JP4544411B2 - Method for producing organosilica composite material - Google Patents

Description

  The present invention relates to a method for producing an organic silica composite material in which a skeleton is formed with silicon atoms, oxygen atoms, and organic groups as main components.

  In recent years, silica-based mesoporous materials in which meso-sized pores (mesopores) having a pore diameter of about 1 to 30 nm are regularly arranged have attracted attention as materials for adsorbing and storing various substances. Research on the synthesis and functional development of such silica-based mesoporous materials has been actively conducted. As one of such studies, in Japanese Patent Application Laid-Open No. 2000-219770 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2001-114790 (Patent Document 2) in which a part of the present invention and the inventor overlap, As a silica-based mesoporous material that can be applied to the fields of catalysts, sensors, electronic devices, etc., it has mainly silicon atoms, oxygen atoms, and organic groups. A mesoporous material made of an organic silica composite material having a skeleton formed as a component is disclosed. As described in these publications, all of the organic silica composite materials in which the organic group and the silica form a covalent network structure have heretofore been mainly alkoxysilanes mainly having alkoxy groups as hydrolyzable groups. It has been manufactured using as a raw material.

However, since such alkoxysilanes are highly reactive and easily hydrolyze, purification techniques for obtaining such alkoxysilanes are limited to distillation under strict water-free conditions. Therefore, in the conventional method for producing an organic silica composite material using alkoxysilanes as raw materials, alkoxysilanes containing relatively high molecular weight organic groups that are difficult to purify by distillation cannot be used as raw materials. There has been a problem that it is difficult to produce an organic silica composite material containing such a high molecular weight organic group. In addition, since the purification method by distillation requires more labor and cost than the purification method by column chromatography, the conventional method for producing an organic silica composite material requires labor and cost to purify the raw material by distillation. There is also a problem that there is a limit to the labor and cost required for manufacturing the silica composite material.
JP 2000-219770 A JP 2001-114790 A

  The present invention has been made in view of the above-described problems of the prior art, and it is possible to purify raw materials by column chromatography, which requires less labor and cost compared to distillation, and therefore labor required for producing an organic silica composite material. An organic silica composite material that can be efficiently manufactured even if it is an organic silica composite material containing a relatively high molecular weight organic group, which has been difficult to manufacture. An object is to provide a manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors have found that an allylsilane compound having a specific structure is stable against hydrolysis, and thus can be purified by column chromatography. Since it is possible to produce an organic silica composite material even if it is used as the above, it has been found that the above object can be achieved by using such an allylsilane compound as a raw material, and the present invention has been completed.

  That is, the method for producing an organic silica composite material of the present invention is a method for obtaining an organic silica composite material by subjecting an organic silane compound to hydrolysis and polycondensation reaction in a solvent, wherein the organic silane compound is represented by the following general formula ( 1):

[Wherein R ¹ represents an organic group selected from the group consisting of a phenyl group, a biphenyl group, a phenylene group and a biphenylene group , R ^{2 to} R ⁶ each represents a hydrogen atom , and X ¹ represents a substituent (second the substituents) Ki置 substituent also alkoxy group (before have represents a mercapto group, an amino group, at least one selected from the group consisting of carboxyl group and an epoxy group.), m Represents 1 or 2, and n represents 2 . ]
It is an allylsilane compound represented by these.

  In the method for producing an organic silica composite material of the present invention, the surfactant is introduced into the organic silica composite material by hydrolysis and polycondensation reaction of the allylsilane compound in a solvent containing the surfactant. After obtaining the porous precursor, the surfactant contained in the porous precursor may be removed, whereby an organic silica composite material that is a porous body can be obtained. In this way, a mesoporous material having a central pore diameter of 1 to 30 nm is suitably obtained as the organic silica composite material that is the porous material.

  Furthermore, in the method for producing the organic silica composite material of the present invention, a material having a periodic structure of 5 nm or less resulting from the regular arrangement of the organic group is suitably obtained as the organic silica composite material.

  According to the present invention, it is possible to purify the raw material by column chromatography, which is less labor and cost than distillation, so that it is possible to reduce the labor and cost required for the production of the organic silica composite material. Therefore, it is possible to provide a method for producing an organic silica composite material, which can be efficiently produced even with an organic silica composite material containing a relatively high molecular weight organic group, which has been difficult to achieve.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  In the method for producing an organic silica composite material of the present invention, an allylsilane compound represented by the following general formula (1) is used as an organic silane compound as a raw material.

In the general formula (1), R ¹ represents an organic group having at least one carbon atom bonded to a silicon atom. The organic group represented by R ^{1 according} to the present invention may have at least one carbon atom bonded to a silicon atom, and may be a monovalent group bonded to one silicon atom, or two or more silicon atoms. Those having a valence of 2 or more bonded to an atom can be mentioned. Examples of such a monovalent or divalent or higher valent organic group include, for example, a monovalent organic group formed by removing one hydrogen from a hydrocarbon such as alkane, alkene, alkyne, benzene, cycloalkane or the like, or two or more Examples thereof include, but are not limited to, divalent or higher-valent organic groups generated by removing hydrogen. In such organic groups, some of the hydrogen atoms are substituted with substituents such as amide group, amino group, imino group, mercapto group, sulfone group, carboxyl group, ether group, acyl group, vinyl group and the like. It may be. Moreover, the organic silica composite material of the present invention may contain only one kind of the above organic group or may contain two or more kinds.

