JP5120684B2 - Spherical silica-based mesoporous material, catalyst and adsorbent using the same - Google Patents

Description

  The present invention relates to a spherical silica-based mesoporous material, a catalyst using the same, and an adsorbent.

  In recent years, silica-based mesoporous materials having meso-sized pores (mesopores) with a pore diameter of about 1 to 50 nm have attracted attention as materials and catalysts for adsorbing and storing various substances, and research on functional development. Has been actively conducted. As such a silica-based mesoporous material, a silica-based mesoporous material into which a sulfonic acid group or an amino group is introduced has been reported.

  Examples of such a silica-based mesoporous material into which a sulfonic acid group has been introduced include those in which a sulfonic acid is introduced into a silica-based mesoporous material such as MCM or HMS (WMV Rhijn, et al. Chem. Commun., 1998, pp. 317 to 318 (Non-patent Document 1)), and a silica-based mesoporous material as described above, in which a fluorine-based sulfonic acid that is a strong acid is introduced (D J. Macquarrie, et al., Chem. Commun., 2005, page 2363-2365 (Non-patent Document 2)) is known.

  In addition, as a silica-based mesoporous material into which an amino group has been introduced, for example, JP-A-2003-112051 (Patent Document 1) discloses a silica-based mesoporous material in which an amino group is directly bonded to a silicon atom, A silica-based mesoporous material in which an amino group is introduced into FSM-16 is disclosed.

  Further, as a silica-based mesoporous material, for example, a silica-based mesoporous material obtained by radially arranging pores using tetraethoxysilane and cetyltrimethylammonium salt is known (G. Van Tendero, O. I. Lebedev, O. Collart, P. Cooland EF Vansant, “J. Phys. Condens. Matter”, Vol. 15, 2003, p3037-p3046 (Non-patent Document 3)). Furthermore, in JP-A-2005-89218 (Patent Document 2), a silica raw material and a specific surfactant are mixed in a specific solvent, and the surfactant is introduced into the silica raw material. It is obtained by a production method comprising a first step of obtaining porous precursor particles and a second step of obtaining a spherical silica-based mesoporous material by removing the surfactant contained in the porous precursor particles. A spherical silica-based mesoporous material is disclosed. In addition, a silica-based mesoporous material into which two types of organic groups having different polarities (for example, 3- [2- (2-aminoethylamino) ethylamino] propyl group and ureidopropyl group) are introduced by a copolymerization method Has also been reported (see Seong Huh, et al., J. Am. Chem. Soc., Vol. 126, 2004, p1010 to p1011 (Non-patent Document 4)).

However, the spherical silica-based mesoporous materials described in Non-Patent Documents 1 to 4 and Patent Documents 1 and 2 cannot always exhibit sufficient catalytic activity when used as a catalyst.
JP 2003-112051 A JP 2005-89218 A W. M.M. V. Rhijn, et al. , Chem. Commun. , 1998, pages 317-318 D. J. et al. Macquarrie, et al. , Chem. Commun. , 2005, 2363-2365. G. Van Tendeloo, O.D. I. Lebedev, O.M. Collart, P.M. Cooland E.M. F. Vansant, “J. Phys. Condens. Matter”, Vol. 15, 2003, p3037-p3046 See Seong Huh, et al. , J. et al. Am. Chem. Soc. , Vol. 126, 2004 issue p1010-p1011

  The present invention has been made in view of the above-described problems of the prior art, and when used as a catalyst or an adsorbent, can exhibit a high selectivity for a substrate or an adsorbent, and is a sufficiently high catalyst. It is an object of the present invention to provide a spherical silica-based mesoporous material that can exhibit performance or adsorption performance, and a catalyst and an adsorbent using the same.

  As a result of intensive studies to achieve the above object, the present inventors have radial pores having an average particle diameter of 0.01 to 3 μm, a central pore diameter of 1 to 10 nm, and are specified. When used as a catalyst or adsorbent, the first organic group having the functional group and the spherical silica-based mesoporous material into which the specific second organic group has been introduced. It has been found that high selectivity can be exhibited and sufficiently high catalytic performance or adsorption performance can be exhibited, and the present invention has been completed.

That is, the spherical silica-based mesoporous material of the present invention has radial pores having an average particle diameter of 0.01 to 3 μm, a central pore diameter of 1 to 10 nm, and
A first organic group having at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group and an amino group, and a group consisting of an aliphatic compound-based organic group and a cyclic compound-based organic group At least one selected second organic group is introduced.

  The first organic group according to the present invention is a chain hydrocarbon group which may have a linear or branched hetero atom having 18 or less carbon atoms, or a hetero atom having 18 or less carbon atoms. It is preferable that the functional group is bonded to a cyclic hydrocarbon group which may have, and the first organic group is a methyl group, an ethyl group, a linear or branched chain Propyl group, linear or branched butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched chain Octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched chain Tetradecyl group, linear or branched hexadecyl group, linear or branched octet Selected from the group consisting of decyl, allyl, vinyl, phenyl, alkylphenyl, biphenyl, naphthyl, cyclohexyl, pyridyl, pyrimidyl, quinolyl, isoquinolyl, imidazole, indole and purine groups It is more preferable that the functional group is bonded to at least one kind of group.

In addition, as the second organic group according to the present invention, an aliphatic compound-based organic group which may have a linear or branched hetero atom having 18 or less carbon atoms, and 18 or less carbon atoms. It is preferably at least one selected from the group consisting of cyclic compound-based organic groups optionally having heteroatoms, and further, a methyl group, an ethyl group, a linear or branched propyl group, Linear or branched butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, Linear or branched nonyl group, linear or branched decyl group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched tetradecyl group, Linear or branched hexadecyl group, linear or branched Octadecyl group, an allyl group, a vinyl group, a phenyl group, alkylphenyl group, a biphenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group, pyrimidyl group, quinolyl group, isoquinolyl group, imidazole group, indole group, a purine group, and,
These groups include at least selected from the group consisting of hydroxyl group, carbonyl group, aldehyde group, imino group, cyano group, azo group, azide group, nitro group, thiol group, amide group, ureido group, ester group and ether group. A group to which an organic group having a functional group containing one kind of heteroatom is bonded;
More preferably, it is at least one selected from the group consisting of:

The catalyst of the present invention is a catalyst for use in a Friedel-Crafts alkylation reaction or an ester hydrolysis reaction, and is characterized by comprising the spherical silica-based mesoporous material of the present invention.

  Furthermore, the adsorbent of the present invention is characterized by comprising the spherical silica mesoporous material of the present invention.

  The reason why the above object is achieved by the spherical silica-based mesoporous material of the present invention is not necessarily clear, but the present inventors speculate as follows. That is, in the conventional silica-based mesoporous materials described in Non-Patent Documents 1 to 3 and Patent Documents 1 and 2, since the substrate and the adsorbed material cannot be efficiently taken in, it is not always possible to exhibit sufficient activity or the like. Inferred. In addition, in the conventional silica-based mesoporous materials described in Non-Patent Documents 1 to 4 and Patent Document 1, since the particle diameters are irregular and the direction of the pores is irregular, It is difficult to move in the pores, and the pores may be blocked, and it is assumed that sufficient activity cannot always be exhibited when used as a catalyst. On the other hand, the spherical silica-based mesoporous material of the present invention has an average particle size of 0.01 to 3 μm and has radial pores. Thus, in the present invention, since the average particle diameter of the spherical silica-based mesoporous material is 0.01 to 3 μm, the reactant can be efficiently diffused into the inside thereof, and a sufficiently high catalyst The characteristic is exhibited. Further, in the present invention, since the pores are radial as described above, the structure is suitable for a catalyst and an adsorbent with a small outer surface, and mass transfer of a substrate or a product is facilitated. Sufficiently high activity is exhibited. Furthermore, since mass transfer is easy, it is assumed that blockage of pores is sufficiently prevented and high activity can be maintained. In addition, in the spherical silica-based mesoporous material of the present invention, a first organic group having a high affinity with a specific substrate is introduced, and a first substrate capable of efficiently causing a catalytic reaction with the specific substrate. It is possible to introduce organic groups. Therefore, when the spherical silica-based mesoporous material of the present invention is used as a catalyst, a specific substrate can be taken in with high selectivity by the second organic group, and the functional group of the first organic group The catalytic reaction can proceed more efficiently, and sufficiently high catalytic performance is exhibited. In addition, when the spherical silica-based mesoporous material is used as an adsorbent, a second organic group having a high affinity with the adsorbent is introduced, and the adsorbent can be chemically bonded to the first organic group. By introducing a group, the second organic group can function as a selection point of an adsorbing substance, and the first organic group can function as an adsorption point, and the present inventor can exhibit high adsorption performance. Et al.

  According to the present invention, when used as a catalyst or an adsorbent, a spherical silica-based mesoporous material that can exhibit high selectivity to a substrate and can exhibit sufficiently high catalyst performance or adsorption performance. As well as a catalyst and an adsorbent using the same.

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

First, the spherical silica-based mesoporous material of the present invention will be described. That is, the spherical silica-based mesoporous material of the present invention has radial pores having an average particle diameter of 0.01 to 3 μm, a central pore diameter of 1 to 10 nm, and
A first organic group having at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group and an amino group, and a group consisting of an aliphatic compound-based organic group and a cyclic compound-based organic group At least one selected second organic group is introduced.

As such a first organic group,
(I) a linear hydrocarbon group which may have a linear or branched hetero atom having 18 or less carbon atoms, or
(Ii) a cyclic hydrocarbon group optionally having a hetero atom having 18 or less carbon atoms,
What the said functional group couple | bonded is preferable.

