KR20050022259A - New Nanoporous Organic Polymer and its Synthesis Method thereof and application for catalysis - Google Patents

Abstract

PURPOSE: Provided are a novel nanoporous organic polymer composite which is improved in structural regularity, mechanical strength, thermal stability and chemical resistance, and its preparation method. CONSTITUTION: The nanoporous organic polymer composite comprises a mesoporous silica or carbon molecular sieve provided with a micropore with a size of 2-50 n m in the mesopore wall; and an organic polymer which is supported in the micropore of the molecular sieve and is coated to the wall face of the molecular sieve. Preferably the amount of the organic polymer is 1-100 wt% based on the weight of the mesoporous molecular sieve. Preferably an organic functional group is introduced into the nanopore wall of the molecular sieve. The composite is used as a porous catalyst in the acid-based catalyst reaction such as esterification, alkylation, Knoevenagel reaction, aldol condensation reaction, isomerization, etc. and the oxidation-reduction reaction such as benzene-alcohol oxidation reaction, etc.

Description

New nanoporous organic polymer material and its preparation method and application to catalysts {New Nanoporous Organic Polymer and its Synthesis Method about and application for catalysis}

The present invention relates to a nanoporous organic polymer material, a method for producing the same, and an application thereof to a catalyst, and more particularly, to a structured nanoporous organic polymer material having excellent mechanical strength, thermal stability, and chemical resistance, and a method for preparing the same. The present invention relates to a material exhibiting excellent catalytic properties compared to a porous catalyst material according to the prior art.

In the field of materials science, many studies have been conducted on nanostructured organic polymers having uniform nanopores in the range of several nanometers and enhanced mechanical strength, thermal stability, and chemical resistance. Recently, many reports on the successful synthesis of such nanostructured organic polymers have been made. Conventional techniques in the art use supramolecule liquid crystal templating routes to allow organic materials to have periodic arrays of nanoscale domains in the solid state, and then to nanoscale domains. Has been suggested to obtain a solid structure that retains the orderly nanopores by selectively removing one type of region. In addition, another method of synthesizing the structure-regulated nanoporous organic high molecular material includes a method of polymerizing a mesoporous silica mold and then removing the silica mold with hydrofluoric acid.

However, the nanoporous material made of the pure organic material skeleton made of the prior art has a problem that mechanical strength, thermal stability, stability to organic solvents are significantly lower than those of silica and carbon materials. In addition, there are many limitations in controlling the size and structure of the pores in the manufacture of such materials.

The nanoporous organic polymeric material according to the present invention is one of new nanoporous materials that exhibit excellent catalytic properties in catalytic applications. Porous catalysts used up to now include porous carbon materials and porous silica materials having a size of several nanometers to several tens of nanometers. Recently, a new concept of hybrids in which organic molecules are bonded to porous molecular sieves has emerged. did.

In the prior art, methods for treating the nanoporous silica molecular sieve with organic materials can be roughly divided into grafting, coating, and co-condensation. In the grafting method, hydroxyl groups present on the surface of porous silica (mesoporous silica or amorphous silica) are used to attach low-reactivity alkyl chains or phenyl groups to the surface, resulting in a porous material. Increased the lipophilic of the surface. Coating (coating) is a technique that shows a slight difference from the bonding, a method of modifying the surface with an organic monomer after hydration of the hydroxyl group (hydroxyl group) of the surface. Co-condensation (co-condensation) is a method of proceeding the reaction at once by adding an organic monomer or a material to be modified during the process of forming a porous material. Through this method, mesoporous silica organic-inorganic complexes made by jointly reacting tetraalkoxysilane with one or more organosilanes are known.

By the conventional three representative methods, such as to impart functionality to the surface or wall of the nanoporous material or to graf the organic material, which has been widely applied to metals, polymers, etc. as well as organic monomers. These materials have been used as porous catalysts for acid-base reactions, oxidation-reduction reactions and other catalysis. However, there is still a difficulty in designing a new porous catalyst material because the mechanisms for the catalytic properties and activity exhibited by these porous materials are not exactly understood.

