JP3455133B2 - Method for producing high concentration particulate carrier - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-concentration fine particle-supported material, and more specifically to a method of adsorbing high-concentration fine particles of metal and / or metal oxide on a carrier.
The present invention relates to a method for producing a high-concentration fine particle-supported material which can be used as a catalyst for removing carbon monoxide, removing malodorous components such as mercaptans and amines, and synthesizing various compounds.

[0002]

2. Description of the Related Art It is known that a catalyst material carrying fine particles obtained by adsorbing and immobilizing a fine particle dispersion composite on an inorganic compound carrier such as titanium oxide has high catalytic activity. In order to further increase the activity of this catalyst material, it was necessary to increase the amount of fine particles supported, and for that reason, it was necessary to increase the concentration of fine particles in the fine particle-dispersed composite material as a raw material.

Therefore, as a conventional method for producing fine particles, there is a method for producing fine particles in a solution or in a gas phase. When producing fine particles in a solution, a compound such as chloroauric acid was dissolved in an aqueous solution, and then a reducing agent was put in the aqueous solution to colloid the gold ions.

On the other hand, in the case of a method for producing fine particles in a gas phase, 1) metal fine particles obtained by evaporation are attached to a substrate and the obtained fine particles are peeled from the substrate, 2) evaporated. The fine particles of the metal obtained by contacting with the vapor of the surfactant are dropped into a colloid. 3) The fine particles of the metal obtained by evaporation are trapped on the oil to prevent grain growth. There is a method such as collecting in.

Further, as another method, Japanese Patent Publication No. 6-995.
In Japanese Patent Publication No. 85, after melting a polymer material, a metal layer is brought into close contact with the surface of the polymer layer in a thermodynamically non-equilibrium state in which the resulting substance is rapidly solidified, and then the polymer layer is equilibrated. A method is disclosed in which a metal or a metal oxide, which is a fine particle of the metal layer, is dispersed in the polymer layer by relaxing the metal layer to the state.

[0006]

However, in the method for producing fine particles in a solution, there is a problem that impurities such as a reducing agent other than the fine gold particles exist in the aqueous solution, and the fine gold particles are unstable as they are. Yes, a surfactant or the like was usually added for stabilization. On the other hand, even in the method of producing fine particles in a gas phase, in 1) the fine particles cannot be dispersed and used for other purposes, and in 2) when they are made solid, they cannot be dispersed again, and 3 In (), since it cannot be stabilized as a colloid, it is agglomerated and it is difficult to obtain high-concentration fine particles.

That is, when a method using a reduction reaction in a solution or a gas phase reaction is used to obtain high-concentration fine particles, there is a problem that the fine particles cannot be separated due to aggregation.
Further, when trying to obtain high-concentration fine particles, there is a problem that the fine particles cannot be separated due to aggregation. For this reason,
It was difficult to obtain a material having a high concentration of fine particles and having a high catalytic activity.

The present invention solves these problems, and a high-concentration fine particle-supported material having a high catalytic activity by preparing a high-concentration fine-particle-dispersed composite to support high-concentration fine particles is provided. A method of manufacturing the is provided.

[0009]

That is, according to the first aspect of the present invention, a complex in which fine particles of a metal and / or a metal oxide are dispersed in a matrix material is dissolved in an alcoholic solvent and bonded to the fine particles. The matrix material is removed to prepare a high-concentration fine particle-dispersed composite, the obtained composite is dissolved in a solvent to form a fine particle dispersion, and a carrier is put into this dispersion to convert the fine particles into a polymer or an oligomer. In a method for producing a high-concentration fine particle-supported material which is adsorbed on a carrier through a matrix material made of, the complex is dissolved in an alcoholic solvent to be present around fine particles of metal and / or metal oxide. It is possible to obtain a concentrated fine particle-dispersed composite by removing low-molecular substances that have not been bound to, and use this to support fine particles of high concentration on a carrier. It is possible to obtain.

According to the second aspect of the present invention, after adsorbing fine particles to a carrier through a matrix material composed of a polymer or an oligomer, the carrier is burned at a decomposition temperature of the matrix material or higher, and a high-concentration fine particle-supported material is carried out. In the manufacturing method, the polymer or oligomer attached to the fine particles is thermally decomposed, and only the fine particles are independently fixed to the carrier.

The third aspect of the present invention relates to a method for producing a high-concentration fine particle-supported material, in which the composite material and the alcoholic solvent are mixed and stirred, and then the matrix material not bound to the fine particles is removed and only the precipitate is taken out. is there.

