JPH11253820A - Production of particulates-carrying material excellent in catalytic activity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain excellent catalytic activity by sticking particulates on the surface of a carrier from a particulates dispersion obtained by preventing the aggregation or the grain growth of the particulates of a metal or the oxide in a high polymer or an oligomer having a specific functional group and firing the carrier twice under different environment. SOLUTION: A film of the high polymer or the oligomer having at least one kind of the functional group selected from cyano group, amino group and thiol group on the terminal or side chain of the molecule is formed. The particulates of the metal, the metal oxide or the mixture are dispersed in the film by vapor depositing the metal on the film and the resultant composite material is dissolved in a solvent to prepare the particulate dispersion. The particulates-carrying material 10 having the particulates 4 fixed on the surface of the carrier 9 and excellent in catalytic activity is produced by charging the carrier into the particulates dispersion to adsorb the particulates with the high polymer or the oligomer, firing under a reduced pressure at a temp. equal to or above the decomposition temp. of the high polymer or the oligomer and further firing in the air at the temp. equal to or above the decomposition temp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a particulate carrier having excellent catalytic activity. More specifically, the present invention relates to a method in which a carrier is charged into a fine particle dispersion to adsorb the fine particles on the carrier, and at least the carrier is added to the carrier. The present invention relates to a method for producing a particulate carrier having excellent catalytic activity by baking twice or more at a decomposition temperature of a polymer or oligomer.

[0002]

2. Description of the Related Art 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 preparing fine particles in a solution, a compound such as chloroauric acid is dissolved in an aqueous solution, and then a reducing agent is added to the aqueous solution to colloid the gold ions.

On the other hand, in the case of a method of producing fine particles in the gas phase, 1) fine particles of metal obtained by evaporation are attached to a substrate, and the obtained fine particles are peeled off from the substrate. The fine metal particles obtained by the above process are exposed to the vapor of a surfactant to drop the fine metal particles into a colloid. 3) The fine metal particles obtained by evaporation are captured on oil so as not to cause grain growth. And collect them.

Further, as another method, Japanese Patent Publication No. 6-995
No. 85 discloses that after melting a polymer material, a metal layer is brought into close contact with the surface of a thermodynamically non-equilibrium polymer obtained by rapidly solidifying the resulting material and then equilibrating the polymer layer. A method is disclosed in which a metal or a metal oxide in which the metal layer is finely dispersed is dispersed in a polymer layer by relaxing the metal layer until the metal layer becomes a state.

[0005]

However, in the method of producing fine particles in a solution, there is a problem that an impurity such as a reducing agent other than the fine gold particles is present in the aqueous solution. Since it is stable, a surfactant or the like is usually added for stabilization. On the other hand, even in the method of producing fine particles in the gas phase, 1) cannot disperse the fine particles and use them for other purposes. Since it cannot be stabilized as a colloid, there has been a problem of aggregation. Furthermore, it is difficult to increase the dispersion concentration of the fine particles by the method of dispersing the finely divided metal or metal oxide in the polymer layer.

The present invention has been made to solve the above problems, and it is intended to prevent the aggregation and growth of fine particles of metal and / or oxide thereof in a polymer or oligomer having a specific functional group. A method for producing a finely particulate-supported material having excellent catalytic activity, wherein fine particles are fixed to the surface of a carrier from the obtained fine particle dispersion, and the carrier is calcined at least twice in a different environment to fix the fine particles on the surface of the carrier. I do.

