Ordered porous organic silica material and method for producing ordered porous organic silica material

Abstract

To provide a porous silica material having a structure including silicon atoms crosslinked by an acetylene linker.SOLUTION: An ordered porous organic silica material having a structure including a portion with silicon atoms crosslinked with each other by an acetylene linker, a portion with the silicon atoms bonded to each other via an oxygen atom, and an ethoxy group bonded to a silicon atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to ordered porous organosilica materials and methods for making ordered porous organosilica materials. [Background technology]

[0002] Porous silica materials are used in a variety of fields, including gas adsorption, solvent permeation, and catalysis. Research into the properties of porous silica materials, such as the state of the material, pore size, and pore wall regularity, is highly advanced. Among porous silica materials, those in which silicon atoms are bridged by organic linkers, resulting in a regular arrangement of pore and pore wall molecules, are called periodic mesoporous organosilica (PMO) materials. The properties of PMO materials, which combine the properties of the organic linkers with those of the porous silica materials mentioned above, are being extensively and in-depth researched.

[0003] Among the organic linkers that make up PMO materials, the ethane linker (Si-CH2-CH2-Si) and the ethylene linker (Si-CH=CH-Si) have particularly simple structures. Ethane and ethylene linkers have simple structures. Therefore, linker precursors with ethane and ethylene skeletons that can be used as raw materials for PMO materials are commercially available. For this reason, research on PMO materials crosslinked by ethane and ethylene linkers is also maturing.

[0004] Acetylene (HC≡CH) is the most basic molecule among compounds with a carbon-carbon triple bond. Therefore, the acetylene linker (Si-C≡C-Si) is an organic linker with a simple structure, similar to the ethane and ethylene linkers mentioned above. For this reason, linker precursors with an acetylene skeleton that can be used as raw materials for PMO materials are now commercially available.

[0005] Silica materials in which silicon atoms are crosslinked with each other by an acetylene linker include, for example, those described in Non-Patent Documents 1 to 3. These silica materials are used as permeable membranes. [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] T.Tsuru and co-workers,ACS Appl.Mater.Interfaces 2014,6,12,9357-9364. [Non-patent document 2] M. Kanezashi, T. Tsuru and co-workers, J. Membrane Sci.2019,584,15,56-65. [Non-patent document 3] M. Kanezashi and co-workers, Ind. Eng. Chem. Res. 2021, 60, 23, 8527-8537. Summary of the Invention [Problem to be solved by the invention]

[0007] However, conventional silica materials in which silicon atoms are crosslinked by acetylene linkers do not have pores, and there have been no ordered porous organic silica materials crosslinked by acetylene linkers.

[0008] The present invention has been made in view of the above circumstances, and has as its object to provide an ordered porous organosilica material having a structure in which silicon atoms are crosslinked by acetylene linkers. Another object of the present invention is to provide a method for producing an ordered porous organosilica material, which can produce an ordered porous organosilica material having a structure in which silicon atoms are crosslinked by acetylene linkers. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems and to produce an ordered porous organosilica material having a structure in which silicon atoms are crosslinked by acetylene linkers. However, surprisingly, even though acetylene-based linker precursors that can be used as raw materials for PMO materials are commercially available, using these instead of ethane- or ethylene-based linker precursors did not produce ordered porous organosilica materials with silicon atoms bridged by acetylene linkers. This is because the Csp-Si bond in the acetylene linker is very susceptible to cleavage, resulting in the acetylene linker being released during the production process.

[0010] Therefore, the present inventors have conducted extensive research into raw materials and production methods for an ordered porous organosilica material having a structure in which silicon atoms are crosslinked by acetylene linkers. As a result, the present inventors discovered that a precursor material having pores retaining the surfactant can be produced by using 1,2-bis(triethoxysilyl)acetylene ((C2H5O)3-Si-C≡C-Si-(C2H5O)3) as a raw material and adding the raw material to a first mixed solution comprising an aqueous acid solution of a specific acid concentration, with an acid dissociation constant pKa of 0 or less, and a specific nonionic surfactant and / or a specific surfactant, and reacting the raw material therewith. The precursor material thus produced has pores retaining the surfactant, and the resulting precursor material is dispersed in a second mixed solution comprising an alcohol and an aqueous acid solution with an acid dissociation constant pKa of 0 or less to form a dispersion, and the surfactant is eluted from the precursor material in the dispersion, thereby achieving the present invention. That is, the present invention relates to the following items.

[0011] [1] A portion in which silicon atoms are bridged by an acetylene linker; A portion where silicon atoms are bonded to each other via oxygen atoms; and an ethoxy group bonded to a silicon atom.

[0012] [2] The ordered porous organosilica material according to [1], having pores with a pore diameter of 2 nm to 50 nm. [3] Degree of ordered porosity 100 The ordered porous organosilica material according to [1], wherein the average particle size is 2.0 nm to 50 nm. [4] The specific surface area calculated by the BET method is 8.0 × 10 2 m 2 / g~1.5×10 3 m 2 / g of the ordered porous organosilica material according to [1].

[0013] [5] A first step of adding 1,2-bis(triethoxysilyl)acetylene to a first mixed solution comprising an acid aqueous solution having an acid dissociation constant pKa of 0 or less and a surfactant, wherein the acid concentration in the acid aqueous solution is 1 mol / L to 9 mol / L or less, and the surfactant is a nonionic surfactant having an unbranched linear polyethylene glycol skeleton and an alkyl group having a chain structure bonded to its terminal, and / or an ionic surfactant containing a quaternary ammonium salt, to thereby produce a precursor material having pores in which the surfactant is retained, by reacting the first mixed solution; a second step of dispersing the precursor material in a second mixed solution containing an alcohol and an aqueous acid solution having an acid dissociation constant pKa of 0 or less to form a dispersion, and eluting the surfactant from the precursor material in the dispersion.

[0014] [6] The method for producing an ordered porous organic silica material according to [5], wherein the acid aqueous solution contained in the first mixed solution has an acid dissociation constant pKa value of −15 or more. [7] The method for producing an ordered porous organic silica material according to [5], wherein the aqueous acid solution contained in the first mixed solution is one or more selected from an aqueous perchloric acid solution, an aqueous hydrochloric acid solution, and an aqueous sulfuric acid solution.

[0015] [8] The method for producing an ordered porous organic silica material according to [5], wherein the first mixed solution further contains a sodium salt or a lithium salt of the acid contained in the acid aqueous solution.

[0016] [9] The method for producing an ordered porous organic silica material according to [5], wherein the nonionic surfactant comprises one or more compounds selected from the group consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2):

[0017] [ka] (n in formula (1-1) 1 indicates the number of repeating units.) (n in formula (1-2) 2 indicates the number of repeating units.)

[0018]

[10] The method for producing an ordered porous organic silica material according to [5], wherein the 1,2-bis(triethoxysilyl)acetylene is added to the first mixed solution and reacted at a first temperature of 25°C to 50°C, and then the reaction solution is maintained at a second temperature of 60°C to 90°C and allowed to stand.

[0019]

[11] The method for producing an ordered porous organic silica material according to [5], wherein the acid aqueous solution contained in the second mixed solution has an acid dissociation constant pKa value of −15 or more.

[12] The method for producing an ordered porous organic silica material according to [5], wherein the aqueous acid solution contained in the second mixed solution is one or more selected from the group consisting of an aqueous hydrochloric acid solution, an aqueous trifluoromethanesulfonic acid solution, an aqueous perchloric acid solution, an aqueous sulfuric acid solution, and an aqueous nitric acid solution.

