JP6131081B2 - ORGANIC-INORGANIC COMPOSITE, STRUCTURE AND METHOD FOR PRODUCING ORGANIC-INORGANIC COMPOSITE - Google Patents

Description

  The present invention relates to an organic-inorganic composite, a structure, and a method for producing the organic-inorganic composite.

  Conventionally, the organic-inorganic composite has a structure in which polystyrene is dispersed in an inorganic matrix having a silica matrix structure, and a phenyl group between the phenyl group of the silica gel component of the inorganic matrix and the phenyl group of polystyrene. Those having a phenyl group interaction have been proposed (see, for example, Patent Document 1). This organic-inorganic composite has low optical loss that can be used for polymer optical waveguides and other materials for optical integrated circuits, and allows precise refractive index control. In addition, organic / inorganic composites are proposed in which inorganic particles such as silica are coated with a polymer having a cation exchange group, and the counter ion of the cation exchange group is an alkaline earth metal ion such as calcium. (For example, refer to Patent Document 2). This organic-inorganic composite is said to have higher rust prevention properties and excellent stability and sustainability of the rust prevention effect. In addition, the organic-inorganic composite includes an organic polymer composed of sulfonic acid-modified polystyrene and an inorganic substance mainly composed of silica prepared from tetramethoxysilane. The thing which couple | bonded the sulfonic acid and the inorganic substance through the ionic bond is proposed (for example, refer patent document 3). This composite can provide a novel composite material having transparency.

JP-A-11-109154 JP 2007-217732 A Japanese Patent Laid-Open No. 11-310720

  However, in the organic-inorganic composite described in Patent Document 1, transparency has been studied, but other functions, for example, separation performance of fluid such as gas have not been studied. Moreover, in the organic-inorganic composite described in Patent Document 2, the surface of the silica particles is covered with a resin, but the silica particles and the resin are simply mixed, and the inorganic and organic substances are easily separated. The mechanical strength was inferior. Moreover, in the organic-inorganic composite described in Patent Document 3, the polystyrene-containing sulfo group and silica are bonded by ionic bonds. For example, when the sulfo group exhibits a desired function, Since the sulfo group is used for bonding with silica, its function could not be fully exhibited.

  This invention is made | formed in view of such a subject, and it aims at providing the manufacturing method of the organic inorganic composite which can improve functionality and mechanical strength more, a structure, and an organic inorganic composite. And

  As a result of diligent research to achieve the main object described above, the present inventors have made an organic-inorganic composite by combining π-π interaction between molecules of an inorganic compound and an organic compound to form a composite. When the body has a cation exchange group, it has been found that the functionality and mechanical strength can be further increased, and the present invention has been completed.

That is, the organic-inorganic composite of the present invention is
An inorganic compound;
An organic compound,
At least one of the inorganic compound and the organic compound has a cation exchange group, and a π-π interaction works between molecules of the inorganic compound and the organic compound. .

  The structure of the present invention comprises a base material and the organic-inorganic composite described above formed on the base material.

The method for producing the organic-inorganic composite of the present invention comprises:
A method for producing an organic-inorganic composite comprising an inorganic compound and an organic compound,
Using a substance having no cation exchange group as a raw material for the inorganic compound and the organic compound, the inorganic compound and the organic compound are combined in a state where a π-π interaction acts between molecules. Introducing a cation exchange group, or using a substance having a cation exchange group in at least one of the inorganic compound and the organic compound as a raw material in a state in which a π-π interaction works between molecules A compounding step of compounding the compound with the organic compound to obtain an organic-inorganic complex.

  The method for producing an organic-inorganic composite, structure and organic-inorganic composite of the present invention can further improve functionality and mechanical strength. This reason is guessed as follows, for example. For example, since an inorganic compound and an organic compound are hybridized, the mechanical strength is excellent. In this respect, it is considered that the π-π interaction works between molecules of the inorganic compound and the organic compound, so that the inorganic compound and the organic compound are more strongly bonded. Furthermore, since the mechanical strength is enhanced by the π-π interaction, many cation exchange groups can be introduced into the organic-inorganic hybrid material without impairing the function of the cation exchange groups. Furthermore, functions such as affinity with the compound, adsorptivity and catalytic activity can be expressed more highly by the metal cation bound to the cation exchange group.