Accordingly, the technical problem to be achieved by the present invention with respect to the problems of the prior art is to provide a nanoporous organic polymer material with increased structural regularity, in particular mechanical strength, thermal stability and chemical resistance is increased new To provide a structure-regular nanoporous organic polymer material

In addition, another technical problem of the present invention is to provide a method for easily preparing the nanostructured porous organic polymer.

In addition, the material according to the present invention is to provide a nanoporous organic polymer exhibiting excellent catalytic properties compared to the porous catalyst material according to the prior art.

The present invention as a means for achieving the above object,

A nanoporous organic polymer material comprising: a mesoporous molecular sieve having micropores in a wall; and an organic porous polymer supported on the inside of the micropore and coated on a wall of the mesoporous molecular sieve. Provide organic polymer materials.

Hereinafter, the content of the present invention will be described in more detail.

The mesoporous molecular sieve is not particularly limited, but means a molecular sieve having a meso-sized pore distribution in the range of 2 to 50 nm. The mesoporous molecular sieve in the above preferably comprises mesoporous silica molecular sieve or mesoporous carbon molecular sieve.

Silica molecular sieve has already been known a variety of materials. As a representative example, materials such as MCM-41, SBA-15, MSU-H, etc. having a hexagonal pore array, and MCM-48, SBA-1, SBA-16 having a cubic pore array are known. It is. In a preferred embodiment of the present invention to be described below, a mesoporous silica molecular sieve having a preferred structure in which an organic polymer polymer can be supported by introducing a new synthetic condition that can control the distribution of micropores present in the mesoporous wall is disclosed. will be.

As another example of mesoporous molecular sieves, carbon molecular sieves have many micropores (less than 2 nm) in the mesoporous walls, which are already synthesized by Prof. Yu Ryong, a professor at Korea Advanced Institute of Science and Technology (CMK-n). by KAIST, n = serial number). (Reference: Patent Registration No. 10-0307692, Papers: Nature 2001 , 412 , 169)

According to existing studies on carbon molecular sieves, carbon molecular sieves have advantages of high thermal stability, hydrothermal stability, chemical resistance and organic properties, compared to other metal oxide-based molecular sieve materials. However, conventionally released carbon molecular sieves have a relatively uniform pore size distribution than activated carbon, but have a small pore size and a wide pore size distribution, which is very limited in application and lacks overall structural regularity.

The materials belonging to the CMK-n as described above are materials obtained by aligning carbon nanowires or carbon nanotubes of uniform size in pores with mesoporous silica molecular sieve as a template, and then removing the silica molecular sieve. Along with the various pore arrays in the cubic system, the pore diameter is about 2 to 10 nm and has uniform characteristics.

The mesoporous molecular sieve may preferably contain a greater amount of organic polymer as the more micropores capable of supporting the organic monomer inside the wall. Therefore, the degree of distribution of micropores is not particularly limited in the present invention as long as it can accommodate the organic polymer to be introduced into the molecular sieve. In addition, the nanoporous organic polymer material according to the present invention is formed on the wall surface of the mesoporous molecular sieve as a thin film having a predetermined thickness within a range that does not significantly reduce the size of the mesopores. Such a structure provides a nanoporous organic polymer material having excellent mechanical strength, thermal stability and chemical resistance by forming the composite skeleton together with the silica or carbon skeleton.

In addition, in the nanoporous organic polymer material of the present invention, a predetermined functional group may be introduced into the nanopore wall. By introducing functional groups into the surface to modify the nanopore walls, hydrophilic or lipophilic properties can be imparted to the nanoporous organic polymeric material. Such functional groups are not particularly limited and need not be limited. Examples thereof include sulfone groups, carboxyl groups, nitro groups, amine groups, phosphone groups, and the like.

The nanoporous organic polymer material according to the present invention comprises impregnating an organic monomer in a mesoporous molecular sieve having micropores in the wall, and polymerizing the organic monomer to the inside of the micropores and the wall surface of the mesoporous molecular sieve. It may be prepared through the step of forming an organic polymer.

The organic monomer is loaded into the mesoporous structure and completely filled with micropores formed in the wall, as well as absorbed into the mesoporous wall by capillary condensation. The organic monomers filled and absorbed as above become organic polymers through a polymerization process to form a thin film on the mesoporous wall.