As described above, the organic group represented by R ^{1 according} to the present invention may be a monovalent organic group or a divalent or higher valent organic group, and suitable monovalent organic groups include alkyl groups (preferably, A lower alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group), an alkenyl group (preferably a lower alkenyl group having 1 to 10 carbon atoms such as an allyl group or a vinyl group), an aryl group (preferably a phenyl group). In particular, an allyl group, a phenyl group and the like are preferable from the viewpoint that further derivatization is easy.

Moreover, as an organic group represented by R < ¹ > concerning this invention, it is preferable that the valence of an organic group is bivalent from a viewpoint that the organic silica composite material of moderate bridge | crosslinking degree is obtained. Examples of such a divalent organic group include a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —), a trimethylene group (—CH ₂ CH ₂ CH ₂ —), and a tetramethylene group (—CH ₂ CH ₂ CH ₂ CH ₂ —), 1,2-butylene group (—CH (C ₂ H ₅ ) CH—), 1,3-butylene group (—CH (CH ₃ ) CH ₂ CH ₂ —), phenylene Group (—C ₆ H ₄ —), biphenylene group (—C ₆ H ₄ —C ₆ H ₄ —), diethylphenylene group (—C ₂ H ₄ —C ₆ H ₄ —C ₂ H ₄ —), vinylene group (—CH═CH—), propenylene group (—CH ₂ —CH═CH ₂ —), butenylene group (—CH ₂ —CH═CH—CH ₂ —), amide group (—CO—NH—), dimethylamino group _{(-CH 2 -NH-CH 2 -} ), trimethylamine group _{(-CH 2 -N (CH 3)} -CH 2 -) , etc. And the like. Among these, from the viewpoint that an organic silica composite material having high crystallinity can be obtained, the organic group represented by R ¹ is preferably a methylene group, an ethylene group, a phenylene group, or a biphenylene group.

  A silicon atom is bonded to the same or different carbon atom in the organic group. In the organosilica composite material of the present invention, the organic group, the silicon atom, and the oxygen atom are bonded by a covalent bond or the like to form a skeleton, and the number of silicon atoms bonded to the organic group or bonded to the silicon atom Depending on the number of oxygen atoms to be produced, an organic silica composite material having a different skeleton (straight, ladder, network, branched, etc.) is generated.

  In the present invention, the organic group is bonded to one or more silicon atoms (m in the general formula (1) is an integer of 1 or more), and the silicon atom is bonded to one or more oxygen atoms. It is incorporated into the silicon oxide framework. As a result, the organic silica composite material of the present invention exhibits both organic and inorganic surface characteristics. Further, unlike the surface-modified composite material in which an organic group is simply added to the surface of silicon oxide, the organic silica composite material of the present invention has reduced organic group detachment due to heating or the like, for example, for adsorbents and catalysts. When used as a carrier, performance degradation is sufficiently suppressed.

Moreover, in the allylsilane compound represented by the general formula (1) according to the present invention, 1 to 3 silicon atoms (wherein n in the general formula (1) is an integer of 1 to 3) allyl groups (- CH ₂ —CH═CH ₂ ) or an allyl group having a substituent of R ^{2 to} R ⁶ is bonded, and such allyl group bonded to one silicon atom (including an allyl group having a substituent) The number of is preferably 2 to 3, and more preferably 2.

R ^{2 to} R ⁶ in the general formula (1) may be the same or different and are each a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a pentyl group, a hexyl group, or a cyclohexyl group. And any one selected from the group consisting of a phenyl group optionally having a first substituent. The first substituent is at least one selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxy group, a mercapto group, an isopropyl group, and a phenyl group. Further, the position of the first substituent may be any of ortho-position, meta-position and para-position, and the number of first substituents may be singular or plural, but is preferably singular. When R ^{2 to} R ⁶ are other than these, the allyl group (including an allyl group having a substituent) is hardly detached in the reaction step described later, and a stable siloxane bond (Si—O—Si) is sufficient. It tends to be difficult to form.

As such an allyl group (including an allyl group having a substituent), an allyl group (—CH ₂ —CH═CH ₂ ), a phenyl group as a substituent, from the viewpoint of enhancing nucleophilicity to a silicon atom. An allyl group is preferable.

Furthermore, in the allylsilane compound represented by the general formula (1) according to the present invention, 0 to 2 groups represented by X ¹ are bonded to the silicon atom, and the bond is bonded to one silicon atom. The number of groups represented by X ¹ is preferably 0 to 1, and more preferably 1.

Such a group represented by X ¹ is a hydrogen atom, a halogen atom (a chlorine atom, a fluorine atom, a bromine atom, an iodine atom), a hydroxyl group, or an alkoxy group which may have a second substituent (preferably , A methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, a lower alkoxy group having 1 to 10 carbon atoms such as a phenoxy group), and an acyloxy group which may have a second substituent (preferably, A C1-C10 lower alkoxy group such as an acetoxy group or a benzoyloxy group) and an alkyl group optionally having a second substituent (preferably a C1-C10 such as a methyl group or an ethyl group) A lower alkyl group), an alkenyl group optionally having a second substituent (preferably a lower alkenyl group having 1 to 10 carbon atoms such as a vinyl group, excluding an allyl group), and a second Replace It is any selected from the group consisting of an aryl group (preferably a phenyl group, a biphenyl group, etc.) that may have a group. The second substituent is at least one selected from the group consisting of a mercapto group, an amino group, a carboxyl group, and an epoxy group.