According to a fourth aspect of the present invention, as a method for producing the above composite, a matrix material composed of a polymer or an oligomer is housed in a container placed under a reduced pressure environment, and the matrix material is heated and melted. In a method for producing a high-concentration fine particle-supported material, the fine particles of a metal and / or a metal oxide are dispersed in the melted matrix material after the metal material is evaporated and captured in the melt of the matrix material, When the evaporated metal reaches the surface of the molten matrix material, it is captured by strong interaction with the matrix material,
The particles are stabilized in the form of fine particles of metal and / or metal oxide, and since the matrix material is heated and convected in the container, it becomes possible to disperse the particles uniformly in the matrix material. Has a high dispersion speed and can disperse many fine particles.

According to a fifth aspect of the present invention, the matrix material is a regenerated polymer produced by thermally decomposing a polymer material to vaporize it, and then cooling this vaporized material, which is a high-concentration particulate support material. There is a manufacturing method.

According to a sixth aspect of the present invention, the matrix material is a polymer or oligomer having at least one functional group selected from a cyano group, an amino group and a thiol group at the terminal or side chain of the molecule. It is a method for producing a fine particle-supported material having a high concentration.

The invention according to claim 7 is a synthetic polyamide in which the matrix material is polymerized so as to limit the molecular weight in the range of 400 to 7000, and H ₂ N- (CH ₂ ) _n C
An amino acid monomer represented by a molecular formula of OOH (n is 1 to 36), R- (CH ₂ ) m —NH ₂ (m is 1 to 36,
R is a group selected from CH ₃ —, a cyano group, an amino group, and a thiol group), and an amine or polyamine having an amine group at the molecular end, and a cyano group, an amino group on the side chain of the amine or polyamine, and A method for producing a high-concentration fine particle-supported material, which is obtained by polymerizing an amine having at least one functional group selected from thiol groups or at least one polymerization inhibitor selected from polyamines in the presence of a catalyst. .

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an example of an apparatus for producing a composite used in the present invention, and its schematic view is shown. In this manufacturing apparatus 1, a heating device 4 is arranged in a vacuum device 3 equipped with a decompression device 2, and a container 6 is placed thereon. The container 6 contains a matrix material 5 composed of a polymer or an oligomer, and the matrix material 5 is heated and melted, and then the metal material 8 placed in the crucible 7 in the container 3 is evaporated and After being captured by the melt of the matrix material 5, fine particles 9 of metal and / or metal oxide are dispersed in the melted matrix material 5. Since the heated matrix material 5 in the container 6 is convective, the fine particles 9 can be uniformly dispersed in the matrix material 5, and the dispersion speed of the fine particles 9 is high.
Many fine particles 9 can also be dispersed.

Further, in the manufacturing method, as shown in FIG. 1, a container 6 containing a matrix material 5 in a vacuum device 2 is installed on a heating device 4 such as a heater, and the heating device 4 is set to 70-2.
It is heated at 00 ° C. to melt the matrix material 5 and always maintain a constant viscosity. Then, the vacuum pump 2 is operated to reduce the pressure in the vacuum device 2 to 5 × 10 ⁻⁵ torr, and then gold, silver, platinum, copper, iron, nickel, cobalt, tin, zinc, cerium, which are evaporation sources, By evaporating at least one metal material 8 selected from yttrium or the like by resistance heating and capturing fine particles 9 of metal and / or metal oxide in the melt of the matrix material 5,
The fine particles 9 are dispersed in the matrix material 5 to obtain the composite 10. Since the matrix material 5 is heated, it is constantly convected, and a large amount of the fine particles 9 are uniformly dispersed.

As the material of the matrix material used here, a polyamide resin composed of nylon 11, nylon 6, nylon 66, nylon 6.10, etc. is heated and pyrolyzed in a closed container under a reduced pressure. After vaporization, the regenerated polymer obtained by cooling the vaporized product is used.

Further, as another matrix material, a polymer or oligomer having at least one functional group selected from a cyano group, an amino group and a thiol group at the terminal or side chain of the molecule can be used. Specifically, the polymer or oligomer is terminated or side chain cyano group of a molecule (-CN), amino group (-NH _2), and at least one functional selected from a thiol group (-SH) It has a group, and its skeleton consists of nylon 11, nylon 6, nylon 66, nylon 6.10, etc.,
Its melting point or softening point is 40 to 100 ° C. The average molecular weight of the oligomer is not particularly limited, but is 500 to 6
It is about 000. The above-mentioned functional group is particularly likely to form a covalent bond or a coordinate bond with a metal atom on the surface of the fine particles, suppresses grain growth, and enhances dispersibility of the fine particles.

