JPS5811046A - Porous anion exchange resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain a porous anion exchange resin of high reaction rate, adsorptive force and exchange capacity by using the resin that has cross-linked polystyrene skeleton, has specific exchange groups and is made to a fixed value or more in spcific surface area and pore volume. CONSTITUTION:The resin having the constitution wherein the skeleton is cross- linked polystyrene and the exchange groups are substantially of the formulaIor formula II (where R1=H, alkyl groups, etc., R2, R3, R4, alkyl groups or hydroxy alkylene groups, Y=alkylene groups) and having >=0.5m<2>/g specific surface area or 0.1ml/g pore capacity is used as a porous anion exchange resin. Since this resin is porous, it has high reaction rate and adsorptive power and since its skeleton is porous cross-linked polyvinyl alcohol, it has high ion exchange capacity and provides the monofunctional resin of small degree of swelling.

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.

Anion exchange resins that are currently widely used have a crosslinked polystyrene skeleton and therefore exhibit 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 a 7th amino group to a tertiary ammonium group. Furthermore, an anion exchange resin having a backbone of polyvinyl alcohol has been proposed, but this resin is a gel-type dark resin due to its manufacturing method.

The present inventors investigated porous anion exchange resins with a polyvinyl alcohol skeleton because porous resins with internal physical pores have many advantages over gel-type resins. , completed the invention.

In the porous anion exchange resin according to the present invention, the exchange group is substantially (in the formula, R1 represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and R2, R3, and R4 represent an alkyl group or a hydroxyalkyl group). (Y represents an alkylene group.) It has a structure represented by θ, and Y represents an alkylene group. /? It is characterized by at least one of the following specific surface area and the pore volume (θ, /ml/y).

Still, the present invention provides a method for reacting an aminoaldehyde or its acetal with a porous crosslinked polyvinyl alcohol characterized by at least one of a specific surface area of θs m2/g or more and a pore volume of 7 ml/y or more. The present invention provides a method for producing a porous anion exchange resin by reacting an acetal of a haloaldehyde or a haloaldehyde and then reacting 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 m''/ It is characterized by at least one of a specific surface area of f or less and a pore volume of 0.7 ml/2 or more. Preferably, the porous anion exchange resin according to the present invention has θ, tn? It is characterized by both a specific surface area of 2/2 or more, especially 5 m2/7 or more, and a pore volume of 7 ml/2 or more.

The porous anion exchange resin according to the present invention uses porous crosslinked polyvinyl alcohol as a raw material, reacts it with an amino acetal, or reacts it with a haloaldehyde or its acetal, and then aminates it with an amine. It can be easily manufactured by

Porous crosslinked polyvinyl alcohol is produced by reacting polyvinyl alcohol and a crosslinking agent in water in which a salt is dissolved or suspended. In a preferred step, an aqueous resin suspension containing a salt, polyvinyl alcohol, and a crosslinking agent is dispersed in an oily 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. The water-soluble salts usually include chlorides such as sodium chloride, potassium chloride, and cassillum chloride, sodium nitrate, potassium nitrate,
Nitrates such as calcium nitrate, sulfates such as magisium sulfate, and phosphates such as phosphoric acid and lithium are used. It is thought that the water-soluble salt of Kowara has the effect of precipitating the polyvinyl alcohol from the reaction medium through a salting-out effect when the molecular weight increases due to the reaction of the polyvinyl alcohol with the crosslinking agent. The formation of a precipitate in the reaction medium is estimated by the fact that the reaction medium becomes cloudy shortly after the start of the reaction). Therefore, it is necessary to use Towa et al.'s water-soluble salt-1 at a concentration n' sufficient to exhibit the salting-out action described in Section 2. The concentration varies depending on the type of salt, and for sodium chloride, the concentration is very high.
For calcium chloride, it is more than 2θ. Generally speaking, the concentration of salt used is within the range of / - - θ.

As water-insoluble salts, sulfates such as calcium sulfate, barium sulfate, and lead sulfate are usually used. The amount used is usually j to 70 ft, preferably 2θ to 6θ g per 100 fK of polyvinyl alcohol aqueous KIj.

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.

