JPS6028849B2 - Manufacturing method of composite ion exchange membrane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for manufacturing a composite ion exchange membrane.

There is an increasing demand for ion exchange membranes with better functionality.

Generally, ion exchange membranes are used for seawater concentration salt production by electrodialysis, desalination of salt water, separation of ionic and nonionic substances, diffusion dialysis, electrolysis of aqueous alkali metal salt solutions, organic synthesis electrolytic reactions, reverse osmosis, ultra-horizontal filtration, etc. It is widely used in technical fields. What governs the function of such ion exchange membranes is
It is an ion exchange group bonded to a polymer membrane. The concentration of this ion exchange group in the membrane (fixed ion concentration),
The function of the ion exchange membrane becomes completely different depending on the state of distribution of the ion exchange groups within the membrane and the manner in which different types of ion exchange groups are present in the membrane. Conventionally known composite ion exchange membranes include bipolar ion exchange membranes that integrate a cation exchange membrane and an anion exchange membrane;
Intestinal ion exchange membranes and anion exchange membranes in which only the surface layer of the ion exchange membrane has a thin layer with a high concentration of fixed ions, as disclosed in 7567, are used as diaphragms for electrolysis of aqueous alkali metal salt solutions, for example. Tokuseki Showa 50-108
Examples include fluorine-containing ion exchange membranes such as those disclosed in No. 182.

However, although these known composite ion-exchange membranes have excellent functionality, their manufacturing methods are complicated, and in order to prevent the introduction and distribution of ion-exchange groups from becoming non-uniform, It is difficult to control and it is not possible to easily manufacture the target product in large quantities.

The present inventors have conducted extensive research in order to compensate for the deficiencies associated with the production of conventional composite ion exchange membranes.

As a result, we completed and proposed a technology to continuously manufacture high-performance composite ion exchange membranes. The present invention holds a membrane-like coating material and an ion-exchange membrane or a polymeric membrane-like material into which ion exchange groups can be easily introduced in separate holders, and After continuously adhering a monomer having a vinyl group and/or an aryl group or a mixture of the monomers to a polymer membrane into which groups are introduced, a membrane coating material and an ion exchange membrane or This is a method for producing a composite ion-exchange membrane, in which polymeric membranes into which ion-exchange membranes can be easily introduced are laminated, the monomers are then polymerized, and ion-exchange groups are introduced as necessary.

Note that the composite ion exchange membrane as used in the present invention is a general term for cation exchange membranes or anion exchange membranes in which the cross section of the membrane differs in at least one of the concentration, type, and distribution of ion exchange groups.

The membrane-like coating material used in the present invention is not particularly limited and any known material can be used; however, in general, it is used on the surface or inside of an ion-exchange membrane or a polymer membrane into which ion-exchange groups can be easily introduced. A monomer having a vinyl group and/or an aryl group or a mixture of the monomers (hereinafter also referred to as immersion liquid)
It is preferable to use a material that does not swell.

Specific examples include cellulose-based film (product name: Cellophane); polyvinyl alcohol-based film (
(trade name, Pinylon); polyester films such as polyethylene terephthalate; - films made of rattan or biaxially oriented polyethylene or polypropylene; furthermore, polytetrafluoroethylene, polymonofluoroethylene,
Copolymerized film made from polyvinyl IJden, polytrifluoride-ethylene chloride, etc.; or copolymer of tetrafluoroethylene and hexafluoropropylene, tetrafluoroethylene and perfluoroalkyl vinyl A fluorine-containing film such as a copolymer of ether and the like can be suitably used. Particularly in industrial implementation, cellulose-based, polyvinyl alcohol-based, polyester-based films, etc. are desirable. Of course, a laminated film is also effective instead of a single film, such as a polypynyl alcohol film laminated in a thin film form on a polyjethylene film. In any case, there are no particular limitations as long as the material is flexible, has a coating ability, and is less likely to swell due to counterfeit liquid. The thickness of the film-like coating suitably used varies depending on the purpose of use and cannot be unconditionally limited, but it is generally 0.0002 to 0.1 arc thick, preferably 0.0002 to 0.1 arc thick.
．． 001 to 0.08 skin is most widely used. As the ion exchange membrane or the polymer membrane into which ion exchange groups can be easily introduced for use in the present invention, conventionally known ion exchange membranes or raw membranes of ion exchange membranes can be used without any limitations.

