JP3012153B2 - Mosaic charged membrane and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mosaic charged membrane, and more particularly to a cation having at least one domain which is useful for separating or eluting an electrolyte, for separating or desalting a non-electrolyte, and which is made of a porous material. The present invention relates to a mosaic charged membrane composed of an anionic polymer domain and an anionic polymer domain.

[0002]

2. Description of the Related Art A mosaic-charged membrane in which cationic domains and anionic domains are alternately arranged has a function that a low molecular electrolyte can be dialyzed through a membrane, but a non-electrolyte cannot be dialyzed. For example, it is highly expected for desalination and desalination of seawater or the like, and various researches have been conventionally made.

As a method for forming a mosaic pattern, a method using a styrene-diene block copolymer is well known. In this method, for example, a microdomain structure having a lamella or a cylinder structure is formed by utilizing the phase separation of two kinds of block polymers of a polystyrene block and a polybutadiene block. Due to the quantitative constraints and the anisotropic structure of both, different polymer layers alternate in the cross section of the membrane, and it is technically difficult to make the front and back of the membrane communicate with the same polymer phase. In addition, such a phase-separated structure is anisotropic, and it is difficult to prepare a lamella structure or a cylinder structure.

In the epitaxy method, a mosaic pattern is used.
Each ionic polymer phase is grown on the membrane, but very strict control is required for the formation and growth of the mosaic pattern ultra-thin film, and there is a problem in producing a large-area membrane. Furthermore, in any of the conventional methods, the formed membrane is very thin, has low mechanical strength, and cannot form a relatively thick membrane having high mechanical strength and excellent performance.

[0005]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a mosaic charged membrane which is useful for separating or eluting electrolytes, for separating or desalting non-electrolytes.

[0006]

The above problems are achieved by the present invention described below. That is, the present invention relates to a mosaic charged membrane comprising a cationic polymer domain and an anionic polymer domain, wherein at least one domain is a domain comprising a porous body in which microgels of a cationic or anionic polymer are interconnected. And a method for producing the same.

[0007]

According to the mosaic charged membrane of the present invention, at least one domain of the mosaic charged membrane composed of a cationic polymer domain and an anionic polymer domain is connected to a microgel of any one of the ionic polymers. By doing
Separation and elution of the electrolyte, separation or desalination of the non-electrolyte are possible, and a mosaic charged membrane having improved mechanical strength and the like can be provided at a low cost without using a liquid-permeable support. .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The ionic polymer domain of the present invention includes a cationic polymer domain having a primary or secondary amino group, a quaternary ammonium group, or a salt group such as a pyridinium salt in the polymer, and a sulfonic acid, a carboxylic acid, or a sulfuric acid in the polymer. An anionic polymer domain having a salt group such as an ester or a phosphate. In the case of a salt group, for the former ionic group, for example,
Anions such as hydrochloric acid, sulfuric acid, phosphoric acid and organic acids are used, and cations such as alkali metals, ammonia, amines and alkanolamines are used for the latter ionic groups. In addition, after forming a domain with a nonionic polymer, amination and quaternary ammoniumation, hydrolysis,
The ionic domain may be formed by a chemical modification treatment such as sulfonation and sulfate esterification.

[0009] At least one of the cationic polymer domain (hereinafter sometimes referred to as a domain) and the anionic domain of the present invention is a cationic or anionic polymer microgel (hereinafter simply referred to as a microgel). Is a domain consisting of a porous body formed by connecting with each other. In the present invention,
Microgels have a diameter of 0.01 to 100 μm.
Of cross-linked cationic or anionic polymer
Fair (sphere). A preferred method of forming the porous body is, for example, a method of dispersing a cationic or anionic microgel in a polymer matrix, infiltrating a monomer constituting the microgel into the microgel, polymerizing, and then removing the polymer matrix. is there. Hereinafter, this method will be described in detail.