As the polyvinyl alcohol, one having a degree of polymerization of several tens to several thousand, preferably λθθ to −θθθ, and a degree of saponification of 50 molar or more, preferably f tamol or more is used. Polyvinyl alcohol is 2-30%, preferably 5-75%
It is used for the crosslinking reaction by dissolving it in water so that -8=.

As a crosslinking agent, dialdehydes such as glyoxal, glutaraldehyde, and terephthalaldehyde;
2-3. <Jepoxy compounds such as t-jepoxybutane; glycidyl ethers such as bis-evogicibrobyl ether, ethylene glycol bisepoxypropyl ether, gobutanediol bisepoxypropyl ether; epihalohydrins such as epichlorohydrin and epibromhydrin, etc. 2 between the polyvinyl alcohol molecules of
Those capable of forming a crosslinking moiety having 1 or more carbon atoms are used. The crosslinking agent is the hydroxyl group 1 of polyvinyl alcohol.
Usually from 0.07 to 0.0% per mole. /, 1'mol is used.

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, a resin with a small exchange capacity may be obtained in the end. If the amount of crosslinking agent is too small, the degree of swelling of the 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. As a dispersion medium, aromatic hydrocarbons and their halogen derivatives such as toluene, benzene, chlorobenzene, and dichlorobenzene, and aliphatic hydrocarbons such as n-hebutane, n-hexane, liquid paraffin, cyclohexane, dichloromethane, and dichloroethane are usually used. , alicyclic hydrocarbons and their halogen derivatives. These dispersion media are usually used alone, but two or more types may be used in combination. The amount of the Fl medium to be used is at least 2 (volume) times that of the polyvinyl alcohol aqueous solution, preferably 3 to 6 (volume)
It's double. In addition, 1. Oil-soluble cellulose such as ethyl cellulose, cellulose acetate butyrate, ethyl hydroxyethyl cellulose,
It is preferable to add an oil-soluble dispersion stabilizer such as gum arabic, sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate. The amount is usually θ, θ~/θ relative to the dispersion medium, preferably θ, /~
5tl).

The crosslinking reaction is preferably carried out using θC/θθC1.
to θC for 7 to 20 hours, preferably
It's been an hour and it's been an hour now.

During the crosslinking reaction, an acid such as hydrochloric acid or sulfuric 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 monohydrophilic 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 crosslinked polyvinyl alcohol used for acetalization is preferably θ, s, , l/. It is necessary to have a specific surface area of /1 or more. 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 in a trench containing salt, and then the insoluble salt may be removed from the acetalized product using hydrochloric acid or the like. In either case, when the insoluble salts contained in the cross-linked polyvinyl alcohol are extracted and removed, θ, /
It is necessary to have a pore volume of ml/f or more. The pore volume can be easily varied by adjusting the suspension concentration of the insoluble salt.

In addition, as crosslinked polyvinyl alcohol, θ, yew?
/2 or more, preferably a specific surface area of 72 or more and /
Alternatively, as long as it has a pore volume of θ, /me/f or more, those obtained by methods other than the above can also be used in the next acetalization reaction.

The porous crosslinked polyvinyl alcohol thus obtained is then reacted with haloaldehyde or 12- or its acetal to form a haloacetal compound of crosslinked polyvinyl alcohol.

Examples of the haloaldehyde include chloroacetaldehyde, bromoacetaldehyde, α-chloropropionaldehyde, α-bromopropionaldehyde, β-chloropropionaldehyde, β-bromopropionaldehyde, etc., with the general formula % formula % (wherein, X is a halogen atom and Y represents an alkylene group) Any haloaliphatic aldehyde represented by the following formula can be used. 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 acetal 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. Reaction beam θ~/θθC1 preferably 6θ~2θC, 2~
The treatment is carried out for 3θ hours, preferably from 5 to 50 minutes in the evening. The haloaldehyde or its acetal is usually used in an amount of o, trt mole or more, preferably 0.9 to 3 moles, per mole of the hydroxyl group of the crosslinked polyvinyl alcohol. The concentration of haloaldehyde or its acecool in the reaction medium is usually between 5 and
60 degrees, preferably 10 degrees.

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 in the reaction medium is generally above /θ-2 normal, preferably between /θ-1
/ Used because it is a regulation.

