogen in the haloacetalized crosslinked polyethylene glycol, but usually 1 to 3 times (mole) is used. Instead of the above method in which porous crosslinked polyvinyl alcohol is reacted with a haloaldehyde and an amine in sequence, an anion exchange resin can also be produced in one step by reacting an amine acetal. This reaction, like haloacetalization,
This can be easily carried out using an acid as a catalyst and water as a reaction medium. As aminoacetals, 2,
2-dimethoxyethylamine, 2,2-diethoxyethylamine, N-ethyl-2,2-dimethoxyethylamine, N,N-dimethyl-2,2-dimethoxyethylamine, N-ethyl-2,2-dimethoxyethylamine, N , N-diethyl-2,
Aminoacetal having a primary to tertiary amino group such as 2-dimethoxyethylamine, N,N-dimethyl-2,2-diethoxyethylamine, or N,N,N-trimethyl-2,2-dimethoxyethylammonium, N ,N,N-triethyl-
2,2-dimethoxyethylammonium, N,
Aminoacetals having a quaternary ammonium group such as N,N-trimethyl-2,2-diethoxyethylammonium are usually used, but it is of course possible to use amine acetals other than those mentioned above. The aminoacetal is usually present in a concentration of 10% or more, preferably 20-70% in the reaction medium. The amount used is 1 hydroxyl group of cross-linked polyvinyl alcohol.
Usually 0.4 mol or more, preferably 0.9 to 0.9 mol
It is 1.8 mol. As the catalytic acid, in addition to mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid can also be used. The acid is usually in the reaction medium
It is used so that it is 10 ^-2 normal or more, preferably 10 ^-1 to 5 normal. The reaction temperature is usually 40 to 100°C, preferably 60 to 80°C, and the reaction time is usually 3 hours or more, preferably 5 to 15 hours. In addition to using porous crosslinked polyvinyl alcohol as a raw material as described above, the anion exchange resin according to the present invention is also made from porous crosslinked polyvinyl alcohol that has been converted into a haloacetal in one step by the reaction of polyvinyl alcohol, a crosslinking agent, and haloaldehyde. It can also be produced by aminating it by the method described above. In this case,
It is preferable to use a dialdehyde as a crosslinking agent and conduct the reaction under conditions similar to those for producing crosslinked polyvinyl alcohol described above. Moreover, in this case, if the above-mentioned aminoacetal is used in place of the haloaldehyde, the anion exchange resin according to the present invention can be produced in one step. Since the anion exchange resin according to the present invention is porous, the reaction rate is high and the adsorption power for various substances is high. Moreover, since the skeleton is porous crosslinked polyvinyl alcohol, a monofunctional resin having a large ion exchange capacity and a low degree of swelling can be easily obtained. Among the anion exchange resins according to the present invention, a practically preferred one has a swelling degree of 5 ml/g.
The exchange capacity under this condition is
It is 0.4meq/ml or more. Particularly suitable resins have a swelling degree of 3.5 ml/g or less and an exchange capacity in this state of 0.6 meq/ml or more. Such a resin has the advantage of low pressure loss and large exchange capacity of the column when used in a column. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In this specification, the specific surface area, pore volume, exchange capacity, and degree of swelling were measured as follows. Measurement of specific surface area and pore volume After thoroughly washing the resin treated with an aqueous caustic soda solution with water, the water is replaced with acetone, and the acetone is further replaced with toluene. This resin was dried at 30° C. for 24 hours in a vacuum dryer at 10 mmHg, and the following measurements were performed. Specific surface area: Measured using Cantersolve (manufactured by Yuasa Battery Co., Ltd.) using the BET method that utilizes nitrogen gas adsorption. Pore volume: Mercury intrusion porosimeter (Carlo
Measured by Elva Co., Ltd.). Exchange capacity, water content and swelling degree: Place the OH type resin, which has been regenerated with aqueous caustic soda solution and thoroughly washed with demineralized water, into a 10 ml measuring cylinder, and accurately weigh out 10 ml by tapping the bottom. This resin was dehydrated using a centrifuge at 350G for 5 minutes, and then its weight (a ₁ g) was accurately weighed. This resin is then placed in 200 ml of 0.2N hydrochloric acid and shaken at room temperature for 24 hours. Titrate 20 ml of this hydrochloric acid with a 0.1N aqueous solution of caustic soda. Separately, weigh out exactly 10 ml of resin in the same manner as above, dehydrate it in the same manner as above, and then calculate its weight (a ₂
g) Accurately weigh. Next, this resin was heated to 10mm at 60℃.