[0007]

That is, the invention described in claim 1 of the present application is to provide at least one functional group selected from a cyano group, an amino group, and a thiol group at the terminal and / or the side chain of the molecule. A polymer or oligomer film having the following formula is prepared, and a metal is vapor-deposited on the film to disperse it as fine particles of metal or metal oxide or fine particles of both in the film. After dissolving into a fine particle dispersion, a carrier is introduced into the fine particle dispersion, and the fine particles are adsorbed on the carrier via the polymer or oligomer, and then the carrier is baked under reduced pressure at a temperature higher than the decomposition temperature of the polymer or oligomer. Further, the present invention is directed to a method for producing a particulate carrier having excellent catalytic activity, which is calcined in the air at the decomposition temperature or higher. When a metal is deposited on a polymer or oligomer film, fine particles of the metal and / or its oxide reach the film in the form of atoms or clusters, where some atoms or clusters gather and grow. In particular, the functional group of the polymer or oligomer interacts with the metal and / or oxide fine particles to suppress the grain growth, and as a result, a matrix of 1 to 20 nm as metal and / or oxide fine particles is formed. Highly trapped in molecules or oligomers. When the carrier is introduced into a fine particle dispersion obtained by dissolving the obtained composite in a solvent, the fine particles having the polymer or oligomer attached thereto are adsorbed on the carrier via the polymer or oligomer, and the carrier is further reduced under reduced pressure. The organic matter such as the polymer or the oligomer is once removed into a carbide by a two-stage baking in which the baking is performed at a temperature equal to or higher than the decomposition temperature of the polymer or the oligomer and the above-described decomposition temperature in the air. Exhibits excellent catalytic activity on the interacting surface.

The invention described in claim 2 of the present application is a synthetic polyamide obtained by polymerizing a polymer or an oligomer so as to limit the molecular weight to a range of 400 to 7000, and comprising H ₂ N-
An amino acid monomer represented by the molecular formula of (CH ₂ ) _n COOH (n is 1 to 36); and 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), an amine or polyamine having an amino group at a molecular terminal, and a side chain of the amine or polyamine Supported on a fine particle which is a synthetic polyamide obtained by polymerizing at least one polymerization inhibitor selected from an amine or a polyamine having at least one functional group selected from a cyano group, an amino group, and a thiol group in the presence of a catalyst. Product manufacturing method.

According to the invention of claim 3 of the present application, the carrier is at least one transition metal oxide selected from titanium oxide, zirconia, iron oxide, nickel oxide and cobalt oxide, and the carrier surrounding the fine particles. Molecules or oligomers bind and become easily adsorbed.

The invention according to claim 4 of the present application has at least one functional group selected from a cyano group, an amino group and a thiol group at the terminal and / or the side chain of the molecule and makes the skeleton water-soluble. By preparing a polymer or oligomer film and depositing a metal on the film, a composite obtained by dispersing the metal and / or its oxide as fine particles in the film can be mixed with water or water. A method for producing a particulate carrier dissolved in an aqueous solvent,
The functional group of the polymer or oligomer interacts with the metal and / or its oxide fine particles to suppress the growth of the particles, disperse the fine particles in an aqueous solvent, and obtain an aqueous solution containing no harmful substances. be able to.

[0011] The invention according to claim 5 of the present application is a method for producing a fine-particle-supported material having excellent catalytic activity, in which the polymer or oligomer has a skeleton of polyethylene oxide, polyethylene glycol or polyvinyl alcohol.

[0012]

1 to 3 show a process for producing fine particles. FIG. 1 is a sectional view showing a state in which a polymer or oligomer film is formed on a substrate. More specifically, a film 2 is prepared by applying a paste-like material obtained by dissolving a polymer or oligomer in a solvent onto a substrate 1.

The polymer or oligomer has at least one functional group selected from a cyano group (—CN), an amino group (—NH ₃ ), and a thiol group (—SH) at the terminal and / or side chain of the molecule. Whose skeleton is made of polyethylene oxide, polyethylene glycol, polyvinyl alcohol, nylon 11, nylon 6, nylon 66, nylon 6.10, polyethylene terephthalate, polystyrene, etc., and whose melting point or softening point is 40 to 100. ° C. The average molecular weight of the oligomer is not particularly limited, but is about 500 to 3000. The functional group particularly easily forms a covalent bond or a coordination bond with a metal atom on the surface of the fine particles, suppresses grain growth, and enhances the dispersibility of the fine particles.

