JP6958631B2 - Interlayer cross-linked layered inorganic compound and its manufacturing method - Google Patents

Description

The present invention relates to a layered inorganic compound crosslinked between layers and a method for producing the same. More specifically, the layered inorganic compound crosslinked between layers by modifying the layers with a coupling agent and then crosslinking a crosslinkable functional group between the layers. The present invention relates to a compound and a method for producing the same.

As a method of cross-linking the layers of the layered inorganic compound, a method of hydrolyzing and polycondensing the metal alkoxide between the layers and then firing, or a silylating agent having two hydrolyzable silyl sites are layered so as to face each other between the layers. A method of cross-linking between layers by a modification reaction with a hydroxyl group derived from an inorganic compound is known.

For example, in Non-Patent Document 1, layers of layered sodium titanate, which is a layered inorganic compound, are modified with several types of ammonium having different alkyl chain lengths, such as propylammonium, and then ethyl orthosilicate, which is a cross-linking agent, is mixed. A method is described in which a molecular sieve, which is an inorganic compound having a different pore diameter, is produced by cross-linking the layers with an inorganic material by inserting the layers into layers and firing the stripped residue.

Further, in Non-Patent Document 2, ialite is used as a layered inorganic compound, which is treated with hydrochloric acid to protonate the layers, and further treated with hexylamine for 2 days to expand the layers, and then a cross-linking agent. As a result, 4,4'-bis (triethoxysilyl) biphenyl having two alkoxysilyl moiety was allowed to act on the organic moiety for 7 days, and the residue obtained by centrifugation was dried for 5 days, and further dried with hydrogen chloride for 5 days. A method of treating to produce a layered inorganic compound interlayer-crosslinked with an organic-inorganic composite material is described.

Further, in Non-Patent Document 3, zeolite is used as a layered inorganic compound, the layers are modified with hexadecyltrimethylammonium to expand the layers, and then 1,4-, which has two alkoxysilyl moieties in the organic moiety as a cross-linking agent. Described is a method for producing a layered inorganic compound cross-linked with an organic-inorganic composite material by allowing bis (triethoxysilyl) benzene to act to crosslink the layers and further removing unnecessary hexadecyltrimethylammonium by acid treatment. ing.

J. Am. Chem. Soc. , 1991,113,3189-3190 J. Mater. Chem. , 2005, 15, 551-553 J. Am. Chem. Soc. , 2010, 132, 15011-15021

However, in Non-Patent Document 1, since a firing step is required, it is industrially disadvantageous from the viewpoint of energy consumption, and since organic components are removed, the layers (inside the pores) are modified with organic groups. Alternatively, it is not possible to obtain an interlayer-crosslinked layered inorganic compound in which flexibility or a functional group is introduced into the crosslinked structure. Therefore, the obtained compound is a so-called molecular sieve, and the crosslinked structure is inflexible because it is a completely inorganic compound, and it has only a function of adsorbing only chemical substances matching the size of the generated pore diameter. Poor sex. Furthermore, since a metal alkoxide such as ethyl orthosilicate is used as the interlayer cross-linking agent, hydrolysis / polycondensation of the cross-linking agent may proceed during the treatment operation to form silica gel or the like as a by-product. Is a gel that is insoluble in a solvent or the like and cannot be removed.

Further, since the crosslinked structure of the interlayer crosslinked type layered inorganic compound described in Non-Patent Document 2 is a biphenyl group, it is tough and inflexible, there is no variety of interlayer distances, and its properties are also derived from aromatics. , The chemical substances adsorbed between layers are limited, and the versatility is poor. Further, in such a cross-linking agent having two trialkoxysilyl sites in the organic site, a gel component in which hydrolysis / polycondensation has progressed between the cross-linking agent molecules may be produced as a by-product during the cross-linking treatment. Since the product is a gel insoluble in a solvent or the like, it cannot be removed.

Further, in Non-Patent Document 3, one molecule of 1,4-bis (triethoxysilyl) benzene, which is a cross-linking agent, cannot react with silanol, which is a layered inorganic compound between layers, to cross-link, and the cross-linking agent 2 cannot be cross-linked. It is described that the condensed molecules are crosslinked. Therefore, the central portion of the crosslinked structure of the interlayer crosslinked type layered inorganic compound always has a single bond of Si—O—Si (siloxane), but this bond is easily broken in the coexistence of an alkali or an acid. Therefore, it is difficult to maintain the crosslinked structure of the interlayer crosslinked layered inorganic compound under relatively long-term use not only under strongly alkaline and acidic conditions but also under weak alkaline and acidic conditions, which is not practical. .. Further, in such a cross-linking agent having two trialkoxysilyl sites in the organic site, a gel component in which hydrolysis / polycondensation has progressed between the cross-linking agent molecules may be produced as a by-product during the cross-linking treatment. Since the product is a gel insoluble in a solvent or the like, it cannot be removed.

Further, there are almost no commercially available organic-inorganic composite materials (crosslinking agents) having reactive sites such as two alkoxysilyl sites in the organic sites described in Non-Patent Documents 2 and 3, and the organic sites. However, since it is limited to aromatic and aliphatic hydrocarbon compounds, various layers are cross-linked via covalent bonds in an organic-inorganic composite structure having a variety of interlayer distances and interlayer environments. Inorganic compounds cannot be obtained, and it is industrially extremely disadvantageous to use them to produce layered inorganic compounds cross-linked.

In view of the above situation, in view of the above situation, by introducing an organic-inorganic composite crosslinked structure having various chemical structures between layers, the interlayer distance can be varied, and various compounds can be adsorbed between the layers. It is an object of the present invention to provide an interlayer crosslinked type layered inorganic compound having a substantially stable crosslinked structure and a method for producing the same.

As a result of diligent studies to solve the above problems, the present inventor modifies the layers of the layered inorganic compound with a coupling agent such as a silane coupling agent, and then causes the crosslinkable functional group to undergo a cross-linking reaction between the layers. It has been found that the interlayer-crosslinked layered inorganic compound obtained in the above-mentioned method can solve the above-mentioned problems, and the present invention has been completed.

That is, the present invention is an interlayer crosslinked type layered inorganic compound having an organic-inorganic composite crosslinked structure represented by the following formula (1) between layers of the layered inorganic compound.

(In the formula (1), M ¹ and M ² independently represent Si, Al, Ti or Zr, respectively, and R ^{a and R b} are independent linear or branched chains having 1 to 20 carbon atoms, respectively. Saturated or unsaturated alkylene group, saturated or unsaturated cycloalkylene group which may have a branch of 3 to 20 carbon atoms, arylene group of 6 to 20 carbon atoms or aralkylene group of 7 to 20 carbon atoms, R ^c Indicates an organic group consisting of 1 to 40 carbon atoms and may contain a heteroatom, a linear structure, a branched structure, a cyclic structure, an unsaturated bond and an aromatic structure, and R ¹ has 1 to 20 carbon atoms. Saturated or unsaturated alkyl group of straight or branched chain, saturated or unsaturated cycloalkyl group which may have branched chain having 3 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms or 7 to 20 carbon atoms. Indicates an aralkyl group, where Z is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and a carbon number of carbon atoms. Saturated or unsaturated heterocycloalkyloxy groups from 1 to 8, halogen atoms, hydroxyl groups, amino groups, saturated or unsaturated alkylamino groups with 1 to 6 carbon atoms or branched chains, directly from 1 to 6 carbon atoms Indicates an oxygen atom derived from a saturated or unsaturated dialkylamino group or layered inorganic compound of a chain or branched chain, ^{and when M 1} and M ² are either Si, Ti or Zr, the corresponding x is 2. , And n is an integer from 0 to 2, and when M ¹ and M ² are Al, the corresponding x is 1 and n is 0 or 1.)

Further, the present invention is a method for producing an interlayer cross-linking type layered inorganic compound, which comprises modifying the layers of a layered inorganic compound with a coupling agent and then carrying out a cross-linking reaction of a crosslinkable functional group derived from the coupling agent.

Since the interlayer-crosslinked layered inorganic compound of the present invention has various crosslinked structures, it can have various interlayer distances, and it is possible not only to construct an appropriate space between the layers according to the purpose, but also to form a long chain. Since the cross-linking agent itself having an alkylene structure has flexibility, the interlayer distance can be flexibly changed according to the application and the compound to be adsorbed even if the same interlayer cross-linking type layered inorganic compound is used.
Further, since the crosslinked structure itself has various functional groups, it has an organic-inorganic composite crosslinked structure between layers that appropriately interacts with the target compound, and various compounds can be adsorbed between the layers. can. Further, since it does not have a single bond of Si—O—Si (siloxane) in the middle of the crosslinked structure, it is difficult to be cleaved even in the coexistence of alkali or acid. Therefore, the crosslinked structure of the interlayer crosslinked layered inorganic compound can be stably maintained not only under strongly alkaline and acidic conditions but also under weak alkaline and acidic conditions for a long period of time, and is versatile. It is practical.

Further, according to the method for producing an interlayer cross-linking type layered inorganic compound of the present invention, since the interlayer is modified with a coupling agent, the modification rate between layers can be increased, and the cross-linking density can be widely set according to the purpose. Can be done. In addition, since various coupling agents such as silane coupling agents can be used, a wide range of interlayer distances can be set according to the purpose, and hydrophilic groups, hydrophobic groups, aromatic groups, heterocyclic groups, and hydrogen can be used between the layers. Various functional groups such as bond-forming groups can be introduced.
Furthermore, since a coupling agent is used, unlike the conventional method using a cross-linking agent having two metal alkoxides or alkoxysilyl sites, there is no gel by-product during production, and the desired interlayer-crosslinked layered inorganic compound is purified. Is high and can be obtained efficiently.
Therefore, the interlayer crosslinked layered inorganic compound of the present invention can be widely used as various fillers, adsorbents, host compounds of functional molecules, and the like.

It is a figure which shows the time-dependent change of the thiazole compound concentration in the adsorption test of the thiazole compound of Example 8 and Comparative Example 2.

Hereinafter, in the interlayer cross-linked type layered inorganic compound of the present invention, an organic-inorganic composite cross-linked structure for cross-linking the layers of opposite layered inorganic compounds via covalent bonds will be described.

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, hectrite, fluorohect) Wright, etc.), Kaolin (kaolinite, etc.), Magadite, Kenyaite, Kanemite, etc.) and layered compound hydroxides.
Of these, layered silicates, layered clay minerals and layered metal oxides are preferably used because of their availability, etc., but either naturally produced or artificially synthesized ones are used. May be good.

The organic-inorganic composite crosslinked structure in the present invention is a structure represented by the above formula (1).
In the above formula (1), M ¹ and M ² are metals capable of forming a covalent bond with an oxygen atom derived from a layered inorganic compound, and the crosslinked structure is unlikely to cause a decomposition reaction such as hydrolysis and is easily available. Therefore, Si (silicon), Al (aluminum), Ti (titanium) and Zr (zylconium) are mentioned, and Si which is easily available is preferable in order to construct various crosslinked structures.