For example, those with or without a covalent cross-linked structure; polymeric or condensed types when viewed from the polymer structure: ion exchange membranes with a homogeneous distribution of ion exchange groups Or a heterogeneous type; in terms of material, a hydrocarbon type or a copper-containing type can be used without any restriction. In addition, in terms of the types of ion exchange groups, ion exchange membranes with conventionally known intestinal ion exchange groups or anion exchange groups such as strong acidic groups, weak acidic groups, strong basic groups, and weak basic groups, or these A polymer membrane having a functional group into which a cation exchange group or an anion exchange group can be easily introduced can be used without any restriction. However, especially in the production method of the present invention, preferred ion exchange membranes or polymer membranes into which ion exchange groups can be easily introduced include polypynyl and polyaryl compounds such as divinylbenzene, diaryl, diacrylate, and dimethacrylate. It has a three-dimensional crosslinked structure as one component.

Other components in this case generally include, for example, styrene;
Chlormethylstyrenes: vinylpyridines, alkylated styrenes such as vinyltoluene; acrylonitrile; vinylimidazoles, vinylpiverazines; compounds with reactive functional groups such as vinyl compounds with nucleobases; acrylic acid and its salts or Esters: methacrylic acid and its salts or esters: vinylsulfonic acid and its salts or esters: styrenesulfonic acid and its salts or esters, and the like. In this case, the amount of the polyvinyl or polyaryl compound relative to the total monomers is preferably 0.5 to 50% from the viewpoint of the properties of the produced ion exchange membrane. The ion exchange membrane used in the present invention or a polymer membrane into which ion exchange groups can be easily introduced is generally made of an inert material such as silk, woven fabric, nonwoven fabric, or knitted fabric in order to maintain high mechanical strength. Those with a base material for strength retention are preferably used.

In addition, inert low-molecular compounds such as plasticizers, polyvinyl chloride, polyethylene fine powder, butadiene-acrylonitrile, butadiene-styrene, natural rubber, and other inert polymers with good solubility and dispersibility. There is no problem even if the compounds coexist. Furthermore, as the monomer or monomer mixture having a vinyl group and/or aryl group, that is, the dipping liquid used in the present invention, any known monomer used in the production of ion exchange membranes can be used without any restriction.

The composition and components in this case vary depending on the purpose of the composite ion exchange membrane to be manufactured. Typical examples are as follows. 1 When making a composite ion exchange membrane with different concentrations of ion exchange groups in the cross section of the ion exchange membrane,
The concentration of fixed ions is higher than the concentration of ion exchange groups (fixed ion concentration) possessed by an ion exchange membrane or a polymer membrane into which ion exchange groups can be easily introduced (hereinafter also referred to as original ion exchange membrane) as an immersion solution. A composition with a high or low concentration is selected.

2. When making a composite ion-exchange membrane with different cross-linking densities in terms of the cross-section of the ion-exchange membrane, select a dipping solution with a composition different from the cross-linking agent concentration used in producing the original ion-exchange membrane.

3 Regarding the cross section of the ion exchange membrane, when making a composite ion exchange membrane in which ion exchange components made of other copolymers are uniformly dispersed, a composition with good permeability to the original ion exchange membrane is added as an impregnating liquid. Select.

4. When manufacturing a composite ion exchange membrane, which is a bipolar ion exchange membrane, it is bonded to the original ion exchange membrane.

or has an opposite charge to the ion exchange group to be introduced,
Alternatively, a dipping solution containing at least one component of a monomer into which an ion exchange group of opposite charge can be easily introduced is selected. 5 Regarding the cross section of the ion exchange membrane, when manufacturing a composite ion exchange membrane having an amphoteric layer only in the surface layer of the ion exchange membrane, it must have both cation exchange groups and anion exchange groups, or An immersion liquid containing a monomer mixture that can easily introduce both intestinal ion exchange groups and anion exchange groups after polymerization is selected.

An example of the selection of a bonding liquid in the case of manufacturing a composite ion exchange membrane has been described above, but the selection of the bonding liquid may be carried out depending on the type and purpose of the composite ion exchange membrane to be manufactured.

Furthermore, the above-mentioned immersion liquid mainly contains a monomer having a vinyl group and/or an aryl group, but other components may also be involved in polymerization to accelerate or slow down the penetration of the immersion liquid into the raw ion exchange membrane. You may add a solvent that does not contain the For example, paraffin, dioxane, higher alcohol, benzene, naphthalene, kerosene, dioctyl phthalate, etc. In addition, in order to control the thickness of the heterogeneous layer present on the surface layer of the composite ion exchange membrane, fine powders such as polyvinyl chloride and polyethylene are dispersed as viscosity modifiers in the immersion liquid, or styrene-butadiene rubber, natural Rubber, soluble rubber such as butadiene-acrylonitrile rubber may be melted. Furthermore, in order to carry out polymerization after adhering the soaking liquid to the surface of the raw ion exchange membrane, it is necessary to dissolve a polymerization initiator, which is a conventionally known radical polymerization initiator. is between 30℃ and 160oo, preferably 50qo
to 13,000 is preferably used. A feature of the present invention is that the membrane coating material and the original ion exchange membrane are kept in separate retention odors.

