JP2018150200A - Production method of silanized laminar inorganic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a silanized laminar inorganic compound that silanizes for modification efficiently an interlayer of many kinds of laminar inorganic compounds.MEANS FOR SOLVING THE PROBLEM: A production method of a silanized laminar inorganic compound is characterized in that an exchangeable cation of a laminar inorganic compound is subjected to cation exchange with an onium group at a rate of 25-75 mole% in terms of an ion-exchange capacity to obtain a precursor, which is silanized by a silanization agent. The silanized laminar inorganic compound is used as a various fillers, adsorbents, a host compound of a functional molecule or the like.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a silylated layered inorganic compound in which a layer of a layered inorganic compound is chemically modified with a silylating agent.

As a method for silylation modification between layers of a layered inorganic compound, an exchangeable cation existing between layers is exchanged with an onium such as an organic onium such as an alkylonium to increase the interlayer distance, and then chlorosilanes [R _n SiCl _{4 -n]} or alkoxysilanes ^{_{[R 5 n Si (oR 6}} ) 4-n] was allowed to act, methods are known to react with hydroxyl groups or alkoxylate present between layers and the silanes.

  For example, in Non-Patent Document 1, magadiaite is used as a layered inorganic compound, dodecyltrimethylammonium chloride is allowed to act on magadiite, and sodium ions that are exchangeable cations between layers are exchanged with dodecyltrimethylammonium to increase the interlayer distance. It is described that, after spreading, 3-methacryloxypropyltrimethoxysilane is allowed to act as a silylating agent so that the interlayer is 3-methacryloxypropylsilylated.

  In Non-Patent Document 2, magadiaite is used as a layered inorganic compound, dodecyltrimethylammonium chloride is allowed to act on magadiite, and sodium ions which are exchangeable cations between layers are exchanged with dodecyltrimethylammonium to increase the interlayer distance. After spreading, octyltrichlorosilane is allowed to act as a silylating agent to octylsilylate the interlayer.

Chem. Mater. 2000, 12, 1702-1707 Chem. Mater. 2003, 15, 3134-3141 React. Solids, 1988, 5,167-175

However, in Non-Patent Document 1, in order to proceed with the inter-layer silylation reaction, the alkoxysilanes 3-methacryloxypropyltrimethoxysilane have a large excess of about 35 mol times with respect to the reaction point, that is, the ion exchange capacity. It is necessary to use a quantity and is unsuitable industrially.
In addition, when 3-methacryloxypropyldichloromethylsilane, which is a chlorosilane having high silylation reactivity, is used, by the action of hydrogen chloride produced as a by-product, secondary hydrolysis such as ester hydrolysis and Michael addition of hydrogen chloride to the vinyl group occurs. It is described that the use of chlorosilanes is not preferred because the reaction proceeds.

Here, the ion exchange capacity represents the amount of ion exchange per unit weight of the ion exchanger, and is usually milliequivalent (meq / g) per gram of ion exchanger or milliequivalent (meq / 100 g) per 100 g of ion exchanger. , And a molar amount per kg of ion exchanger (mol _c / kg), a centimole amount per kg of ion exchanger (cmol _c / kg), and the like.
For example, the chemical formula of sodium magadiite is Na ₂ Si ₁₄ O ₂₉ .nH ₂ O, where n = 0, the formula weight is 903.2, and all sodium can be regarded as exchangeable cations. Therefore, the ion exchange capacity in this case can be expressed as 2.21 mol _c / kg.

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, since a large amount of hydrogen chloride is produced as a by-product, the production equipment may corrode, and it is necessary to use a special production equipment, and it is necessary to dispose of a large amount of hydrogen chloride. Industrially unsuitable. Furthermore, since the types of chlorosilane-based silylating agents that are commercially available are limited, the types of interlayer modification of layered inorganic compounds using these are limited, and the interlayer modification according to the application is limited. Is disadvantageous.

Moreover, in the said nonpatent literature 1, although 3-methacryloxypropyl trimethoxysilane which is alkoxysilanes is used as a silylating agent in large excess, silylation reaction is carried out, but the sodium ion which is an exchangeable cation is carried out at this time. The ratio of the onium group of the precursor substituted with organic onium dodecyltrimethylammonium is 80 mol% with respect to the ion exchange capacity.
In general, it is known that the exchangeable cation between layers of a layered inorganic compound is sufficiently exchanged with organic onium to increase the interlayer distance before the silylation reaction. For example, Non-Patent Document 3, which is a cited document of Non-Patent Document 1, describes that a large excess of organic onium salt of 12 mol times or more of the ion exchange capacity of sodium-magadiite, which is a layered inorganic compound, is allowed to act. ing.
Further, Non-Patent Document 2 shows that organic onium is sufficiently introduced between layers by repeating the operation of acting an excess of an organic onium salt of 3 mole times or more. However, there is no description or suggestion that when the amount of the organic onium between the layers of the precursor layered inorganic compound subjected to the silylation reaction is within a specific range, the silylation rate of the silylation reaction is improved.

  In view of the above situation, an object of the present invention is to provide a method for producing a silylated layered inorganic compound in which the layers of the layered inorganic compound are efficiently silylated and modified over a wide variety.

  As a result of diligent studies to solve the above problems, the present inventor has made the ratio of onium groups in the precursor before the silylation reaction with the silylating agent within a specific range, and then the precursor is converted into the silylating agent. It was found that the above-mentioned problems can be solved by silylation by means of, and the present invention has been completed.