  When the carbon number of such a chain hydrocarbon group (i) or cyclic hydrocarbon group (ii) exceeds the upper limit, the pore volume decreases, and mass transfer, catalytic reaction and adsorption in the pores are reduced. It tends to be less likely to occur. Further, such a chain hydrocarbon group (i) or cyclic hydrocarbon group (ii) is appropriately selected according to the use of the obtained spherical silica-based mesoporous material, and is particularly limited. It is not a thing.

  Examples of such a chain hydrocarbon group (i) include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group. Group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl Group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched tetradecyl group, linear or branched hexadecyl group, linear or branched octadecyl group Group, allyl group or vinyl group is preferred.

  The cyclic hydrocarbon group (ii) includes a phenyl group, an alkylphenyl group, a biphenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, an imidazole group, an indole group, or a purine group. preferable.

  In such a first organic group, the chain hydrocarbon group (i) or the cyclic hydrocarbon group (ii) has another organic group having a hetero atom (for example, a hydroxyl group, a carbonyl group, an aldehyde group, An organic group having another functional group containing a hetero atom such as an imino group, a cyano group, an azo group, an azido group, a nitro group, a thiol group, an amide group, a ureido group, an ester group, an ether group, etc. May be.

  Furthermore, the first organic group in the case of having an amino group as the functional group according to the present invention may be any of primary, secondary and tertiary. When the functional group according to the present invention has an amino group, the first organic group is a cyclic group such as the aforementioned pyridyl group, pyrimidyl group, quinolyl group, isoquinolyl group, imidazole group, indole group or purine group. The hydrocarbon group (ii) may contain an amino group. In addition, the first organic group having such an amino group may be one having two or more amines in the molecule, for example, N 2 having two amines. -(2-Aminoethyl) 3-aminopropyl group and the like are mentioned, and those having three amines include 3- [2- (2-aminoethylamino) ethylamino] propyl group and the like.

  Moreover, the 2nd organic group concerning this invention should just be at least 1 sort (s) selected from the group which consists of an aliphatic compound type organic group and a cyclic compound type organic group, and is not restrict | limited in particular. As such an aliphatic compound-based organic group, an aliphatic compound-based organic group which may have a linear or branched hetero atom having 18 or less carbon atoms is preferable. When the number of carbon atoms of such an aliphatic compound-based organic group exceeds the upper limit, the pores become small, and the substrate and the adsorbing material tend not to enter the pores.

  Moreover, as said cyclic compound type organic group, the cyclic compound type organic group which may have a C18 or less hetero atom is preferable. When the carbon number of such a cyclic compound-based organic group exceeds the above upper limit, the pores become small, and the substrate and the adsorbing material tend to be difficult to enter the pores.

  Further, such an aliphatic compound-based organic group or a cyclic compound-based organic group is appropriately selected depending on the use of the obtained spherical silica-based mesoporous material, and is not particularly limited. However, examples of the aliphatic compound-based organic group include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, and a linear chain. Or a branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, a linear or branched nonyl group, a linear or branched decyl group, a linear Or branched undecyl group, linear or branched dodecyl group, linear or branched tetradecyl group, linear or branched hexadecyl group, linear or branched octadecyl group, allyl group , Vinyl groups, or aliphatic compounds thereof The organic group is at least selected from the group consisting of hydroxyl group, carbonyl group, aldehyde group, imino group, cyano group, azo group, azide group, nitro group, thiol group, amide group, ureido group, ester group and ether group A group in which an organic group having a functional group containing one kind of hetero atom is bonded is more preferable. Examples of the cyclic compound-based organic group include a phenyl group, an alkylphenyl group, a biphenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, an imidazole group, an indole group, a purine group, or These cyclic compound-based organic groups consist of a hydroxyl group, a carbonyl group, an aldehyde group, an imino group, a cyano group, an azo group, an azide group, a nitro group, a thiol group, an amide group, a ureido group, an ester group, and an ether group. A group to which an organic group having a functional group containing at least one hetero atom selected from the group is bonded is more preferable. For example, when the substrate or the adsorbing substance has hydrophobicity, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched chain Pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched chain Decyl group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched tetradecyl group, linear or branched hexadecyl group, linear or branched chain In the case where an octadecyl group, a phenyl group, an alkylphenyl group, a biphenyl group, a naphthyl group, a cyclohexyl group, or the like is suitably used and the substrate or the adsorbing substance has hydrophilicity, the aliphatic compound-based organic group or Cyclic organic group , A hydroxyl group, a carbonyl group, an aldehyde group, an imino group, a cyano group, an azo group, an azido group, a nitro group, a thiol group, an amide group, a ureido group, an ester group, and an ether group. A group to which an organic group having a functional group containing an atom is bonded is preferably used.

  Moreover, the average particle diameter of the spherical silica type mesoporous material of the present invention is 0.01 to 3 μm. When the average particle size is less than 0.01 μm, the particles are aggregated, resulting in low reaction efficiency. On the other hand, when the average particle size is more than 3 μm, spherical particles are difficult to form and at the same time, when used as a catalyst, the particles enter the catalyst. It takes time for the reactants to diffuse and the reaction efficiency is lowered.

  Furthermore, in the present invention, it is preferable that 90% by weight or more of all the particles of the spherical silica-based mesoporous material have a particle size within a range of ± 10% of the average particle size. If the particles having a particle size in the range of ± 10% of the average particle size are less than 90% by weight of the total particles, the aggregation of the particles increases, and the reaction efficiency tends to decrease.

  In the present invention, the spherical silica-based mesoporous material has radial pores. The radial pores are pores having a so-called radial type structure in which the pores are arranged radially from the center to the outside. As described above, since the pores are arranged from the center of the particle toward the outside while maintaining regularity, the outer surface is reduced and a structure suitable as a catalyst or an adsorbent is obtained. In addition, it is confirmed that spherical silica-based mesoporous materials have a so-called radial structure by introducing a metal such as gold or platinum into the pores and observing the cross section with a scanning electron microscope. Is possible. Further, it is not necessary that all the pores in the spherical silica-based mesoporous material of the present invention are arranged radially from the center to the outside, and 50% or more (more preferably 70% or more) of all the pores. ) Are preferably arranged in this way. Since the spherical silica-based mesoporous material has radial pores as described above, the outer surface is reduced and the pores can be effectively used up to the inside.

  Furthermore, the central pore diameter of such radial pores is 1 nm to 10 nm (more preferably 1 nm to 5 nm). When the central pore diameter is less than 1 nm, sufficient acid catalyst performance cannot be exhibited for bulky reactants. On the other hand, when the diameter of the central pore exceeds 10 nm, it tends to be difficult to form spherical particles.

  In addition, the spherical silica-based mesoporous material of the present invention preferably includes 60% or more of the total pore volume in the range of ± 40% of the center pore diameter in the pore diameter distribution curve. A spherical silica-based mesoporous material that satisfies such conditions means that the pore diameter is very uniform. Here, the center 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. The pore size distribution curve can be obtained by the method described below. That is, silica-based mesoporous particles are 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. And the adsorption amount of nitrogen gas for 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, Dollimore-Heal method, BJH method or the like.

  The term “spherical” as used in the present invention is not limited to a true sphere, but includes a substantially sphere having a minimum diameter of 80% or more (preferably 90% or more) of the maximum diameter. In the case of a substantially spherical body, the particle size is an average value of the minimum diameter and the maximum diameter in principle.

  The spherical silica-based mesoporous material of the present invention has a highly crosslinked network structure based on a skeleton —Si—O— in which silicon atoms are bonded via oxygen atoms. Such a spherical silica-based mesoporous material only needs to have silicon atoms and oxygen atoms as main components, and at least some of the silicon atoms form carbon-silicon bonds at two or more organic groups. It may be a thing.

Moreover, there is no restriction | limiting in particular about the specific surface area of the spherical silica type mesoporous material of this invention, However, It is preferable that it is 700 m < ² > / g or more. Such a specific surface area can be calculated as a BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation.

  Furthermore, the spherical silica-based mesoporous material of the present invention preferably has one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more in the X-ray diffraction 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 nm or more means that the pores are regularly arranged at intervals of 1 nm or more.

  Further, the pores of the spherical silica-based mesoporous material of the present invention are formed not only on the surface of the porous material but also on the 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. 680, 1993; S. Inagaki, et al., Bull. Chem. Soc. Jpn., 69, 1449, 1996, Q. Huo, et al., Science, 268, 1234, 1995). Moreover, the porous body having a cubic pore arrangement structure means that the arrangement of the pores is a cubic structure (JC Vartuli, et al., Chem. Mater., 6, 2317, 1994). Q. Huo, et al., Nature, 368, 317, 1994). Further, that the porous body has a disordered pore arrangement structure means that the arrangement of the pores is irregular (PT Tanev, et al., Science, 267, 865, 1995; S; A. Bagshaw, et al., Science, 269, 1242, 1995; R. Ryoo, et al., J. Phys. Chem., 100, 17718, 1996). The cubic structure is preferably Pm-3n, Im-3m or Fm-3m symmetric. The symmetry is determined based on a space group notation.