After drying in a Hg vacuum dryer for 24 hours, the weight (Cg) is accurately weighed again. Water content = a ₂ - C/a ₂ × 100 (%) Swelling degree = 10/C (ml/g) Exchange capacity = (h ₀ - h) × 0.1 × f × 200/20/a ₁ × C/a ₂ = (h ₀ - h) x f x a ₂ / a ₁ x C (meq/g) where h ₀ and h are the caustic soda aqueous solution required for titration before and after adding the resin, respectively. The amount (ml), f is the factor of the caustic soda aqueous solution. Example 1 A Production of porous cross-linked polyvinyl alcohol In a 300 ml round bottom flask equipped with a condenser and a stirrer, 173 ml of water, 20 g of common salt, and 26 g of calcium chloride dihydrate were dissolved, and then polyvinyl alcohol ( 20 g of Gohsenol NL-05 (trade name, manufactured by Nippon Gosei Co., Ltd.) was dispersed.
This was heated at 96°C for 30 minutes to dissolve the polyvinyl alcohol, and then cooled with 20°C water for 30 minutes. To this were added 8 ml of 25% glutaraldehyde aqueous solution and 20 ml of 1N hydrochloric acid, and after stirring quickly, the mixture was dispersed in dichloroethane as described below. 500 ml of dichloroethane was placed in a separable flask equipped with a condenser and a stirrer, and 0.2 ml of cellulose acetate butyrate (manufactured by Eastman Kodak Co., Ltd., trademark CAB381-20) was added.
Dissolve g in advance. The above-mentioned aqueous polyvinyl alcohol solution was dispersed therein. After stirring at room temperature for 1 hour, the mixture was heated at 60° C. for 3.5 hours to carry out a crosslinking reaction. After cooling to room temperature, dichloroethane was extracted and 500 ml of 10% saline was added. The condenser was removed and the mixture was heated to 85°C to azeotropically remove remaining dichloroethane. After cooling to room temperature, it was washed with water to remove salt. The crosslinked polyvinyl alcohol thus obtained had a water content of 78% and a specific surface area of 47 m ² /g. B Chloracetalization of cross-linked polyvinyl alcohol Add 40 g (9 g dry weight) of the porous cross-linked polyvinyl alcohol produced in A to a 300 ml round bottom flask equipped with a condenser and stirrer, add 55 ml dioxane, and 90 g 40% chloroacetaldehyde aqueous solution. , 8 ml of 1N hydrochloric acid was added thereto, and the mixture was heated at 60°C for 2.5 hours and then at 80°C for 12 hours while stirring. After cooling to room temperature, it was filtered and washed with dioxane and water. The obtained chloroacetalized polyvinyl alcohol had a dry weight of 14 g and a yield of 89%. Further, the chlorine content determined by elemental analysis was 20%. The specific surface area of this resin was 20 m ² /g. C. Amination of chloroacetalized polyvinyl alcohol In a glass autoclave with a capacity of 100 ml and equipped with a stirrer, put 18 g of the chloroacetalized polyvinyl alcohol produced in B (14 g in dry weight), 15 ml of dioxane, and 31 ml of 50% dimethylamine aqueous solution, and stir. The mixture was heated at 40°C for 4.5 hours and at 80°C for 25 hours. After the reaction was completed, it was filtered after cooling to room temperature and washed with water. Then transfer to a column,
2N hydrochloric acid, water, 2N sodium hydroxide, and water were sufficiently poured in this order to obtain free dimethylaminoacetalized crosslinked polyvinyl alcohol (weakly basic anion exchange resin). The obtained resin has a water content of 51% and an exchange capacity of 1.91meq/
g, swelling degree 2.8ml/g, specific surface area 16.5m ² /g,
The pore volume was 0.1 ml/g. Example 2 Chloracetalized multi-crosslinked polyvinyl alcohol produced in the same manner as in Example 1 was reacted with trimethylamine. In a glass autoclave with a 100ml capacity stirrer,
Chloracetalized polyvinyl alcohol 11g
(moisture content: 50%), 24 ml of dioxane, and 40 ml of 30% trimethylamine, and heated at 60℃ for 3 hours while stirring.