  That is, according to the first invention of the present invention, the cation exchange of the exchangeable cation of the layered inorganic compound with an onium group at a rate of 25 to 75 mol% as an ion exchange capacity is performed with respect to a silyl group. It is a method for producing a silylated layered inorganic compound, characterized in that a silylation reaction is carried out with an agent.

  In the second invention of the present invention, an organic onium salt in a layered inorganic compound and an exchangeable cation that has not been cation-exchanged with the organic onium salt by reacting an organic onium salt with the layered inorganic compound. A method for producing a silylated layered inorganic compound according to the first aspect of the present invention, which is obtained by converting a part of a hydroxyl group into a hydroxyl group.

Moreover, 3rd invention is a manufacturing method of the silylated layered inorganic compound as described in 2nd invention whose organic onium salt is a compound represented by following formula (1).
^{R 1 R 2 R 3 R 4} N + X - (1)
(In the formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different, each having an alkyl group having 1 to 22 carbon atoms and an aralkyl having 7 to 22 carbon atoms. Group, an aryl group having 6 to 22 carbon atoms, — (CH ₂ —CH (CH ₃ ) O) _a —H group or — (CH ₂ —CH ₂ —O) _b —H group, wherein a and b are 1 (It is an integer of ˜20, and X ⁻ represents a halide ion.)

Moreover, 4th invention is a manufacturing method of the silylated layered inorganic compound in any one of 1st invention-3rd invention whose silylating agent is a compound represented by following formula (2).
[R ⁵ _n Si (OR ⁶ ) _4-n ] (2)
(In Formula (2), each R ⁵ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a saturated or unsaturated alkyl group having 1 to 8 carbon atoms. A saturated cycloalkyl group, an aryl group having 1 to 20 carbon atoms, and an aralkyl group having 1 to 20 carbon atoms, each of which includes a vinyl group, an epoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, an alkylamino group, It may be substituted with an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanate group, a carboxyl group, a halogen atom, or an alkoxysilyl group, and each R ⁶ is independently a hydrogen atom or a saturated group having 1 to 8 carbon atoms. Or an unsaturated alkyl group, a C1-C8 saturated or unsaturated cycloalkyl group, a trimethylsilyl group, a dimethylsilyl group Or a saturated or unsaturated heterocycloalkyl group having 1 to 8 carbon atoms, and n represents an integer of 0 to 4.)

  Furthermore, the 5th invention is a manufacturing method of the silylated layered inorganic compound in any one of the 1st invention-the 4th invention in which a layered inorganic compound contains either a layered silicate, a layered clay mineral, and a layered metal oxide. It is.

If the method for producing a silylated layered inorganic compound of the present invention is used, the interlayer of the layered inorganic compound can be efficiently silylated with a relatively low-reactivity silylating agent such as alkoxysilanes. Depending on the situation, various silylated layered inorganic compounds can be obtained. Silylated layered inorganic compounds can be used as various fillers, adsorbents, functional compound host compounds, and the like.
The silylated layered inorganic compound can be used in a state in which the structure in which the nanosheets constituting it are laminated is maintained, or can be used in a state in which the nanosheets are peeled off.

FIG. 1 is a conceptual diagram showing silylation modification of a layered inorganic compound by a silylating agent in the present invention. FIG. 2 is a graph showing the relationship between the proportion of the onium group of the precursor and the silylation rate in the examples.

The present invention will be described in detail below. Unless otherwise specified, parts are parts by mass, and% is mass%.

The layered inorganic compound in the present invention is not particularly limited, but graphite, layered metal chalcogenides, layered metal oxides (for example, layered perovskite compounds mainly composed of titanium oxide and niobium oxide, titanium / niobate, molybdate) Etc.), layered metal oxyhalides, layered metal phosphates (eg, layered antimony phosphates, etc.), layered clay minerals, layered silicates (eg, mica, smectite groups (montmorillonite, saponite, hectorite, fluorohect) Light), kaolin group (kaolinite, etc.), magadiite, kenyaite, kanemite, etc.) and layered double hydroxides.
Of these, layered silicates, layered clay minerals and layered metal oxides are preferably used because of their availability, etc., and these are either naturally produced or artificially synthesized. Also good.

In the present invention, it is obtained by reacting an exchangeable cation such as an alkali metal such as sodium and potassium present in the layered inorganic compound and a metal cation such as an alkaline earth metal such as magnesium and calcium with an organic onium salt. The layered inorganic compound having an expanded interlayer is a precursor of the silylated layered inorganic compound.
The precursor is a compound substituted with an onium group in an ion exchange capacity of 25 to 75 mol% with respect to the exchangeable cation of the layered inorganic compound, and the proportion of the onium group is 30 to 70 mol%. Preferably, it is 35 to 70 mol%.

  In order to adjust the ratio of the onium group in the precursor, a method in which an organic onium salt is reacted with the layered inorganic compound and then a part of the onium group in the layered inorganic compound is converted into a hydroxyl group with an acid is preferable.

