JP2003238140A - Production method for silylated porous silica - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method for a porous silica in which the silanol group of silica is efficiently silylated and thereby, a silylated porous silica having uniform mesopores can be obtained. <P>SOLUTION: The production method for the silylated porous silica having uniform mesopores is characterized by reacting an organic silicone compound with an organic-inorganic composite comprising a surfactant and a siloxane compound in the presence of the surfactant, and then removing the surfactant. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing silylated porous silica having uniform mesopores, which can be applied to optical functional materials, electronic functional materials, catalyst carriers, adsorption materials and the like.

[0002]

2. Description of the Related Art A porous inorganic compound having uniform mesopores (2 to 50 nm) has a large pore diameter and a large pore volume as compared with conventional oxides such as zeolite, and is impossible with zeolite. It is possible to adsorb and carry molecules of several nm size such as dyes, enzymes or inorganic clusters in the pores, and it is possible to provide new materials in the fields of optical functional materials and electronic functional materials. In addition, since the pores are more evenly distributed than conventional inorganic oxides such as siloxane compound gels, they may exhibit new functions as materials such as catalyst carriers and permeable membranes that exhibit shape selectivity. There is. Therefore, in recent years, application studies have been made in various fields.

As a method for producing an oxide having such uniform mesopores, a method utilizing structural control of an inorganic substance using a surfactant has attracted attention. In particular, an oxide having uniform mesopores synthesized by utilizing self-organization of a surfactant and an inorganic compound has a large pore volume and surface area as compared with conventional oxides such as zeolite. As a method for producing an oxide having uniform mesopores by utilizing self-organization of a surfactant and an inorganic compound, for example, WO91
/ 11390, a method of manufacturing by hydrothermal synthesis in a heat-resistant container in which a siloxane compound gel and a surfactant are sealed is disclosed in Bull. Chem. Soc. J
p. Magazine 63, pp. 988, 1990 discloses a method for producing by ion exchange between kanemite, which is a kind of layered silicate, and a surfactant.

Silanol groups are present on the surface of silica having such uniform mesopores, and it has been reported that a functional composite material is formed by utilizing the interaction between the silanol groups and a substance to be adsorbed or supported. ing. However, the type and amount of substance that can be adsorbed or supported is limited depending on the chemical and physical properties of the silanol group. Also,
Since this silanol group is hydrophilic, it has water absorbability, and therefore, there have been problems that the regularity of pores is broken down with time, and the pores are crushed.

Therefore, various functional groups are introduced into the silanol groups of silica having such uniform mesopores to develop new adsorption or loading properties, or to make them hydrophobic, thereby solving the problem. Have been reported. This method utilizes a silylation reaction using an organosilicon compound having a surface silanol group and various functional groups, which is the most general method for modifying the surface of silica. The silylation reaction referred to here is Si-OH.
Shows a reaction to form a Si-O-Si bond.
For example, a heavy metal selective adsorbent modified with a silyl compound containing a thiol group (for example, Adv. Mater., 1997,
9, 500), a catalyst in which a metal complex is introduced after modification with an amino group-containing silyl compound (for example, Chem. Commun. 1997,
65), it has been reported that trimethylsilylation with hexamethylene disilazane prevents the adsorption of water and maintains the insulating property (for example, WO0039028). Thus, it is understood that functionalizing a silica surface with uniform mesopores is a very important approach for creating functional materials.

However, it is reported that not all surface silanol groups of silica having uniform mesopores react with organosilicon compounds (for example, J. Phy.
S. Chem. B 1997, 101, 6525). According to this, the silanol groups on the silica surface having uniform mesopores are mainly S
There are those that exist as i-OH (this is called an isolated silanol group) and those that hydrogen bond with an oxygen atom of an adjacent silanol group (this is called a crosslinked silanol group), and the crosslinked silanol group is It has been reported that even highly reactive trimethylsilyl chloride cannot be silylated. From this, it is easily conjectured that the presence of unreacted silanol groups that have not reacted with the organosilicon compound exerts an inhibitory effect on functionality. Also, according to this report,
In order to eliminate the crosslinked silanol groups, it has been proposed to dehydrate by firing. However, this method cannot effectively utilize all the silanol groups originally present.