Next, the soaking liquid is continuously applied to the membrane coating material and/or the original ion exchange membrane taken out from the holder. The attachment means may be any method such as spraying the immersion liquid onto the membrane coating material or the raw ion exchange membrane, painting, or applying the membrane coating material or the raw ion exchange membrane to the immersion liquid. Generally, the latter method is industrially easiest. After the film-like coating material to which the above-mentioned bonding solution was attached and the original ion exchange membrane are laminated,
Polymerize the soaking liquid. Generally, laminates can be subjected to polymerization in a laminated state, but if polymerization takes a long time, the laminate may be wound up once and then polymerized in the rolled up state.
I can also do it. A composite ion-exchange membrane can be obtained by polymerizing an immersion solution, but if an ion-exchange group or an easily introduced polymer membrane is used as the original ion-exchange membrane, or if the polymerization of the immersion solution is If an ion exchange group is not included in the combination, an ion exchange group may be introduced in a post-treatment if necessary. As a method for introducing the ion exchange group, a method known as a method for manufacturing an ion exchange membrane may be adopted. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to explain the method of the present invention in detail, the method will be described below with reference to the accompanying drawings.

FIGS. 1 to 8 show typical principles for producing the composite ion exchange membrane of the present invention. These are fundamental principles, and the present invention is not restricted thereby. First, if it is necessary to attach the soaking liquid to both sides of the raw ion exchange membrane, the methods shown in Figures 1, 2, 3, 5, and 8 may be adopted; If it is necessary to attach only the wafer, it may be manufactured according to the method shown in FIGS. 4, 6, and 7. In the figure, 1 is a winding roll, 2 is a film-like covering material, 3 is an ion exchange membrane or a polymer film-like material into which ion exchange groups can be easily introduced, 4 is a striped roll, 5 is a guide roll, and 6 is a The extractor/underrolls are shown respectively. 2 and 3 are fixed to separate cylindrical retainers and rotate.

From FIG. 2 onwards, the expander roll 6 is used as appropriate to ensure that the membrane coating material and the raw ion exchange membrane are wound up smoothly, or to eliminate wrinkles, sagging, and uneven film thickness.
The number of guide rolls 5, follow-on rolls 4, etc. may be increased or decreased. Figures 1 to 3 show a method in which an original ion exchange membrane is continuously produced while being immersed in a dipping solution. The amount of adhering liquid to the raw ion exchange membrane can be controlled by changing the feeding speed of the polymer membrane and the pressure of the clamping roll. Generally, the time for immersing the bond in the immersion liquid in this case is appropriately selected from 1 second to 7 hours. The bonding temperature is usually carried out at around room temperature, but it is preferable to overflow to increase the amount of the bonding solution deposited, or to cool it to reduce the amount. Generally, it is preferable to carry out the reaction at a temperature above the temperature at which the soaking liquid does not solidify or below a temperature at which polymerization does not start. FIGS. 4 to 8 show a method of attaching a membrane-like coating material by soaking it in a dipping solution.

In this case, the amount of adhesion can generally be controlled by the difference in affinity between the film-like coating material and the soaking liquid. It is also possible to deposit a large amount by using a film-like coating material that has an affinity for the bonding liquid. Alternatively, the surface layer of the membrane-like covering material may be made sparse so that more of the immersion liquid can adhere thereto. In order to minimize the amount of adhesion, a membrane-like coating material with low affinity for the bonding solution is used, and a cloth,
You can also layer it by wiping some of it off with a spongy material.
When winding up, it is preferable that the membrane-like coating material and the original ion exchange membrane be sufficiently laminated to prevent air bubbles from entering between the two. After forming the fin layer, it is possible to polymerize continuously as it is, but it is common to polymerize by winding it up on a winding roll.