The organic monomers that can be used in the above process may include any that can be synthesized into a polymer in the pores of the mesoporous material through various polymer polymerization methods which are classified into step growth polymerization and chain growth polymerization. Representative examples include ethylene, 1-alkyl olefins, 1,3-dienes, which can cause chain growth polymerization using radicals, cations or anions as initiators. Styrene, methyl styrene, halogenated olefins, vinyl esters, acrylates, methacrylates, acrylonitrile, meta Methacrylonitrile, acrylamide, methacrylamide, vinyl ethers, vinyl carbazole, vinyl pyrrolidone, aldehyde (aldehydes), ketones, and the like. In addition, polymer monomers are known organic monomers, such as acenaphthalene, ethyl vinyl ether, propene, n-butyl vinyl ether, and isobutyl vinyl ether. butyl vinyl ether, p-methoxystyrene, isobutylene, allyl acetate, allyl acetate, vinyl acetate, para-bromostyrene, allyl chloride (ally chloride), isoprene, 2-vinylpyridine, vinyl chloride, m-nitrostyrene, vinylylidene chloride, methyl methacrylate ), Methacrylic acid, methyl acrylate, vinyl fluoride, n-butyl acrylate, acrylic acid, 1-hexene (1- hexene), methyl vinyl ketone, Diethyl, maleate, tetrafluoroethylene, orthochlorostyrene, diethyl fumarate, fumaronitrile, maleic anhydride (maleic anhydride) and the like can be a suitable example that can be used for this purpose, these organic monomers are composed of one monomer or two or more monomers, synthesized as a single polymer polymer or copolymer. The content of the organic monomer is not particularly limited, but in order for the organic polymer material to be coated in the form of a thin film in the pores while maintaining the structural regularity of the silica or carbon molecule, the organic monomer is within 100% by weight of the mesoporous molecular sieve. It is preferable to be controlled within 100% by weight depending on the distribution of micropores present in the nanoporous molecular sieve, and can be selected by those skilled in the art according to the desired properties in this range.

Typically, a crosslinking agent, an initiator and an appropriate amount of solvent may be required together in the process of polymerizing the organic monomer. All of these components are those already known in the art. As the crosslinking agent, dihydric or trivalent or higher alcohols, amines, vinyl group derivatives and the like can be used. Preferred examples suitable for the present invention include 1,2-ethanedioldiacrylate, 1,3-propanedioldiacrylate, 1,3-butanedioldiacrylate (1 , 3-butanedioldiacrylate), 1,4-butanedioldiacrylate, 1,5-pentanedioldiacrylate, 1,6-hexanedioldiacrylate (1 , 6-hexanedioldiacrylate, divinyl benzene, ethyleneglycoholdiacrylate, propyleneglycoholacrylate, butyleneglycoholdiacrylate, triethyleneglycoholacrylate ), Polyethyleneglycoholdiacrylate, polypropyleneglycoholdiacrylate, polybutylene glycol diacrylate (polyb) utyleneglycoholdiacrylate), allyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propanedioldimethacrylate, 1,3 Butanediol dimethacrylate (1,3-butanediolmethacrylate), 1,4-butanediol dimethacrylate (1,4-butanediolmethacrylate), 1,5-pentanediol dimethacrylate (1,5-pentanedioldimethacrylate), 1 6-hexanediol dimethacrylate (1,6-hexanediolmethacrylate), ethylene glycol dimethacrylate (ethyleneglycoholmethacrylate), propylene glycol dimethacrylate (propyleneglycoholmethacrylate), butylene glycol dimethacrylate (butyleneglycoholdimethacrylate), triethylene Glycol dimethacrylate (triethyleneglycoholdimethacrylate), polyethylene glycol dimethacrylate (polyethyleneglycoholmethacrylate), polypropylene glycol dimethacrylate (polypropyleneglycoholmethacrylate), poly Butylene glycol dimethacrylate (polybutyleneglycoholdimethacrylate), allyl methacrylate (allyl methacrylate), diallyl maleite (diallyl maleite) and the like are used. In addition, the initiator is azobisisobutyronitrile, benzoyl peroxide, acetyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl peracetate Cumyl peroxide, tert-butyl peroxide, t-butyl hydroperoxide, t-butyl hydroperoxide, potassium persulfate and the like are typically used. The solvent does not require any particular limitation, but is a solvent capable of simultaneously dissolving the used organic monomer, the crosslinking agent and the initiator, and having a condition that is more readily volatilized at a lower temperature than the organic monomer and the crosslinking agent, and preferred examples thereof include methylene chloride and diethyl ether. (diethyl ether), ether (ether), ethanol (ethanol), toluene (toluene), acetone (acetone) and the like. The polymerization process of the polymer may be performed for several hours to several days at room temperature to less than 300 ℃ in the mesoporous molecular sieve.