The microgel used in the present invention has a diameter in the range of 0.01 to 100 μm, preferably 0.02 to 1 μm.
Crosslinked cationic or anionic polymer spheres (spheres) in the range of 0 μm. If the diameter of the microgel is less than 0.01 μm, it is difficult to polymerize the monomer infiltrated into the microgel and form pores generated when the microgels are interconnected with the produced polymer, while the diameter of the microgel is 100 μm If the ratio exceeds the above, when the microgel is dispersed in the polymer matrix to form a film, the microgel sediments, and the mutual connection of the microgel by the above operation becomes insufficient, and the uniformity of the formed pores is reduced.

Representative monomers for preparing microgels of cationic and anionic polymers include styrene derivatives such as styrene, α-methylstyrene and chloromethylstyrene, methyl (meth) acrylate, (meth)
Ethyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, hydroxypropyl (meth) acrylate, (meth)
(Meth) acrylate derivatives such as polypropylene glycol acrylate, (meth) acrylamide, N-
(Meth) acrylamide derivatives such as methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, acrylonitrile, vinyl acetate, (meth) acrylic acid (or a salt thereof) , Styrenesulfonic acid (or salt thereof), (meth) acryloyloxypropylsulfonic acid (or salt thereof), sulfopropyl (meth) acrylate (or salt thereof),
2- (meth) acrylic acid-2-sulfoethyl (or a salt thereof), 2- (meth) acryloylamino-2-methyl-
1-propanesulfonic acid (or a salt thereof), 2- (meth) acryloylamino-2-propanesulfonic acid (or a salt thereof), vinylsulfonic acid (or a salt thereof), 4-vinylpyridine, 2-vinyl Pyridine and quaternary compounds thereof, dimethylaminoethyl (meth) acrylate (or a salt thereof), diethylaminoethyl (meth) acrylate (or a salt thereof), 4-vinylbenzyldimethylamine (or a salt thereof), -Hydroxy-3
-(Meth) acryloxypropyldimethylamine (or a salt thereof) and the like. These monomers are used in combination so that the obtained polymer becomes cationic or anionic, and the optimum combination of monomers and the use ratio thereof are determined according to the intended use of the membrane of the present invention. The use ratio of each is not particularly limited.

The crosslinkable monomers used in combination with the above monomers include divinylbenzene, methylenebis (meth)
Acrylamide, ethylene glycol dimethacrylate,
Examples thereof include dimethacrylic acid-1,3-butylene glycol and other trifunctional and tetrafunctional (meth) acrylates. These crosslinkable monomers are used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the monomers constituting the polymer.

A typical method for converting the above-mentioned monomer and crosslinking monomer into a microgel is radical polymerization.
The polymerization may be carried out in either an aqueous or non-aqueous medium.
Examples of the form of polymerization include polymerization methods such as emulsion polymerization, soap-free polymerization, suspension polymerization, and dispersion polymerization. In the present invention, it goes without saying that a nonionic microgel is formed, and a microgel cationized or anionized by the above-mentioned chemical post-treatment can also be used. Furthermore, after forming a porous body using a nonionic microgel, it may be cationized or anionized by a chemical post-treatment.

In order to form a porous body to be a porous domain, the microgel obtained as described above is dispersed in a polymer matrix which is incompatible with the microgel, and the microgel used is ionic or non-ionic. It is preferable to select the type of the matrix polymer depending on the nature. When the microgel is nonionic, a water-soluble polymer such as, for example, polyvinyl alcohol, carboxymethylcellulose, or polyethylene oxide is used as the polymer matrix. In the case of an ionic microgel, a polymer soluble in a non-aqueous solvent such as polystyrene, polyvinyl acetate, polyvinyl butyral, and polyurethane is used as the matrix polymer.

It is also possible to use a degradable polymer as the matrix polymer. Those which decompose into low molecular weight compounds by heat or those which change to easily soluble in water or solvent are used. Among them, poly-α-methylstyrene, polypropylene oxide, aldehyde resin and the like having a low half-life temperature Th (temperature at which the weight is reduced to half by heating for 30 minutes) during thermal decomposition are particularly useful. The amount of the polymer used as the polymer matrix is in the range of 10 to 500 parts by weight, preferably 20 to 2 parts by weight, per 100 parts by weight of the microgel.
It is in the range of 00 parts by weight. Examples of the method for dispersing the microgel in the polymer matrix include a usual dispersion method such as ultrasonic treatment or stirring with a homomixer, a stirrer, or the like, of the polymer solution to which the microgel is added. Dispersion containing the obtained microgel,
The solvent is removed by coating C, drying or the like by a known coating method such as casting or a coater on a flat substrate to obtain a polymer matrix film having a predetermined thickness in which microgels are dispersed.

