JP6915297B2 - Method for Producing Cyrilized Layered Inorganic Compound - Google Patents

Description

The present invention relates to a method for producing a silylated layered inorganic compound, which chemically modifies the layers of the layered inorganic compound with a silylating agent.

As a method of silylating and modifying the layers of the layered inorganic compound, the metal cations existing between the layers are exchanged with organic onium such as alkylonium to widen the interlayer distance, and then chlorosilanes [R _n SiCl _4-n ] or A method is known in which alkoxysilanes [R ¹ _n Si (OR ² ) _4-n ] are allowed to act to react the hydroxyl groups or metal alkoxylates existing between layers with the silanes.

For example, in Non-Patent Document 1, magadiate is used as a layered inorganic compound, and dodecyltrimethylammonium chloride is allowed to act on the magadiate to exchange sodium ions, which are interlayer cations, with dodecyltrimethylammonium, and then the interlayer distance is widened. It has been described that 3-methacryloxypropyltrimethoxysilane is allowed to act as a silylating agent to form 3-methacryloxypropyl silylation between layers.

Further, in Non-Patent Document 2, magadiaite is used as a layered inorganic compound, and dodecyltrimethylammonium chloride is allowed to act on the magadiaite to exchange sodium ion as an interlayer cation with dodecyltrimethylammonium, and then the interlayer distance is widened. It has been described that octyl trichlorosilane is allowed to act as a silylating agent to form octylsilylation between layers.

Chem. Mater. 2000, 12,1702-1707 Chem. Mater. 2003, 15,3134-3141

However, in Non-Patent Document 1, in order to proceed with the interlayer silylation reaction, it is necessary to use a large excess amount of 3-methacryloxypropyltrimethoxysilane, which is an alkoxysilane, about 35 mol times as much as the reaction site. It is industrially unsuitable.
In addition, when 3-methacryloxypropyldichloromethylsilane, which is a chlorosilane having a high silylation reactivity, is used, the action of hydrogen chloride produced as a by-product causes the hydrolysis of the ester and the addition of hydrogen chloride to the vinyl group by Michael. It is stated that the use of chlorosilanes is not preferable because the reaction proceeds.

Further, Non-Patent Document 2 describes that the silylation reaction between layers proceeds almost quantitatively by using octyltrichlorosilane which is a chlorosilane as a silylating agent.
However, when chlorosilane is used, a large amount of hydrogen chloride is produced as a by-product, which may corrode the manufacturing equipment. Therefore, it is necessary to use a special manufacturing equipment and to dispose of a large amount of hydrogen chloride. Industrially unsuitable. Further, since the types of chlorosilane-based silylating agents on the market are limited, the types of interlayer modification of inorganic layered compounds using these are limited, and the interlayer modification according to the application is limited, so that it is industrial. Is disadvantageous to.

In view of the above circumstances, it is an object of the present invention to provide a method for producing a silylated layered inorganic compound that efficiently silylates and modifies a wide variety of layers of layered inorganic compounds.

As a result of diligent studies to solve the above problems, the present inventor has found that the above problems can be solved by adding a specific range of water to the silylation reaction system, and completes the present invention. I arrived.

That is, in the first invention of the present invention, when silylating and modifying a layered inorganic compound with a silylating agent in the presence of an organic solvent, 0.1 to 3 is applied to the total amount of hydroxyl groups and alkoxy groups in the layered inorganic compound. A method for producing a silylated layered inorganic compound, which comprises adding 0.0 mol times water to carry out a silylation reaction.

The second invention is the method for producing a silylated layered inorganic compound according to the first invention, wherein the silylating agent is represented by the following formula (1).
[R ¹ _n Si (OR ² ) _4-n ] (1)
(In the formula (1), R ¹ is independently a hydrogen atom, a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 8 carbon atoms, respectively. Saturated cycloalkyl groups, aryl groups with 1 to 20 carbon atoms, and aralkyl groups with 1 to 20 carbon atoms, which are vinyl groups, epoxy groups, oxetanyl groups, acryloxy groups, metharoxy groups, hydroxyl groups, amino groups, alkylamino groups, respectively. It may be substituted with an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanato group, a carboxyl group or a halogen atom, and R ² is independently a hydrogen atom and a saturated or unsaturated alkyl having 1 to 8 carbon atoms, respectively. A group, a saturated or unsaturated cycloalkyl group having 1 to 8 carbon atoms, a trimethylsilyl group, a dimethylsilyl group, or a saturated or unsaturated heterocycloalkyl group having 1 to 8 carbon atoms, where n represents an integer of 0 to 4. .)

