KR20140122060A - Preparation method of organoclay using polar organic solvent - Google Patents

Abstract

The present invention relates to a method for preparing organoclay using a polar organic solvent, and more specifically, to a method for preparing organoclay using a polar organic solvent, including a step of adding 1 part by weight of activated clay to 4 to 100 parts by weight of a polar organic solvent, adding 1 to 5 parts by weight of an organifier thereto and reacting the mixture, and drying an obtained product. The method enhances solubility of an organifier by using a polar organic solvent when preparing organoclay, even if an organic defoamer agent is not used, reduces energy for a drying process, and enhances drying speeds, thereby improving productivity of the organoclay and lowering water content in finally obtained organoclay.

Description

Preparation method of organoclay using polar organic solvent < RTI ID = 0.0 >

The present invention relates to a method for producing an organic clay having a high solubility of an organic agent by using a polar organic solvent as a solvent without using water as a solvent and increasing the amount of feed per unit reactor, And a method for producing organic clay that can improve productivity.

Clay minerals are hydrated aluminum silicate minerals with cations such as potassium, calcium, and magnesium. In general, clay minerals are classified by crystal structure, not by particle size, but they are classified by types of rocks and petrological features, equipment and media for transporting sediments, time and route for transportation, Depending on the environment and the climatic conditions in the area.

For this reason, clay minerals are very helpful for geological research, and clay minerals as well as geological studies have been applied to various places due to various characteristics.

In particular, organic clays substituted by cations of clay minerals have high chemical affinity with other organic materials and have been used as paints, lubricants, greases, putties, adhesives, thickeners and antifoams. In recent years, as a result of adsorption studies between organic clay and organic contaminants which are combined with organic cations have been known, they have been used as adsorbents (purification materials) for organic pollutants in wastewater, and active researches are still under way in advanced countries.

Korean Patent No. 10-0788498 discloses a process for preparing a polyester nano-composite material by preparing a polyester-reactive organic clay by adding cation-exchange reaction between a layered clay and a specific alkylbenzenetriarylphosphine salt as an organizing agent, I am suggesting.

Korean Patent Laid-Open Publication No. 2005-0001551 discloses an amino group-modified polypropylene; Organic layered clay; Layer structure clay nanocomposite comprising the amino group-modified polypropylene and the polypropylene resin in which the organic layer-structured clay is dispersed, wherein the nanocomposite has excellent affinity with respect to rigidity, heat resistance, And mechanical properties such as impact resistance are far superior to polypropylene resins.

Korean Patent Laid-Open Publication No. 2008-0006744 discloses that when an organic clay is mixed with a resin such as polyamide, it has excellent mechanical strength, is excellent in an oxygen barrier property, an organic solvent barrier property, It can be used for single layer, multilayer blow molding and film processing.

Korean Patent Publication No. 2012-0025252 mentions that water-soluble organic clay only exerts an effect of selectively suppressing harmful algae because it affects only the cell membrane of harmful algae and does not affect any other marine ecosystem.

The application of organic clay in various fields is accomplished through the cation exchange reaction of clay minerals.

For example, in Korean Patent No. 10-0473300, an aqueous slurry of smectite-type clay having a cation exchange capacity of at least about 75 milliequivalents per 100 g of clay on a 100% active clay basis is prepared, 100 C < / RTI > to produce an organic clay.

Korean Patent Publication No. 2002-0006904 discloses a pro-organic clay containing a quaternary ammonium salt and a method for producing the same, and a method for producing a quaternary ammonium salt by reacting an aqueous solution of a quaternary ammonium salt containing a water-dispersed clay and a derivative of a phenyl group with a quaternary ammonium salt And the reaction product is dried by a weight ratio of 1: 2 to 5, and the quaternary ammonium salt is produced.

And WO 2008/156032 discloses a process for swelling a layered clay mineral having a number average particle diameter of 10 to 300 nm with water or an aqueous solvent to swell the swollen layered clay minerals; And then cation exchange treatment of interlayer metal cations of the layered clay mineral with an organic onium ion in an amount corresponding to 60 to 120% of the methylene blue (MB) adsorption equivalent by adding an organic onium salt And suggests a method for producing organic clay.