When a metal cation is present between the layers as an exchangeable cation, the silylation rate by a silylating agent such as alkoxysilanes is reduced, and therefore it is preferable to reduce the metal cation by acid treatment.
Therefore, as a method for introducing an onium group between layers of a layered inorganic compound, an onium salt having an amount equal to or greater than the cation exchange capacity is reacted, and then an acid is used. Although there is a method of reacting a salt, a method of reacting an acid after reacting an onium salt of the former equivalent or more in order to further improve the silylation rate is more preferable.
In addition, as a method for adjusting and introducing the amount of onium groups between layers of the layered inorganic compound, a mixture of an onium salt and an acid in an appropriate amount may be reacted with the layered inorganic compound, and an appropriate amount of acid is firstly added. The onium salt may be reacted after the reaction (preferably less than the equivalent of the cation exchange capacity).

In the present invention, the onium salt to be reacted with the layered inorganic compound is not particularly limited, but organic onium is preferable, for example, organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium, organic oxonium, organic sulfonium, organic sulfoxonium, Organic selenonium, organic carbonium, organic diazonium, organic iodonium, organic pyririnium, organic pyrrolidinium, organic carbenium, organic acylium, organic thiazolinium, organic arsonium, organic stibonium, organic telluronium, and the like, among these, organic ammonium, organic Pyridinium, organic imidazolium, organic phosphonium and organic sulfonium salts are preferred, and these onium salts may be used alone or in combination of two or more. .
The is not particularly limited as organic groups, for example, an alkyl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, an aryl group having 6 to 22 carbon _{atoms, - (CH 2 -CH (CH} 3) O) _a —H group, — (CH ₂ —CH ₂ —O) _b —H group, and a and b are integers of 1 to 20, vinyl group, epoxy group, oxetanyl group, acryloxy group, methacryloxy Group, hydroxyl group, thiol group, isocyanate group, halogen atom, basic group such as amino group and alkylamino group, acidic group such as carboxyl group, photoacid generating group, thermal acid generating group, photobase generating group, thermal base It may be substituted with a functional group such as a generating group, a photo radical generating group and a thermal radical generating group.

More preferably, it is an organic onium salt represented by the following formula (1).
^{R 1 R 2 R 3 R 4} N + X - (1)
(In the formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different, each having an alkyl group having 1 to 22 carbon atoms and an aralkyl having 7 to 22 carbon atoms. Group, an aryl group having 6 to 22 carbon atoms and — (CH ₂ —CH (CH ₃ ) O) _a —H group or — (CH ₂ —CH ₂ —O) _b —H group, wherein a and b are 1 (It is an integer of ˜20, and X ⁻ represents a halide ion.)

The organic onium salt represented by the formula (1) is not particularly limited. For example, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, octadecyltrimethylammonium chloride, dimethyloctadecylphenylammonium chloride, Triethylbensyl ammonium chloride, 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 dichloride Polyethylene oxide ammonium Methylstearyl dipolypropylene oxide ammonium chloride, benzylmethyl dipolyethylene oxide ammonium chloride, benzylmethyl dipolypropylene oxide ammonium chloride, 1-ethylpyridinium bromide, 1-octadecylpyridinium chloride, 3-methyl-1-propylimidazolium bromide, chloride Examples include 3-methyl-1- (2-naphthyl) imidazolium, triphenyl (tetradecyl) phosphonium bromide, ethyldimethylsulfonium chloride, and triphenylsulfonium bromide.
Among these, Preferably, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dimethyl octadecyl phenyl ammonium chloride, triethyl benzyl acyl ammonium chloride, and dodecyl ammonium chloride are mentioned.

The method for modifying the interlayer of the layered compound with an onium group is not particularly limited, and a known method can be used. For example, by mixing organic onium and halide ions such as chloride ions, bromide ions, and iodide ions with layered inorganic compounds in a solvent such as water, alcohols such as methanol, and polar solvents such as acetonitrile. The interlayer can be modified with an onium group by a cation exchange reaction between an exchangeable cation and an organic onium in the layered inorganic compound.
The water used as the reaction solvent may be neutral, acidic or alkaline, and is not particularly limited, but is preferably ion exchange water, distilled water, pure water or ultrapure water.

There is no particular limitation on the amount of the organic onium salt used to modify the layer of the layered compound by cation exchange with an onium group, and it can be arbitrarily set according to the purpose, but the cation exchange capacity of the layered inorganic compound On the other hand, it is preferably 20 to 2000 mol% (0.2 to 20 equivalents), more preferably 50 to 1000 mol% (0.5 to 10 equivalents), still more preferably 100 to 500 mol% (1 ~ 5 equivalents).
Although the reaction temperature in the said cation exchange reaction is not specifically limited, Preferably it is 0-100 degreeC, More preferably, it is 10-60 degreeC, More preferably, it is 15-40 degreeC.

  The amount of the solvent used in the cation exchange reaction is not particularly limited, but is 1 to 100 times by mass, more preferably 5 to 70 times by mass, and still more preferably 10 to the layered inorganic compound used as a raw material. -50 mass times.

In order to adjust the ratio of the onium group in the precursor having the organic onium group, after reacting the organic onium salt with the layered inorganic compound, a part of the onium group in the layered inorganic compound is converted into a hydroxyl group by an acid. The method of making it preferable is.
The amount of the acid to be actuated can be arbitrarily set according to the purpose. Preferably, when the cation exchange capacity of the layered inorganic compound is 100 mol%, 100 mol%-[organic onium group to be left between layers] It is more preferable to increase or decrease the amount of acid as appropriate.

