JP2009265047A - Solid-liquid contact device and separation medium by hierarchical porous body containing mesopore having long-range order - Google Patents

Abstract

The present invention manufactures inorganic and organic-inorganic hybrid porous materials having precisely controlled macropores in addition to mesopores with controlled narrow pore size distribution and regularity and shape over long distances. It is an object of the present invention to provide a new manufacturing method that can be used.
In the present invention, an amphiphilic substance as a template component is dissolved in an aqueous solution containing a sol-gel reaction catalyst component, and an inorganic low molecular compound or an organic inorganic low molecular compound having a hydrolyzable functional group is added thereto. From the starting solution obtained, a gel containing a solvent-rich phase that becomes macropores is prepared by a sol-gel method, and then the solvent is removed by drying, and the template component is further removed by thermal decomposition or the like.
[Selection] Figure 1

Description

  The present invention relates to a liquid-flowing device that can be used as a solid-liquid contact medium and various modes of liquid chromatography separation media using a material composed of inorganic and organic-inorganic hybrid porous materials as a stationary phase. The production method and product of the present invention include a chromatographic separation column, a medium for separating blood and plasma components, an adsorption medium for a hygroscopic agent, a low molecular adsorption medium such as deodorant, or a porous body for an enzyme carrier and a catalyst carrier. It is suitably used as a production method and a product thereof.

As porous materials used for the above-mentioned applications, those made of organic polymers such as styrene / divinylbenzene copolymer, those made of inorganic materials such as silica gel, and more recently, It is well known that a part thereof is substituted with an organic-inorganic hybrid containing a bond between a metal atom and a carbon atom. Generally, these porous materials are formed into fine particles and then packed into a column for use.
A column made of an organic material has problems such as low pressure resistance due to low strength, swelling / shrinkage with a solvent, and inability to sterilize by heating. Therefore, especially when trying to increase productivity by operation at high temperature and high pressure, inorganic materials that do not have such difficulties, particularly silica gel, are widely used.

In general, an inorganic porous material such as silica gel is produced by a sol-gel method which is a liquid phase reaction. In the sol-gel method, an inorganic low molecular weight compound having a hydrolyzable functional group is used as a starting material, and finally an inorganic low molecular weight is obtained by a sol-gel reaction, that is, hydrolysis and subsequent polymerization (polycondensation) reaction. A general method for obtaining an aggregate or polymer mainly composed of a metal oxide from a compound. Metal alkoxides are the most well-known inorganic low-molecular compounds used as starting materials. In addition, metal salts having hydrolyzable functional groups such as metal chlorides, nitrates, and oxychlorides, carboxy groups, and β -Coordination compounds having hydrolyzable functional groups such as diketones, solutions containing water-soluble condensed oxide ions such as water glass, and metal amines.
When a porous material is used as various carriers, an optimum pore size depending on the size of a substance that is supported on the surface of the pores and exhibits a function, and a pore size distribution that is as narrow as possible are required. Therefore, an attempt has been made to control the pore size of the porous material obtained by the sol-gel method by controlling the reaction conditions during the gel synthesis.

In particular, many researchers have recently made so-called amphiphilic substances such as surfactants and block copolymers (more precisely, molecular aggregates formed by self-organization of amphiphilic substances) coexist as template components. It has been reported that the pore structure in the nanometer region can be controlled with high accuracy by synthesizing a porous material by a sol-gel method.
However, the conventional porous material obtained by the sol-gel method usually has only pores in the nanometer range (so-called mesopores), and the form thereof is often a powder, a thin film or an irregularly shaped particle. Is. Even when a massive material of several millimeters or more is obtained, there are very few examples in which pore structures (so-called macropores) having a scale larger than the nanometer range are controlled systematically. As an example, an inorganic porous material consisting of amorphous (not showing periodicity over a long distance like crystals) mesopores and macropores of uniform size is known. The regularity over the shape and long distance is not controlled (Patent Document 1).