From this, it has been strongly desired to develop a method of highly efficiently silylating and functionalizing silanol groups on the surface of silica having uniform mesopores with an organosilicon compound.

[0008]

It is an object of the present invention to react a silanol group with an organosilicon compound very efficiently, and thus it can be applied to photofunctional materials, electronic functional materials, catalyst carriers, adsorbent materials, etc. A method for producing a silylated porous silica having the above.

[0009]

SUMMARY OF THE INVENTION As a result of intensive studies to solve the above problems, an organic-inorganic composite formed from a surfactant and a siloxane compound was treated in the presence of a surfactant without substantially removing the surfactant. To react with an organosilicon compound,
Then, it was found that by removing the surfactant, the silanol group and the organosilicon compound react extremely efficiently to obtain silylated porous silica having uniform mesopores.

That is, according to the known method, the surfactant is first removed from the organic-inorganic composite consisting of the surfactant and the siloxane compound to obtain porous silica having uniform mesopores, and then the organosilicon. It was common to silylate with compounds. The reason why the method was carried out by this method is that it was considered that the organic-inorganic composite in the state of being complexed with the surfactant did not react with the silanol group because the organosilicon compound could not enter the mesopores. However, surprisingly, even in an organic-inorganic composite in a state of being composited with a surfactant, silanol groups are silylated by an organosilicon compound, and furthermore, silylated porous silica can be obtained extremely efficiently. Found.

In the method for producing silylated porous silica having uniform mesopores according to the present invention, an organic-inorganic composite composed of a surfactant and a siloxane compound is substantially mixed with an organosilicon compound and a surfactant. It is characterized in that it is reacted in the presence of a surfactant without being removed.

The reaction between the organic-inorganic composite and the organosilicon compound can be carried out in an organic solvent, or in a vapor phase in which the organosilicon compound is vaporized.
The temperature during the reaction is preferably in the range of 0 to 120 ° C. The organosilicon compound has the general formula R ¹ R ² R ³ S
iX (wherein R ¹ , R ² , and R ³ are H, C ₆ H ₅ , C _a H _{2a + 1} ,
_{CF 3 (CF 2) b (} CH 2) c, CH 2 CH (CH 2) d, Y
CH ₂ (CH ₂ ) _e , CH ₃ COO (CH ₂ ) _f , CH
_{2 (O) CHCH 2 O (} CH 2) g, CH 2 = C (CH 3) C
OO (CH ₂ ) _h , OC _i H _{2i + 1} and F are shown, and a is 1 to 1.
8 is an integer up to 8, b is an integer from 0 to 10, C
Is an integer from 1 to 4, d is an integer from 1 to 4, e is an integer from 1 to 4, f is an integer from 1 to 4, and g is 1 to 4. Is an integer, h is an integer from 1 to 4, i is an integer from 1 to 4, and Y is N
H ₂ , SH, halogen, CN, OH, NCO, X
Represents OC _n H _{2n + 1} , Cl, Br, I, and n is an integer of 1 to 4), and is preferably at least one or more compounds.

The organosilicon compound has the general formula R
¹ R ² R ³ SiNHSiR ¹ R ² R ³ (wherein R ¹ , R ² , R ³
Is preferably C _a H _{2a + 1} , and a is an integer of 1 to 3). The surfactant, (wherein, n is an integer of up to 6 to 24) the general formula C _n H _{2n + 1} NH ₂ is preferably alkyl amines represented by.

Further, the surfactant is represented by the general formula C _n H
_{2n + 1} RX (In the formula, n is an integer from 8 to 24, R is N (CH ₃ ) ₃ or NC ₅ H ₅ , and X is a halide ion, HSO ₄ ⁻ or an organic anion. It is also desirable that the alkyl ammonium salt or the alkyl pyridium salt represented by Further, it is desirable that the surfactant is at least one kind of surfactant selected from compounds having a polyalkylene oxide structure.