[13] The method for producing an ordered porous organic silica material according to [5], wherein the alcohol contained in the second mixed solution is one or more selected from ethanol, methanol, isopropyl alcohol, butanol, and trifluoroethanol. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide an ordered porous organosilica material having a structure including a portion in which silicon atoms are crosslinked by an acetylene linker, a portion in which silicon atoms are bonded via an oxygen atom, and an ethoxy group bonded to a silicon atom. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is an IR spectrum obtained by performing the measurement (1) on the organosilica material of Example 1. [Figure 2] FIG. 2 shows NMR spectra obtained in measurements (2) to (4) for the organosilica materials of Examples 1 to 3. [Figure 3] FIG. 3 shows NMR spectra obtained in measurements (2) to (4) for the organosilica materials of Examples 4 to 7. [Figure 4] FIG. 4 shows NMR spectra obtained in measurements (2) to (4) for the organosilica materials of Comparative Examples 1, 2, and 6. [Figure 5] FIG. 5 is a graph showing nitrogen adsorption / desorption isotherms prepared in the measurement (5) for the organosilica materials of Examples 1 to 7. [Figure 6] FIG. 6 is a graph showing nitrogen adsorption / desorption isotherms prepared in the measurement (5) for the organosilica materials of Comparative Examples 1 to 5. [Figure 7] FIG. 7 is a graph showing nitrogen adsorption / desorption isotherms prepared in the measurement (5) for the organosilica materials of Comparative Examples 6 to 10. [Figure 8] FIG. 8 shows X-ray diffraction spectra obtained by carrying out the measurement (6) on the organosilica materials of Examples 1 to 7. [Figure 9] FIG. 9 shows X-ray diffraction spectra obtained by performing the measurement (6) on the organosilica materials of Comparative Examples 1, 2, and 6. [Figure 10] FIG. 10 is a graph showing the relationship between the ratio of the number of pores with a specific pore size to the total number of pores in the organosilica material of Example 1 (number of pores with a specific pore size / total number of pores) and the pore size. [Figure 11] FIG. 11 is a micrograph of the organosilica material of Example 1 taken using a scanning electron microscope. DETAILED DESCRIPTION OF THE INVENTION

[0022] The ordered porous organic silica material and the method for producing the ordered porous organic silica material of the present invention are described in detail below. The scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present invention. Furthermore, when multiple upper and lower limit values ​​are specified for a specific parameter, any of these upper and lower limit values ​​can be combined to form a suitable numerical range.

[0023] <Ordered porous organic silica materials> The ordered porous organic silica material of this embodiment has a structure including a portion in which silicon atoms are crosslinked by an acetylene linker, a portion in which silicon atoms are bonded via an oxygen atom, and an ethoxy group bonded to a silicon atom.

[0024] The ordered porous organic silica material of this embodiment is an organic silica material having a structure including a portion where silicon atoms are crosslinked by an acetylene linker, a portion where silicon atoms are bonded via an oxygen atom, and an ethoxy group bonded to a silicon atom, when it satisfies all of the following requirements (1) to (4):

[0025] (1) In the IR spectrum obtained by ATR (Attenuated Total Reflection)-IR (Infrared Absorption Spectrometry) measurement of the ordered porous organosilica material, -1 ~2000cm -1 A peak indicating a carbon-carbon triple bond (C≡C) is observed in the nearby region.

[0026] (2) Solid-state characterization of ordered porous organosilica materials measured by CP / MAS (Cross Polarization (CP) and Magic Angle Spinning (MAS))-NMR (Nuclear Magnetic Resonance) method 13 In the C-NMR spectrum, a peak indicating that silicon atoms are bonded to each other via carbon-carbon triple bonds (Si-C≡C-Si) is observed at a chemical shift (δ) value of approximately 103 ppm, which is stronger than the peaks observed at chemical shift (δ) values ​​of approximately 94 ppm and 80 ppm, which indicate the presence of silicon atoms not bonded to carbon atoms (in other words, the cleavage of the structure in which silicon atoms are bonded to each other via carbon-carbon triple bonds).

[0027] (3) Ordered porous organosilica materials were measured by CP / MAS-NMR 13 In the C-NMR spectrum, peaks indicating the presence of ethoxy groups (—Si—O—C2H5) bonded to silicon atoms are observed at chemical shift (δ) values ​​of approximately 59 ppm and 16 ppm.

[0028] (4) Solid state analysis of ordered porous organosilica materials using CP / MAS-NMR 29 In the Si-NMR spectrum, a peak indicating that silicon atoms are bonded to each other via oxygen atoms (C≡C-Si-O-Si) is observed at a chemical shift (δ) value of approximately 92 ppm, which is stronger than the peak indicating the presence of silicon atoms not bonded to carbon atoms (in other words, the cleavage of the structure in which silicon atoms are bonded to each other via carbon-carbon triple bonds), which is observed at a chemical shift (δ) value of approximately 102 ppm.

[0029] Furthermore, whether the ordered porous organosilica material of this embodiment is porous and has pores with diameters of 2 nm to 50 nm can be confirmed by satisfying the following requirement (5). (5) The relationship between the relative pressure (P (nitrogen pressure at -173°C) / P0 (saturated vapor pressure of nitrogen at -173°C)) and the adsorption amount (cm) was created using the results of measuring the relationship between the nitrogen adsorption amount and pressure for 10 mg to 20 mg of ordered porous organosilica material at -173°C. 3 (STP)g -1 In the nitrogen adsorption / desorption isotherm, which shows the relationship between the adsorption amount and the vapor pressure, a constriction (a curve where the adsorption amount increases rapidly before reaching the saturated vapor pressure) is observed in the adsorption curve, indicating the presence of mesopores with pore diameters of 2 nm to 50 nm.

[0030] Furthermore, whether the ordered porous organosilica material of this embodiment is ordered porous can be confirmed by satisfying the following requirement (6). (6) In the X-ray diffraction spectrum obtained by powder X-ray diffraction measurement of the ordered porous organosilica material, a diffraction peak indicating the (100) plane is observed at a diffraction angle (2θ) of 0.4 deg to 5 deg.

[0031] The ordered porous organosilica material of this embodiment preferably has pores (mesopores) with a pore size of 2 nm to 50 nm. The average pore size of the pores in the ordered porous organosilica material of this embodiment is preferably 2 nm to 50 nm, and may be in the range of 2 nm to 10 nm. When the average pore size of the pores in the ordered porous organosilica material is 2 nm to 50 nm, the material can be produced with a good yield by the production method described below.

[0032] The average pore size of the pores in the ordered porous organosilica material of this embodiment is calculated by the following method. The relative pressure (P (nitrogen pressure at -173°C) / P0 (saturated vapor pressure of nitrogen at -173°C)) and adsorption amount (cm 3 (STP)g -1 ) and are analyzed and calculated using the non-localized density functional theory (NLDFT analysis method).

[0033] The ordered porous organosilica material of this embodiment has a degree of ordered porosity, d 100is preferably in the range of 2.0 nm to 50 nm, and more preferably in the range of 2 nm to 10 nm. 100 An ordered porous organosilica material having a particle size of 2.0 nm to 50 nm can be produced with a good yield by the production method described below.

[0034] In the ordered porous organosilica material of this embodiment, d indicates the degree of ordered porosity. 100 was calculated using the method shown below. The width of the diffraction peak representing the (100) plane in the X-ray diffraction spectrum obtained when confirming the above-mentioned requirement (6) is analyzed and calculated.

[0035] The ordered porous organosilica material of this embodiment has a specific surface area of ​​8.0 × 10 calculated by the BET method. 2 m 2 / g~1.5×10 3 m 2 / g, and preferably 9.0×10 2 m 2 / g~1.1×10 3 m 2 / g. 2 m 2 / g~1.5×10 3 m 2 The ordered porous organic silica material having a solubility of 1 / g can be produced with a high yield by the production method described below.

[0036] <Method for producing ordered porous organic silica materials> The method for producing an ordered porous organic silica material of this embodiment includes a first step of adding 1,2-bis(triethoxysilyl)acetylene ((C2H5O)3-Si-C≡C-Si-(C2H5O)3) to a first mixed solution containing an aqueous acid solution having an acid dissociation constant pKa of 0 or less and a surfactant, and reacting them to produce a precursor material having pores in which the surfactant is retained; and a second step of dispersing the precursor material in a second mixed solution containing an alcohol and an aqueous acid solution having an acid dissociation constant pKa of 0 or less to form a dispersion, and eluting the surfactant from the precursor material in the dispersion.