Next, the microgels dispersed in the polymer matrix film are interconnected. As a method of connecting the microgels, seed polymerization is carried out by infiltrating a monomer or a monomer and a crosslinkable monomer into the microgel with a solvent as necessary, using the microgel as a seed. The monomer for performing the seed polymerization and the crosslinkable monomer may be of the same type as the monomer constituting the microgel, or may be of a different kind as long as it is a monomer and a crosslinkable monomer that penetrates the microgel.

The amount of the monomer used is in the range of 10 to 2,000 parts by weight, preferably 5 to 100 parts by weight of the microgel.
It is in the range of 0 to 1000 parts by weight. The amount of the crosslinking monomer used is in the range of 20 parts by weight or less, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the monomer.

As the polymerization initiator, in the case of a nonionic monomer, 2,2'-azobisisobutyronitrile,
2,2'-azobis (methyl isobutyrate), 2,
2'-azobis (2,4-dimethylvaleronitrile),
Examples thereof include oil-soluble polymerization initiators such as 1,1'-azobis (cyclohexane-1-carbonitrile), cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, and lauryl peroxide.

In the case of an ionic monomer, 2,2'-
Azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (2-amidinopropane) diacetate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, ammonium persulfate, And water-soluble polymerization initiators such as potassium persulfate.

When the monomer, the cross-linking monomer and the polymerization initiator are penetrated into the microgel in the polymer matrix membrane, if the microgel is nonionic, in order to sufficiently penetrate the monomer into the microgel, acetone, dioxane, A good solvent for the microgel, such as methanol, and a good solvent for the water-soluble polymer matrix, such as water, are mixed, and the polymer matrix film in which the microgel is dispersed is immersed in the mixture at a temperature of room temperature or lower.

When the microgel is an ionic microgel, a good solvent for the microgel, such as water, and a good solvent for the polymer matrix, such as isopropyl alcohol and dioxane, and a monomer are mixed. The polymer matrix film is immersed at a temperature below room temperature.

After the monomer and the like have sufficiently penetrated the microgel, polymerization is carried out. Since the optimum polymerization conditions (polymerization temperature and polymerization time) differ depending on the type of the monomer and the type of the polymerization initiator to be used, it is desirable to confirm the optimum polymerization conditions by a preliminary experiment. After the polymerization, in order to remove the polymer matrix from the Porimamato <br/> click scan film, isopropyl alcohol and the polymer matrix film -
Immersion in a solvent such as toluene, dioxane or water to extract and remove the polymer matrix. The membrane-like porous body thus obtained is a porous body in which pores are microscopic and continuous, and microgels having a structure in which the pore size and shape are uniform are interconnected. The pore size can be arbitrarily adjusted depending on the particle size of the microgel, the mixing ratio of the microgel with the polymer matrix, and the like.

When the polymer constituting the porous body has an aromatic ring such as a benzene ring, sulfonation of the benzene ring with sulfuric acid, quaternization of a methyl halide group with a tertiary amine, and sodium sulfite Sulfonation,
Chemical modification such as quaternization of the pyridine ring with methyl halide or the like can also be performed.

In the present invention, the interconnection of the microgels is
It is conceivable to occur as follows. That is, as the seed polymerization using the microgel as a seed progresses, the compatibility between the polymers decreases and phase separation occurs. At this time, it is considered that the phase separation is concentrated so that the interfacial energy is reduced, and as a result, the microgel is coated and / or impregnated with the polymer phase and connected.

Finally, the mosaic charged membrane of the present invention can be obtained by forming the other domain on the film-like porous body (forming one domain of the present invention) in which the microgels are interconnected. The mosaic charged membrane of the present invention can be manufactured by using the above-described porous membrane and arbitrarily combining the following methods.