 The nanoporous organic polymer composite synthesized by the above method exhibits excellent properties for structural stability as described below. In particular, the nanoporous organic polymer composite can be safely structured even under such extreme conditions by using the advantage of stability against strong acidic or basic solutions or organic solvents. This suggests the possibility of introducing functional groups to the surface while maintaining Therefore, the nanoporous organic polymer complex is added to various kinds of acidic solutions (sulfuric acid, nitric acid, phosphoric acid, acetic acid, etc.) or basic solution (caustic soda water, ammonia water, etc.), and after appropriate treatment time and method, Various functional groups such as sulfone groups, nitro groups, phosphoric groups, carboxyl groups, hydroxyl groups, and amine groups can be introduced to the surface. In the present invention, a method for preparing a nanoporous organic polymer composite having a sulfone group introduced on its surface will be described in detail with reference to Examples, and the excellent catalytic properties of the nanoporous organic polymer will be described in detail with reference to Examples.

The nanoporous organic polymer composite according to the present invention may be catalyzed as a representative application, and showed higher catalytic activity compared to conventional porous catalyst materials. Catalytic reactions to which the above materials can be applied include, but are not limited to, acid catalyzed reactions represented by esterification, alkylation, Knovenagel reaction, Aldol condensation reaction, and isomerization. It is suggested that the present invention can be used for the redox reaction including aerobic oxidation reactions such as benzene-alcohol oxidation reaction as well as base catalyst reaction represented by

As described below, in Example 1 of the present invention, an example in which SBA-15 silica molecular sieve is used as a support and ethylene glycol methacrylate (HEMA) is polymerized is used. Examples 2 to 4 show CMK-3 carbon molecular sieve. Nanoporous organic polymeric materials are disclosed, each being used as a support and made from styrene as a monomer.

The properties of the polymer / silica or polymer / carbon nanoporous material prepared according to the above embodiment can be confirmed through the following results.

X-ray diffraction analysis of the results showed that polyethylene glycol / SBA-15 (PHEMA / SBA-15) had an increased X-ray diffraction intensity than that of SBA-15. The same result can be obtained when carbon molecular sieve is used, that is, polystyrene / CMK-3 (PS / CMK-3) shows an increased X-ray diffraction intensity than that of CMK. These results are shown through FIGS. 1, 2 and 3.

In addition, it can be confirmed through nitrogen adsorption that the ratio of micropores present in the silica or carbon molecular sieve after polymer polymerization is reduced compared to mesopores. This fact is shown in FIG. 4 and will be explained in more detail in Example 2. FIG.

In addition, the X-ray diffraction results observed after pressing the material at a pressure of 1.5 × 10 ⁴ kg / cm ² for 10 minutes showed the same diffraction pattern and intensity as before the pressing, and this phenomenon indicates that the material is a pure organic material. It can be seen that the stability to mechanical strength is higher than that of the material composed of the skeleton. Results of structural stability and surface properties of the material are shown in FIGS. 5 and 6, and experiments using surface properties will be described in more detail with reference to Examples 3 and 4.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