  Such a spherical silica-based mesoporous material may be used as it is, but may be molded and used 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 place of use and method, and examples thereof include a columnar shape, a crushed shape, a spherical shape, a honeycomb shape, an uneven shape, and a corrugated plate shape. In addition, the spherical silica-based mesoporous material of the present invention has a spherical shape and radial pores, and thus exhibits high catalytic action, and the first organic group and the second organic group are arranged on the silica in the silicate. Introducing a second organic group having high affinity with a specific substrate and introducing a first organic group capable of efficiently causing a catalytic reaction with the specific substrate. Therefore, since it is possible to exhibit high catalytic activity, it is very useful as a catalyst material. For example, Friedel-Crafts alkylation and acylation reaction, Mukaiyama-Aldol reaction, Diels-Alder reaction, use as a catalyst used for ester hydrolysis and the like can be mentioned. Furthermore, the spherical silica-based mesoporous material of the present invention introduces a second organic group having a high affinity with the adsorbing material, and introduces a first organic group capable of chemically binding the adsorbing material. Thus, since the second organic group can function as the selection point of the adsorbing substance and the first organic group can function as the adsorption point, it is also very useful as an adsorbent.

  Next, a method suitable as a method capable of producing such a spherical silica-based mesoporous material of the present invention will be described.

As a method capable of producing such a spherical silica-based mesoporous material, basically,
In a solvent, a surfactant and a mixture of silica raw materials including the first silica raw material and the second silica raw material are mixed to precipitate porous precursor particles in which the surfactant is introduced into silica. A first step;
A second step of removing the surfactant contained in the porous precursor particles;
It is a method including. In the method for producing such a spherical silica-based mesoporous material, when the first silica raw material contains a precursor of the first organic group, the precursor is converted into the first organic group. The method further includes a third step of performing the processing. Hereinafter, it demonstrates for every process.

(First step)
In the first step, a porous precursor particle in which a surfactant and a mixture of silica raw materials including a first silica raw material and a second silica raw material are mixed in a solvent, and the surfactant is introduced. Is a step of precipitating.

  Here, the term “precipitation” refers to the time when the diffraction peak on the 100 plane of hexagonal pores begins to appear by X-ray diffraction measurement of the reaction solution, and the diffraction peak gradually increases. The time when it reaches a certain value is defined as the end time of deposition.

As long as such first silica raw material is capable of forming a silicon oxide (including a silicon composite oxide) into which a first organic group or a precursor of the first organic group is introduced. Well, not particularly limited. Precursors of such first organic group is a sulfonic acid group may be any organic group having a functional group capable of converting to a carboxylic acid group or amino group, for example, a mercapto group and a cyano group Examples thereof include an organic group in which a functional group selected from the group is bonded to the above-mentioned chain hydrocarbon group (i) or cyclic hydrocarbon group (ii).

  Moreover, as such a 1st silica raw material, the 1st alkoxysilane which has a precursor of a 1st organic group or a 1st organic group is mentioned.

  Examples of such first alkoxysilane include trialkoxysilane having three alkoxy groups in addition to the first organic group or the precursor of the first organic group, the first organic group, or the first organic group. In addition to the precursor, dialkoxysilane having two alkoxy groups can be used as appropriate. The type of such an alkoxy group is not particularly limited, but those having a relatively small number of carbon atoms in the alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group (about 1 to 4 carbon atoms) From the viewpoint of reactivity.

  Examples of such first alkoxysilane include 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-cyanopropyl. Trimethoxysilane, 3-cyanoethyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl] aniline, (N, N-dimethylaminopropyl) trimethoxysilane, 3- (methylamino) propyltrimethoxysilane, 3 -Diethylaminopropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) -ethyltrimethoxysilane, N- (trimethoxysilylpropyl) -4,5-dihydroimidazole, 2- (trimethoxysilylethyl) pyridine, 2- Trimethoxysilylpi Gin, 3- (trimethoxysilylethyl) pyridine, 3-trimethoxysilylpyridine, 4-aminobutyltrimethoxysilane, (aminoethylaminoethyl) phenethyltrimethoxysilane, N- (6-aminohexyl) aminomethyltrimethoxy Silane, N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, 3- (aminophenoxy) propyltrimethoxysilane, aminophenyltrimethoxysilane N-3- [amino (polypropyleneoxy)] aminopropyltrimethoxysilane, bis (trimethylsilyl) cytosine, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3- Minopropyltriethoxysilane, 3-cyanopropyltriethoxysilane, 3-cyanoethyltriethoxysilane, N- [3- (triethoxysilyl) propyl] aniline, (N, N-dimethylaminopropyl) triethoxysilane, 3- (Methylamino) propyltriethoxysilane, 3-diethylaminopropyltriethoxysilane, 2- (4-chlorosulfonylphenyl) -ethyltriethoxysilane, N- (triethoxysilylpropyl) -4,5-dihydroimidazole, 2- (Triethoxysilylethyl) pyridine, 2-triethoxysilylpyridine, 3- (triethoxysilylethyl) pyridine, 3-triethoxysilylpyridine, 4-aminobutyltriethoxysilane, (aminoethylaminoethyl) phenethyl rie Toxisilane, N- (6-Aminohexyl) aminomethyltriethoxysilane, N- (6-Aminohexyl) aminopropyltriethoxysilane, N- (2-aminoethyl) -11-aminoundecyltriethoxysilane, 3- (Aminophenoxy) propyltriethoxysilane, aminophenyltriethoxysilane, N-3- [amino (polypropyleneoxy)] aminopropyltriethoxysilane, bis (triethylsilyl) cytosine and the like.

  The second silica raw material is not particularly limited as long as it can form silicon oxide (including silicon composite oxide) into which the second organic group is introduced. Such a second silica raw material includes a second alkoxysilane having a second organic group.

  Such a second alkoxysilane is not particularly limited as long as it is an alkoxysilane having a second organic group. For example, a trialkoxysilane having three alkoxy groups in addition to the second organic group, A dialkoxysilane having two alkoxy groups in addition to the two organic groups can be used. Examples of such second alkoxysilane include methyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, allyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, and the like. Ethoxysilane, propyltriethoxysilane, hexyltriethoxysilane, octadecyltriethoxysilane, phenyltriethoxysilane, allyltriethoxysilane, (1-naphthyl) triethoxysilane, [2- (cyclohexenyl) ethyl] triethoxysilane, Dimethoxydimethylsilane, diethoxydimethylsilane, diethoxy-3-glycidoxypropylmethylsilane, dimethoxydiphenylsilane, dimethoxydimethylphenylsilane, Rutrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, isopropyltrimethoxysilane, pentyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetra Decyltrimethoxysilane, hexadecyltrimethoxysilane, phenylethyltrimethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, isopropyltriethoxysilane, pentyltriethoxysilane, heptyltriethoxysilane, octyltriethoxy Silane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tetradecylto Silane, hexadecyl triethoxysilane, phenyl triethoxysilane, trimethyl methoxy silane, trimethyl ethoxy silane, 3-chloropropyl dimethylmethoxysilane, and the like.

  Moreover, in the mixture of the silica raw material containing the first silica raw material and the second silica raw material, it is preferable to further add another silica raw material not having the first organic group and the second organic group. Such other silica raw materials are not particularly limited, and alkoxysilanes not having the first organic group and the second organic group can be suitably used. As such an alkoxysilane as another silica raw material, tetraalkoxysilane having 4 alkoxy groups, trialkoxysilane having 3 alkoxy groups, and dialkoxysilane having 2 alkoxy groups can be used. Such alkoxy groups are the same as those described for the first alkoxysilane. Further, when the alkoxysilane has 3 or 2 alkoxy groups, an organic group other than the first organic group and the second organic group, a hydroxyl group, or the like is bonded to the silicon atom in the alkoxysilane. May be. Such other silica raw materials not having the first organic group and the second organic group are not particularly limited. For example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxy Examples include diethoxysilane.

  Such other silica raw materials that do not have the first organic group and the second organic group can be used alone or in combination of two or more. Moreover, in the other silica raw material which does not have such a first organic group, a monoalkoxysilane having one alkoxy group is combined with an alkoxysilane having 2 to 4 alkoxy groups as described above. It is also possible to use it.

  Furthermore, the first silica raw material, the second silica raw material, and the other silica raw material generate silanol groups by hydrolysis, and the generated silanol groups are condensed to form a silicon oxide. In this case, an alkoxysilane having a large number of alkoxy groups in the molecule has many bonds generated by hydrolysis and condensation. Therefore, in the present invention, it is preferable to use tetraalkoxysilane having many alkoxy groups as the other silica raw material. As such a tetraalkoxysilane, it is particularly preferable to use tetramethoxysilane or tetraethoxysilane from the viewpoint of reaction rate.

  Moreover, when using the mixture which mixed said 1st silica raw material, said 2nd silica raw material, and said other silica raw material as a mixture of the silica raw material containing said 1st silica raw material and 2nd silica raw material In, it is preferable that the content rate of the 1st alkoxysilane in a mixture is 0.1-20 mol% with respect to the whole quantity of a mixture. When the content ratio of the first alkoxysilane is less than the lower limit, the catalyst and the adsorption performance tend to be lowered. On the other hand, when the upper limit is exceeded, the pores are blocked and the substrate or the adsorbent is difficult to enter the pores. Thus, the catalyst and the adsorption performance tend to decrease. Moreover, it is preferable that the content rate of the 2nd alkoxysilane in the said mixture is 0.1-20 mol% with respect to the whole quantity of a mixture. If the mixing ratio of the second alkoxysilane is less than the lower limit, the selectivity to the substrate and the adsorbent tends to be reduced. On the other hand, if the upper limit is exceeded, the pores are blocked, and the substrate or adsorbent is contained in the pores Tends to be difficult to enter. The method for producing such a mixture is not particularly limited. For example, the mixture has a first alkoxysilane, a second alkoxysilane, a first organic group, and a second organic group in a dry nitrogen stream. It is possible to employ a method of mixing with other silica raw materials that are not.