The acid is not particularly limited, and examples thereof include hydrochloric acid (hydrogen chloride), odorous acid (hydrogen bromide), carboxylic acids (for example, formic acid, acetic acid, and oxalic acid), phosphoric acid, nitric acid, sulfuric acid, and methanesulfonic acid. Known acids such as sulfonic acids can be mentioned, and among these, hydrochloric acid (hydrogen chloride) is preferable in terms of excellent reactivity.
It is preferable to adjust the amount of onium salt present between layers to a specific range by reacting with an onium salt between layers using these acids because interlayer silanols are generated and silylation reaction points increase.
When using an onium salt in an amount less than the equivalent of the cation exchange capacity, metal cations such as sodium remain between the layers, so that the alkoxylates derived from hydroxyl groups such as silanols that act as reaction sites bind strongly to the metal cations. May interfere with the silylation reaction.

  The organic solvent used during the treatment with the acid is not particularly limited, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl-1 Alcohols such as 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 methyl ketone Ketones such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alkanes such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate, chloroform and dichloro Such as halogenated hydrocarbons such as Tan and the like.

  Among these, ethers, nitriles and ketones which are alcohols and aprotic polar solvents are preferable, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2 Alcohols such as -propanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol are more preferable and have high boiling point and high polarity. Therefore, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 1-methoxy-2-propanol are more preferable.

  Although the reaction temperature in the said acid treatment is not specifically limited, Preferably it is 0-200 degreeC, More preferably, it is 50-160 degreeC, More preferably, it is 70-150 degreeC. Usually, the reaction is preferably carried out at the boiling point (under heating and reflux) of the organic solvent used as the reaction solvent.

The precursor layered inorganic compound obtained by the cation exchange reaction and acid treatment is preferably dried after isolation and washing. The method for isolating, washing and drying is not particularly limited, and a known method 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 still, or after solid-liquid separation by centrifugation, the supernatant is removed by decantation, or by filtration operations such as natural filtration, pressure filtration, and vacuum filtration. For example, the layered inorganic compound may be collected by filtration.
The pressure during pressure filtration is not particularly limited, and may be in the range of 1 to 5 atmospheres, for example. The pressure at the time of vacuum filtration is not particularly limited, and may be in the range of 0 to 1 atm.

As for the washing method, after the solid obtained after decantation is redispersed in water or an organic solvent, the solid is decanted in the same manner, or the solid is washed by pouring water or an organic solvent over the filtered solid. The method of doing is mentioned.
The water used for washing may be neutral, acidic or alkaline, and is not particularly limited, but is preferably ion exchange water, distilled water, pure water or ultrapure water.
The organic solvent used for washing 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, it can be air-dried at normal temperature and pressure, or the organic solvent can be removed while heating or cooling at normal temperature under reduced pressure.
The pressure at the time of decompression is not particularly limited, and may be, for example, in the range of 0 to 1 atmosphere. Moreover, there is no restriction | limiting in particular, Preferably it is -10-200 degreeC, More preferably, it is 0-150 degreeC, Especially preferably, it is 10-100 degreeC.

As described above, the precursor in the present invention is a compound substituted with an onium group in an ion exchange capacity of 25 to 75 mol% with respect to the exchangeable cation of the layered inorganic compound.
If the proportion of the precursor onium salt is 25 to 75 mol%, the hydroxyl group as the silylation reaction point is increased, and there is an effect that the silylating agent is easily inserted between the layers by forming a space between the layers. The conversion rate is improved.
In addition, the introduction of interlaminar onium groups within a specific range provides a good inter-layer environmental atmosphere (balance between hydrophilicity and hydrophobicity) and facilitates intercalation of water intervening in the reaction between the silylation reaction. Infer that it will be easier to progress.
On the other hand, when the proportion of the onium group exceeds 75 mol%, the effect is reduced, and when it is less than 25 mol%, the effect of the onium salt extending the interlayer distance is reduced, and the silylation rate is lowered.

  In the silylated layered inorganic compound of the present invention, as shown in FIG. 1, the precursor hydroxyl group and onium group counter anion (alkoxylate) are all or partly silylated with a silylating agent to form a silylated layered compound. Inorganic compounds are produced.

  The silylating agent in the present invention means all compounds that cause a silylation reaction, and so-called silane coupling agents are also included in the silylating agent in the present invention.

Although it does not specifically limit as a silylating agent in this invention, What is a hydrolyzable group is an alkoxy group instead of the chlorosilanes by-producing hydrogen chloride, for example, the compound represented by following formula (2) Is preferred.
[R ⁵ _n Si (OR ⁶ ) _4-n ] (2)
(In Formula (2), each R ⁵ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a saturated or unsaturated alkyl group having 1 to 8 carbon atoms. A saturated cycloalkyl group, an aryl group having 1 to 20 carbon atoms, and an aralkyl group having 1 to 20 carbon atoms, each of which includes a vinyl group, an epoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, an alkylamino group, It may be substituted with an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanate group, a carboxyl group, a halogen atom, or an alkoxysilyl group, and each R ⁶ is independently a hydrogen atom or a saturated group having 1 to 8 carbon atoms. Or an unsaturated alkyl group, a C1-C8 saturated or unsaturated cycloalkyl group, a trimethylsilyl group, a dimethylsilyl group Or a saturated or unsaturated heterocycloalkyl group having 1 to 8 carbon atoms, and n represents an integer of 0 to 4.)