(1) A monomer, a polymerization initiator, and, if necessary, a cross-linking agent, which constitute another ionic polymer (anionic if the porous material is, for example, cationic). A method in which a monomer or the like is infiltrated and polymerized to form an ionic polymer as the other domain in the gap between the porous bodies as the one domain. (2) A method of permeating a solution of an ionic (ionic meaning is the same as described above, hereinafter the same) polymer forming the other domain into the gaps of the porous body and removing the solvent. (3) A method of permeating a dispersion of a sphere (sphere) of an ionic polymer forming the other domain into the gaps of the porous body to remove the solvent. (4) A method of permeating a dispersion of a microgel of an ionic polymer forming the other domain into the gaps of the porous body to remove the solvent. (5) The method described below, wherein the porous body and the porous body forming the other domain are combined.

A membrane in which both domains are porous is prepared by the following series of operations. (A) Prepare two types of microgels, one cationic or anionic and the other nonionic. (B) Both microgels are dispersed in a solution of a water-soluble polymer such as polyvinyl alcohol, and a film is formed to obtain a polymer matrix film in which the microgels are dispersed. (C) The nonionic microgel in the polymer matrix film is impregnated with a monomer comprising the microgel or a monomer containing a crosslinkable monomer and a solvent, and then the monomer is polymerized to form a nonionic microgel. Create interconnected domains. (D) hydrophobizing the water-soluble polymer; (E) Permeating a monomer and a medium containing a monomer or a crosslinkable monomer constituting the microgel into the ionic microgel in the polymer matrix membrane,
Polymerizes the ionic microgel to create interconnected domains. (F) Solvent extraction and removal of the polymer matrix. (G) Ionize non-ionic domains. The polymer spheres or microgels used above are mixed to form a film, and then the polymer spheres or microgels in the film are destroyed or deformed by a solvent or pressure, thereby further ensuring the connection of the same type of ion. In addition, the mechanical strength of the film can be further improved.

[0028]

Next, the present invention will be described more specifically with reference to examples. In the following, "parts" and "%" are based on weight unless otherwise specified. Reference Example 1 (Preparation of poly-4-vinylpyridine microgel) 10 parts of 4-vinylpyridine, 1 part of acrylamide, 1 part of divinylbenzene, and 0.2 parts of 2,2'-azobis (2-methylamidinopropane) ) Charge dihydrochloride and 500 parts of water into a flask and place in a nitrogen stream at 8
Polymerization was carried out at 0 ° C. for 8 hours. Purification by dialysis gave a microgel dispersion. The particle size of the obtained microgel was 250 nm as measured by a dynamic light scattering method.

[0029] Reference Example 2 (Po Li styrenesulfonic oxygen - da Preparation) 10 parts of styrene sulfonic oxygen - da and 3.3 parts of a hydroxyethyl methacrylate and 3.3 parts of methyl methacrylate 0.2 Parts of 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride and 3
3.3 parts of water and 33.3 parts of methanol were charged into a flask, polymerized at 60 ° C. for 10 hours under a nitrogen stream, and the polymer was purified by acetone-water reprecipitation method and then dried at room temperature.

Reference Example 3 (Preparation of Sodium Polystyrene Sulfonate Microgel) 10 parts of soda styrene sulfonate, 2 parts of hydroxyethyl methacrylate, 1 part of methylenebisacrylamide, 0.2 part of 2,2 2′-Azobis (2-amidinopropane) diacetate and 247 parts of water were charged into a flask, and polymerized at 60 ° C. for 10 hours under a nitrogen stream. Methano
Was added to precipitate a polymer. The particle size of the obtained microgel was 30 n when measured with a scanning electron microscope.
m.