Examples of such groups represented by X ^1, from the standpoint of ease of higher siloxane bond formation, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, isopropoxy group, phenoxy group.

  The method for synthesizing the allylsilane compound represented by the general formula (1) is not particularly limited, and various allylsilane compounds can be synthesized by appropriately using a known synthesis method. For example, regarding 1,4-bridged silylbenzene, which is a kind of a suitable allylsilane compound, 1,4-Bis (diallylethoxysilyl) benzene (BDAEB) and 1,4-Bis (triallylsilyl) benezene (BTAB) are as follows. Can be synthesized. That is, first, the starting material 1,4-Bis (triehoxysilyl) benzene (BTEB) can be prepared by the Barbier Grignard reaction on 1,4-dibromobenzene. Next, by adding an allyl Grignard reagent to BTEB, BDAEB in which two ethoxy groups on silyl are substituted with allyl groups can be obtained with a good isolation yield. Further, when an allyl lithium reagent is added immediately before the above reaction, BTAB in which all ethoxy groups are substituted with allyl groups is obtained.

  The allylsilane compound represented by the general formula (1) described above can be sufficiently purified easily and at low cost by column chromatography (for example, silica gel column chromatography), compared with conventional alkoxysilanes. It shows great stability against hydrolysis.

  In the method for producing the organic silica composite material of the present invention, the allylsilane compound represented by the general formula (1) as a raw material is used, and the allylsilane compound is hydrolyzed and polycondensed in a solvent to form the organic silica composite material. Get.

When the allylsilane compound represented by the general formula (1) is polymerized (hydrolysis and polycondensation reaction), allyl groups (including allyl groups having a substituent) in the general formula (1) are basically removed. The siloxane bond (Si—O—Si) is formed in the portion by hydrolysis and subsequent condensation reaction. Further, using allyl silane compound, an alkoxy group as the group represented by X ^1, a hydroxyl group, a halogen atom, if you have a hydrolyzable group such as an acyloxy group, also eliminated these hydrolyzable groups, Even in this portion, a siloxane bond (Si—O—Si) is formed by hydrolysis and subsequent condensation reaction.

Thus, the organic silica composite material obtained by polymerizing the allylsilane compound has a skeleton formed mainly of an organic group (R ¹ ), a silicon atom (Si), and an oxygen atom (O). It has a crosslinked network structure.

  A method for polymerizing the allylsilane compound is not particularly limited, but water or a mixed solvent of water and an organic solvent may be used as a solvent, and the allylsilane compound may be hydrolyzed and polycondensed in the presence of an acid or a base catalyst. preferable. Examples of the organic solvent suitably used here include alcohol, acetone and the like, and the content of the organic solvent in the mixed solvent is preferably about 5 to 50% by weight. Examples of the acid catalyst used include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and the solution in the case of using the acid catalyst is acidic with a pH of 6 or less (more preferably 2 to 5). preferable. Furthermore, examples of the base catalyst used include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like. When using the base catalyst, the basic solution has a pH of 8 or more (more preferably 9 to 11). It is preferable that

  The content of the allylsilane compound in such a polymerization step is preferably about 0.0055 to 0.33 mol / L in terms of silicon concentration. Further, various conditions (temperature, time, etc.) in the polymerization step are not particularly limited, and are appropriately selected according to the allylsilane compound to be used, the target organic silica composite material, and the like. It is preferable to hydrolyze and condense the allylsilane compound at a temperature of about 1 to 48 hours.

The organic silica composite material obtained by polymerizing the allylsilane compound usually has an amorphous structure, but can have a periodic structure resulting from a regular arrangement of the organic groups (R ¹ ) depending on synthesis conditions. Such periodicity depends on the molecular length of the allylsilane compound to be used, but a periodic structure of 5 nm or less is preferable. This periodic structure is maintained even after the allylsilane compound is polymerized. The formation of this periodic structure can be confirmed by the appearance of a peak in a region of d = 5 nm or less by X-ray diffraction (XRD) measurement. Even when such a peak is not confirmed in the X-ray diffraction measurement, a periodic structure may be partially formed. Such a periodic structure is generally formed with a layered structure described later, but is not limited to this case.

Examples of suitable synthesis conditions for forming a periodic structure resulting from such a regular arrangement of organic groups include the following conditions.
(i) Since the periodic structure is formed by an interaction between allylsilane compounds, it is preferable to use an organic group (R ¹ ) that increases the interaction between allylsilane compounds, that is, benzene, biphenyl, naphthalene, and anthracene.
(ii) The pH of the solution is preferably 1 to 3 (acidic) or 10 to 12 (basic), and more preferably 10 to 12 (basic).

  Furthermore, in the method for producing an organic silica composite material of the present invention, pores are formed in the obtained organic silica composite material by mixing a surfactant when the allylsilane compound is polymerized (hydrolysis and polycondensation reaction). It is possible to form. That is, a surfactant micelle or liquid crystal structure serves as a template to form a porous body having pores.