Example 1 Preparation of PHEMA / SBA-15

Silica molecular sieve is a solution in which TEOS (tetraethylorthosilicate) and Na-silicate (Sodium silicate) are used as silica sources and dissolved hydrochloric acid, water, and surfactant according to a known method (Refer to Chem. Mater. 2000 , 12 , 1961). And a silica source were mixed and stirred to synthesize. However, the concentration of hydrochloric acid was reduced from 1M concentration to 0.3M concentration, and the amount of water used was reduced in half. In addition, the quantity of the added silica was set to 75 weight% with respect to surfactant. To 1 g of silica synthesized in the above manner, to coat 30% by weight of polymer, 0.217 g of ethylene glycol methacrylate (HEMA), 0.083 g of ethylene glycol dimethacrylate (EDMA), and azobisiso 0.012 g of butyronitrile and 1 ml of diethyl ether were used as a solvent. The rest of the above components except for silica were mixed and supported in silica pores, and then dried in an oven at 35 ° C. for 6 hours. This process is to remove the added solvent (diethyl ether) to help the diffusion of the organic monomer in the pores. The mixed material was then sealed under an argon atmosphere and allowed to stand in an oven at 100 ° C. and 150 ° C., respectively. After the reaction was completed, the reaction product was taken out, washed with ethanol and dried under vacuum to obtain polyethylene glycol methacrylate / silica nanoporous organic polymer material (PHEMA / SBA-15). 1 shows the results of X-ray diffraction analysis of this material.

Example 2 Preparation of PS / CMK-1 ~ 3

Carbon molecules used in the experiments related to the present embodiment are CMK-1 to 3, which are synthesized using different mesoporous silica as templates, and thus, there are differences in the detailed characteristics of the structure and the total volume of the pores according to the arrangement of the pores. (See FIG. 2). However, except for the difference in the characteristics described in the essential content of the present invention are all the same and will be described in detail below for the CMK-3.

CMK-3 carbon molecular sieve was obtained by pyrolysis by sucrose in SBA-15 mesoporous silica and synthesized according to a known method ( J. Am. Chem. Soc . 2000 , 122 , 10712). Specifically, 1.25 g of sucrose is dissolved in 5 g of water, dissolved by adding 0.14 g of sulfuric acid, and then mixed in 1 g of SBA-15. It is dried for 6 hours in an oven at 100 ° C. and subsequently heated to 160 ° C. for further 6 hours. After the sample was taken out and cooled to room temperature, a solution prepared by dissolving 0.8 g of sucrose and 0.09 g of sulfuric acid in 5 g of water was poured into the sample above, and then mixed well, followed by drying at 100 ° C. and 160 ° C. for 6 hours, respectively. After this process, the sample was taken out and finally carbonized under nitrogen or vacuum atmosphere at 900 ° C., and the sample was washed with 50% aqueous hydrofluoric acid solution to remove silica to finally obtain CMK-3 carbon molecular sieve. The divinylbenzene and styrene monomers used as the crosslinking agent were purified by passing through an alumina column.

Each component is used to form as much as 30% by weight of polymer based on 1 g of CMK-3, with 0.0715 g of divinylbenzene (DVB), 0.2285 g styrene (ST), 0.0162 g 2,2′-azo Bisisobutyronitrile, 1.5 ml methylene chloride (MC) was applied. Of the above ingredients except for CMK-3, the mixed materials were mixed and supported in CMK-3, and then dried in an oven at 60 ℃ for 6 hours. This process is to remove the added solvent (methylene chloride (MC)) to help the diffusion of the organic monomer in the pores. The mixed material was then sealed under an argon atmosphere and left in a 100 ° C. and 150 ° C. oven for one or two days, respectively. When the reaction was complete, the resultant was taken out, washed with chloroform and dried under vacuum to obtain a crosslinked polystyrene / carbon nanoporous organic polymer (PS / CMK-3).