[0037] (1st step) In the first step, first, a first mixed solution is prepared. The first mixed solution can be produced by mixing an aqueous acid solution having an acid dissociation constant pKa of 0 or less, a surfactant, and a sodium salt or lithium salt of an acid contained in the aqueous acid solution, which may be contained as needed, using a known method, and stirring the mixture as needed using a known method.

[0038] The aqueous acid solution contained in the first mixed solution, which has an acid dissociation constant pKa of 0 or less, functions to promote a polymerization reaction in the first step in which silicon atoms in the 1,2-bis(triethoxysilyl)acetylene molecules bond with silicon atoms in other molecules via oxygen atoms (C≡C-Si-O-Si), while maintaining the (Si-C≡C-Si) structure in which silicon atoms in the 1,2-bis(triethoxysilyl)acetylene molecules are bonded with each other via carbon-carbon triple bonds.

[0039] The acid dissociation constant pKa value of the acid aqueous solution in this embodiment is a value listed in Evans' pKa Table (http: / / ccc.chem.pitt.edu / wipf / MechOMs / evans_pKa_table.pdf).

[0040] Because the acid dissociation constant pKa of the first mixed solution is 0 or less, the polymerization reaction in which silicon atoms in the 1,2-bis(triethoxysilyl)acetylene molecules are bonded to silicon atoms in other molecules via oxygen atoms (C≡C-Si-O-Si) can proceed sufficiently while suppressing cleavage of the structure in which silicon atoms in the 1,2-bis(triethoxysilyl)acetylene molecules are bonded to silicon atoms in other molecules via oxygen atoms (C≡C-Si-O-Si). This produces a precursor material in the first step that maintains the (Si-C≡C-Si) structure in which silicon atoms are bonded to each other via carbon-carbon triple bonds and also includes a portion in which silicon atoms are bonded to each other via oxygen atoms. Consequently, it is presumed that the ordered porous organosilica material of this embodiment, in which silicon atoms are crosslinked by acetylene linkers, can be produced by performing the second step described below.

[0041] Furthermore, it is preferable that the acid dissociation constant pKa of the aqueous acid solution contained in the first mixed solution is -15 or higher. When the acid dissociation constant pKa of the aqueous acid solution contained in the first mixed solution is -15 or higher, the function of the surfactant contained in the first mixed solution is fully exerted, and the precursor material generated in the first step has sufficient pores retaining the surfactant. As a result, by performing the second step described below, the ordered porous organic silica material of this embodiment having pores with pore diameters of 2 nm to 50 nm can be obtained.

[0042] The aqueous acid solution contained in the first mixed solution, which has an acid dissociation constant pKa of 0 or less, can be one or more selected from the group consisting of perchloric acid (pKa -10), hydrochloric acid (pKa -8), sulfuric acid (pKa -3), trifluoromethanesulfonic acid (pKa -14), nitric acid (pKa -1.3), methanesulfonic acid (pKa -2.6), and trifluoroacetic acid (pKa -0.25). Among these, the aqueous acid solution contained in the first mixed solution is preferably one or more selected from the group consisting of perchloric acid, hydrochloric acid, and sulfuric acid. By using these aqueous acids, the ordered porous organosilica material of this embodiment can be produced with high yield, while maintaining a (Si-C≡C-Si) structure in which silicon atoms are bonded to each other via carbon-carbon triple bonds and including a portion in which silicon atoms are bonded to each other via an oxygen atom.

[0043] The acid concentration in the aqueous acid solution contained in the first mixed solution, whose acid dissociation constant pKa is equal to or less than 0, is 1 mol / L to 9 mol / L. In this embodiment, when the first mixed solution contains two or more aqueous acid solutions, the acid concentration in the aqueous acid solution used in the first mixed solution is the acid concentration in the total of all the aqueous acid solutions contained in the first mixed solution.

[0044] Since the acid concentration in the acid aqueous solution used in the first mixed solution is 1 mol / L or more, the effect of including the acid aqueous solution in the first mixed solution can be sufficiently obtained.The acid concentration in the acid aqueous solution used in the first mixed solution is preferably 4 mol / L or more. Furthermore, since the acid concentration in the acid aqueous solution used in the first mixed solution is 9 mol / L or less, the function of the surfactant contained in the first mixed solution is fully exerted, and the precursor material generated in the first step has pores that retain the surfactant. As a result, by performing the second step described below, the ordered porous organic silica material of this embodiment having pores with pore diameters of 2 nm to 50 nm is obtained. The acid concentration in the acid aqueous solution contained in the first mixed solution is preferably 5 mol / L or less.

[0045] The volume ratio of the aqueous acid solution to 1,2-bis(triethoxysilyl)acetylene contained in the first mixed solution is preferably 20:1 to 80:1, and more preferably 30:1 to 60:1 (aqueous acid solution: 1,2-bis(triethoxysilyl)acetylene). When the volume ratio of the aqueous acid solution to 1,2-bis(triethoxysilyl)acetylene contained in the first mixed solution is within the above range, the ordered porous organic silica material of this embodiment can be produced with good yield.

[0046] The surfactant contained in the first mixed solution is a nonionic surfactant having an unbranched, straight-chain polyethylene glycol skeleton with a chain-like alkyl group bonded to the end, and / or an ionic surfactant containing a quaternary ammonium salt. The first mixed solution may contain only one type of surfactant, or two or more types of surfactants.

[0047] The surfactant contained in the first mixed solution contributes to the formation of pores in the ordered porous organosilica material of this embodiment. More specifically, the surfactant contained in the first mixed solution surrounds each 1,2-bis(triethoxysilyl)acetylene molecule in the first mixed solution to form a micellar structure. The 1,2-bis(triethoxysilyl)acetylene molecules bond together, resulting in a state surrounded by the 1,2-bis(triethoxysilyl)acetylene molecules. The surfactant surrounded by the 1,2-bis(triethoxysilyl)acetylene molecules forms a precursor material together with the bound 1,2-bis(triethoxysilyl)acetylene molecules, generating a precursor material having pores in which the surfactant is retained. The surfactant retained in the precursor material is eluted by performing the second step described below. It is presumed that this results in the formation of spaces that become pores in the ordered porous organosilica material.

[0048] The nonionic surfactant having an unbranched linear polyethylene glycol skeleton and an alkyl group having a chain structure bonded to the terminal may be one in which the alkyl group having a chain structure bonded to the terminal is directly bonded to the unbranched linear polyethylene glycol skeleton, or may be one in which the two are bonded via a divalent linking group. Examples of the divalent linking group include a phenylene group.

[0049] The number of carbon atoms in the unbranched, linear polyethylene glycol skeleton of the nonionic surfactant can be, for example, 5 to 200, and preferably 20 to 100. The number of carbon atoms in the chain alkyl group bonded to the terminal of the nonionic surfactant can be, for example, 8 to 30, and preferably 15 to 20.

[0050] Specifically, the nonionic surfactant preferably contains one or more selected from the compound represented by the following formula (1-1) and the compound represented by the following formula (1-2): When the nonionic surfactant contains one or more selected from the compound represented by the formula (1-1) and the compound represented by the following formula (1-2), a precursor material from which an ordered porous organic silica material having ordered porosity and pores with a pore size of 2 nm to 50 nm can be easily produced by carrying out the second step described below.

[0051] [ka] (n in formula (1-1) 1 indicates the number of repeating units.) (n in formula (1-2) 2 indicates the number of repeating units.)

[0052] n in the compound represented by formula (1-1) 1 indicates the number of repeating units. 1can be, for example, 5 to 100, and preferably 10 to 50. When the compound represented by formula (1-1) is contained as the nonionic surfactant, only one kind of the compound represented by formula (1-1) may be used, or n 1 Two or more types having different numbers of ions may be used. n in the compound represented by formula (1-2) 2 indicates the number of repeating units. 2 can be, for example, 5 to 100, and preferably 10 to 50. When the compound represented by formula (1-2) is contained as the nonionic surfactant, only one kind of the compound represented by formula (1-2) may be used, or n 2 Two or more types having different numbers of ions may be used.