  Thus, it is preferable to use a surfactant together with the allylsilane compound because a mesoporous material having mesopores having a central pore diameter of 1 to 30 nm in the pore diameter distribution curve can be obtained. The central pore diameter is a curve (pore diameter distribution curve) in which a value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). ) At the maximum peak, and can be determined by the method described below. That is, the porous body is cooled to a liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is determined by a constant volume method or a gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased, The adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted to obtain an adsorption isotherm. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as Cranston-Inklay method, Pollimore-Heal method, BJH method or the like.

Such a mesoporous material preferably contains 60% or more of the total pore volume in a range of ± 40% of the center pore diameter in the pore diameter distribution curve. A mesoporous material satisfying this condition means that the pore diameter is very uniform. The specific surface area of the mesoporous material is not particularly limited, but is preferably 700 m ² / g or more. The specific surface area can be calculated as a BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation.

  Further, such a mesoporous material preferably has one or more peaks at a diffraction angle corresponding to a d value of 1.5 to 30.5 nm in its X-ray diffraction (XRD) pattern. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. Therefore, having one or more peaks at a diffraction angle corresponding to a d value of 1.5 to 30.5 nm indicates that the pores are regularly arranged at intervals of 1.5 to 30.5 nm. means.

  Moreover, the pore which such a mesoporous body has is formed not only on the surface of the porous body but also inside. The arrangement state (pore arrangement structure or structure) of the pores in such a porous body is not particularly limited, but is preferably a 2d-hexagonal structure, a 3d-hexagonal structure, or a cubic structure. Such a pore arrangement structure may have a disordered pore arrangement structure.

  Here, that the porous body has a hexagonal pore arrangement structure means that the arrangement of the pores is a hexagonal structure (S. Inagaki et al., J. Chem. Soc., Chem. Commun., p.680 (1993), S. Inagaki et al., Bull. Chem. Soc. Jpn., 69, p.1449 (1996), Q. Huo et al., Science, 268, p.1324 (1995) ). Further, the porous body having a cubic pore arrangement structure means that the arrangement of the pores is a cubic structure (JCVartuli et al., Chem. Mater., 6, p. 2317 (1994), Q. Huo et al., Nature, 368, p. 317 (1994)). Further, that the porous body has a disordered pore arrangement structure means that the arrangement of the pores is irregular (PTTanev et al., Science, 267, p.865 (1995), SABagshaw et al., Science, 269, p. 1242 (1995), R. Ryoo et al., J. Phys. Chem., 100, p. 17718 (1996)). The cubic structure is preferably Pm-3n, Ia-3d, Im-3m, or Fm-3m symmetry. The symmetry is determined based on a space group notation.

  As described above, when the organic silica composite material of the present invention has pores, it adsorbs other metal having a catalytic action on the porous body and a functional component such as a luminescent compound (physical adsorption and / or chemical). Can be combined).

  The surfactant used for obtaining the mesoporous material is not particularly limited, and may be any of cationic, anionic, and nonionic, specifically, alkyl. Chloride, bromide, iodide or hydroxide such as trimethylammonium, alkyltriethylammonium, dialkyldimethylammonium, benzylammonium; fatty acid salt, alkylsulfonate, alkylphosphate, polyethylene oxide nonionic surfactant, Primary alkylamine and the like can be mentioned. These surfactants may be used alone or in combination of two or more.

Among the above surfactants, examples of the polyethylene oxide nonionic surfactant include a polyethylene oxide nonionic surfactant having a hydrocarbon group as a hydrophobic component and polyethylene oxide as a hydrophilic portion. . Such surfactants, for example, is represented by the general formula _{C n H 2n + 1 (OCH} 2 CH 2) m OH, n is 10 to 30, m can be used favorably those which are 30 . As such a surfactant, an ester of a fatty acid such as oleic acid, lauric acid, stearic acid, palmitic acid and sorbitan, or a compound obtained by adding polyethylene oxide to these esters can also be used.

Further, as such a surfactant, a triblock copolymer type polyalkylene oxide may be used. Examples of such surfactants include those composed of polyethylene oxide (EO) and polypropylene oxide (PO) and represented by the general formula (EO) _x (PO) _y (EO) _x . x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is preferably 13 to 106, and y is more preferably 29 to 70. Examples of the triblock copolymer include (EO) ₁₉ (PO) ₂₉ (EO) ₁₉ , (EO) ₁₃ (PO) ₇₀ (EO) ₁₃ , (EO) ₅ (PO) ₇₀ (EO) ₅ , (EO). ₁₃ (PO) ₃₀ (EO) ₁₃ , (EO) ₂₀ (PO) ₃₀ (EO) ₂₀ , (EO) ₂₆ (PO) ₃₉ (EO) ₂₆ , (EO) ₁₇ (PO) ₅₆ (EO) ₁₇ , ( EO) ₁₇ (PO) ₅₈ (EO) ₁₇ , (EO) ₂₀ (PO) ₇₀ (EO) ₂₀ , (EO) ₈₀ (PO) ₃₀ (EO) ₈₀ , (EO) ₁₀₆ (PO) ₇₀ (EO) ₁₀₆ , (EO) ₁₀₀ (PO) ₃₉ (EO) ₁₀₀ , (EO) ₁₉ (PO) ₃₃ (EO) ₁₉ , (EO) ₂₆ (PO) ₃₆ (EO) ₂₆ . These triblock copolymers are available from BASF, Aldrich, etc., and triblock copolymers having desired x and y values can be obtained at a small scale production level.