The third invention is, I organic solvent aprotic polar solvents der, in ethers, method for producing a nitrile or the first invention or silylated layered inorganic compound according to the second aspect Ru ketones der be.

Further, the fourth invention is the method for producing a silylated layered inorganic compound according to any one of the first to third inventions, wherein the layered inorganic compound contains any one of a layered silicate, a layered clay mineral and a layered metal oxide. Is.

By using the method for producing a silylated layered inorganic compound of the present invention, it is possible to efficiently silylate and modify the layers of the layered inorganic compound even with a silylating agent having a relatively low reactivity such as alkoxysilanes, depending on the application. Various silylated layered inorganic compounds can be obtained. The silylated layered inorganic compound can be used as various fillers, adsorbents, host compounds for functional molecules, and the like.

It is a conceptual diagram which shows the silylation modification of a layered inorganic compound by a silylating agent. It is a figure which shows the thermogravimetric analysis result of the silylated layered inorganic compound.

Hereinafter, the present invention will be described in detail. Unless otherwise specified, the number of copies represents parts by mass and% represents mass%.

The layered inorganic compound in the present invention is not particularly limited, but is graphite, a layered metal chalcogenide, a layered metal oxide (for example, titanium oxide, a layered perovskite compound mainly composed of niobide oxide, titanium niobate, molybdenate). Etc.), layered metal oxyhalides, layered metal phosphates (eg layered antimonate phosphates, etc.), layered clay minerals, layered silicates (eg mica, smectites (montmorillonite, saponite, hectolite, fluorohect) Wright, etc.), Kaolin (kaolinite, etc.), Magadite, Kenyaite, Kanemite, etc.) and layered compound hydroxides.
Among these, layered silicates, layered clay minerals and layered metal oxides are preferably used because of their availability, etc., but these may be either naturally produced or artificially synthesized. May be good.

In the present invention, first, an alkali metal such as sodium and potassium existing in the layered inorganic compound and a metal cation such as an alkaline earth metal such as magnesium and calcium are exchanged with alkylonium or the like to cause a layered inorganic compound. It is necessary to widen the layers of the above, and as a method of widening the layers, a known method such as interlayer modification with a long-chain alkylammonium salt can be applied.
In the silylated layered inorganic compound in the present invention, as shown in FIG. 1, after the layers of the layered inorganic compound are modified with organic onium or the like and expanded, all or a part of the hydroxyl groups and alkoxy groups of the layered inorganic compound are silylated. A silylated layered inorganic compound is produced by silylation modification (silylation reaction) with an agent.
The organic onium used in the present invention is not particularly limited, and for example, organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium, organic oxonium, organic sulfonium, organic sulfoxonium, organic selenonium, organic carbonium, organic diazonium, and organic Salts such as iodonium, organic pyririnium, organic pyrrolidinium, organic carbenium, organic asylium, organic thiazolinium, organic alsonium, organic stibonium, organic telluronium, etc., among others, of organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium and organic sulfonium. Salts are preferable, and these onium salts are used alone or in combination of two or more.
Although there is no particular limitation on the organic group include an alkyl group of C1 to C22, aralkyl group C7～C22, aryl group _{C6~C22, - (CH 2 -CH (} CH 3) O) m -H group, -(CH _2- CH _2- O) _n −H groups, m and n are integers from 1 to 20.
The method for modifying the layers of the layered compound with organic onium is not particularly limited, and a known method can be used. For example, by mixing organic onium and a salt such as a halide ion such as chloride ion, a bromide ion, or a cation ion with a layered inorganic compound in a solvent such as water or alcohols such as methanol, the layered inorganic compound can be mixed. The layers can be modified with organic onium by the cation exchange reaction between the exchangeable metal cation and the organic onium.
The organic cation salt used for interlayer modification is not particularly limited, and for example, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, octadecyltrimethylammonium chloride, dimethyloctadecylphenylammonium chloride, triethylbenzylammonium chloride, etc. Dodecyl ammonium chloride, dimethyl dipolyethylene oxide ammonium chloride, dimethyl dipropylene oxide ammonium chloride, dimethyl polyethylene oxide polypropylene oxide ammonium chloride, dimethyl stearyl polyethylene oxide ammonium chloride, dimethyl stearyl polypropylene oxide ammonium chloride, methyl stearyl dipolyethylene oxide ammonium chloride, methyl chloride Stearyldipolypropylene oxide ammonium, benzylmethyldipolyethylene oxideammonium chloride, benzylmethyldipolypropylene oxideammonium chloride, 1-ethylpyridinium bromide, 1-octadecylpyridinium chloride, 3-methyl-1-propylimidazolium bromide, 3-chloride Examples thereof include methyl-1- (2-naphthyl) imidazolium, triphenyl (tetradecyl) phosphonium bromide, ethyldimethylsulfonium chloride, and triphenylsulfonium bromide.