  The surfactant used in the first step is not particularly limited, and a known surfactant that can be used when producing a spherical silica mesoporous material can be appropriately used. Moreover, as such surfactant, the following general formula (1):

[Wherein R ¹ , R ² and R ³ may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms, X represents a halogen atom, and n represents an integer of 7 to 25, respectively. ]
The alkyl ammonium halide represented by these is preferable.

R ¹ , R ² and R ³ in the general formula (1) may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, and a propyl group, and these may be mixed in one molecule. From the viewpoint of symmetry of the surfactant molecule, R ¹ , R ² , R ³ Are preferably the same. When the symmetry of the surfactant molecule is excellent, aggregation of the surfactants (formation of micelles, etc.) tends to be facilitated. ^Furthermore, R ^1, it is preferable that at least one of R 2, ^{R 3} is a methyl ^group, and more preferably all of R ^1, R 2, ^{R 3} is a methyl group.

  Moreover, n in General formula (1) shows the integer of 7-25, and it is more preferable that it is an integer of 9-17. In the case of the alkyl ammonium halide having n of 6 or less, a spherical porous body tends not to be obtained, and the central pore diameter becomes smaller than 1.0 nm, and the catalytic reactivity in the pore is reduced. There is a tendency. On the other hand, in the case of the alkylammonium halide having n of 26 or more, the hydrophobic interaction of the surfactant is too strong, so that a layered compound is generated and a spherical porous body cannot be obtained.

  Furthermore, X in the general formula (1) represents a halogen atom, and the kind of such a halogen atom is not particularly limited, but X is preferably a chlorine atom or a bromine atom from the viewpoint of easy availability.

Therefore, as the surfactant represented by the general formula (1), all of R ¹ , R ² and R ³ are methyl groups and alkyltrimethylammonium halides having a long-chain alkyl group having 10 to 26 carbon atoms. Among them, decyltrimethylammonium halide, dodecyltrimethylammonium halide, tetradecyltrimethylammonium halide, hexadecyltrimethylammonium halide, octadecyltrimethylammonium halide, eicosyltrimethylammonium halide, and docosyltrimethylammonium halide are more preferable.

  Such a surfactant forms a complex in the solvent together with the silica raw material. The silica raw material in the composite is changed to silicon oxide by the reaction, but silicon oxide is not generated in the part where the surfactant is present, so pores are formed in the part where the surfactant is present. Will be. That is, the surfactant is introduced into the silica raw material and functions as a template for pore formation. In the present invention, the surfactant can be used alone or in combination of two or more, but as described above, the surfactant acts as a template for forming pores in the reaction product of the silica raw material, Since the type greatly affects the pore shape of the porous body, it is preferable to use only one type of surfactant in order to obtain a more uniform spherical porous body.

  Moreover, when synthesizing the porous precursor particles in which the surfactant is introduced into the silica raw material, it is preferable to use an aqueous solvent having an alcohol content of 80% by volume or less as the solvent. When the alcohol content exceeds 80% by volume, it is difficult to control the particle size and particle size distribution, and the particle size uniformity of the obtained spherical silica-based mesoporous material is lowered. In addition, from the viewpoint of enabling generation and growth of uniform spheres and controlling the particle diameter of the obtained porous precursor particles highly uniformly, the alcohol content is 10 to 10. More preferably, 80% by volume of a mixed solvent is used. When the alcohol content is less than 10% by volume, it is difficult to control the particle size and particle size distribution, and the uniformity of the particle size of the obtained porous precursor particles tends to be low. In addition, by using such an aqueous solvent containing a relatively large amount of alcohol, generation and growth of uniform spheres are realized, and the particle diameter of the obtained spherical silica-based mesoporous material is highly uniformly controlled. Will be.

  Further, in the present invention, by changing the ratio of water and alcohol in the aqueous solvent, the particle size of the obtained spherical silica mesoporous material can be easily maintained while maintaining the particle size uniformity at a high level. Can be controlled. That is, when the water ratio is high, the porous body is likely to precipitate, so the particle size is small. Conversely, when the alcohol ratio is high, a porous body having a large particle size can be obtained.

  Furthermore, when the porous material precursor particles are obtained by mixing the mixture of the silica raw material and the surfactant in the aqueous solvent, the concentration of the surfactant described above is 0.0001 to the total volume of the solution. 0.03 mol / L (more preferably 0.0005 to 0.02 mol / L) is preferable, and the concentration of the silica raw material mixture described above is 0.0005 to 0.03 mol / liter based on the total volume of the solution. L (preferably 0.003 to 0.015 mol / L) is preferable. By strictly controlling the concentrations of the surfactant and the silica raw material in this way, the generation and growth of uniform spherical bodies can be realized in combination with the use of the aqueous solvent described above, and the resulting spherical silica meso The particle size of the porous body is highly uniformly controlled. When the concentration of the surfactant is less than 0.0001 mol / L, a sufficient porous body cannot be obtained because the amount of the surfactant to be a template is insufficient, and the particle size and particle size distribution are controlled. The uniformity of the particle size of the spherical silica-based mesoporous material obtained becomes difficult. On the other hand, when the concentration of the surfactant exceeds 0.03 mol / L, a porous body having a spherical shape cannot be obtained at a high ratio, and control of the particle size and particle size distribution becomes difficult. There is a tendency that the uniformity of the particle size of the resulting spherical silica-based mesoporous material is lowered. Moreover, when the concentration of the silica raw material mixture is less than 0.0005 mol / L, a porous body having a spherical shape cannot be obtained at a high ratio, and control of the particle size and particle size distribution becomes difficult. The uniformity of the particle size of the obtained spherical silica-based mesoporous material tends to be low. On the other hand, when the concentration of the silica raw material mixture exceeds 0.03 mol / L, a sufficient porous body cannot be obtained because the ratio of the surfactant to be a template is insufficient, and the particle size and particle size are further reduced. There is a tendency that the uniformity of the particle size of the spherical silica-based mesoporous material obtained when the distribution is difficult to control becomes low.

  Moreover, when mixing the said silica raw material mixture and the said surfactant, it is preferable to mix on basic conditions. The silica raw material generally reacts under basic and acidic conditions and changes to silicon oxide. However, when adjusting the concentration of the silica raw material mixture and the surfactant as described above, The concentration is considerably lower than that of the prior art method, and the reaction hardly proceeds under acidic conditions. Therefore, from such a viewpoint, it is preferable to react a mixture of silica raw materials under basic conditions. In addition, when the silica raw material is reacted under basic conditions, the reaction point of silicon atoms is increased when the reaction is performed under basic conditions, and a silicon oxide having excellent physical properties such as moisture resistance and heat resistance is obtained. Can do. Therefore, mixing under basic conditions is also advantageous in this respect.

  Moreover, as pH value of such a basic solvent, it is preferable that it is 7.5-13, and it is more preferable that it is 8-12. When such a pH value is less than the lower limit, it tends to be difficult to form pores of the porous precursor particles. On the other hand, when the upper limit is exceeded, the precipitation amount of the porous precursor particles tends to decrease. It is in. In addition, the method for adjusting the pH value of such a basic solvent is not particularly limited, but a method of appropriately adjusting the pH value by adding a basic substance such as an aqueous sodium hydroxide solution to the solvent described later can be mentioned. .

  The reaction conditions (reaction temperature, reaction time, etc.) in the first step are not particularly limited, and the reaction temperature is, for example, -20 ° C to 100 ° C (more preferably 0 ° C to 80 ° C, more preferably 10 ° C). ~ 40 ° C). In addition, the reaction is preferably allowed to proceed with stirring. Specific reaction conditions are preferably determined based on the type of silica raw material used.

  For example, when a mixture of the first silica raw material, the second silica raw material and another silica raw material is used, porous precursor particles can be obtained as follows. First, a surfactant and a basic substance are added to a mixed solvent of water and alcohol to prepare a basic solution containing the surfactant, and the silica raw material mixture is added to this solution. The mixture added in this manner is hydrolyzed (or hydrolyzed and condensed) in the solution, and porous precursor particles (white powder) are precipitated within a few seconds to several tens of minutes after the addition. In this case, the reaction temperature is preferably 0 ° C to 80 ° C, more preferably 10 ° C to 40 ° C. The solution is preferably stirred. The porous precursor particles obtained in this way have the silica modified with the first organic group and / or the precursor of the first organic group and the second organic group.

(Second step)
Next, the second step will be described. The second step is a step of removing the surfactant contained in the porous precursor particles.

  Examples of the method for removing such a surfactant include a method for treating with an organic solvent and an ion exchange method. In the case of employing such a method of treating with an organic solvent, the surfactant is extracted by immersing the porous precursor particles in a good solvent having high solubility in the used surfactant. When the ion exchange method is employed, the porous precursor particles are immersed in an acidic solution (such as ethanol containing a small amount of hydrochloric acid) and stirred while heating at, for example, 50 to 70 ° C. Thereby, the surfactant existing in the pores of the porous precursor particles is ion-exchanged with hydrogen ions. In addition, although hydrogen ions remain in the hole by ion exchange, the problem of blockage of the hole does not occur because the ion radius of the hydrogen ion is sufficiently small.