In the silylating agent represented by the formula (2), 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 exists. Alternatively, 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 with an appropriate protecting group.
Among these, the hydrolyzable group is preferably a methoxy group, an ethoxy group, and a propoxy group, and particularly preferably a methoxy group and an ethoxy group because of excellent silylation reactivity and no generation of hydrogen chloride.

  Examples of the silylating agent represented by the formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 Acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl 3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Propyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 7-octenyltrimethoxysilane, 4 -(Trimethoxysilyl) butyric acid, 4- (trimethoxysilyl) butyric acid 1,1-dimethylethyl, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxy Silane, 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.

Moreover, although it does not specifically limit, silylating agents other than alkoxysilane can also be used. For example, hexamethyldisilazane, chlorotrimethylsilane, hexamethyldisilazane, trimethylsilyl trifluoromethanesulfonate, triethylchlorosilane, tertiary butyldimethylchlorosilane, 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.
In these silylating agents, when a plurality of hydrolyzable groups are present in one molecule, a plurality of hydrolyzable groups such as alkoxy groups, halogen atoms, alkylamino groups, etc. may be present. May be mixed.

  Further, even when a titanium coupling agent, an aluminum coupling agent, a zirconia coupling agent, or the like is used instead of the silylating agent, the same effects as those of the present invention are exhibited.

The organic solvent used for the silylation reaction in the present invention is not particularly limited, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl- 1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, alcohols such as 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, acetone and ethylmethyl Ketones such as ketones, amides such as N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide, alkanes such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate, chloroform and Dicro Such as halogenated hydrocarbons such as methane. Among them, ethers are alcohols and aprotic polar solvents, nitriles and ketones are preferable.
More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol, and preferably has a boiling point of 80 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 100 ° C. or higher.

  The aprotic polar solvent is not particularly limited, but nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, ketones such as acetone, ethyl methyl ketone, diethyl ketone and methylene isopropyl ketone, N, N- Examples thereof include amides such as dimethylformamide, and sulfoxides such as dimethylsulfoxide.

The secondary or tertiary alcohol is not particularly limited, but 2-propanol, 2-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, Examples thereof include aromatic alcohols such as hexanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-methyl-2-propanol and phenol.
Among these, acetonitrile, tetrahydrofuran, methyl isopropyl ketone, 2-propanol, 2-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and 1-propoxy-2-propanol are preferable, and 2-butanol and 1 More preferred is -methoxy-2-propanol.

When an aprotic polar solvent or a secondary or tertiary alcohol is used as the organic solvent for the silylation reaction, an O-alkylation reaction that is a side reaction of a hydroxyl group and an alkoxylate derived from the layered inorganic compound hardly occurs. It is inferred that since the boiling point of the organic solvent used is high, the silylation reaction temperature rises, the silylation reaction is accelerated, and the silylation rate is increased.
Furthermore, it is preferable to use secondary or tertiary alcohols because side reactions such as silanol by-products and condensation between silylating agents due to hydrolysis of the silylating agent described later are suppressed. It is inferred that this is a solvent effect due to alcoholic hydroxyl groups.

During the silylation reaction in the present invention, it is preferable to add water to the reaction system. The water to be added may be neutral, acidic or alkaline, and is not particularly limited, but is preferably ion exchange water, distilled water, pure water or ultrapure water.
The amount of water added is preferably 0.05 to 4.0 moles with respect to the total amount of alkoxylates as the counter anion of the hydroxyl group and onium group which are the reaction points of the layered inorganic compound, that is, the ion exchange capacity. 0.1 to 3.0 mole times is particularly preferable.
If the amount of water added is less than 0.05 mol times, the effect of addition is small, and if it exceeds 4.0 mol times, side reactions such as hydrolysis and condensation between silylating agents may proceed.

The amount of the silylating agent to be used in the silylation reaction is not particularly limited, but is preferably 0. 0 with respect to the total amount of the alkoxylate which is the counter anion of the hydroxyl group and the onium group, ie, the ion exchange capacity. It is 1-30 mol times, More preferably, it is 0.05-20 mol times, More preferably, it is 1.0-10 mol times.
When the amount of the silylating agent used is less than 0.1 mol times, the silylation reaction rate is reduced. On the other hand, when it exceeds 30 mol times, it is industrially disadvantageous in terms of raw material costs.

The reaction point between the layers of the layered inorganic compound, that is, the silylation rate with respect to the ion exchange capacity is selected according to the purpose, and is not particularly limited, but the silylation rate is preferably 15 mol% or more, More preferably, it is 25 mol% or more.
On the other hand, if the silylation rate exceeds 200 mol%, the interlayer of the layered inorganic compound may be excessively covered with a component derived from a silylating agent, which is not preferable.

  Although the reaction temperature in the said silylation reaction is not specifically limited, Preferably it is 0-200 degreeC, More preferably, it is 50-160 degreeC, More preferably, it is 70-150 degreeC. Usually, the reaction is carried out at the boiling point (under heating and 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 still more preferably 10 to the layered inorganic compound used as a raw material. -20 mass times.

The silylation reaction in the present invention may or may not use a catalyst, but includes carboxylic acids such as hydrogen chloride, formic acid, acetic acid and oxalic acid, sulfonic acids such as phosphoric acid, nitric acid, sulfuric acid and methanesulfonic acid. Known acids and known bases such as ammonia, trimethylamine, triethylamine, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide can be added as catalysts.
In this case, the amount of the catalyst to be added is not particularly limited, but is 0.001 to 1.0 mol based on the total amount of the alkoxylate which is the counter anion of the hydroxyl group and the onium group as the reaction site, that is, the ion exchange capacity. It is preferable that the ratio is double, more preferably 0.01 to 0.1 mole.