Explanatory drawing showing an example of the organic inorganic composite of this invention. Explanatory drawing showing the specific example of an organic inorganic composite. FIG. 3 is an explanatory diagram illustrating an example of a schematic configuration of a structure body.

  An embodiment of the structure of the present invention will be described with reference to the drawings. Drawing 1 is an explanatory view showing an example of an organic inorganic composite which is one embodiment of the present invention. FIG. 2 is an explanatory diagram illustrating a specific example of an organic-inorganic composite. FIG. 3 is an explanatory diagram illustrating an example of a schematic configuration of the structure 10. The organic-inorganic composite of the present invention comprises an inorganic compound and an organic compound, and at least one of the inorganic compound and the organic compound has a cation exchange group. A π-π interaction is acting between molecules with the compound.

  The inorganic compound may have, for example, a metal matrix structure and an aromatic hydrocarbon structure bonded to the metal matrix structure. The metal matrix structure may be, for example, a chain structure of metal and oxygen or a three-dimensional structure. The aromatic hydrocarbon structure may be bonded to a metal in the metal matrix structure. This aromatic hydrocarbon structure may be bonded to the main chain of the metal matrix structure, or may be an aromatic hydrocarbon group bonded to a side chain. The inorganic compound may be a compound containing one or more selected from Si, Ti, Al, and Zr and O. A compound containing these metals tends to have a structure with high mechanical strength due to bonding with oxygen. In addition, a chain structure or a three-dimensional structure is preferable. In the inorganic compound, the aromatic hydrocarbon structure includes, for example, a benzene ring structure, a structure in which a part of the benzene ring is substituted with a substituent, and a naphthalene ring structure. Examples of the substituent include an alkyl group, halogen, and hydroxyl group. In addition, the aromatic hydrocarbon group includes, for example, a naphthyl group in addition to a phenyl group, a benzyl group, a tolyl group, a xylyl group, etc. in which a part of the phenyl group is substituted with a substituent.

  The inorganic compound may be a hydrolyzed compound of a metal alkoxide. Metal alkoxide is preferable because it is easily hydrolyzed and polymerized. This metal alkoxide may have, for example, the above aromatic hydrocarbon structure. As the metal alkoxide, for example, when the metal is Si, trimethoxyphenylsilane, triethoxyphenylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, paratolyltrimethoxysilane, orthotolyltrimethoxysilane, methallyltrimethoxy Examples include silane, paraxyltrimethoxysilane, orthoxylmethoxysilane, and metaxyltrimethoxysilane. When the metal is Ti, phenyltriisopropoxytitanium and the like are listed.

  The organic compound may have a carbon structure in which carbon atoms are bonded and an aromatic hydrocarbon structure bonded to the carbon structure. This carbon structure may be a chain structure or a three-dimensional structure. The aromatic hydrocarbon structure may be bonded to the main chain of the carbon structure, or may be an aromatic hydrocarbon group bonded to the side chain. Such can include polymers. Examples of the polymer include a phenol resin, polyester (polyethylene terephthalate, polyarylate, etc.), polycarbonate, and the like as those containing an aromatic hydrocarbon structure in the main chain. Examples of the polymer include those containing an aromatic hydrocarbon group in the side chain, such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and styrene-divinylbenzene copolymer. . Among these, those having polystyrene as a basic skeleton are preferable. The aromatic hydrocarbon structure (including the aromatic hydrocarbon group) may be the same as that described for the inorganic compound, and may be the same as or different from the aromatic hydrocarbon structure of the inorganic compound. This organic compound may be a polymer having a cation exchange group. Examples of the cation exchange group include a sulfo group, a carboxyl group, a phosphate group, and a hydroxyl group. Among these, a carboxyl group and a sulfo group are preferable because they easily hold metal ions. Examples of the cation bonded to the cation exchange group include metal cations such as Au, Ag, Cu, Pt, Pd, Ni, Co, Fe, and alkali metals, and H and ammonium ions. Of these, Ag is particularly preferable because it can be used for olefin separation. The cation exchange group may be bonded to an organic compound or an inorganic compound, but is preferably bonded to an organic compound. Of the inorganic compounds and organic compounds, the compound having a cation exchange group preferably has a cation exchange group before the inorganic compound and the organic compound are combined. That is, it is preferable to combine the inorganic compound and the organic compound after the cation exchange group is introduced into the compound. By doing so, it is not necessary to perform a step of introducing a cation exchange group such as sulfonation after the complexation, and it is preferable because the influence on the organic-inorganic complex such as a decrease in strength due to the sulfonation can be further reduced.

