JP5886145B2 - Substrate-supported catalyst and method for producing substrate-supported catalyst - Google Patents

Description

  The present invention relates to a substrate-supported catalyst and a method for producing a substrate-supported catalyst.

  When the catalyst is supported on a support and used, the catalyst and the reaction product can be easily separated from the complicated system after the reaction. Therefore, a catalyst supported on a carrier (hereinafter referred to as a supported catalyst) can be easily recovered and reused, and is an effective means particularly when an expensive noble metal is used as the catalyst (for example, Patent Documents 1 and 2). reference).

  However, in the supported catalyst, the binding force between the catalyst and the carrier is not necessarily strong. For this reason, the catalyst may be detached from the carrier during use, and the detached catalysts may aggregate with each other. In that case, the catalytic activity was gradually decreased by repeatedly using the supported catalyst.

Japanese Patent Laid-Open No. 2000-140643 JP 2010-22980 A

  As a method for suppressing the deterioration of the activity of the supported catalyst due to repeated use, for example, there is a method described in Patent Document 1. In Patent Document 1, a mixture of a thermosetting resin and a catalyst composed of a metal or a metal compound or a precursor thereof is heated to 500 ° C. or more in a non-oxidizing atmosphere to carbonize the thermosetting resin. Alternatively, a metal compound is supported on the carbide. When the cured body of the thermosetting resin is carbonized, it is carbonized while maintaining its shape although it is reduced. On the other hand, many catalysts made of metals or metal compounds are stable under the condition that the thermosetting resin is carbonized. For this reason, after mixing a catalyst etc. with a thermosetting resin, the thermosetting resin is hardened and carbonized, and the carbon material which fixed the catalyst substance firmly is obtained.

  In Patent Document 2, fine particles having catalytic activity are supported on the surface of spherical resin particles, and a coating layer having a specific thickness made of a thermosetting resin is formed so as to cover the spherical resin particles. Is described. By providing a coating layer made of a thermosetting resin in this way, the detachment of fine particles having catalytic activity during use is suppressed, and separation and recovery from reaction products after use is facilitated. .

  In the supported catalysts described in Patent Documents 1 and 2, the carriers may aggregate. When the carriers are aggregated, the reaction product is less likely to come into contact with the catalyst, resulting in a reduction in reaction efficiency. That is, the activity per carrier is reduced.

  When the thermosetting resin is carbonized as in Patent Document 1, the thermosetting resin becomes a porous cured body. When the catalyst is supported on the cured body, the catalyst may be taken into the pores of the carbide. In general, the catalytic reaction proceeds on the surface of the support where the reactants can reach. For this reason, the catalyst fine particles taken into the inside of the carbide, particularly where the reactant is difficult to reach, have a low contact efficiency with the reactant, and thus are difficult to use for the catalytic reaction. In this regard, the present inventors have found that improving the reaction efficiency of the catalyst leads to an improvement in the catalytic activity.

  When the catalyst is covered with a coating layer made of a thermosetting resin as in Patent Document 2, the contact between the catalyst and the reactant is inhibited by the coating layer. For this reason, in the catalyst of patent document 2, since the location which is hard to contact with a reaction material exists, there was room to raise the contact efficiency with a reaction material. In this regard, the present inventors have found that improving the reaction efficiency of the catalyst leads to an improvement in the catalytic activity.

  The present inventors have studied to improve the catalyst reaction efficiency in a supported catalyst using a cured product of a thermosetting resin as a catalyst carrier. As a result, it has been found that the reaction efficiency can be improved by using a cured product of a thermosetting resin having a phenolic hydroxyl group as a catalyst carrier and forming the catalyst carrier on the substrate surface.

  The present invention has been made in view of the above circumstances, and provides a substrate-supported catalyst having excellent catalytic activity.