Also, a star diblock copolymer in which two polyethylene oxide (EO) chains-polypropylene oxide (PO) chains are bonded to two nitrogen atoms of ethylenediamine can be used. Examples of such star diblock copolymers include those represented by the general formula ((EO) _x (PO) _y ) ₂ NCH ₂ CH ₂ N ((PO) _y (EO) _x ) ₂ . Here, x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is 13 to 106, and y is 29 to 70. preferable.

Among such surfactants, a mesoporous material with high crystallinity can be obtained, and therefore a salt of alkyltrimethylammonium [C _p H _{2p + 1} N (CH ₃ ) ₃ ] (preferably a halide salt). Is preferably used. In that case, the alkyl group in the alkyltrimethylammonium preferably has 8 to 22 carbon atoms. Examples include octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, octyltrimethylammonium bromide, docosyltrimethylammonium chloride, and the like. It is done.

  In the method for producing an organic silica composite material of the present invention, the surfactant is introduced into the organic silica composite material by hydrolyzing and polycondensing the allylsilane compound in the solvent containing the surfactant. In this case, the concentration of the surfactant in the solution is preferably 0.05 to 1 mol / L. If this concentration is less than the lower limit, the formation of pores tends to be incomplete. On the other hand, if the concentration exceeds the upper limit, the amount of unreacted surfactant remaining in the solution increases, resulting in uniform pores. Tend to decrease.

  Furthermore, in the method for producing an organic silica composite material of the present invention, a porous organic silica composite material is obtained by removing the surfactant contained in the porous precursor thus obtained. As a method for removing the surfactant, the following methods can be mentioned. That is, for example, (i) a method of removing the surfactant by immersing the porous precursor in an organic solvent (for example, ethanol) having high solubility in the surfactant, and (ii) removing the porous precursor from 300 (Iii) Ion exchange method in which the porous body precursor is immersed in an acidic solution and heated to exchange the surfactant with hydrogen ions, etc. Can do.

  The organosilica composite material obtained by the present invention may be used as a powder, but may be used after being molded as necessary. Any molding means may be used, but extrusion molding, tablet molding, rolling granulation, compression molding, CIP and the like are preferable. The shape can be determined according to the location and method of use, and examples thereof include a columnar shape, a crushed shape, a spherical shape, a honeycomb shape, an uneven shape, and a corrugated shape.

  Moreover, in the manufacturing method of the organic silica composite material of this invention, it is also possible to obtain the organic silica composite material which is a thin film form, for example with the following method.

  That is, when obtaining a thin-film organic silica composite material, first, the reaction (partial hydrolysis and partial condensation reaction) is carried out by stirring the allylsilane compound in an acidic solution (aqueous solution of hydrochloric acid, nitric acid or the like or an alcohol solution). To obtain a sol solution containing the partial polymer. Such hydrolysis reaction of the allylsilane compound is likely to occur in a low pH region, and therefore partial polymerization can be promoted by lowering the pH of the system. At this time, the pH is preferably 2 or less, and more preferably 1.5 or less. Moreover, the reaction temperature in that case can be made into about 15-25 degreeC, and reaction time can be made into about 30 to 90 minutes.

  Next, a thin-film organic silica composite material can be produced by applying this sol solution to a substrate by various coating methods. In addition, as various coating methods, it can apply | coat using a bar coater, a roll coater, a gravure coater, etc. Moreover, dip coating, spin coating, spray coating, etc. are also possible. Furthermore, it is also possible to form a patterned organic silica composite material on a substrate by applying a sol solution by an inkjet method.

  Next, the obtained thin film is preferably heated to about 70 to 150 ° C. and dried, and the polycondensation reaction of the partial polymer is advanced to form a three-dimensional crosslinked structure. By adding the above-mentioned surfactant to the sol solution, it becomes possible to form a regular pore structure in the thin-film organic silica composite material.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, a comparative example, and a synthesis example, this invention is not limited to a following example.

(Synthesis Example 1: Synthesis of 1,4-Bis (triethoxysilyl) benzene (BTEB))
1,4-Bis (triethoxysilyl) benzene (BTEB) was synthesized by the following synthesis method. The reaction scheme at that time is shown below.

  That is, first, a rotor was placed in a three-necked flask (capacity: 2 liters) equipped with a reflux condenser, a nitrogen gas introduction tube, and a dropping funnel with a side tube, and the inside of the system was replaced with a nitrogen atmosphere. Next, 15 g (0.62 mol) of magnesium (Mg) piece, 300 ml of dry tetrahydrofuran (THF) and 450 ml of dry tetraethoxysilane (TEOS) were added. Subsequently, 100 ml of a THF solution of 48 g (0.20 mol) of 1,4-dibromobenzene was added to the dropping funnel, and the mixture was slowly added dropwise with heating and stirring until the reaction started. When the reaction started, the remaining halogen compound was added dropwise at such a rate that gentle reflux continued. After completion of dropping over about 5 hours, the mixture was further refluxed for 1 hour, cooled to room temperature, and then 500 ml of dry hexane was added to precipitate a magnesium salt. The obtained supernatant was filtered under a nitrogen gas atmosphere, and the solvent was distilled off, followed by distillation under reduced pressure (0.2 mmHg, −140 ° C.) to obtain the desired 1,4-Bis (triethoxysilyl) benzene. The yield was 41.1 g (yield 50%). In addition, spectral data of the obtained compound are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ) δ 1.16 (t, J = 7.0 Hz, 18 H), 3.79 (q, J = 7.0 Hz, 12 H), 7.60 (s, 4 H). ¹³ C-NMR (125 MHz, CDCl ₃ ) δ18.1,58.6,133.0,134.0. ²⁹ Si-NMR (99 MHz, CDCl ₃ ) δ-57.5.Elemental Anal.Calcd.for C ₁₈ H ₃₄ O ₆ Si ₂ : C, 53.70; H, 8.51. Found: C, 53.67; H, 8.56.