The silylating agent in the present invention means all of the compounds that cause a silylation reaction, and so-called silane coupling agents are also included in the silylating agent in the present invention.
The silylating agent in the present invention is not particularly limited, but is preferably one in which the hydrolyzable group is an alkoxy group, not chlorosilanes as a by-product of hydrogen chloride, and for example, a compound represented by the following formula (1). Is preferable.
[R ¹ _n Si (OR ² ) _4-n ] (1)
(In the formula (1), R ¹ is independently a hydrogen atom, a saturated or unsaturated alkyl group of a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated group of a linear or branched chain having 1 to 8 carbon atoms, respectively. Saturated cycloalkyl group, aryl group having 1 to 20 carbon atoms, and aralkyl group having 1 to 20 carbon atoms, which are vinyl group, epoxy group, oxetanyl group, acryloxy group, methacryloxy group, hydroxyl group, amino group, alkylamino group, respectively. It may be substituted with an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanato group, a carboxyl group and a halogen atom, and R ² is independently a hydrogen atom and a saturated or unsaturated alkyl having 1 to 8 carbon atoms, respectively. A group, a saturated or unsaturated cycloalkyl group having 1 to 8 carbon atoms, a trimethylsilyl group, a dimethylsilyl group, or a saturated or unsaturated heterocycloalkyl group having 1 to 8 carbon atoms, where n represents an integer of 0 to 4. .)

In the silylating agent represented by the formula (1), when a plurality of hydrolyzable groups are present in one molecule, a single hydrolyzable group such as a methoxy group, an ethoxy group or a propoxy group is present. However, a plurality of them may be mixed, and may be substituted with a higher alkoxy group such as a butoxy group or a pentoxy group. Further, the functional group may be protected by an appropriate protecting group.
Among these, those having a hydrolyzable group of methoxy group, ethoxy group and propoxy group are preferable, and those of methoxy group and ethoxy group are particularly preferable, because they are superior in silylation reactivity.

Examples of the silylating agent represented by the formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, and the like. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropyl dimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri Methoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-triethoxysili-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-amino Hydrochloride of propyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyandiapropyltriethoxysilane , 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 7-octenyltrimethoxysilane, 4- (trimethoxy) Cyril) butyric acid, 4- (trimethoxysilyl) butyrate 1,1-dimethylethyl, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n- Propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, Dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, 1,2-bis (trimethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,4- Examples thereof include bis (trimethoxysilyl) benzene, trifluoropropyltrimethoxysilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, triethoxysilane, tetramethoxysilane and tetraethoxysilane.

Further, although not particularly limited, a silylating agent other than alkoxysilane can also be used. For example, hexamethyldisilazane, chlorotrimethylsilane, hexamethyldisilazane, trimethylsilyltrifluoromethanesulfonate, triethylchlorosilane, tertiarybutyldimethylchlorosilane, chlorotriisopropylsilane, 1,3-dichloro-1,1,3,3-tetra. Isopropyldisiloxane, chloromethyltrimethylsilane, triethylsilane, allyltrimethylsilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosisilane, tris (N, N-dimethylamino) methylsilane, bis (N, N) -Dimethylamino) dimethylsilane and (N, N-dimethylamino) trimethylsilane and the like.
In these silylating agents, when a plurality of hydrolyzable groups are present in one molecule, even if a single hydrolyzable group such as an alkoxy group, a halogen atom or an alkylamino group is present, a plurality of hydrolyzable groups are present. May be mixed.

Further, even if a titanium-based coupling agent, an aluminum-based coupling agent, a zirconia-based coupling agent, or the like is used instead of the above silylating agent, the same effect as that of the present invention is exhibited.

The organic solvent used for the silylation reaction in the present invention is not particularly limited, but is not particularly limited, but is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl. Alcohols such as -1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, acetone and ethyl Ketones such as methyl ketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alcohols such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate, chloroform And halogen-based hydrocarbons such as dichloromethane.
Among these, ethers, nitriles and ketones which are alcohols and aprotonic polar solvents are preferable, and ethers, nitriles and ketones which are aprotonic polar solvents are more preferable.

