JP3453056B2 - Manufacturing method of charged mosaic membrane - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a charge mosaic membrane that selectively permeates an electrolyte, a charge mosaic membrane,
The present invention relates to a method of using a charge mosaic film and an apparatus including the charge mosaic film.

[0002]

2. Description of the Related Art Heretofore, there have been known charge mosaic membranes in which a cationic polymer domain and an anionic polymer domain are arranged and penetrate substantially alternately in the cross-sectional direction of the membrane. The membrane has the function that low molecular weight electrolytes can be dialyzed but non-electrolytes cannot be dialyzed or the dialysis rate is very slow.

As a method of manufacturing the above charged mosaic film,
A method using a block copolymer and a method using cationic and anionic polymer particles have been proposed. The method using a block copolymer is a very difficult method to produce, while the method using a cationic or anionic polymer fine particle is very easy to produce. There is.

[0004]

In the method using polymer fine particles described above, when a charged mosaic film is produced by using microspheres as the polymer fine particles, the chargeability and isotropy of the microspheres are relatively high. The charged mosaic film can be easily manufactured. However, in this method, since most of the constituent components of the film are ionic polymers, the film formed tends to shrink when the film is dried or to become a brittle film, which is not suitable for the production of a large-area film. There was a problem.

[0005] As this improvement, Japanese Application flat 8-263747
The publication proposes the use of a flexible component as the matrix component of the charged mosaic membrane. This method facilitated the production of large-area charge mosaic membranes and improved the durability and handling during use, but it took a long time to form the membranes, and the chargeable polymer components were charged with each other or charged with each other. There are some problems in the mixing and dispersion stability of the polymer component and the matrix component,
Further, it is difficult to manufacture a thin film having a uniform film thickness.
Therefore, the object of the present invention is to solve the above problems in the production of a charged mosaic membrane, to shorten the film formation time, to charge the chargeable polymer components with each other, or to mix the chargeable polymer component and the matrix component,
An object of the present invention is to provide a method for producing a charge mosaic film which is excellent in dispersion stability, has a uniform film thickness, and is a thin film.

[0006]

The above object can be achieved by the following method. That is, in the present invention, the cationic polymer component and the anionic polymer component (hereinafter, both components may be referred to as “chargeable polymer component”) are matrix polymers.
In the method for producing a non-porous charge mosaic film dispersed in a layer , the chargeable polymer component is a granular polymer, and the chargeable polymer component is dispersed in a nitrogen- containing organic solvent , Ma
Apply the coating solution prepared by dissolving the Trix polymer onto the substrate.
Cloth, or coating, impregnation or casting on a support,
Process for producing a charge mosaic membrane characterized that you drying a coating liquid, charge mosaic membrane obtained in this way, a device having a method and the charged mosaic use of the charged mosaic membrane.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The present invention is characterized in that, when the charge mosaic film is formed, the chargeable polymer component is dispersed in a nitrogen-containing basic organic solvent to form the film. In the present invention, the chargeable polymer component constituting the charge mosaic film is a crosslinked polymer particle, and the average particle size is preferably 0.01 to 20 μm, more preferably 0.02 to 10 μm. .

The nitrogen-containing basic organic solvent used in the present invention is used to prepare a coating solution for film formation by dispersing the chargeable polymer component described below, and for example, N -Methyl-2-pyrrolidone, N-ethyl-2-
2-Pyrrolidones such as pyrrolidone and N-vinyl-2-pyrrolidone; formamides such as N, N-dimethylformamide and N, N-diethylformamide; acetamide such as N, N-dimethylacetamide and N, N-diethylacetamide The kind is mentioned. These are used alone or in combination of two or more.