  The inventors of the present invention have made extensive studies on improving the reaction efficiency of a catalyst in a substrate-supported catalyst using a cured product of a thermosetting resin as a catalyst carrier. As a result, it has been found that a substrate-supported catalyst having excellent catalytic activity can be provided by using a nonpolar substrate as the substrate, and the present invention has been achieved. Here, the material constituting the nonpolar substrate is formed from a compound or polymer that does not contain a polar functional group such as a carbonyl group, an imide group, an amino group, an amide group, and a hydroxy group in the chemical structure. Is preferred.

That is, according to the present invention, a nonpolar substrate,
A cured body of a thermosetting resin formed on the surface of the nonpolar substrate;
Fine particles having catalytic activity carried on the surface of the cured body;
Including
The thermosetting resin is a substrate-supported catalyst having a phenolic hydroxyl group ,
The nonpolar substrate is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polybutene, polybutadiene, polystyrene, polyisobutylene, polytetrafluoroethylene and other fluororesin, natural rubber, styrene butadiene rubber and butyl rubber A substrate-supported catalyst including the above is provided.

  As a conventional catalyst, a catalyst in which fine particles having catalytic activity are supported using a cured body of a thermosetting resin as a catalyst carrier is provided. On the other hand, the catalyst carrier can be dispersed on the nonpolar substrate by forming a cured body of a thermosetting resin having a phenolic hydroxyl group as a catalyst carrier on the nonpolar substrate. . By supporting the catalyst fine particles on the cured body of the thermosetting resin that is the catalyst carrier formed on the nonpolar substrate in this way, aggregation of the catalyst fine particles can be prevented. By doing so, it is possible to prevent a decrease in the catalyst activity accompanying the aggregation of the catalyst fine particles. That is, since the contact efficiency between the reactant and the catalyst can be improved, the reaction efficiency is improved, and a substrate-supported catalyst having excellent catalytic activity can be provided.

  The substrate-supported catalyst is preferably plate-shaped or sheet-shaped, and more preferably a porous body. By carrying out like this, it leads to increasing the reaction field in a base material carrying catalyst, and can improve reaction activity.

Furthermore, according to the present invention, a step of preparing a nonpolar substrate;
Forming a cured body of a thermosetting resin on the surface of the nonpolar base material, and supporting fine particles having catalytic activity on the surface of the cured body;
Including
The method for producing a substrate-supported catalyst, wherein the thermosetting resin is a cured product having a phenolic hydroxyl group ,
The nonpolar substrate is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polybutene, polybutadiene, polystyrene, polyisobutylene, polytetrafluoroethylene and other fluororesin, natural rubber, styrene butadiene rubber and butyl rubber A method for producing a substrate-supported catalyst including the above is provided.

  According to the present invention, a substrate-supported catalyst having excellent catalytic activity can be provided.

  Hereinafter, the substrate-supported catalyst of the present invention will be described.

(Base material)
The material which comprises the base material in this embodiment is a nonpolar base material. Here, the material constituting the nonpolar substrate is formed from a compound or polymer that does not contain a polar functional group such as a carbonyl group, an imide group, an amino group, an amide group, and a hydroxy group in the chemical structure. Is preferred.
In addition, the nonpolar base material which concerns on this embodiment is although it does not specifically limit, It is preferable that an interaction (wetting property) with a thermosetting resin is scarce. Examples of the nonpolar substrate include polyethylene, polypropylene, polymethylpentene, polybutene, polybutadiene, polystyrene, polyisobutylene, polytetrafluoroethylene, and other fluorine resins, natural rubber, styrene butadiene rubber, and butyl rubber. The reason for this is not necessarily clear, but because the wettability between the nonpolar substrate and the phenolic hydroxyl group of the thermosetting resin is poor, the phenolic hydroxyl group is other than the surface where the cured body of the thermosetting resin and the substrate contact. It is easy to orient at the location. For this reason, it is considered that fine particles having catalytic activity (hereinafter also referred to as “catalyst fine particles”) can be efficiently supported on the phenolic hydroxyl group. That is, it is considered that more catalyst fine particles can be supported on the catalyst carrier.