Polymerization is generally preferably carried out by heating using a radical polymerization initiator, but polymerization may also be carried out by ionizing radiation such as light, Y-rays, and X-rays. Furthermore, polymerization can also be carried out using only ionizing radiation in the absence of a radical polymerization initiator. When polymerizing by heating, it depends on the type of polymerization initiator added to the soaking liquid, decomposition conditions, etc. The polymerization temperature is lower than the temperature at which the polymer of the produced dipping solution or the original ion exchange membrane decomposes. After the imbibing liquid adhering to the original ion exchange membrane has polymerized, it is preferable to peel off the membrane-like coating material. Even if the cellulose-based or polyvinyl alcohol-based film-like coating material is not removed and the next ion-exchange group introduction reaction is performed as it is, there may be no problem in introducing the ion-exchange group. For example, if the membrane-like coating material decomposes during the sulfonation reaction, it will be naturally removed during the reaction, and the amination reaction will proceed even in the presence of the membrane-like coating material, and it will peel off after the reaction. You may. However, generally, the ion exchange group introduction reaction is carried out after the film-like coating material is peeled off and removed. For the introduction of the ion exchange group, conventionally known means can be employed without any restrictions. For example, hydrolysis, oxidation, reduction, sulfonation, amination, alkylation, etc. The composite ion exchange membrane thus produced is used in various fields depending on its purpose. To describe some examples of the composite ion exchange membrane of the present invention, for example, the composite ion exchange membrane made by the method of the present invention, which has anisotropy in the concentration of ion exchange groups with respect to the cross section of the membrane, has low electrical resistance, It has excellent mechanical strength, and when the fixed ion concentration is increased only in the surface layer, it exhibits extremely high selectivity between ions of opposite signs in electrodialysis of highly concentrated salt, acid, and base solutions and as a diaphragm for electrolytic reactions. Alternatively, if layers with opposite charges are formed, a bipolar membrane is formed, which exhibits high hydrolysis efficiency over a long period of time. Alternatively, it also exhibits monovalent ion selective permselectivity, and forming a thin layer of opposite charge with a high fixed ion concentration generally reduces the multivalent ion permeability ability in regions of high salt concentration to the conventional singly charged ion selectivity. Although it is inferior to membranes, it is effective even in high-concentration conditions, and is effective in removing harmful ions such as calcium, magnesium, and strontium that are present in high-concentration saline solutions, such as when used in saline electrolysis. It has the ability to laterally exclude multivalent ions even if they contain species. The composite ion exchange membrane produced by the method of the present invention can be used in all processes using conventionally known ion exchange membranes. Also known as electrodialysis, electrolysis,
It can be applied to all devices such as diffusion dialysis, reverse osmosis, ultra-dialysis, ion electrodes, etc. The content of the present invention will be explained with reference to the following examples, but the content of the present invention is not restricted in any way by the following examples. In addition, in the example,
The electrical resistance of the membrane is 1 at 25,000 in 0.5N saline.
000 cycles of AC.

The transport number is a value calculated using the Nernst equation from the membrane potential measured at 25.0 oo by inserting a membrane between 0.5N saline and 2.5N saline. The cation exchange capacity of the membrane is determined by equilibrating the membrane in acid form with hydrochloric acid and 0.8N saline.
The ion-exchanged hydrogen ions were determined using 1/1 normal caustic soda. The anion exchange capacity of the membrane is determined by immersing the membrane in 1N hydrochloric acid to form a chloride ion type, washing thoroughly with methanol to remove the chlorine ions adsorbed on the membrane, and then soaking the membrane in 0.2N sodium nitrate solution. The chloride ions were eluted from the membrane several times and the amount was determined by analysis. The moisture content of the membrane is determined by measuring the wet weight of the sodium type or chloride ion type membrane, then drying it in an air dryer at 80 qC for 2 hours, storing it in a desiccator using calcium chloride as a desiccant, and then weighing it. was determined as the dry membrane weight, and the difference between the wet weight and the dry membrane weight was divided by the dry membrane weight. Exchange capacity is determined by dry membrane (Na type or C
Type I) Expressed as exchange capacity per gram. Seawater concentration was then performed to evaluate membrane performance.

Seawater from Tokuyama Bay was filtered through a sand filter, and then hydrochloric acid was added to adjust the pH to 5.5 to 6.01 before use. The average chloride ion concentration in seawater was 0.496 normal. The temperature was controlled to 3000. The electrodialysis tank is a clamping type electrodialysis tank with an effective current-carrying area of 1d force, and the thickness of the seawater side is 1 mm, so that the concentrated liquid overflows from each pair. At a current density of 3 A/d, the seawater flow velocity was 1 at 6 Se relative to the membrane surface. After continuous concentration and equilibrium, samples were taken several times and the average value is also shown. The pure salt rate was measured on the membrane itself, and then a 20 μm aqueous solution of polyethyleneimine was applied to the membrane surface twice.
The pure salt ratio was measured again after contacting for 4 hours at a flow rate of c-1.