  Porous substances consisting only of pores (mesopores) in the nanometer range as described above are generally used as filters, carrier materials, etc. after being finely pulverized or filled with a pulverized material bound thereto. The That is, the substance to be treated (gas or liquid as the mobile phase) is introduced into the mesopores through the gaps between the porous particles generated by filling and binding of the pulverized material, and a predetermined function of the porous substance is obtained. Is demonstrated. However, these gaps are generally irregular and often do not provide sufficient porosity, so the desired effect is often not obtained. An attempt was made to obtain a massive sample with a porous aggregate state that facilitates contact of the target substance from the outside with pores (mesopores) in the nanometer region and a macroporous structure that satisfies such conditions. In this case, a complicated and long molding process is required.

WO2003 / 002458

It is an object of the present invention to produce inorganic and organic-inorganic hybrid porous materials that have precisely controlled macropores in addition to mesopores with controlled narrow pore size distribution and regularity and shape over long distances. An object of the present invention is to provide a new manufacturing method that can be used, and to provide a solid-liquid contact device and a separation medium using the porous material obtained by the above-described manufacturing method. In particular, the sol-gel transition of the reaction solution under normal conditions and the normal temperature and temperature are eliminated without using a complicated method such as concentration and gelation while removing the solvent from the reaction solution or using a supercritical drying method for drying the gel. Inorganic and organic inorganic materials that have precisely controlled macropores in addition to mesopores with controlled narrow pore size distribution and long-range regularity and shape, only by drying under normal pressure and normal heat treatment. Provided is a method for producing a hybrid porous material, and the porous material is molded as a bulk material of an appropriate size necessary for the construction of a solid-liquid contact device and a separation medium, and has a new performance superior to existing products It is to provide a device as well as a separation medium.

The present inventor made the sol-gel transition and the phase separation process occur simultaneously in the production of an inorganic porous material by the sol-gel method in the presence of an amphiphilic substance as a template component. Ingredients that stabilize the aggregation state of the components coexist, or 2) Select an inorganic low molecular weight compound having a hydrolyzable functional group that causes favorable phase separation in a solution composition that stabilizes the aggregation state of the template component 3) It has been found that the above object can be achieved by satisfying at least one of the following conditions: 3) selecting a solvent composition in which the assembly state of the template component is stable.
Thus, according to the present invention, macropores having controlled pore size distribution in addition to long-range order and controlled mesopores of shape and pore size distribution, characterized by comprising the following steps: A method for producing inorganic and organic-inorganic hybrid porous materials is also provided.
(i) a step of preparing a homogeneous solution by dissolving an amphiphile as a template component in an aqueous solution containing a sol-gel reaction catalyst component;
(ii) preparing a solution or dispersion in the homogeneous solution using a solvent composition or an additive component in which a molecular assembly formed by self-organization of an amphiphile is stabilized in the solution;
(iii) An inorganic low molecular weight compound having a hydrolyzable functional group or an organic inorganic low molecular weight compound is added to the solution or dispersion to perform a sol-gel reaction, and a solvent rich phase rich in solvent, An inorganic oxide polymer generated from the inorganic low molecular weight compound or an organic-inorganic hybrid polymer generated from the organic inorganic low molecular weight compound by a gel reaction, which is fixed on the surface of the template component composed of the amphiphilic substance. Forming a continuous three-dimensional network wet gel comprising a skeleton phase rich in oxide polymers or organic-inorganic hybrid polymers;
(iv) drying the wet gel to form macropores by evaporating and removing the solvent from the solvent-rich phase; and
(v) A step of forming mesopores in the skeletal phase by removing the template component from the dried gel by thermal decomposition or extraction.