The haloacecooled crosslinked polyvinyl alcohol is then reacted with an amine to form an aminated anion exchange resin. This reaction is also generally carried out using water as a solvent. If a solvent that swells the haloacetalized crosslinked polyvinyl alcohol, such as dioxane or dimethylformamide, is used, the reaction will proceed more easily. The reaction is 30~/l θC
The treatment is preferably carried out at a beam angle of θ to /θθC for 3 to 3θ hours, preferably from 5 to 70 hours in the evening. Amines generally include 7th class amines such as methylamine, ethylamine, ethanolamine, and propanolamine, secondary amines such as dimethylamine, diethylamine, jetanolamine, and dibrobanolamine, trimethylamine, triethylamine, triethanolamine, and dimethylethanol. Tertiary amines such as amines are used, but other amines can also be used.

It is preferable to use the amine as an aqueous solution in the reaction medium at a concentration of at least /θ. The amount of amine used may be at least equimolar to the halogen in the haloacetalized crosslinked polyethylene glycol, but it is usually 7 to 3 times (
mole) 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 aminoacetal. Like haloacetalization, this reaction can also be easily carried out using an acid as a catalyst and water as a reaction medium. As aminoacetals, 2,2-dimethoxyethylamine, 2゜cordiethoxyethylamine, N-methyl-2゜-1-dimethoxyethylamine, N,N-dimethyl-2,1,-dimethoxyethylamine, N-ethyl-2 , 2-dimethoxyethylamine, N,N-diethyl-2,,2-dimethoxyethylamine, 1jN-dimethyl-2,2-dimethoxyethylamine, etc. Aminoacetals having a 7th, secondary, or tertiary amino group; , N, N-trimethyl-, X,
, N-triethyl-2-1-dimethoxyethylammonium, N,N,N-)dimethyl-+2,2-diethoxyethylammonium, and other aminoacetals having a positive ammonium group are usually used, but aminoacetals other than the above may be used. Of course, you can also use it. The concentration of the aminoacetal in the reaction medium is usually greater than or equal to IO, preferably -4j to θ to 7θ. The amount used is usually θ for 1 mole of hydroxyl group of crosslinked polyvinyl alcohol.
, ¥ mol or more, preferably 0.9 to ¥ mole. As the catalyst acid, in addition to mineral acids such as d-sulfuric acid and hydrochloric acid, organic acids such as I)-) toluenesulfonic acid can also be used. The acid in the reaction medium is usually /θ-2 normal or higher, preferably phantom, /θ
It is used as a rule from Friday to Sunday. The reaction temperature is usually θ~
/θθC1 Preferably, Otsuθ~ and θC, and the reaction time is usually 3 hours or more, preferably 5 to 75 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 haloacecooled 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 to 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, practically preferred ones have a swelling degree of r
The exchange capacity in the condition below ml/y is θ
,t,t meq/me or more. Particularly suitable resins have a degree of swelling of 3.5me/? The exchange capacity in this state is θ, 6 meq 7 ml or more, which is 19−. Such a resin has the advantage that when it is packed in a column and used, there is little pressure loss and the exchange capacity of the column is large.

Next, the present invention will be explained in more detail with reference to Examples.
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 the resin treated with an aqueous caustic soda solution is sufficiently washed with water, the water is replaced with acetone, and the acetone is further replaced with toluene. This resin was dried at 3θ in a vacuum drying mold of /θmnHg.
The following measurements were performed on the sample dried at C for 29 hours.

B using specific surface area Nikantersolp (manufactured by Yuasa Battery IA) and adsorption of nitrogen gas.

Measured by E, T, method.

Pore volume: d type using a human porosimeter for mercury (Kalkuchi Elleva (4/l) j11!!).

Replacement capacity, moisture content, and swelling degree After regenerating with an aqueous caustic soda solution and thoroughly washing with demineralized water, the OH type resin is placed in a /θml graduated cylinder, and 10 ml of the resin is accurately weighed by tapping the bottom. This resin was dehydrated for 5 minutes using a centrifuge at 35θG, and then its weight (α1f) was accurately weighed. Next, this resin was poured into 20 ml of 2N hydrochloric acid and shaken at room temperature for 2Z hours.