Further, as matrix materials other than the above,
It is obtained by polymerizing a synthetic polyamide so that the molecular weight is limited to the range of 400 to 7,000. In this case, when the molecular weight is less than 400, the metal and / or the metal oxide is likely to be evaporated during the deposition under reduced pressure.
If it exceeds, it becomes difficult for the fine particles to be dispersed.

Specifically, as a method for producing the synthetic polyamide, H ₂ N- (CH ₂ ) _n COOH (n is 1 to 3)
6) Amino acid monomer represented by the molecular formula, a polymerization inhibitor comprising a polyamine having at least two or more amino groups at the molecular ends or side chains, and a catalyst such as N-methylpyrrolidone, a solvent such as dimethylacetamide, While stirring, the temperature is raised to 100 to 150 ° C., polymerization is performed while flowing nitrogen gas, and after completion of the polymerization, the temperature is cooled to room temperature. The reaction product was poured into ethyl acetate, toluene, hexane, etc., and left to stand overnight for precipitation, and then the precipitate was collected by filtration, washed, and dried at 40 to 70 ° C.

The above H ₂ N- (CH ₂ ) _n COOH (n is 1
The amino acid monomers represented by the molecular formulas (1) to (36) include 11-aminoundecanoic acid and 9-aminononanoic acid.

As the polymerization inhibitor, R- (CH₂) M
-NH₂ (M is 1-36, R is CH ₃-, Cyano group,
A group selected from a mino group and a thiol group)
Amine or polyamido having an amine group at the molecular end
And cyano on the side chain of the amine or polyamine
Groups, amino groups, and functional groups selected from thiol groups
Amines or polyamines with at least one or more
Hexamethylenedia
Min, ε-aminocapronitrile, ethylenediamine, etc.
Is used.

As the catalyst, quinoline, triphenylphosphite or the like is used.

The method of manufacturing the composite material in this embodiment is not limited to the above-mentioned method, and a matrix material is applied onto a glass substrate to form a thin film, and a metal vapor deposition film is formed on the thin film. After stacking, heat to make metal and /
Alternatively, fine particles of metal oxide can be dispersed in a thin film to prepare a composite. This method is disclosed in Japanese Patent Publication No. 6-99585.

Therefore, in the present invention, as shown in the model diagram of the manufacturing process of the concentrated fine particle-dispersed composite of FIG. 2, the composite 10 is the fine particles 9 of metal and / or metal oxide.
Are held by a matrix 13 composed of surrounding oligomers or polymers, and when an alcohol solvent is added to this complex 10 and the mixture is agitated and left to stand, the liquid 1
1 and the precipitate 12 are separated. The liquid material 11 contains a matrix 13a composed of an oligomer or polymer which is not bound to the fine particles 9 of metal and / or metal oxide.
Contained, and is removed to take out only the precipitate 12. The precipitate 12 is composed of a matrix 13b bonded to the fine particles 9 of metal and / or metal oxide, and is a concentrated fine particle dispersed composite 15.

That is, an alcohol solvent such as methyl alcohol, propyl alcohol or butyl alcohol was added to a complex prepared in advance with a metal content not causing gelation, and the mixture was stirred at room temperature and then allowed to stand to precipitate. To get After that, this is filtered to remove the matrix dissolved in the alcohol solvent, which is not bound to the fine particles of metal and / or metal oxide, whereby only the precipitate is taken out.
The precipitate is 4-6 times more concentrated than the original complex. The concentrated complex is dissolved in an organic solvent such as dichloromethane, 1,2,3-trichloropropane or metacresol to prepare a concentrated fine particle dispersion solution.

Subsequently, in order to remove the adsorbed water on the surface, a pre-heated granular or powdery carrier is put into the above concentrated fine particle dispersion solution and left to stand, and the fine particles pass through the polymer or oligomer to form a carrier. Is adsorbed on the surface of the carrier and the surface of the carrier is discolored. FIG. 2 is a model diagram of a state in which the fine particles 9 are adsorbed on the surface of the carrier 19 via the matrix 13b bonded to the fine particles 9. A cyano group or an amino group at the molecular end or side chain of the matrix 13b bonded to the fine particles 9;
Alternatively, it is chemically bonded to the fine particles 9 by a functional group such as a thiol group, and the other end is chemically bonded to the carrier 19. Even if the carrier 19 having the fine particles 9 adsorbed thereon is washed with water or left in a solvent, the surface color of the carrier 19 does not change, and the fine particles 9 are not separated from the carrier 19.