  In addition, in order to use the porous material obtained by the above-described production method as a separation medium for a solid-liquid contact device or a liquid chromatography column, the liquid is gradually decomposed into a starting solution in a solution such as urea. By adding a substance that changes the property, and strengthening the gel structure during the sol-gel reaction and in the aging stage after the reaction, a cylindrical or disk-shaped lump sample without cracks or deformation is obtained. I can do it. Especially when the chemical composition of the porous material is silicon dioxide (silica), the sol-gel reaction is performed in the presence of urea using a weakly acidic catalyst such as acetic acid, and the reaction solution is solidified by the sol-gel transition. After that, by aging in a sealed state at 60 ° C. or higher, it is possible to obtain a massive material having high mechanical strength without cracking or deformation.

  When the porous material thus obtained is used as a separation medium typified by a liquid chromatography column, the reaction solution is sealed in a cylindrical container so as to be molded into a cylindrical shape. After solidifying, aging, drying, and heat treatment, the side surfaces are covered with a resin that does not allow liquid to penetrate, and joints that can be joined to a chromatograph device are attached to both ends, so that it can be used as a column. In addition, when used as a solid-liquid contact device that circulates a liquid in a porous material such as solid phase extraction by attaching it to the tip of a syringe, a cylindrical or disk-shaped porous substance is attached to the pipette tip. By fixing the tip so that there is no gap, the liquid is circulated through the porous substance and the liquid carried by the syringe is brought into contact with the liquid and the liquid carried by the syringe. Can be promoted.

  A feature of the method for producing an inorganic porous material of the present invention is that a sol-gel is obtained by coexisting a molecular assembly of an amphiphile having a shape and an aggregation state stabilized by an appropriate additive component as a template component. When producing an inorganic porous material by the method, by adjusting the reaction conditions so that sol-gel transition and phase separation occur simultaneously, a solvent-rich phase capable of forming macropores in the subsequent drying step, and And a step of preparing a gel composed of a skeletal phase capable of forming mesopores therein by the pyrolysis step. On the other hand, according to the conventional method of synthesizing a porous material by the sol-gel method in the presence of an amphiphile as a template component, as described above, the obtained porous material has only mesopores. Met. This is considered to be because, in the conventional method, an oxide polymer is locally formed on the surface of the template component at an early stage and precipitates and separates from the system. In addition, a porous body made by a sol-gel reaction with phase separation that is made without adding a component that stabilizes the molecular assembly has well-defined macropores, but mesopores with uniform sizes are amorphous. However, the order and the shape of the pores over a long distance were not controlled.

  It should be noted that the terms “macropore” and “mesopore” used in the present invention are defined according to the well-known proposal by IUPAC. That is, a macropore refers to a pore having a diameter of 50 nanometers (nm) or more, and a mesopore is an intermediate between a macropore and a micropore (diameter 2 nm or less), that is, a diameter of 2 to The porous material obtained by designating pores in the range of 50 nm and obtained by the present invention generally has a narrow pore distribution centering on mesopores having a diameter of about 2 to 10 nm, but also has micropores. Yes.

The principle of the present invention is applied to various inorganic compounds and organic-inorganic hybrids known to be capable of producing oxide polymers from low-molecular compounds by the sol-gel method as described above in connection with the background art. However, the method of the present invention is particularly preferably applied when the inorganic oxide polymer constituting the porous body is a silica and / or organic functional group-containing siloxane polymer.
In order to produce a porous material composed of silica or siloxane polymer according to the present invention and having both mesopores and macropores, the sol-gel reaction step is carried out at least in the acidic region, and the sol-gel In the reaction, it is necessary to adjust the reaction conditions so that the amount of water containing the catalyst component is in the range of 1.0 to 100.0 g with respect to 1.0 g of silica in the reaction system (as weight of anhydrous silica). Thus, the sol-gel transition and the phase separation occur simultaneously, and a gel composed of a solvent-rich phase and a skeleton phase is generated.