Titrate θml of this hydrochloric acid with an aqueous sodium hydroxide solution of θ/normal.

Separately, accurately weigh / Omg of resin in the same manner as above, dehydrate it in the same manner as above, and then calculate its weight (a2y
). Next, this resin was heated to 6θC1/θmmH.
After drying in the f1 vacuum drying mold for 2 hours, the weight (Cg) was accurately weighed again.

2 Swelling degree -/θ/c (ml/f?)20-α1 Here, h and h are the amount of caustic soda aqueous solution required for titration (m) before and after adding the resin, respectively.
l) and f are factors for the caustic soda aqueous solution.

Example/A Production of porous cross-linked polyvinyl alcohol A 3θθml round bottom flask equipped with a cooler and a stirring device was charged with water i.
After adding and dissolving 73g of common salt λθ, and 26g of calcium chloride dihydrate, polyvinyl alcohol manufactured by Honsei ■, trade name Gohsenol NL-θj)λθV was dispersed therein. Heat the stiffness for 3θ minutes at 2°C to dissolve the polyvinyl alcohol, and then heat it at 3θ with water at 5°C.
Cooled for minutes.

23% glutaraldehyde aqueous solution and me/
After adding λθml of normal hydrochloric acid and stirring quickly, the mixture was dispersed in dichloroethane described below.

Dichloroethane is prepared by removing the condenser and stirring device.
In a 4/l separable flask, 500 ml of cellulose acetate butyrate (manufactured by Eastman Kodak Co., trade name: CAB3, !?/--θ) θ1.27 was dissolved 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 6θC for 3 and a half hours to carry out a crosslinking reaction.

After cooling to room temperature, dichloroethane is extracted and /
5θθml of θ-related saline solution was added.

The condenser was removed and the reactor was heated to C to remove remaining dichloroethane by azeotropy. After cooling to room temperature, it was washed with water to remove salt. The water content of the cross-linked polyvinyl alcohol obtained in this way is 2 degrees, and the ratio is as follows. Take Og of polyvinyl alcohol (dry weight: 97) and add dioxane (3') to 1.
e1 ri θ circulation loracetaldehyde water m liquid w θ 7, /
Add 1 mL of normal hydrochloric acid, and stir at 6θC for 2 hours.
The reaction was carried out at J for 1 hour and then at θC for 72 hours).

After cooling to room temperature, it was filtered and washed with dioxane and water. The obtained chloroacetalized polyvinyl alcohol has a dry weight of 15% and a yield ratio of 100%. What is the chlorine content determined by elemental analysis? I was in charge of θ.

The specific surface area of the resin was θm2/7.

Amination capacity of C chloroacetalized polyvinyl alcohol/θθml in a stirrer glass autoclave, B
Chloracetalized boron 23-rivinyl alcohol/1 (dry type/Fugu), dioxane/ml, rθ-related dimethylamine aqueous solution 37ml
1! Add it, stir it until it reaches <10C, then let it cool down to 0.00℃.
in,! It heated up in the evening.

After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed with water. The mixture was then transferred to a column and thoroughly flushed with λ normal hydrochloric acid, water, normal sodium hydroxide, and water in this order to obtain free dimethylaminoacetalized crosslinked polyvinyl alcohol (weakly basic anion exchange resin). The obtained resin has a water content of 1/2, an exchange capacity of 9/mθq/g, and a swelling degree of Jfm.
l/? , specific surface area 7t,,5'n? /', pore volume θ, /ml! It was /f/.

Example 2 Chloracetalized porous crosslinked polyvinyl alcohol produced in the same manner as in Example 2 was reacted with trimethylamine.

Into a glass autoclave equipped with a stirrer with a capacity of θθme, put chloroacecooled polyvinyl alcohol//2 (moisture content: θ), dioxane, 29ml, 24-3θ of trimethylamine θme, and stir for 3 hours at toC. , /θθC for 72 hours. The post-reaction procedure was carried out in the same manner as in Jllil-1 and Jitnoi 1 Concentration Example.

The resulting resin has a water content of 7%, an exchange capacity of /, /7me
q/? , specific surface +1'f 3.21r+2/? , pore volume o ml/? Deatsu/ko.