In the various patents, clay minerals are generally swollen in water during the production of organic clays. In order to increase the dispersibility when water is added, defoamers for removing bubbles are essentially used have.

Korean Patent No. 10-0788498 Korean Patent Publication No. 2008-0006744 Korean Patent Publication No. 2012-0025252 Korean Patent No. 10-0473300 Korea Patent Publication No. 2002-0006904 WO 2008/156032 United States Patent Application Publication No. 2008-0242778

Therefore, the inventors of the present invention have conducted various studies on a production method for performing the reaction without any additives such as defoaming agents and improving the productivity of the organic clay. As a result, it has been found that when a polar organic solvent is used as a solvent, It is confirmed that the solubility is high and the drying speed is increased without foaming, thereby completing the present invention.

Accordingly, an object of the present invention is to provide a method for producing a new organic clay without using additives such as water and defoamer.

In order to achieve the above object, the present invention provides a method for producing an activated clay comprising the steps of adding 1 part by weight of active clay to 4 to 100 parts by weight of a polar organic solvent, adding 1 to 5 parts by weight of an organic agent to the mixture, ,

Wherein the polar organic solvent comprises one selected from the group consisting of methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, diethyl ketone, and combinations thereof.

The method proposed by the present invention is based on the use of a polar organic solvent in the production of organic clay, so that even when a defoaming agent is not used, bubbles are rarely generated and the solubility of the organic agent is high. Not only the productivity is improved but also the moisture content in the final obtained organic clay can be lowered.

Fig. 1 is a photograph showing the organic clay prepared in Example 1. Fig.
2 is an X-ray diffraction spectrum of Example 1. Fig.
3 is an X-ray diffraction spectrum of Example 2. Fig.
4 is an X-ray diffraction spectrum of Example 3. Fig.
5 is an X-ray diffraction spectrum of Example 4. Fig.
6 is an X-ray diffraction spectrum of Comparative Example 5;
7 is an X-ray diffraction spectrum of Example 6. Fig.
8 is an X-ray diffraction spectrum of Comparative Example 1. Fig.
9 is an X-ray diffraction spectrum of Comparative Example 2. Fig.
10 is an X-ray diffraction spectrum of Comparative Example 3. Fig.
11 (a) is a scanning electron microscope image of Example 3, and (b) is an enlarged image thereof.
12 (a) is a scanning electron microscope image of Example 4, and (b) is an enlarged image thereof.
13 (a) is a scanning electron microscope image of Example 5, and (b) is an enlarged image thereof.
14 (a) is a scanning electron microscope image of Example 6, and (b) is an enlarged image thereof.
15 (a) is a scanning electron microscope image of Comparative Example 1, and (b) is an enlarged image thereof.

Hereinafter, the present invention will be described in more detail.

Conventionally, it is common to use water as a solvent in the production of organic clay, and United States Patent Application Publication No. 2008-0242778 discloses an organic clay produced by dispersing montmorillonite in an organic solvent such as toluene and then using an ammonium salt or a phosphonium salt. It took a long time of 20 hours or longer and the organic clay produced at this time showed a low yield of about 60%.

In the present invention, in the production of organic clay, productivity can be increased by reacting clay with an organizing agent in a specific polar organic solvent other than water or toluene, and the moisture content in the finally obtained organic clay can be lowered.

Preferably, a polar organic solvent is selected as the solvent. Such a polar organic solvent easily dissolves the organic agent rather than water, and the bubbles are small and the use of an additional additive such as defoamer is not required. The reaction proceeds at a relatively lower temperature than water and can be easily dried, Thereby reducing the overall cost. In particular, since the drying speed is faster than that of water, productivity is improved, and since the final obtained organic clay has a low water content, there is no need for an additional drying step, thereby enhancing the competitiveness of the product.

However, not all polar organic solvents are possible, and the solvent should be such that the active clay can be dispersed uniformly without precipitation or aggregation. The polar organic solvent that can be used is one or more selected from the group consisting of methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, diethyl ketone, and combinations thereof, preferably ethanol.