(Synthesis Example 2: Synthesis of 1,4-Bis (diallylethoxysilyl) benzene (BDAEB))
1,4-Bis (diallylethoxysilyl) benzene (BDAEB) was synthesized by the following synthesis method. The reaction scheme at that time is shown below.

  Specifically, first, 13.4 g (33.3 mmol) of 1,4-Bis (triethoxysilyl) benzene was added to a three-necked flask (capacity 500 ml) equipped with a rubber septum and a nitrogen gas introduction tube, and cooled to 0 ° C. Next, 200 ml (0.20 mol) of an ether solution of 1.0M allylmagnesium bromide was slowly added dropwise, the cold water bath was removed, and the mixture was stirred at room temperature for 9 hours. Subsequently, 150 ml of 5% hydrochloric acid aqueous solution was added, followed by extraction three times with ether. The obtained organic layers were combined, washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The resulting crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 40: 1) to obtain the desired 1,4-Bis (diallylethoxysilyl) benzene. The yield was 11.8 g (yield 92%). In addition, spectral data of the obtained compound are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ) δ 1.12 (t, J = 7.0 Hz, 6H), 1.83-1.89 (m, 8H), 3.69 (q, J = 7.0 Hz, 4H), 4.81-4.89 (m , 8H), 5.70-5.79 (m, 4H), 7.50 (s, 4H). 13 C-NMR (125MHz, CDCl 3) δ18.3,21.1,59.2,114.7,132.8,133.1,136.8. 29 Si-NMR (99 MHz, CDCl ₃ ) δ-1.78. Elemental Anal. Calcd. For C ₂₂ H ₃₄ O ₂ Si ₂ : C, 68.34; H, 8.86. Found: C, 68.61; H, 8.99.

(Synthesis Example 3: Synthesis of 1,4-Bis (triallylsilyl) benezene (BTAB))
1,4-Bis (triallylsilyl) benezene (BTAB) was synthesized by the following synthesis method. The reaction scheme at that time is shown below.

  That is, first, a three-necked flask (capacity 500 ml) equipped with a reflux condenser and a dropping funnel with a side tube was replaced with a nitrogen atmosphere, and 100 ml of dry THF and 8.4 g (1.20 mol) of lithium pieces were added. Next, the flask was cooled to −10 ° C. with a salt-ice bath, and 50 ml of a THF solution of 13.7 ml (0.10 mol) of allyl phenyl ether was added dropwise with rapid stirring. When the reaction started, the solution turned pale green. The dropwise addition was completed over about 2 hours, and the mixture was further stirred at −10 ° C. for 1 hour. Subsequently, the supernatant of the allyllithium solution prepared in 100 ml of anhydrous THF solution of 3.2 g (8.0 mmol) of 1,4-Bis (triethoxysilyl) benzene cooled to 0 ° C. was added using a cannula and stirred at 0 ° C. for 1 hour. . Thereafter, 100 ml of water was added, the organic layer was separated, and the aqueous layer was extracted twice with ether. The obtained organic layers were combined, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 40: 1) to obtain the desired 1,4-Bis (triallylsilyl) benezene as a clear solution. The yield was 2.29 g (76% yield). In addition, spectral data of the obtained compound are shown below.

¹ H-NMR (500 MHz, CDCl ₃ ) δ 1.78-1.79 (m, 12H), 4.80-4.86 (m, 12H), 5.69-5.74 (m, 6H), 7.41 (s, 4H). ¹³ C-NMR (125MHz, CDCl ₃ ) δ19.4,114.3,133.3,133.7,136.4. ²⁹ Si-NMR (CDCl ₃ ) δ-7.60.Elemental Anal.Calcd.for C ₂₄ H ₃₄ Si ₂ : C, 76.12; H, 9.05.Found : C, 76.05; H, 9.09.

(Synthesis Example 4: Synthesis of Phenyldiallylethoxysilane)
Phenyldiallylethoxysilane was synthesized by the following synthesis method. The reaction scheme at that time is shown below.

  That is, Phenyltriethoxysilane was obtained by Barbier Grignard reaction of bromobenzene in a tetraethoxysilane (TEOS) solution in the same manner as in Synthesis Example 1 except that 75 g of bromobenzene was used instead of 1,4-dibromobenzene. It was. The yield at that time was 84.2 g (72% yield).

  Next, by adding 2 equivalents of allyl Grignard reagent to Phenitriethoxysilane in the same manner as in Synthesis Example 2 except that 15 g of Phenyltriethoxysilane was used instead of 1,4-Bis (triethoxysilyl) benzene (BTEB) Phenyldiallylethoxysilane was prepared. The yield at that time was 10.6 g (73% yield).