Among them, polymers or oligomers having polyethylene oxide, polyethylene glycol or polyvinyl alcohol as a skeleton are soluble in water or an aqueous solvent such as acetone or alcohol which can be mixed with water. Can be.

As a method for producing the film 2 other than the above, a synthetic polyamide is polymerized so that the molecular weight is limited to a range of 400 to 7,000, and then a solution obtained by dissolving the same in a solvent is formed on a substrate. You can also. In this case, if the molecular weight is less than 400, the synthetic polyamide tends to evaporate during the deposition of the metal and / or its oxide under reduced pressure, and if it exceeds 7,000, the dispersion of the fine particles becomes difficult.

The molecular weight was measured using a gel permeation chromatograph (manufactured by Shimadzu Corporation).
Using a mobile phase of chloroform or chloroform and meta-cresol in a volume ratio of 4: 1, the synthetic polyamide obtained by a gel permeation chromatography column was separated and analyzed, and the retention time was compared with that of a commercially available polystyrene of known molecular weight as a standard sample. Was determined to determine the molecular weight of the synthetic polyamide.

Specifically, as a method for producing the above-mentioned synthetic polyamide, H ₂ N— (CH ₂ ) _n COOH (where n is 1 to 5)
36) an amino acid monomer represented by the molecular formula:
(CH ₂ ) _m —NH ₂ (m is 1 to 36, R is CH ₃ —,
An amine (including a polyamine) having an amino group at the molecular terminal represented by a cyano group, an amino group, and a thiol group; and a side chain of the amine selected from a cyano group, an amino group, and a thiol group At least one polymerization inhibitor selected from amines having at least one functional group and a catalyst or the like are charged with a solvent such as N-methylpyrrolidone or dimethylacetamide, and the temperature is raised to 100 to 150 ° C. with stirring. Then, the mixture is polymerized while flowing a nitrogen gas. After the polymerization, the mixture is cooled to room temperature. The reaction product was poured into ethyl acetate, toluene, hexane, and the like, and allowed to stand overnight to precipitate. The precipitate was collected by filtration, washed, and dried at 40 to 70 ° C.

Examples of the amino acid monomer represented by the molecular formula of H ₂ N— (CH ₂ ) _n COOH (where n is 1 to 36) include 11-aminoundecanoic acid and 9
-Aminononanoic acid.

As the polymerization inhibitor, R- (CH ₂ )
_m -NH ₂ (m is 1 to 36, R is CH ₃ -, cyano group,
An amine or a polyamine having an amino group at the molecular terminal represented by an amino group or a thiol group), and at least a functional group selected from a cyano group, an amino group, and a thiol group in a side chain of the amine or the polyamine. It is selected from amines or polyamines having one or more, specifically, hexamethylenediamine, ε-aminocapronitrile, ethylenediamine and the like are used.

As the catalyst, quinoline, triphenyl phosphite or the like is used.

Subsequently, as shown in FIG. 2, a metal is vacuum-deposited on the film 2. In the present invention, a vacuum degree of 10 ^-4 to 10 ^-6 Torr and a vapor deposition rate of 0.1 to 10 ^-6 Torr are obtained using a vacuum vapor deposition apparatus.
A metal is vacuum deposited on the film 2 at a rate of 1 to 100 μm / min, preferably 0.5 to 5 μm / min. The deposited metal becomes fine particles 4 of the metal and / or its oxide and is densely packed on the film 2, and some of the fine particles 4 enter the film 2 and start to be dispersed. The boundary between the dense layer of the fine particles 4 and the film 2 cannot be clearly distinguished. It is preferable to heat the film 2 formed on the substrate 1 during the vapor deposition in order to promote the dispersion of the fine particles 4 of metal and / or oxide thereof in the film 2.