In the organic-inorganic composite crosslinked structure represented by the above formula (1) via a covalent bond with the layered inorganic compound, the fact that the crosslinked structure and the layered inorganic compound are bonded via a plurality of covalent bonds connects the layers. More preferably from the viewpoint of chemical stability of cross-linking, when M ¹ and M ² are Si, Ti and Zr, n is more preferably 0 or 1, and when Al, n is more preferably 0. Also in the case of, it is more preferable that at least one of Z contains an oxygen atom derived from a layered inorganic compound. Further, Z of the organic-inorganic composite crosslinked structures in the vicinity of each other may be hydrolyzed and condensed to form M ¹ −O −M ¹ , M ¹ −O−M ² and M ² −O−M ^2. ..

Among the organic-inorganic composite crosslinked structures represented by the above formula (1), those capable of being constructed by reacting the crosslinkable functional groups of various coupling agents are general and preferable, and the following formulas (4) to (4) to the following formulas are preferable. The one represented by (18) is more preferable.

(In formulas (4) to (18), R ¹ may have a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms and a branched chain having 3 to 8 carbon atoms. It represents a saturated cycloalkyl group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ² and R ¹³ are independently saturated or saturated linear or branched chains having 1 to 20 carbon atoms, respectively. An unsaturated alkylene group, a saturated or unsaturated cycloalkylene group which may have a branch of 3 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms, R ³ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is an alkylene group having 1 to 6 carbon atoms, a phenylene group or an aralkylene group having 7 to 10 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ and R ¹² are independent hydrogen atoms, linear or branched saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, and branched chains having 3 to 8 carbon atoms, respectively. There may be saturated or unsaturated cycloalkyl groups, aryl groups with 6 to 20 carbon atoms or aralkyl groups with 7 to 20 carbon atoms, where R ¹¹ is the saturation of linear or branched chains with 1 to 20 carbon atoms. Alternatively, an unsaturated alkylene group, a saturated or unsaturated cycloalkylene group which may have branches having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or an aralkylene group having 6 to 24 carbon atoms. It represents a polyphenylene group, and any R ¹¹ may be substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom and a substituent consisting of 1 to 10 atoms containing the sulfur atom, and Z is a hydrogen atom and a carbon atom. Saturated or unsaturated alkyloxy group of number 1-8, saturated or unsaturated cycloalkyloxy group of 3-8 carbon number, trimethylsilyloxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyl group of number 1-8 An oxygen atom derived from an oxy group, a halogen atom, a hydroxyl group, an amino group, a saturated or unsaturated alkylamino group having 1 to 6 carbon atoms or a branched chain or a layered inorganic compound, and I is derived from a polymerization initiator. The groups may be the same or different, where Y is a group derived from an acid-derived conjugated base, n is an integer of 0 to 2, m and h are integers of 0 or 1, and k is 0 to 0. Indicates an integer of 4.)

The organic-inorganic composite crosslinked structure can be constructed by treating the layers with a coupling agent, modifying the layers by silylation or the like, and then crosslinking the crosslinkable functional groups between the layers to form a crosslink of the coupling agent. An organic-inorganic composite cross-linking agent having two or more hydrolyzable sites is prepared by cross-linking a sex functional group in advance, and this is inserted between layers to be constructed by a modification reaction with a hydroxyl group derived from a layered inorganic compound. However, since there is no side reaction and no gel component is produced as a by-product, the former method of reacting the crosslinkable functional group derived from the coupling agent between the layers is preferable.
In order to construct a crosslinked structure by modifying the layers with silylation or the like and then reacting the crosslinkable functional groups between the layers, if the layers are modified with the same coupling agent and then subjected to a crosslink reaction, the manufacturing process becomes more complete. The above formulas (4) to (8) and the above formulas (13) to (17) are more preferable as the organic-inorganic composite crosslinked structure because the number is small and it is more industrially advantageous, and the crosslinking reaction can be easily carried out under mild conditions. The formulas (4) to (8) and the formulas (15) to (17) are further added because they can be advanced to introduce various chemical structures, flexibility and rigidity, and the length of the crosslinks is also diverse. preferable.

Next, the interlayer crosslinked layered inorganic compound of the present invention will be described in detail along with the method for producing the compound. Unless otherwise specified, the number of copies represents parts by mass and% represents mass%.

In the present invention, it is obtained by reacting an alkali metal such as sodium and potassium present in a layered inorganic compound and an exchangeable cation such as a metal cation such as an alkaline earth metal such as magnesium and calcium with an organic onium salt or the like. The layered inorganic compound having wide layers is a precursor (in the case of silylation, the silylated layered inorganic compound) that undergoes silylation or the like with a coupling agent such as a silane coupling agent.
The precursor is a compound in which an exchangeable cation of a layered inorganic compound is substituted with an arbitrary ratio of onium groups as an ion exchange capacity, and the ratio of onium groups is used when increasing the reaction rate such as silylation. Is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and even more preferably 35 to 70 mol%.

Here, the ion exchange capacity represents the amount of ion exchange per unit weight of the ion exchanger, and is usually the milliequivalent per 1 g of the ion exchanger (meq / g) or the milliequivalent per 100 g of the ion exchanger (meq / 100 g). , And the molar amount per 1 kg of the ion exchanger (mol _c / kg), the centimol amount per 1 kg of the ion exchanger (cmol _c / kg), and the like.
For example, the chemical formula of sodium-magadiate is Na ₂ Si ₁₄ O ₂₉ · nH ₂ O, where n = 0, the formula quantity is 903.2, and all sodium is regarded as an exchange cation. In this case, the ion exchange capacity can be expressed as _{2.21 mol c / kg.}

If a metal cation is present between layers as an exchangeable cation, the interlayer modification rate (silylation rate in the case of a silane coupling agent) by a coupling agent such as a silane coupling agent decreases. Therefore, the metal cation is treated with an acid. It is preferable to reduce.
Therefore, as a method of introducing an onium group between layers of a layered inorganic compound, a method of reacting an onium salt having an equivalent amount or more with a cation exchange capacity and then allowing an acid to act, and an onium having an equivalent amount less than the cation exchange capacity in advance. There are methods such as reacting with a salt, but in order to further improve the interlayer modification rate, a method in which an acid is allowed to act after reacting with an onium salt equal to or more than the former equivalent is more preferable.
Further, as a method for adjusting and introducing the amount of onium groups between the 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 the acid may be added in an appropriate amount first. After the reaction (preferably less than the equivalent of the cation exchange capacity), the onium salt may be reacted.

In the present invention, the onium salt used for producing the precursor is not particularly limited, but organic onium is preferable, and for example, organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium, organic oxonium, organic sulfonium, and organic sulfoxonium. , Organic selenonium, organic carbonium, organic diazonium, organic iodonium, organic pyrilinium, organic pyrrolidinium, organic carvenium, organic asylium, organic thiazolinium, organic alsonium, organic sulphonium, organic telluronium, etc. Salts of organic pyridinium, organic imidazolium, organic phosphonium and organic sulfonium are preferable, and these onium salts are used alone or in combination of two or more.
The organic group in the onium salt is not particularly limited, but 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, and-(CH _2- CH (CH 2-CH). CH ₃ ) O) _p −H group, − (CH ₂ −CH ₂ −O) _q −H group, p and q are integers from 1 to 20, vinyl group, epoxy group, oxetanyl group, acryloxy. Group, methacryloxy group, hydroxyl group, thiol group, isocyanato group, halogen atom, basic group such as amino group and alkylamino group, acidic group such as carboxyl group, photoacid generating group, thermoacid generating group, photobase generating group , It may be substituted with a functional group such as a thermal group generating group, a photoradical generating group or a thermal radical generating group.

As the organic onium salt, an organic onium salt represented by the following formula (3) is more preferable.
^{R 13 R 14 R 15 R 16} N + X - (3)
(In the formula (3), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are independently an alkyl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, and an aryl group having 6 to 22 carbon atoms, respectively. And − (CH ₂ −CH (CH ₃ ) O) _p −H group or − (CH ₂ −CH ₂ −O) _q −H group, p and q are integers from 1 to 20, and X ^- is Indicates a halide ion.)

The organic onium salt represented by the formula (3) is not particularly limited, and for example, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, octadecyltrimethylammonium chloride, dimethyloctadecylphenylammonium chloride, and the like. Triethylbenzylammonium chloride, dodecylammonium chloride, dimethyldipolyethylene oxideammonium chloride, dimethyldipropylene oxideammonium chloride, dimethylpolyethylene oxidepolyoxideammonium chloride, dimethylstearylpolyethylene oxideammonium chloride, dimethylstearylpolypropylene oxideammonium chloride, methylstearyldipolychloride Ammonium ethylene oxide, methylstearyl dipolypropylene oxide ammonium chloride, benzylmethyl dipolyethylene oxide ammonium chloride, benzylmethyl dipolypropylene oxide ammonium chloride, 1-ethylpyridinium bromide, 1-octadecylpyridinium chloride, 3-methyl-1-propylimidazole bromide Examples thereof include ammonium, 3-methyl-1- (2-naphthyl) imidazolium, triphenyl (tetradecyl) phosphonium bromide, ethyldimethylsulfonium chloride, and triphenylsulfonium bromide.
Among these, preferably dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, octadecyltrimethylammonium chloride, icosyltrimethylammonium chloride, dimethyloctadecylphenylammonium chloride, triethylbenzylammonium chloride and dodecyl chloride. Ammonium.

The method of reacting with an onium salt to modify the layers of the layered inorganic compound with an onium group is not particularly limited, and a known method can be used. For example, by mixing organic onium and salts such as halide ions such as chloride ion, bromide ion, and cation ion with layered inorganic compounds in a solvent such as water, alcohols such as methanol, and polar solvents such as acetonitrile. The layers can be modified with onium groups by a cation exchange reaction between exchangeable cations in the layered inorganic compound and organic onium.

The amount of the organic onium salt in the cation exchange reaction is not particularly limited and can be arbitrarily set depending on the intended purpose, but is preferably 20 to 2000 mol% (preferably 20 to 2000 mol%) based on the cation exchange capacity of the layered inorganic compound. 0.2 to 20 equivalents), more preferably 50 to 1000 mol% (0.5 to 10 equivalents), and even more preferably 100 to 500 mol% (1 to 5 equivalents).
The reaction temperature in the cation exchange reaction is not particularly limited, but is preferably 0 to 100 ° C, more preferably 10 to 60 ° C, and even more preferably 15 to 40 ° C.

The water used as the solvent for the cation exchange reaction 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 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, still more preferably 10 times by mass with respect to the layered inorganic compound used as a raw material. ~ 50 times by mass.

