JP2012232271A - Organic-inorganic composite, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic-inorganic composite that has high metal content and is easily prepared, and also is highly active and highly durable to a cross coupling reaction, and functions as an insoluble catalyst having a small amount of metal and leaking into a reaction system, and to provide a method for producing the same.SOLUTION: The organic-inorganic composite is a composite of a polymer (PA) of a polymerizable composition (A) and metal nanoparticles, wherein the polymerizable composition (A) includes: a polymerizable compound (a) having (1) an amino group, an imino group, an urea bond or amide bond, and a vinyl group; and a polymerizable compound (b) having a branched 4-12C alkylene group and two or more vinyl groups.

Description

  The present invention relates to an organic-inorganic composite formed by a polymer of a polymerizable composition containing a polymerizable compound having a vinyl group and metal nanoparticles, and particularly has high activity and high durability against cross-coupling reactions. In addition, the present invention relates to an organic-inorganic composite that functions as an insoluble solid catalyst with a small amount of metal leaking into the reaction system, and a method for producing the same.

  Chemical reactions using catalysts containing transition metals such as palladium, platinum, ruthenium, rhodium, gold, silver, and rhenium, as represented by cross-coupling reactions, today's pharmaceutical production and synthesis of liquid crystals, conductive materials, and dyes Is recognized as the most important catalytic reaction. Generally, since these transition metal catalysts are expensive, repeated use is required. In a homogeneous catalyst, the catalyst is dissolved in the reaction solution, so that it is not easy to separate and recover the catalyst after the reaction from the solution. Therefore, use of a heterogeneous catalyst in which a transition metal catalyst is immobilized in an insoluble solid has been studied.

  An important issue for developing an immobilized catalyst with high durability for repeated use is to effectively suppress leakage of a metal component immobilized on an insoluble carrier into the reaction system. Leakage of metal components into the reaction system not only affects the durability of repeated use of the catalyst, but is also considered as a major issue related to the incorporation of trace metals into the reaction product and the accompanying increase in purification costs. ing. In addition, the collection of trace metals and disposal of waste liquids has become a major issue due to social demands for environmentally conscious process development that can mitigate global warming and reduce greenhouse gas emissions, which has been increasing in recent years. Yes.

  With such a situation as a background, in Patent Document 1, sulfur is immobilized on the surface of a semiconductor substrate such as a gallium arsenide substrate, a metal compound is bonded thereto, and then heat treatment is performed in an organic solvent, whereby the metal compound is It has been reported that by performing fixing treatment, a substrate-bound metal catalyst can be obtained in which the catalytic activity does not decrease even after repeated use and the leakage of the metal component into the reaction system can be suppressed. However, this method requires large-scale equipment such as MBE (Molecular Beam Epitaxy) and high-temperature conditions for the preparation of the semiconductor substrate and the fixation of sulfur, and is also exposed to a high temperature in the solvent for bonding and fixing of the metal. There is a need.

  In Patent Document 2, a crosslinkable polymer having an aromatic side chain, a divalent palladium salt and an alkali metal salt are bonded by heating in a solvent, cooled and precipitated, and then the polymer is crosslinked. Reported a method for producing a polymer-immobilized palladium catalyst that can be used repeatedly for cross-coupling reactions and that almost no metal leakage is observed. This method has disadvantages such as requiring a multi-step synthesis of the crosslinkable polymer and complicated preparation of the polymer-immobilized palladium catalyst.

  In Patent Document 3, the present inventors simply mixed a polymerizable composition containing a vinyl group-introduced dendrimer or polyethyleneimine with a metal salt such as palladium, and carried out a polymerization reaction, whereby a small particle size was easily obtained. It has been reported that an immobilized metal catalyst carrying crystalline Pd nanoparticles can be obtained. It has been shown that this catalyst has a high metal content, exhibits high activity for cross-coupling reactions, and can be easily recovered and reused. There is no disclosure of leakage of metal components into the reaction system.