  Moreover, it is preferable to use polyolefin, such as polyethylene and polypropylene, from the viewpoint of uniformly dispersing the catalyst fine particles on the nonpolar substrate. Thus, by using polyolefin as a base material, it can prevent that the thermosetting resin which has covered the base material surface peels from the base material surface.

  Next, the shape of the nonpolar substrate is not particularly limited, but a particle shape, a sheet shape, or a plate shape is used. Among these, a sheet shape or a plate shape is preferable.

  The nonpolar base material is preferably a porous body or a mesh structure, and more preferably a mesh structure. By doing so, it is possible to increase the surface area, and it becomes possible to form more cured bodies of thermosetting resin on the substrate surface as catalyst carriers. For this reason, more catalyst fine particles can be carried. Therefore, the reaction field in the substrate-supported catalyst is increased, and the reaction activity can be improved. Here, the porous body may have a plurality of irregularities or may be provided with a plurality of holes (hereinafter referred to as communication holes) communicating from the front surface to the back surface.

  Furthermore, the nonpolar base material according to the present embodiment is more preferably a plate having a mesh structure. By doing so, it is possible to significantly improve the contact efficiency between the catalyst fine particles and the reactant. That is, the reaction activity can be improved, and a substrate-supported catalyst having a further excellent catalytic activity can be provided.

  In addition, by using a plate-like nonpolar base material having a mesh structure, it is possible to always supply unreacted reactants to the catalyst fine particles forming the reaction field. This is very effective in improving the reaction efficiency when a flow type reaction vessel using a liquid or gaseous reactant is used in the reaction apparatus. Thus, since the unreacted reactant can be always supplied to the catalyst fine particles, the activity of the catalyst fine particles can be improved.

  When the nonpolar base material is provided with communication holes, the communication holes may form a honeycomb structure. In this case, the mechanical strength of the substrate itself can be improved. It is also possible to disperse the catalyst fine particles uniformly and at a high density.

(Hardened body of thermosetting resin)
The cured body of the thermosetting resin is used as a catalyst carrier in the substrate-supported catalyst according to the present embodiment. The cured body of the thermosetting resin is formed on the surface of the substrate. The formation state of the cured body of the thermosetting resin is not particularly limited with respect to the base material, but may be formed in, for example, a particle shape, a film shape, or a uniform layer shape. The thermosetting resin before the curing treatment is not particularly limited as long as it is a thermosetting resin having a phenolic hydroxyl group, but it is particularly preferable to include a phenol resin or a derivative thereof.

  Like the substrate-supported catalyst according to the present embodiment, the catalyst is provided with excellent repetitive characteristics (lifetime) by forming a cured body of a thermosetting resin as a catalyst carrier so as to be dispersed on the surface of the substrate. can do. The reason is not necessarily clear, but is considered as follows. A cured body of a thermosetting resin having a phenolic hydroxyl group as a catalyst carrier is exposed on the surface of the substrate. For this reason, a phenolic hydroxyl group is present at the site where the catalyst fine particles are supported, and the supported catalyst fine particles are stabilized by the phenolic hydroxyl group. Therefore, it is considered that the catalyst repetitive characteristics are improved by suppressing the detachment of the catalyst during use.

  Further, in the cured body of the thermosetting resin according to the present embodiment, the phenolic hydroxyl group equivalent of the thermosetting resin is 500 g / eq or less, preferably 400 g / eq or less, more preferably 350 g / eq or less. is there. When the phenolic hydroxyl group equivalent of the thermosetting resin is in this range, a substrate-supported catalyst having excellent catalytic activity can be provided. In addition, when the phenolic hydroxyl group equivalent of a thermosetting resin exceeds the said upper limit, since the phenolic hydroxyl group on the surface of a hardening body will decrease and the retention strength of a catalyst will become weak, it is unpreferable. The phenolic hydroxyl group equivalent can be quantified by a known method such as an acetylation method.