X-ray diffraction patterns of CMK-3 and PS / CMK-3 are shown in FIG. 3. In general, when the guest material is supported in the mesopores, the intensity of the X-ray diffraction peak is decreased, and the position of the guest material can be determined through the change of the X-ray diffraction intensity. However, specifically, PS / CMK-3 with polystyrene supported on CMK-3 shows increased X-ray diffraction intensity. This is because the polymerization of styrene in the micropores in the carbon skeleton fills the micropores, so that the structural defects can be compensated for. Therefore, the structural regularity is increased, and the mesopores are reduced by reducing the micropores. This shows a significant increase in the density of the walls. This can be seen through the result of FIG. 4. That is, the mesopores were reduced in size by only 7% despite the polymerization of 45% by weight of the polymer. This can be confirmed from the pore size analysis using the BJH algorithm from the mesopore size of 4.1 nm to 3.8 nm (about 7% reduction).

Example 3 Preparation of PS / CMK-3 Introduced with Sulfone Group

1 g of the PS / CMK-3 nanoporous material synthesized according to the method described in Example 2 was added to 20 ml of 98% concentrated sulfuric acid, and boiled at 100 ° C. for 4 hours to the surface of the polystyrene / CMK-3 nanoporous material. A sulfone group (-HSO ₃ ) was introduced. The specific surface area of the final material was 650 m ² / g, and the pore size distribution was the same as before the introduction of sulfone groups. The density of the introduced sulfone group was confirmed to be 4 × 10 ⁻³ mol per 1 g of polymer through NaOH titration. The polystyrene / CMK-3 nanoporous material may contain as much as 20 mol% of divinylbenzene as a crosslinking agent. Commercially crosslinked polystyrene resins having a divinylbenzene content of usually 2 to 8% by weight have a Na ⁺ ion exchange capacity of 1.8 to 4.8 x 10 ^-3 molg ^-1 and an increased content of divinylbenzene The result is quite surprising given the rapid decrease in ion exchange capacity. In addition, the material shows almost the same X-ray diffraction pattern as before the introduction of the sulfone group (-HSO ₃ ), which means that the regular nanostructures are preserved after the reaction. Through these experiments, it can be seen that the polymer / carbon nanoporous organic polymer material has thermal and chemical resistance properties, and thus, a functional group can be introduced into the material more freely. It can also be seen that the large surface area of the material facilitates the introduction of large amounts of functional groups.

Example 4 Surface Characteristics of PS / CMK-3 Nanoporous Material

The PS / CMK-3 nanoporous organic polymeric material was modified to a nanopore wall with a sulfone as in Example 3, then packed into a column and adsorbed a Direct Blue-15 organic dye. Similarly, after adsorbing the dye to a column filled with CMK-3 mesoporous carbon molecules, the degree of the adsorbed dye was eluted while flowing the solvent. The solvent used was a mixture of water and ethanol in an appropriate ratio, and the eluted dye solution was analyzed for concentration using UV absorption spectrum at 600 nm wavelength.

As shown in FIG. 5, in the case of the polystyrene / carbon nanoporous organic polymer material substituted with a sulfone group, elution concentrations are different depending on the water and ethanol composition in the solvent. In the case of CMK-3, regardless of the composition of the solvent, It can be seen that the dye does not elute at all. In the case of CMK-3, which has a pure carbon surface, the affinity for dye is very strong, so it is semipermanently adsorbed regardless of solvent effect.However, in the case of polystyrene / carbon nanoporous organic polymer materials, the polymer is It is due to the fact that it is completely coated and this strong affinity does not exist. These results indicate that the nanopore walls are effectively coated with a polystyrene polymer thin film, which suggests that the surface properties can be controlled by controlling the type and amount of functional groups bonded to the polymer.

Example 5

The PS / SBA-15 nanoporous organic polymer material was modified with a sulfone group as shown in Example 3, followed by catalytic reactivity of esterification of benzoic acid and hexanoic acid. Investigate. For the reaction, 0.5 molar concentration of benzoic acid, hexanoic acid, and toluene solution was used, and the initial concentration of the reactant was 20 times the concentration of sulfonic acid of the catalyst material. The reaction proceeded at 75 ° C. and the reaction progress and selectivity were examined by gas chromatography. For comparative experiments, Amberlyst ^?? , a polymer containing commercially available sulfonic acid as well as PS / SBA-15 ^? 15, SBA-15 was treated with organosilane to try to combine the sulfonic acid conjugated material as a catalyst. The comparison result of the catalytic reaction is shown through FIG. 6. As can be seen in Figure 6 PS / SBA-15 nanoporous organic polymer material showed a higher catalytic activity than any catalyst used in the other examples, Amberlyst ^?? Compared to 85% of 15, 92% showed improved response selectivity. However, almost no catalytic activity was observed in SBA-15 conjugated with organosilanes having the same structure.