JP 2007-54790 A JP 2007-61669 JP 2010-70753 A

  The problem to be solved by the present invention is to provide an organic-inorganic composite that has a high metal content and can be easily prepared, and has high activity and durability against cross-coupling reactions. Another object of the present invention is to provide an organic-inorganic composite that functions as an insoluble solid catalyst with a small amount of metal leaking into the reaction system and a method for producing the same.

  As a result of various studies, the present inventors have found that a metal is contained in a polymer of a polymerizable compound having an amino group or a urea bond and a crosslinkable polymerizable compound having an optionally branched alkylene group having 4 to 12 carbon atoms. The present inventors have found that an organic-inorganic composite containing or dispersing nanoparticles can solve the above problems. Here, it is presumed that the amino group, imino group, urea bond and amide bond contained in the polymer can strongly interact with the metal component by the coordination bond. On the other hand, although the mechanism of action is not clear, the crosslinkable polymerizable compound having 4 to 12 alkylene groups which may be branched does not significantly impair the activity of the polymer as a catalyst, and the catalytic reaction It is assumed that it functions effectively to significantly reduce the amount of metal leaking into the system.

That is, the present invention provides a polymer of the polymerizable composition (A) and (P _A) a complex of a metal nanoparticle, the polymerizable composition (A) is,
(1) a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group;
(2) a polymerizable compound (b) having an optionally branched alkylene group having 4 to 12 carbon atoms and two or more vinyl groups;
The organic-inorganic composite characterized by including this.

  The present invention also provides a catalyst characterized by using the above organic-inorganic composite.

  The present invention also relates to a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an optionally branched alkylene group having 4 to 12 carbon atoms, and two or more. A composition (X) in which a polymerizable composition (A) containing a polymerizable compound (b) having a vinyl group, a metal compound (c) and a solvent (M) are mixed is prepared, and the composition (X) The organic-inorganic composite comprising the step (α-1) of reducing the metal compound (c) at the same time as polymerizing the polymer to form metal nanoparticles and then removing the solvent (M). A manufacturing method is provided.

Further, the invention relates to (1) a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an optionally branched alkylene group having 4 to 12 carbon atoms, and 2 A composition (Y) in which a polymerizable composition (A) containing a polymerizable compound (b) having at least one vinyl group and a solvent (M) were mixed was prepared, and the composition (Y) was polymerized. Thereafter, the step of removing the solvent (M) (α-3),
(2) The polymer (P _A ) is brought into contact with the solution (I) containing the metal compound (c) to adsorb the metal compound (c) to the polymer (P _A ), and then the polymer (P A _A ) separating the solution (I) from the solution (I) (α-4),
(3) The metal compound (c) is reduced by bringing the polymer (P _A ) containing the metal compound (c) into contact with the solution (H) containing the reducing agent (d) to produce metal nanoparticles. Then, the step (α-5) of separating the polymer (P _A ) containing the generated metal nanoparticles from the solution (H) is sequentially performed.
A method for producing the above organic-inorganic composite is provided.

Furthermore, the present invention provides (1) a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an optionally branched alkylene group having 4 to 12 carbon atoms, and A polymerizable composition (A) containing a polymerizable compound (b) having two or more vinyl groups, a metal compound (c), a reducing agent (d), and a solvent (Q) compatible with these were mixed. Preparing a composition (Z), reducing the metal compound (c) in the composition to produce metal nanoparticles (α-6),
(2) A composition (V) prepared by mixing the composition containing the metal nanoparticles and a solvent (R) compatible with the composition is prepared, and the composition (V) is polymerized to contain the metal nanoparticles. _A method for producing an organic-inorganic composite in which a polymer (P _A ) is produced and then the steps (α-7) of removing the solvents (Q) and (R) are sequentially performed,
Production of the organic-inorganic composite described above, wherein the mixed solvent in which the solvent (Q) and the solvent (R) are mixed does not dissolve or swell the polymer (P _A ) of the polymerizable composition (A). Provide a method.