In order to adjust the proportion of onium groups in the precursor having an organic onium group, the layered inorganic compound is reacted with an organic onium salt, and then a part of the onium groups in the layered inorganic compound is converted into a hydroxyl group by an acid. The method of causing is preferable.
The amount of acid to act can be arbitrarily set according to the purpose, but when the cation exchange capacity of the layered inorganic compound is 100 mol%, 100 mol%-[ratio of organic onium groups to be left between layers (Mol%)] is set, and the amount of acid is more preferably increased or decreased as appropriate.

The acid is not particularly limited, and includes hydrochloric acid (hydrogen chloride), bromide (hydrogen bromide), carboxylic acid (for example, formic acid, acetic acid and oxalic acid), phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid and the like. Known acids such as sulfonic acids can be mentioned, and among these, hydrochloric acid (hydrogen chloride) is preferable because of its excellent reactivity.
When the amount of onium salt existing between layers is adjusted to a specific range by reacting with the onium salt between layers using these acids, hydroxyl groups such as interlayer silanol are generated and the number of modification reaction points such as silylation increases. Therefore, it is preferable.
When an onium salt in an amount smaller than the equivalent of the cation exchange capacity is used, a metal cation such as sodium remains between the layers, so that the alkylate derived from a hydroxyl group such as silanol, which is the reaction point, is firmly bonded to the metal cation. Therefore, it may interfere with the interlayer modification reaction such as the silylation reaction.

The organic solvent used when converting a part of the onium salt into a hydroxyl group is not particularly limited, but is 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, nitriles such as acetonitrile, tetrahydrofuran and the like. Ethers, ketones such as acetone and ethyl methyl ketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alcohols such as hexane, aromatics such as benzene and toluene, ethyl acetate. Examples thereof include esters such as, and halogen-based hydrocarbons such as chloroform and dichloromethane.

Among these, alcohols and ethers, nitriles and ketones which are aprotonic polar solvents are preferable, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-2 are preferable. Alcohols such as -propanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol are more preferred, with higher boiling points and higher polarity. Therefore, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 1-methoxy-2-propanol are more preferable.

The reaction temperature in the acid treatment 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 precursor obtained by the cation exchange reaction and the acid treatment is preferably dried after isolation and washing. The method for isolation, washing and drying is not particularly limited, and known methods for isolating, washing and drying layered inorganic compounds, inorganic fine particles and the like can be used.
For example, as an isolation method, the reaction solution is allowed to stand, or after centrifugation to separate the solid solution, the supernatant solution is removed by decantation, or filtration operations such as natural filtration, pressure filtration, and reduced pressure filtration are performed. 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 the solid is washed by pouring water or an organic solvent over the decantation or the solid that has been filtered. 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 used for cleaning 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, for example. 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.

As described above, the precursor in the present invention may be a compound obtained by substituting an arbitrary ratio of onium groups with respect to the exchangeable cations of the layered inorganic compound, but the ratio of the ion exchange capacity is 25 to 75 mol%. Therefore, it is preferable that the compound is substituted with an onium group.
When the ratio of the onium salt of the precursor is 25 to 75 mol%, the number of hydroxyl groups, which are modification reaction points for silylation and the like, increases, and a space is created between the layers, which makes it easier for the silylating agent and the like to be inserted between the layers. The silylation rate and the like are improved.

Next, all or a part of the counter anion (alkoxylate) of the hydroxyl group and the onium group of the precursor is subjected to an interlayer modification reaction with a coupling agent such as a silane coupling agent, and the layers are crosslinked via a covalent bond. A layered inorganic compound having a functional group is produced.

The coupling agent is not particularly limited as long as it is an organic-inorganic composite agent having an organic functional group capable of cross-linking with a hydrolyzable group in the same molecule. For example, a silane coupling agent or a titanium-based coupling agent. Examples thereof include a coupling agent, an aluminum-based coupling agent, a zirconium-based coupling agent, and the like, and a compound represented by the following formula (19) is preferable.

(In the formula (19), R ¹ is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms. , An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, where A is a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. It represents a saturated or unsaturated cycloalkyl group which may have 8 branched chains, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and a vinyl group, an epoxy group, an oxetanyl group, an acryloxy group, respectively. It may be substituted with a methacryloxy group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanato group, a carboxyl group or a halogen atom. D is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and 1 to 8 carbon atoms. Saturated or unsaturated heterocycloalkyloxy group, halogen atom, hydroxyl group, amino group, linear or branched chain with 1 to 6 carbon atoms Saturated or unsaturated alkylamino group or linear or branched chain with 1 to 6 carbon atoms Indicates a saturated or unsaturated dialkylamino group of, M represents Si, Al, Ti or Zr, and when M is any of Si, Ti or Zr, p is 3 and n is 0-2. When M is Al, p is 2 and n is 0 or 1.)

Further, among the coupling agents, the silane coupling agent is more preferable because of the abundance of types, availability, handling and controllability of the hydrolysis reaction. The silane coupling agent is not particularly limited, but for example, a compound represented by the following formula (2) is preferable.

(In the formula (2), R ¹ is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms. , An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, where A is a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. It represents a saturated or unsaturated cycloalkyl group which may have 8 branched chains, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and a vinyl group, an epoxy group, an oxetanyl group, an acryloxy group, respectively. It may be substituted with a methacryloxy group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanato group, a carboxyl group or a halogen atom. D is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and 1 to 8 carbon atoms. Saturated or unsaturated heterocycloalkyloxy group, halogen atom, hydroxyl group, amino group, linear or branched chain with 1 to 6 carbon atoms Saturated or unsaturated alkylamino group or linear or branched chain with 1 to 6 carbon atoms Indicates a saturated or unsaturated dialkylamino group of, and n represents an integer of 0 to 2.)

In the silane coupling agent represented by the formula (2), the crosslinkable functional group may be protected by an appropriate protecting group.
Among the silane coupling agents, the hydrolyzable group has an extremely low risk of causing a side reaction with the crosslinkable functional group because it does not generate an acid such as hydrogen chloride as a by-product, and does not cause corrosion of the reactor and is a by-product. Alkoxysilanes that do not require the disposal treatment of the acid are preferable, those having a methoxy group, an ethoxy group and a propoxy group having excellent silylation reactivity are more preferable, and those having a methoxy group and an ethoxy group are particularly preferable.

Examples of the silane coupling agent represented by the formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, and 3 -Glycydoxypropyl dimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Ethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 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-mercaptopropyltrimethoxy Silane, 3-Ixionpropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 7-octenyl Trimethoxysilane, 4- (trimethoxysilyl) butyric acid, 4- (trimethoxysilyl) butyrate 1,1-dimethylethyl, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxy Silane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decylt Remethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethyl Examples thereof include silane and triethoxysilane.

Further, silane coupling agents other than alkoxysilanes 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, (N, N-dimethylamino) trimethylsilane and the like can be mentioned.
In these silane coupling agents, when a plurality of hydrolyzable groups are present in one molecule, a single hydrolyzable group such as an alkoxy group, a halogen atom, an alkylamino group, or a dialkylamino group is present. However, a plurality of things may be mixed.

Further, instead of the silane coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, a zirconium-based coupling agent, or the like can be used in the same manner.

The organic solvent used for the reaction with the coupling agent 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, 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 , Halogen-based hydrocarbons such as dichloromethane, and among these, alcohols and ethers, nitriles, and ketones which are aprotonic polar solvents are preferable.
More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol having a boiling point of 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher.

Examples of the aprotonic polar solvent include nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, ketones such as acetone, ethylmethyl ketone, diethyl ketone and methylene isopropyl ketone, and amides such as N, N-dimethylformamide. Examples include sulfoxides such as dimethyl sulfoxide.

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-. Examples thereof include aromatic alcohols such as hexanol, 1-ethoxy-2-propanol, 1-propanol-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-propanol-2-propanol are preferable, 2-butanol and 1-Methyl-2-propanol is more preferred.

When an aprotic polar solvent or a secondary or tertiary alcohol is used as the organic solvent for the reaction, the O-alkylation reaction, which is a side reaction of the hydroxyl group and the alkoxylate derived from the layered inorganic compound, is unlikely to occur, and the O-alkylation reaction is unlikely to occur. It is inferred that since the boiling point of the organic solvent used is high, the silylation reaction temperature rises, the interlayer modification reaction such as the silylation reaction is accelerated, and the interlayer modification rate such as the silylation rate increases.
Further, when secondary or tertiary alcohols are used, hydroxyl groups such as silanol are produced by hydrolysis of the coupling agent such as the silane coupling agent described later, and the coupling agents such as the silane coupling agent are condensed with each other. It is preferable because side reactions such as are suppressed. It is inferred that this is the solvent effect due to the alcoholic hydroxyl group.

During the reaction, 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 ion-exchanged water, distilled water, pure water and ultrapure water are preferable.
The amount of water added is preferably 0.05 to 4.0 mol times the total amount of the hydroxyl group, which is the reaction point of the layered inorganic compound, and the alkoxylate, which is the counter anion of the onium group, that is, the ion exchange capacity. , 0.1 to 3.0 mol times is particularly preferable.
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 coupling agents such as silane coupling agents may proceed. There is.

The amount of the coupling agent such as the silane coupling agent in the reaction is not particularly limited, but is preferably with respect to the total amount of the hydroxyl group as the reaction point and the alkoxylate as the counter anion of the onium group, that is, the ion exchange capacity. It is 0.1 to 30 mol times, more preferably 0.05 to 20 mol times, and even more preferably 1.0 to 10 mol times.
If the amount of the coupling 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 reaction point between the layers of the layered inorganic compound, that is, the interlayer modification rate such as the silylation rate with respect to the ion exchange capacity is selected according to the purpose and is not particularly limited, but the interlayer modification rate such as the silylation rate is 15 mol. % Or more, more preferably 25 mol% or more.
On the other hand, if the interlayer modification rate such as the silylation rate exceeds 200 mol%, the layers of the layered inorganic compound may be excessively covered with the components derived from the coupling agent, which is not preferable.

The reaction temperature in the interlayer modification 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, the reaction is carried out 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 interlayer modification 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 interlayer modification reaction such as the silylation reaction with the coupling agent of the present invention may or may not use a catalyst, but carboxylic acids such as hydrogen chloride, formic acid, acetic acid and oxalic acid, phosphoric acid, nitric acid, sulfuric acid, Known acids such as sulfonic acids such as methanesulfonic acid and known bases such as ammonia, trimethylamine, triethylamine, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide can be added as catalysts.
In that case, the amount of the catalyst to be added is not particularly limited, but is 0.001 to 1.0 mol with respect to the total amount of the hydroxyl group as the reaction point and the alkoxylate as the counter anion of the onium group, that is, the ion exchange capacity. It is preferably double, more preferably 0.01 to 0.1 molar times.