Example 3 Chloracetalized porous crosslinked polyvinyl alcohol produced in the same manner as in Example 3 was reacted with jetanolamine.

In a glass autoclave with a stirrer of capacity /θθme, chloracecooled polyvinyl alcohol //? (moisture content jo), 9 ml of dioxane, 79 ml of water, and 9 me of jetanol were added to the cuff, and the reaction was carried out at θC for 3 hours and at /θθC for 72 hours while stirring. Post-treatment of the reaction was carried out in the same manner as in Example.

The obtained resin has a water content of 1 L, an exchange capacity of θ, and an exchange capacity of 3 me.
q/f, specific surface area, 2:z m2/? Met.

Example A Chloracecooled porous crosslinked polyvinyl alcohol production In a /l round bottom flask equipped with a cooler and a stirring device,
Add 3 θrd of water and vOd of table salt and dissolve, then polyvinyl alcohol (manufactured by Nippon Gosei ■, trade name: Gohsenol N).
TJθ5) and θ2 were dispersed. Stiffness is 3 with 96'Q
After heating for 0 minutes to dissolve the polyvinyl alcohol, the mixture was cooled at θC for 3C minutes. For example, add 76 ml of glutaraldehyde aqueous solution. After adding 2 tml of a 22/N hydrochloric acid aqueous solution of loracetaldehyde with θ and stirring quickly, the mixture was dispersed in dichloroethane as described below.

Dichloroethane was equipped with a condenser and a stirring device. 2
In a separable flask of T/l, cellulose acetate phthylate (ys) Mankodak Company'lL
The trademark CAB 3ir/-20)/f/ is dissolved in advance. The above-mentioned aqueous polyvinyl alcohol solution was dispersed therein. After stirring for 3C at room temperature, 60C
So 2. A crosslinking reaction and a chloroacetalization reaction were carried out by heating at θC for a certain period of time during the evening sky. Post-treatment of the reaction was carried out in the same manner as in Example.

In this way, the yield of chloroacetalized polyvinyl alcohol resin was 3%, water-containing dust was 36%,
The specific surface R' was 5 m''/y.

The chlorine content determined by elemental analysis was 0.6%.

B Amination capacity of chloroacetalized polyvinyl alcohol/θθm1. Stirrer in old glass autoclave,
Chloracetalized polyvinyl alcohol produced in A/3v, dioxane/3ml 1. ! 25 me of the θ-related dimethylamine water bath solution was added, and the mixture was heated and reacted with stirring at θC″c time of go’6 for 13 hours. Post-treatment of the reaction was carried out in the same manner as in Example.

The obtained resin has a water-containing dust content of 66% and an exchange capacity of: z, 7/
meq/y, degree of swelling <t, 3rJ/? , specific surface area, θn? / f, pore volume θ, o3ml/?
Met.

Example 2 Porous crosslinked polyvinyl alcohol produced in the same manner as Example/A was mixed with dimethylaminoacetal hydrochloride (N,N
-dimethyl-2,2-dimethoxyethelamine hydrochloride)
A weakly basic anion exchange resin was obtained.

Porous crosslinked polyvinyl alcohol 72 (dry weight) and 5 ml of dioxantha were added to a round bottom flask of θθm/V equipped with a condenser and a stirrer and allowed to swell. 25ml of aqueous solution of N,N-dimeteru,2-dimethoxyethylamine hydrochloride specified for kneading! , normal hydrochloric acid and mi were added, and the reaction was carried out at 60C for 1 hour and then at 75C for 1 hour.

Post-treatment of the reaction was carried out in the same manner as in Example.

The obtained resin has a water content of ♂/m, an exchange capacity of t, and i%.
mθq/y, specific surface area 1. θrr? /? Met.

Example 6 Porous crosslinked polyvinyl alcohol produced in the same manner as Example/A was mixed with trimethylammonium acetal hydrochloric acid 1
g, (N, N, N -l dimethyl-2゜λ-jethoxyethylammonium chlorite) to obtain a strongly basic anion exchange resin.