The metal to be used is at least one selected from copper, gold, silver, platinum, palladium, iron, nickel, cobalt, tin, zinc, cerium, yttrium and the like, and particularly gold, silver, palladium and the like. Noble metal is good.

Subsequently, the metal and / or oxide fine particles 4 densely packed on the film 2 are heated. When heating, heating from 10 to 40 ° C. lower than the melting point or softening point of the polymer or oligomer 3 to 5 to 10 ° C. higher than the melting point or softening point promotes uniform dispersion of the fine particles 4, Fine particles 4 having a high concentration of 20% by weight or more can be produced.

At this time, it can be seen that the fine particles 4 exhibit an intrinsic coloring due to the interaction with the polymer or the oligomer 3, and the fine particles 4 have penetrated into the polymer or the oligomer 3. Also, this color depends on the type of metal or metal oxide, particle size,
It can vary depending on the type of polymer or oligomer. The fine particles thus obtained are separated and dispersed independently. In some cases, it is not necessary to heat a film obtained by vacuum-depositing a metal on the film 2.

FIG. 3 is a cross-sectional view of the composite 5 showing a state in which fine particles 4 of a metal and / or an oxide thereof are dispersed in the polymer or oligomer 3 film 2. The fine particles 4 dispersed in the polymer or oligomer 3 may be metal oxides such as Cu ₂ O, ZnO, and Y ₂ O _{3 in} addition to the metal fine particles.

FIG. 4 shows a composite 5 obtained by dispersing fine particles 4 of metal and / or oxide thereof in a polymer or oligomer 3 and converting the compound 5 to a solvent 6 such as an aqueous or organic solvent.
FIG. 7 is a model diagram of a fine particle dispersion 7 obtained by dissolving
The individual fine particles 4 surrounded by the polymer or oligomer 3 are dispersed independently in the solvent 6. The surface of the fine particles 4 and the polymer or oligomer 3 are bonded via the above functional group.

Subsequently, a pre-heated particle or powdered carrier 9 is introduced into the fine particle dispersion liquid 7 in order to remove water adsorbed on the surface, and then left alone. Adsorbed on the surface of the carrier 9, the carrier 9
Discolors the surface. FIG. 5 is a model diagram showing a state in which the fine particles 4 are adsorbed on the surface of the carrier 9 via the polymer or the oligomer 3. The polymer or oligomer 3 is chemically bonded to the fine particles 4 by a functional group including a cyano group, an amino group, and a thiol group at the terminal and / or side chain of the molecule, and the other end is bonded to the carrier 9. Even if the carrier 9 in which the fine particles 4 are adsorbed via the polymer or oligomer 3 is washed with water or left in a solvent, the surface color of the carrier 9 does not change, and the fine particles 4 do not detach from the carrier 9.

The carrier 9 is made of titanium oxide, zirconia,
It is at least one transition metal oxide selected from iron oxide, nickel oxide, and cobalt oxide, and has an active group for attaching a polymer or oligomer 3 to the surface.

The carrier 9 having the fine particles 4 adsorbed thereon via the polymer or oligomer 3 is placed in a high-temperature sintering apparatus capable of replacing the atmosphere and reducing the pressure, for example, under a reduced pressure of 1 to 10 ^-3 Torr and at a temperature of 300 to 600 ° C. Is fired in advance at a temperature not lower than the decomposition temperature of the polymer or oligomer, and further fired in the air at a temperature not lower than the decomposition temperature of the polymer or oligomer at 400 to 600 ° C. As a result, the polymer or oligomer 3 is thermally decomposed as shown in FIG.
A fine particle carrier 10 having a large number of fine particles 4 independently adhered to the surface can be obtained.

The particulate carrier 10 has an extremely large catalytic activity of the finely divided metal, and has an excellent catalytic function, for example, for an oxidation reaction of carbon monoxide to carbon dioxide.
Further, by applying this characteristic, it can be applied to catalysts for purifying exhaust gas, purifying odors, preventing smoke, using gas sensors, producing petrochemicals, and flameless combustion.