The interlayer-modified layered inorganic compound obtained by the interlayer modification reaction such as 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 the solid solution, the supernatant solution is removed by decantation, or filtration operations such as natural filtration, pressure filtration, and reduced pressure filtration are performed. 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, after the solid obtained after decantation is redispersed in water or an organic solvent, the solid is washed by pouring water or an organic solvent over the decantation or the solid that has been filtered out in the same manner. The method etc. can be mentioned.
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 used for cleaning 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.
When reducing or removing commutative cations such as onium groups and metal cations remaining after an interlayer modification reaction such as a silylation reaction, acid treatment can be carried out using a known acid and solvent in the same manner as described above. ..

Next, a method for producing an interlayer crosslinked type layered inorganic compound by reacting a layered inorganic compound having layers modified with a coupling agent with a crosslinkable functional group derived from the coupling agent will be described.
The cross-linking reaction by a cross-linking functional group derived from a coupling agent such as a silane coupling agent is not particularly limited, and is an addition reaction, a substitution reaction, a condensation reaction, an ionic reaction, an electron-forming reaction, a nucleophilic reaction, and a pericyclic reaction. Various generally known chemical reactions such as reactions and radical reactions can be used, and so-called click reactions can also be used. A radical is generated from an alkyl group for a cross-linking reaction, an alkyl halide group is converted into an anionic species as a greeninal reagent for a nucleophilic reaction, or a hydroxyl group, an alkoxy group, or an amino group is used with respect to the alkyl halide group. A cross-linking method in which a nucleophilic species such as the above is allowed to act to cause a nucleophilic substitution reaction can be mentioned, but since the coupling agent is easily available and the cross-linking reaction proceeds under relatively mild conditions, the following formula (20) to The reaction represented by (34) is preferable, and if the layers are modified with the same coupling agent and then crosslinked, the number of manufacturing steps is reduced, which is more industrially advantageous. Therefore, the formulas (20) to (24) and The cross-linking reactions represented by the formulas (29) to (33) are more preferable, the cross-linking reaction proceeds easily under mild conditions, various chemical structures, flexibility and rigidity can be introduced, and the length of the cross-linking varies. The cross-linking reactions represented by the formulas (20) to (24) and the formulas (31) to (33) are more preferable because they can have properties.

When the cross-linking reactions represented by the formulas (20) to (22) and the formula (31) are used, the cross-linking functional groups have a similar or similar structure, and the cross-linking structure to be reacted or produced is relatively simple. Moreover, it is possible to control the interlayer distance and the interlayer environment (hydrophobicity, hydrophilicity, aromaticity, etc.) of the layered inorganic compounds relatively easily according to the structures of R ² , R ⁴ and R ^13. It has features.
Further, when the cross-linking reactions represented by the formulas (23), (24), (32) and (33) are used, it is relatively easy depending on the structures of ^{R 2} , R ⁴ and R ^13. Not only can the interlayer distance and flexibility of layered inorganic compounds and the environment between layers (hydrophilicity, hydrophilicity, aromaticity, hydrogen bond formation, etc.) be controlled, but also various available amines and diamines can be used. Since it can be introduced into the crosslinked structure, the interlayer distance and flexibility of the layered inorganic compound and the environment between layers (hydrophilicity, hydrophilicity, aromaticity, hydrogen bond formation, heterocycle, etc.) can be easily and freely controlled. It has the feature that it can be used.

(In formulas (20) to (34), R ¹ may have a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms and a branched chain having 3 to 8 carbon atoms. It represents a saturated cycloalkyl group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ² and R ¹³ are independently saturated or saturated linear or branched chains having 1 to 20 carbon atoms, respectively. An unsaturated alkylene group, a saturated or unsaturated cycloalkylene group which may have a branch of 3 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms, R ³ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is an alkylene group having 1 to 6 carbon atoms, a phenylene group or an aralkylene group having 7 to 10 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ and R ¹² are independent hydrogen atoms, linear or branched saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, and branched chains having 3 to 8 carbon atoms, respectively. There may be a saturated or unsaturated cycloalkyl group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ is a saturated or branched linear or branched chain having 1 to 20 carbon atoms. Unsaturated alkylene group, saturated or unsaturated cycloalkylene group which may have a branch of 3 to 20 carbon atoms, arylene group of 6 to 20 carbon atoms, aralkylene group of 7 to 20 carbon atoms or polyphenylene having 6 to 24 carbon atoms. A group is indicated, and any R ¹¹ may be substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom, etc. and a substituent consisting of 1 to 10 atoms containing the sulfur atom, and Z is a hydrogen atom and a carbon number of carbon atoms. Saturated or unsaturated alkyloxy groups 1 to 8, saturated or unsaturated cycloalkyloxy groups having 3 to 8 carbon atoms, trimethylsilyloxy groups, dimethylsilyloxy groups, saturated or unsaturated heterocycloalkyloxy groups having 1 to 8 carbon atoms Group, halogen atom, hydroxyl group, amino group, saturated or unsaturated alkylamino group of linear or branched chain with 1 to 6 carbon atoms, saturated or unsaturated dialkylamino of linear or branched chain with 1 to 6 carbon atoms Indicates an oxygen atom derived from a group or a layered inorganic compound, I is a group derived from a polymerization initiator and may be the same or different, Y is a group derived from a conjugated base derived from an acid, n is an integer of 0 to 2, m. And h represent an integer of 0 or 1, and k represents an integer of 0-4.

Further, in the cross-linking reactions represented by the formulas (20) to (34), cross-linking derived from a coupling agent composed of titanium (Ti), aluminum (Al), zirconium (Zr) or the like instead of silicon atom (Si). Cross-linking reactions of sex functional groups can be utilized.

In the above-mentioned cross-linking reaction, the cross-linking point in the carbon-carbon double bond cross-linking reaction may be either the head or the tail of the double bond, and the cross-linking point in the ring-opening cross-linking reaction of the epoxy group and the oxetanyl group is a cyclic ether group. It may be any of two carbon atoms existing adjacent to each other.

In order to promote the cross-linking reaction, if necessary, known polymerization initiators such as thermal radical generators, photoradical generators, thermal anion generators, photocation generators, thermoacid generators, photoacid generators, etc. Thermobase generators and photobase generators, known inorganic acids such as hydrochloric acid, sulfuric acid, nitrate, formic acids, acetic acid, oxalic acid, citric acid, methanesulfonic acid, paratoluenesulfonic acid and other known organic acids, ammonia, water Known inorganic bases such as sodium oxide, potassium hydroxide and calcium hydroxide, organic bases such as known organic amines such as methylamine, diethylamine and triethylamine, known ammonium salts such as tetramethylammonium hydroxy and succinic anhydride, anhydrous. A known catalyst such as a known acid anhydride such as phthalic acid or maleic anhydride, a curing agent, or an oxidizing agent such as bromine or iodine can be used in combination.

The polymerization initiator is not particularly limited, and a known polymerization initiator used in the polymerization reaction of the polymerizable monomer is used, and a thermal polymerization initiator and / or a photopolymerization initiator is used. A thermal polymerization initiator is more preferable because a cross-linking reaction system containing a layered inorganic compound modified with a coupling agent may be suspended between layers, making it difficult for light such as ultraviolet rays to pass through.

Various compounds can be used as the thermal polymerization initiator, and when the polymerizable group is a radically polymerizable group, for example, in the case of the above formula (20) and the above formula (30), it is excessive. Oxide and azo-based initiators are preferred.

Specific examples of peroxides include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate, and potassium persulfate; 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1. -Bis (t-hexyl peroxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3 5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,5-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) Cyclododecane, t-hexyl peroxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl -2,5-di (m-toluole peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2 , 5-Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t) -Butylperoxy) Valerate, di-t-butylperoxyisophthalate, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di ( t-Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthan hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin- 3. Diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide, etc. Includes organic peroxides.

Specific examples of the azo-based initiator include 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, and 2-. Examples thereof include azo compounds such as phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane, which may be used alone or in combination of two or more. Is also good.
In addition, peroxides, ascorbic acid, sodium ascorbate, sodium erythorbicate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfite, sodium sulfite, sodium sulfite, sodium metabisulfite, quaternary chloride It is also possible to carry out a redox reaction by combining it with a redox polymerization initiation system in which a reducing agent such as iron is used in combination.

The amount of the thermal polymerization initiator used is selected depending on the type and polymerization conditions, but is usually 1 to 1000 mol, more preferably 5 to 500 mol, based on 100 mol of the polymerizable functional group. It is more preferably 50 to 200 mol.

Specific examples of the photopolymerization initiator include benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one when the polymerizable group is a radically polymerizable group. , 1- [4- (2-Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methyl) Vinyl) Phenyl] Propanone, 2-Hydroxy-1- [4- [4- (2-Hydroxy-2-methyl-propionyl) benzyl] Phenyl] -2-Methylpropan-1-one, 2-Methyl-1- [ 4- (Methylthio)] Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2-one Acetphenone compounds such as (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one; benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4' -Benzophenyl compounds such as dimethylaminobenzophenone;
Acyls such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Phosphine oxide compounds; as well as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2- Il-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride, fluorothioxanthone and other thioxanthone compounds can be mentioned.
Examples of the compound other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, methyl phenylglioxyate, ethyl anthraquinone, phenanthrenequinone, camphorquinone and the like.

The amount of the photopolymerization initiator used is selected depending on the type and polymerization conditions, but is 1 to 1000 mol, more preferably 5 to 500 mol, based on 100 mol of the polymerizable functional group. More preferably, the amount is 50 to 200 mol.

When the polymerizable group is a cationically polymerizable group, for example, in the cases of the above formula (21), the above formula (22) and the above formula (31), various known cationic polymerization initiators are used. Examples of the thermal cationic polymerization initiator include sulfonium salts, phosphonium salts, and quaternary ammonium salts. Among these, a sulfonium salt is preferable.
Examples of the counter anion in the thermal cationic polymerization initiator include AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ^{− and the} like.

Examples of the sulfonium salt include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium arsenide hexafluoride, tri (4-methoxyphenyl) sulfonium arsenide hexafluoride, and diphenyl (4-phenylthiophenyl). ) Sulfonium arsenic hexafluoride and the like.
Commercially available products can also be used as the sulfonium salt. Specifically, for example, "ADEKA OPTON CP-66" (trade name) and "ADEKA OPTON CP-77" (trade name) manufactured by ADEKA, Sanshin Chemical Co., Ltd. Examples thereof include "Sun Aid SI-60L" (trade name), "Sun Aid SI-80L" (trade name) and "Sun Aid SI-100L" (trade name) manufactured by Kogyo Co., Ltd.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoride antimony and tetrabutylphosphonium hexafluoride antimony.
Examples of the quaternary ammonium salt include N, N-dimethyl-N-benzylanilinium hexafluoride antimony, N, N-diethyl-N-benzylanilinium tetrafluoride boron, and N, N-dimethyl-N-benzyl. Pyridinium hexafluoride antimony, N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoride antimony, N, N-diethyl-N-( 4-methoxybenzyl) pyridinium hexafluoride antimony, N, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoride antimony, N, N-dimethyl-N- (4-methoxybenzyl) toluidinium hexafluoride antimony And so on.