  The spherical silica-based mesoporous material thus obtained has radial pores with an average particle diameter of 0.01 to 3 μm, a central pore diameter of 1 to 10 nm, and the first organic group and A spherical silica-based mesoporous material into which the precursor of the first organic group and the second organic group are introduced is obtained. And when the 1st organic group is introduce | transduced into the silica in such a spherical silica type mesoporous material, the spherical silica type mesoporous material of this invention is obtained by such a 2nd process. . On the other hand, when the precursor of the first organic group is introduced into the silica in the spherical silica-based mesoporous material, the spherical silica of the present invention can be obtained by performing the third step described below. A system mesoporous material is obtained.

(Third step)
The third step is a step of performing a process of converting the precursor of the first organic group introduced into the silica in the spherical silica-based mesoporous material into the first organic group.

  The method for converting the precursor of the first organic group into the first organic group is not particularly limited as long as it is a method capable of converting the precursor into the first organic group. Various methods can be adopted depending on the type of the first organic group precursor and the type of the first organic group to be converted, etc., and the functional group of the precursor includes sulfonic acid, carboxylic acid group and You may employ | adopt suitably the well-known method which can be converted into the at least 1 sort (s) of functional group selected from the group which consists of an amino group.

  As the treatment for converting into such a first organic group, for example, when the functional group of the precursor of the first organic group is a mercapto group, and this is converted into a sulfonic acid group, an oxidizing agent is used. It is possible to employ a method of oxidizing. The method of oxidizing using such an oxidizing agent is not particularly limited as long as it is a method capable of oxidizing a mercapto group and converting it into a sulfonic acid group using an oxidizing agent. The oxidizing agent is not particularly limited as long as it can oxidize a mercapto group and convert it into a sulfonic acid group, and examples thereof include hydrogen peroxide, nitric acid, sulfuric acid, and crown ether. It is done. Among these oxidizing agents, hydrogen peroxide is preferable from the viewpoints of high reactivity and pore retention. In addition, conditions such as reaction temperature and reaction time in the method of oxidizing using such an oxidizing agent are not particularly limited, but the reaction temperature is 100 ° C. or less (more preferably 10 to 80 ° C.). The reaction time is preferably within 30 minutes to 6 hours. When the reaction temperature and reaction time are less than the lower limit, the mercapto group is hardly oxidized, and it tends to be difficult to oxidize the mercapto group and convert it to a sulfonic acid group. In addition, the pores of the spherical silica-based mesoporous material are partly collapsed, and when used as an acid catalyst, the acid catalyst performance tends to decrease.

  In addition, as a treatment for converting into such a first organic group, the functional group of the precursor of the first organic group is a cyano group, and when this is converted into a carboxylic acid group, an oxidizing agent is used. It is possible to employ a method of oxidizing. Such an oxidizing agent is not particularly limited as long as it can oxidize a cyano group to be converted into a carboxylic acid group. For example, an acid such as sulfuric acid, hydrochloric acid, acetic acid, formic acid, or a peroxidic acid can be used. Examples thereof include hydrogen and crown ether. Among such oxidizing agents, sulfuric acid is preferable from the viewpoints of high reactivity and pore retention. In addition, conditions such as reaction temperature and reaction time in the method of oxidizing using such an oxidizing agent are not particularly limited. However, when sulfuric acid having a concentration of 1 mol / L or more is used, it is 25 to 150 ° C. ( More preferably, the mixture is refluxed for about 1 to 24 hours under a temperature condition of 50 to 130 ° C.

  In addition, when the functional group of the precursor of the first organic group is a chlorosulfonylphenyl group and this is converted into a sulfonic acid group, the surfactant is extracted using an acidic solution in the third step described above. At this time, a method of exchanging the sulfonic acid group with the acidic solution may be adopted.

  Although the spherical silica-based mesoporous material of the present invention has been described above, the catalyst of the present invention will be described below.

  The catalyst of the present invention comprises the spherical silica-based mesoporous material of the present invention. In the catalyst of the present invention, since the spherical silica mesoporous material of the present invention is used, the type of the first organic group and the type of the second organic group are selected according to the type of the substrate for the catalytic reaction, etc. Thus, a catalyst having a desired design in which the second organic group functions as an adsorption point of the substrate and the first organic group functions as an active site can be obtained. Therefore, according to such a catalyst of the present invention, a specific substrate can be adsorbed with high selectivity, and a catalytic reaction can be efficiently performed.

  In the catalyst of the present invention, it is preferable to use a second organic group having a high affinity with the substrate and a low interaction with the substrate. By using a second organic group that has a high affinity with the substrate and a low interaction with the substrate, it becomes possible to incorporate the substrate with a higher selectivity and to bring the substrate into the interior more efficiently. It tends to be possible to move. In addition, when an organic group having a low affinity with the substrate is selected as the second organic group, it tends to be difficult to incorporate the substrate into the pores, and as the second organic group, When an organic group having a strong interaction with the substrate is selected, it tends to be difficult to move the substrate.

  Furthermore, the catalyst of the present invention can be suitably used as an acidic catalyst when the first organic group has a sulfonic acid group or a carboxylic acid group. On the other hand, when the first organic group has an amino group, it can be suitably used as a basic catalyst.

  The adsorbent of the present invention comprises the spherical silica mesoporous material of the present invention. In the adsorbent of the present invention, since the spherical silica-based mesoporous material of the present invention is used, by selecting the type of the first organic group and the second organic group according to the type of the adsorbent, respectively. The adsorbent having a desired design in which the second organic group functions as a selection point of the adsorbing substance and the first organic group functions as the adsorption point can be obtained. Therefore, according to such an adsorbent of the present invention, a specific adsorbent can be taken in with high selectivity and can be adsorbed efficiently.

  In the adsorbent of the present invention, it is preferable to use a material having high affinity with the adsorbing substance and low interaction as the second organic group. By using a second organic group that has a high affinity with the adsorbent and a low interaction, it is possible to incorporate the adsorbent with higher selectivity, and more efficiently incorporate the adsorbent into the interior. It tends to be possible to move. When an organic group having a low affinity with the adsorbing material is selected as the second organic group, it tends to be difficult to incorporate the adsorbing material into the pores.

  Furthermore, when the first organic group has a sulfonic acid group or a carboxylic acid group, the adsorbent of the present invention is suitable for basic substances, biological substances, metal compounds and the like that are chemically bonded to these functional groups. It can be suitably used as an adsorbent. On the other hand, when the first organic group has an amino group, it can be suitably used as an adsorbent for acidic substances, biological substances, metal compounds and the like that are chemically bonded to these functional groups.

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

(Example 1: <first organic group> 3-propylsulfonic acid group, <second organic group> propyl group)
7.04 g of hexadecyltrimethylammonium chloride was dissolved in 1600 g of a water / methanol mixed solution (50/50 = w / w) and stirred at 25 ° C. in a constant temperature water bath to obtain a solution. Next, 6.84 g of a 1 mol / L sodium hydroxide solution was added to the solution thus obtained to obtain a basic solution. Next, a mixture (moles) of tetramethoxysilane (TMOS) / 3-mercaptopropyltrimethoxysilane (MPTMS) / propyltrimethoxysilane (PTMS) previously mixed in a dry nitrogen stream as a mixture of silica raw materials into the basic solution. Ratio 18/1/1) 3.47 × 10 ⁻² mol was added. Thus, when the mixture of the silica raw material was added to the basic solution, precipitation of particles was observed in a few minutes, and the mixture became cloudy. And after adding the mixture of the said silica raw material to the said basic solution, it stirred for about 8 hours, and left still overnight. Thereafter, the operation of filtering the product produced in the basic solution and redispersing in water was repeated twice, followed by drying overnight at a temperature of 45 ° C. to introduce the surfactant into silica. The obtained porous precursor particles were obtained.

  Next, 1 g of the porous precursor particles obtained as described above was dispersed in 100 mL of ethanol, 1 mL of hydrochloric acid was added, and the mixture was stirred in an oil bath at 60 ° C. for 3 hours to extract the surfactant. After the surfactant was extracted in this manner, the obtained particles were sufficiently washed with ethanol and dried at 45 ° C. to obtain a silica-based mesoporous material. The silica-based mesoporous material thus obtained was obtained by modifying the silica in the porous material with a 3-mercaptopropyl group and a propyl group.

  Next, 0.5 g of the obtained silica-based mesoporous material is added to 10 ml of 30% by mass hydrogen peroxide (oxidant), and the mixture is stirred for 6 hours at a temperature of 50 ° C., thereby introducing the introduced mercapto group. Conversion to sulfonic acid groups. Then, the obtained particles are filtered and dried under a temperature condition of 45 ° C., whereby the first organic group is a 3-propylsulfonic acid group and the second organic group is a propyl group. A silica-based mesoporous material was obtained.

(Example 2: <first organic group> 3-propylsulfonic acid group, <second organic group> phenyl group)
As a mixture of silica raw materials, a mixture of tetramethoxysilane (TMOS) / 3-mercaptopropyltrimethoxysilane (MPTMS) / phenyltrimethoxysilane (PhTMS) (molar ratio 18/1/1) 3.47 × 10 ⁻² mol Except having used, it carried out similarly to Example 1, and obtained the spherical silica type mesoporous material of this invention whose 1st organic group is a 3-propylsulfonic acid group and a 2nd organic group is a phenyl group.