3 s of water, λθ7 of anhydrous sodium sulfate, and 10 ml of concentrated sulfuric acid were added to a 2θ Oml round bottom flask equipped with a condenser and a stirrer. After the heat of dilution subsides and cools to room temperature, porous cross-linked polyvinyl alcohol (with water-containing dust/%), -2N, N, N-)dimethyl-2,
2-diethoxyethelammonium chloride aqueous solution 3
The reaction was carried out for 7 hours at 0C and 7 hours at θC. Post-treatment of the reaction was carried out in the same manner as in Example.

Is the obtained resin water-containing dust? θ relation, exchange capacity group θmθq
/P, specific surface area 37? ? It was 2/S'.

Example 7 Water 6θme and salt tag were added to a 6θml round bottom flask equipped with a condenser and stirrer. After dispersing stiff polyvinyl alcohol (manufactured by Nippon Gosei F411, trade name Gohsenol NT, -05)/θ7,
The mixture was heated at 9 g C for 3θ minutes to obtain a homogeneous solution. λθC-
After cooling at t, λ defined N,N,N-)dimethyl-
A mixed solution of 3ml of 2,2-diethoxyenal ammonium chloride aqueous solution, 2ml of sodium chloride, 3ml of water, and 1ml of 2% glutaraldehyde was prepared. After adding 7 liters of normal hydrochloric acid and stirring thoroughly, the mixture was dispersed in chlorobenzene as described below.

In a separable flask equipped with a condenser and a stirrer, add 2 ml of chlorobenzene and cellulose acetate butyrate (Trademark C manufactured by Eastman Kodak Company).
AB 3e/-, ;zo) θ, 22 are added. The above polyvinyl alcohol aqueous solution was dispersed in this. After stirring at room temperature for 7 hours, the mixture was allowed to react at θC for λ and a half. At this point, the transformation was complete. Add to this 2. chlorosulfonic acid. After dropwise addition of ♂ml of dichloroethane j0me solution, the temperature was raised, and the reaction was carried out at zoC during the evening sun and at θC.

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, normal hydrochloric acid, and water in that order,
It was made into a free form using a normal aqueous sodium hydroxide solution, and its physical properties were measured.

The resulting resin has a moisture content of 9/v and an exchange capacity/re of 3 meq.
, / ′? , and the specific surface area was 7 m''/S'.

Patent applicant: Mitsubishi Chemical Industries, Ltd.

Claims (1)

Scope of Claims: (1) The exchange group is substantially (in the formula, R1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, R2, R3, and R4 represent an alkyl group or a hydroxyalkyl group, and Y indicates an alkylene group.) It has a structure represented by 0.5n? /f or more specific surface area and θ, tmi/? A porous anion exchange resin characterized by at least one of a pore volume of at least one of the following: (210, 5rr?/specific surface area of 1i' or more and θ
,/rr? , porous cross-linked polyvinyl alcohol characterized by at least one of the following pore volumes and halogenation represented by the general formula % (wherein X represents a halogen atom and Y represents an alkylene group). A method for producing a porous anion exchange resin, which comprises reacting an aldehyde with its acetal in the presence of an acid to obtain a haloacetal of porous crosslinked polyvinyl alcohol, and then reacting this with an amine. . (3) An aqueous salt solution containing linear polyvinyl alcohol, a crosslinking agent, and a halogenated aldehyde represented by the general formula % (in the formula, X represents a halogen atom and Y represents an alkylene group) is subjected to suspension polymerization. 1. A method for producing a porous anion exchange resin, which comprises obtaining a haloacetal of porous crosslinked polyvinyl alcohol, and then reacting this with an amine. (4) A porous crosslinked polyvinyl alcohol characterized by at least one of a specific surface area of θ, -5'm"/f1 or more and a pore volume of θ,/m2/2 or more, and the following general formula (in the formula , R1 represents a hydrogen atom or an alkyl group, R2
, R3 and -R4 represent an alkyl group, and Y represents an alkylene group) A method for producing a porous anion exchange resin, which comprises reacting an acetal of an aminoaldehyde represented by the following in the presence of an acid. (5) Linear polyvinyl alcohol, crosslinking agent and general formula (wherein R1 represents an argyl group with the same size as a hydrogen atom, R2
, R3 and R4 represent an alkyl group, and Y represents an alkylene group) A method for producing a porous anion exchange resin, which comprises subjecting an aqueous salt solution containing an acetal of an aminoaldehyde represented by W to turbid polymerization.