JPH06154624A - Production of intercalation compound cation exchanger - Google Patents

Abstract

PURPOSE:To decrease a required quantity of a reaction medium and an onium salt, to improve yield and to reduce reaction time at the time of obtaining a cation exchanger of an intercalation compd. by the use of an onium salt slightly soluble or insoluble in water. CONSTITUTION:In a method for producing the cation exchanger of the intercalation compd. by cation exchanging an exchangeable cation of the intercalation compd. having the exchangeable cation in the interlayer with the onium salt, the intercalation compd. and the onium salt are dispersed in a nonaqueous solvent and the dispersed solution is mixed with a high dielectric solvent hardly dissolving the onium salt and having excellent swelling property for the intercalation compd. In this case, a quaternary ammonium salt, phosphonium salt and a cation dye which are slightly soluble or insoluble in water are used as the onium salt and a montmorillonite group is used as the intercalation compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for obtaining an intercalation compound cation exchanger by ion-exchanging exchangeable cations between intercalation compounds using an onium salt.

[0002]

2. Description of the Related Art Montmorillonite has a layered structure formed by repeating a three-layer structure having an octahedron as a basic skeleton, and has an alkali metal ion as an exchangeable cation between layers. Regarding an intercalation compound having an exchangeable cation in the background, a cation exchanger in which the exchangeable cation is ion-exchanged with an onium salt is used for a pigment, a display composition, a photographic paper, etc. in the field of image forming method. (Japanese Patent Application Laid-Open No. 2-292084, Japanese Patent Application No. 3-89592)
Etc.).

Conventionally, as a method for producing such a cation exchanger of a clay-based intercalation compound, the intercalation compound is dispersed or swollen in a liquid in which a water-soluble onium salt is dissolved or uniformly dispersed, and then filtered to form an interlayer. Method of obtaining a cation exchanger of the compound, or conversely, the intercalation compound is dispersed in water to swell, the onium salt is dissolved or dispersed in the aqueous dispersion in which the intercalation compound is swollen, and then filtered to remove the intercalation compound The technique of obtaining a cation exchanger is used.

[0004]

However, when following the above-mentioned method of using a water-soluble onium salt and using an onium salt that is hardly soluble or insoluble in water, the following problems occur. Was there.

That is, a desired cation exchanger can be obtained by using a mixed solvent of water and a non-aqueous solvent as a reaction medium, but such a mixed solvent is used to dissolve or homogenize an onium salt. In order to disperse and sufficiently swell the intercalation compound, a large amount of the mixed solvent must be used, which increases the filtration time for collecting the target substance and increases the wastewater treatment amount. Therefore, there was a problem of lack of mass productivity.

Further, since the above-mentioned conventional cation exchange reaction is basically an equilibrium reaction, in order to improve the yield and shorten the reaction time, an excessive amount of onium ion must be present in the reaction system. However, when using a sparingly soluble or insoluble water-soluble onium salt as described above, a large amount of the mixed solvent used as the reaction medium must be used.Therefore, excess onium ions are present in the reaction system. Therefore, there is a problem that the yield cannot be improved and the reaction time cannot be shortened.

The present invention is intended to solve the above problems of the prior art, and is necessary even when a cation exchanger of an intercalation compound is obtained using an onium salt that is sparingly soluble or insoluble in water. To reduce the amount of the reaction medium and the amount of onium salt required for the reaction so that the cation exchanger can be economically obtained, and to improve the yield and shorten the reaction time. It is intended to obtain a cation exchanger of an intercalation compound with high mass productivity.

[0008]

Means for Solving the Problems The inventors of the present invention used a nonaqueous solvent, which is a good solvent for onium salts, as a first solvent to disperse an intercalation compound and an onium salt, and then used a poor solvent for the onium salts. In addition, they have found that when a high dielectric constant solvent that easily swells the intercalation compound is mixed as the second solvent, ion exchange is efficiently promoted, and the present invention has been completed.

That is, the present invention provides a method for producing an intercalation compound cation exchanger by cation exchange of an intercalation compound having an exchangeable cation between layers with an onium salt. A salt and a non-aqueous solvent, and then this dispersion is mixed with a high-dielectric-constant solvent that is a poor solvent for the onium salt and has an excellent swelling property for the intercalation compound. A method for manufacturing an ion exchanger is provided.