The silylated layered inorganic compound obtained by the silylation reaction is preferably dried after isolation and washing. The method for isolating, washing and drying is not particularly limited, and a known method for isolating, washing and drying the layered inorganic compound and the inorganic fine particles can be used.
For example, as an isolation method, the reaction solution is allowed to stand still, or after solid-liquid separation by centrifugation, the supernatant is removed by decantation, or by filtration operations such as natural filtration, pressure filtration, and vacuum filtration. For example, the layered inorganic compound may be collected by filtration.
There is no restriction | limiting in particular in the pressure at the time of pressure filtration, For example, it may be the range of 1-5 atmospheres. The pressure at the time of vacuum filtration is not particularly limited, and may be in the range of 0 to 1 atm.

As for the washing method, after the solid obtained after decantation is redispersed in water or an organic solvent, the solid is decanted in the same manner, or the solid is washed by pouring water or an organic solvent over the filtered solid. The method of doing is mentioned.
The water used for washing may be neutral, acidic or alkaline, and is not particularly limited, but is preferably ion exchange water, distilled water, pure water or ultrapure water.
The organic solvent used for washing 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, it can be air-dried at normal temperature and pressure, or the organic solvent can be removed while heating or cooling at normal 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. Moreover, there is no restriction | limiting in particular, Preferably it is -10-200 degreeC, More preferably, it is 0-150 degreeC, Especially preferably, it is 10-100 degreeC.
When exchangeable cations such as onium groups and metal cations remaining after the silylation reaction are reduced or removed, acid treatment can be performed using a known acid and solvent in the same manner as described above.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
<Synthesis Example 1> Synthesis of sodium magadiite (hereinafter referred to as Na-magadiite) 18.34 g of sodium silicate (manufactured by Fuji Chemical Co., Ltd., trade name: sodium silicate 4), silica gel (manufactured by Wako Pure Chemical Industries, Ltd.) , Trade name: Wakogel Q-63) 7.28 g and pure water 54.37 g were mixed and sealed in a high pressure reaction decomposition vessel (trade name: HU-100, manufactured by Sanai Kagaku Co., Ltd.) at 170 ° C. Heated for 30 hours. The product was collected by suction filtration, washed with a dilute aqueous NaOH solution (pH: 9 to 10) and pure water, and dried at 40 ° C. for 2 days to obtain 15.9 g of Na-magadiite.
When the composition of Na-magadiaite was calculated using an atomic absorption analyzer (manufactured by Shimadzu Corporation, AA-6200) and a thermogravimetric analyzer, it was Na ₂ Si ₁₄ O ₂₉ · nH ₂ O, and n = 0 The calculated ion exchange capacity was 2.21 mol _c / kg.
Moreover, it was 1.54 nm when the bottom face space | interval of Na-magadiite obtained using the X-ray-diffraction apparatus (The product made from BRUKER, brand name: D8 ADVANCE) was calculated | required.

Synthesis Example 2 Synthesis of dodecyltrimethylammonium (hereinafter referred to as DTMA) -Magadiaite (intercalation modification of Na-Magadiite with dodecyltrimethylammonium chloride)
100 g of Na-magadiite (chemical formula: Na ₂ Si ₁₄ O ₂₉ · nH ₂ O) obtained in Synthesis Example 1, 6500 g of pure water and 175 g of dodecyltrimethylammonium chloride were mixed and stirred at room temperature for 7 days. Thereafter, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C. to obtain 94 g of DTMA-Magadiite.
As a result of measuring the Na mass in the obtained DTMA-magadiite using an atomic absorption analyzer (manufactured by Shimadzu Corporation, AA-6200), the Na content was less than 0.04% by mass, almost a cation. Confirmed that it was replaced.
When the composition of DTMA-Magadiite obtained using an elemental analyzer (manufactured by Yanaco Analytical Co., Ltd., CHN coder MT-5) and a thermogravimetric analyzer (Hitachi High-Tech Science Co., Ltd., TG / DTA6300) was calculated, DTMA _1.66 H _0.34 Si ₁₄ O ₂₉ .nH ₂ O, and the proportion of onium groups was 83 mol% with respect to the ion exchange capacity.
Moreover, it was 2.80 nm when the bottom face space | interval of DTMA-magadiite obtained using the X-ray-diffraction apparatus (The product made from BRUKER, D8 ADVANCE) was calculated | required.

<Example 1>
(1) Synthesis of partially protonated DTMA-magadiite (precursor) by treatment of DTMA-magadiite with hydrochloric acid 100 g of DTMA-magadiite obtained in Synthesis Example 2 and 624 g of 0.025 mol / L hydrochloric acid were mixed at room temperature. Stir for 1 day. Thereafter, the solid was collected by suction filtration, washed with pure water, and dried at 60 ° C. to obtain 92.9 g of partially protonated DTMA-magadiite.
Calculation of the composition of partially protonated DTMA-Magadiite obtained using an elemental analyzer (manufactured by Yanaco Analytical Co., Ltd., CHN Coder MT-5) and thermogravimetric analyzer (Hitachi High-Tech Science Co., Ltd., TG / DTA6300) As a result, it was DTMA _1.39 H _0.61 Si ₁₄ O ₂₉ .nH ₂ O, and the ratio of the onium group was 70 mol% with respect to the ion exchange capacity.