[0031]

Next, the present invention will be described in more detail with reference to specific examples. Example 1 An average molecular weight of 700 (G) having cyano groups at both ends of the molecule
Nylon 11 oligomer (by PC measurement) was mixed with a small amount of meta-cresol to prepare a paste. This paste was passed through an ink roll to make it uniform.

Next, the paste is printed on a glass substrate by a screen printing machine, and dried at 150 ° C. for several minutes.
A film with a thickness of microns was obtained.

The inside of the tank having the electron beam evaporation source is set to 55 in advance.
The film held on the glass was placed in a vacuum deposition apparatus heated to ° C., and after adjusting the degree of vacuum to about 5 × 10 ⁻⁵ Torr, the gold in the crucible placed in the vacuum deposition apparatus was replaced with an electron. It was heated using a beam and evaporated. The evaporated gold was deposited on the nylon 11 oligomer film. The amount of gold evaporated was controlled to a thickness of 600 nm on the quartz oscillator.

The inside of the vacuum evaporation apparatus was returned to the atmospheric pressure, and the nylon 11 oligomer held by the glass was taken out. The gold deposited on the nylon 11 oligomer interacts with the cyano group of the nylon 11 oligomer at the same time as the deposition and is held in the form of fine particles of several nm, and the surface of the film has a matte gold color. It was red when viewed through glass. The film was heated at 150 ° C. for 30 minutes in the air to make the dispersion of the gold fine particles uniform. The gold color on the film surface disappeared, and a film having a red color as a whole was obtained.

When 50 mg of this film was dissolved in 2 ml of dichloromethane, the solution became a red fine colloidal dispersion of gold colloid. To this fine particle dispersion, 2 parts of titanium oxide powder (AEROSILT 805 manufactured by Nippon Aerosil Co., Ltd.) were added.
After heating at 00 ° C for 1 hour, add 500g and add
Left for a day. The surface of the titanium oxide powder was colored reddish purple due to the adsorption of the fine gold particles, and the red color of the supernatant of the solution disappeared.
The titanium oxide powder was filtered out and washed several times with dichloromethane. There was no change in the coloring of the titanium oxide powder even after washing.

In Example 1, a sample of the titanium oxide powder on which the fine gold particles were adsorbed was placed in a high-temperature sintering apparatus capable of substituting the atmosphere and reducing the pressure, and placed at 500 ° C. under reduced pressure (10-1 Torr).
After firing at 60 ° C. for 60 minutes, the sample was further placed in a muffle furnace and fired in air at 400 ° C. for 60 minutes. On the other hand, as Comparative Example 1, a sample of titanium oxide powder on which fine gold particles were adsorbed was placed in a muffle furnace and baked at 400 ° C. for 60 minutes in air.

The obtained powdery fine particle carrier is Au /
The composition of TiO ₂ = 1 / 2.5, the nylon 11 oligomer surrounding the gold fine particles was not thermally decomposed, and the surface of the titanium oxide powder was blue-violet. The conversion of carbon monoxide to carbon dioxide in these samples was measured by the following method.

In this measuring method, a constant flow rate of air containing 1% by volume of carbon monoxide (33 ml / m 3)
in) was passed through a drying member and further passed through a powdery fine particle carrier placed in a reaction tube, and the peak value of carbon dioxide was determined by gas chromatography to obtain a conversion rate (Conversi).
on) (%) was measured. Further, before the reaction is performed, the powdery particulate carrier is heated at 200 ° C. for 30 minutes while flowing dry air in a state where the particulate carrier is placed in the reaction tube to remove water adsorbed on the powdery particulate carrier. Removed. A heating / cooling device capable of controlling the temperature was placed around the reaction tube, and the temperature was measured with a thermocouple.