Example 1 100 parts of the poly4-vinylpyridine microgel dispersion of Reference Example 1 was mixed with 9.5 parts of 10% by weight polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd., average degree of polymerization 550 ± 5).
0) The mixture was mixed with an aqueous solution for 10 hours to form a film on a Teflon plate at room temperature. This film was prepared by adding 4.4 parts of 4-vinylpyridine and 0.1 part of 4-vinylpyridine.
05 parts of divinylbenzene and 0.05 parts of 2,2'-
Immersion in a mixed solution of azobis (methyl isobutyrate), 20 parts of acetone and 7 parts of water for 24 hours, infiltration of the monomers into the microgel,
Seed polymerization was performed at 8 ° C. for 8 hours. After the polymerization, the membrane was immersed in hot water of 80 ° C., further washed with water to remove polyvinyl alcohol, and dried. As a result of observation by a scanning electron microscope, it was confirmed that this film was a porous body having a pore structure with a very uniform arrangement.

Next, 12.5 parts of styrene sulfonate sodium
3. 4.2 parts of hydroxylethyl methacrylate and 4.
It is immersed in a mixed solution of 2 parts of methyl methacrylate, 0.2 parts of 2,2'-azobis (2-amidinopropane) dihydrochloride and 150 parts of water, and is immersed in a stream of nitrogen under a stream of nitrogen.
And polymerized for 10 hours.

Next, 8.5 parts of the porous material membrane was added to 50%
After being immersed in an aqueous glutaraldehyde solution, a film was formed on a Teflon plate and air-dried. The obtained film was left in a hydrochloric acid gas atmosphere at room temperature for 3 hours, washed with water and air-dried, and further left in a methyl iodide atmosphere at room temperature for 1 day to completely quaternize the nitrogen atom of 4-vinylpyridine. To obtain a mosaic charged membrane of the present invention.

The dialysis properties of the electrolyte and the non-electrolyte of the membrane were measured using the apparatus shown in FIG. In a container 1, a 0.05 mol / l aqueous solution of potassium chloride as an electrolyte and a 0.05 mol / l glucose as a non-electrolyte are contained.
20 ml of each of the aqueous solutions, and 40 ml of pure water
Then, the above-described membrane of the present invention was sandwiched between the two containers, and the mixture was kept at 25 ° C., stirred and subjected to a dialysis test, and the concentrations of the electrolyte and the non-electrolyte in the containers were measured. As a result, the mosaic-charged membrane of the present invention selectively separated potassium chloride as an electrolyte and exhibited excellent dialysis.

[0035] The porous film made of poly-4-vinyl pyridine obtained in Example 1, obtained in Reference Example 2 Po Li styrenesulfonic oxygen - da 20.8 parts 83.2 parts Was immersed in a mixed solution of an aqueous solution dissolved in water and 19 parts of a 50% by weight glutaraldehyde aqueous solution, and then formed into a film on a Teflon plate and air-dried. After leaving this film in a hydrochloric acid gas atmosphere at room temperature for 3 hours,
The membrane was washed with water and air-dried, and further allowed to stand in a methyl iodide atmosphere at room temperature for one day to completely quaternize the nitrogen atom of 4-vinylpyridine to obtain a mosaic charged membrane of the present invention. The dialysis performance of this membrane was similar to that of Example 1.

Example 3 The procedure of Example 2 was repeated, except that the polystyrene sulfonate soda microgel obtained in Reference Example 3 was replaced with the polystyrene sulfonate soda of Example 2. 12.5 parts of styrene sulfonic acid microgel was mixed and dispersed in 237.5 parts of water for 5 hours. The porous body film made of poly-4-vinylpyridine obtained in Example 1 was immersed in a mixture of this dispersion and 19 parts of a 50% by weight glutaraldehyde aqueous solution, and then formed on a Teflon plate. After treatment with hydrochloric acid gas, the mixture was washed with water and air-dried, and the nitrogen atom of 4-vinylpyridine was completely quaternized with methyl iodide. The membrane was placed on a stainless steel porous body and pressed at a pressure of 200 kg / cm ² . The mosaic-charged membrane of the present invention thus obtained exhibited a more excellent desalination effect by applying pressure to the aqueous solution of the salt to be dialyzed.