(Example 3: <First organic group> 3-aminopropyl group, <Second organic group> phenyl group)
7.04 g of hexadecyltrimethylammonium chloride was dissolved in 1600 g of a water / methanol mixed solution (50/50 = w / w) and stirred at 25 ° C. in a constant temperature water bath to obtain a solution. Next, 6.84 g of a 1 mol / L sodium hydroxide solution was added to the solution thus obtained to obtain a basic solution. Next, a mixture (moles) of tetramethoxysilane (TMOS) / 3-aminopropyltrimethoxysilane (APTMS) / phenyltrimethoxysilane (PhTMS) mixed in advance in a dry nitrogen stream as a mixture of silica raw materials into the basic solution. Ratio 18/1/1) 3.47 × 10 ⁻² mol was added. Thus, when the mixture of the silica raw material was added to the basic solution, precipitation of particles was observed in a few minutes, and the solution became cloudy. And after adding the mixture of the said silica raw material to the said basic solution, it stirred for about 8 hours, and left still overnight. Thereafter, the operation of filtering the product produced in the basic solution and redispersing in water was repeated twice, followed by drying overnight at a temperature of 45 ° C., and the surfactant was introduced into the silica. Porous precursor particles were obtained.

  Next, 1 g of the porous precursor particles obtained as described above was dispersed in 100 mL of ethanol, 1 mL of hydrochloric acid was added, and the mixture was stirred in an oil bath at 60 ° C. for 3 hours to extract the surfactant. After extracting the surfactant in this way, the obtained particles are thoroughly washed with ethanol and dried overnight at a temperature condition of 45 ° C., and the first organic group is a 3-aminopropyl group, A spherical silica mesoporous material of the present invention in which the second organic group was a phenyl group was obtained.

(Example 4: <first organic group> 3-aminopropyl group, <second organic group> phenyl group)
A mixture of tetramethoxysilane (TMOS) / 3-aminopropyltrimethoxysilane (APTMS) / phenyltrimethoxysilane (PhTMS) (molar ratio 17/1/2) 3.47 × 10 ⁻² mol as a mixture of silica raw materials A spherical silica mesoporous material of the present invention was obtained in the same manner as in Example 3 except that the first organic group was a 3-aminopropyl group and the second organic group was a phenyl group.

(Example 5: <First organic group> 3-aminopropyl group, <Second organic group> propyl group)
As a mixture of silica raw materials, a mixture of tetramethoxysilane (TMOS) / 3-aminopropyltrimethoxysilane (APTMS) / propyltrimethoxysilane (PTMS) (molar ratio 18/1/1) 3.47 × 10 ⁻² mol A spherical silica mesoporous material of the present invention was obtained in the same manner as in Example 3 except that the first organic group was a 3-aminopropyl group and the second organic group was a propyl group.

(Example 6: <First organic group> 3-aminopropyl group, <Second organic group> allyl group)
As a mixture of silica raw materials, a mixture of tetramethoxysilane (TMOS) / 3-aminopropyltrimethoxysilane (APTMS) / allyltrimethoxysilane (ALTMS) (molar ratio 18/1/1) 3.47 × 10 ⁻² mol A spherical silica mesoporous material of the present invention was obtained in the same manner as in Example 3 except that the first organic group was a 3-aminopropyl group and the second organic group was an allyl group.

(Example 7: <First organic group> N- (2-aminoethyl) -3-aminopropyl group, <Second organic group> phenyl group)
As a mixture of silica raw materials, a mixture of tetramethoxysilane (TMOS) / N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (AEAPTMS) / phenyltrimethoxysilane (PhTMS) (molar ratio 18/1/1) The first organic group is N- (2-aminoethyl) -3-aminopropyl group and the second organic group is the same as in Example 3 except that 3.47 × 10 ⁻² mol is used. A spherical silica-based mesoporous material of the present invention having a phenyl group was obtained.

(Example 8: <First organic group> N- (2-aminoethyl) -3-aminopropyl group, <Second organic group> propyl group)
As a mixture of silica raw materials, a mixture of tetramethoxysilane (TMOS) / N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (AEAPTMS) / propyltrimethoxysilane (PTMS) (molar ratio 18/1/1) The first organic group is N- (2-aminoethyl) -3-aminopropyl group and the second organic group is the same as in Example 3 except that 3.47 × 10 ⁻² mol is used. A spherical silica-based mesoporous material of the present invention having a propyl group was obtained.

(Example 9: <first organic group>: 3-propyl carboxyl group, <second organic group>: phenyl group)
7.04 g of hexadecyltrimethylammonium chloride was dissolved in 1600 g of a water / methanol mixed solution (50/50 = w / w) and stirred at 25 ° C. in a constant temperature water bath to obtain a solution. Next, 6.84 g of a 1 mol / L sodium hydroxide solution was added to the solution thus obtained to obtain a basic solution. Next, a mixture (moles) of tetramethoxysilane (TMOS) / 3-cyanopropyltrimethoxysilane (CPTMS) / phenyltrimethoxysilane (PhTMS) mixed in advance in a dry nitrogen stream as a mixture of silica raw materials into the basic solution. Ratio 18/1/1) 3.47 × 10 ⁻² mol was added. Thus, when the mixture of the silica raw material was added to the basic solution, precipitation of particles was observed in a few minutes, and the solution became cloudy. And after adding the mixture of the said silica raw material to the said basic solution, it stirred for about 8 hours, and left still overnight. Thereafter, the operation of filtering the product produced in the basic solution and redispersing in water was repeated twice, followed by drying overnight at a temperature of 45 ° C., and the surfactant was introduced into the silica. Porous precursor particles were obtained.

  Next, 1 g of the porous precursor particles obtained as described above was dispersed in 100 mL of ethanol, 1 mL of hydrochloric acid was added, and the mixture was stirred in an oil bath at 60 ° C. for 3 hours to extract the surfactant. After the surfactant was extracted in this manner, the obtained particles were thoroughly washed with ethanol and dried overnight at a temperature of 45 ° C. to obtain a silica-based mesoporous material. The silica-based mesoporous material thus obtained was obtained by modifying the silica in the porous material with a 3-cyanopropyl group and a phenyl group.

  Next, 6.3 ml of 18 mol / L concentrated sulfuric acid (oxidant) and 3.7 ml of water were mixed and allowed to stand, and cooled to about 50 ° C., and obtained as described above. 0.5 g of a silica-based mesoporous material was added and heated to reflux at 100 ° C. for 6 hours to convert the cyano group introduced into the silica-based mesoporous material into a carboxyl group. The obtained particles are filtered and dried under a temperature condition of 45 ° C., whereby the first organic group is a 3-propylcarboxyl group and the second organic group is a phenyl group of the present invention. A system mesoporous material was obtained.

(Example 10: <first organic group>: 3-propyl carboxyl group, <second organic group>: propyl group)
As a mixture of silica raw materials, a mixture of tetramethoxysilane (TMOS) / 3-cyanopropyltrimethoxysilane (CPTMS) / propyltrimethoxysilane (PTMS) (molar ratio 18/1/1) 3.47 × 10 ⁻² mol A spherical silica mesoporous material of the present invention in which the first organic group was a 3-propylcarboxyl group and the second organic group was a propyl group was obtained in the same manner as Example 9 except that it was used.

(Comparative Example 1)
7.04 g of hexadecyltrimethylammonium chloride (surfactant) was dissolved in 1600 g of a mixed solution of water and methanol (water / methanol: 50/50 = w / w), stirred at 25 ° C. in a constant temperature water bath, A solution was obtained. Next, 6.84 g of 1 mol / L sodium hydroxide solution was added to the resulting solution to obtain a basic solution. Thereafter, a mixture of tetramethoxysilane (TMOS) / 3-mercaptopropyltrimethoxysilane (MPTMS) prepared by mixing in the basic solution in advance in a dry nitrogen stream as a mixture of silica raw materials (molar ratio: (TMOS)) / (MPTMS) = 9/1) 3.47 × 10 ⁻² mol was added. Thus, when the mixture of the silica raw material was added to the basic solution, precipitation of particles was observed in a few minutes, and the solution became cloudy. And after adding the mixture of the said silica raw material to the said basic solution, it stirred for about 8 hours, and left still overnight. Thereafter, the product produced in the basic solution is filtered and re-dispersed in water twice, followed by drying overnight at a temperature of 45 ° C. to introduce the surfactant. Body particles were obtained.

  Next, after dispersing 1 g of the obtained porous particles in 100 mL of ethanol, 1 mL of hydrochloric acid was added, and the surfactant was extracted from the porous particles by stirring at 60 ° C. for 3 hours in an oil bath. After the surfactant was extracted in this manner, the obtained particles were sufficiently washed with ethanol and dried at 45 ° C. to obtain a silica-based mesoporous material modified with a 3-mercaptopropyl group.

  Next, 0.5 g of the obtained silica-based mesoporous material is added to 10 ml of 30% by mass hydrogen peroxide (oxidant), and stirred for 6 hours at a temperature of 50 ° C., thereby converting mercapto groups into sulfonic acid groups. Converted. Thereafter, the obtained particles were filtered and dried under a temperature condition of 45 ° C. to obtain a comparative spherical silica-based mesoporous material modified with a 3-propylsulfonic acid group.

(Comparative Example 2)
In the same manner as in Comparative Example 1 except that a mixture of tetramethoxysilane (TMOS) / propyltrimethoxysilane (PTMS) (molar ratio 9/1) 3.47 × 10 ⁻² mol was used as a silica raw material, A modified spherical silica-based mesoporous material was obtained as a comparison.