Example 1
Using the phenyldiallylethoxysilane obtained in Synthesis Example 4 as a raw material, an organic silica composite material was obtained as follows. The reaction scheme at that time is shown below.

  That is, first, phenyldiallylethoxysilane 1.0 g was added to an aqueous solution containing 1.5 g of Octadecyltrimethylammonium chloride (ODTMA) and 2.86 ml of 6M NaOH aqueous solution in 80 g of ion-exchanged water, followed by heating and stirring at 95 ° C. Solid started to precipitate. The stirring was continued for another 7 days. The precipitated solid was separated by centrifugation (3600 rpm), washed with distilled water, and then dried in an oven (100 ° C.) to obtain a white solid (1.7 g).

  Next, 15 g of 35% HCl aqueous solution was added to the obtained solid in 400 ml of an ethanol solution, and the surfactant in the solid was removed by stirring at 70 ° C. for 3 days. The obtained solid was separated by centrifugation, washed with ethanol and distilled water, and then dried by heating to obtain a white powder (90 mg).

(Comparative Example 1)
A white powder (172 mg) was obtained in the same manner as in Example 1 except that 1.0 g of Phenyltriethoxysilane was used instead of Phenyldiallylethoxysilane. The reaction scheme at that time is shown below.

<IR spectrum confirmation test>
The IR spectrum of the white powder obtained in Example 1 and the IR spectrum of the white powder obtained in Comparative Example 1 were measured and compared. Therefore, it was confirmed that the white powder obtained in Example 1 and the white powder obtained in Comparative Example 1 are organic silica composite materials having the same composition.

(Example 2)
Using 1,4-Bis (diallylethoxysilyl) benzene (BDAEB) obtained in Synthesis Example 2 as a raw material, an organic silica composite material was obtained as follows. The reaction scheme at that time is shown below.

  That is, first, 0.75 g of BDAEB was added to an aqueous solution containing 0.72 g of Octadecyltrimethylammonium chloride (ODTMA) and 0.5 g of 6M NaOH aqueous solution in 33 g of ion-exchanged water, followed by heating and stirring at 95 ° C. Solid started to precipitate. The stirring was continued for another 20 hours. The precipitated solid was separated by centrifugation (3600 rpm), washed with distilled water, and then dried in an oven (100 ° C.) to obtain a white solid.

  Next, 35% HCl aqueous solution was added to the obtained solid in an ethanol solution, and the surfactant in the solid was removed by stirring at 70 ° C. for 3 days. The obtained solid was separated by centrifugation, washed with ethanol and distilled water, and then dried by heating to obtain a white powder.

<Confirmation test of X-ray diffraction pattern>
FIG. 1 shows the X-ray diffraction pattern of the organic silica composite material (benzene-silica hybrid mesoporous material) obtained in Example 2 before removing the surfactant, and FIG. 1 shows the X-ray of the organic silica composite material after removing the surfactant. The diffraction pattern is shown in FIG.

The organic silica composite material obtained in Example 2 had a peak of d ₁₀₀ value at 41.6 angstroms before removal of the surfactant and 45.7 angstroms after removal of the surfactant, and 2θ = It had sharp peaks at d = 7.6, 3.8 and 2.5 angstroms at 10-40 °. From this X-ray diffraction pattern, it was confirmed that the pores were arranged at intervals of 7.6 angstroms, and the pore walls had crystalline pore walls having structural periodicity.

  Such an X-ray diffraction pattern is similar to the X-ray diffraction pattern of a conventional organic silica composite material obtained in the same manner under basic conditions using 1,4-Bis (triethoxysilyl) benzene as a raw material. there were.

  Further, in the organic silica composite material obtained in Example 2, the one before the removal of the surfactant had a lattice constant of a = 48.1 angstroms, whereas the one after the removal of the surfactants a It has a two-dimensional hexagonal structure (p6mn) having a lattice constant of 52.8 angstroms, and it was confirmed that the periodicity at the molecular level was completely maintained even after removal of the surfactant.

<Adsorption isotherm confirmation test>
In order to examine the pore structure of the organic silica composite material obtained in Example 2, an N ₂ adsorption isotherm was measured. The obtained N ₂ adsorption isotherm is shown in FIG. The obtained pore size distribution curve is shown in FIG. The obtained adsorption isotherm is of type IV (IUPAC standard), has no hysteresis and is confirmed to have a typical mesoporous structure, the pore diameter by the BJH method is 23.5 angstroms, the ratio by the BET method The surface area was 744 m ² / g and the pore volume was 0.53 cm ³ / g.

<Confirmation test of NMR spectrum>
In order to investigate the structure of the pore walls of the organic silica composite material obtained in Example 2, ¹³ C and ²⁹ Si NMR spectra were measured. The obtained results are shown in FIGS. 5 and 6, respectively.

From the obtained NMR spectrum, the organic silica composite material (benzene-silica hybrid mesoporous material) obtained in Example 2 has a three-dimensional O _1.5 Si—C ₆ H ₆ —SiO _1.5 unit. It has a pore wall composed of a bonded network structure, and it was confirmed that no Si-C bond splitting occurred during the synthesis.