The water added during the silylation reaction in the present invention may be neutral, acidic or alkaline, and is not particularly limited, but ion-exchanged water, distilled water, pure water and ultrapure water are preferable.
The amount of water added during the silylation reaction in the present invention is 0.05 to 4.0 mol times the total amount of the hydroxyl groups and the alkoxyl groups which are the reaction points of the layered inorganic compound, and is 0.1 to 3. It is preferably 0 mol times.
If the amount of water added is less than 0.05 mol times, the addition effect is small, and if it exceeds 4.0 mol times, side reactions such as hydrolysis and condensation between the silylating agents may proceed.

The silylation reaction with a silylating agent is generally a reaction under water-free conditions, and even in the preceding documents (Non-Patent Documents 1 and 2), the precursor to be subjected to the silylation reaction, that is, the layers are modified with alkylammonium. The layered inorganic compound is sufficiently dried and then reacted. In this case, it is necessary to react a large excess of silylating agent (3-methacryloxypropyltrimethoxysilane) of about 35 mol times with respect to the reaction site.
If the amount of the silylating agent to react under such water-reactive conditions is reduced to one-fifth of that in Non-Patent Document 1, the silylation reaction rate is significantly reduced, but the silylating agent is not inactivated. When water in the above range is added, the silylation reaction rate between layers can be improved with almost no progress of side reactions of the silylating agent.

The amount of the silylating agent used in the silylation reaction is not particularly limited, but is preferably 0.1 to 30 mol times, more preferably 1 with respect to the total amount of the hydroxyl group and the alkoxy group which are the reaction points. It is ~ 20 mol times, more preferably 1-10 mol times.
If the amount of the silylating agent used is less than 0.1 mol times, the silylation reaction rate becomes low, while if it exceeds 30 mol times, it is industrially disadvantageous in terms of raw material cost.

The silylation rate with respect to the ion exchange capacity of the reaction point between the layers of the layered inorganic compound is not particularly limited because it is selected according to the purpose, but the silylation rate is preferably 0.7 or more. On the other hand, if the silylation rate exceeds 2.0, the layers of the layered inorganic compound may be excessively covered with the silylating agent-derived component, which is not preferable. By adding a specific amount of water of the present invention, the amount of the silylating agent required to achieve the desired silylation rate can be reduced as compared with the case where no water is added.

The reaction temperature in the silylation reaction is not particularly limited, but is preferably 0 to 200 ° C, more preferably 50 to 160 ° C, and even more preferably 70 to 150 ° C. Usually, it is preferable to react at the boiling point (under heating / reflux) of the organic solvent used as the reaction solvent.

The amount of the organic solvent used in the silylation reaction is not particularly limited, but is 1 to 30 times by mass, more preferably 5 to 25 times by mass, and further preferably 10 times the amount of the layered inorganic compound used as a raw material. ~ 20 times by mass.

The silylation reaction in the present invention may or may not use a catalyst, but may include carboxylic acids such as hydrogen chloride, formic acid, acetic acid and oxalic acid, and sulfonic acids such as phosphoric acid, nitric acid, sulfuric acid and methyl sulfonic acid. Known acids and known bases such as ammonia, trimethylamine, triethylamine, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide can be added as catalysts.
In that case, the catalyst to be added is preferably 0.01 to 1 mol times, more preferably 0.01 to 0.1 mol times, the total amount of the hydroxyl group and the alkoxy group which are the reaction points.

The silylated layered inorganic compound obtained by the silylation reaction is preferably isolated, washed and then dried. The method for isolation, washing and drying is not particularly limited, and known methods for isolating, washing and drying layered inorganic compounds and inorganic fine particles can be used.
For example, as an isolation method, the reaction solution is allowed to stand, or after centrifugation to separate solid and liquid, the supernatant is removed by decantation, or by filtration operations such as natural filtration, pressure filtration, and reduced pressure filtration. Examples include filtering the layered inorganic compound.
The pressure during pressure filtration is not particularly limited, and may be in the range of 1 to 5 atm, for example. The pressure during vacuum filtration is not particularly limited and may be in the range of 0 to 1 atm.

As a cleaning method, the solid obtained after decantation is redispersed in water or an organic solvent, and then decanted in the same manner, or water or an organic solvent is poured over the collected solid to wash the solid. How to do it.
The water used for cleaning may be neutral, acidic or alkaline, and is not particularly limited, but is preferably ion-exchanged water, distilled water, pure water and ultrapure water.
The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol and ethanol, ketones such as acetone and ethyl methyl ketone, alkanes such as hexane, and aromatics such as toluene. At this time, in order to improve the contact between the layered inorganic compound and water, an organic solvent such as an appropriate polar solvent can be used in combination.