Further, it is desirable that the porous silica has one or more diffraction peaks corresponding to a d-spacing value in the range of 2 to 50 nm by X-ray diffraction measurement and / or electron beam diffraction measurement.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The method for producing silylated porous silica according to the present invention will be specifically described below. According to the invention, the silylated uniform mesopores (2-50
(nm) has a porous silica having an interface of the organic-inorganic composite composed of the surfactant and the siloxane compound before substantially removing the surfactant from the organic-inorganic composite composed of the surfactant and the siloxane compound. It can be obtained very efficiently by reacting the silanol group present in the above with the organosilicon compound and then removing the surfactant.

The organic-inorganic composite composed of the surfactant and the siloxane compound is one in which the hydrophilic group of the surfactant and the silanol group of the siloxane compound are formed by electrical interaction. The electrical interaction mentioned here means a state in which the hydrophilic group of the surfactant and the silanol group of the siloxane compound are bonded by hydrogen bond or ionic bond. Due to the complexing mechanism, the surfactant and the silanol group are present as a pair, so that the cross-linking (cross-linking silanol) due to the hydrogen bond between the silanol groups is suppressed. It is important to react with the organosilicon compound in such a state that the surfactant and the silanol group are paired in order to extremely efficiently silylate the silanol group.

The organosilicon compound only functions as a silylating agent and does not function as a uniform mesopore forming agent.
The surfactant serves as a mesopore-forming agent, and the removal thereof produces mesopores. Therefore, first, an organic-inorganic composite in which a surfactant, which is a mesopore-forming agent, is uniformly dispersed in a siloxane compound in a size of 1 to 50 nm is produced, and then reacted with an organosilicon compound to perform silylation. There is a need to.

In order to produce an organic-inorganic composite utilizing the self-organization of such a surfactant and a siloxane compound, (1) alkoxysilanes are added to a solution in which the surfactant is dissolved and hydrolyzed. Method for producing powdery organic-inorganic composite by gelation by decomposition and condensation reaction (2) Solution prepared by adding surfactant to sol partially hydrolyzed and condensed alkoxysilanes (3) A solution prepared by adding a surfactant to a sol obtained by partially hydrolyzing and condensing alkoxysilanes and spray-drying the solution. Then, a method for producing a fine-particle organic-inorganic composite can be mentioned.

Examples of such alkoxysilanes include:
Specifically, quaternary alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane; trimethoxyfluorosilane, triethoxyfluorosilane, triisopropoxyfluorosilane, tributoxyfluorosilane, etc. Tertiary alkoxyfluorosilanes; Tertiary alkoxyalkylsilanes such as trimethoxymethylsilane, triethoxymethylsilane, trimethoxyethylsilane, triethoxyethylsilane, trimethoxypropylsilane, triethoxypropylsilane; trimethoxyphenylsilane,
3 such as triethoxyphenylsilane, trimethoxychlorophenylsilane, triethoxychlorophenylsilane, etc.
Primary alkoxyaryl silanes; tertiary alkoxyphenethylsilanes such as trimethoxyphenethylsilane and triethoxyphenethylsilane; secondary alkoxyalkylsilanes such as dimethoxydimethylsilane and diethoxydimethylsilane. Of these, tetraethoxysilane is preferably used. In the present invention, the alkoxysilanes can be used alone or in combination of two or more.

As the surfactant, a compound having a long chain alkyl group and a hydrophilic group is usually used. The long-chain alkyl group preferably has 6 to 24 carbon atoms.
Examples of the hydrophilic group include quaternary ammonium salt, pyridinium salt, amino group, nitroso group, hydroxyl group and carboxyl group. In particular, (wherein, n is an integer of up to 6 to 24) surfactants general formula C _n H _{2n + 1} NH ₂ preferably used an alkyl amine represented by.

Specific examples of such alkylamines include octylamine, decylamine and dodecylamine. Further, a compound having a polyalkylene oxide structure can also be preferably used as the surfactant. Examples of the polyalkylene oxide structure include a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, ether type compounds such as polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan. Examples thereof include ether ester type compounds such as fatty acid ester, polyethylene sorbitol fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester and sucrose fatty acid ester.