The nanoporous organic polymer material according to the present invention is excellent in mechanical strength, thermal stability and chemical resistance. In addition, according to the method for producing a nanoporous organic polymer material according to the present invention, it is possible to produce a nanoporous organic polymer material having a nanoporous wall coated with a polymer polymer and arranged regularly in a mesoporous molecular sieve structure. . In addition, the functional groups can be freely introduced to facilitate surface modification of the nanopore walls.

In addition, by modifying the surface of the nanoporous silica molecular sieve with various organic materials and showing superior catalytic activity characteristics than the prior art in which these materials are applied to the catalytic reaction, new materials showing breakthrough characteristics in the field of catalytic application can be provided.

FIG. 1 shows X-ray diffraction results of a conventional silica molecular sieve (SBA-15) and a nanoporous organic polymer material (PHEMA / SBA-15) according to the present invention.

FIG. 2 shows X-ray diffraction results of a nanoporous organic polymer material (PS / CMK-1) synthesized using a conventional carbon molecule, CMK-1, as a support.

FIG. 3 shows the results of X-ray diffraction experiments on nanoporous organic polymer materials (PS / CMK-3) synthesized using a conventional carbon molecule, CMK-3.

FIG. 4 is an isotherm graph showing a case where nitrogen gas (N ₂ ) is adsorbed and desorbed on a conventional carbon molecular material CMK-3 and a nanoporous organic polymer material PS / CMK-3 according to the present invention.

FIG. 5 illustrates direct blue 15 adsorbed onto a conventional carbon molecular material CMK-3 and PS / CMK-3, which is a nanoporous organic polymer material according to the present invention, followed by elution concentration according to water and ethanol composition ratio.

6 is a comparison of the stability of the mechanical strength from the difference in the strength and form of the X-ray diffraction of the conventional carbon molecule CMK-3 and the nanoporous organic polymer material PS / CMK-3 according to the present invention.

FIG. 7 is a graph illustrating a comparison of catalyst properties exhibited in an esterification catalyst reaction between a nanoporous organic polymer material according to the present invention, a material synthesized according to the prior art, and a commercial catalyst.

Claims (8)

Nanoporous having mesoporous silica or carbon molecular sieve having micropores of 2 to 50 nm in the mesoporous wall, and an organic polymer polymer supported inside the micropores of the molecular sieve and coated on the wall surface of the molecular sieve. Organic polymer complex. The method of claim 1, The organic polymer is a nanoporous organic polymer composite within 1 to 100% by weight based on the weight of the mesoporous molecular sieve. The method according to claim 1 or 2, Nanoporous organic polymer complex incorporating organic functional group into nanopore wall of molecular sieve The method of claim 3, wherein Nanocomposite organic polymer, characterized in that the complex is used as a porous catalyst in the oxidation-reduction reaction represented by acid-base catalysis, benzene-alcohol oxidation, such as esterification, alkylation, Novena gel reaction, aldol condensation reaction, etc. Complex. (A) preparing a mesoporous molecular sieve having micropores in the wall; (B) impregnating the molecular sieve with an organic monomer diluted in a solvent; (C) polymerizing the organic monomer-impregnated molecular sieve to form an organic polymer in the micropores and on the wall of the mesoporous molecular sieve; Method for preparing nanoporous organic polymer composite having The method of claim 5, Mesoporous molecular sieve is a method for producing a nanoporous organic polymer material which is a mesoporous silica molecular sieve or a mesoporous carbon molecular sieve The method of claim 6, The organic polymer polymer is a method for producing a nanoporous organic polymer material which is 1 to 100% by weight based on the weight of the mesoporous molecular sieve. The method of manufacturing a nanoporous organic polymer composite according to any one of claims 5 to 7, further comprising introducing an organic functional group into the nanopore wall of the organic polymer polymer prepared in (C).