The carrier is silica (SiO ₂ ), alumina (Al ₂ O ₃ ), zeolite, titanium oxide, zirconia,
At least one inorganic oxide selected from heteropolyacids is preferable, and it has an active group for attaching a polymer or an oligomer to the surface.

Further, in this embodiment, the carrier 19 having the fine particles 9 adsorbed through the matrix 13b bonded thereto is baked at a temperature not lower than the decomposition temperature of the matrix 13b, so that the matrix 13b is thermally decomposed and a large amount of the surface of the carrier 19 is present. It is possible to obtain the fine particle-supported material 20 to which the fine particles 9 of (4) are independently attached. This fine particle carrier 20 has a very large catalytic activity of fine particles of metal and / or metal oxide, and further, it is expected that a very large memory capacity is expected by making it into a magnetic memory, a light or heat responsive material, a heat exchange film, It is applied to large capacity capacitor materials and various gas sensors.

[0031]

Next, the present invention will be described in more detail with reference to specific examples. Example 1 Nylon 11 pellets were used as the polymer material, and 100 g of the pellets were heated and melted at 525 ° C. to obtain decomposed ointment-like low molecular weight nylon 11. 1000 g of 20 g of ointment-like low molecular weight nylon 11 was placed in the vacuum device.
A low-molecular-weight nylon 11 was heated to 80 to 100 ° C. with an infrared heater in a ml container, and the matrix material was liquefied and kept at a constant viscosity. Then, 2.5 g of gold (total amount) was placed in each of the three tungsten boards, and the vacuum pump was activated to set the inside of the vacuum device to 5 × 10.
After reducing the pressure to ^-5 torr, a voltage was applied to heat and evaporate the gold, thereby capturing the fine particles of gold in the matrix material. After returning the vacuum device to atmospheric pressure and turning off the power of the infrared heater, the matrix material in the container taken out from the device had a red color, and gold fine particles having an average particle diameter of 5.5 nm were dispersed. understood. The dispersion concentration of the fine gold particles in the matrix material was about 14% by weight.

20 ml of methyl alcohol was added to 1 g of the composite material in which fine gold particles were dispersed in this matrix material, and the mixture was stirred well. After that, when left to stand, precipitation occurred. The color of the liquid became yellowish brown. The above liquid was separated by pressure filtration with a 0.8 μm Teflon filter, and the filtered product was thoroughly washed with methyl alcohol. Methyl alcohol was evaporated at room temperature and the precipitate was dried to give about 160 mg of a golden glossy solid.

When this solid was immersed in dicyclomethane and irradiated with ultrasonic waves, the solid was dissolved in dicyclomethane, and a red transparent solution was obtained. The light absorption spectrum of this solution was measured by UV / VIS spectrophotometer UV-VIS-3100PC.
When measured with (manufactured by Shimadzu Corp.), plasmon resonance absorption due to fine particles of gold was observed at about 530 nm. The content of gold measured by Rigaku thermogravimetric analyzer is about 73% by weight.
It was confirmed that the gold content was significantly higher than that of the original composite.

160 mg of a concentrated gold fine particle dispersion composite having a gold content of about 73% by weight was dispersed in 50 ml of dicyclomethane while irradiating ultrasonic waves to obtain a gold fine particle dispersion solution. While stirring this with a magnetic stirrer, titanium oxide powder 34 was dried at 200 ° C for 1 hour.
0 mg was added. The fine gold particles were quickly adsorbed on titanium oxide, and a reddish purple powder was precipitated. This was filtered at 200 ° C. with a Teflon membrane filter and then thoroughly washed with dicyclomethane. The filtered product was dried in an oven at 40 ° C to obtain titanium oxide having gold fine particles adsorbed thereon. When the concentration of gold adsorbed on the titanium oxide was measured by a fluorescent X-ray analyzer (manufactured by Seiko Instruments Inc.), the result was about 23% by weight.