  In the present invention, the polymerizable composition (A) is polymerized by using a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond in an arbitrary ratio, and metal nanoparticles are incorporated into the polymer. Since it produces | generates, an organic inorganic composite with a high metal content can be provided. Moreover, the polymeric property containing the crosslinkable polymeric compound which has the polymeric compound (a) which has an amino group, an imino group, a urea bond, or an amide bond, and the C4-C12 alkylene group which may be branched. An organic-inorganic composite containing metal nanoparticles can be easily produced by mixing the composition and a metal compound and performing a metal reduction reaction simultaneously with the polymerization reaction. By using such an organic-inorganic composite, it is possible to provide an organic-inorganic composite that functions as an insoluble solid catalyst that has high activity and high durability against cross-coupling reactions and has a small amount of metal leaking into the reaction system. . In addition, the organic-inorganic composite of the present invention can be used for various applications depending on the characteristics of the metal contained, such as fuel cells and other energy conversion materials, optical materials such as light emission and phosphorescence, antibacterial and gas barriers, etc. It is possible to provide functional materials that suppress metal leakage during use, such as food packaging materials.

4 is a transmission electron micrograph of an organic-inorganic composite [P-4] obtained in Example 4. 4 is a scanning electron micrograph of the organic-inorganic composite [P-4] obtained in Example 4.

Hereafter, the principal part for implementing this invention is demonstrated.
[Structure of organic-inorganic composite]
Organic-inorganic composite of the present invention is an organic-inorganic composite polymer of a polymerizable composition (A) and (P _A) consisting of metal nanoparticles, wherein the polymerizable composition (A) is an amino group, A polymerizable compound (a) having an imino group, a urea bond or an amide bond, and a vinyl group, and a polymerizable compound having an optionally branched alkylene group having 4 to 12 carbon atoms and two or more vinyl groups ( b) and an organic-inorganic composite characterized in that

  The polymerizable compound (a) having an amino group, imino group, urea bond or amide bond and a vinyl group used in the present invention may be any compound such as radical polymerizable, anionic polymerizable, or cationic polymerizable. It's okay. Of these, a compound having radical polymerizability is preferably used, and a (meth) acryloxy group, a (meth) acrylamide group or a styryl group is preferably selected as the vinyl group. An amino group, an imino group, a urea bond, and an amide bond act as an interaction site with a metal in the organic-inorganic composite. As the amino group, a primary amino group, a secondary amino group, and a tertiary amino group are arbitrarily used, but the tertiary amino group is preferably used because it hardly causes a side reaction other than an interaction with a metal. . Examples of such polymerizable compounds include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylamide, 2-aminoethyl (meth) acrylate, 4-vinylaniline and the like. .

A polymerizable compound having an imino group is synthesized and used because there is no commercially available compound. Although there is no restriction | limiting in a synthesis method, The method of making the compound or ketone compound which has an aldehyde group react with the polymeric compound which has a primary amino group or a secondary amino group, and a vinyl group is used preferably. Examples of the polymerizable compound having a primary amino group or a secondary amino group and a vinyl group include 3-aminopropyl (meth) acrylamide, 2-aminoethyl (meth) acrylate, 4-vinylaniline and the like. Examples of the compound having an aldehyde group include acetaldehyde, propionaldehyde, benzaldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, and the like. Examples of the ketone compound include acetone, 2-butanone, acetophenone, and benzophenone.
A polymerizable compound having a urea bond is synthesized and used because there is no commercially available compound. Although there is no restriction | limiting in a synthesis method, The method of making the compound which has a primary amino group or a secondary amino group react with the polymeric compound which has an isocyanato group and a vinyl group is used preferably. Examples of the polymerizable compound having an isocyanato group and a vinyl group include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxy). And methyl) ethyl isocyanate and 4'-vinylphenyl isocyanate. The compound having a primary amino group or a secondary amino group is not particularly limited, but monoamine compounds having an alkyl chain such as methylamine, ethylamine, butylamine, hexylamine, dodecylamine, ethylenediamine, butylenediamine, hexylene. A diamine compound having an alkylene group such as diamine and dodecylenediamine is preferably used. Moreover, the method of making the compound which has an isocyanato group react with the polymeric compound which has a primary amino group or a secondary amino group, and a vinyl group can also be used preferably. Examples of the polymerizable compound having a primary amino group or a secondary amino group and a vinyl group include 3-aminopropyl (meth) acrylamide, 2-aminoethyl (meth) acrylate, 4-vinylaniline and the like. Examples of compounds having an isocyanato group include monoisocyanate compounds having an alkyl chain such as methyl isocyanate, ethyl isocyanate, butyl isocyanate, hexyl isocyanate, and dodecyl isocyanate, ethylene diisocyanate, butylene diisocyanate, hexylene diisocyanate, dodecylene diisocyanate, and isophorone diisocyanate. A diisocyanate compound having an alkylene group such as is preferably used.
Moreover, when a polymerizable compound having an isocyanato group is reacted using a compound having both a primary amino group or a secondary amino group and a tertiary amino group, a polymerizable compound having both a tertiary amino group and a urea bond is obtained. Can do. These can be preferably used in the present invention. Examples of such compounds include polymerizable compounds prepared by reacting an isocyanate group-containing polymerizable compound using N, N-dimethylethylenediamine or tris (2-aminoethyl) amine as the amino group-containing compound. In particular, compounds prepared by reacting with 2- (meth) acryloyloxyethyl isocyanate are effectively used.