[0053] The ionic surfactant may be any surfactant containing a quaternary ammonium salt. 21 H 46 NCl, C 22 H 48 NCl, C 19 H 44 NCl, C 16 H 36 NCl, C 21 H 46 NBr, C 21 H 46 It is preferable to use one or more selected from NI. These ionic surfactants have a sufficiently long linear alkyl chain, so that in the first step, they can easily form a micelle structure by surrounding the 1,2-bis(triethoxysilyl)acetylene molecules in the first mixed solution. Moreover, the above-mentioned ionic surfactants are less likely to cause unexpected side reactions due to counter anions. Therefore, when the above-mentioned ionic surfactants are used, by carrying out the second step described below, it is possible to easily produce a precursor material from which an ordered porous organic silica material having ordered porosity and pores with a pore diameter of 2 nm to 50 nm can be obtained. Among the above, C is an example of an ionic surfactant. 21 H 46 It is preferred to use NCl.

[0054] The surfactant is preferably contained in the first mixed solution at a concentration of 10 g / L to 50 g / L, more preferably 20 g / L to 30 g / L. When the concentration of the surfactant contained in the first mixed solution is 10 g / L or more, the effect of containing the surfactant in the first mixed solution can be fully obtained. When the concentration of the surfactant contained in the first mixed solution is 50 g / L or less, the surfactant contained in the first mixed solution can be completely dissolved in the first mixed solution, and the effect of containing the surfactant in the first mixed solution can be fully obtained.

[0055] The first mixed solution comprises an aqueous acid solution having an acid dissociation constant pKa of 0 or less and the surfactant, and may further contain a sodium salt or lithium salt of the acid contained in the aqueous acid solution in the first mixed solution, as necessary. Examples of the sodium salt or lithium salt of the acid contained in the aqueous acid solution include sodium perchlorate, lithium perchlorate, sodium chloride, and sodium sulfate.

[0056] When the first mixed solution contains a sodium salt or lithium salt of the acid contained in the acid aqueous solution, the polymerization reaction in which the silicon atom of the 1,2-bis(triethoxysilyl)acetylene molecule bonds with the silicon atom of another molecule via an oxygen atom (C≡C-Si-O-Si) is promoted. Therefore, the polymerization reaction proceeds more efficiently than when the acid aqueous solution does not contain a sodium salt or lithium salt of the acid, and the precursor material can be formed more efficiently. Furthermore, by performing the second step described below, a precursor material that can be used to obtain an ordered porous organosilica material with a smaller average pore size can be easily produced. The sodium salt or lithium salt of the acid contained in the acid aqueous solution is preferably a sodium salt, since it can produce a precursor material that can be used to obtain an ordered porous organosilica material with a clearer order.

[0057] The sodium salt or lithium salt of the acid contained in the acid aqueous solution is preferably contained in the first mixed solution at a concentration of 1 mol / L to 5 mol / L, more preferably 1 mol / L to 2 mol / L. When the concentration of the sodium salt or lithium salt of the acid contained in the acid aqueous solution in the first mixed solution is 1 mol / L or more, the effect of the first mixed solution containing the sodium salt or lithium salt of the acid contained in the acid aqueous solution can be fully obtained. When the concentration of the sodium salt or lithium salt of the acid contained in the acid aqueous solution in the first mixed solution is 5 mol / L or less, the sodium salt or lithium salt of the acid contained in the acid aqueous solution is less likely to remain in the ordered porous organic silica material, which is the target product, and is therefore preferred.

[0058] In the first step of this embodiment, 1,2-bis(triethoxysilyl)acetylene is added to the first mixed solution, and the mixture is stirred as necessary by a known method to cause a reaction, thereby producing a precursor material having pores in which the surfactant is retained. A known method can be used to add 1,2-bis(triethoxysilyl)acetylene to the first mixed solution. For example, a method can be used in which 1,2-bis(triethoxysilyl)acetylene is added to the stirred first mixed solution at a flow rate of 0.5 mL / hour to 2.0 mL / hour using a pump or the like.

[0059] In this embodiment, the time required to add 1,2-bis(triethoxysilyl)acetylene to the stirred first mixed solution can be appropriately determined depending on the composition of the first mixed solution, the ratio of the aqueous acid solution and 1,2-bis(triethoxysilyl)acetylene contained in the first mixed solution, the reaction temperature, and other factors. It can be, for example, 0.5 to 3 hours, and preferably 1 to 2 hours. When the time required to add 1,2-bis(triethoxysilyl)acetylene is 0.5 hours or longer, the first mixed solution and 1,2-bis(triethoxysilyl)acetylene are uniformly mixed, facilitating the production of a precursor material for an ordered porous organic silica material with clear regularity. Furthermore, when the time required to add 1,2-bis(triethoxysilyl)acetylene is 3 hours or shorter, the precursor material can be produced efficiently, resulting in improved productivity of the ordered porous organic silica material.

[0060] In this embodiment, in the first step, 1,2-bis(triethoxysilyl)acetylene is added to the first mixed solution while stirring, and the reaction is preferably carried out at a first temperature of 25°C to 50°C, more preferably at a first temperature of 40°C to 50°C. By carrying out the reaction at a first temperature of 25°C or higher in the first step, the aqueous acid solution contained in the first mixed solution functions effectively. As a result, the cleavage of the structure in which silicon atoms in 1,2-bis(triethoxysilyl)acetylene molecules are bonded by carbon-carbon triple bonds can be suppressed, while promoting a polymerization reaction in which silicon atoms in 1,2-bis(triethoxysilyl)acetylene molecules bond with silicon atoms in other molecules via oxygen atoms (C≡C-Si-O-Si), thereby efficiently producing the precursor material. Furthermore, carrying out the reaction at a first temperature of 50°C or lower in the first step is preferable because it facilitates uniform dissolution or dispersion of the surfactant and 1,2-bis(triethoxysilyl)acetylene in the first mixed solution and prevents unexpected decomposition reactions from occurring in the first step.

[0061] In the first step of this embodiment, it is preferable to add 1,2-bis(triethoxysilyl)acetylene to a stirred first mixed solution and react it at a first temperature of 25°C to 50°C, then stop stirring the reaction solution containing the generated precursor material, and keep the reaction solution at a second temperature of 60°C to 90°C and let it stand to react. By maintaining and allowing to react at a second temperature of 60°C or higher in the first step, a precursor material can be produced that will give a more uniformly formed ordered porous organosilica material with a clearer order and a greater number of pores (mesopores). A second temperature of 70°C or higher is more preferred. Furthermore, maintaining and allowing to react at a second temperature of 90°C or lower in the first step is also preferred, as this makes it less likely that an unexpected decomposition reaction will occur in the first step. A second temperature of 80°C or lower is more preferred.

[0062] In this embodiment, the reaction time for adding 1,2-bis(triethoxysilyl)acetylene to the stirred first mixed solution can be appropriately determined depending on the composition of the first mixed solution, the ratio of the aqueous acid solution and 1,2-bis(triethoxysilyl)acetylene contained in the first mixed solution, the reaction temperature, and the like, and can be, for example, 16 to 30 hours, preferably 20 to 24 hours. Setting the reaction time in the first step to 16 hours or longer allows the first mixed solution and 1,2-bis(triethoxysilyl)acetylene to react sufficiently. Setting the reaction time in the first step to 30 hours or less allows the precursor material to be produced efficiently, improving the productivity of the ordered porous organic silica material.

[0063] Furthermore, in the first step, after 1,2-bis(triethoxysilyl)acetylene is added to the stirred first mixed solution to react, the stirring of the reaction solution containing the generated precursor material is stopped and the reaction solution is maintained at the second temperature and allowed to stand. In this case, the reaction time (standing time) at the second temperature can be, for example, 16 to 30 hours, preferably 20 to 24 hours. By setting the reaction time at the second temperature to 16 hours or longer, a precursor material can be generated that can yield an ordered porous organic silica material with better pore distribution and pore regularity. Setting the reaction time at the second temperature to 30 hours or shorter is preferable because it can suppress the decomposition reaction of the precursor material.