Titanium oxide adsorbed with about 23% by weight of fine gold particles was calcined at a reduced pressure of about 1 torr at 500 ° C. for 1 hour, and subsequently at atmospheric pressure in the atmosphere at 500 ° C. for 1 hour. , The organic components were removed, and the fine gold particles were directly supported on titanium oxide. When the concentration of the fine gold particles supported on titanium oxide was measured by a fluorescent X-ray analyzer (manufactured by Seiko Instruments Inc.), it was about 23% by weight. The titanium oxide carrying the fine gold particles showed catalytic activity in the oxidation reaction of oxygen monoxide to oxygen dioxide.

[0036]

As described above, in the invention described in the claims of the present application, a matrix in which fine particles of a metal and / or a metal oxide are dispersed in a matrix material is dissolved in an alcohol solvent and is not bonded to the fine particles. The material is removed to prepare a composite in which high-concentration fine particles are dispersed, this composite is dissolved in a solvent to form a fine particle dispersion liquid, and a carrier is put into this dispersion liquid, and the fine particles consist of a polymer or an oligomer. There is a method for producing a high-concentration fine particle-supported material which is adsorbed on a carrier through a matrix material, and the complex is dissolved in an alcoholic solvent so that it is present around the fine particles of metal and / or metal oxide and is bound to this To prepare a fine particle-dispersed composite that is concentrated by removing low-molecular substances that are not present, and to use this to obtain a fine particle-supported material in which high-concentration fine particles are adsorbed on a carrier. It can be.

[Brief description of drawings]

FIG. 1 is an example of an apparatus for producing a composite used in the present invention and is a schematic view thereof.

FIG. 2 is a model diagram showing a state in which fine particles are adsorbed on the surface of a carrier through a matrix bonded thereto in the present invention.

[Explanation of symbols]

1 Manufacturing equipment 2 decompression device 3 vacuum equipment 4 heating device 5 Matrix material 6 containers 8 metal materials 9 Fine particles 10 complex 11 Liquid 12 sediment 13a Matrix not bound to fine particles 13b Matrix bound to fine particles 15 Concentrated fine particle dispersion composite 19 carriers 20 Particle support

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 B01J 35/02

Claims (7)

(57) [Claims] 1. A high-concentration fine particle-dispersed composite obtained by dissolving a complex in which fine particles of metal and / or metal oxide are dispersed in a matrix material in an alcoholic solvent to remove the matrix material not bonded to the fine particles. Was prepared, and the obtained composite was dissolved in a solvent to form a fine particle dispersion, and the carrier was put into this dispersion, and the fine particles were adsorbed to the carrier through a matrix material composed of a polymer or an oligomer. A method for producing a high-concentration fine particle-supported material, which is characterized. 2. The production of a high-concentration fine particle-supported product according to claim 1, wherein the fine particles are adsorbed on a carrier through a matrix material composed of a polymer or an oligomer, and then the carrier is baked at a decomposition temperature of the matrix material or higher. Method. 3. The method for producing a high-concentration fine particle-supported material according to claim 1, wherein only the precipitate is taken out by removing the matrix material not bound to the fine particles after mixing and stirring the complex and the alcohol solvent. . 4. The method for producing the composite, wherein a matrix material made of a polymer or an oligomer is contained in a container placed under a reduced pressure environment, the matrix material is heated and melted, and then the metal material is evaporated. The method for producing a high-concentration fine particle-supported material according to claim 1, 2 or 3, wherein fine particles of a metal and / or a metal oxide are dispersed in the melted matrix material after being captured by the melt of the matrix material. . 5. The production of a high-concentration fine particle-supported material according to claim 4, wherein the matrix material is a regenerated polymer produced by thermally decomposing and vaporizing a polymer material and then cooling the vaporized material. Method. 6. The high concentration according to claim 4, wherein the matrix material is a polymer or oligomer having at least one kind of functional group selected from a cyano group, an amino group and a thiol group at the terminal or side chain of the molecule. The method for producing a fine particle-supported article. 7. The matrix material has a molecular weight of 400 to 7
Polyamide Polymerized to Limit to 000 Range
And H₂ N- (CH₂ )_n COOH (n is 1 to 3
6) an amino acid monomer represented by the molecular formula, R- (C
H₂ ) M-NH ₂ (M is 1-36, R is CH₃ −, Shea
(A group selected from an amino group, an amino group, and a thiol group)
The indicated amine or amine having an amine group at the end of the molecule
The side chain of the amine or polyamine
Functionality selected from ano group, amino group, and thiol group
Amine or polyamido having at least one group
Of at least one polymerization inhibitor selected from
The high-concentration fine particles according to claim 4, which are polymerized in the presence of
A method for producing a particle-supported material.