The structure of the obtained organic-inorganic composite can be observed by X-ray diffraction measurement and / or electron diffraction measurement or transmission electron microscope (TEM), and X-ray diffraction measurement and electron beam diffraction measurement can be performed. Due to d in the range of 2 to 50 nm
It is preferable to have one or more peaks at the diffraction angle corresponding to the value. Within this range, uniform mesopores applicable to photofunctional materials, electronic functional materials, catalyst carriers, adsorption materials, etc. can be maintained even after silylation with an organosilicon compound.

The organic-inorganic composite thus obtained is treated with an organosilicon compound as a silylating agent in the presence of a surfactant without substantially removing the surfactant contained therein. React. The organosilicon compound as the silylating agent may be any functional group bonded to the silicon atom as long as at least one functional group reactive with a silanol group is bonded to the silicon atom.
¹ R ² R ³ SiX (in the formula, R ¹ , R ² , R ³ and X are the same as above). An alkoxy group, a halogen group, and an isocyanate group are mentioned as a functional group with a preferable reactivity with a silanol group. More preferably, it is a halogen group.
Specifically, dimethylsilane chloride, trimethylsilane chloride, triethylsilane chloride, tri-n-butylsilane chloride, n-propyldimethylsilane chloride, n-butyldimethylsilane chloride, t-butyldimethylsilane chloride, n-octyldimethyl chloride. Halogenated alkylsilanes such as silyl, n-decyldimethylsilane chloride, octadecyldimethylsilane chloride, triacontyldimethylsilane chloride, diphenylsilane chloride, triphenylsilane chloride,
Halogenated arylsilanes such as tribenzylsilane chloride, phenyldimethylsilane chloride, phenethyldimethylsilane chloride, p-tolyldimethylsilane chloride, diphenylmethylsilane chloride, 3,3,3-trifluoropropyldimethylsilane chloride, heptadecafluorochloride. -1,
Halofluoroalkylsilanes such as 1,2,2-tetrahydrodecyldimethylsilane and tridecafluoro-1,1,2,2-tetrahydrooctyldimethylsilane chloride are used.

The organosilicon compound has the general formula R ¹ R ^{2
R 3 SiNHSiR 1 R 2 R 3} ( ^{wherein, R 1, R 2, R} 3 is C _a
The disilazanes represented by H _{2a + 1} and a is an integer of 1 to 3 also have a preferable reactivity with a silanol group. The reaction (silylation reaction) between the organosilicon compound and the organic-inorganic composite is carried out in a liquid phase or gas phase atmosphere. When it is carried out in the liquid phase, it may be carried out using an organic solvent. Examples of the organic solvent used include alcohols such as methanol, ethanol, n-propyl alcohol and isopropyl alcohol, diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, ethers such as tetrahydrofuran, benzene, toluene,
Examples include aryl alkanes such as xylene.

When carried out in the gas phase, the organosilicon compound may be diluted with a gas. The diluent gas used is
Examples include air, nitrogen, argon, hydrogen and the like. The reaction temperature for silylation with an organosilicon compound is preferably in the range of 0 to 120 ° C. More preferably 20-100
It is in the range of ° C. Within this range, the reaction does not proceed because the temperature is low, and the temperature is too high to cause a side reaction, so that the silylation proceeds efficiently.

Although the time required for silylation depends on the reaction temperature, it is several minutes to 40 hours, preferably 10 minutes to 24 hours. The silylated porous silica having uniform mesopores can be obtained by silylating an organic-inorganic composite consisting of a surfactant and a siloxane compound, and then removing the surfactant.

The surfactant can be used by selectively removing only the surfactant from the obtained silylated porous silica by calcination, thermal decomposition, solvent extraction or the like.
However, depending on the functional group of the organosilicon compound, it may be unstable in heat resistance and oxidation resistance as compared with the surfactant. Therefore, solvent extraction is preferable as a removal method with less damage.