Examples of the intercalation compound which can be ion-exchanged by the method of the present invention include montmorillonite minerals. Montmorillonite minerals, the following general formula _{(X, Y) 2 ~3 Z} 4 O 10 (OH) 2 · mH 2 O ·
(W _1/3 ) [where X = Al, Fe (III), Mn (III), C
n (III), Y = Mg, Fe (II), Mn (II)
, Ni, Zn, Li, Z = Si, Al, W = K, N
a and Ca, H ₂ O represents interlayer water, and m represents an integer. ] It is a clay mineral represented by. Here, depending on the combination of X and Y and the difference in the substitution number, montmorillonite, magnesian montmorillonite, iron montmorillonite, iron magnesian montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontronite, saponite, aluminian saponite, Many types of hectorite, sauconite, etc. exist as natural products, but in addition to these natural products, synthetic products in which the OH group in the above formula is substituted with halogen such as fluorine are also commercially available, and both are used. can do.

In addition to the above montmorillonite group minerals, sodium silicic mica, sodium teniolite,
Mica group minerals such as lithium teniolite can be used. Kaolinite, talc, pyrophyllite, etc., which have a layered structure but do not have exchangeable cations between layers, are not preferable. Further, although zeolite has an alkali metal ion or an alkaline earth metal ion as an exchangeable cation, its performance is remarkably inferior because its structure is reticulated and its pore size is small, which is not preferable.

Examples of onium salts that can be used in the method of the present invention include quaternary ammonium salts, which are sparingly soluble or insoluble in water, phosphonium salts and cationic dyes. As such an onium salt, for example, in the case of a quaternary ammonium salt, one having a bulky cation in which the number of carbon atoms of four alkyl groups is 4 or more can also be used, and the phosphonium salt can also be an alkylphosphonium ion, Those having a bulky cation such as an arylphosphonium ion can be preferably used.

In the method of the present invention, such an intercalation compound and an onium salt are first dispersed in a non-aqueous solvent. Here, the non-aqueous solvent depends on the type of the onium salt used. A solvent that gives a good solvent is used appropriately.

Next, a high dielectric constant solvent which is a poor solvent for the onium salt and is excellent in the swelling property of the intercalation compound is mixed with a dispersion liquid in which the intercalation compound and the onium salt are dispersed in a non-aqueous solvent. Here, as the high dielectric constant solvent, those which are compatible with the original non-aqueous solvent are preferable. For example, when ethanol or acetone is used as the non-aqueous solvent, water can be used as the high dielectric constant solvent. Thereby, the cation exchanger of the intercalation compound can be efficiently deposited in the dispersion liquid.

The deposited ion exchanger can be filtered and washed by a conventional method.

[0016]

The ion exchange in the method of the present invention is considered to proceed as follows. First, when an intercalation compound and an onium salt are dispersed in a non-aqueous solvent, the non-aqueous solvent disperses the onium salt well, but since the action of swelling the intercalation compound and the action of ion dissociation are poor, the intercalation compound at this time is Does not occur. Next, when this dispersion is mixed with a high dielectric constant solvent which is a poor solvent for an onium salt and easily swells an intercalation compound, first, swelling and ionic dissociation occur between layers of the intercalation compound, resulting in partial hydrophobicity between the layers. A surface is formed, and then the reaction medium becomes poorly soluble in the onium salt, so that the onium salt moves to the hydrophobic surface between the layers having a high affinity with the onium salt, and ion exchange proceeds rapidly.

As described above, according to the method of the present invention, by controlling the solubility of the intercalation compound and the onium salt, the equilibrium in the ion exchange reaction is greatly disrupted and the reaction is promoted. Therefore, the reaction yield is increased. Also, since the reaction field of ion exchange is limited to the vicinity of the interlayer of the intercalation compound,
The frequency of collision between the intercalation compound and the onium ion increases, and the ion exchange reaction is completed in a short time. Furthermore, the amount of solvent required for the ion exchange reaction is the minimum necessary (about 1 /
(About 50) is sufficient, and the required amount of onium salt is about the same amount as the ion exchange capacity of the intercalation compound without being excessively large. Therefore, ion exchange can be economically achieved. Further, this makes it possible to reduce the amount of solvent to be treated after the reaction, so that the treatment time after the reaction can be shortened.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 70.3 g of tetra-n-decyl ammonium bromide
(Equivalent to 71.2 meq) was dissolved in 220 g of ethanol, and synthetic smectite (trade name: Smecton S was added to this.
A, manufactured by Kunimine Industries Co., Ltd.) was dispersed using a homogenizer to obtain a viscous dispersion. Next, add this dispersion to 2
It was immediately put into a beaker containing 20 g of water, stirred for 30 minutes, and left to stand, whereupon a white precipitate was deposited.