According to Experimental Example 1 of the present invention, organic clays were produced at a high yield of 87% or more in Examples 1 to 9 in which organic clays were prepared using methanol, ethanol, isopropyl and acetone as polar organic solvents. In contrast, in Comparative Example 4 using toluene as the solvent, the content was low at 45%. In Comparative Example 5 using butanol similar to methanol and the like, the active clay was not dispersed smoothly and the reaction hardly proceeded. Organic clay was prepared in the yield. Also, in the reaction time, the reaction was completed in 3 to 4 hours in the case of Examples 1 to 4 such as methanol, but the reaction was performed for 20 to 24 hours in the case of using toluene as a solvent.

In addition, the polar organic solvent according to the present invention has a low boiling point (bp, 占 폚) and specific heat characteristics, so that drying can be performed in a short time. Table 1 below shows boiling point (bp, ° C) and specific heat at 20 ° C according to the solvent.

bp (占 폚) Specific heat (J / gK), 20 ℃ water 100 4.18 Methanol 64.7 2.34 Isopropanol 82.5 2.68 Acetone 56-57 2.16 ethanol 78.4 2.44 Methyl ethyl ketone 79.6 2.19 Diethyl ketone 102 2.23 Butanol 118 1.72 toluene 111 3.72

Referring to Table 1, when a polar organic solvent is used as a solvent, a fast drying time can be secured at the same temperature. From these results, it can be seen that productivity and energy saving can be achieved by using a polar organic solvent.

From these results, it can be seen that the yield, the reaction time and the drying time are largely affected by the solvent in the production of the organic clay. In the case of using the solvent of the present invention, the reaction time and the drying time are relatively shortened It can be seen that the organic clay can be produced at a high yield in addition to the shortening of the manufacturing process time.

The production of the organic clay using the polar organic solvent is carried out by reacting the active clay with the organizing agent in a polar organic solvent, followed by drying.

The active clay is not particularly limited in the present invention, and any of those conventionally used in this field can be used. Representative examples include clay, montmorilonite, bentonite, hectorite, saponite, attapulgite, sepiorite, laponite, beadelite, Swellable layered silicates including beidellite, nontronite, vermiculite, and the like, each of them, or a combination thereof.

The particles of the active clay are not particularly limited in the present invention and may vary depending on the application field of the finally obtained organic clay. Specifically, the particle size varies from several nanometers to thousands of microns. When the organic clay particles are to be applied at the nano level, the active clay used as the starting material is nanoparticles, and a few micron organic clay If you want to get a micron-level particle is used.

These active clays have adsorbed cations such as H ⁺ , Na ⁺ , Mg ²⁺ , K ⁺ , Ca ²⁺ , and Al ³⁺ on the surface, which can attach other functional groups by ion exchange. These functional groups can be introduced by reaction with an organic agent.

The organizing agent which can be used is not particularly limited in the present invention, and any organic compound can be used as long as it contains onium which can be substituted with the cation of the active clay.

Examples of the organizing agent include primary to quaternary ammonium, phosphonium, maleate, succinate, acrylate, benzylic hydrogens, And oxazoline. Preferably, a quaternary ammonium salt is used. The quaternary ammonium salt may be used alone or in combination of two or more.

The preferred ammonium salt is a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R 1 to R 4 are the same or different from each other and each represents H, a C1 to C18 alkyl group, a C1 to C18 hydroxyalkyl group, a C3 to C20 aryl group, a C3 to C20 acryl group, a polyalkylene (C1 to C4) And X is a chloride, bromide, iodide, nitride, hydroxide, sulfate, methyl sulfate or acetate group.