The solvent used for the silylation can be used for removing the surfactant by solvent extraction, and it is usually carried out at 20 to 100 ° C. for several minutes to 24 hours. The silylated porous mesoporous silica obtained according to the present invention is ²⁹ Si
From the NMR measurement, it was confirmed that the ratio of silanol groups was smaller than that of the porous silica having uniform mesopores obtained by the general silylation method performed after removing the surfactant, and that the silylation was extremely efficient. Was done. Further, such silylated porous silica has one or more diffraction peaks corresponding to the d-spacing value in the range of 2 to 50 nm, as determined by X-ray diffraction measurement and / or electron beam diffraction measurement. It was confirmed that the uniform mesopores were retained even after the silylation.

[0030]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. (Preparation of organic-inorganic composite consisting of surfactant and siloxane compound) Octylamine (Wako Pure Chemical Industries) in a 1 L flask.
After mixing 10.0 g and 50.6 g of ion-exchanged water and stirring for 10 minutes, 0.5 mL of concentrated hydrochloric acid (Wako Pure Chemical Industries, Ltd.) was added. After stirring at 35 ° C for 40 minutes, a mixed solution of 23.4 g of ethanol (Wako Pure Chemical Industries) and 16.2 g of tetraethoxysilane (Wako Pure Chemical Industries, Ltd.) was added dropwise. 35 ℃ after adding the whole amount
It was stirred for 18 hr. After filtration, wash with 100 L of deionized water to 100
It was dried at ℃, to obtain an organic-inorganic composite (hereinafter referred to as precursor A) consisting of a surfactant and a siloxane compound. X
The line spacing d value was 3.1 nm as measured by line diffraction. ^{2 9} Si
Table 1 shows the results of determining the proportions of Q ³ and Q ⁴ species of silicon (see FIG. 1) by NMR measurement. (Preparation of Porous Silica with Surfactant Removed by Calcination) Precursor A was calcined in the presence of air at 650 ° C for 3 hours to remove the surfactant before silylation to prepare porous silica (hereinafter referred to as precursor Body B)). The interplanar spacing d value was 3.1 nm according to the X-ray diffraction measurement of this porous silica. ²⁹ Si NM
Table 1 shows the results of determining the proportions of Q ³ and Q ⁴ species of silicon (see FIG. 1) by R measurement. Table 2 shows specific surface area values, central pore diameter values and total pore volume values measured by N ₂ gas adsorption measurement. (Preparation of Porous Silica from Which Surfactant Was Removed by Solvent Extraction) 3 g of the precursor A was subjected to solvent extraction for 3 hr under reflux in 100 mL of dehydrated ethanol. After washing with 100 mL of ethanol,
Porous silica was prepared by drying at 80 ° C. and removing the surfactant before silylation (hereinafter referred to as precursor C). The interplanar spacing d value was 3.1 nm as measured by X-ray diffraction. ²⁹ Si
Table 1 shows the results of determining the proportions of Q ³ and Q ⁴ species of silicon (see FIG. 1) by NMR measurement.

[0031]

[Example 1] Trimethylsilyl chloride (Azmax)
To a mixed solution of 11 g and dehydrated toluene (Wako Pure Chemical Industries, Ltd.) 50 mL, precursor A 1.0 g was added. The mixture was stirred at 20 ° C for 3 hours. It was filtered, washed with 60 mL of dehydrated toluene (Wako Pure Chemical Industries), and dried at 80 ° C. 100 mL of the obtained white powder in ethanol (Wako Pure Chemical Industries)
The solvent was extracted for 3 hr under reflux. After filtration and washing with 100 mL of ethanol (Wako Pure Chemical Industries), 80
Drying at ° C gave a silylated porous silica.

X-ray diffraction of this silylated porous silica
As a result of folding measurement, the interplanar spacing d value was 3.0 nm.²⁹Si N
T of silicon by MR measurement³, Q³And Q^FourSpecies (see Figure 1)
Table 1 shows the results of the determination of the ratio. Cyril of these
The peak that appears due to ³Is. N₂Gas adsorption measurement
Specific surface area, central pore size and total pores measured by
The volume values are shown in Table 2.