  In the substrate-supported catalyst according to this embodiment, the cured body of the thermosetting resin is formed so as to cover the surface of the substrate. The content of the cured body of the thermosetting resin is preferably 0.5% by weight or more based on the total amount of the base material and the cured body of the thermosetting resin. By being in this range, a substrate-supported catalyst having an excellent catalytic activity can be provided.

The phenol resin in this embodiment is obtained by reacting phenols and aldehydes in the presence of an alkaline or acidic catalyst, and has at least one phenolic hydroxyl group in the molecule. Yes.
Examples thereof include a phenol resin, a cresol resin, a resorcin resin, a xylenol resin, a naphthol resin, a bisphenol A resin, an aralkyl phenol resin, a biphenyl aralkyl phenol resin, and a modified phenol resin using cashew nut oil having a phenolic hydroxyl group. Also used are xylene-modified phenol resins containing substances having phenolic hydroxyl groups, and various modified phenol resins such as phenol-modified rosin, oil-modified phenol resins modified with terpene oil, rubber-modified phenol resins modified with rubber, etc. can do.

  As the phenols used for obtaining the phenol resin, those having a phenolic hydroxyl group in the aromatic ring are preferable, and further, a substituent other than the phenolic hydroxyl group may be included. For example, cresols such as phenol, o-cresol, m-cresol, p-cresol, mixed cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4- Xylenol, xylenol such as 3,5-xylenol, ethylphenol such as o-ethylphenol, m-ethylphenol and p-ethylphenol, butylphenol such as isopropylphenol, butylphenol and p-tert-butylphenol, p-tert-amylphenol Alkylphenols such as p-octylphenol, p-nonylphenol and p-cumylphenol, halogenated phenols such as fluorophenol, chlorophenol, bromophenol and iodophenol, p-phenol Monohydric phenol substituents such as ruphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol, and monovalent naphthols such as 1-naphthol and 2-naphthol, resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, Examples thereof include hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol E, bisphenol S, and cashew nut oil composed of a substance having a phenolic hydroxyl group, such as dihydroxynaphthalene. These can be used alone or in combination of two or more. Moreover, you may use the copolymer of the phenols which have these phenolic hydroxyl groups, and the substance which does not contain other phenolic hydroxyl groups. Thereby, the phenol resin which has at least 1 or more phenolic hydroxyl group in a molecule | numerator can be obtained.

  Examples of the aldehydes used to obtain the phenol resin include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, capro Examples include aldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, paraxylene dimethyl ether and the like. These may be used alone or in combination of two or more.

  It does not specifically limit as a method with which the said phenols and aldehydes are made to react, A well-known method is employable.

  The catalyst for obtaining the phenol resin is not particularly limited, and examples thereof include an acid catalyst, a base catalyst, and a transition metal salt catalyst. Examples of the acid catalyst that can be used include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acids, and organic acids such as oxalic acid, p-toluenesulfonic acid, and organic phosphonic acid. Examples of the base catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, ammonia, alkylamine and the like. These amines can be used. Furthermore, examples of the transition metal salt catalyst include zinc oxalate and zinc acetate.

  The shape of the phenol resin in the present embodiment is not particularly limited. Examples thereof include solid, powder, solution, and liquid, and any form can be used.

Next, a method for curing the thermosetting resin will be described.
Although it does not specifically limit as a hardening processing method of the thermosetting resin in this embodiment, A well-known method is employable.

  When a resol type phenol resin is used as the thermosetting resin, it can be cured by heating. Alternatively, a method of mixing acids such as p-toluenesulfonic acid and phenolsulfonic acid and curing at normal temperature or by heating can be used.

  Moreover, when a novolak type phenol resin is used as the phenol resin, a curing agent such as hexamethylenetetramine is mixed with an additive compound and heated to cure, a thermosetting resin such as an epoxy resin, a polyisocyanate, or a melamine resin. And a method of mixing with an additive compound and curing by heating.