FIG. 7 shows the result. According to this, firing was performed under reduced pressure as firing conditions, followed by firing in air.
In the case of multi-stage firing, the conversion rate is higher than only when firing in air, and the conversion rate is higher even at low temperatures,
It turns out that it has excellent catalytic properties.

Example 2 0.05 mol of 11-aminoundecanoic acid and hexamethylenediamine were varied and placed in a flask equipped with a condenser.
67 ml of N-methylpyrrolidone were added. To this, 43 ml of quinoline and 0.005 mol of triphenyl phosphite were added. The flask was immersed in an oil bath, heated at a temperature of 115 to 130 ° C. while stirring with a magnetic stirrer for a predetermined time, and then cooled to room temperature.
During the reaction, nitrogen gas was flowed into the flask. After cooling to room temperature, the reaction mixture was poured into ethyl acetate and the precipitate was collected by filtration. After washing with ethyl acetate, 1N aqueous sodium hydroxide solution and distilled water, drying was performed at 60 ° C.

The obtained product was dissolved in chloroform / metacresol = 4/1, and the molecular weight was determined by gel permeation chromatography using polystyrene as a standard. Further, the product was mixed with potassium bromide, and an infrared absorption spectrum was measured with a Fourier transform infrared spectrometer, and it was confirmed that an amide bond and an amino group were present in the molecule.

A mixture of a synthetic polyamide and meta-cresol so as to have an appropriate viscosity was formed on a slide glass using a spin coater, and dried at 80 ° C. for 30 minutes. In a vacuum, gold was evaporated by resistance heating, and gold was deposited on the polyamide film with a quartz oscillator to a thickness of 10 nm. Next, the polyamide film on which gold was deposited was heated in an oven at 140 ° C. for 10 minutes. When this was dissolved in meta-cresol, a clear blue solution was obtained, and there was no precipitation, indicating that gold was protected by the synthetic polyamide and was stably dispersed in the solution.

Titanium oxide powder (AEROSIL T805, manufactured by Nippon Aerosil Co., Ltd.) was added to the colloid solution at 200 ° C.
After heating for 1 hour, 500 g was added and left for one day. The titanium oxide powder was placed on a slide glass and dried to remove meta-cresol, so that a slightly reddish powder was applied thinly on the slide glass.

The titanium oxide powder on which the fine gold particles were adsorbed was placed in a high-temperature sintering apparatus capable of replacing the atmosphere and depressurizing a sample of the titanium oxide powder on which the fine gold particles were adsorbed in the same manner as in Example 1 to reduce the pressure (10%). -1 Torr) at 500 ° C,
After firing for 60 minutes, the sample was further placed in a muffle furnace and fired in air at 400 ° C. for 60 minutes. On the other hand, as Comparative Example 1, a sample of titanium oxide powder on which fine gold particles were adsorbed was placed in a muffle furnace and baked at 400 ° C. for 60 minutes in air.

The resulting powdery fine particle carrier was Au /
Nylon 11 oligomer, which had a composition of TiO ₂ = 1/25 and surrounded the gold fine particles, was not thermally decomposed and disappeared.
The surface of the titanium oxide powder was blue-purple. The conversion of carbon monoxide to carbon dioxide in these samples was measured. FIG. 7 shows the result.

According to this, in the case of the two-stage firing in which firing was performed under reduced pressure as the firing conditions and then firing in air, the conversion rate was higher than that in the case of firing only in air, and even at low temperatures. , Which indicates that the catalyst has excellent catalytic properties.