From the interplanar spacing d values before and after the silylation, it was confirmed that the structure did not change even after the silylation. In addition, from the NMR measurement results, it was found that the Q ³ species was greatly reduced and the T ³ species was large, indicating that the silylation was extremely efficient. In addition, it was found from the N ₂ gas adsorption measurement result (see FIG. 2) that it had uniform mesopores.

[0034]

Example 2 2.0 g of precursor A was packed in a glass tube, and N ₂ gas was used.
It was dried at 100 ° C for 1 hr under a flow rate of 40 mL / min. N ₂ gas was passed through a bubbler containing trimethylsilyl chloride to introduce trimethylsilyl chloride into the glass tube. After 1 hr, the introduction of trimethylsilyl chloride was stopped, the mixture was cooled to 30 ° C under N ₂ gas flow of 40 mL / min, and the obtained white powder was ethanol (Wako Pure Chemical Industries) 10
The mixture was added to 0 mL, and the solvent was extracted with the surfactant for 3 hours under reflux. After filtration and washing with 100 mL of ethanol (Wako Pure Chemical Industries), 80
Drying at ° C gave a silylated porous silica.

The interplanar spacing d value of the silylated porous silica measured by X-ray diffraction was 3.0 nm. ²⁹ Si N
MR measurements of T ³ , Q ³ and Q ⁴ species of silicon (see Figure 1)
Table 1 shows the results of the determination of the ratio. Table 2 shows specific surface area values, central pore diameter values and total pore volume values measured by N ₂ gas adsorption measurement. From the interplanar spacing d value before and after the silylation, it was confirmed that the structure did not change even after the silylation. In addition, from the NMR measurement results, it was found that the Q ³ species was greatly reduced and the T ³ species was large, indicating that the silylation was extremely efficient. In addition, N ₂ gas adsorption measurement results (see Figure 3)
It was found to have more uniform mesopores.

[0036]

[Comparative Example 1] Trimethylsilyl chloride (Asmax) 0.
1.0 g of precursor B was added to a mixed solution of 11 g and 50 mL of dehydrated toluene (Wako Pure Chemical Industries, Ltd.). The mixture was stirred at 20 ° C for 3 hours. After filtering, washing with 60 mL of dehydrated toluene (Wako Pure Chemical Industries), drying at 80 ° C,
A silylated porous silica was obtained.

The interplanar spacing d value was 3.0 nm according to the X-ray diffraction measurement of this silylated porous silica. ²⁹ Si N
MR measurements of T ³ , Q ³ and Q ⁴ species of silicon (see Figure 1)
Table 1 shows the results of the determination of the ratio. Table 2 shows specific surface area values, central pore diameter values and total pore volume values measured by N ₂ gas adsorption measurement. From the interplanar spacing d value before and after silylation, it was confirmed that the structure did not change even after silylation and that it had uniform mesopores from the N ₂ gas adsorption measurement results, but from the NMR measurement results, It was found that the silylation was insufficient because the silanol groups before the silylation were reduced by the calcination.

[0038]

[Comparative Example 2] Trimethylsilyl chloride (Azmax) 0.
1.0 g of the precursor C was added to a mixed solution of 11 g and 50 mL of dehydrated toluene (Wako Pure Chemical Industries, Ltd.). The mixture was stirred at 20 ° C for 3 hours. After filtering, washing with 60 mL of dehydrated toluene (Wako Pure Chemical Industries), drying at 80 ° C,
A silylated porous silica was obtained.

The interplanar spacing d value was 3.0 nm according to the X-ray diffraction measurement of the silicified porous silica. ²⁹ Si N
MR measurements of T ³ , Q ³ and Q ⁴ species of silicon (see Figure 1)
Table 1 shows the results of the determination of the ratio. Table 2 shows specific surface area values, central pore diameter values and total pore volume values measured by N ₂ gas adsorption measurement. From the d-value of the interplanar spacing d before and after silylation, it was confirmed that the structure did not change even after silylation and that it had uniform mesopores from the N ₂ gas adsorption measurement results. Was found to be insufficient. It is considered that this is because the adjacent silanol groups were inactive against silylation because many of them were crosslinked by hydrogen bonds.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

According to the present invention, it is possible to provide a method for producing a material that can be applied to an optical functional material, an electronic functional material, a catalyst carrier, an adsorbent material, and the like.