More specifically, when a porous material mainly composed of silica is produced by a sol-gel reaction using an amphiphilic material as a template, the size of the template component depends on the acidic, neutral or basic catalyst conditions. It has been known that a uniform mesopore can be obtained. However, in order to produce a gel separated into a solvent-rich phase and a skeleton phase according to the present invention, homogeneous hydrolysis and gel formation may occur. A reaction in an easy acidic region is necessary. Alternatively, the liquidity that was acidic at the beginning of the reaction is gradually changed to basic by a homogeneous reaction from within the reaction solution (for example, urea is added to the reaction solution, and this urea is gradually hydrolyzed. To generate ammonia) and may induce homogeneous hydrolysis and gel formation.
That is, the sol-gel reaction is composed of the formation of a binding site (polycondensation reaction site: typically a hydroxyl group) by hydrolysis and gel formation by a polycondensation reaction via the binding site. Then, the hydrolysis reaction is promoted to form many polycondensation reaction sites, and it is considered that the polycondensation reaction (gel formation) occurs homogeneously through these many sites. On the other hand, if it is basic from the beginning of the sol-gel reaction, the polycondensation reaction is promoted, and inhomogeneous gel formation is induced. The catalyst component of the sol-gel reaction includes mineral acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as acetic acid and citric acid, weak bases such as ammonia and amines, strong acids such as sodium hydroxide and potassium hydroxide. Although bases can be mentioned, since adjustment of liquidity is an important factor, it is not limited to these substances.

  In addition, the amount of water in the sol-gel reaction is an important factor for obtaining a porous material composed of silica or a siloxane polymer and having macropores in addition to mesopores according to the present invention. The amount of water containing the catalyst component is 1.0 to 100.0 g, preferably 2.0 to 50.0 g, more preferably 3.0 to 30.0 g with respect to 0.0167 mol of atoms (1.0 g in terms of anhydrous silica). If the amount of water is too large, a polymer whose degree of polymerization does not sufficiently increase will precipitate in water, making it difficult to form a uniform gel. Since this phenomenon depends on the reactivity and reaction temperature of the starting material, it is difficult to describe the composition range and reaction conditions in general, but it is based on the sol-gel method in which an amphiphile coexists as a template component. In the conventional method for producing a porous body having only mesopores, the amount of water defined as described above is generally 50 g or more, and many are 100 g or more.

As described above, in the present invention, the solvent-rich phase and oxide rich in the solvent (water) are prepared by adjusting the sol-gel reaction step so that the sol-gel transition and the phase separation occur substantially simultaneously. A gel consisting of a polymer rich backbone phase is produced, which is confirmed by the cloudiness of the solution without precipitation. This product solidifies as a solid mass rather than a powder or precipitate, so it is aged for a while (to warm slightly if necessary) to increase its strength and then dried and pyrolyzed (or extracted) The target porous body is obtained by subjecting to the above.
Thus, in order to produce an inorganic porous material having both mesopores and macropores according to the method of the present invention, first, an amphiphile is dissolved as a template component in an aqueous solution containing a sol-gel reaction catalyst component to prepare a uniform solution. To do. When a component that stabilizes the molecular assembly of the amphiphilic substance is added to the homogeneous solution as necessary, an inorganic low-molecular compound having a hydrolyzable functional group is added to perform a sol-gel reaction. As described above, a gel separated into a solvent-rich phase and a skeleton phase is generated.
The solvent-rich phase is a three-dimensional network-like continuous phase having a diameter corresponding to the macropores, which is obtained by observing the structure after removing the solvent by drying with an electron microscope as described later. This can be confirmed (see FIG. 1).
The skeletal phase is rich in an inorganic oxide polymer or an organic-inorganic hybrid polymer formed from an inorganic low-molecular compound by a sol-gel reaction, and is also a continuous three-dimensional network phase. This phase is formed by adhering to the surface of the amphiphilic substance (strictly speaking, a molecular assembly formed by self-organization of the amphiphile) as the template component. Further, when the template component (amphiphilic compound) is removed later, it can be confirmed that pores (mesopores) are formed inside the skeleton phase (see FIG. 6). That is, the oxide polymer has a hydroxyl group on the surface, and this part strongly interacts with the proton-accepting part of the amphiphile to form a self-organized structure formed by the template component in the gel network. Can be transferred to the inside.
After the product (gel) of the sol-gel reaction has solidified, after passing through an appropriate aging time, when the solvent is removed by drying, macropores in which the space occupied by the solvent-rich phase is continuously penetrated are formed. Next, when the template component composed of the amphiphile is thermally decomposed or extracted and removed, pores (mesopores) having a uniform size in the nanometer region formed by the self-organized structure of the template component are obtained.