The chargeable polymer component used in the present invention is a cationic polymer component having a cationic group such as a primary to tertiary amino group, a quaternary ammonium group and a pyridinium group, and a salt group thereof. It is a polymer component having an anionic group such as a sulfonic acid group, a carboxylic acid group, a sulfuric acid ester group and a phosphoric acid ester group, and a salt thereof as a combined component and an anionic polymer component. When the ionic group is used as the salt group, acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and organic acids are used for the cationic group, and alkali metal is used for the anionic group. Alkalis or bases such as ammonia, amines, alkanolamines, etc. are used. Alternatively, the chargeable polymer component may be prepared by a chemical modification treatment such as amination, quaternary ammonium conversion, hydrolysis, sulfonation, and sulfuric acid esterification after the nonionic polymer component is prepared.

Typical monomers used for preparing the chargeable polymer component are, for example, (meth) acrylic acid (or a salt thereof), styrenesulfonic acid (or a salt thereof), (meth). Acryloyloxypropyl sulfonic acid (or a salt thereof), sulfopropyl (meth) acrylate (or a salt thereof), (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 them) Anion monomer such as vinyl sulfonic acid (or a salt thereof); 4-vinylpyridine, 2-vinylpyridine and a quaternary compound thereof, dimethylaminoethyl (meth) acrylate (or a salt thereof), ( Diethylaminoethyl methacrylic acid (or salts thereof), 4-vinylbenzyldimethylamine (or salts thereof), 2-hydroxy-3-
Examples thereof include cationic monomers such as (meth) acryloxypropyldimethylamine (or salts thereof). When polymerizing these anionic or cationic monomers,
A known non-charged monomer may be added if necessary, and examples thereof include lauryl (meth) acrylate and stearyl (meth) acrylate.

Typical monomers used for preparing the chargeable polymer component by the chemical modification treatment include, for example, styrene derivatives such as styrene, α-methylstyrene, chloromethylstyrene and hydroxymethylstyrene; (Meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, hydroxypropyl (meth) acrylate, polypropylene glycol (meth) acrylate Acrylic ester derivative: (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N,
(Meth) acrylamide derivatives such as N-dimethylacrylamide; acrylonitrile, vinyl acetate and the like. When polymerizing the above-mentioned monomers, it is also possible to add a known non-charged monomer that is not substantially subjected to a chemical modification treatment reaction, for example, lauryl (meth) acrylate, stearyl (meth) acrylate. Etc.

A crosslinkable monomer is used in order to crosslink a granular polymer prepared using the above monomer.
Examples of the crosslinkable monomer include divinylbenzene, methylenebis (meth) acrylamide, ethylene glycol dimethacrylate, dimethacrylic acid-1,3-butylene glycol, and other 3 to 4 functional (meth) acrylates. These crosslinkable monomers are used in an amount of preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the monomers constituting the polymer.

A typical method for preparing a granular polymer component using the above-mentioned monomer and crosslinkable monomer is radical polymerization in either an aqueous system or a non-aqueous system. Examples of the polymerization form include emulsion polymerization, soap-free polymerization, suspension polymerization, dispersion polymerization, reverse phase emulsion polymerization, and the like, but the form of polymerization is not particularly limited. Examples of the radical polymerization initiator include 2,2′-
Azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis (2,4-
Dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauryl peroxide, 2,2′-azobis (2-amidinopropane) Initiation of polymerization of dihydrochloride, 2,2'-azobis (2-amidinopropane) diacetate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, ammonium persulfate, potassium persulfate, etc. Agents.

In the present invention, a matrix polymer may be used together with the chargeable polymer component, if necessary. The matrix polymer is a polymer that is soluble in the above basic organic solvent and has the property of forming a film by heating and drying when forming the charge mosaic film. Examples of such a polymer include acrylic resin such as polymethylmethacrylate resin, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylic rubber, polyisoprene rubber, ethylene-vinyl acetate copolymer, polyvinyl butyral. Polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, and other (co) polymer resins and rubbers, polyesters, polyamides, polyimides, polyamideimides, polyurethane resins and elastomers, silicone rubbers, polysulfones, polyether sulfones And polysulfone-based resins such as sulfonated polysulfone. The above-mentioned copolymer may contain a random, block, or graft bonding mode. These polymers can be used alone or in combination of two or more.