[Brief description of drawings]

FIG. 1 is an NM of silylated porous silica.
T silicon by R measured ^3, Q ^3, a diagram illustrating a Q ⁴ species.

FIG. 2 is a diagram showing a pore distribution of porous silica silylated according to Example 1.

FIG. 3 is a diagram showing a pore distribution of porous silica silylated according to Example 2.

Continued front page    (72) Inventor Takeshi Kubota             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Yoshito Kurano             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Masami Murakami             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F term (reference) 4G072 AA25 BB15 GG03 HH14 HH28                       HH33 MM01 QQ06 UU11 UU17

Claims (10)

[Claims] 1. A uniform meso-scale, characterized in that an organic-inorganic composite comprising a surfactant and a siloxane compound is reacted with an organosilicon compound in the presence of the surfactant, and then the surfactant is removed. A method for producing a silylated porous silica having pores. 2. The method for producing porous silica according to claim 1, wherein the reaction between the organic-inorganic composite and the organic silicon compound is performed in a liquid phase. 3. The method for producing porous silica according to claim 1, wherein the reaction is carried out in a gas phase using a vaporized organosilicon compound. 4. The method for producing porous silica according to claim 1, wherein the reaction temperature is in the range of 0 to 120 ° C. 5. The organosilicon compound has the general formula R ¹ R ²
R ³ SiX (wherein R ¹ , R ² and R ³ are H, C ₆ H ₅ and C _a H
_{2a + 1, CF 3 (CF} 2) b (CH 2) c, CH 2 CH (C
_{H 2) d, YCH 2 (} CH 2) e, CH 3 COO (CH 2) f,
CH ₂ (O) CHCH ₂ O (CH ₂ ) _g , CH ₂ = C (C
_{H 3) COO (CH 2)} h, shows the _{OC i H 2i + 1, F} , a is an integer from 1 to 18, b is an integer from 0, C is up to 1-4 Is an integer, d is an integer from 1 to 4, e is an integer from 1 to 4, and f is 1 to 4
An integer from, g is an integer from 1 to 4, h is an integer from 1 to 4, i is an integer from 1 to 4, Y is NH _2, SH, halogen, CN, OH, NCO
, X represents OC _n H _{2n + 1} , Cl, Br, I, and n
Is an integer of 1 to 4), and the method for producing porous silica according to claim 1, wherein the compound is represented by at least one compound. 6. The organosilicon compound has the general formula R ¹ R ^{2
R 3 SiNHSiR 1 R 2 R 3} ( ^{wherein, R 1, R 2, R} 3 is C _a
The method for producing porous silica according to any one of claims 1 to 4, wherein the disilazane is represented by H _{2a + 1} and a is an integer of 1 to 3. 7. The surfactant has the general formula C _n H _{2n + 1} N
Alkyl amines represented by H ₂ (wherein n is an integer of 6 to 24).
7. The method for producing porous silica according to any one of 6 above. 8. The surfactant has the general formula C _n H _{2n + 1.}
RX (In the formula, n is an integer from 6 to 24, and R is N.
(CH ₃ ) ₃ or NC ₅ H ₅ and X is a halide ion, HSO ₄ ⁻ or an organic anion. 7. The method for producing porous silica according to any one of claims 1 to 6, which is an alkylammonium salt or an alkylpyridinium salt represented by the formula (1). 9. The method for producing porous silica according to claim 1, wherein the surfactant is at least one kind of surfactant selected from compounds having a polyalkylene oxide structure. 10. The porous silica has one or more diffraction peaks corresponding to a d-spacing value in the range of 2 to 50 nm, as measured by X-ray diffraction measurement and / or electron beam diffraction measurement. The method for producing porous silica according to any one of 1 to 9.