  Preferred as the amphiphilic substance used as a template in the method of the present invention is a cationic surfactant or nonionic hydrophilic part containing a hydrophilic part such as a quaternary ammonium salt and a hydrophobic part mainly composed of an alkyl group, A surfactant comprising a hydrophobic part such as an alkyl group, or a block copolymer having a hydrophilic part and a hydrophobic part. Specific examples thereof include halogenated alkyl ammonium, polyoxyethylene alkyl ether, ethylene oxide-propylene oxide- Examples thereof include, but are not limited to, ethylene oxide block copolymers. The amphiphilic substance used in the present invention is preferably one that is uniformly dissolved in the reaction solution, such as a surfactant or the above block copolymer. Further, as can be understood from the above description, the amphiphilic substance in the present invention is a solvent-rich material that forms macropores in addition to the function of adjusting the diameter of nanometer-scale pores (mesopores) as a template component. It is a component that also functions as a coexisting substance that produces a structure having a phase.

  In the method of the present invention, the above-mentioned molecular assembly of the amphiphile is stabilized, and an order that can be detected by a technique such as X-ray diffraction over a long distance (typically 100 nm or more) with a uniform shape is developed. In addition, as an appropriate additive for transferring the ordered structure as pores in the structure of inorganic and organic-inorganic hybrid gels, aprotic organic liquids such as trimethylbenzene and chloroform are suitable. However, a slightly polar long chain alcohol can also be used, but is not limited thereto. When using an alkoxide that causes phase separation that produces macropores in a relatively water-rich composition as a starting material, the molecular assembly of the amphiphile is stabilized without using the above-mentioned additives, It is also possible to develop an order that can be detected by techniques such as X-ray diffraction over a long distance. In this case, the above-mentioned additives are added mainly for controlling the mesopore diameter. In addition, if the above additives are added excessively to the amphiphile beyond the appropriate concentration range where long-range order is obtained, the molecular aggregate of the amphiphile is again converted into a low order state. However, in that case, a mesopore structure consisting of relatively large mesopores typically having a diameter of 20 nm or more is obtained. This structure is called Mesostructured Cellular Foam and is already known in the form of powder and precipitate by sol-gel reaction containing amphiphile. The structure can also be transferred into a gel skeleton that provides controlled macropores. A suitable addition amount of the additive for stabilizing the molecular assembly of the amphiphile is 0 to 100%, preferably 0 to 70%, more preferably 0 to 0 by weight with respect to the amphiphile. The range is 50%. Additives usually have low solubility in the solvent of the sol-gel reaction system, so if they are added in large excess, the additives that could not be completely dissolved in the molecular assembly of the amphiphile will drop into the reaction solution. In order to obtain a structure with well-defined macropores, in order to disperse the solution and make the solution inhomogeneous and to form droplet-like heterogeneous macropores in the resulting gel porous structure It is necessary to avoid this.