Preferably, the quaternary ammonium salt is selected from the group consisting of trimethylalkyl (C1-C18) ammonium salts, triethylalkyl (C1-C18) ammonium salts, tributylalkyl (C1-C18) ammonium salts such as dialkyl (C1-C18) ammonium salts, methylbenzyl dialkyl (C1-C18) ammonium salts, dibenzyl dialkyl , Trialkyl (C1-C18) butylammonium salts; Quaternary ammonium salts having an aromatic ring such as benzylmethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride; Quaternary ammonium salts derived from aromatic amines such as trimethylphenyl ammonium; Quaternary ammonium salts having heterocyclic rings such as alkyl (C1-C18) pyridinium salts and imidazolium salts; An alkyl quaternary ammonium salt having three polyethylene glycol chains, a dialkyl quaternary ammonium salt having two polypropylene glycol chains, a trialkyl (C1 to C18) quaternary ammonium salt having one polyethylene glycol chain, and a polypropylene glycol chain having 1 And trialkyl quaternary ammonium salts having one to three carbon atoms. Among them, mention may be made of lauryltrimethylammonium salt, stearyltrimethylammonium salt, trioctylmethylammonium salt, dimethyldioctadecylammonium salt, dialkyldimethylammonium salt, distearyldibenzylammonium salt, N-polyoxyethylene-N-lauryl-N, An ammonium salt, and an alkyl quaternary ammonium salt having three polyethylene glycol chains are preferable. These quaternary ammonium salts may be used singly or in combination of two or more kinds. Among these ammonium salts, trioctylmethylammonium salt or dimethyldioctadecylammonium salt and polyoxyethylene alkyl (C8-C18) methylammonium salt (alkyl quaternary ammonium salt having three polyethylene glycol chains) are preferably used in combination.

The quaternary phosphonium salt is not particularly limited and includes, for example, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, Stearyltributylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethylphosphonium salt, distearyldibenzylphosphonium salt, and the like can be given. These quaternary phosphonium salts may be used alone or in combination of two or more. Among the above phosphonium salts, the use of tributyldodecylphosphonium salt and stearyltributylphosphonium salt is preferred

In the preferred and comparative examples of the present invention, dimethyloctadecylammonium salt, coconut bis (2-hydroxyethyl) methylammonium salt, hexadecyltrimethylammonium salt, tetrabutylammonium salt and trimethylstearylammonium salt were used.

In the production of the organic clay containing the above-mentioned composition, 1 part by weight of the active clay is added to 4 to 100 parts by weight of a polar organic solvent, and 1 to 5 parts by weight of an organic agent is added thereto.

If the content of the polar organic solvent is less than the above range, the organic agent is not sufficiently dissolved or the active clay is not uniformly dispersed. On the other hand, when the amount exceeds the above range, it takes a longer time to remove the polar organic solvent, and the cost is increased due to excessive use of the polar organic solvent.

At this time, the reaction is carried out with stirring at 20 to 80 ° C for 30 minutes to 6 hours, and the temperature range is varied depending on the kind of the polar organic solvent. If the reaction is carried out at a temperature lower than the above temperature, the organic agent may not sufficiently dissolve or the dispersibility of the active clay may be lowered, resulting in a slow reaction rate or a low yield. Conversely, if the temperature is exceeded, The dispersibility of the clay may be lowered.

Adding the ingredients contained in the mixture, adding the ingredients, and / or adding them all together, or using an agitator. The type of the stirrer used is not particularly limited and may be a conventional stirrer, a double helix mixer, a high-speed emulsifier, a homogenizer, a high shear blender or an ultrasonic homogenizer homogenizer) and the like can be used, and they can be selectively used depending on the amount of the raw material to be supplied.

The stirring is carried out at 50 to 1000 rpm, and is suitably used in consideration of the size of the reactor, the content of the reactant, and the like.

If necessary, ultrasonic waves are applied before the reaction, whereby each active clay can be finely pulverized and homogeneously dispersed.

When the reaction is completed, the organic clay is recovered through filtration and drying is performed at 40 to 80 ° C for 30 minutes to 72 hours to sufficiently remove the polar organic solvent. This drying temperature has the advantage that it can proceed at a lower temperature than when water is used as the solvent. At this time, if necessary, the drying is carried out under reduced pressure.

Through the drying, the organic cation existing in the surface of the active clay is replaced with the cation of the organizing agent to produce an organic clay having various functional groups introduced on its surface.