  Although it does not specifically limit as hardening processing temperature of the thermosetting resin in this embodiment, It is preferable that it is 250 degrees C or less. When the curing temperature is not more than the above upper limit, an economical curing rate can be obtained, and decomposition of the main chain of the phenol resin can be suppressed.

(Catalyst fine particles)
The catalyst fine particles supported on the surface of the cured body of the thermosetting resin in the present embodiment may be any metal, metal oxide, and metal compound as long as they have catalytic activity, and are particularly limited. It is not a thing. For example, metals such as titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, platinum, iron, zinc, manganese, magnesium, calcium, silver, vanadium, tin, oxides thereof, and other organic titanium And at least one selected from the group consisting of metal compounds and complexes. Moreover, the composite_body | complex containing at least 2 or more types of these can also be used. Among these, palladium or platinum is particularly preferably used.

  The catalyst fine particles preferably have an average particle size of 1 μm or less. Further, nano-sized metal fine particles having an average particle diameter of 1 nm to 100 nm can also be used. The mass ratio of the cured body of the base material and the thermosetting resin and the catalyst fine particles can be appropriately determined. For example, (sum of the cured body of the base material and the thermosetting resin): catalyst fine particles = 1: 1 to 10,000. : 1.

(Base material supported catalyst)
Since the substrate-supported catalyst according to the present embodiment is in the form of a sheet or a plate, it can be deformed into various shapes according to the shape of the reaction apparatus. The shape of the catalyst sheet can be changed into various shapes according to the shape of the reaction tube in the reaction apparatus, such as a folded state or a rolled state. When the communication hole is provided in the sheet-like substrate-supported catalyst, it can be used as a catalyst filter.

  Hereinafter, the manufacturing method of the base material supported catalyst which concerns on this embodiment is demonstrated.

(Method of forming a cured body of thermosetting resin on the surface of the substrate)
In this embodiment, the method of forming the cured body of the thermosetting resin on the surface of the nonpolar substrate can be appropriately selected depending on the shape of the nonpolar substrate. For example, when the non-polar substrate is mesh-like, a method of impregnating and curing a solid or powder resin solution or liquid resin on the non-polar substrate, and heating and melting the solid or powder resin to impregnate the non-polar substrate A curing method or the like is used. On the other hand, when the nonpolar substrate is in the form of particles, a method of coating and curing a thermosetting resin is used. By carrying out like this, it is possible to form the hardening body of a thermosetting resin uniformly with respect to a nonpolar base material.

(Supporting method of catalyst fine particles)
Next, a method for supporting catalyst fine particles on a nonpolar base material in which a cured body of a thermosetting resin that is a catalyst carrier in the present embodiment is dispersedly formed on the surface will be described in detail. In this embodiment, it is preferable to form catalyst thermosetting resin on the surface of the nonpolar substrate and then support the catalyst fine particles on the surface of the thermosetting resin curing body as a carrier. By doing so, it is possible to prevent the catalyst fine particles from being embedded in the cured body of the thermosetting resin that is the catalyst carrier.