  Here, “π-π interaction” refers to an interaction that works between aromatic rings. In general, when compound X and compound Y each have an aromatic ring, when compound X and compound Y are mixed, the π electron of the aromatic ring of compound X and the π electron of the aromatic ring of compound Y In the meantime, π-π interaction works.

  The organic-inorganic composite of the present invention preferably has a mechanical strength of 50 MPa or more. Further, this mechanical strength is, for example, more preferably 60 MPa or more, and further preferably 80 MPa or more. This mechanical strength shall be the result of measuring the tensile stress (breaking) according to ISO 527-2.

  The organic-inorganic composite of the present invention may have a function of selectively transmitting a specific component contained in a fluid composed of a plurality of components. Examples of the fluid include liquid and gas. For example, the organic-inorganic composite may have an olefin / paraffin separation function. At this time, the cation bonded to the cation exchange group may exhibit or enhance the separation function. Moreover, the organic-inorganic composite of the present invention may have a function of separating the first component contained in the fluid and the second component contained in the fluid.

For example, as shown in FIG. 1, the organic-inorganic composite of the present invention includes an inorganic compound having a metal matrix structure containing a metal M and oxygen and an aromatic hydrocarbon group R ¹ , a cation exchange group B, comprising an organic compound having an aromatic hydrocarbon group R ² cation a, a, between the molecules of the aromatic hydrocarbon group R ² of the aromatic hydrocarbon groups R ¹ and organic compound of an inorganic compound It is good also as what has a pi-pi interaction working. The valence of the cation exchange group B and the cation A is arbitrary as long as it is 1 or more. More specifically, for example, as shown in FIG. 2, an inorganic compound having a Si matrix structure in which phenyl groups are bonded, and an organic compound that is a polymer having a phenyl group in which Ag ions and sulfo groups are bonded; The π-π interaction may be exerted by the phenyl groups of each other.

  Next, a method for producing this organic-inorganic composite will be described. In this production method, an inorganic compound and an organic compound are combined in a state where a π-π interaction is exerted between molecules using at least a substance having no cation exchange group as a raw material for the inorganic compound and the organic compound. And then a cation exchange group is introduced to obtain an organic-inorganic composite. Alternatively, this production method uses at least one substance having a cation exchange group in at least one of the raw materials of the inorganic compound and the organic compound, and the inorganic compound and the organic compound in a state in which π-π interaction works between molecules. A compounding step of compounding the compound to obtain an organic-inorganic complex.

  In the compounding step, for example, a metal alkoxide having an aromatic hydrocarbon structure is used as a raw material for an inorganic compound, a polymer having an aromatic hydrocarbon structure is used as an organic compound, and a metal containing a metal alkoxide and a polymer is used in a solution. By hydrolyzing the alkoxide, an inorganic compound may be generated, and the inorganic compound and the organic compound may be combined. In this complexing step, it is preferable to use a polymer having a cation exchange group as the organic compound. That is, it is preferable that the polymer of the organic compound has a cation exchange group before the inorganic compound and the organic compound are combined. In this case, it is not necessary to perform a step of introducing a cation exchange group such as sulfonation after the formation of the complex. For example, the influence of the sulfonation on the organic-inorganic composite can be further reduced, which is preferable.

  The compounding step includes, for example, a precursor generation step in which a metal alkoxide is added to a solution in which an organic compound that is a polymer having a cation exchange group is dissolved, and hydrolysis and polymerization are performed to prepare a precursor sol, and a precursor A calcination step of drying and calcination of the sol and an ion exchange step of exchanging the cation of the cation exchange group with a metal ion having a desired function may be included. This ion exchange step may be performed at any timing from before the precursor generation step to after the firing step. In the precursor generation step, as the polymer solution, for example, the polymer may be dissolved in a mixed solution of an organic solvent such as N-methyl-2-pyrrolidone (NMP), an alcohol, and water. The metal alkoxide preferably has, for example, one or more metals selected from Si, Ti, Al and Zr and an aromatic hydrocarbon structure. In the firing step, the precursor sol is formed into a predetermined shape and dried to form a gel, for example, heat treatment at a temperature of 60 ° C. or higher and 300 ° C. or lower. In the ion exchange step, for example, the cation of the cation exchange group is preferably exchanged with a cation such as Au, Ag, Cu, Pt, Pd, Ni, Co, Fe, and an alkali metal. Through these steps, the organic-inorganic composite shown in FIGS. 1 and 2 can be manufactured.