(2) Interlayer silylation of partially protonated DTMA-magadiite by 3-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as MAC-TRIMS) treatment 100 g of partially protonated DTMA-magadiite obtained in (1) above 1-methoxy-2-propanol (hereinafter referred to as PGM) 1850 g dried with molecular sieve 3A, pure water 3.0 g, MAC-TRIMS 290 g (relative to the reaction point) The mixture was stirred for 2 days while refluxing under a nitrogen atmosphere. Thereafter, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C. to obtain silylated magadiite (hereinafter referred to as MACPS-magadiite).
CHN elemental analyzer (manufactured by Yanaco Analytical Co., Ltd., CHN coder MT-5), thermogravimetric analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., TG / DTA6300) and atomic absorption analyzer (manufactured by Shimadzu Corporation, AA-6200) ) Was used to calculate the composition of MACPS-magadiite obtained using 3-methacryloxypropylsilyl (MACPS) _1.40 DTMA _0.08 Me _0.52 Si ₁₄ O ₂₉ .nH ₂ O, and the silylation rate was the ion exchange capacity. It was 70 mol% with respect to.
It was 2.29 nm when the bottom face space | interval of MACPS-magadiite obtained using the X-ray-diffraction apparatus (The product made from BRUKER, D8 ADVANCE) was calculated | required.
Further, when analyzed by ²⁹ Si nuclear magnetic resonance (NMR) (manufactured by JEOL Ltd., JNM-ECA 400 type), the silylated modification reduced the peak of Q ³ derived from silanol of magadiite, and the Q ⁴ Since it increased, it was confirmed that the silylation reaction proceeded between the layers.

<Example 2>
A silylated magadiite was obtained in the same manner as in Example 1 except that the concentration of hydrochloric acid in (1) of Example 1 was changed to 0.1 mol / L and the amount of hydrochloric acid used was changed to 655 g.
The proportion of the onium group in the precursor was 51 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 80 mol%.
It was 2.34 nm when the bottom face space | interval of MACPS-magadiite obtained using the X-ray-diffraction apparatus (The product made by BRUKER, D8 ADVANCE) was calculated | required.

<Example 3>
A silylated magadiite was obtained in the same manner as in Example 1 except that the amount of hydrochloric acid used in (1) of Example 1 was changed to 853 g.
The proportion of the onium group in the precursor was 38 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 60 mol%.
It was 2.19 nm when the bottom face space | interval of MACPS-magadiite obtained using the X-ray-diffraction apparatus (The product made by BRUKER, D8 ADVANCE) was calculated | required.

<Comparative Example 1>
Without the hydrochloric acid treatment of (1) of Example 1, the same treatment as (2) of Example 1 was performed using the DTMA-magadiite obtained in Synthesis Example (2) as a silylation precursor, Silylated magadiite was obtained.
The proportion of the onium group in the precursor was 83 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 48 mol%.
It was 2.30 nm when the bottom face space | interval of MACPS-magadiite obtained using the X-ray-diffraction apparatus (The product made from BRUKER, D8 ADVANCE) was calculated | required.

<Example 4>
A silylated magadiite was obtained in the same manner as in Example 2 except that the silylating agent was changed from MAC-TRIMS to hexyltrimethoxysilane.
The proportion of the onium group in the precursor was 51 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 62 mol%.
In the spectrum of HxS-magadiite obtained using an X-ray diffractometer (manufactured by BRUKER, D8 ADVANCE), two signals corresponding to a bottom surface spacing of 2.03 and 2.23 nm were observed.

<Example 5>
A silylated magadiite was obtained in the same manner as in Example 3 except that the silylating agent was changed from MAC-TRIMS to hexyltrimethoxysilane.
The proportion of the onium group in the precursor was 38 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 24 mol%.
In the spectrum of HxS-magadiite obtained using an X-ray diffractometer (manufactured by BRUKER, D8 ADVANCE), two signals corresponding to a bottom spacing of 1.93 and 2.80 nm were observed.

<Comparative Example 2>
A silylated magadiite was obtained in the same manner as in Comparative Example 1 except that the silylating agent was changed from MAC-TRIMS to hexyltrimethoxysilane.
The proportion of the onium group in the precursor was 83 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 11 mol%.
In the spectrum of HxS-magadiite obtained using an X-ray diffractometer (manufactured by BRUKER, D8 ADVANCE), three signals corresponding to a bottom surface spacing of 1.84, 2.83 and 3.16 nm were observed.

<Example 6>
A silylated magadiite was obtained by performing the same treatment as in Example 2 except that the silylating agent was changed from MAC-TRIMS to phenyltrimethoxysilane.
The proportion of the onium group in the precursor was 51 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 65 mol%.
The distance between the bottom surfaces of the PhS-magadiite obtained using an X-ray diffractometer (manufactured by BRUKER, D8 ADVANCE) was 2.16 nm.

<Example 7>
A silylated magadiite was obtained in the same manner as in Example 3 except that the silylating agent was changed from MAC-TRIMS to phenyltrimethoxysilane.
The proportion of the onium group in the precursor was 38 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 55 mol%.
The distance between the bottom surfaces of the PhS-magadiite obtained using an X-ray diffractometer (manufactured by BRUKER, D8 ADVANCE) was 2.22 nm.