To produce the charged mosaic membrane of the present invention,
A dispersion liquid (coating liquid) of the above basic organic solvent of a crosslinked granular polymer which is a chargeable polymer component is prepared. As needed,
The basic organic solvent solution of the above matrix polymer and the dispersion are mixed and used. When the basic organic solvent solution of the matrix polymer is mixed with the above dispersion liquid and used, the ratio of the matrix polymer used is 2 in the charge mosaic film.
The range is preferably 90 to 90% by weight, more preferably 10 to
It is in the range of 80% by weight. In the preparation of the above-mentioned coating solution, for example, ultrasonic treatment;

Next, the coating solution obtained above is applied as it is or on a substrate using a known coater or the like, or is applied, impregnated or cast on a support and dried to form a film.
The charge mosaic film of the present invention can be obtained by performing heat fusion treatment, heat pressure press treatment, quaternization treatment, and the like, if necessary. Examples of the above-mentioned substrate include a glass plate, an aluminum plate, a plastic sheet such as Teflon, polypropylene, and polyethylene, a film, or a molded plate. Examples of the support include woven cloth, non-woven cloth, mesh-like material, paper, filter paper-like material, hollow fiber, porous material, and the like. Materials of these supports include stainless steel, aluminum, ceramics, Polyester, nylon, polyamide, polycarbonate, polypropylene,
Examples thereof include polyethylene, cellulose, chitin, Teflon, polyurethane and polysulfone.

Examples of the coating method of the coating liquid on the base material and the support include roll coating, blade coating, knife coating, squeeze coating, air doctor coating, gravure coating, rod coating, spray coating, and the like.
Conventionally known coating methods such as impregnation and internal addition can be mentioned. After the application, the charged mosaic film of the present invention is formed by drying by a method such as drum drying, blast drying or infrared lamp drying. The preferred thickness of such a membrane is 0.1
Range of 1,000 μm, more preferably 0.5 to 200
It is in the range of μm. The shape of the charge mosaic film of the present invention produced as described above has a flat film shape, a spiral shape,
The shape of the membrane is not particularly limited, although it may be cylindrical, pleated, hollow fiber, or the like.

The charge mosaic membrane of the present invention has a structure in which a cationic polymer domain and an anionic polymer domain are substantially alternately arranged and penetrated in the cross-sectional direction of the membrane, and have a low molecular weight. The electrolyte can be dialyzed, but the non-electrolyte cannot be dialyzed, or the dialysis rate is very slow. Therefore, the charge mosaic membrane of the present invention is a low molecular weight electrolyte, for example, for desalting sodium chloride, potassium chloride, sodium sulfate, sodium phosphate, calcium chloride, and further, hydrochloric acid, acetic acid, sodium hydroxide and the like. It is useful as deionization, for example, for beverages,
Desalination in water treatment industry such as industrial water, pure water, ultrapure water,
Desalination of industrial wastewater such as chemical industry, metal industry, desalination of dyes and pigments in dye manufacturing industry, desalination of biochemical products such as fermentation industry and food industry, desalination of pharmaceuticals, adsorption of dye as recording medium It is useful for etc. In particular, the charge mosaic membrane of the present invention is desalted of proteins, DNA, etc., desalted of dyes, pigments, surfactants, etc. Conventionally, in electrodialysis, alteration of a target substance due to heat generation, membrane contamination by ionic adsorption, etc. It is useful in the fields that could not be applied by. Further, since the charge mosaic membrane of the present invention has the membrane structure as described above, electrodialysis, diffusion dialysis, electrolysis, a diaphragm for a battery, etc. utilizing the properties of the membrane such as conductivity and ion permeability. Is also useful.

[0019]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples. The parts and% in the text are based on weight.

Synthesis Example 1 ( Polymer A ; Cationic Granular Polymer) 4-Vinylpyridine 20.0 parts Divinylbenzene 2.0 parts 2,2'-Azobis (2-amidinopropane) dihydrochloride 0.4 parts Water 1,000 parts of the above ingredients were placed in a flask, and the contents were kept at 80 ° C under a nitrogen stream for 8
Polymerized for hours. The polymerization product was freeze-dried to obtain a crosslinked granular polymer. The average particle size of the granular polymer was about 350 nm as measured by a scanning electron microscope.