(Comparative Example 3)
8.00 g of hexadecyltrimethylammonium chloride was dissolved in 250 ml of 0.2 mmol / L sodium hydroxide aqueous solution to obtain a basic solution. Next, the obtained basic solution was heated to 70 ° C. while stirring. Subsequently, after reaching 70 ° C., tetramethoxysilane (TMOS) / 3-mercaptopropyltrimethoxysilane (MPTMS) / propyltrimethoxysilane mixed in advance in a dry nitrogen stream as a mixture of silica raw materials with the basic solution. A mixture of (PTMS) (molar ratio 18/1/1) 2.50 × 10 ⁻² mol was added. The basic solution to which the silica raw material mixture was added was stirred at 70 ° C. for 3 hours, and then a 2 mol / L aqueous HCl solution was added dropwise until the pH reached 7.5. Thereafter, the solution in which the aqueous HCl solution was dropped was continuously stirred, and after 2 hours, the pH was adjusted again to 7.5. After 1 hour, the stirring was stopped and the mixture was allowed to cool to room temperature. Next, the operation of filtering the product produced in the solution and redispersing it in water was repeated twice, followed by drying at 45 ° C. overnight to form the amorphous silica porous material into which the surfactant was introduced. A precursor was obtained.

  Next, 1 g of the obtained amorphous silica porous material precursor was dispersed in 100 mL of ethanol, 1 mL of hydrochloric acid was added, and the mixture was stirred in an oil bath at 60 ° C. for 3 hours to remove the surfactant from the porous particles. Extracted. After the surfactant is extracted in this manner, the resulting particles are thoroughly washed with ethanol and dried at 45 ° C. to obtain an amorphous silica porous body modified with 3-mercaptopropyl groups and propyl groups. It was.

  Next, 0.5 g of the obtained silica-based mesoporous material is added to 10 ml of 30% by mass hydrogen peroxide (oxidant), and stirred for 6 hours at a temperature of 50 ° C., thereby converting mercapto groups into sulfonic acid groups. Converted. Thereafter, the obtained particles are filtered, dried at a temperature of 45 ° C., and a comparative amorphous silica-based mesoporous material (FSM type) modified with 3-propylsulfonic acid group and propyl group is obtained. Obtained.

(Comparative Example 4)
Comparative Example 1 was used except that a mixture of tetramethoxysilane (TMOS) / 3-aminopropyltrimethoxysilane (AEAPTMS) (molar ratio 19/1) 3.47 × 10 ⁻² mol was used as the silica raw material mixture. Thus, a comparative spherical silica-based mesoporous material modified with a 3-aminopropyl group was obtained.

(Comparative Example 5)
A mixture of tetramethoxysilane (TMOS) / N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (AEAPTMS) (molar ratio 19/1) 3.47 × 10 ⁻² mol is used as the silica raw material mixture. A spherical silica-based mesoporous material as a comparison modified with an N- (2-aminoethyl) -3-aminopropyl group was obtained in the same manner as in Comparative Example 1 except that.

(Comparative Example 6)
7.04 g of hexadecyltrimethylammonium chloride was dissolved in 1600 g of a water / methanol mixed solution (50/50 = w / w), and the solution was obtained by stirring at 25 ° C. in a constant temperature water bath. Next, 6.84 g of 1 mol / L sodium hydroxide solution was added to the solution to obtain a basic solution. Thereafter, a tetramethoxysilane (TMOS) / 3-cyanopropyltrimethoxysilane (CPTMS) mixture (molar ratio 19/1) 3.47 previously mixed with the basic solution as a mixture of silica raw materials in a dry nitrogen stream. × 10 ⁻² mol was added. Thus, when the mixture of the silica raw material was added to the basic solution, precipitation of particles was observed within a few minutes, and the solution became cloudy. And after adding the mixture of the said silica raw material to the said basic solution, it stirred for about 8 hours, and left still overnight. Thereafter, the operation of filtering the product produced in the basic solution and redispersing in water was repeated twice, followed by drying overnight at a temperature of 45 ° C., and the surfactant was introduced into the silica. Porous particles were obtained.

  Next, 1 g of the porous particles obtained as described above was dispersed in 100 mL of ethanol, 1 mL of hydrochloric acid was added, and the mixture was stirred in an oil bath at 60 ° C. for 3 hours to extract the surfactant from the porous particles. . After the surfactant was extracted in this manner, the obtained particles were sufficiently washed with ethanol and dried at 45 ° C. to obtain a silica-based mesoporous material modified with a 3-cyanopropyl group.

  Next, 6.3 ml of 18 mol / L concentrated sulfuric acid (oxidant) and 3.7 ml of water were mixed and allowed to stand, and cooled to about 50 ° C., and obtained as described above. 0.5 g of a silica-based mesoporous material was added and heated to reflux at 100 ° C. for 6 hours to convert the cyano group introduced into the silica-based mesoporous material into a carboxyl group. The obtained particles were filtered and dried under a temperature condition of 45 ° C. to obtain a comparative spherical silica-based mesoporous material modified with a 3-propyl carboxyl group.

[Evaluation of characteristics of spherical silica-based mesoporous materials obtained in Examples 1 to 10 and Comparative Examples 1 to 6]
<Confirmation of organic group structure>
The structure of the organic group introduced into the porous body was confirmed by Raman spectrum measurement and FT-IR measurement.

<Measurement of pore structure by X-ray diffraction>
The regularity of the mesopore structure of the spherical silica-based mesoporous material obtained in Examples 1 to 10 and Comparative Examples 1 to 6 was measured using a Rigaku powder XRD apparatus RINT-2200. The obtained results are shown in Tables 1 and 2. Moreover, the X-ray-diffraction pattern of the spherical silica type mesoporous material obtained in Examples 1-2 and Comparative Example 1 is shown in FIG.

As is clear from the results shown in FIG. 1, peaks of (100), (110), (200) corresponding to the hexagonal arrangement of the pores are observed in all particles, and the regularity of the pores is high. confirmed. In addition, as is apparent from the results of the peak of d ₁₀₀ value shown in Tables 1 and 2, the spherical silica-based mesoporous materials obtained in Examples 1 to 10 and Comparative Examples 1 to 6 have regularity of pores. Was confirmed to be high.

<Measurement of particle morphology, average particle size and standard deviation>
The particle morphology was measured at an acceleration voltage of 19 eV using a scanning electron microscope (SEM) SIGMA-V manufactured by Akashi Seisakusho. And using the SEM photograph of each particle | grain of the spherical silica type mesoporous material obtained in Examples 1-10 and Comparative Examples 1-6, the diameter of 50 particle | grains is measured and an average particle diameter and a standard deviation are calculated. did. The obtained results are shown in Tables 1 and 2. Further, a scanning electron microscope (SEM) photograph of the spherical silica-based mesoporous material obtained in Example 1 is shown in FIG. 2, and a scanning electron microscope (SEM) photograph of the spherical silica-based mesoporous material obtained in Example 3 is shown. Is shown in FIG.

  As is apparent from the average particle diameter and standard deviation values shown in Tables 1 and 2 and the results shown in FIGS. 2 and 3, the spherical silica systems obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were used. It was confirmed that each particle of the mesoporous material was monodispersed spherical. From these results, in Examples 1 to 10, it was confirmed that a monodispersed spherical silica-based mesoporous material was obtained even when the first organic group and the second organic group were introduced.

<Measurement of specific surface area, central pore diameter and pore volume>
The N ₂ adsorption isotherm of the spherical silica-based mesoporous material obtained in Examples 1 to 10 and Comparative Examples 1 to 6 was subjected to a constant volume under the condition of liquid N ₂ temperature (77 K) using Belsorb-mini manufactured by Nippon Bell. Measured by the method. Before the measurement, the sample was vacuum degassed at 100 ° C. for 2 hours. Then, to calculate the pore volume from N ₂ adsorption isotherm obtained, to calculate the specific surface area by using further the BET adsorption isotherm equation. Furthermore, the central pore diameter was calculated from the obtained N ₂ adsorption isotherm by the BJH method. The obtained results are shown in Tables 1 and 2.

<Measurement of acid catalyst performance (functional group: sulfonic acid group)>
The spherical silica-based mesoporous material obtained in Examples 1-2 and Comparative Examples 1-2 and the amorphous silica-based mesoporous material obtained in Comparative Example 3 were used as catalysts for Friedel-Crafts alkylation reaction, respectively. The performance as an acidic catalyst was measured. That is, 60 mg of a catalyst was added to 0.6 g of 2-methylfuran and 1.39 ml of acetone, and the reaction was performed at a temperature of 50 ° C., and the product turnover after 1 hour, 2 hours, and 4 hours. Number was measured. A graph showing the relationship between the reaction time and the turnover number is shown in FIG. The turnover number was calculated by filtering the reaction mixture, removing the catalyst and washing with acetone, then performing GC-measurement of the resulting solution, quantifying the product. In addition, quantification was performed using a 2-methylfuran standard solution.

  As is clear from the results shown in FIG. 4, acid-catalyzed reaction hardly occurred in Comparative Example 2 (in which propyl group was introduced) containing no sulfonic acid group. Further, the spherical silica-based mesoporous material of the present invention (Example 1) in which an organic group containing a sulfonic acid group (first organic group) and a propyl group (second organic group) are introduced, and sulfonic acid The spherical silica-based mesoporous (Example 2) of the present invention in which an organic group containing a group (first organic group) and a phenyl group (second organic group) are introduced is an organic compound containing a sulfonic acid group. It was confirmed that the acid catalyst activity was sufficiently improved as compared with a spherical silica mesoporous (Comparative Example 1) as a comparison in which only a group was introduced. Further, the spherical silica mesoporous material of the present invention obtained in Example 1 had a turnover number about 1.6 times that of the comparative spherical silica mesoporous material obtained in Comparative Example 1. As a result, in the spherical silica-based mesoporous material of the present invention obtained in Example 1, since the hydrophobic propyl group was introduced, the hydrophobic 2-methylfuran as the substrate was pored. The present inventors presume that this is caused by the fact that the acid catalyzed reaction easily occurs due to the sulfonic acid group existing in the vicinity.