  The method for supporting the catalyst fine particles is not particularly limited. However, the catalyst fine particles are chemically deposited and supported in the liquid phase, the powdered catalyst fine particles are electrostatically coated on the surface of the carrier, or the carrier is immersed in the catalyst fine particles. There are methods. By adopting such a method, a substrate-supported catalyst in which catalyst fine particles are uniformly supported on the support surface can be obtained.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Hereinafter, examples of the reference form will be added.
<1>
A non-polar substrate;
A cured body of a thermosetting resin formed on the surface of the nonpolar substrate;
Fine particles having catalytic activity carried on the surface of the cured body;
Including
A substrate-supported catalyst in which the thermosetting resin has a phenolic hydroxyl group.
<2>
The nonpolar substrate is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polybutene, polybutadiene, polystyrene, polyisobutylene, polytetrafluoroethylene and other fluororesin, natural rubber, styrene butadiene rubber and butyl rubber The substrate-supported catalyst according to <1>, including the above.
<3>
The substrate-supported catalyst according to <1> or <2>, wherein the thermosetting resin is a phenol resin.
<4>
The substrate-supported catalyst according to any one of <1> to <3>, wherein the nonpolar substrate is plate-shaped or sheet-shaped.
<5>
The substrate-supported catalyst according to any one of <1> to <4>, wherein the nonpolar substrate is a porous body.
<6>
The substrate-supported catalyst according to any one of <1> to <4>, wherein the nonpolar substrate is a mesh.
<7>
Any one of <1> to <6>, wherein the content of the cured body of the thermosetting resin is 0.5% by weight or more based on the total amount of the cured body of the nonpolar base material and the thermosetting resin. The substrate-supported catalyst according to any one of the above.
<8>
The substrate-supported catalyst according to any one of <1> to <7>, wherein a phenolic hydroxyl group equivalent in the thermosetting resin is 500 g / eq or less.
<9>
The substrate-supported catalyst according to any one of <1> to <8>, wherein the fine particles are supported on the surface of the cured body after the thermosetting resin is cured.
<10>
The substrate-supported catalyst according to any one of <1> to <9>, wherein the fine particles are made of a material containing at least one of a metal, a metal oxide, and a metal compound.
<11>
Preparing a non-polar substrate;
Forming a cured body of a thermosetting resin on the surface of the nonpolar base material, and supporting fine particles having catalytic activity on the surface of the cured body;
Including
A method for producing a substrate-supported catalyst, wherein the thermosetting resin is a cured product having a phenolic hydroxyl group.
<12>
<11> The method for producing a substrate-supported catalyst according to <11>, wherein the fine particles are supported after forming a cured body of the thermosetting resin on the surface of the nonpolar substrate.
<13>
After the nonpolar substrate is dipped in the thermosetting resin in the form of a solution and dried, the thermosetting resin is cured to form a cured body of the thermosetting resin on the surface of the nonpolar substrate. <11> or <12> for producing a substrate-supported catalyst according to <12>.
<14>
In the step of supporting the fine particles,
The method for producing a substrate-supported catalyst according to any one of <11> to <13>, wherein the fine particles are supported by being electrostatically coated or immersed on a surface of a cured body of the thermosetting resin. .

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.

Example 1
(Production of cured phenol resin)
A sheet-like polypropylene nonwoven fabric (manufactured by Japan Vilene Co., Ltd.) is immersed in a phenolic resin solution in which liquid phenolic resin (Sumitomo Bakelite Co., Ltd., Sumilite Resin PR-50087) and methanol are mixed at a weight ratio of 1: 1, at room temperature for 1 minute. Air-dried at room temperature for 30 minutes. After drying, it was heated at 90 ° C. for 30 minutes, and further heated at 150 ° C. for 30 minutes to obtain a plate-like phenol resin carrier having a mesh structure containing 30% by weight of phenol resin.

(Preparation of resin-supported catalyst)
10 mg of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of the above-mentioned phenol resin carrier as a carrier, 0.3 mL of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and 10 mL of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) In a sealed tube, it was heated at 100 ° C. for 12 hours. Subsequently, the phenol resin carrier was taken out with tweezers, washed and dried to obtain a phenol resin-supported catalyst on which palladium particles were supported. The amount of palladium catalyst supported in the phenol resin supported catalyst was 1 mmol%. The amount of palladium catalyst supported was measured using a commercially available atomic absorption spectrophotometer.

(Example 2)
1 mg of palladium acetate (manufactured by Wako Pure Chemical Industries), 1 g of a phenol resin carrier prepared in the same manner as in Example 1, 0.3 mL of triethylamine (manufactured by Wako Pure Chemical Industries), and acetonitrile (manufactured by Wako Pure Chemical Industries) 10 mL was blended and heated in a sealed tube at 100 ° C. for 12 hours. Subsequently, the phenol resin carrier was taken out with tweezers, washed and dried to obtain a phenol resin-supported catalyst on which palladium particles were supported. The amount of palladium catalyst supported in the phenol resin supported catalyst was 0.1 mmol%.