As a method for drying the solid obtained above, the organic solvent can be air-dried at normal temperature and pressure, or the organic solvent can be removed while appropriately heating or cooling at room temperature under reduced pressure.
The pressure at the time of depressurization is not particularly limited and may be in the range of 0 to 1 atm. The temperature is also not particularly limited, preferably −10 to 200 ° C., more preferably 0 to 150 ° C., and particularly preferably 10 to 100 ° C.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
<Synthesis Example 1> Synthesis of sodium magadiate (hereinafter referred to as Na-magadiate) 18.34 g of sodium silicate (manufactured by Fuji Chemical Industries, Ltd., trade name: sodium silicate No. 4), silica gel (manufactured by Wako Pure Chemical Industries, Ltd., Product name: Wakogel Q-63) 7.28 g and pure water 54.37 g are mixed, then sealed in a high-pressure reaction decomposition container (manufactured by San-ai Scientific Co., Ltd., product name: HU-100), and 30 at 170 ° C. Heated for hours. The product was collected by suction filtration, washed with a dilute aqueous NaOH solution (pH: 9-10) and pure water, and dried at 40 ° C. for 2 days to obtain 15.9 g of Na-magadiate.
The bottom spacing of Na-magadite obtained using an X-ray diffractometer (manufactured by BRUKER, trade name: D8 ADVANCE) was determined to be 1.54 nm.

<Synthesis Example 2> Synthesis of DTMA-magadiate, which is a precursor of silylated-modified magadiate (layer-related modification of Na-magadiate with dodecyltrimethylammonium (hereinafter referred to as DTMA))
Obtained in Synthesis Example 1 Na-magadiite _{(Formula: Na 2 Si 14 O 29 ·} nH 2 O) 50g, mixed pure water 3250g and dodecyltrimethylammonium chloride 87.7 g, and stirred at room temperature for 7 days. Then, the solid was sucked and collected, washed with methanol, and dried at 60 ° C. to obtain 47 g of DTMA-magadiate.
As a result of measuring the mass of Na in the obtained DTMA-magadite using an atomic absorption spectrometer (AA-6200, manufactured by Shimadzu Corporation), the Na content was less than 0.04% by mass, and almost all cations were exchanged. I confirmed that it was done.
The composition of DTMA-magadiate obtained using an elemental analyzer (Yanako Analytical Industry Co., Ltd., CHN coder MT-5) and a thermogravimetric analyzer (Hitachi High-Tech Science Corporation, TG / DTA6300) was calculated. _{It was 1.57} H _0.35 Si ₁₄ O ₂₉ · nH ₂ O.
Further, the bottom surface interval of DTMA-magadite obtained by using an X-ray diffractometer (D8 ADVANCE manufactured by BRUKER) was determined to be 2.80 nm.

<Example 1>
5.0 g of DTMA-magadiate obtained in Synthesis Example 2 was dried under reduced pressure at 100 ° C. and about 100 Pa for 2 hours, and then dispersed in 78.2 g of acetonitrile dried with Molecular Sieve 3A. 18 mg of pure water and 10.8 g (hereinafter referred to as MAC-TRIMS) of 3-methacryloxypropyltrimethoxysilane (hereinafter referred to as MAC-TRIMS) were mixed thereto, and heated under reflux in a nitrogen atmosphere for 48 hours. Stirred. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C. to obtain 4.8 g of silylated magadite (hereinafter referred to as MACPS-magadite).
CHN element analyzer (Yanako Analytical Industry Co., Ltd., CHN coder MT-5), thermogravimetric analyzer (Hitachi High-Tech Science Co., Ltd., TG / DTA6300) and atomic absorption spectrometer (Shimadzu Corporation, AA-6200) The composition of MACPS-magadiate obtained using) was calculated to be 3-methacryloxypropylsilyl (MACPS) _1.65 Me _0.35 Si ₁₄ O ₂₉ · nH ₂ O.
The bottom surface spacing of MACPS-magadite obtained using an X-ray diffractometer (D8 ADVANCE manufactured by BRUKER) was determined and found to be 2.35 nm.
^Also, 29 Si nuclear magnetic resonance (NMR) (JEOL Ltd., JNM-ECA 400 type) was analyzed by the shift by silylation modification thereto peak of ^{Q 3} from silanol magadiite is approximately ^{Q 4} Therefore, it was confirmed that the silylation reaction proceeded between the layers.