Examples of the photocationic polymerization initiator include onium salts such as iodonium salt, sulfonium salt, diazonium salt, selenium salt, pyridinium salt, ferrosenium salt and phosphonium salt. Among these, iodonium salt and sulfonium salt are preferable.
When the cationic photopolymerization initiator is an iodonium salt or sulfonium salt, as a counter anion, for _{^{example, BF 4 -, AsF 6 -}} , SbF 6 -, PF 6 -, B (C 6 F 5) 4 - and the like include Be done.

Examples of the iodonium salt include (tricmil) iodonium tetrakis (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetrafluoroborate, and diphenyl iodonium tetrakis (pentafluorophenyl). Borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate , 4-Methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-( Examples thereof include 1-methylethyl) phenyliodonium tetrafluoroborate and 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate.
As the iodonium salt, a commercially available product can be used. Specifically, for example, GE Toshiba Silicone Co., Ltd. "UV-9380C" (trade name), Rhodia Co., Ltd. "RHODOSIL PHOTOINITIATOR 2074" (trade name), Japanese Examples thereof include "WPI-016" (trade name), "WPI-116" (trade name) and "WPI-113" (trade name) manufactured by Kojun Yakuhin Kogyo Co., Ltd.

Examples of the sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- (diphenylsulfonio). Nio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] Sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] Sulfide bishexafluoroantimonate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) Ethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, etc. Be done.
Commercially available products can also be used as the sulfonium salt. Specifically, for example, "Cyracure UVI-6990" (trade name), "Cyracure UVI-6992" (trade name) and "Cyracure UVI-6992" (trade name) manufactured by Dow Chemical Japan Co., Ltd. Cyracure UVI-6974 ", ADEKA's" Adeka Putmer SP-150 "(trade name)," Adeka Putmer SP-152 "(trade name)," Adeka Putmer SP-170 "(trade name) and" Adeka Optomer SP-172 (trade name), Wako Pure Chemical Industries, Ltd. "WPAG-593" (trade name), "WPAG-596" (trade name), "WPAG-640" (trade name) and "WPAG-" 641 ”(trade name) and the like.

Examples of the diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate and the like.

When the polymerizable group is an anionic polymerizable group, for example, in the case of the above formula (20), various known anionic polymerization initiators can be used, and the thermal cationic polymerization initiator may be used. For example, amines, thiols, imidazoles and the like can be used. Examples of amines include diethylenetriamine, triethylenetetramine, isocyanateolonediamine, xylylenediamine, diaminodiphenylmethane, 1,3,4,6-tetrakis (3-aminopropyl) glycoluryl and the like, and examples of thiols include trimethylol. Propyltris (3-mercaptopropionate), tris (2-mercaptoethyl) isocyanurate, 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluryl and the like can be mentioned, and imidazoles include 2-. Examples thereof include methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

Examples of the photoanionic polymerization initiator include acetphenone O-benzoyloxime, nifedipine, and 2- (9-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4,4,0] deca-. 5-ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate, 1,2 -Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate and the like can be mentioned.

The amine represented by the following formula (35) that can be used for cross-linking the epoxy group represented by the formula (23) and the formula (32) is not particularly limited, but for example, ammonia, methylamine, ethylamine, propylamine, etc. Butylamine, pentylamine, hexylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, icosylamine, isopropylamine, allylamine, alkylamines such as 2-cyclohexylethylamine, cyclopentylamine, cyclohexylamine, cyclooctylamine, 3-cyclo Cyclic alkylamines such as hexenylamine, phenylamines, 1-naphthylamines, 2-naphthylamines, 2-aminoanthracenes, 1-aminopyrene, 3-aminobiphenyls and other arylamines, benzylamines, 2-phenylethyl groups, 1- (1) Examples thereof include aralkylamines such as −naphthyl) ethylamine, 1- (2-naphthyl) ethylamine, and 2- (7-methoxy-1-naphthyl) ethylamine.

H ₂ NR ⁸ (35)
(In formula (35), R ⁸ is 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 cyclo having a branched chain having 3 to 8 carbon atoms. It indicates an alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)

The amine represented by the following formula (36) that can be used for cross-linking the epoxy group represented by the formula (24) and the formula (33) is not particularly limited, but for example, diaminomethane, urea, thiourea, 1 , 2-Diaminoethane, 1,2-bis (methylamino) ethane, N-methylmethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1, 4-Diaminobutane, 1,4-bis (methylamino) -2-butene, 1,6-diamihexane, 1,8-dimethyloctane, N, N-bis (2-aminoethyl) methylamine, 1,3- Diaminocyclohexane, 1,4-diaminocyclohexane, 3-aminopyrrolidin, 4,4'-methylenebis (2-methylcyclohexylamine), bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-phenylenediamine , 1,4-phenylenediamine, 1,2,4-triaminobenzene, N, N'-diphenyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2,7-diaminofluorene, 4,4'-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethylbiphenyl, 3,3', 4,4'-tetraaminobiphenyl, 1,5-diaminonaphthalene, 2,6-diaminoanthraquinone , 1,6-diaminopyrene, 1,8-diaminopyrene, 3- (aminomethyl) benzylamine, 4- (aminomethyl) benzylamine and the like.

R ⁹ HR ¹¹ NHR ¹⁰ (36)
(In the formula (36), R ⁹ and R ¹⁰ each independently have a hydrogen atom, a linear or unsaturated alkyl group having 1 to 20 carbon atoms, and a branched chain having 3 to 8 carbon atoms. Saturated or unsaturated cycloalkyl groups may be represented, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ is a saturated or unsaturated linear or branched chain having 1 to 20 carbon atoms. Saturated alkylene group, saturated or unsaturated cycloalkylene group which may have branching of 3 to 20 carbon atoms, arylene group of 6 to 20 carbon atoms, aralkylene group of 7 to 20 carbon atoms or polyphenylene group of 6 to 24 carbon atoms. , And any R ¹¹ may be substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom and a substituent consisting of 1 to 10 atoms containing the same.)

In the case of the reaction represented by the above formula (29), an oxidizing agent can be used in combination, and for example, a known oxidizing agent that promotes the disulfide formation reaction, such as using bromine or iodine under basic conditions, is used. be able to.

When the cross-linking reaction between layers is carried out by heating, the reaction temperature is not particularly limited and may be appropriately selected. For example, 0 to 200 ° C. is preferable, 25 to 180 ° C. is more preferable, and 40 to 150 ° C. is preferable. ° C is more preferred. At this time, from the viewpoint of ease of crosslinking and cost, it is preferable to appropriately contain a thermal polymerization initiator in the reaction system.

Examples of the active energy ray for irradiating the active energy ray to carry out the cross-linking reaction between the layers include ultraviolet rays, visible light, and electron beam. When ultraviolet rays or visible rays are used as the active energy rays, it is preferable to contain a photopolymerization initiator from the viewpoint of ease of cross-linking and cost.

Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, and an ultraviolet light emitting diode (UV-LED).
The irradiation energy may be appropriately set according to the type of active energy ray and the compounding composition, and varies depending on the thickness and illuminance of the reaction system. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is used. For example, 5 to 10,000 mJ / cm ² is preferable. When a UV-LED is used, its emission peak wavelength is preferably 350 to 420 nm, and the irradiation energy is preferably 5 to 10,000 mJ / cm ² .

When an electron beam is used as the active energy ray, it can be cured by an electron beam without containing a photopolymerization initiator, but it can also be added in a small amount if necessary in order to improve the curability.
Various devices can be used as the electron beam irradiation device, and examples thereof include Cockcroft-Walton type, Van de Graaff type, and resonance transformer type devices.
The absorbed dose of the electron beam is preferably 1 to 1000 kGy, for example.
The oxygen concentration in the electron beam irradiation atmosphere is preferably 500 ppm or less, more preferably 300 ppm or less.

When carrying out the cross-linking reaction between layers, a reaction solvent can be used, but such a solvent is not particularly limited and may be appropriately selected, 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, 1-hexanol, 2- Alcohols such as hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, ketones such as acetone and ethylmethylketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide, hexane, etc. Alcans, aromatics such as benzene and toluene, esters such as ethyl acetate, halogen-based hydrocarbons such as chloroform and dichloromethane, etc. Among these, alcohols and ethers which are aprotonic polar solvents. Classes, nitriles and ketones are preferred.
More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol having a boiling point of 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher.

The aprotonic polar solvent is not particularly limited, but is limited to nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, ketones such as acetone, ethylmethyl 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-. Examples include aromatic alcohols such as hexanol, 1-ethoxy-2-propanol, 1-propanol-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-propanol-2-propanol are preferable, 2-butanol and 1-Methyl-2-propanol is more preferred.

The reaction concentration in the cross-linking reaction between layers is not particularly limited and may be appropriately selected. For example, the mass% of the interlayer-modified layered inorganic compound is preferably 1 to 50% by mass, preferably 3 to 40% by mass. More preferably, 5 to 30% by mass is further preferable.

Further, any functional group or modifying group may be present between the layers of the interlayer crosslinked type layered inorganic compound of the present invention in addition to the organic-inorganic composite crosslinked structure. For example, an exchangeable metal cation such as sodium, potassium or calcium may be present, may be modified with an organic onium group such as alkylammonium or alkylphosphonium, or a hydroxyl group derived from a layered inorganic compound may be present. Often, the hydroxyl group may be sealed and converted to an alkoxy group such as a methoxy group, and an organic silyl group such as an alkylsilyl group, an arylsilyl group, an aralkylsilyl group and a group derived from an uncrosslinked silane coupling agent, It may be modified with an organic-inorganic composite modifying group containing a metal such as titanium, aluminum or zirconium.