(Comparative Example 1)
1 mg of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of a sheet-like polypropylene nonwoven fabric (manufactured by Nippon Vilene Co., Ltd.), 0.3 mL of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) ) 10 mL was mixed and heated in a sealed tube at 100 ° C. for 12 hours. Subsequently, the polypropylene non-woven fabric was taken out with tweezers, washed and dried to obtain a polypropylene-supported catalyst on which palladium particles were supported. The amount of palladium catalyst supported in the polypropylene supported catalyst was 0.1 mmol%.

(Comparative Example 2)
(Production of cured phenol resin)
A filter paper (No. 424, manufactured by Advantech Toyo Co., Ltd.) is soaked at room temperature for 1 minute in a phenol resin solution in which liquid phenolic resin (manufactured by Sumitomo Bakelite, Sumilite Resin PR-50087) and methanol are mixed at a weight ratio of 1: 1. Air-dried at room temperature for 30 minutes. After drying, it was heated at 90 ° C. for 30 minutes, and further heated at 150 ° C. for 30 minutes to obtain a porous sheet-like phenol resin carrier containing 30% by weight of phenol resin.

(Preparation of resin-supported catalyst)
10 mg of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of the above-mentioned phenol resin carrier as a carrier, 0.3 mL of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and 10 mL of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) In a sealed tube, it was heated at 100 ° C. for 12 hours. Subsequently, the phenol resin carrier was taken out with tweezers, washed and dried to obtain a phenol resin-supported catalyst on which palladium particles were supported. The amount of palladium catalyst supported in the phenol resin supported catalyst was 1 mmol%. The amount of palladium catalyst supported was measured using a commercially available atomic absorption spectrophotometer.

(Comparative Example 3)
1 mg of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of a phenol resin carrier prepared in the same manner as in Comparative Example 2, 0.3 mL of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 10 mL was blended and heated in a sealed tube at 100 ° C. for 12 hours. Subsequently, the phenol resin carrier was taken out with tweezers, washed and dried to obtain a phenol resin-supported catalyst on which palladium particles were supported. The amount of palladium catalyst supported in the phenol resin supported catalyst was 0.1 mmol%.

(Comparative Example 4)
A commercially available palladium-activated carbon (produced by Wako Pure Chemical Industries, Ltd., palladium-activated carbon) was used as Comparative Example 4. The amount of palladium catalyst supported on this palladium-activated carbon was 5% by weight.

(Evaluation test)
The catalytic activity of the supported catalyst was evaluated by the reaction yield of trans-methyl cinnamate obtained by Heck reaction between iodobenzene and methyl acrylate.
230 μL (2.0 mmol) of iodobenzene, 230 μL (2.5 mmol) of methyl acrylate, and 350 μL (2.5 mmol) of triethylamine were dissolved in acetonitrile (20 mL). 500 mg of the supported catalyst was added to the obtained solution. The mixture was heated using an oil bath and stirred at 120 ° C. for 12 hours. After completion of the reaction, the supported catalyst was removed by tweezers or collected by filtration.

The reaction solution obtained by filtration was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (n-hexane: ethyl acetate = 5: 1) to obtain trans-methyl cinnamate. If necessary, a certain amount of the reaction solution was collected without taking out trans-methyl cinnamate and analyzed using liquid chromatography. Hereinafter, unless otherwise specified, the reaction yield was calculated from the area ratio of the chromatogram before and after the reaction. Here, the reaction yield is defined by (C ₀ -C _f ) / C ₀ × 100 (%), where C ₀ is the number of moles of iodobenzene before the reaction, and C _f is the number of moles of iodobenzene after the reaction. It is.