[0064] In this embodiment, after the completion of Step 1, the precursor material produced in Step 1 may be washed as needed before carrying out Step 2. As a method for washing the precursor material, for example, a method can be used in which, after the completion of Step 1, water is added to a reaction solution containing the precursor material that has been cooled to room temperature, the solution is filtered, and the residue is washed with water.

[0065] (2nd process) In the second step, first, a second mixed solution is prepared. The second mixed solution can be produced by mixing an alcohol, an aqueous acid solution having an acid dissociation constant pKa of 0 or less, and other compounds that may be contained as needed using a known method, and stirring the mixture as needed using a known method.

[0066] The aqueous acid solution contained in the second mixed solution, which has an acid dissociation constant pKa of 0 or less, has the function of maintaining the structure of the precursor material and efficiently eluting the surfactant from the precursor material in the second step. The aqueous acid solution used in the second mixed solution and having an acid dissociation constant pKa of 0 or less can be, for example, the same aqueous acid solution as the aqueous acid solution that can be used in the first mixed solution and having an acid dissociation constant pKa of 0 or less. The aqueous acid solution contained in the first mixed solution and the aqueous acid solution contained in the second mixed solution may be the same or different.

[0067] The acid dissociation constant pKa of the aqueous acid solution contained in the second mixed solution is equal to or less than 0, so that the effect of maintaining the structure of the precursor material due to the inclusion of the aqueous acid solution in the second mixed solution is sufficiently obtained. Therefore, by carrying out the second step, the surfactant held in the precursor material can be eluted while maintaining the structure of the precursor material.

[0068] In this embodiment, the acid dissociation constant pKa of the aqueous acid solution contained in the second mixed solution is preferably -15 or higher. When the acid dissociation constant pKa of the aqueous acid solution contained in the second mixed solution is -15 or higher, the structure of the precursor material is maintained while the surfactant held in the precursor material can be efficiently extracted. As a result, by performing the second step, the ordered porous organic silica material of this embodiment can be easily obtained.

[0069] The aqueous acid solution contained in the second mixed solution and having an acid dissociation constant pKa of 0 or less is preferably one or more selected from the group consisting of an aqueous hydrochloric acid solution, an aqueous trifluoromethanesulfonic acid solution, an aqueous perchloric acid solution, an aqueous sulfuric acid solution, and an aqueous nitric acid solution. By using these aqueous acids, the surfactant can be efficiently eluted from the precursor material while maintaining the structure of the precursor material. As the aqueous acid solution contained in the second mixed solution and having an acid dissociation constant pKa of 0 or less, it is particularly preferable to use hydrochloric acid.

[0070] The acid concentration of the aqueous acid solution contained in the second mixed solution, which has an acid dissociation constant pKa of 0 or less, is preferably 5 mol / L to 15 mol / L. In this embodiment, when the second mixed solution contains two or more aqueous acid solutions, the acid concentration of the aqueous acid solution contained in the second mixed solution is the acid concentration in the total of the aqueous acid solutions contained in the second mixed solution.

[0071] When the acid concentration of the aqueous acid solution contained in the second mixed solution is 5 mol / L or more, the effect of the second mixed solution containing the aqueous acid solution can be sufficiently obtained. Furthermore, it is preferable that the acid concentration in the acid aqueous solution contained in the second mixed solution is 15 mol / L or less, since this makes it difficult for undesired hydrolysis of the precursor material and the final material to occur.

[0072] In the second step, the alcohol contained in the second mixed solution has the function of eluting the surfactant contained in the precursor material and removing the water contained in the precursor material. The alcohol contained in the second mixed solution is preferably one or more selected from the group consisting of ethanol, methanol, isopropyl alcohol, butanol, and trifluoroethanol. By using these alcohols, the surfactant can be efficiently eluted from the precursor material. As the alcohol contained in the second mixed solution, ethanol is particularly preferably used.

[0073] The alcohol contained in the second mixed solution and the aqueous acid solution having an acid dissociation constant pKa of 0 or less are contained in a volume ratio (alcohol:aqueous acid) of preferably 200:1 to 10:1, more preferably 150:1 to 15:1. When the ratio of alcohol to aqueous acid solution contained in the second mixed solution is 200:1 to 10:1, the surfactant can be efficiently eluted from the precursor material.

[0074] The second mixed solution may contain other compounds within the range that does not impair the properties of the second mixed solution, such as volatile organic solvents such as acetone, ethyl acetate, and diethyl ether.

[0075] In the second step of this embodiment, the precursor material produced in the first step is dispersed in a second mixed solution to form a dispersion, and the surfactant is eluted from the precursor material in the dispersion, thereby obtaining the ordered porous organosilica material of this embodiment. The second mixed solution used in the second step is preferably used in a ratio of 100 mL to 300 mL per gram of 1,2-bis(triethoxysilyl)acetylene used as the raw material. Using 100 mL or more of the second mixed solution per gram of raw material is preferable because it allows the surfactant to be sufficiently eluted from the precursor material produced in the first step. Furthermore, even if the amount of the second mixed solution used per gram of raw material exceeds 300 mL, the effect of eluting the surfactant from the precursor material remains unchanged, so it is preferable that the amount be 300 mL or less.

[0076] In the second step, the temperature at which the surfactant is eluted from the precursor material in the dispersion can be appropriately determined depending on the amount of the second mixed solution used, the time for eluting the surfactant from the precursor material, etc. The temperature at which the surfactant is eluted from the precursor material in the dispersion can be, for example, 60°C to 90°C, and preferably 70°C to 80°C. By setting the temperature at which the surfactant is eluted from the precursor material in the dispersion to 60°C or higher, the surfactant can be efficiently eluted from the precursor material. Furthermore, by setting the temperature at which the surfactant is eluted from the precursor material in the dispersion to 90°C or lower, the second mixed solution does not volatilize, preventing the surfactant from being difficult to elute from the precursor material, and the reaction that decomposes the ordered porous organic silica material can be suppressed.

[0077] In the second step, the time for eluting the surfactant from the precursor material in the dispersion can be appropriately determined depending on the amount of the second mixed solution used, the temperature at which the surfactant is eluted from the precursor material, and the like. The time for eluting the surfactant from the precursor material in the dispersion can be, for example, 180 to 960 minutes, and preferably 240 to 420 minutes. By setting the time for eluting the surfactant from the precursor material in the dispersion to 180 minutes or more, the surfactant in the precursor material can be sufficiently eluted. By setting the time for eluting the surfactant from the precursor material in the second step to 960 minutes or less, the reaction that decomposes the ordered porous organic silica material can be suppressed.

[0078] The second step in this embodiment may be repeated multiple times, as necessary, by removing the second mixed solution contained in the dispersion together with the surfactant dissolved in the dispersion and replacing it with unused second mixed solution. The following method can be used, for example, to remove the second mixed solution contained in the dispersion together with the surfactant dissolved in the dispersion and replace it with unused second mixed solution. That is, the dispersion after the first second step is filtered to remove the surfactant dissolved in the dispersion together with the second mixed solution. Thereafter, the precursor material that is the residue is washed with the alcohol used in producing the second mixed solution. Then, the washed precursor material is placed again in unused second mixed solution and dispersed to obtain a dispersion.

[0079] By performing the second step in this embodiment two or more times, the surfactant can be eluted from the precursor material to an extent equal to or greater than that when the second step is performed only once, even when any one or more conditions selected from the following are met: reducing the amount of the second mixed solution used, lowering the elution temperature, and shortening the elution time, compared to when the second step is performed only once. When the second step is carried out two or more times, the conditions such as the amount of the second mixed solution used, the elution temperature, and the elution time may all be the same as those in the first second step, or some or all of them may be different.