Example 4 3.0 parts of a polystyrene sodium sulfonic acid-based microgel of Reference Example 3 and 13 parts of a 10% polystyrene (Dialex HF-77 manufactured by Mitsubishi Monsanto Co.) dioxane solution were mixed and dispersed for 10 hours. A film was formed on a Teflon plate at room temperature. This membrane was coated with 9.0 parts of sodium styrenesulfonate, 1.8 parts of hydroxyethyl methacrylate, 0.5 parts of methylenebisacrylamide and 0.3 parts of 2,2'-azobis (2-amidino Propane) diacetate and 100
Of water and 35 parts of a dioxane mixed solution for 24 hours, and a monomer was permeated into the microgel in the membrane, and subjected to seed polymerization in a flask at 55 ° C. for 8 hours under a nitrogen stream.

After the polymerization, the membrane was immersed in a dioxane solution to dissolve and remove the polystyrene matrix and air-dried. The obtained porous membrane made of polystyrene sulfonate soda was mixed with 312.9 parts of the poly4-vinylpyridine microgel dispersion obtained in Reference Example 1 and 19 parts of a 50% aqueous solution of glutaraldehyde. After immersion in the solution, a film was formed on a Teflon plate. This film was left in a hydrochloric acid gas atmosphere at room temperature for 3 hours, washed with water and air-dried, and further left in a methyl iodide atmosphere at room temperature for 1 day to completely quaternize the nitrogen atom of 4-vinylpyridine. Mosaic charged membrane was obtained. The dialysis performance of this mosaic-packed membrane was the same as in Example 1.

Example 5 A dispersion composed of 100 parts of the poly4-vinylpyridine microgel dispersion of Reference Example 1, 3.8 parts of sodium polystyrene sulfonate microgel of Reference Example 3, and 72.2 parts of water. Was mixed with 18 parts of a 10% by weight aqueous solution of polyvinyl alcohol for 10 hours to form a film on a Teflon plate. This membrane
A mixed solution of 4.4 parts of 4-vinylpyridine, 0.1 part of divinylbenzene, 0.2 parts of 2,2'-azobis (methylmethylisobutyrate), 20 parts of acetone and 7 parts of water The polymer was immersed in a poly (vinylvinyl pyridine microgel) for 24 hours, and subjected to seed polymerization at 55 ° C. for 8 hours in a flask under a nitrogen stream.

This film was placed in a butyraldehyde atmosphere for 40 minutes.
After leaving at room temperature for 1 day, the mixture was further left at room temperature in a hydrochloric acid gas atmosphere for 3 hours, washed thoroughly with water, and butyralized the polyvinyl alcohol. This membrane was further treated with 8.6 parts of sodium styrenesulfonate, 1.7 parts of hydroxyethyl methacrylate, 0.9 parts of methylenebisacrylamide and 0.2 parts of
Of 2,2'-azobis (2-amidinopropane) dihydrochloride, 90 parts of water and 45 parts of isopropyl alcohol for 24 hours, and the monomer was added to the polystyrene sodium sulfonate microgel in the matrix. −8 at 55 ° C. under a nitrogen stream in the flask.
The polymer was subjected to seed polymerization for an hour.

This film was placed in a glutaraldehyde atmosphere for 4 hours.
Leave at 0 ° C for 1 day, and further in a hydrochloric acid gas atmosphere at room temperature for 3 days.
Left for hours. Then, it was sufficiently washed with water and air-dried. Next, it was left at room temperature for one day in a methyl iodide atmosphere to completely quaternize the nitrogen atom of 4-vinylpyridine to obtain a mosaic charged membrane of the present invention. This mosaic charged membrane has an IPN structure (interpenetrating network structure),
It had excellent mechanical strength. Further, the dialysis performance of the mosaic charged membrane was the same as in Example 1.

[0042]

According to the present invention as described above, in the mosaic charged membrane, at least one of the microgels is connected to each other by using a domain formed of a porous body in which the microgels are connected to each other, thereby ensuring the connection between the microgels in the membrane. Further, the mechanical strength of the membrane can be improved without using a liquid-permeable support. Therefore, according to the present invention, a mosaic charged membrane useful for separating or eluting an electrolyte, separating or desalting a non-electrolyte is provided at low cost.