The time for introducing any functional group or modifying group other than the organic-inorganic composite crosslinked structure existing between the above layers may be before, after, or at the same time as the interlayer modification with the coupling agent for constructing the crosslinked structure. Further, it may be before or after the interlayer cross-linking reaction of the cross-linking functional group derived from the coupling agent introduced between the layers, and it may be arbitrarily selected in consideration of the reactivity of various functional groups, modifying groups and the coupling agent. be able to.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
<Example 1> Synthesis of P-MACPS (methacryloyloxypropyl) -magadiate crosslinked by a reaction of methacryloxy (corresponding to the organic-inorganic composite crosslinked structure of the above formula (4)).
(1) Synthesis of sodium-magadiate (hereinafter referred to as Na-magadiate).
After mixing 18.34 g of sodium silicate (manufactured by Fuji Chemical Industries, Ltd., trade name: No. 4 sodium silicate), 7.28 g of silica gel (manufactured by Wako Pure Chemical Industries, Ltd., trade name: Wakogel Q-63) and 54.37 g of pure water. , It was sealed in a high-pressure reaction decomposition container (manufactured by San-ai Kagaku Co., Ltd., trade name: HU-100) and heated at 170 ° C. for 30 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.
As a result of calculating the composition of Na-magadiate using an atomic absorption spectrometer (AA-6200, manufactured by Shimadzu Corporation) and a thermogravimetric analyzer (TG / DTA6300, manufactured by Hitachi High-Tech Science), Na ₂ Si ₁₄ O ₂₉ -NH ₂ O, and the ion exchange capacity calculated assuming n = 0 was 2.21 mol _c / kg.
Further, as a result of determining the bottom surface spacing of Na-magadite obtained by using an X-ray diffractometer (manufactured by BRUKER, trade name: D8 ADVANCE), it was 1.54 nm.

(2) Synthesis of dodecyltrimethylammonium (hereinafter referred to as DTMA) -magadiate (synthesis of silylation precursor by interlayer ammonium formation by dodecyltrimethylammonium chloride treatment of Na-magadiate).
100 g of Na-magadiate, 6500 g of pure water and 175 g of dodecyltrimethylammonium chloride obtained above were mixed 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 94 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.
As a result of calculating the composition of DTMA-magadiate obtained by using an elemental analyzer (manufactured by Yanako Analytical Industry Co., Ltd., CHN coder MT-5) and a thermogravimetric analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., TG / DTA6300), DTMA _{It was 1.66} H _0.34 Si ₁₄ O ₂₉ · nH ₂ O.
Further, in the same manner as described above, the bottom surface spacing of the obtained DTMA-magadiaite was determined to be 2.80 nm.

(3) Interlayer silylation of DTMA-magadiaite by 3-methacryloxypropyltrimethoxysilane (hereinafter referred to as MAC-TRIMS) treatment (introduction of metharoxy-crosslinkable functional group).
100 g of DTMA-magadiate obtained above was dried under reduced pressure at 100 ° C. and about 100 Pa for 2 hours, and then 1850 g of 1-methoxy-2-propanol (hereinafter referred to as PGM) dried with molecular sieve 3A, pure water 2. 8 g and 39.1 g of MAC-TRIMS (equal to the reaction point) were mixed, and the mixture was stirred for 2 days while heating under reflux in a nitrogen atmosphere. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C. to obtain silylated magadite (hereinafter referred to as MACPS-magadite).
As a result of calculating the composition of the obtained MACPS-magadiate in the same manner as described above, it was 3-methacryloxypropylsilyl (MACPS) _0.52 DTMA _0.51 Me _0.97 Si ₁₄ O ₂₉ · nH ₂ O.
As a result of determining the bottom surface spacing of the obtained MACPS-magadiaite in the same manner as described above, it was 2.16 nm.

(4) Synthesis of interlayer cross-linked layered inorganic compound by cross-linking reaction of MACPS-magadiate.
100 g of MACPS-magadiate and 1450 g of toluene obtained above were mixed, and nitrogen gas was bubbled for 1 hour while cooling in an ice bath to remove oxygen in the system. Then, 7.88 g of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added, and the mixture was stirred at 60 ° C. for 24 hours. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C. to obtain a magadite having a crosslinked methacryloxy group (hereinafter referred to as P-MACPS-magadite).
As a result of calculating the composition of the P-MACPS-magadiaite obtained in the same manner as above, the crosslinked methacryloyloxypropyl group (P-MACPS) was _0.13 MACPS _0.39 DTMA _0.42 Me _1.06 Si ₁₄ O ₂₉ · nH ₂ O. The bottom spacing was 2.11 nm.

<Example 2> Synthesis of P-MACOS (methacryloyloxyoctyl) -magadiaite crosslinked by a reaction of methacryloxy The silylating agent used in Example 1 (3) was used from 39.1 g of MAC-TRIMS to 3-methacryloxyoctylli. The same treatment as in Example 1 was carried out except that the amount was changed to 50.1 g of methoxysilane (hereinafter referred to as MAC-O-TRIMS), and the methacryloxy group was crosslinked with the magadiate (hereinafter referred to as P-MACOS-magadiate). I will write).
As a result of calculating the composition of the P-MACOS-magadiite obtained in the same manner as above, the crosslinked methacryloyloxyoctyl group (P-MACOS) _0.52 MACOS _0.42 DTMA _0.49 Me _0.57 Si ₁₄ O ₂₉ · nH ₂ O. The bottom spacing was 2.85 nm.

<Example 3> An interlayer silylation-modified compound (interlayer crosslinked layered inorganic compound having a thiol group between layers) by treatment with 3-mercaptopropyltrimethoxysilane (hereinafter referred to as MP-TRIMS) of P-MACPS-magadiate. Synthesis (corresponding to the organic-inorganic composite crosslinked structure of the above formula (4)).
100 g of P-MACPS-magadiate obtained in Example 1 (4) was dried under reduced pressure at 100 ° C. and about 100 Pa for 2 hours, and then dried with Molecular Sieve 3A, PGM 1850 g, pure water 3.3 g, MP-TRIMS 920 g (reaction). (25 mol times with respect to the point) was mixed, and the mixture was stirred for 2 days while heating under reflux in a nitrogen atmosphere. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C. to obtain P-MACPS-magadiate (hereinafter referred to as P-MACPS-MPS-magadiate) into which a mercaptopropylsilyl group was introduced. ..
As a result of calculating the composition of the obtained P-MACPS-MPS-magadite in the same manner as in Example 1, P-MACPS _0.13 MACPS _0.39 DTMA _0.07 , mercaptopropylsilyl (MPS) _0.35 Me _1.06 Si ₁₄ O ₂₉ · nH ₂ It was O and the bottom spacing was 2.29 nm.

<Example 4> Synthesis of an interlayer silylation-modified compound (interlayer-crosslinked layered inorganic compound having a phenyl group between layers) by treatment with phenyltrimethoxysilane (hereinafter referred to as Ph-TRIMS) of P-MACPS-magadiate (described above). Corresponds to the organic-inorganic composite crosslinked structure of formula (4)).
The same treatment as in Example 3 was carried out except that the silylating agent was changed from MP-TRIMS 920 g to Ph-TRMIS 1810 g (50 mol times relative to the reaction site), and P-MACPS-magadiate (P-MACPS-magadiate) into which a phenylsilyl group was introduced. Hereinafter, P-MACPS-PhS-magadiate) was obtained.
As a result of calculating the composition of the obtained P-MACPS-PhS-magadite in the same manner as in Example 1, P-MACPS _0.13 MACPS _0.39 DTMA _{0.02 PhS 0.38} Me _1.08 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom surface spacing Was 1.95 nm.

<Example 5> Synthesis of P-MACPS-magadiate (M) having a relatively high crosslink density (corresponding to the organic-inorganic composite crosslinked structure of the above formula (4)).
(1) Synthesis of MACPS-magadiate (M) with a large amount of MACPS introduced The reaction solvent was 1850 g to 1560 g of acetonitrile, the amount of MAC-TRIMS used was 39.1 g to 274 g (7 mol times with respect to the reaction site), and pure water. The same treatment as in Example 1 (3) was carried out except that the amount used was changed from 2.8 g to 1.4 g, to obtain MACPS-magadiate (M).
As a result of calculating the composition of the obtained MACPS-magadiate (M) in the same manner as in Example 1, MACPS _1.94 Me _0.06 Si ₁₄ O ₂₉ · nH ₂ O was obtained, and the bottom surface spacing was 2.53 nm.

(2) Synthesis of an interlayer cross-linked layered inorganic compound by a cross-linking reaction of MACPS-magadiate (M).
The same treatment as in Example 1 (4) was carried out except that the amount of AIBN used was changed from 7.88 g to 26.0 g and the amount of toluene used was changed from 1450 g to 2600 g. Obtained.
As a result of calculating the composition of the obtained MACPS-magadiite in the same manner as in Example 1, P-MACPS _0.22 MACPS _1.72 Me _0.06 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom spacing was 2.52 nm.

<Example 6> Synthesis of P-GPS-A-magadiate crosslinked by reaction of epoxy group (corresponding to the organic-inorganic composite crosslinked structure of the above formula (6))
(1) Synthesis of partially protonated DTMA-magadiate (silylation precursor) by hydrochloric acid treatment of DTMA-magadiate.
100 g of DTMA-magadiate obtained in Example 1 (2) and 655 g of 0.1 mol · dm- ³ hydrochloric acid were mixed and stirred at room temperature for 1 day. Then, the solid was sucked and collected, washed with pure water, and then dried at 60 ° C. to obtain a partially protonated DTMA-magadiate.
As in Example 1, the composition of the obtained partially protonated DTMA-magadite was calculated to be DTMA _1.11 H _0.89 Si ₁₄ O ₂₉ · nH ₂ O, and the ratio of ammonium groups to the ion exchange capacity was 56. It was mol%.
As a result of analyzing the bottom spacing of the partially protonated DTMA-magadiate in the same manner as in Example 1, no clear diffraction peak was observed. It is presumed that this is because most of the layered structure of the obtained partially protonated DTMA-magadiaite is broken.

(2) Interlayer silylation of partially protonated DTMA-magadiaite by 3-glycidyloxypropyltrimethoxysilane (hereinafter referred to as GP-TRIMS) treatment (introduction of epoxy crosslinkable functional group).
With respect to 100 g of the partially protonated DTMA-magadiaite obtained above, the silylating agent to be used is from 39.1 g of MAC-TRIMS to 300 g of GP-TRMIS (7 mol times with respect to the reaction site), and from 2.8 g of pure water. The same treatment as in Example 1 (3) was carried out except that the amount was changed to 3.3 g, to obtain glycidyloxypropylsilylated magadite (hereinafter referred to as GPS-magadite).
As a result of calculating the composition of the obtained GPS-magadite in the same manner as in Example 1, glycidyloxypropyl (GPS) _0.96 DTMA _0.40 Me _0.64 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom surface spacing was 2.23 nm. there were.