Synthesis Example 2 ( Polymer B ; Cationic Granular Polymer) Poly-4-vinylpyridine particles of Polymer A are dispersed in methyl alcohol, and methyl iodide is added to the dispersion to prepare 1
After stirring for 2 hours, salt exchange was performed with hydrochloric acid, and the product was washed sufficiently with water to obtain a quaternary product of poly-4-vinylpyridine. The average particle size of the freeze-dried granular polymer was about 360 nm.

Synthesis Example 3 ( Polymer C ; Anionic Granular Polymer) Styrene 41.6 parts Acrylonitrile 7.1 parts Hydroxyethyl methacrylate 8.1 parts Divinylbenzene 8.7 parts Potassium persulfate 0.5 parts Water 1,000 Parts The above ingredients were placed in a flask and placed under a nitrogen stream at 80 ° C for 8 hours.
Polymerized for hours. The average particle size of the obtained polymer is about 180.
was nm. 100 parts of a white polymer obtained by filtering, drying and crushing the above-mentioned granular polymer was gradually added to 650 parts of 98% concentrated sulfuric acid, and the mixture was heated at 50 ° C. for 24 hours and then at 80 ° C.
And stirred for 3 hours. Then, it cooled and poured the reaction liquid mixture into a large amount of ice water. After neutralizing with sodium carbonate, it was filtered and washed thoroughly with water. The obtained granular polymer was confirmed to have almost one sulfonic acid group introduced into the aromatic ring by analysis such as infrared absorption spectrum and ion chromatography. The average particle size of this granular polymer was about 240 nm.

Synthesis Example 4 ( Polymer D ; Anionic Granular Polymer) Sodium styrenesulfonate 25.0 parts Styrene 10.0 parts Butyl acrylate 5.0 parts Acrylamide 2.8 parts Divinylbenzene 1.8 parts 2,2 ' -Azobis (2-amidinopropane) dihydrochloride 1.0 part Water 1,000 parts The above ingredients were charged into a flask and then at 75 ° C under a nitrogen stream at 1 ° C.
Polymerization was carried out for 0 hours. The obtained polymer was purified by a reprecipitation method with acetone-water. The average particle size of this granular polymer is about 1
It was 00 nm.

Example 1 4.5 parts of Polymer A was added to N, N-dimethylformamide 1
Dispersed in 0.6 parts, and a 30% N, N-dimethylformamide solution of the dispersion and a styrene-butadiene copolymer 5
0 parts were mixed for 1 hour, and further, 10.5 parts of the polymer C and 24.4 parts of N, N-dimethylformamide were mixed to prepare a coating solution. The coating solution was applied onto a glass plate with a knife coater and dried with hot air. Further, after leaving it in a methyl iodide atmosphere at room temperature for 12 hours, the glass plate was removed in water and air-dried to obtain a charged mosaic film of the present invention. The charge mosaic film formed by the above method was about 50 μm and had a uniform thickness.

(Evaluation of Membrane) 100 ml of a 0.1 mol / liter potassium chloride aqueous solution as an electrolyte and 100 ml of a 0.1 mol / liter glucose aqueous solution as a non-electrolyte were placed in a container A shown in FIG. Ionized water, 25 ℃
When dialysis was carried out under normal pressure at 10 ° C., sufficient dialysis separation performance was exhibited as shown in FIG.

Example 2 3.6 parts of Polymer A were dispersed in 8.5 parts of N, N-dimethylformamide, and the dispersion and polysulfone (molecular weight 30,000, Tg 190 ° C.) in 20% N, N-dimethylformamide were dispersed. 60 parts were mixed for 1 hour, and further 8.4 parts of Polymer D and N, N-dimethylformamide 19.
A coating liquid was prepared by mixing 5 parts of the dispersion liquid. The above coating solution was applied onto a polyester nonwoven fabric with a knife coater and dried with hot air. Further, it was left in a methyl iodide atmosphere at room temperature for 12 hours to obtain a charged mosaic film of the present invention. The charge mosaic film formed by the above method had a thickness of about 30 μm and had a uniform thickness, and was more flexible than the charge mosaic film of Example 1. The dialysis separation performance of the electrolyte was evaluated in the same manner as in Example 1, but the results were almost the same as in Example 1, and the durability and handling during use were good.