[Brief description of the drawings]

FIG. 1 shows a dialysis evaluation apparatus used in Examples 1 to 5.

[Explanation of symbols]

 1: Container 1 2: Container 2 3: Membrane 4: Stirrer

Continuation of the front page (72) Michie Nakamura 1-7-6, Bakurocho, Nihonbashi, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-5-7745 (JP, A) JP-A-Hei 6-262047 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B01D 61/70-71/82 500

Claims (15)

(57) [Claims] 1. A mosaic charged membrane comprising a cationic polymer domain and an anionic polymer domain, wherein at least one domain is a domain comprising a porous body in which microgels of a cationic or anionic polymer are interconnected. A featured mosaic charged membrane. 2. The mosaic charged membrane according to claim 1, wherein the other domain is formed in a gap between the one porous domain. 3. A mosaic charged membrane according to claim 2 consisting of the other domain harm on polymer. 4. A mosaic charged membrane according to claim 2 consisting of spheres of the other domains harm on polymer. 5. The mosaic charged membrane according to claim 2, wherein the other domain comprises a microgel of an ionic polymer. 6. An anionic porous body in which the cationic polymer domains are composed of a cationic porous body in which microgels of a cationic polymer are interconnected, and the anionic polymer domains are in an interconnected form of microgels of an anionic polymer. The mosaic charged membrane according to claim 1, which is a domain consisting of: 7. The cationic or anionic polymers Mi
Black mosaic charged membrane of claim 1 in which the gel is linked with a polymer of each polymer and same or different. 8. A cationic polymer characterized by impregnating a monomer capable of forming another ionic polymer into a porous material membrane in which microgels of a cationic or anionic polymer are interconnected and polymerizing the same. A method for producing a mosaic charged membrane comprising domains and anionic polymer domains. 9. The method for producing a mosaic charged membrane according to claim 8, wherein a crosslinkable monomer is used together with the monomer. 10. A method for producing a mosaic charged membrane according to claim 8 or 9 using a solvent having an affinity for the porous material with the monomer. 11. A cationic polymer domain characterized by impregnating a porous membrane formed by interconnecting microgels of a cationic or anionic polymer with a solution of the other ionic polymer and removing the solvent. And a method for producing a mosaic charged membrane comprising an anionic polymer domain. 12. A cationic polymer characterized by impregnating a porous membrane composed of interconnected cationic or anionic polymer microgels with a dispersion of the other ionic polymer sphere and removing the solvent. A method for producing a mosaic charged membrane comprising domains and anionic polymer domains. 13. A cationic or anionic polymer.
The other gel is attached to the porous membrane formed by interconnecting
Impregnated with a dispersion of on-polymer microgel,
Cationic polymer domain characterized by removing
A method for producing a mosaic charged membrane comprising anionic and anionic polymer domains . 14. The method according to claim 14, wherein the porous membrane is formed by infiltrating a cationic or anionic polymer microgel dispersed in a polymer matrix with a monomer capable of forming the ionic polymer directly or by post-treatment and polymerizing the polymer.
The method for producing a mosaic charged membrane according to claim 8 or 11, which is obtained by removing a polymer matrix. 15. A mosaic charged membrane comprising a cationic polymer domain and an anionic polymer domain, wherein both the cationic polymer domain and the anionic polymer domain are domains comprising a porous body, and prepared by the following operation. Manufacturing method. (A) Prepare two types of microgels, a microgel of a cationic or anionic polymer and a microgel of a nonionic polymer. (B) Both microgels are dispersed in a water-soluble polymer solution, and a film is formed to obtain a polymer matrix film in which the microgels are dispersed. (C) Permeating a monomer and a medium containing a monomer constituting the microgel or a crosslinkable monomer into the microgel of the nonionic polymer in the polymer matrix membrane, and then polymerizing the monomer. (D) hydrophobizing the water-soluble polymer; (E) A monomer and a solvent including a monomer constituting the microgel or a crosslinkable monomer are infiltrated into the microgel of the ionic polymer in the polymer matrix, and then the monomer is polymerized. (F) Solvent extraction and removal of the polymer matrix. (G) ionizing the non-ionic polymer;