The reaction was carried out at 100°C for 12 hours. Post-treatment of the reaction was carried out in the same manner as in Example 1. The resulting resin has a water content of 87% and an exchange capacity
1.17meq/g, specific surface area 32m ² /g, pore volume 1.0
It was ml/g. Example 3 Chloracetalized porous crosslinked polyvinyl alcohol produced in the same manner as in Example 1 was reacted with diethanolamine. In a glass autoclave with a 100ml capacity stirrer,
Chloracetalized polyvinyl alcohol 11g
(moisture content: 50%), dioxane (19 ml), water (19 ml), and diethanolamine (19 ml) were added, and the reaction was carried out at 60°C for 3 hours and at 100°C for 12 hours while stirring. Post-treatment of the reaction was carried out in the same manner as in Example 1. The resulting resin has a moisture content of 52% and an exchange capacity
It had a specific surface area of 0.63 meq/g and a specific surface area of 22 m ² /g. Example 4 A Production of chloroacetalized porous cross-linked polyvinyl alcohol 360 ml of water and 40 g of common salt were put into a round bottom flask (No. 1) equipped with a cooler and a stirrer and dissolved, and then polyvinyl alcohol (manufactured by Nippon Gosei Co., Ltd.,
40 g of Gohsenol NL05 (trade name) was dispersed. This was heated at 96°C for 30 minutes to dissolve the polyvinyl alcohol, and then cooled at 0°C for 30 minutes. To this, 25% glutaraldehyde aqueous solution 16
ml, 50% chloroacetaldehyde aqueous solution 142g,
After adding 24ml of 1N hydrochloric acid and stirring quickly,
It was dispersed in dichloroethane as described below. One dichloroethane was placed in two separable flasks equipped with a condenser and a stirrer,
1 g of cellulose acetate butyrate (manufactured by Eastman Kodak Co., Ltd., trademark CAB381-20) is dissolved in advance. The above-mentioned aqueous polyvinyl alcohol solution was dispersed therein. Stir at room temperature for 30 minutes, then at 60°C for 2.5 hours at 80°C.
The mixture was heated for 11.5 hours to carry out a cross-linking reaction and a cross-acetalization reaction. Post-treatment of the reaction was carried out in the same manner as in Example 1. The yield of the chloroacetalized polyvinyl alcohol resin thus obtained was 83%, the water content was 336%, and the specific surface area was 5.5 m ² /g. Also,
The elementary content determined by elemental analysis was 16%. B. Amination of chloroacetalized polyvinyl alcohol In a 100ml glass autoclave equipped with a stirrer, put 13g of chloroacetalized polyvinyl alcohol produced in A, 13ml of dioxane, and 25ml of 50% dimethylamine aqueous solution, and while stirring,
The mixture was heated and reacted at 40°C for 4 hours and at 80°C for 13 hours. Post-treatment of the reaction was carried out in the same manner as in Example 1. The resulting resin has a moisture content of 66% and an exchange capacity
2.71meq/g, swelling degree 4.3ml/g, specific surface area 4.0
m ² /g, and pore volume was 0.03 ml/g. Example 5 Porous crosslinked polyvinyl alcohol produced in the same manner as in Example 1A was reacted with dimethylaminoacetal hydrochloride (N,N-dimethyl-2,2-dimethoxyethylamine hydrochloride) to form a weakly basic anion exchange resin. I got it. 7 g of porous cross-linked polyvinyl alcohol in a 200 ml round bottom flask equipped with a condenser and stirrer.
(dry weight) and 55 ml of dioxane were added to swell.