[0080] In this embodiment, after performing the second step once or multiple times, it is preferable to remove the second mixed solution contained in the dispersion together with the surfactant dissolved in the dispersion, and then vacuum-dry the resulting powder, thereby separating the ordered porous organic silica material from the dispersion.

[0081] According to the method for producing the ordered porous organic silica material of this embodiment, it is possible to produce the ordered porous organic silica material of this embodiment, which has a structure including a portion where silicon atoms are crosslinked by an acetylene linker, a portion where silicon atoms are bonded via an oxygen atom, and an ethoxy group bonded to a silicon atom. The ordered porous organosilica material of this embodiment can be suitably used in a variety of applications, such as gas separation, solvent permeable membranes, catalyst supports, and porous glass precursors. [Example]

[0082] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0083] [Examples 1 to 11, Comparative Examples 1 to 10] (1st step) 80 mL of an acid aqueous solution having an acid concentration shown in Table 1 or Table 2, a salt shown in Table 1 or Table 2, 2.0 g of a surfactant shown in Table 1 or Table 2, and a stirrer were placed in a 300 mL recovery flask and stirred at 45°C for 16 hours to obtain a first mixed solution having a salt concentration shown in Table 1 or Table 2 of 0.14 mmol.

[0084] 1,2-bis(triethoxysilyl)acetylene (BTESA) (manufactured by Gelest) was loaded into a 12 mm inner diameter, 5 mL syringe (manufactured by Terumo). 2.8 mL of 1,2-bis(triethoxysilyl)acetylene was added to the stirred first mixed solution at a flow rate of 1.0 mL / hour using a syringe pump, and the mixture was stirred continuously at a temperature of 45°C for 24 hours to react and produce a precursor material. Then, stirring of the reaction solution containing the precursor material was stopped, and the reaction solution was maintained at a second temperature of 90°C and allowed to stand for 24 hours, completing the first step. After the first step was completed, 80 mL of water was added to the reaction solution containing the precursor material that had been air-cooled to room temperature, and the mixture was filtered using a Kiriyama funnel. The residue was washed with water to obtain a precursor material consisting of a white powder.

[0085] [Table 1]

[0086] [Table 2]

[0087] The surfactants in Tables 1 and 2 are as follows: Brij (registered trademark) S10 (compound represented by formula (1-1), number average molecular weight (Mn) 700, manufactured by Sigma-Aldrich) Triton X-100 (compound represented by formula (1-2), number average molecular weight (Mn) 647, manufactured by Sigma-Aldrich) IGEPAL (registered trademark) CA-630 (compound represented by formula (1-2), number average molecular weight (Mn) 603, manufactured by Sigma-Aldrich) C 21 H 46 NCl (molecular weight 348.06, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0088] Pluonic P123 (a compound represented by the following formula (1-3), number average molecular weight (Mn) 5800, manufactured by Sigma-Aldrich) Tween 80 (a compound represented by the following formula (1-4), number average molecular weight (Mn) 1310, manufactured by Tokyo Chemical Industry Co., Ltd.) PEG600 (a compound represented by the following formula (1-5), number average molecular weight (Mn) 600, manufactured by Tokyo Chemical Industry Co., Ltd.) C 14 SO3Na (compound represented by the following formula (1-6), weight average molecular weight (Mw) 300.43, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0089] [ka] (In formula (1-3), x, y, and z represent the number of repeating units.) (In formula (1-4), x, y, z, and w represent the number of repeating units.) (n in formula (1-5) represents the number of repeating units.)

[0090] (2nd process) A second mixed solution was prepared containing an alcohol shown in Table 1 or Table 2 and an aqueous acid solution having an acid concentration shown in Table 1 or Table 2, in the volume ratio shown in Table 1 or Table 2. The precursor material produced in the first step was then placed in 200 mL of the second mixed solution and dispersed to form a dispersion, which was then stirred at a temperature of 80°C for 6 hours, thereby carrying out a first second step in which the surfactant was eluted from the precursor material.

[0091] Thereafter, the second mixed solution contained in the dispersion was removed together with the surfactant dissolved in the dispersion by the method described below, and replaced with unused second mixed solution. That is, the dispersion after the first second step was filtered to remove the surfactant dissolved in the dispersion together with the second mixed solution. Then, the precursor material, which was the residue, was washed with the alcohol used in producing the second mixed solution. Then, the washed precursor material was again dispersed in 200 mL of unused second mixed solution to obtain a dispersion.

[0092] Thereafter, similarly to the first second step, the dispersion was stirred at a temperature of 80° C. for 6 hours to carry out a second second step for eluting the surfactant from the precursor material. The dispersion after the second step was then filtered to remove the second mixed solution contained in the dispersion together with the surfactant dissolved in the dispersion, and the resulting powder was vacuum dried for 4 hours to produce the organic silica materials of Examples 1 to 11 and Comparative Examples 1 to 10.

[0093] The organic silica materials thus obtained in Examples 1 to 11 and Comparative Examples 1 to 10 were subjected to the following measurements (1) to (6) and evaluated based on the following criteria. The results are shown in Tables 3 and 4 and in Figures 1 to 9.

[0094] [Table 3]

[0095] [Table 4]

[0096] (1) In the IR spectrum obtained by performing ATR (attenuated total reflection measurement)-IR (infrared absorption spectroscopy) measurement using a total reflection infrared absorption measurement device (product name: ALPHA II ULTRA, manufactured by Bruker), the wavelength of 2260 cm -1 ~2000cm -1 If a peak indicating a carbon-carbon triple bond (C≡C) was observed in the nearby region, it was evaluated as "present," and if not, it was evaluated as "absent."

[0097] (2) Solid state measurements by CP / MAS (cross polarization / magic angle spinning)-NMR (nuclear magnetic resonance) using a nuclear magnetic resonance spectrometer (product name: Avance 400WB, manufactured by Bruker). 13 In the C-NMR spectrum, when a peak (hereinafter referred to as "peak A") was observed at a chemical shift (δ) value of approximately 103 ppm, which is stronger than the peaks indicating the presence of silicon atoms not bonded to carbon atoms (in other words, the cleavage of the structure in which silicon atoms are bonded to each other by a carbon-carbon triple bond), and which indicates that silicon atoms are bonded to each other by a carbon-carbon triple bond (Si-C≡C-Si), the peak was evaluated as "present," and when it was not observed, the peak was evaluated as "absent."

[0098] (3) Measurement was performed by CP / MAS-NMR using a nuclear magnetic resonance spectrometer (product name: Avance 400WB, manufactured by Bruker). 13 In the C-NMR spectrum, peaks indicating the presence of ethoxy groups (-Si-O-C2H5) bonded to silicon atoms (hereinafter referred to as "E peaks") were observed at chemical shift (δ) values ​​of approximately 59 ppm and 16 ppm, and were evaluated as "present" when they were observed, and "absent" when they were not observed.

[0099] (4) Solid state measurements were performed by CP / MAS-NMR using a nuclear magnetic resonance spectrometer (product name: Avance 400WB, manufactured by Bruker). 29 In the Si-NMR spectrum, a peak is observed at a chemical shift (δ) value of approximately 102 ppm, indicating the presence of silicon atoms not bonded to carbon atoms. 3 The peak "T" is a peak that is stronger than the "T" peak, and is located at a chemical shift (δ) value of about 92 ppm, indicating that silicon atoms are bonded to each other via oxygen atoms (C≡C-Si-O-Si). 3 When the peak was observed, it was evaluated as "present", and when it was not observed, it was evaluated as "absent".

[0100] (5) For 10 mg to 20 mg of organic silica material, the relationship between the amount of nitrogen adsorption and pressure at a temperature of -173°C was measured using a nitrogen adsorption / desorption measuring device (trade name: BELSORP MAX-II, manufactured by Microtrac-Bell). Using the results, the relationship between the relative pressure (P (nitrogen pressure at a temperature of -173°C) / P0 (saturated vapor pressure of nitrogen at a temperature of -173°C)) and the amount of adsorption (cm 3 (STP)g -1 In the obtained nitrogen adsorption / desorption isotherms, if a curve (a characteristic curve (neck)) in which the amount of adsorption rapidly increases before reaching saturated vapor pressure, indicating the presence of mesopores with pore diameters of 2 nm to 50 nm, was observed in the adsorption curve, it was evaluated as "present," and if not, it was evaluated as "absent."