  Further, as is apparent from the results shown in FIG. 4, the amorphous silica-based mesoporous material (Comparative Example 3) into which an organic group containing a sulfonic acid group and a propyl group are introduced (Comparative Example 3) has some activity, Compared with the spherical silica-based mesoporous material of the present invention (Example 1) in which an organic group containing a sulfonic acid group and a propyl group were introduced, the acid catalyst activity was low. These results show that the spherical silica-based mesoporous material of the present invention has radial pores, so that the outer surface is small and the material is easily accessible, while the amorphous silica-based mesoporous material as a comparison is comparative. The present inventors presume that the porous body (Comparative Example 3) is caused by the fact that there are many outer surfaces and the access to the substance is limited.

<Measurement of basic catalyst performance (A) (functional group: 3-aminopropyl group)>
The spherical silica mesoporous materials obtained in Examples 3 to 6 and Comparative Example 4 were used as catalysts for the ester hydrolysis reaction, and the performance as a basic catalyst was measured. That is, 20 mg of the catalyst was added to a mixed solution of 300 μL of 0.1 M nitrophenol acetate solution (dissolved in DMSO) and 1200 μL of 10 mM Tris / HCl solution (pH 7.5), and shaken at room temperature, and the decomposition product p -The relationship between the amount of nitrophenol produced and the reaction time was measured. A graph showing the relationship between the reaction time and the concentration of p-nitrophenol is shown in FIG. The amount of p-nitrophenol produced was quantified by separating the catalyst from the reaction mixture by centrifugation and measuring the absorbance at 405 nm of the resulting supernatant.

  As is apparent from the results shown in FIG. 5, the 3-aminopropyl group (first organic group) was compared with the spherical silica-based mesoporous material (Comparative Example 4) in which only the 3-aminopropyl group was introduced. It was confirmed that the spherical silica-based mesoporous material of the present invention (Examples 3 to 6) in which the second organic group was introduced together with the group) sufficiently improved the catalyst performance. As a result, in the spherical silica mesoporous material of the present invention (Examples 3 to 6), since the hydrophobic organic group was introduced, the hydrophobic nitrophenol acetate serving as the substrate was contained in the pores. This is presumably due to the fact that a base-catalyzed reaction easily occurs with a 3-aminopropyl group present in the vicinity. In addition, when the spherical silica-based mesoporous materials obtained in Example 3 and Example 4 in which the introduction amount of the phenyl group as the second organic group is different are compared, the introduction amount of the phenyl group is increased twice. It was confirmed that the spherical silica-based mesoporous material obtained in Example 4 has higher catalyst performance. The present inventors presume that such a result is attributed to the fact that as the number of phenyl groups increases, the hydrophobicity becomes stronger and the substrate easily enters the pores.

<Measurement of basic catalyst performance (B) (functional group: N- (2-aminoethyl) -3-aminopropyl group)>
Except for using the spherical silica-based mesoporous material obtained in Examples 7 to 8 and Comparative Example 5 as a catalyst, the same method as the above-described measurement (A) of basic catalyst performance was adopted as a basic catalyst. The performance of was evaluated. A graph showing the relationship between the reaction time and the concentration of p-nitrophenol is shown in FIG.

  As is apparent from the results shown in FIG. 6, N as compared with the spherical silica-based mesoporous material (Comparative Example 5) in which only the N- (2-aminoethyl) -3-aminopropyl group was introduced was compared with N The spherical silica-based mesoporous material of the present invention (Examples 7 to 8) in which the second organic group is introduced together with the-(2-aminoethyl) -3-aminopropyl group (first organic group) has catalytic performance. It was confirmed that it was sufficiently improved. As a result, in the spherical silica-based mesoporous material of the present invention (Examples 7 to 8), the hydrophobic organic group was introduced, so that the hydrophobic nitrophenol acetate as the substrate was contained in the pores. The present inventors presume that this is caused by the fact that the base catalyzed reaction easily occurs at the N- (2-aminoethyl) -3-aminopropyl group present in the vicinity.

<Dye adsorption test (functional group: carboxylic acid group)>
The spherical silica-based mesoporous materials obtained in Examples 9 to 10 and Comparative Example 6 were used as samples, and the amount of dye adsorbed was measured. That is, 100 mL (1000 mg / L) of methylene blue was added to 0.1 g of each sample, shaken at 22 ° C. for 1 hour, filtered, and the absorbance of the resulting solution was measured at 291 nm. The adsorption amount of methylene blue was measured. The obtained results are shown in Table 3.

  As is clear from the results shown in Table 3, the organic group containing a carboxyl group (Comparative Example 6) compared to a spherical silica-based mesoporous material for comparison in which an organic group containing a carboxyl group was introduced (Comparative Example 6) The spherical silica-based mesoporous material (Examples 9 to 10) of the present invention in which the hydrophobic second organic group is introduced together with the first organic group) (Examples 9 to 10) sufficiently improves the amount of adsorption of the basic dye methylene blue. It was confirmed. As a result, in the spherical silica-based mesoporous material (Examples 9 to 10) of the present invention, since the second organic group was introduced, a highly hydrophobic dye (methylene blue) was added to the second organic group. The inventors presume that this is caused by selective incorporation by a group and chemical bonding to the first organic group present in the vicinity thereof.

  As described above, according to the present invention, when used as a catalyst or an adsorbent, it can exhibit a high selectivity for a substrate or an adsorbent, and exhibits a sufficiently high catalytic performance or adsorption performance. It is possible to provide a spherical silica-based mesoporous material that can be used, and a catalyst and an adsorbent using the same.

  Therefore, the spherical silica-based mesoporous material of the present invention is particularly useful as a material such as an acidic catalyst, a basic catalyst, or various dye adsorbents.

It is a graph which shows the X-ray-diffraction pattern of the spherical silica type mesoporous material obtained in Examples 1-2 and Comparative Example 1. 2 is a scanning electron microscope (SEM) photograph of the spherical silica-based mesoporous material obtained in Example 1. 4 is a scanning electron microscope (SEM) photograph of a spherical silica-based mesoporous material obtained in Example 3. It is a graph which shows the relationship between the reaction time at the time of using the spherical silica type mesoporous material obtained in Examples 1-2 and Comparative Examples 1-3 as an acidic catalyst, and a turnover number. It is a graph which shows the relationship between the reaction time at the time of using the spherical silica type mesoporous material obtained in Examples 3-6 and Comparative Example 4 as a basic catalyst, and the density | concentration of p-nitrophenol. It is a graph which shows the relationship between the reaction time at the time of using the spherical silica type mesoporous material obtained in Examples 7-8 and Comparative Example 5 as a basic catalyst, and the density | concentration of p-nitrophenol.

Claims (7)

Having an average particle diameter of 0.01 to 3 μm, radial pores having a central pore diameter of 1 to 10 nm, and
A first organic group having at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group and an amino group, and a group consisting of an aliphatic compound-based organic group and a cyclic compound-based organic group A spherical silica mesoporous material, wherein at least one selected second organic group is introduced.   The first organic group has a linear or branched hetero atom having 18 or less carbon atoms, or a hetero atom having 18 or less carbon atoms. The spherical silica-based mesoporous material according to claim 1, wherein the functional group is bonded to a good cyclic hydrocarbon group.   The first organic group is a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, a linear or branched chain Hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched chain Undecyl group, linear or branched dodecyl group, linear or branched tetradecyl group, linear or branched hexadecyl group, linear or branched octadecyl group, allyl group, vinyl group, At least one selected from the group consisting of phenyl group, alkylphenyl group, biphenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrimidyl group, quinolyl group, isoquinolyl group, imidazole group, indole group and purine group Based spherical mesoporous silica material according to claim 1 or 2, wherein the functional group is obtained by coupling.   The second organic group has an aliphatic compound-based organic group which may have a linear or branched heteroatom having 18 or less carbon atoms, and a heteroatom having 18 or less carbon atoms. The spherical silica-based mesoporous material according to any one of claims 1 to 3, which is at least one selected from the group consisting of cyclic compound-based organic groups that may be present. The second organic group is a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, a linear or branched chain Hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched chain Undecyl group, linear or branched dodecyl group, linear or branched tetradecyl group, linear or branched hexadecyl group, linear or branched octadecyl group, allyl group, vinyl group, Phenyl, alkylphenyl, biphenyl, naphthyl, cyclohexyl, pyridyl, pyrimidyl, quinolyl, isoquinolyl, imidazole, indole, purine, and
These groups include at least selected from the group consisting of hydroxyl group, carbonyl group, aldehyde group, imino group, cyano group, azo group, azide group, nitro group, thiol group, amide group, ureido group, ester group and ether group. A group to which an organic group having a functional group containing one kind of heteroatom is bonded;
The spherical silica-based mesoporous material according to claim 1, wherein the spherical silica-based mesoporous material is at least one selected from the group consisting of: A catalyst for use in a Friedel-Crafts alkylation reaction or an ester hydrolysis reaction, the catalyst comprising the spherical silica-based mesoporous material according to any one of claims 1 to 5. An adsorbent comprising the spherical silica-based mesoporous material according to any one of claims 1 to 5.