The organic clay thus prepared can be used as an additive, an adsorbent, and a water treatment agent in various fields. Organic clay is highly miscible with organic components and can be used for agricultural (soil improvement agent, fertilizer mixture, pesticide additive, soil mixture), fishery (marine pollution prevention agent, red tide prevention agent, (Wastewater treatment agent, desiccant, ceramics raw material, pharmaceutical raw material, crude oil, building material, filter agent) for livestock (odor removing agent, water purification agent, feed additive) , Fillers), ion exchangers, catalysts, adsorbents, dehydrating agents, deodorants and the like to improve flame retardancy, insulation, strength, conductivity, corrosion resistance, barrier properties and abrasion resistance.

The method for producing organic clay according to the present invention can provide the following advantages by using a polar organic solvent instead of the conventional method.

Firstly, even when the defoaming agent is not used, bubbles are not generated during the reaction, and the increase in cost and the troubles in the process due to the use of the defoaming agent can be solved.

Secondly, the use of a polar organic solvent does not require the introduction of additional additives or processes for improving the solubility, because the solubility of the organizing agent is higher than that of water.

Third, there is an advantage that the energy for the drying process is small and the drying speed is high, thereby improving the productivity of the organic clay.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrating the present invention, and the scope of the present invention is not limited to these examples.

[Example]

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

Example 1

After 1.97 g of tetrabutylammonium salt was dissolved in 95 g of ethanol, 5 g of montmorillonite was added, stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 1.46 nm

Example 2

After 2.39 g of trimethylstearyl ammonium salt was dissolved in 95 g of ethanol, 5 g of montmorillonite was added, stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and filtered. The filtered filtrate was washed with distilled water and vacuum dried at 80 DEG C to prepare an organic clay. The interlayer distance shown in XRD was 1.83 nm

Example 3

7.02 g of dimethyldioctadecylammonium salt was dissolved in 90 g of methanol, 10 g of montmorillonite was added, stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 2.83 nm

Example 4

7.02 g of dimethyldioctadecylammonium salt was dissolved in 90 g of ethanol and 10 g of montmorillonite was added thereto. The mixture was stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 2.58 nm

Example 5

7.02 g of dimethyldioctadecylammonium salt was dissolved in 90 g of acetone and 10 g of montmorillonite was added thereto. The mixture was stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 3.20 nm

Example 6

In the reactor, 7.02 g of dimethyldioctadecylammonium salt was dissolved in 90 g of isopropanol, 10 g of montmorillonite was added, stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and then filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 2.23 nm

Example 7

4.12 g of coconut bis (2-hydroxyethyl) methylammonium salt was dissolved in 90 g of acetone, 10 g of montmorillonite was added, stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and then filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 1.80 nm

Example 8

7.02 g of dimethyl dioctadecylammonium salt was dissolved in 95 g of methyl ethyl ketone, 10 g of montmorillonite was added, stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and then filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 2.54 nm

Example 9

In the reactor, 7.02 g of dimethyldioctadecylammonium salt was dissolved in 90 g of diethyl ketone, 10 g of montmorillonite was added, stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and then filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 2.65 nm

Comparative Example 1

3.51 g of dimethyl dioctadecylammonium salt was dissolved in 95 g of distilled water, and 5 g of montmorillonite was added thereto. The mixture was stirred at 60 rpm, reacted at 80 ° C for 4 hours, and filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 3.42 nm

Comparative Example 2

After 2.06 g of coconut bis (2-hydroxyethyl) methylammonium salt was dissolved in 95 g of distilled water, 5 g of montmorillonite was added, stirred at 60 rpm, reacted at 80 ° C for 4 hours, and then filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 1.81 nm

Comparative Example  3

2.06 g of hexadecyltrimethylammonium salt was dissolved in 95 g of distilled water, 5 g of montmorillonite was added, stirred at 60 rpm, reacted at 80 DEG C for 4 hours, and then filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay. The interlayer distance shown in XRD is 1.91 nm

Comparative Example 4

An organic clay was prepared in the same manner as in Example 1 using toluene as disclosed in U.S. Patent No. 2008/0242778. Specifically, 1.97 g of tetrabutylammonium salt was dissolved in 95 g of toluene, 5 g of montmorillonite was added, and the mixture was stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay.