  Next, the structure of the present invention will be described. The structure of the present invention comprises a base material and any one of the organic-inorganic composites described above formed on the base material. Although a base material is not specifically limited, For example, organic materials, such as resin, an inorganic material, a metal material, etc. can be used. Examples of the inorganic material include one or more selected from cordierite, Si-bonded SiC, recrystallized SiC, aluminum titanate, mullite, silicon nitride, sialon, zirconium phosphate, zirconia, titania, alumina, and silica. it can. The organic-inorganic composite may be formed on the substrate as a film, for example. At this time, the thickness of the organic-inorganic composite can be, for example, about 0.01 μm to several tens of μm.

  A specific example of this structure will be described. As shown in FIG. 3, the structure 10 of the present invention includes a porous partition wall portion 14 as a base material for forming a plurality of cells 12 serving as a flow path for a mixed fluid, and the partition wall formed of the organic-inorganic composite described above. And a functional layer 16 provided on the inner surface 15 of the portion 14. In addition, a seal portion 18 is formed on the end surface 17 of the partition wall portion 14. The seal portion 18 is formed of a dense material such as glass, ceramics, or resin, and prevents inflow or outflow of fluid from the end surface 17 of the partition wall portion 14. In the structure 10, the functional layer 16 functions as a separation membrane that separates the mixed fluid. Specifically, among the mixed fluid entering the cell 12 from the inlet side, the fluid having a high affinity with the cation bonded to the cation exchange group of the organic-inorganic composite of the functional layer 16 forms the functional layer 16. It passes through the porous partition wall 14 and is concentrated and discharged from the side surface of the structure 10 as a concentrated fluid. On the other hand, a fluid that has a low affinity for cations and cannot pass through the functional layer 16 flows along the flow path of the cell 12 and is discharged from the outlet side of the cell 12 as a separation fluid. The partition wall portion 14 may have a multilayer structure of two or more layers in which a fine particle portion 14b having a small pore diameter is formed on the surface of a coarse particle portion 14a having a large pore diameter. The pore diameter of the coarse particle portion 14a can be set to, for example, about 0.1 μm to several hundred μm. The pore diameter of the fine-grained portion 14b only needs to be smaller than the pore diameter of the coarse-grained portion 14a. For example, the pore diameter can be about 0.001 to 1 μm. If it carries out like this, the permeation | transmission resistance of the partition part 14 can be reduced. Thus, the structure 10 can be formed and an organic-inorganic composite can be utilized.

  According to the organic-inorganic composite described above, since the inorganic compound and the organic compound are hybridized, the mechanical strength is excellent. In addition, since the π-π interaction works between molecules of the inorganic compound and the organic compound, the inorganic compound and the organic compound are more firmly bonded. Furthermore, since the mechanical strength is enhanced by the π-π interaction, a large number of cation exchange groups can be introduced into the organic-inorganic composite without impairing the function of the cation exchange groups. Furthermore, functions such as affinity with the compound, adsorptivity and catalytic activity can be expressed more highly by the metal cation bound to the cation exchange group. Therefore, functionality and mechanical strength can be further increased.

  It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.

  For example, in the above-described embodiment, the structure 10 includes a plurality of cells 12 and fluid flows. However, if the structure 10 includes a base material and an organic-inorganic composite formed on the base material, It is not limited to this shape. For example, it may be a tubular shape with one cell. Alternatively, the organic-inorganic composite of the present invention may be used in a powder state. The organic-inorganic composite powder can be used, for example, as an adsorbent or a catalyst.

  In the above-described embodiment, the functional layer 16 made of an organic-inorganic composite functions as a separation membrane that separates a mixed fluid as a fluid. However, the functional layer 16 is not limited to this, and sterilization that sterilizes and purifies liquids and gases. -It may function as a purification membrane. The structure 10 provided with the functional layer 16 as such a sterilization / purification film can be used as a sterilization / purification filter.