[0047]

As described above, the invention of each claim of the present application is:
Preparation of polymer or oligomer film having at least one functional group selected from cyano group, amino group, and thiol group at the terminal and / or side chain of the molecule, and depositing metal on this film By dispersing in a film as fine particles of a metal or a metal oxide or fine particles of both of these, the resulting composite is dissolved in a solvent to form a fine particle dispersion, and a carrier is introduced into the fine particle dispersion to convert the fine particles. After being adsorbed on a carrier via a polymer or oligomer, the carrier is calcined at a temperature not lower than the decomposition temperature of the polymer or oligomer under reduced pressure, and then calcined in air at a temperature not lower than the decomposition temperature. In particular, the method in which fine particles are adsorbed to a carrier via a polymer or an oligomer is converted to a polymer or a polymer under reduced pressure. And fired at a temperature higher than the decomposition temperature of the oligomer is further calcined at the decomposition temperature or higher in the air 2
An organic substance such as a polymer or an oligomer is once converted into a carbide by the step baking, and then removed, and there is an effect that excellent catalytic activity is exhibited by a strong interaction surface between the fine particles and the carrier.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a state in which a polymer or oligomer film is formed on a substrate.

FIG. 2 is a cross-sectional view showing a state where a metal is deposited on a polymer or oligomer film.

FIG. 3 is a cross-sectional view showing a state in which a metal and / or an oxide thereof is dispersed in a polymer or oligomer film.

FIG. 4 is a model diagram of a fine particle dispersion obtained by dissolving a composite obtained by dispersing fine particles of a metal and / or an oxide thereof in a polymer or oligomer in an aqueous solvent.

FIG. 5 is a model diagram showing a state in which fine particles are adsorbed on the surface of a carrier via a polymer or an oligomer.

FIG. 6 is a model diagram showing a state in which a large number of fine particles are independently attached to the surface of a carrier.

FIG. 7 is a graph showing the relationship between the conversion rate of carbon monoxide to carbon dioxide and the temperature of the particulate carrier.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Film 3 Polymer or oligomer 4 Fine particle 5 Composite 6 Solvent 7 Fine particle dispersion 9 Carrier 10 Fine particle carrier

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C23C 14/20 B01D 53/36 104Z

Claims (5)

[Claims] 1. A film of a polymer or an oligomer having at least one functional group selected from a cyano group, an amino group and a thiol group at the terminal and / or the side chain of the molecule is prepared. The metal is vapor-deposited thereon and dispersed as fine particles of metal or metal oxide or both in the film.The resulting composite is dissolved in a solvent to form a fine particle dispersion, and the carrier is dispersed in the fine particle dispersion. After charging and adsorbing the fine particles on the carrier via the polymer or oligomer, firing the carrier at a temperature not lower than the decomposition temperature of the polymer or oligomer under reduced pressure, and further firing at a temperature not lower than the decomposition temperature in air. A method for producing a particulate carrier having excellent catalytic activity. 2. A polymer or oligomer having a molecular weight of 4
A synthetic polyamide polymerized so as to be restricted to the range of 00 to 7000, and an amino acid monomer represented by a molecular formula of H ₂ N— (CH ₂ ) _n COOH (n is 1 to 36);
_{- (CH 2) m -NH 2} (m is 1 to 36, R is CH
_3- , a cyano group, an amino group, and a thiol group), an amine or polyamine having an amino group at the molecular terminal, and a side chain of the amine or polyamine having a cyano group, an amino group, and a thiol group. 2. The particulate carrier having excellent catalytic activity according to claim 1, which is a synthetic polyamide obtained by polymerizing at least one polymerization inhibitor selected from amines or polyamines having at least one selected functional group in the presence of a catalyst. Manufacturing method. 3. The particulate carrier having excellent catalytic activity according to claim 1, wherein the carrier is at least one transition metal oxide selected from titanium oxide, zirconia, iron oxide, nickel oxide, and cobalt oxide. Production method. 4. 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 and / or side chain of the molecule and having a water-soluble skeleton. A film is prepared, and a composite obtained by dispersing metal or metal oxide fine particles or both fine particles in the film by depositing a metal on the film is mixed with water or water. The method for producing a particulate carrier having excellent catalytic activity according to claim 1, which is dissolved in a solvent. 5. The method according to claim 4, wherein the polymer or oligomer has a skeleton of polyethylene oxide, polyethylene glycol or polyvinyl alcohol.