Comparative Example 5

Organic clay was prepared in the same manner as in Example 1 except that butanol was used as a solvent. Specifically, 1.97 g of tetrabutylammonium salt was dissolved in 95 g of butanol, 5 g of montmorillonite was added, and the mixture was stirred at 60 rpm, reacted at a reflux temperature for 4 hours, and filtered. The filtered filtrate was washed with distilled water and vacuum-dried at 80 ° C to prepare an organic clay.

division Furtherance Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 clay Montmorillonite 5g 5g 10g 10g 10g 10g 10g Organic agent Dimethyl dioctadecylammonium salt - - 7.02 g 7.02 g 7.02 g 7.02 g - Coconut bis (2-hydroxyethyl) methylammonium salt - - - - - - 4.12 g Hexadecyltrimethylammonium salt - - - - - - - Tetrabutylammonium salt 1.97 g - - - - - - Trimethylstearylammonium salt - 2.39 g - - - - - Reaction temperature Stirring Mantle Heat Reflux temperature Reflux temperature Reflux temperature Reflux temperature Reflux temperature Reflux temperature Reflux temperature Reaction solvent Methanol - - 90g - - - - ethanol 95g 95g - 90g - - - Acetone - - - - 90g - 90g Isopropanol - - - - 90g -

division  Product Name Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 clay Montmorillonite 10g 10g 5g 5g 5g 5g 5g Organic agent Dimethyl dioctadecylammonium salt 7.02 g 7.02 g 3.51 g - - - - Coconut bis (2-hydroxyethyl) methylammonium salt - - - 2.06 g - - - Hexadecyltrimethylammonium salt - - - - 2.22 g - - Tetrabutylammonium salt - - - - - 1.97 g 1.97 g Trimethylstearylammonium salt - - - - - - - Reaction temperature Stirring Mantle Heat Reflux temperature Reflux temperature 80 ℃ 80 ℃ 80 ℃ Reflux temperature Reflux temperature Reaction solvent Methyl ethyl ketone 95g - - - - - - Diethyl ketone - 95g - - - - - Distilled water - - 95g 95g 95g - - toluene - - - - - 95g - Butanol - - - - - - 95g

Experimental Example 1: Yield Measurement

The yield and reaction time of the organic clay obtained in the above Examples and Comparative Examples were measured and are shown in Table 4 below.

yield Reference (reaction solvent / reaction time) Example 1 92% Ethanol (4 hours) Example 2 90% Ethanol (4 hours) Example 3 89% Methanol (4 hours) Example 4 91% Ethanol (4 hours) Example 5 87% Acetone (4 hours) Example 6 88% Isopropanol (4 hours) Example 7 89% Acetone (4 hours) Example 8 87% Methyl ethyl ketone (4 hours) Example 9 90% Diethyl ketone (4 hours) Comparative Example 1 45% Distilled water (4 hours) Comparative Example 2 43% Distilled water (4 hours) Comparative Example 3 35% Distilled water (4 hours) Comparative Example 4 41% Toluene (4 hours) Comparative Example 5 5% Butanol (4 hours)

Referring to Table 4, the yields of organic clays produced by the methods of Examples 1 to 9 according to the present invention were as high as 87% or higher, and in Comparative Examples 1 to 5 prepared by the same method, 5 to 45% And the yield was very low.

Specifically, it can be seen that the organic clay can be produced at a high yield of at least two times, compared with Comparative Examples 1 to 3 in which distilled water is used as a reaction solvent. In the case of Comparative Example 4, the production yield of organic clay was lower than that of Example 1 by 50% or more even when toluene was used as a reaction solvent. In the case of Comparative Example 5, clay minerals were not dispersed in butanol but precipitated and subjected to ultrasound-assisted reaction. However, organic clay was prepared at a very low yield. As a result, butanol was found to be inadequate as a reaction solvent.

Experimental Example 2: X-ray diffraction analysis

X-ray diffraction analysis was performed to confirm the structure of the organic clay obtained in the above Examples and Comparative Examples, and the interlayer distances are shown in Table 5 below.