  Although not described in the above-described embodiment, in the method for producing an organic-inorganic composite, the compounding step includes a substance having a cation exchange group in at least one of the inorganic compound and the organic compound as a raw material. An inorganic compound and an organic compound are combined with a π-π interaction between molecules used, and then a cation exchange group is introduced into the inorganic compound and / or organic compound to obtain an organic-inorganic composite. It may be a thing. Even in this case, functionality and mechanical strength can be further increased. In addition, when using the raw material which has a cation exchange group previously, although the process of introduce | transducing a subsequent ion exchange group may be included, since the influence on organic-inorganic composites, such as a strength fall, can be reduced, it abbreviate | omits. Is preferred.

  Hereinafter, an example in which an organic-inorganic composite is specifically produced will be described as an experimental example. Experimental examples 1 to 5 and 8 correspond to examples of the present invention, and experimental examples 6 to 7 correspond to comparative examples.

[Experiment 1]
First, a precursor sol was synthesized. A polymer solution was prepared by mixing 2 g of polystyrene sulfonate as a polymer and 80 g of a mixed solvent of N-methyl-2-pyrrolidone (NMP) and water (1: 1 by volume) as a solvent. Next, 1 g of nitric acid as a catalyst was added to the polymer solution. 10 g of trimethoxyphenylsilane as a raw material for the inorganic compound was added to the polymer solution and stirred. Then, hydrolysis and polymerization of trimethoxyphenylsilane proceeded to obtain a precursor sol. This precursor sol was put in a petri dish and dried to prepare a gel. The obtained gel was baked at 150 ° C. for 2 hours to prepare a fired body. The fired body was pulverized to an appropriate size. Subsequently, an ion exchange treatment was performed. An AgBF ₄ aqueous solution (0.5 mol / L) was prepared, and the fired body was immersed therein. Thereafter, the fired body was taken out from the aqueous solution, washed and dried, and the obtained organic-inorganic composite was used as Experimental Example 1.

[Experimental Examples 2 and 3]
The same steps as in Experimental Example 1 were performed except that sodium polystyrene carboxylate was used instead of sodium polystyrene sulfonate, and the obtained organic-inorganic composite was taken as Experimental Example 2. Further, in the steps of hydrolysis and polymerization of metal alkoxide, the same steps as in Experimental Example 1 were performed except that phenyltriisopropoxytitanium was used instead of trimethoxyphenylsilane, and the obtained organic-inorganic composite was tested. Example 3 was used.

[Experimental Example 4]

A polymer solution was prepared by mixing 2 g of polystyrene as a polymer and 80 g of a mixed solvent of tetrahydrofuran and water (1: 1 by volume) as a solvent. Next, 1 g of nitric acid as a catalyst was added to the polymer solution. 10 g of trimethoxyphenylsilane as a raw material for the inorganic compound was added to the polymer solution and stirred. Then, hydrolysis and polymerization of trimethoxyphenylsilane proceeded to obtain a precursor sol. This precursor sol was put in a petri dish and dried to prepare a gel. The obtained gel was baked at 150 ° C. for 2 hours to prepare a fired body. The fired body was pulverized to an appropriate size. Subsequently, sulfonation treatment was performed. The fired body was immersed in anhydrous sulfuric acid and kept at 25 ° C., and then the fired body was taken out from anhydrous sulfuric acid, washed and dried. By this treatment, a sulfo group was introduced into the phenyl group of the fired product. Then, the fired body was immersed in an AgBF ₄ aqueous solution (0.5 mol / L). Then, this fired body was taken out from the aqueous solution, washed and dried, and the obtained organic-inorganic composite was used as Experimental Example 4.

[Experimental Example 5]
A polymer solution was prepared by mixing 2 g of a phenol resin as a polymer and 80 g of a mixed solvent of methanol and water (1: 1 by volume) as a solvent. Next, 1 g of nitric acid as a catalyst was added to the polymer solution. 10 g of trimethoxyphenylsilane as a raw material for the inorganic compound was added to the polymer solution and stirred. Then, hydrolysis and polymerization of trimethoxyphenylsilane proceeded to obtain a precursor sol. This precursor sol was put in a petri dish and dried to prepare a gel. The obtained gel was baked at 150 ° C. for 2 hours to prepare a fired body. The fired body was pulverized to an appropriate size. Subsequently, sulfonation treatment was performed. The fired body was immersed in anhydrous sulfuric acid and kept at 25 ° C., and then the fired body was taken out from anhydrous sulfuric acid, washed and dried. By this treatment, a sulfo group was introduced into the phenyl group of the fired product. Then, the fired body was immersed in an AgBF ₄ aqueous solution (0.5 mol / L). Then, this fired body was taken out from the aqueous solution, washed and dried, and the obtained organic-inorganic composite was used as Experimental Example 5.