<Comparative example 1>
During the silylation reaction of DTMA-magadiate, the same treatment as in Example 1 was carried out except that pure water was not added, to obtain MACPS-magadiate.

<Examples 2 to 6>
During the silylation reaction of DTMA-magadiate, the amount of pure water added was changed from 18 mg (0.125 mol times the cation exchange equivalent of DTMA-magadiaite) to 36 mg (0.25 mol times) and 72 mg (0.5 mol times). MACPS- Got Magadite.

<Comparative example 2>
The same treatment as in Example 1 was carried out except that the amount of pure water added was changed to 715 mg (5.0 mol times the cation exchange equivalent of DTMA-magadiate) to obtain MACPS-magadiate.

The compositions of the silylated layered inorganic compounds obtained in Examples 1 to 6 and Comparative Examples 1 and 2 are CHN elemental analysis (manufactured by Yanaco Analytical Industry Co., Ltd., trade name: CHN coder MT-5), thermoweight analysis (stock). It was calculated by Hitachi High-Tech Science Co., Ltd., trade name: TG / DTA6300) and Na elemental analysis (manufactured by Shimadzu Corporation, trade name: elemental absorptiometer AA-6200), and the results are shown in Table 1.
Regarding the silylation rate in Table 1, a maximum of two silylating agents capable of directly reacting with the total amount of hydroxyl groups and alkoxy groups derived from _{Si 14} O ₂₉ derived from the main skeleton of the layered inorganic compound magadite. Therefore, it is a value obtained by dividing the analysis value of MACPS ( _{molar ratio to Si 14} O ₂₉ ) by 2.

The following abbreviations in Table 1 mean:
MACPS: 3-methacryloxypropylsilyl DTMA: dodecyltrimethylammonium Me: methyl N. D: Not detected

As can be seen from Table 1, Examples 1 to 6 in which water was added and the silylation reaction was carried out had a higher silylation rate and were efficiently silylated as compared with Comparative Example 1 in which water was not added. ..
Further, when the ratio of the amount of water added is changed and water is added 0.125 to 3.0 mol times, the silylation rate improves as the amount of water added increases.
On the other hand, in the case of Comparative Example 2 in which water was added 5.0 mol times, it was estimated from the thermogravimetric analysis result (FIG. 2) that the silylation rate exceeded 2.0 and some silylating agents formed a network. Will be done. That is, in Comparative Example 2, it is presumed that the thermogravimetric reduction in the vicinity of about 300 ° C. to 400 ° C. was significantly smaller than that in Examples 1 to 6, and that many siloxane networks in which the silylating agents were condensed were formed. Will be done.

Claims (4)

When silylating and modifying a layered inorganic compound with a silylating agent in the presence of an organic solvent, water of 0.1 to 3.0 mol times the total amount of hydroxyl groups and alkoxy groups in the layered inorganic compound was added. A method for producing a silylated layered inorganic compound, which comprises carrying out a silylation reaction. The method for producing a silylated layered inorganic compound according to claim 1, wherein the silylating agent is represented by the following formula (1).
[R ¹ _n Si (OR ² ) _4-n ] (1)
(In the formula (1), R ¹ is independently a hydrogen atom, a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 8 carbon atoms, respectively. Saturated cycloalkyl groups, aryl groups with 1 to 20 carbon atoms, and aralkyl groups with 1 to 20 carbon atoms, which are vinyl groups, epoxy groups, oxetanyl groups, acryloxy groups, metharoxy groups, hydroxyl groups, amino groups, alkylamino groups, respectively. It may be substituted with an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanato group, a carboxyl group or a halogen atom, and R ² is independently a hydrogen atom and a saturated or unsaturated alkyl having 1 to 8 carbon atoms, respectively. A group, a saturated or unsaturated cycloalkyl group having 1 to 8 carbon atoms, a trimethylsilyl group, a dimethylsilyl group, or a saturated or unsaturated heterocycloalkyl group having 1 to 8 carbon atoms, where n represents an integer of 0 to 4. .) Manufacturing method of the organic solvent is I aprotic polar solvents der, ethers, nitriles or ketones der Ru claim 1 or silylated layered inorganic compound according to claim 2. The method for producing a silylated layered inorganic compound according to any one of claims 1 to 3, wherein the layered inorganic compound contains any one of a layered silicate, a layered clay mineral and a layered metal oxide.

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