(Repeated test)
After completion of the reaction, the supported catalyst was recovered from the reaction solution and washed. Thereafter, the Heck reaction was performed using the recovered supported catalyst. A series of these Heck reactions was repeated until the reaction yield of trans-methyl cinnamate was below 80%. The results are shown in Table 1 below. The supported catalyst of Comparative Example 4 is a conventionally used supported catalyst.

The phenol resin supported catalyst of the Example had a high reaction yield compared with the comparative example. This result shows that, when the substrate-supported catalyst described in the examples is used, a catalytic activity superior to that of the conventional supported catalyst or the substrate-supported catalyst using a substrate having a polar group can be realized. . From the viewpoint of repeated use of the catalyst, the substrate-supported catalyst of the examples retains a higher activity for a long period of time than a conventional catalyst or a substrate-supported catalyst using a substrate having a polar group. That is, when the substrate-supported catalyst described in the examples is used, excellent catalytic activity can be maintained for a long time without exchanging the catalyst.

Claims (13)

A non-polar substrate;
A cured body of a thermosetting resin formed on the surface of the nonpolar substrate;
Fine particles having catalytic activity carried on the surface of the cured body;
Including
The thermosetting resin is a substrate-supported catalyst having a phenolic hydroxyl group ,
The nonpolar substrate is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polybutene, polybutadiene, polystyrene, polyisobutylene, polytetrafluoroethylene and other fluororesin, natural rubber, styrene butadiene rubber and butyl rubber A substrate-supported catalyst comprising the above . The substrate-supported catalyst according to claim 1, wherein the thermosetting resin is a phenol resin. The substrate-supported catalyst according to claim 1 or 2 , wherein the nonpolar substrate is plate-shaped or sheet-shaped. The substrate-supported catalyst according to any one of claims 1 to 3 , wherein the nonpolar substrate is made of a porous material. The substrate-supported catalyst according to any one of claims 1 to 3 , wherein the nonpolar substrate has a mesh shape. The content of the cured product of the thermosetting resin, wherein the total amount of the cured product of the nonpolar substrate and a thermosetting resin, any of claims 1 to 5 is 0.5 wt% over a The substrate-supported catalyst according to Item. The substrate-supported catalyst according to any one of claims 1 to 6 , wherein a phenolic hydroxyl group equivalent in the thermosetting resin is 500 g / eq or less. The fine particles, the substrate supported catalyst according to any one of claims 1 to 7 for the surface before Symbol cured product obtained by curing the thermosetting resin is one that is supported. The substrate-supported catalyst according to any one of claims 1 to 8 , wherein the fine particles are made of a material containing at least one of a metal, a metal oxide, and a metal compound. Preparing a non-polar substrate;
Forming a cured body of a thermosetting resin on the surface of the nonpolar base material, and supporting fine particles having catalytic activity on the surface of the cured body;
Including
The method for producing a substrate-supported catalyst, wherein the thermosetting resin is a cured product having a phenolic hydroxyl group ,
The nonpolar substrate is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polybutene, polybutadiene, polystyrene, polyisobutylene, polytetrafluoroethylene and other fluororesin, natural rubber, styrene butadiene rubber and butyl rubber The manufacturing method of the base-material supported catalyst containing the above . The method for producing a substrate-supported catalyst according to claim 10 , wherein the fine particles are supported after a cured body of the thermosetting resin is formed on the surface of the nonpolar substrate. After the nonpolar substrate is dipped in the thermosetting resin in the form of a solution and dried, the thermosetting resin is cured to form a cured body of the thermosetting resin on the surface of the nonpolar substrate. The method for producing a substrate-supported catalyst according to claim 10 or 11 , wherein the catalyst is formed. In the step of supporting the fine particles,
The method for producing a substrate-supported catalyst according to any one of claims 10 to 12 , wherein the fine particles are supported by being electrostatically coated or immersed on the surface of a cured body of the thermosetting resin.