[Experimental Example 6]
The addition of the catalyst and the addition of the metal alkoxide in Experimental Example 1 were omitted, and Experimental Example 6 was the one containing no inorganic compound.

[Experimental Example 7]
Instead of adding trimethoxyphenylsilane, the same process as in Experimental Example 1 was performed except that silica particles (average primary particle size 0.016 μm) were added, and the obtained result was taken as Experimental Example 7.

[Experimental Example 8]
The precursor sol produced in Experimental Example 1 was applied on a porous alumina substrate having a diameter of 10 mm, a length of 10 cm, and a surface pore diameter of 0.1 μm, dried, and then fired at 150 ° C. for 2 hours to obtain a structure. Produced. One end of this structure was sealed, and a glass tube was connected to the other end. Subsequently, an ion exchange treatment of this structure was performed. An AgBF ₄ aqueous solution (0.5 mol / L) was prepared, and the structure was immersed therein. Then, this structure was taken out from the aqueous solution and dried, and the resulting structure was designated as Experimental Example 8.

(Mechanical strength measurement)
The mechanical strength was measured using the fired bodies before the ion exchange treatment in Experimental Examples 1 to 7. As the measurement of mechanical strength, tensile stress (rupture) was measured according to ISO 527-2. The measurement temperature was 23 ° C.

(Durability evaluation of adsorption performance)
The measurement regarding the gas separation function of Experimental Examples 1 to 7 was performed using a high-pressure gas adsorption amount measuring apparatus (MSB-AD-H manufactured by Nippon Bell Co., Ltd.) having a magnetic floating balance. Here, the separation function of olefin / paraffin was considered, and as a model, ethylene and ethane adsorption measurements were repeated 10 times. If either ethylene or ethane is more adsorbed, it can be determined that the olefin / paraffin separation function is higher. The adsorption measurement was carried out using ethylene simple gas or ethane simple gas under measurement conditions of 23 ° C. and 0 MPa to 1 MPa. Using the results of adsorption measurement, (ethylene adsorption amount at 1 MPa) / (ethane adsorption amount) was defined as selectivity. Further, (selectivity at the 10th measurement) / (selectivity at the first measurement) was defined as the selectivity maintenance rate. It can be determined that the higher the selectivity maintenance rate, the higher the durability of the gas separation function.

(Evaluation of gas permeability of structure)
The measurement regarding the gas separation function of Experimental Example 8 was performed. The gas permeability was evaluated using an ethylene / ethane mixed gas (1: 1) under measurement conditions of 23 ° C. and 1 MPa.

(Results and discussion)
Table 1 summarizes the configurations of the organic-inorganic composites, the presence or absence of post-treatment, the mechanical strength, and the selectivity maintenance ratio of Experimental Examples 1 to 7. As shown in Table 1, in Experimental Examples 6 and 7, the mechanical strength was low and the gas selectivity maintenance rate was extremely low. In Experimental Example 7, the mechanical strength was improved as compared with Experimental Example 6 as an effect of the addition of silica particles, but the ratio was low. This is presumed to be because the affinity between the inorganic compound composed of silica particles and the organic compound is low, and peeling occurs between the inorganic compound and the organic compound. On the other hand, in Experimental Examples 1 to 5, it was found that the mechanical strength was as high as 50 MPa or more and the gas selectivity maintenance ratio was 0.50 or more, and the durability was also improved. Considering this, it is presumed that the inorganic compound has a metal matrix structure having a metal-oxygen bond, and a phenyl group is bonded to the metal matrix structure. On the other hand, polystyrene-based organic compounds have a phenyl group. For this reason, it was considered that a π-π interaction worked between molecules of the phenyl group of the inorganic compound and the phenyl group of the organic compound. It was speculated that the inorganic compound and the organic compound are strengthened by the π-π interaction. Moreover, since the inorganic compound and the organic compound are strengthened by the π-π interaction, it is presumed that the function of the cation exchange group is not impaired and a higher function is exhibited. Considering Experimental Examples 4 and 5 in which a sulfo group, which is a cation exchange group, was introduced after the complexation, as compared with Experimental Examples 4 and 5, Experimental Example 1 having a sulfo group before the complexing The mechanical strength and selectivity retention ratio of ˜3 were high. Regarding this, it was speculated that if the sulfonation treatment was performed after the complexation, the structure of the complex was adversely affected. Therefore, it was found that it is preferable to perform a composite of an inorganic compound and an organic compound after sulfonation. Moreover, as a result of evaluating gas permeability in Experimental Example 8, it was confirmed that ethylene permeates selectively as compared with ethane.