Interstory distance Reference (reaction solvent / reaction time) Example 1 1.46 nm Ethanol (4 hours) Example 2 1.83 nm Ethanol (4 hours) Example 3 2.83 nm Methanol (4 hours) Example 4 2.58 nm Ethanol (4 hours) Example 5 3.20 nm Acetone (4 hours) Example 6 2.23 nm Isopropanol (4 hours) Example 7 1.80 nm Acetone (4 hours) Example 8 2.54 nm Methyl ethyl ketone (4 hours) Example 9 2.65 nm Diethyl ketone (4 hours) Comparative Example 1 3.42 nm Distilled water (4 hours) Comparative Example 2 1.81 nm Distilled water (4 hours) Comparative Example 3 1.91 nm Distilled water (4 hours) Comparative Example 4 2.28 nm Toluene (4 hours) Comparative Example 5 3.22 nm Butanol (4 hours)

Figs. 2 to 10 are X-ray diffraction spectra of the organic clay prepared in Examples and Comparative Examples. Fig. 2 shows the results of Example 1, Fig. 3 shows Example 2, Fig. 4 shows Example 3 and Fig. Example 4, Fig. 6 is an X-ray diffraction analysis spectrum of the organic clay prepared in Example 5, Fig. 7 is Example 6, Fig. 8 is Comparative Example 1, Fig. 9 is Comparative Example 2 and Fig. 10 is Comparative Example 3 .

Referring to Table 5 and FIG. 2 to FIG. 10, it can be seen that the interlayer distance of Comparative Example 1 in which water is used as a reaction solvent is 3.42 nm, and the interlayer distance is wider than that of the organic clays of Examples 1 to 6 using ethanol or the like have. However, Examples 5 and 7 using acetone showed almost the same results as those of Comparative Example 1 and Comparative Example 2 using distilled water.

Experimental Example 3: Scanning Electron Microscopy Analysis

Scanning electron microscopy was performed to confirm the state of the particles of the organic clay obtained in the Examples and Comparative Examples, and the results are shown in FIGS. 11 to 15. FIG.

11 to 15 are scanning electron microscope images of the organic clay particles, wherein (b) is an enlarged view of (a). Specifically, FIG. 11 shows the results of Example 3 (methanol), FIG. 12 shows Example 4 (ethanol), FIG. 13 shows Example 5 (acetone), FIG. 14 shows Example 6 (isopropanol) Water).

11, the organic clay prepared in Examples 3 to 6 of the present invention had a plate-like particle state, and in the case of Comparative Example 1 in which water was used as a reaction solvent, the surface of the clay particles had a curved surface and each was folded . This tendency was similar in the organic clays prepared in Examples 7 to 9.

13, in the case of Example 5 using acetone as a solvent, it can be seen that the surface has a curved surface and each is folded like the surface of the clay particles of Comparative Example 1 (see Fig. 15) using water as a solvent.

Claims (6)

Adding 1 to 4 parts by weight of an active agent to 4 to 100 parts by weight of a polar organic solvent, adding 1 to 5 parts by weight of an organic agent to the reaction mixture, and drying the resultant reaction product,
Wherein the polar organic solvent comprises one selected from the group consisting of methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, diethyl ketone, and combinations thereof. The method of claim 1, wherein the active clay is selected from the group consisting of montmorilonite, bentonite, hectorite, saponite, attapulgite, sepiorite, laponite, Characterized in that it comprises one species selected from the group consisting of each of swellable layered silicates including beidellite, nontronite and vermiculite, or a combination thereof. Gt; The method of claim 1, wherein the organic agent is selected from the group consisting of primary to quaternary ammonium, phosphonium, maleate, succinate, acrylate, Wherein the organic clay comprises one selected from the group consisting of benzylic hydrogen, oxazoline, and combinations thereof. The method of claim 1, wherein the organic agent is selected from the group consisting of dimethyloctadecylammonium salt, coconut bis (2-hydroxyethyl) methylammonium salt, hexadecyltrimethylammonium salt, tetrabutylammonium salt, trimethylstearylammonium salt, ≪ / RTI > by weight of the organic clay. The method of claim 1, wherein the reaction is carried out at 20 to 80 ° C for 30 minutes to 6 hours. The method according to claim 1, wherein the drying of the organic clay is carried out at room temperature to 110 ° C for 30 minutes to 72 hours under atmospheric pressure or under vacuum until the water content in the organic clay becomes optimum.

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