Example 1 6 parts of styrene, 6 parts of dipinylbenzene with a purity of 55%,
23 parts of dioctyl phthalate, 2 parts of polyvinyl chloride fine powder
Ikaribe! A plain woven polyvinyl chloride cloth was passed continuously through a vat filled with a sticky paste-like mixture prepared by mixing 1 part of penzoyl peroxide. It was applied uniformly to a plain woven cloth, and then a polyvinyl alcohol film was superimposed thereon, and the excess paste-like mixture was taken up with a nip roll and continuously wound up on the roll.

Next, this was left in a 110 oo autoclave for 4 hours to polymerize, and the polyvinyl alcohol film was peeled off to obtain a polymer membrane (original ion exchange membrane). Next, a raw membrane of a composite ion exchange membrane was produced from this polymeric membrane using the apparatus shown in FIG. That is, each roll had a length of 90 mm, roll 1 had a diameter of 20 mm, and roll 2 had a diameter of 20 mm and was wrapped with a 0.02 mm polyvinyl alcohol film. The roll with cotton has a diameter of 10 arcs and is approximately lk.
I tightened it to 9'c. The membrane feed rate was 2 mjn. The bonding liquid is styrene, purity approximately 55%.
It was prepared by dissolving penzoyl peroxide of approximately 1.5 tones B in 30 parts of divinylbenzene. After about 50 rolls were wound up and sufficiently tightened, the polyvinyl alcohol film was peeled off by heating and polymerizing in an autoclave at 11,000 in a nitrogen atmosphere for 4 hours to obtain a polymer film.
This is wrapped in a polyethylene net and sulfonated with sulfuric acid and chlorosulfonic acid in a ratio of 1:1.
The membrane was soaked for 1 minute, then in concentrated sulfuric acid at room temperature, and then soaked in 80% sulfuric acid, 40% sulfuric acid, water, and 2.5 N carbon soda for about 1 hour each to obtain the ion exchange membrane of the present invention. For comparison, the polymer membrane (original ion exchange membrane) used in carrying out the production method of the present invention was subjected to sulfonation treatment under the same conditions as above. Table 1 shows the properties of the obtained membranes of the present invention and comparative membranes. The numbers in the table are the arithmetic average values of measurements taken by sampling at 10 locations in the film. Specifically, the membrane of the present invention has an electrical resistance of 0.
．． 20-, comparative membranes were within ±0.30 blocks. Table 1: 1. The rate of rope treated with polyethyleneimine using the method described in the specification.

A Neo Sebuta AFS-4T manufactured by Hina Watakuzan Soda Futoshiyama was used for the sea liquid simulation ship. ，
Example 2 The paste-like mixture mainly composed of styrene, divinylbenzene, polyvinyl chloride, etc. used in Example 1 was adhered to a polyvinyl chloride cloth, and a polyvinyl alcohol sheet was layered on the surface to polymerize it. A raw material of the composite ion exchange membrane of the present invention was manufactured using the apparatus shown in FIG.

That is, the length of the rolls was all 90 cm, the roll was 30 cm in diameter, rolls 2 and 3 were 20 cm in diameter, and the tightening roll 4 was 10 cm in diameter. roll 2
Each was wrapped with a polyester film (trade name: Tetron) having a length of 0.05 mm. The original ion exchange membrane was attached to roll 3. As the soaking liquid, 3 parts of styrene-butadiene copolymer rubber was dissolved in a mixed solution of 2 parts of dipinylbenzene and 6 parts of 4-vinylpyridine with a purity of about 55%.
Additionally, 1 part of penzoyl peroxide was melted. This is placed in a soaking liquid vat 7, and the raw ion exchange membrane wound around the roll 3 is soaked at a feed rate of 5/min, and the rolls 4 are tightened together with a pressure of 0.5 [9/min] to form a polyester film. The layers were laminated and wound into roll 1. After sufficiently tightening, it was placed in an 80 qo autoclave and heated under a nitrogen atmosphere for 4 hours to polymerize. Next, the polyester film was peeled off to obtain a polymer film. Next, this was first immersed in a 1:1 solution of 98% sulfuric acid and 90% chlorosulfonic acid at 50 qo for chlorosulfonation treatment, and then sulfuric acid at room temperature, 80% sulfuric acid, 40% sulfuric acid, water, 2. 5
Each was soaked in the specified caustic soda for 1 hour. The membrane was then immersed in an alkylated solution consisting of 4 bases of methyl iodide and 6 bases of n-hexane, and the pyridine ring in the surface layer was alkylated to obtain the ion exchange membrane of the present invention. The ion exchange membrane of the present invention was assembled into a two-chamber cell, and with the membrane surface on which 4-vinylpyridine was attached and polymerized facing the anode, both chambers were filled with 0.5N saline and a current of 1.0 A/d was applied. The pH of both chambers was measured.