  The present invention can be used in the field of functional materials such as filters and honeycomb structures.

  DESCRIPTION OF SYMBOLS 10 Structure, 11 End surface, 12 Cell, 14 Partition part, 14a Coarse grain part, 14b Fine grain part, 15 Inner surface, 16 Functional layer, 17 End surface, 18 Seal part.

Claims (11)

An inorganic compound which is a hydrolyzate of a metal alkoxide and may have a cation exchange group ;
An organic compound that is a polymer that may have a cation exchange group ,
At least one of the inorganic compound and the organic compound has a cation exchange group, and a π-π interaction works between molecules of the inorganic compound and the organic compound,
The cation exchange group is bonded with one or more metal ions selected from Au, Ag, Cu, Pt, Pd, Ni, Co and Fe,
A separation membrane that selectively permeates a specific component contained in a fluid composed of a plurality of components.
Organic inorganic composite.   The organic-inorganic composite according to claim 1, wherein the inorganic compound has a metal matrix structure and an aromatic hydrocarbon structure bonded to the metal matrix structure.   The organic-inorganic composite according to claim 1, wherein the inorganic compound is a compound containing one or more selected from Si, Ti, Al, and Zr and O.   The organic-inorganic composite according to any one of claims 1 to 3, wherein the inorganic compound is a hydrolyzed compound of a metal alkoxide.   The organic-inorganic composite according to any one of claims 1 to 4, wherein the organic compound has a carbon structure in which carbon atoms are bonded and an aromatic hydrocarbon structure bonded to the carbon structure. body.   The organic-inorganic composite according to any one of claims 1 to 5, wherein the organic compound is a polymer having the cation exchange group.   The organic-inorganic composite according to any one of claims 1 to 6, wherein the mechanical strength is 50 MPa or more. A substrate;
The organic-inorganic composite according to any one of claims 1 to 7, formed on the base material,
A structure with An inorganic compound which is a hydrolyzate of a metal alkoxide and may have a cation exchange group, and an organic compound which is a polymer which may have a cation exchange group , the inorganic compound and the At least one of the organic compounds has a cation exchange group, and is a method for producing an organic-inorganic composite that is a separation membrane that selectively permeates specific components contained in a fluid composed of a plurality of components. ,
The inorganic compound and the organic compound are combined in a state where a π-π interaction acts between molecules using at least a substance having no cation exchange group as a raw material for the inorganic compound and the organic compound. Thereafter, a cation exchange group is introduced, or at least one substance having a cation exchange group in at least one of the raw materials of the inorganic compound and the organic compound is used in a state where a π-π interaction works between molecules. A compounding step of compounding an inorganic compound and the organic compound to obtain an organic-inorganic complex,
The cation exchange group is bonded with one or more metal ions selected from Au, Ag, Cu, Pt, Pd, Ni, Co and Fe.
A method for producing an organic-inorganic composite.   The method for producing an organic-inorganic composite according to claim 9, wherein in the complexing step, a polymer having the cation exchange group is used as the organic compound.   In the compounding step, a metal alkoxide having an aromatic hydrocarbon structure is used as a raw material for the inorganic compound, a polymer having an aromatic hydrocarbon structure is used as the organic compound, and the metal alkoxide and the polymer are included. The method for producing an organic-inorganic composite according to claim 9 or 10, wherein the inorganic compound and the organic compound are combined by hydrolyzing the metal alkoxide with a solution.

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