  In addition, as the inorganic low-molecular compound or organic inorganic low-molecular compound having a hydrolyzable functional group used in the present invention, various metal compounds including metal alkoxides as described above in relation to the background art may be used. Although applicable, in the case of producing a porous body composed of silica according to a particularly preferred embodiment of the present invention, a silicon alkoxide monomer and a low molecular weight polymer (oligomer) are preferably used as a silica source. . In the case of producing a porous body comprising an organic functional group-containing siloxane polymer (organic / inorganic hybrid), a silicon alkoxide monomer containing at least one silicon-carbon bond is used as such an organic / inorganic hybrid source. A low molecular weight polymer, or a compound having a structure in which a hydrocarbon chain containing one or more carbons or a hydrocarbon chain containing a hetero atom is bridged between two or more silicon atoms (for example, bistrialkoxysilylalkanes) Can be used. The inorganic porous material of the present invention can also be produced by mixing silica and an organic functional group-containing siloxane polymer at an arbitrary ratio.

  Examples are given below to further clarify the features of the present invention, but the present invention is not limited to these Examples.

(Example 1):
First, 1.80 g of ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO ₂₀ -PO ₇₀ -EO ₂₀ , average molecular weight 5,800, BASF's Pluronic P123 equivalent), an amphiphilic substance, 0.01 mol / L aqueous acetic acid solution 20 g Next, 1.0 g of urea was added, and 5.15 g of tetramethoxysilane was added to the obtained uniform solution under stirring to perform a hydrolysis reaction. After stirring for 5 minutes under ice-cooling, the obtained homogeneous solution was transferred to a closed container and kept in a constant temperature bath at 60 ° C., and after about 40 minutes, the solution solidified following the cloudiness of the solution. The solidified sample is further aged for several hours to several days under sealed conditions, then the solvent is evaporated off at 60 ° C, and then heated to 650 ° C at a rate of 100 ° C / h. After holding for 5 hours, it was cooled to room temperature. As a result, a porous material containing silica as a component was obtained.

The obtained porous body has a structure in which a through-hole with a central pore diameter of about 1.3 μm (= 1300 nm) and a cylindrical gel skeleton with a thickness of about 0.2 μm (= 200 nm) are intertwined in a three-dimensional network. It was confirmed by electron microscope observation (FIG. 1). FIG. 2 shows a cumulative pore size distribution curve obtained by mercury intrusion measurement, and FIG. 3 shows a differential pore size distribution curve obtained by the same measurement. And, inside the cylindrical silica gel skeleton constituting the through-hole, there are many pores having a distribution center near a diameter of 13 nm, and having a specific surface area of 900 m ² / g or more, This was confirmed by nitrogen adsorption measurement. The adsorption isotherm obtained by the nitrogen adsorption measurement is shown in FIG. 4, and the differential pore size distribution curve calculated from the adsorption branch using the analysis by the Barrett-Joyner-Halenda method is shown in FIG. In the field emission scanning electron microscope image of this sample, mesopores aligned in a uniform two-dimensional hexagonal array were observed in the cross section of the gel skeleton forming the macropores (FIG. 6). Therefore, inside the cylindrical gel skeleton of this sample, mesopores with a diameter of about 13 nm and gel walls with a thickness of about 10 nm alternate over a long distance (typically over 100 nm). The entire array was found to have two-dimensional hexagonal symmetry.

(Example 2):
In accordance with the manufacturing method of Example 1, the reaction solution was placed in a resin container having an inner diameter of 6 mm and a length of 150 mm, and a sol-gel reaction and subsequent treatment were performed. Finally, a cylindrical shape having a diameter of 4.6 mm and a length of 83 mm was obtained. A porous silica was prepared. The side surface of the cylindrical porous silica was covered with a heat-shrinkable Teflon resin, and thereafter embedded in a resin tube having an inner diameter of 10 mm using an epoxy resin, and joints were fixed to both ends. This column was loaded into a WATERS RCM8 pressure module, connected to a liquid chromatograph, and a normal phase chromatogram using the silica surface as it was was measured at room temperature. Moreover, after performing the process which couple | bonds an octadecyl silyl group to the silica surface, the reverse phase chromatogram was obtained similarly. The mobile phase velocity was fixed at 1 mL per minute, and each solute was detected by an ultraviolet detector with a wavelength of 254 nm or 210 nm.