Table 2 shows the membrane properties. The membrane for comparison is the original ion exchange membrane which has been subjected to sulfonation treatment.
Table 2 Example 3 A sticky steel paste made by dissolving 5 parts of copolymer rubber of acrylonitrile and butadiene in a mixed solution of 1 part of styrene, 8 parts of chloromethylstyrene, and 1 part of divinylbenzene with a purity of about 55%. Penzoyl peroxide 2 to the mixture
part was dissolved.

Fill the soaking liquid vat 7 with this mixture, pass a polyvinyl chloride plain woven cloth through the paste mixture, and
The strip-like mixture was uniformly adhered to a cloth, and then a polyvinyl alcohol film was superimposed thereon, and at the same time, excess paste-like mixture was removed using a nip roll, and the cloth was continuously wound onto a roll. After polymerization was then carried out by heating in an autoclave at 80 °C for 8 hours under a nitrogen atmosphere, the film was peeled off from the roll and the polypynyl alcohol sheet was peeled off to obtain a polymer membrane (original ion exchange membrane). This polymer film-like material is coated in a coating apparatus shown in FIG.

I set it to rule 3. Each roll is 90cm long
m, and the diameters were 30 mm for roll 1, 20 mm for roll 2, 10 mm for roll 4, and 5 mm for roll 5. The dipping solution used was a solution in which 3 parts of pensol peroxide was dissolved in 2 parts of styrene, 5 parts of chloromethylstyrene, and 3 parts of divinylbenzene having a purity of about 55%. As shown in Figure 5, a polyvinyl alcohol sheet was passed through the soaking solution, wrapped around roll 1, and tightly wrapped, and then heated in a nitrogen atmosphere for 8 hours in an 8000 autoclave. Polymerized. The membrane was then placed in 20 parts of trimethylamine, 4 parts of water, and 40 parts of acetone for 16 hours (
252○) An anion exchange membrane was obtained by soaking and aminating the chloromethyl groups. The properties of the membrane obtained are shown in Table 3. The membrane for comparison is a raw ion exchange membrane that has been subjected to the same amination treatment as in the present invention before being subjected to the immersion treatment. Table 3: 1 Neocepta OH-45T manufactured by Nissara Soda Liquid Nanjinfu was used as the cation exchange membrane during seawater concentration.

Example 4 A paste-like mixture obtained by mixing 10 parts of polyvinyl chloride fine powder, 16 parts of 4-vinylpyridine, 1 part of styrene, 1 part of divinylbenzene with a purity of about 55%, and 25 parts of dioctyl phthalate. 3 parts of penzoyl peroxide was uniformly dissolved.

This was continuously attached to a polypropylene plain woven cloth (50 75 denier threads per inch both vertically and horizontally), and the surface was made with a thickness of 0.025 side of polyester (Teitoron manufactured by Teijin). Cover with a film of...
While removing the excess adhered paste, the mixture was wound around a drum having a diameter of 20 mm, and the temperature was then raised to 8,000 ℃ over 4 hours, followed by heating and polymerization for an additional 4 hours. Next, the polyester film on the surface was peeled off to obtain a polymer membrane. This polymer membrane was soaked in an alkylation solution of 6 parts of n-hexane and 4 parts of methyl chloride (weight ratio) to alkylate the pyridine ring, and then thoroughly washed with 1N hydrochloric acid and chlorinated. It is an ionic type anion exchange membrane. Next, this membrane was dried under reduced pressure, and then used in the apparatus shown in FIG. 2 to obtain the ion exchange membrane of the present invention. Each roll in Figure 2 has a length of 90 skins and 1 roll.
had a diameter of 30 skins, rolls 2 and 3 had a diameter of 20 skins, and roll 4 had a diameter of 10 arcs. The anion exchange membrane obtained above after drying under reduced pressure was attached to roll 3, and roll 2 had a thickness of 0.0.
25 pieces of polyester film were attached and passed through the immersion liquid at a feeding speed of 2 m/min. The soaking liquid used for both ion exchange membranes and polyester films contains 1 part of styrene, 7 parts of chloromethylstyrene,
A mixture of two parts of divinylbenzene and one part of penzoyl peroxide having a purity of about 55% was used. After sufficiently impregnating the anion exchange membrane with the impregnating solution, it was wound up onto a roll 1 and tightened. This was then heated in an autoclave in a nitrogen atmosphere at 8,000 ℃ for 1 hour to polymerize. Next, the polymer membrane obtained by peeling off the polyester film was treated with 2 parts of trimethylamine and 5 parts of acetone.
The anion exchange membrane of the present invention was obtained by soaking and aminating the membrane, which consisted of a pulse part and three water parts. The properties of the anion exchange membrane of the present invention are shown in Table 4. The anion exchange membrane used for comparison is the original ion exchange membrane. Table 4 Rice 1: As an ion exchange membrane for sea core concentration. Neocepta OH-45T manufactured by Kohada Soda Yoko was used.