Corresponds to -71.6 and two sharp resonances -81.9ppm is ^{T n} silica species in ²⁹ Si NMR spectrum ^{(T 2 [SiC (OH)} (OSi) 2] and ^{T 3 [SiC (OH) (} OSi) 3]) From this, it was confirmed that the allyl group was completely eliminated, that is, hydrolyzed and completely deallylated. ^{In the 13} C NMR spectrum, no signal corresponding to the carbon atom constituting the allyl group was observed, which also confirmed that the allyl group was completely eliminated during the synthesis.

( Reference Example 1 )
Using 1,4-Bis (triallylsilyl) benezene (BTAB) obtained in Synthesis Example 3 as a raw material, an organic silica composite material was obtained as follows. The reaction scheme at that time is shown below.

  That is, first, 0.22 g of BTAB was added to an aqueous solution containing 0.24 g of Octadecyltrimethylammonium chloride (ODTMA) and 0.17 g of 6M NaOH aqueous solution in 15 g of ion-exchanged water, followed by heating and stirring at 92 ± 3 ° C. Began to precipitate. The stirring was continued for another 20 hours. The precipitated solid was separated by centrifugation (3600 rpm), washed with distilled water, and then dried in an oven (100 ° C.) to obtain a white solid.

  Next, 35% HCl aqueous solution was added to the obtained solid in an ethanol solution, and the surfactant in the solid was removed by stirring at 70 ° C. for 3 days. The obtained solid was separated by centrifugation, washed with ethanol and distilled water, and then dried by heating to obtain a white powder.

<Confirmation test of X-ray diffraction pattern>
FIG. 7 shows an X-ray diffraction pattern of the organic silica composite material (benzene-silica hybrid mesoporous material) obtained in Reference Example 1 before removing the surfactant, and FIG. 7 shows the X-ray of the organic silica composite material after removing the surfactant. The diffraction pattern is shown in FIG.

In the organic silica composite material obtained in Reference Example 1, 35.5 angstroms the previous one detergent removal, it is that after removal of the surfactant has a peak of d ₁₀₀ value to 40.7 Å, further d = It had peaks at 9.2 to 9.5 and 4.2 to 4.5 angstroms. From this X-ray diffraction pattern, it was confirmed that a mesostructure having a d ₁₀₀ value of 35.5 to 40.7 angstroms was sufficiently formed and had a structural periodicity at the molecular level in the pore wall. .

  As described above, according to the method for producing an organic silica composite material of the present invention, it is possible to purify a raw material by column chromatography, which requires less labor and cost compared to distillation. Therefore, if an organic silica composite material is produced by the method of the present invention, the labor and cost required for the production can be reduced, and a relatively high molecular weight organic group, which has been difficult to produce in the past, can be reduced. Even an organic silica composite material containing it can be efficiently manufactured.

  Therefore, according to the present invention, it is possible to obtain various organic silica composite materials having both organic and inorganic surface characteristics using allylsilane compounds having various organic groups as raw materials. It is very useful as a method for obtaining a mesoporous material composed of an organic silica composite material applicable to the fields of agents, catalysts, sensors, electronic devices and the like.

6 is a graph showing an X-ray diffraction pattern of the organic silica composite material obtained in Example 2 before removing the surfactant. It is a graph which shows the X-ray-diffraction pattern of the thing after removing surfactant in the organic silica composite material obtained in Example 2. FIG. 4 is a graph showing an N ₂ adsorption isotherm of the organic silica composite material obtained in Example 2. 3 is a graph showing a pore size distribution curve of an organic silica composite material obtained in Example 2. FIG. 4 is a graph showing a ¹³ C NMR spectrum of the organic silica composite material obtained in Example 2. FIG. 2 is a graph showing a ²⁹ Si NMR spectrum of the organic silica composite material obtained in Example 2. FIG. It is a graph which shows the X-ray-diffraction pattern of the thing before removing surfactant in the organic silica composite material obtained in Reference Example 1 . It is a graph which shows the X-ray-diffraction pattern of the thing after removing surfactant in the organic silica composite material obtained in Reference Example 1 .

Claims (4)

A method of obtaining an organic silica composite material by subjecting an organic silane compound to hydrolysis and polycondensation reaction in a solvent, wherein the organic silane compound has the following general formula (1):

[In the formula, R ¹ represents an organic group selected from the group consisting of phenyl group, a biphenyl group, a phenylene group and a biphenylene group, R ² to R ⁶ each represent a hydrogen atom, X ¹ is closed the location substituent alkoxy group which may optionally be (Ki置 substituent ago, a mercapto group, an amino group, at least one selected from the group consisting of carboxyl group and an epoxy group.) indicates, m represents 1 or 2 , N represents 2 . ]
A method for producing an organic silica composite material, characterized in that it is an allylsilane compound represented by the formula:   The porous precursor is obtained by hydrolyzing and polycondensing the allylsilane compound in a solvent containing a surfactant to obtain a porous precursor in which the surfactant is introduced into an organic silica composite material. The method for producing an organic silica composite material according to claim 1, wherein the organic silica composite material which is a porous body is obtained by removing the surfactant contained in the product.   The method for producing an organic silica composite material according to claim 2, wherein the organic silica composite material which is the porous body is a mesoporous body having a central pore diameter of 1 to 30 nm.   The organic silica composite material according to any one of claims 1 to 3, wherein the organic silica composite material has a periodic structure of 5 nm or less resulting from a regular arrangement of the organic groups. A method for producing a silica composite material.

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