Example 3 5.9 parts of Polymer B was added to N, N-dimethylformamide 1
Dispersed in 3.7 parts, and the dispersion liquid and a 30% N, N-dimethylformamide solution of polyether polyurethane 50
And 1 part for 1 hour, and 9.2 parts of Polymer C and N, N
A coating liquid was prepared by mixing a dispersion of 21.3 parts of dimethylformamide. The coating solution was applied onto an aluminum plate with a knife coater, dried with hot air, further removed from the aluminum plate in water and air dried to obtain a charged mosaic film of the present invention. The charge mosaic film formed by the above method was about 50 μm and had a uniform thickness. The dialysis separation performance of the electrolyte was evaluated in the same manner as in Example 1, but the results were almost the same as in Example 1.

Example 4 3.6 parts of Polymer A were added to N-methyl-2-pyrrolidone 8.
Dispersed in 4 parts, and a 30% N-methyl-2-pyrrolidone solution containing the dispersion and the styrene-butadiene copolymer 5%
0 part was mixed for 1 hour, and further, a coating liquid was prepared by mixing 11.4 parts of Polymer D and 26.6 parts of N-methyl-2-pyrrolidone. The above coating solution was applied onto a polyester nonwoven fabric with a roll coater and dried with hot air. Further, after leaving it in a methyl iodide atmosphere at room temperature for 12 hours, a charged mosaic film of the present invention was obtained. The dialysis separation performance of the electrolyte of the charged mosaic membrane obtained as described above was almost the same as in Example 1.

[0029]

As described above, according to the present invention, in a method for producing a charge mosaic film in which a chargeable polymer component is dispersed in a specific basic organic solvent to form a film, the chargeable polymer component is a crosslinked granular material. It is a polymer, and the granular polymer is dispersed in a basic organic solvent such as N-methyl-2-pyrrolidone or N, N-dimethylformamide, and a matrix polymer is used in combination if necessary, so that the film-forming time is reduced. It is possible to produce a charge mosaic film which is short and has excellent charge stability and mixing stability of a chargeable polymer component or a mixture of a chargeable polymer component and a matrix polymer and has a uniform film thickness. . The mosaic charged film has excellent physical properties such as chemical resistance, solvent resistance, and water resistance, and is chemically stable and acidic, alkaline,
It was possible to provide a charged mosaic membrane which has high durability against hydrolysis and oxidative decomposition even when used at low temperature and high temperature, and which is excellent in electrolyte transfer, separation, concentration, or adsorption.

[Brief description of drawings]

FIG. 1 is a view showing a dialysis device which is an example of a device using the charge mosaic membrane of the present invention.

FIG. 2 is a diagram showing the dialysis separability of the charged mosaic membrane of Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Naomi Oguma 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) 1-7-6 Seiji Doi Nihonbashi-Bakurocho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. (72) Inventor Mamoru Nakamura 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. (56) Table 1-502673 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) B01D 61/24-61/42

Claims (2)

(57) [Claims] 1. A non-multi- component polymer in which a cationic polymer component and an anionic polymer component (both components are sometimes referred to as "chargeable polymer component" hereinafter) are dispersed in a matrix polymer layer.
A method for producing a porous charge mosaic membrane, charged polymer components are particulate polymer, the nitrogenous basic organic solvent
Disperse the chargeable polymer component and dissolve the matrix polymer.
Apply the coating solution to the base material or the support.
Coating, impregnation or casting method for producing a charge mosaic membrane characterized that you drying the coating solution. 2. A nitrogen-containing basic organic solvent is N-methyl-2.
-Pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylformamide,
The method according to claim 1, wherein the solvent is at least one solvent selected from N, N-diethylformamide, N, N-dimethylacetamide and N, N-diethylacetamide.