(3) Synthesis of an interlayer cross-linked layered inorganic compound by a cross-linking reaction using GPS-magadiate hydrogen chloride.
100 g of the GPS-magadiate obtained above was dried under reduced pressure at 100 ° C. and about 100 Pa for 2 hours, then 2000 g of PGM dried with molecular sieve 3A and 255 g of a 5% hydrogen chloride methanol solution were mixed and heated to reflux under a nitrogen atmosphere. While stirring for 1 day. Then, the solid was sucked and collected, washed with methanol, and then dried at 60 ° C. to obtain GPS-magadite (hereinafter referred to as P-GPS-A-magadite) in which epoxy groups reacted with each other and crosslinked. rice field.
As a result of measuring the chlorine content of P-GPS-A-magadite obtained using a scanning fluorescent X-ray analyzer (ZSX PrimusII manufactured by Rigaku Co., Ltd.), it was 0.273%. As a result of calculating the composition in the same manner as in Example 1, the crosslinked glycidyloxypropyl group (P-GPS-A) _0.08 GPS _0.88 DTMA _0.15 H _0.25 Me _0.64 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom spacing is It was 1.9 nm.

<Example 7> Synthesis of an interlayer cross-linked layered inorganic compound by a cross-linking reaction using ethylenediamine of GPS-magadiate (corresponding to the organic-inorganic composite cross-linked structure of the above formula (8)).
The same treatment as in Example 6 (3) was carried out except that 255 g of the 5% hydrogen chloride methanol solution was changed to 2.63 g of ethylenediamine, and the epoxy group was reacted and crosslinked via ethylenediamine (hereinafter, GPS-magadiate). , P-GPS-EDA-Magadiaite).
As a result of calculating the composition in the same manner as in Example 1, the glycidyloxypropyl group (P-GPS-EDA) crosslinked via ethylenediamine was _0.12 GPS _0.85 DTMA _0.26 Me _0.77 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom spacing was Was 2.15 nm.

<Example 8> Synthesis of an interlayer cross-linking type layered inorganic compound by a cross-linking reaction using 4,4'-methylene dianiline of GPS-magadiate (corresponding to the organic-inorganic composite cross-linking structure of the above formula (8)).
The same treatment as in Example 6 (3) was carried out except that 255 g of the 5% hydrogen chloride methanol solution was changed to 8.66 g of 4,4'-methylene dianiline, and the epoxy group was passed through 4,4'-methylene dianiline. Reacted to obtain a crosslinked GPS-magadite (hereinafter referred to as P-GPS-44MDA-magadite).
As a result of calculating the composition in the same manner as in Example 1, the glycidyloxypropyl group (P-GPS-44MDA) crosslinked via 4,4'-methylenedianiline _0.09 GPS _0.87 DTMA _0.25 Me _0.79 Si ₁₄ O _29. It was nH ₂ O and the bottom spacing was 2.15 nm.

<Comparative Example 1> Synthesis of mercaptopropylsilyl (MPS) -magadiate (non-crosslinked type) (interlayer silylation of partially protonated DTMA-magadiaite by MP-TRIMS treatment).
With respect to 100 g of the partially protonated DTMA-magadiate obtained in Example 6 (1), the silylating agent used was changed from MAC-TRIMS 39.1 g to MP-TRMIS 249 g, except that the silylating agent was changed to Example 1 (3). The same treatment was carried out to obtain a magadite (hereinafter referred to as MPS-magadite) in which the layers were mercaptopropyl silylated and the layers were not crosslinked.
As a result of calculating the composition in the same manner as in Example 1, it was MPS _1.49 DTMA _0.20 Me _0.31 Si ₁₄ O ₂₉ · nH ₂ O.
Moreover, when the bottom surface interval of MPS-magadiate obtained in the same manner as in Example 1 was analyzed, no clear diffraction peak was observed. It is presumed that this is because most of the layered structure of the obtained MPS-magadiaite is broken.

The results of Examples 1 to 8 and Comparative Example 1 are summarized in Table 1 below.

An adsorption test of the thiazole compound on the layered inorganic compound was carried out.
<Example 9> Adsorption test of 2,4,5-trimethylthiazole (hereinafter referred to as TMTO) using P-MACPS-MPS-magadiate (interlayer crosslinked type).
19.1 g of TMTO was added to 1500 g of pure water and stirred well ^{to obtain a 0.1 mol · dm-3} TMTO aqueous solution.
2.5 g of P-MACPS-MPS-magadiate obtained in Example 3 was added to 250 g of the 0.1 mol · dm- ^{3 TMTO aqueous solution, and the mixture was stirred at 25 ° C. for 96 hours.} The TMTO concentration in the supernatant aqueous solution during the test and at the end of the test was analyzed using gas chromatography (Generent Technologies 7820A, column: CP-Sil 5 CB). The result is shown in FIG.
The TMTO concentration in the supernatant aqueous solution at the end of the test was 0.084 mol · dm ^-3 , and the amount of TMTO adsorbed per 1 g of P-MACPS-MPS-magadite was 50.9 mg.

<Comparative Example 2> TMTO adsorption test using MPS-magadiate (non-interlayer crosslinked type).
The adsorption test of TMTO was carried out in the same manner as in Example 8 except that the P-MACPS-MPS-magadite was changed to the MPS-magadite obtained in Comparative Example 1. The result is shown in FIG.
The TMTO concentration in the liquid at the end of the test was 0.090 mol · dm ^-3 , and the amount of TMTO adsorbed per 1 g of MPS-magadiate was 31.8 mg.

（式（１）において、Ｍ ^１ およびＭ ^２ は、それぞれ独立してＳｉ、Ａｌ、ＴｉまたはＺｒを示し、Ｒ ^ａ およびＲ ^ｂ は、それぞれ独立して炭素数１〜２０の直鎖または分岐鎖の飽和もしくは不飽和アルキレン基、炭素数３〜２０の分岐があっても良い飽和もしくは不飽和シクロアルキレン基、炭素数６〜２０のアリーレン基または炭素数７〜２０のアラルキレン基を示し、Ｒ ^ｃ は、炭素数１〜４０から成る有機基を示し、かつヘテロ原子、直鎖構造、分岐構造、環状構造、不飽和結合および芳香族構造を含んでも良く、Ｒ ^１ は、炭素数１〜２０の直鎖または分岐鎖の飽和もしくは不飽和アルキル基、炭素数３〜８の分岐鎖があっても良い飽和もしくは不飽和シクロアルキル基、炭素数６〜２０のアリール基または炭素数７〜２０のアラルキル基を示し、Ｚは、水素原子、炭素数１〜８の飽和もしくは不飽和アルキルオキシ基、炭素数３〜８の飽和もしくは不飽和シクロアルキルオキシ基、トリメチルシリルオキシ基、ジメチルシリルオキシ基、炭素数１〜８の飽和もしくは不飽和ヘテロシクロアルキルオキシ基、ハロゲン原子、水酸基、アミノ基、炭素数１〜６の直鎖または分岐鎖の飽和もしくは不飽和のアルキルアミノ基、炭素数１〜６の直鎖または分岐鎖の飽和もしくは不飽和のジアルキルアミノ基または層状無機化合物由来の酸素原子を示し、Ｍ ^１ およびＭ ^２ がＳｉ、ＴｉまたはＺｒのいずれかの場合には、それに対応するｘは２で、かつ、ｎは０〜２の整数であり、Ｍ ^１ およびＭ ^２ がＡｌの場合には、それに対応するｘは１で、かつ、ｎは０または１である。）
＜２＞
前記層状無機化合物が、層状ケイ酸塩、層状粘土鉱物および層状金属酸化物からなる群より選択される、少なくとも１種の層状無機化合物である＜１＞に記載の層間架橋型層状無機化合物。
＜３＞
層状無機化合物の層間をカップリング剤で修飾した後、該カップリング剤由来の架橋性官能基を、架橋反応させることを特徴とする＜１＞または＜２＞に記載の層間架橋型層状無機化合物の製造方法。
＜４＞
カップリング剤が、シランカップリング剤であることを特徴とする＜３＞に記載の層間架橋型層状無機化合物の製造方法。
＜５＞
シランカップリング剤が、下記式（２）で表されるシランカップリング剤である＜４＞に記載の層間架橋型層状無機化合物の製造方法。

（式（２）において、Ｒ ^１ は、炭素数１〜２０の直鎖または分岐鎖の飽和もしくは不飽和アルキル基、炭素数３〜８の分岐鎖があっても良い飽和もしくは不飽和シクロアルキル基、炭素数６〜２０のアリール基または炭素数７〜２０のアラルキル基を示し、Ａは、水素原子、炭素数１〜２０の直鎖または分岐鎖の飽和もしくは不飽和アルキル基、炭素数３〜８の分岐鎖があっても良い飽和もしくは不飽和シクロアルキル基、炭素数６〜２０のアリール基または炭素数７〜２０のアラルキル基を示し、それぞれビニル基、エポキシ基、オキセタニル基、アクリロキシ基、メタクリロキシ基、水酸基、アミノ基、アルキルアミノ基、アリールアミノ基、アラルキルアミノ基、アンモニウム基、チオール基、イソシアヌレート基、ウレイド基、イソシアナート基、カルボキシル基またはハロゲン原子で置換されていても良く、Ｄは、水素原子、炭素数１〜８の飽和もしくは不飽和アルキルオキシ基、炭素数３〜８の飽和もしくは不飽和シクロアルキルオキシ基、トリメチルシリルオキシ基、ジメチルシリルオキシ基、炭素数１〜８の飽和もしくは不飽和ヘテロシクロアルキルオキシ基、ハロゲン原子、水酸基、アミノ基、炭素数１〜６の直鎖または分岐鎖の飽和もしくは不飽和のアルキルアミノ基または炭素数１〜６の直鎖または分岐鎖の飽和もしくは不飽和のジアルキルアミノ基を示し、ｎは０〜２の整数を示す。）
＜６＞
層状無機化合物が有する交換性陽イオンを、オニウム基で陽イオン交換して得た前駆体に対し、カップリング剤によりシリル化反応を行うことを特徴とする＜３＞〜＜５＞のいずれかに記載の層間架橋型層状無機化合物の製造方法。
＜７＞
前記前駆体が、層状無機化合物に下記式（３）で表される有機オニウム塩を反応させて得られるものである、＜６＞に記載の層間架橋型層状無機化合物の製造方法。
Ｒ ^１３ Ｒ ^１４ Ｒ ^１５ Ｒ ^１６ Ｎ ^＋ Ｘ ⁻ （３）
（式（３）において、Ｒ ^１３ 、Ｒ ^１４ 、Ｒ ^１５ およびＲ ^１６ は、それぞれ独立して炭素数１〜２２のアルキル基、炭素数７〜２２のアラルキル基、炭素数６〜２２のアリール基、−（ＣＨ _２ −ＣＨ（ＣＨ _３ ）Ｏ） _ｐ −Ｈ基または−（ＣＨ _２ −ＣＨ _２ −Ｏ） _ｑ −Ｈ 基を示し、ｐおよびｑは１〜２０の整数であり、Ｘ ⁻ はハロゲン化物イオンを示す。） As can be seen from FIG. 1, the P-MACPS-MPS-magadite (Example 9), which is an interlayer crosslinked MPS-magadite, is compared with the non-interlayer crosslinked MPS-magadite (Comparative Example 2). , The concentration of thiazole in the liquid decreased significantly with time, indicating that the amount of TMTO adsorbed on magadite was large, and the amount adsorbed on 1 g of magadite after 96 hours was 31. It can be seen that the amount was 8 mg, whereas the amount of the interlayer crosslinked type was as large as 50.9 mg.
Further, in FIG. 1, in Comparative Example 2, the concentration of thiazole in the liquid decreased once 24 hours after the start of the test and then increased again, which was the MPS-in which TMTO was adsorbed between layers during the adsorption test. It is shown that the magadiate is layer-peeled and TMTO is re-released into the liquid, which indicates that it is not preferable as an adsorbent.
On the other hand, in Example 9, such behavior was not exhibited, and the TMTO concentration was consistently decreased during the adsorption test, that is, the continuous adsorption of TMTO was shown. This indicates that the interlayer crosslinked layered inorganic compound is a very excellent adsorbent.
The present disclosure also includes the following aspects <1> to <7>.
<1>
An interlayer crosslinked type layered inorganic compound having an organic-inorganic composite crosslinked structure represented by the following formula (1) between layers of the layered inorganic compound.