[0101] (6) In the X-ray diffraction spectrum obtained by powder X-ray diffraction measurement using an X-ray diffractometer (product name: AXS D8 Advance diffractometer, manufactured by Bruker), if a diffraction peak indicating the (100) plane was observed at a diffraction angle (2θ) of 0.4 deg to 5 deg, it was evaluated as “present,” and if not, it was evaluated as “absent.”

[0102] In addition, for the organic silica materials of Examples 1 to 11 and Comparative Examples 1 to 10, the specific surface area was calculated by the BET method, and the d was calculated by analyzing the width of the diffraction peak representing the (100) plane in the X-ray diffraction spectrum obtained using an X-ray diffractometer (product name: AXS D8 Advance diffractometer, manufactured by Bruker) in the measurement of (6) above. 100 The results are shown in Tables 3 and 4. In Table 4, d 100 "n / a" indicates that analysis was not possible or that the data was not observed.

[0103] In addition, for the organic silica materials of Examples 1 to 6, 8, and 9, and Comparative Examples 1 to 10, the relative pressure (P (nitrogen pressure at a temperature of -173°C) / P0 (saturated vapor pressure of nitrogen at a temperature of -173°C)) and the adsorption amount (cm 3 (STP)g -1 ) and the average pore diameter of the pores calculated by analyzing them using the non-localized density functional theory (NLDFT analysis method) were measured. These results are shown in Tables 3 and 4. In Table 4, "n / a" listed for the average pore diameter indicates that analysis was not possible or that it was not observed.

[0104] In addition, for the organic silica materials of Examples 7, 8, and 9, the relative pressure (P (nitrogen pressure at a temperature of -173°C) / P0 (saturated vapor pressure of nitrogen at a temperature of -173°C)) and the adsorption amount (cm 3 (STP)g -1 The analysis was performed using a computer simulation method (GCMC method) in which hardware such as a CPU (Central Processing Unit) inputs a signal from the pores and executes a program (BELMaster), and the average pore diameter of each pore was calculated. These results are shown in Tables 3 and 4. In Table 4, "n / a" next to the average pore diameter indicates that analysis was not possible or that it was not observed.

[0105] As shown in Table 3, the organic silica materials of Examples 1 to 11 were all evaluated as "Yes" in the measurements (1) to (6). This confirmed that the organic silica materials of Examples 1 to 11 were all ordered porous organic silica materials having a structure including a portion where silicon atoms are crosslinked by an acetylene linker, a portion where silicon atoms are bonded via an oxygen atom, and an ethoxy group bonded to a silicon atom, and having mesopores with pore diameters of 2 nm to 50 nm.

[0106] Furthermore, as shown in Table 3, all of the organic silica materials of Examples 1 to 11 had a degree of ordered porosity, d 100 The specific surface area calculated by the BET method is 8.0 × 10 2 m 2 / g~1.5×10 3 m 2 / g, which indicated that the material was a useful ordered porous organosilica material.

[0107] In contrast, as shown in Table 4, the organic silica materials of Comparative Examples 1 and 2, which used a first mixed solution containing a salt other than the sodium salt or lithium salt of the acid contained in the acid aqueous solution, Comparative Example 3, which used a first mixed solution containing no surfactant, Comparative Examples 4, 5, 9, and 10, which used a nonionic surfactant having a polyethylene glycol skeleton with a linear unbranched structure and an alkyl group with a chain structure attached to the end, and / or a surfactant that is not an ionic surfactant containing a quaternary ammonium salt, and Comparative Examples 7 and 8, in which the acid concentration in the acid aqueous solution was more than 5 mol / L, all received an evaluation of "none" in the measurement of (5), and did not have mesopores.

[0108] Furthermore, as shown in Table 4, in the organic silica material of Comparative Example 6, in which an acid aqueous solution having an acid dissociation constant pKa value of more than 0 was used in the first step, no peak of A was observed, and the evaluation of the measurement of (2) was "None", indicating that the silicon atoms were not bonded to each other by carbon-carbon triple bonds. 3 The peak of Q 3 The peak intensity was not higher than that of the peak of

[0109] FIG. 1 is an IR spectrum obtained by performing the measurement (1) on the organosilica material of Example 1. As shown in FIG. 1, the organic silica material of Example 1 emits light at a wavelength of 2260 cm -1 ~2000cm -1 A peak indicating a carbon-carbon triple bond (C≡C) was observed in the nearby region.

[0110] Figure 2 shows NMR spectra obtained in measurements (2) to (4) for the organosilica materials of Examples 1 to 3. Figures 2(a) and 2(b) show NMR spectra for Example 1. Figures 2(c) and 2(d) show NMR spectra for Example 2. Figures 2(e) and 2(f) show NMR spectra for Example 3. FIG. 3 shows NMR spectra obtained in measurements (2) to (4) for the organosilica materials of Examples 4 to 7. FIGS. 3(g) and 3(h) show NMR spectra for Example 4. FIGS. 3(i) and 3(j) show NMR spectra for Example 5. FIGS. 3(k) and 3(l) show NMR spectra for Example 6. FIGS. 3(m) and 3(n) show NMR spectra for Example 7. (a)(c)(e) in Figure 2 and (g)(i)(k)(m) in Figure 3 are solid 13 1C-NMR spectrum. (b)(d)(f) in Fig. 2 and (h)(j)(l)(n) in Fig. 3 are solid 29 This is a Si-NMR spectrum.

[0111] As shown in FIGS. 2 and 3, the organic silica materials of Examples 1 to 7 were all solid. 13 In the C-NMR spectrum, a peak A was observed, which indicates that silicon atoms are bonded to each other by carbon-carbon triple bonds (Si-C≡C-Si), and a peak E was observed, which indicates that ethoxy groups (-Si-O-C2H5) are bonded to silicon atoms. Furthermore, as shown in Figures 2 and 3, for the organic silica materials of Examples 1 to 7, the solid 29In the Si-NMR spectrum, Q indicates the presence of silicon atoms that are not bonded to carbon atoms. 3 The T peak is stronger than the T peak, which indicates that silicon atoms are bonded to each other via oxygen atoms (C≡C-Si-O-Si). 3 A peak was observed.

[0112] FIG. 4 shows NMR spectra obtained in measurements (2) to (4) for the organic silica materials of Comparative Examples 1, 2, and 6. FIGS. 4(a) and 4(b) show the NMR spectra of Comparative Example 1. FIGS. 4(c) and 4(d) show the NMR spectra of Comparative Example 2. FIGS. 4(e) and 4(f) show the NMR spectra of Comparative Example 6. In FIG. 4, (a), (c), and (e) are the NMR spectra of the solid 13 4. (b) (d) (f) in Fig. 4 are the solid C-NMR spectra. 29 This is a Si-NMR spectrum.

[0113] As shown in FIG. 4, the organic silica materials of Comparative Examples 1 and 2, like the organic silica materials of Examples 1 to 7, exhibited a solid 13 In the C-NMR spectrum, peaks A and E were observed, indicating that the solid 29 Q in Si-NMR spectrum 3 T 3 A peak was observed.

[0114] However, in the case of the organic silica material of Comparative Example 6, in which an aqueous solution of phosphoric acid was used as the aqueous acid solution, as shown in FIG. 13 In the C-NMR spectrum, the E peak was observed, but the A peak was not observed. In addition, the organic silica material of Comparative Example 6 was solidified as shown in FIG. 29 In the Si-NMR spectrum, T indicates that silicon atoms are bonded to each other via oxygen atoms (C≡C-Si-O-Si). 3 The peak at Q indicates the presence of silicon atoms that are not bonded to carbon atoms. 3 The peak intensity was weaker than that of the

[0115] Fig. 5 is a graph showing nitrogen adsorption / desorption isotherms created in the measurement (5) for the organic silica materials of Examples 1 to 7. In Fig. 5, (a) is the graph for Example 1, (b) is the graph for Example 2, (c) is the graph for Example 3, (d) is the graph for Example 4, (e) is the graph for Example 5, (f) is the graph for Example 6, and (g) is the graph for Example 7. As shown in FIG. 5, for all of the organic silica materials of Examples 1 to 7, the amount of adsorption rapidly increased before reaching the saturated vapor pressure in the adsorption curve, indicating that the materials had mesopores with pore diameters of 2 nm to 50 nm, and a curve with hysteresis (a characteristic curve) was observed in which the adsorption curve and the desorption curve did not match.