Example 5 A sheet of 0.1 skin of polyvinyl chloride was dissolved in 20 parts of styrene, 5 parts of divinylbenzene with a purity of about 55%, 1 part of dioctyl phthalate, and 0.5 part of woven penzoyl peroxide with 3 parts of dioxane. After soaking, impregnating, and swelling in the polymer membrane, this was layered with cellophane, rolled up, tightened, heated and polymerized in an autoclave to 110 qo in a nitrogen atmosphere, and then the cellophane film was peeled off to form a polymer membrane. I got something like that.

This was sulfonated by soaking it in 98% 6000 concentrated sulfuric acid for 1 hour to obtain a cation exchange membrane (original ion exchange membrane). Now, this cation exchange membrane was made into a cation exchange membrane of the present invention according to the method shown in FIG.

That is, each roll has a length of 90 cm, roll 1 has a diameter of 30 cm, rolls 2 and 3 have a diameter of 20 cm, and roll 4 has a diameter of 10 cm. Roll 3 is equipped with a cation exchange membrane, and roll 2 is coated with cellophane. I installed each one. Next, the soaking liquid was 2 parts styrene, 2 parts methacrylic acid, and had a purity of about 55%.
Using a solution of 1 part of lauroyl peroxide dissolved in 15 parts of divinylbenzene, a film of cellophane was passed through the soaking solution at a feed rate of 1/min to form the cation exchange membrane. It was superimposed on the surface and wound up into roll 1. Next, this was placed in an autoclave in a 100 qo nitrogen atmosphere and polymerized by heating to form a polymer film. This is 6. The carboxylic acid groups on the surface layer were converted to sodium carboxylate by soaking them in the specified caustic soda. The properties of the membrane are shown in Table 5. Note that the membrane for comparison in the table is the original ion exchange membrane itself.

Table 5 *1 This is the result of performing salt electrolysis.

In other words, a three-chamber salt electrolyzer (effective current carrying area: LD) was used, which was equipped with an anode chamber, an intermediate chamber, and a cathode chamber; the anode was a titanium lath coated with titanium oxide and ruthenium oxide, and the cathode was used soft iron lath material.

Saturated saline was supplied to the anode chamber and the intermediate chamber at a current density of 20 A/d, and 6N caustic soda was obtained from the cathode chamber.
The current efficiency was determined from the concentration and liquid volume of the caustic soda obtained and the theoretical current flow rate. The temperature during electrolysis was 70°C. Example 6 A polymer membrane material using the styrene-divinylbenzene-based polyvinyl chloride cloth obtained in Example 1 as a reinforcing material was prepared in Example 1.
The ion exchange membrane of the present invention was prepared using a coating apparatus similar to that shown in FIG.

That is, the dipping solution used was 10 parts of 4-vinylpyridine, 2 parts of divinylbenzene with a purity of 55%, and 1 part of penzoyl peroxide. As the membrane-like covering material, a polyvinyl alcohol sheet having a thickness of 0.02 ribs was used. The feeding speed of the polymer film was slow, 0.1 m/min, to allow it to penetrate sufficiently and uniformly into the polymer film. Next, it was wound onto a take-up roll, and after being tightened, the roll was rotated at room temperature for about 6 hours, and the cross section of the polymer membrane was sufficiently soaked evenly, and then it was heated for 70 minutes in a nitrogen atmosphere.
Polymerization was carried out by heating at ℃ for 1 hour. Next, the polypynyl alcohol sheet was peeled off, and the resulting polymer membrane was sulfonated using a sulfonating compound consisting of sulfuric acid and chlorosulfonic acid in the same manner as in Example 1, and then sequentially immersed in a diluted solution. After that, the membrane was washed with 2.5N caustic soda to obtain an amphoteric ion exchange membrane having sulfonic acid groups and tertiary amino groups. Furthermore, this membrane was immersed in an alkylation system consisting of 4 parts of methyl iodide and 6 parts of methanol to alkylate the pyridine ring to form a quaternary ammonium base. When this membrane was immersed in a 0.5% aqueous solution of crystal violet and allowed to equilibrate, the cross section of the membrane was examined for staining, and was found to be uniformly stained purple. Next, this was sufficiently equilibrated with 0.5N saline solution, washed with water, and repeatedly soaked in 0.2N potassium nitrate solution while changing the solution. The exchange capacity of intestinal ions and anions was measured by exchanging sodium ions with ions and analyzing the dissolved sodium ions and chloride ions. Table 6 shows the properties of the obtained membrane. Table 6 Example 7 The polymer membrane material (original ion exchange membrane) containing the polyvinyl chloride cloth used in Example 1 as a reinforcing material was used in Example 2.
In the same manner as above, the ion exchange membrane of the present invention was prepared using the coating side shown in FIG.