FIG. 7 shows a normal phase chromatogram using toluene, nitrobenzene, and o-nitroanisole as a solute by a column using the silica surface as it is. Further, FIG. 8 shows a reverse phase chromatogram using benzene and an alkylbenzene substituted with a linear alkyl group having 1 to 6 carbon atoms as a solute by a column in which the surface of silica is modified with an octadecylsilyl group.
It can be seen that the porous material of the present invention can be used as a liquid chromatography separation medium having sufficient separation efficiency in both the normal phase and the reverse phase. The separation factor α, calculated from the relative retention values of amylbenzene and hexylbenzene (corresponding to the second and rightmost peaks, respectively), is the conventional value commercially available as Chromolith The value was almost the same as that of the silica-based integrated column (about 1.5). That is, it can be seen that the retention behavior of the entire column in the reverse phase is equivalent to that of a conventional integrated column subjected to octadecylsilylation treatment.
However, when comparing the amount of silica contained in a 4.6 mm diameter and 83 mm (volume 1.38 cc) column, it is 0.37 g for the Chromolith column and 0.12 g for the column of the present invention, The latter contains only about 1/3 of the stationary phase of the former. On the other hand, the porous silica contained in the Chromolith column has a specific surface area of about 300 m ² per gram, but in the column of the present invention, it is about 900 m ² per gram, so the surface area per column is almost the same value. . From the above, the porous material of the present invention has a structure in which pores regularly formed in the nanometer region by a surfactant and a structure in the silica wall containing the pores are low molecular weights in liquid chromatography. The surface on which substances can interact is formed so as to give a specific surface area about 3 times that of the conventional product. Therefore, even if the amount of silica in the column is small, a Chromolith column containing about 3 times more silica and It is reasonably concluded that it gave an equivalent separation factor.
The large surface area available per unit of silica is also beneficial for other forms of solid-liquid contact devices, and the same configuration applies to solid-phase extraction devices that collect by adsorbing specific components in solution. If so, it is possible to realize a collection capacity three times or more that of the conventional product.

  As described above, according to the present invention, a porous body controlled to have a desired pore distribution can be produced. Moreover, since the porous body obtained by the present invention is a porous body having a double pore structure of macropores and mesopores having long-range order, it can be applied as an integrated column, and the conventional disordered meso Compared to an integrated column with pores, the use of fewer porous materials can achieve the same separation, thus contributing to a resource saving process.

The scanning electron micrograph of the porous material obtained in Example 1 is shown. The cumulative pore diameter distribution by the mercury intrusion method of the porous material obtained in Example 1 is shown. The differential pore diameter distribution by the mercury intrusion method of the porous substance obtained in Example 1 is shown. The adsorption isotherm in the liquid nitrogen temperature of the porous substance obtained in Example 1 is shown. The pore diameter distribution curve by the nitrogen adsorption method (BJH method) of the porous substance obtained in Example 1 is shown. 2 shows a field emission scanning electron micrograph of the porous material obtained in Example 1. FIG. The normal phase chromatogram by the liquid chromatography column obtained in Example 1 is shown. The reverse phase chromatogram by the liquid chromatography column obtained in Example 1 is shown.

Claims (2)

The porous material consists mainly of organic-inorganic hybrids containing silicon dioxide or silicon-carbon bonds, and the mesopores with a diameter of 10 to 50 nm present in the solid skeleton structure are cylindrical and two-dimensional hexagonal symmetric. Solid-liquid contact device and separation medium characterized by being controlled with periodicity. The method for producing a solid-liquid contact device and a dispersion medium according to claim 1, wherein the sol-gel reaction is performed in the presence of urea using a weakly acidic catalyst such as acetic acid, and the reaction solution is solidified by sol-gel transition. A solid-liquid contact device and a method for producing a dispersion medium, characterized by aging under sealing at 60 ° C. or higher after

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