The precipitate was collected by filtration, washed with water and ethanol, and dried under reduced pressure at 70 ° C. for 1 hour to obtain a synthetic smectite ion exchanger. On the other hand, the filtrate in this case was collected and the ion exchange rate was determined. As a result, about 60% of the ion exchange capacity of this synthetic smectite was ion-exchanged.

For comparison, when a conventional smectite similar to that of this example was ion-exchanged using tetra-n-decylammonium bromide by a conventional method, about 60% of the ion-exchange capacity was ion-exchanged as in the example. In order to do so, about 50 times more solvent is required, and the processing time is about 2
I had to spend 0 times.

Example 2 A method described in Japanese Patent Application No. 3-10204, using an oxazine-based cationic dye for dyeing acrylic fibers (trade name: AIZEN Catiron Pia Blue 5GH, manufactured by Hodogaya Chemical Co., Ltd.). Ion exchange with dodecylbenzene sulfonic acid according to

[0023]

[Chemical 1] To obtain the lipophilic cationic dye of
0 g was dissolved in acetone, and 30 g of montmorillonite (trade name: Kunipia F, manufactured by Kunimine Industries Co., Ltd.) was dispersed using a homogenizer. After the stirring was stopped by the homogenizer, a part of the precipitate was collected by filtration and washed with a large amount of acetone. As a result, the dye was transferred to the cleaning liquid and a pale blue powder was obtained. From this, it is understood that ion exchange of montmorillonite by this cationic dye does not easily occur in a non-aqueous solvent.

Next, 100 parts of water was prepared by stirring the balance of the dispersion prepared by dispersing the cationic dye and montmorillonite in acetone.
It was added to g and the stirring was continued for about 1 hour. As a result, a blue precipitate was generated, and the supernatant was almost colorless and transparent.
When this precipitate was collected by filtration and washed with a large amount of water and acetone, no elution of the dye was observed in the washing liquid. The washed precipitate was dried, the interplanar spacing of the d001 plane was determined by X-ray diffraction, and the same interplanar spacing was obtained for untreated montmorillonite. The interplanar spacing of the washed precipitate was 17.2 angstroms. In comparison with untreated montmorillonite, it was extended by about 7 angstroms.
From this, it was confirmed that the alkali metal ions present in the initial layer of montmorillonite were completely ion-exchanged by the cationic dye in this precipitate.

For comparison, when montmorillonite was ion-exchanged by a conventional method in which montmorillonite was added to a solution in which a dye was dissolved in an acetone-water (1/2 weight ratio) mixed solvent, it was about 20 times that of this example. Solvent was required.

[0026]

According to the present invention, when an onium salt that is sparingly soluble or insoluble in water is used to obtain a cation exchanger of an intercalation compound, the amount of the reaction medium required is reduced and the reaction is necessary. It is possible to economically obtain a cation exchanger by reducing the amount of such an onium salt. Further, the yield can be improved, the reaction time can be shortened, and the mass productivity can be enhanced.

Claims (4)

[Claims] 1. A method for producing an intercalation compound cation exchanger by cation exchanging an exchangeable cation of an intercalation compound having an exchangeable cation between layers with an onium salt.
An interlayer compound and an onium salt are dispersed in a non-aqueous solvent, and then this dispersion is mixed with a high dielectric constant solvent which is a poor solvent for the onium salt and has excellent swellability of the interlayer compound. A method for producing an intercalation compound cation exchanger. 2. The method for producing an intercalation compound cation exchanger according to claim 1, wherein a quaternary ammonium salt, a phosphonium salt or a cationic dye which is sparingly soluble or insoluble in water is used as the onium salt. 3. The method for producing an intercalation compound cation exchanger according to claim 1, wherein the intercalation compound is selected from the group of montmorillonite minerals. 4. The method for producing an intercalation compound cation exchanger according to claim 1, wherein water is used as the high dielectric constant solvent.