That is, the soaking liquid was prepared by mixing 5 parts of 4-vinylpyridine, 4 parts of styrene, 1 part of divinylbenzene with a purity of about 55%, and 2 parts of penzoyl peroxide. was used. In addition, as a membrane coating material, 0.02
A cellulose-based film (cellophane) was used on the side.
The feeding speed of the polymer film was set at 15 skins/min so that the cellophane film penetrated only into the vicinity of the surface layer of the film, and the cellophane film was overlapped, wound onto the winding roll 1, and quickly autoclaved. 100q in nitrogen atmosphere
Polymerization was carried out by heating at 300° C. for 4 hours to obtain a polymer film. This film increase was 4%. This was then dissolved in 60% of 98% concentrated sulfuric acid.
The sample was immersed in a solution adjusted to 0.00 for 1 hour for sulfonation treatment. Next, it was immersed in 4 bags of methyl iodide and 6 parts of n-hexane (weight ratio) at 2,500 ml for 1 hour,
The intestinal ion exchange membrane of the present invention was obtained by alkylating the pyridine ring in the surface layer of the membrane. In the cation exchange membrane of the present invention, sulfonic acid groups are mainly present in the center and back surface of the membrane, and a layer containing a mixture of quaternary ammonium bases and sulfonic acid groups is formed only in one surface layer of the membrane. It seems that To confirm this, the membrane of the present invention was immersed in a 0.5% aqueous solution of crystal violet and stained, and the cross section was observed. Only the surface of the membrane to which the immersion liquid had adhered and polymerized had a thickness of about 10 microns, and the degree of staining was was getting weaker. Table 7 shows the properties of the membranes measured. The membrane for comparison was an original ion exchange membrane sulfonated under the same conditions as in this example.

Table 7 *1 Neocepta AFS-4T (trade name) manufactured by Tokuyama Soda ■ was used as an anion exchange membrane for seawater concentration.

[Brief explanation of drawings]

FIGS. 1 to 8 are typical principle diagrams for manufacturing the composite ion exchange membrane of the present invention. Each number in the figure indicates the following aspect. 1 is a winding roll, 2
is a film-like coating material, 3 is a polymer film-like material, 4 is a follow-on roll,
5 is a guide roll, 6 is an expander roll, and 7 is an immersion liquid vat. Figure 1 Figure 2 Figure 3 Younger brother's plan Figure 5 Figure 6 Figure 7 Figure 8 Theory

Claims (1)

[Claims] 1. Holding a membrane-like coating material and an ion-exchange membrane or a polymer membrane-like material into which ion-exchange groups can be easily introduced in separate holders,
Continuously attaching a monomer having a vinyl group and/or an aryl group, or a mixture of the monomers, to a membrane coating material, an ion exchange membrane, or a polymer membrane into which ion exchange groups can be easily introduced. After that, the membrane coating material and an ion exchange membrane or a polymer membrane into which ion exchange groups can be easily introduced are laminated,
A method for producing a composite ion exchange membrane, which comprises subsequently polymerizing the monomer and introducing an ion exchange group as necessary. 2. The method for producing a composite ion exchange membrane according to claim 1, wherein the composite ion exchange membrane has a thin layer with a high concentration of fixed ions formed on the surface layer of at least one side of the ion exchange membrane. 3. The method for producing a composite ion exchange membrane according to claim 1, wherein the composite ion exchange membrane is a bipolar membrane. 4. The method for producing a composite ion exchange membrane according to claim 1, wherein the membrane coating material is one type of membrane coating material selected from the group consisting of polyvinyl alcohol, polyester, and cellulose. 5 Claim 1 in which the monomer is a polyvinyl compound
A method for manufacturing the composite ion exchange membrane described above.