[0116] Fig. 6 is a graph showing nitrogen adsorption / desorption isotherms prepared in the measurement (5) for the organic silica materials of Comparative Examples 1 to 5. In Fig. 6, (a) is the graph for Comparative Example 1, (b) is the graph for Comparative Example 2, (c) is the graph for Comparative Example 3, (d) is the graph for Comparative Example 4, and (e) is the graph for Comparative Example 5. Fig. 7 is a graph showing nitrogen adsorption / desorption isotherms prepared in the measurement (5) for the organic silica materials of Comparative Examples 6 to 10. In Fig. 7, (f) is the graph for Comparative Example 6, (g) is the graph for Comparative Example 7, (h) is the graph for Comparative Example 8, (i) is the graph for Comparative Example 9, and (j) is the graph for Comparative Example 10.

[0117] As shown in FIG. 7, for the organic silica material of Comparative Example 6, a characteristic curve was observed, which indicates that the organic silica material has mesopores with pore diameters of 2 nm to 50 nm, similar to the organic silica materials of Examples 1 to 7. However, as shown in FIGS. 6 and 7, for the organosilica materials of Comparative Examples 1 to 5 and 7 to 10, no characteristic curve indicating the presence of mesopores with pore diameters of 2 nm to 50 nm was observed.

[0118] Fig. 8 shows X-ray diffraction spectra obtained by performing the measurement (6) on the organic silica materials of Examples 1 to 7. In Fig. 8, (a) is the X-ray diffraction spectrum of Example 1, (b) is the X-ray diffraction spectrum of Example 2, (c) is the X-ray diffraction spectrum of Example 3, (d) is the X-ray diffraction spectrum of Example 4, (e) is the X-ray diffraction spectrum of Example 5, (f) is the X-ray diffraction spectrum of Example 6, and (g) is the X-ray diffraction spectrum of Example 7. As shown in FIG. 8, for all of the organosilica materials of Examples 1 to 7, a diffraction peak indicating the (100) plane was observed in the X-ray diffraction spectrum at a diffraction angle (2θ) of 0.4 degrees to 5 degrees.

[0119] 9 shows X-ray diffraction spectra obtained by performing measurement (6) on the organosilica materials of Comparative Examples 1, 2, and 6. In FIG. 9, (a) is the X-ray diffraction spectrum of Comparative Example 1, (b) is the X-ray diffraction spectrum of Comparative Example 2, and (c) is the X-ray diffraction spectrum of Comparative Example 6. As shown in FIG. 9, for the organosilica material of Comparative Example 6, similar to the organosilica materials of Examples 1 to 7, a diffraction peak indicating the (100) plane was observed in the X-ray diffraction spectrum. However, as shown in FIG. 9, for the organosilica materials of Comparative Examples 1 and 2, no diffraction peak indicating the (100) plane was observed in the X-ray diffraction spectrum.

[0120] Fig. 10 is a graph showing the relationship between the ratio of the number of pores with a specific pore size to the total number of pores in the organic silica material of Example 1 (number of pores with a specific pore size / total number of pores) and the pore size. Fig. 10 shows the relationship between the relative pressure (P (nitrogen pressure at a temperature of -173°C) / P0 (saturated vapor pressure of nitrogen at a temperature of -173°C)) and the adsorption amount (cm 3 (STP)g -1 ) and the graph was calculated by analysis using the non-localized density functional theory (NLDFT analysis method). From FIG. 10, it was confirmed that the average pore size of the pores in the organosilica material of Example 1 was 4.1 nm.

[0121] FIG. 11 is a micrograph of the organic silica material of Example 1 taken using a field emission scanning electron microscope (SEM, product name: S-4800, manufactured by Hitachi High-Technologies Corporation) at an accelerating voltage of 3 kV and a magnification of 5000 times. As shown in FIG. 11, it was confirmed that the organosilica material of Example 1 had a spherical amorphous structure.

Claims

1. a portion in which silicon atoms are bridged by an acetylene linker; A portion where silicon atoms are bonded to each other via oxygen atoms; and an ethoxy group bonded to a silicon atom.

2. 2. The ordered porous organosilica material according to claim 1, having pores with a pore diameter of 2 nm to 50 nm.

3. Degree of ordered porosity d １００ 2. The ordered porous organosilica material according to claim 1, wherein the average particle size is 2.0 nm to 50 nm.

4. The specific surface area calculated by the BET method is 8.0 × 10 ２ m ２ / g to 1.5 x 10 ３ m ２ / g.

5. a first step of adding 1,2-bis(triethoxysilyl)acetylene to a first mixed solution comprising an acid aqueous solution having an acid dissociation constant pKa of 0 or less and a surfactant, the acid concentration in the acid aqueous solution being 1 mol / L to 9 mol / L, and the surfactant being a nonionic surfactant having an unbranched linear polyethylene glycol skeleton with an alkyl group having a chain structure bonded to its terminal, and / or an ionic surfactant containing a quaternary ammonium salt, thereby generating a precursor material having pores in which the surfactant is retained, by reacting the first mixed solution with the polyethylene glycol skeleton having an unbranched linear polyethylene glycol skeleton and an alkyl group having a chain structure bonded to its terminal; a second step of dispersing the precursor material in a second mixed solution containing an alcohol and an aqueous acid solution having an acid dissociation constant pKa of 0 or less to form a dispersion, and eluting the surfactant from the precursor material in the dispersion.

6. 6. The method for producing an ordered porous organic silica material according to claim 5, wherein the acid aqueous solution contained in the first mixed solution has an acid dissociation constant pKa value of −15 or more.

7. 6. The method for producing an ordered porous organic silica material according to claim 5, wherein the aqueous acid solution contained in the first mixed solution is one or more selected from the group consisting of an aqueous perchloric acid solution, an aqueous hydrochloric acid solution, and an aqueous sulfuric acid solution.

8. The method for producing an ordered porous organosilica material according to claim 5 , wherein the first mixed solution further contains a sodium salt or a lithium salt of the acid contained in the acid aqueous solution.

9. The method for producing an ordered porous organic silica material according to claim 5, wherein the nonionic surfactant comprises one or more compounds selected from the group consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2): 【Chemical 1】 (n in formula (1-1) １ indicates the number of repeating units.) (n in formula (1-2) ２ indicates the number of repeating units.)

10. 6. The method for producing an ordered porous organic silica material according to claim 5, wherein the 1,2-bis(triethoxysilyl)acetylene is added to the first mixed solution and reacted at a first temperature of 25°C to 50°C, and then the reaction solution is maintained and left to stand at a second temperature of 60°C to 90°C.

11. 6. The method for producing an ordered porous organic silica material according to claim 5, wherein the acid aqueous solution contained in the second mixed solution has an acid dissociation constant pKa value of −15 or more.

12. 6. The method for producing an ordered porous organic silica material according to claim 5, wherein the aqueous acid solution contained in the second mixed solution is one or more selected from the group consisting of an aqueous hydrochloric acid solution, an aqueous trifluoromethanesulfonic acid solution, an aqueous perchloric acid solution, an aqueous sulfuric acid solution, and an aqueous nitric acid solution.

13. 6. The method for producing an ordered porous organic silica material according to claim 5, wherein the alcohol contained in the second mixed solution is one or more selected from the group consisting of ethanol, methanol, isopropyl alcohol, butanol, and trifluoroethanol.

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