<Comparative Example 3>
A silylated magadiite was obtained in the same manner as in Comparative Example 1 except that the silylating agent was changed from MAC-TRIMS to phenyltrimethoxysilane.
The proportion of the onium group in the precursor was 83 mol% with respect to the ion exchange capacity, and the silylation rate of silylated magadiite was 28 mol%.
It was 2.29 nm when the space | interval of the bottom face of PhS-magadiite obtained using the X-ray-diffraction apparatus (The product made by BRUKER, D8 ADVANCE) was calculated | required.

The composition of the silylated layered inorganic compounds obtained in Examples 1 to 7 and Comparative Examples 1 to 3 is CHN elemental analysis (manufactured by Yanaco Analytical Co., Ltd., trade name: CHN coder MT-5), thermogravimetric 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 Tables 1-3.
In Tables 1 to 3, the ratio of the onium group and the silylation rate can be exchanged with respect to the total amount of hydroxyl groups and alkoxylates derived from Si ₁₄ O ₂₉ derived from the main skeleton of the layered inorganic compound magadiite. Since there are a maximum of two silylating agents and silylating agents that can react directly, the analytical value of DTMA, MACPS, HxS and PhS (molar ratio to Si ₁₄ O ₂₉ ) is divided by 2 and multiplied by 100 is there.

The following abbreviations in Tables 1 to 3 mean the following.
MACPS: 3-methacryloxypropylsilyl DTMA: dodecyltrimethylammonium Me: methyl HxS: hexylsilyl PhS: phenylsilyl N.I. D: Not detected

As can be seen from Table 1, Examples 1 to 3 in which the amount of onium groups in the precursor was adjusted to a specific range smaller than that of Comparative Example 1 were compared with Comparative Example 1 in which the amount of onium groups was not adjusted as in the case of the prior art. As compared with, the silylation rate is high, and the amount of residual onium groups in the product is small. At this time, it can be seen that the silylation rate is maximized when the amount of onium groups is adjusted to about 50 mol% with respect to the ion exchange capacity (FIG. 2).
When the kind of silylating agent is changed (Examples 4 to 5 and Comparative Example 2, and Examples 6 to 7 and Comparative Example 3), the same tendency is shown.
In FIG. 2, (circle) shows the results of Examples 1 to 3 and Comparative Example 1, ◇ (diamond) shows the results of Examples 4 to 5 and Comparative Example 2, and □ (square) shows the results The results of Examples 6 to 7 and Comparative Example 3 are shown, and each fill indicates a silylation rate, and white indicates the proportion of onium groups.

  In other words, regardless of the type of silylating agent, when the exchangeable cation of the layered inorganic compound is modified by exchanging with an onium group, the amount introduced is more than the amount as much as conventionally known. The silylation rate can be improved by making the specific range (25 to 75 mol%) less, and the introduction amount is about 50 mol% (about half) of the cation exchange capacity of the layered inorganic compound. In some cases it becomes maximal.

Claims (5)

  A silylation reaction is performed with a silylating agent on a precursor obtained by cation exchange of an exchangeable cation of a layered inorganic compound with an onium group at an ion exchange capacity of 25 to 75 mol%. A method for producing a silylated layered inorganic compound.   After the precursor has reacted the organic onium salt with the layered inorganic compound, the organic onium salt in the layered inorganic compound and a part of the exchangeable cation that has not been cation-exchanged with the organic onium salt by an acid are converted to a hydroxyl group. The method for producing a silylated layered inorganic compound according to claim 1, wherein the method is obtained. The method for producing a silylated layered inorganic compound according to claim 2, wherein the organic onium salt is a compound represented by the following formula (1).
^{R 1 R 2 R 3 R 4} N + X - (1)
(In the formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different, each having an alkyl group having 1 to 22 carbon atoms and an aralkyl having 7 to 22 carbon atoms. Group, an aryl group having 6 to 22 carbon atoms, — (CH ₂ —CH (CH ₃ ) O) _a —H group or — (CH ₂ —CH ₂ —O) _b —H group, wherein a and b are 1 (It is an integer of ˜20, and X ⁻ represents a halide ion.) The method for producing a silylated layered inorganic compound according to any one of claims 1 to 3, wherein the silylating agent is a compound represented by the following formula (2).
[R ⁵ _n Si (OR ⁶ ) _4-n ] (2)
(In Formula (2), each R ⁵ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a saturated or unsaturated alkyl group having 1 to 8 carbon atoms. A saturated cycloalkyl group, an aryl group having 1 to 20 carbon atoms, and an aralkyl group having 1 to 20 carbon atoms, each of which includes a vinyl group, an epoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, an alkylamino group, It may be substituted with an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanate group, a carboxyl group, a halogen atom, or an alkoxysilyl group, and each R ⁶ is independently a hydrogen atom or a saturated group having 1 to 8 carbon atoms. Or an unsaturated alkyl group, a C1-C8 saturated or unsaturated cycloalkyl group, a trimethylsilyl group, a dimethylsilyl group Or a saturated or unsaturated heterocycloalkyl group having 1 to 8 carbon atoms, and n represents an integer of 0 to 4.)   The manufacturing method of the silylated layered inorganic compound in any one of Claims 1-4 in which a layered inorganic compound contains either a layered silicate, a layered clay mineral, and a layered metal oxide.

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