To this were added 25 ml of 4N aqueous N,N-dimethyl-2,2-dimethoxyethylamine hydrochloride solution and 8 ml of 1N hydrochloric acid, and the reaction was carried out at 60°C for 2 hours and then at 75°C for 14 hours. Post-treatment of the reaction was carried out in the same manner as in Example 1. The resulting resin has a moisture content of 81% and an exchange capacity
It had a specific surface area of 1.14 meq/g and a specific surface area of 1.0 m ² /g. Example 6 Porous crosslinked polyvinyl alcohol produced in the same manner as in Example 1A was mixed with trimethylammonium acetal hydrochloride (N,N,N-trimethyl-2,
2-diethoxyethylammonium chloride) to obtain a strongly basic anion exchange resin. To a 200 ml round bottom flask equipped with a condenser and stirrer were added 35 ml of water, 20 g of anhydrous sodium sulfate, and 10 ml of concentrated sulfuric acid. After the heat of dilution subsides and cools down to room temperature, porous cross-linked polyvinyl alcohol 26
(water content: 81%) and 34 ml of 2N N,N,N-trimethyl-2,2-diethoxyethylammonium chloride aqueous solution were added thereto, and the reaction was carried out at 80°C for 7 hours and at 90°C for 4 hours. Post-treatment of the reaction was carried out in the same manner as in Example 1. The resulting resin has a water content of 90% and an exchange capacity
It had a specific surface area of 1.50 meq/g and a specific surface area of 3 m ² /g. Example 7 60 ml of water and 5 g of common salt were added to a 200 ml round bottom flask equipped with a condenser and stirrer. After dispersing 10 g of polyvinyl alcohol (manufactured by Nippon Gosei Co., Ltd., trade name Gohsenol NL-05) in this,
A homogeneous solution was obtained by heating at 96°C for 30 minutes. After cooling to 20℃, 2N N,N,N-trimethyl-
A mixed solution of 34 ml of 2,2-diethoxyethylammonium chloride aqueous solution, 5 g of common salt, 15 ml of water, and 4 ml of 25% glutaraldehyde was added. After adding 1 ml of 1N hydrochloric acid and stirring thoroughly, the mixture was dispersed in chlorobenzene as described below. Add 250 ml of chlorobenzene and 0.2 g of cellulose acetate butyrate (trademark CAB381-20, manufactured by Eastman Kodak) to a 500 ml separable flask equipped with a condenser and a stirring device.
The above polyvinyl alcohol aqueous solution was dispersed in this. After stirring at room temperature for 1 hour, the temperature was increased to 60°C.
The mixture was allowed to react for two and a half hours. At this point, gelation was complete. A solution of 2.8 ml of chlorosulfonic acid in 50 ml of dichloroethane was added dropwise to this, and the temperature was raised to 80 ml.
The reaction was carried out at 90°C for 5 hours and at 90°C for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature and filtered. The obtained strongly basic anion exchange resin was washed with acetone to remove chlorobenzene, and then washed with water. After transferring to a column and washing with water, 2N hydrochloric acid, and water in this order, it was made into a free form using a 2N aqueous sodium hydroxide solution, and physical properties were measured. The resulting resin has a water content of 91% and an exchange capacity
The specific surface area was 1.43 meq/g and 7 m ² /g.

Claims (1)

[Scope of Claims] 1 The exchange group is substantially [Formula] or [Formula] (wherein R ¹ represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and R ² , R ³ , and R ⁴ represent an alkyl group or a hydroxyalkyl group, and Y represents an alkylene group), and is characterized by at least one of a specific surface area of 0.5 m ² /g or more and a pore volume of 0.1 ml / g or more. Porous anion exchange resin. 2 Porous crosslinked polyvinyl alcohol characterized by at least one of a specific surface area of 0.5 m ² /g or more and a pore volume of 0.1 ml / g or more, and a porous crosslinked polyvinyl alcohol having the general formula X-Y-CHO (wherein, X is a halogen atom). and Y represents an alkylene group) with a halogenated aldehyde or its acetal in the presence of an acid to obtain a haloacetal of porous crosslinked polyvinyl alcohol, and then reacting this with an amine. A method for producing a porous anion exchange resin characterized by: 3. An aqueous salt solution containing linear polyvinyl alcohol, a crosslinking agent, and a halogenated aldehyde represented by the general formula X-Y-CHO (wherein, X represents a halogen atom and Y represents an alkylene group) was suspended in A crosslinking reaction is carried out to obtain a porous crosslinked polyvinyl alcohol haloacetal product characterized by at least one of a specific surface area of 0.5 m ² /g or more and a pore volume of 0.1 ml / g or more, and then this is reacted with an amine. A method for producing a porous anion exchange resin, characterized by: 4 Porous crosslinked polyvinyl alcohol characterized by at least one of a specific surface area of 0.5 m ² /g or more and a pore volume of 0.1 ml / g or more, and the following general formula [Formula] or [Formula] (in the formula, R ¹ represents a hydrogen atom or an alkyl group,
Production of a porous anion exchange resin characterized by reacting an acetal of an aminoaldehyde represented by (R ² , R ³ , R ⁴ represent an alkyl group, and Y represents an alkylene group) in the presence of an acid. Law. 5 Linear polyvinyl alcohol, crosslinking agent and general formula [Formula] or [Formula] (wherein R ¹ represents a hydrogen atom or an alkyl group
R ² , R ³ , R ⁴ represent an alkyl group, and Y represents an alkylene group ^. Specific surface area greater than g and 0.1
A method for producing a porous anion exchange resin characterized by at least one having a pore volume of ml/g or more.