(In the formula (1), M ¹ and M ² independently represent Si, Al, Ti or Zr ^{, respectively, and Ra} and R ^b independently represent a linear or branched chain having 1 to 20 carbon atoms, respectively. Saturated or unsaturated alkylene group, saturated or unsaturated cycloalkylene group which may have a branch of 3 to 20 carbon atoms, arylene group of 6 to 20 carbon atoms or aralkylene group of 7 to 20 carbon atoms, R ^c. Indicates an organic group consisting of 1 to 40 carbon atoms and may contain a heteroatom, a linear structure, a branched structure, a cyclic structure, an unsaturated bond and an aromatic structure, and R ¹ has 1 to 20 carbon atoms. Saturated or unsaturated alkyl groups of straight or branched chains, saturated or unsaturated cycloalkyl groups that may have branched chains with 3 to 8 carbon atoms, aryl groups with 6 to 20 carbon atoms or aralkyl with 7 to 20 carbon atoms Indicates a group, where Z is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and a carbon number of carbon atoms. Saturated or unsaturated heterocycloalkyloxy groups from 1 to 8, halogen atoms, hydroxyl groups, amino groups, saturated or unsaturated alkylamino groups with 1 to 6 carbon atoms or branched chains, directly from 1 to 6 carbon atoms Indicates an oxygen atom derived from a saturated or unsaturated dialkylamino group or layered inorganic compound of a chain or branched chain, ^{and when M 1} and M ² are either Si, Ti or Zr, the corresponding x is 2. , And n is an integer of 0 to 2, and when M ¹ and M ² are Al, the corresponding x is 1 and n is 0 or 1.)
<2>
The interlayer cross-linked layered inorganic compound according to <1>, wherein the layered inorganic compound is at least one layered inorganic compound selected from the group consisting of layered silicates, layered clay minerals and layered metal oxides.
<3>
The interlayer-crosslinked layered inorganic compound according to <1> or <2>, wherein the layers of the layered inorganic compound are modified with a coupling agent, and then the crosslinkable functional group derived from the coupling agent is subjected to a cross-linking reaction. Manufacturing method.
<4>
The method for producing an interlayer crosslinked layered inorganic compound according to <3>, wherein the coupling agent is a silane coupling agent.
<5>
The method for producing an interlayer crosslinked layered inorganic compound according to <4>, wherein the silane coupling agent is a silane coupling agent represented by the following formula (2).

(In the formula (2), R ¹ is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms. , An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, where A is a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. It represents a saturated or unsaturated cycloalkyl group which may have 8 branched chains, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and a vinyl group, an epoxy group, an oxetanyl group, an acryloxy group, respectively. It may be substituted with a methacryloxy group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanato group, a carboxyl group or a halogen atom. D is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and 1 to 8 carbon atoms. Saturated or unsaturated heterocycloalkyloxy group, halogen atom, hydroxyl group, amino group, linear or branched chain with 1 to 6 carbon atoms Saturated or unsaturated alkylamino group or linear or branched chain with 1 to 6 carbon atoms Indicates a saturated or unsaturated dialkylamino group of, and n represents an integer of 0 to 2.)
<6>
Any of <3> to <5>, wherein the precursor obtained by cation exchange of the exchangeable cation of the layered inorganic compound with an onium group is subjected to a silylation reaction with a coupling agent. The method for producing an interlayer crosslinked layered inorganic compound according to.
<7>
The method for producing an interlayer crosslinked layered inorganic compound according to <6>, wherein the precursor is obtained by reacting a layered inorganic compound with an organic onium salt represented by the following formula (3).
^{R 13 R 14 R 15 R 16} N + X - (3)
(In the formula (3), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ independently have an alkyl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, and an aryl group having 6 to 22 carbon atoms, respectively. _{, - (CH 2 -CH (CH} 3) O) p -H group or _- indicates _{(CH 2 -CH 2 -O) q} -H group, p and q is an integer of 1 to 20, X ^- is Indicates a halide ion.)

Claims (5)

An interlayer-crosslinked layered inorganic compound having an organic-inorganic composite crosslinked structure represented by at least one of the following formulas (4) to (12) and formulas (14) to (18) between layers of the layered inorganic compound.

(In formulas (4) to (12) and formulas (14) to (18), R ¹ is a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Indicates a saturated or unsaturated cycloalkyl group which may have a branched chain of, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ² and R ¹³ have independently 1 carbon atoms, respectively. Saturated or unsaturated alkylene group of a linear or branched chain of ~ 20, saturated or unsaturated cycloalkylene group which may have a branch of 3 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms or 7 to 20 carbon atoms. R ³ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is an alkylene group having 1 to 6 carbon atoms. It represents a phenylene group or an aralkylene group having 7 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ and R ¹² are independently saturated or unsaturated with a hydrogen atom and a linear or branched chain having 1 to 20 carbon atoms, respectively. An alkyl group, a saturated or unsaturated cycloalkyl group which may have a branched chain having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, where R ¹¹ has carbon atoms. Saturated or unsaturated alkylene group of 1 to 20 linear or branched chains, saturated or unsaturated cycloalkylene group which may have branching of 3 to 20 carbon atoms, arylene group of 6 to 20 carbon atoms, 7 to 7 carbon atoms It represents 20 aralkylene groups or polyphenylene groups having 6 to 24 carbon atoms, and any R ¹¹ is substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom and a substituent consisting of 1 to 10 atoms including the sulfur atom. Z may be a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and a carbon number of carbon atoms. Saturated or unsaturated heterocycloalkyloxy groups 1 to 8, halogen atoms, hydroxyl groups, amino groups, saturated or unsaturated alkylamino groups of linear or branched chains having 1 to 6 carbon atoms or oxygen atoms derived from layered inorganic compounds I is a group derived from a polymerization initiator and may be the same or different, Y is a group derived from a conjugated base derived from an acid, n is an integer of 0 to 2, and m and h are 0 or An integer of 1 is indicated, and k is an integer of 0 to 4.) The interlayer cross-linked layered inorganic compound according to claim 1, wherein the layered inorganic compound is at least one layered inorganic compound selected from the group consisting of layered silicates, layered clay minerals and layered metal oxides. A method for producing an interlayer crosslinked type layered inorganic compound having an organic-inorganic composite crosslinked structure represented by the following formula (1) between layers of the layered inorganic compound.
After modifying the layers of a layered inorganic compound with a coupling agent, the method comprising the crosslinkable functional group derived from the coupling agent, the crosslinking reaction,
The coupling agent is a silane coupling agent, and the silane coupling agent is a silane coupling agent represented by the following formula (2).
A method for producing an interlayer crosslinked layered inorganic compound.

(In the formula (1), M ¹ and M ² independently represent Si, Al, Ti or Zr ^{, respectively, and Ra} and R ^b independently represent a linear or branched chain having 1 to 20 carbon atoms, respectively. Saturated or unsaturated alkylene group, saturated or unsaturated cycloalkylene group which may have a branch of 3 to 20 carbon atoms, arylene group of 6 to 20 carbon atoms or aralkylene group of 7 to 20 carbon atoms, R ^c. Indicates an organic group consisting of 1 to 40 carbon atoms and may contain a heteroatom, a linear structure, a branched structure, a cyclic structure, an unsaturated bond and an aromatic structure, and R ¹ has 1 to 20 carbon atoms. Saturated or unsaturated alkyl groups of straight or branched chains, saturated or unsaturated cycloalkyl groups that may have branched chains with 3 to 8 carbon atoms, aryl groups with 6 to 20 carbon atoms or aralkyl with 7 to 20 carbon atoms Indicates a group, where Z is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and a carbon number of carbon atoms. Saturated or unsaturated heterocycloalkyloxy groups from 1 to 8, halogen atoms, hydroxyl groups, amino groups, saturated or unsaturated alkylamino groups with 1 to 6 carbon atoms or branched chains, directly from 1 to 6 carbon atoms Indicates an oxygen atom derived from a saturated or unsaturated dialkylamino group or layered inorganic compound of a chain or branched chain, ^{and when M 1} and M ² are either Si, Ti or Zr, the corresponding x is 2. , And n is an integer of 0 to 2, and when M ¹ and M ² are Al, the corresponding x is 1 and n is 0 or 1.)

(In the formula (2), R ¹ is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms. , An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, where A is a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. It represents a saturated or unsaturated cycloalkyl group which may have 8 branched chains, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and a vinyl group, an epoxy group, an oxetanyl group, an acryloxy group, respectively. It may be substituted with a methacryloxy group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanato group, a carboxyl group or a halogen atom. D is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and 1 to 8 carbon atoms. Saturated or unsaturated heterocycloalkyloxy group, halogen atom, hydroxyl group, amino group, linear or branched chain with 1 to 6 carbon atoms Saturated or unsaturated alkylamino group or linear or branched chain with 1 to 6 carbon atoms Indicates a saturated or unsaturated dialkylamino group of, and n represents an integer of 0 to 2.) The crosslinked layered layer according to claim 3, wherein the precursor obtained by cation exchange of the exchangeable cation of the layered inorganic compound with an onium group is subjected to a silylation reaction with a coupling agent. Method for producing an inorganic compound. The method for producing an interlayer crosslinked layered inorganic compound according to claim 4 , wherein the precursor is obtained by reacting a layered inorganic compound with an organic onium salt represented by the following formula (3).
^{R 13 R 14 R 15 R 16} N + X - (3)
(In the formula (3), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ independently have an alkyl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, and an aryl group having 6 to 22 carbon atoms, respectively. _{, - (CH 2 -CH (CH} 3) O) p -H group or _- indicates _{(CH 2 -CH 2 -O) q} -H group, p and q is an integer of 1 to 20, X ^- is Indicates a halide ion.)

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