  The synthesis reaction of the polymerizable compound containing a urea bond can be performed by, for example, dissolving both compounds used in the reaction in a solvent, mixing, and contacting. A catalyst can be used as needed. When the reaction is performed without a catalyst, the reaction product can be used as it is for the preparation of the subsequent organic-inorganic composite without isolation from the solvent. When the reaction is carried out using a catalyst, the reaction product is purified and isolated, and then used for the preparation of an organic-inorganic composite.

  Examples of the polymerizable compound having an amide bond include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-isobutylacrylamide, N-secbutylacrylamide, N- Tert butyl acrylamide, N-hexyl acrylamide, N-dodecyl acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, and 3-aminopropyl (meth) acrylamide are preferably used. In addition, a polymerizable compound having a carboxy group such as 2-methacryloyloxyethyl succinic acid, a monoamine compound having an alkyl chain such as methylamine, ethylamine, butylamine, hexylamine, dodecylamine, ethylenediamine, butylenediamine, hexylene A compound synthesized by reacting a diamine compound having an alkylene group such as diamine or dodecylenediamine can also be used. In addition, a polymerizable compound having a primary amino group such as 3-aminopropyl (meth) acrylamide, 2-aminoethyl (meth) acrylate, 4-vinylaniline, acetic acid, propionic acid, butanoic acid, hexanoic acid, adipic acid It can be used by reacting a compound having carboxy such as.

In the organic-inorganic composite of the present invention, the polymerizable compound (a) having the amino group, imino group, urea bond or amide bond, and vinyl group has a tertiary amino group and a reactive functional group (Q ₁ ) dendrimer (a1) having, or a polyethyleneimine having a reactive functional group _{(Q 1)} (a2), and the reactive functional group _{(Q 1)} capable of reacting with the reactive functional group _{(Q 2),} vinyl It is an organic-inorganic composite characterized by being a compound obtained by reacting a compound (a3) having a group.

A dendrimer is a dendritic molecule, and is a general term for molecules having a monodispersed molecular weight that are regularly and sequentially branched from the core that is the center of branching. The dendrimer (a1) used in the present invention is not particularly limited as long as it has a tertiary amino group and a reactive functional group (Q ₁ ) and is a molecule included in the dendrimer defined above. For example, “Dendrimers and Dendrons: Concepts, Syntheses, Applications” (2001, published by Wiley-VCH) by GR Newkome, CN Moorefield, F. Vogtle, “Dendrimers and Other Dendritic Polymers (Wiley Series in Polymer by JMJ Frechet, DA Tomalia) Science) "(2002, published by John Wiley & Sons) and the like, and compounds having a basic structure of dendrimers are used. However, a dendrimer having an amidoamine structure represented by the formula (1) or a propyleneimine structure represented by the formula (2) as a repeating unit is preferably used.

（式（１）中、ｘは１〜１０の整数である。）

(In Formula (1), x is an integer of 1-10.)

（式（２）中、ｙは１〜１０の整数である。）

(In formula (2), y is an integer of 1 to 10.)

  As the dendrimer, a commercially available reagent such as a dendrimer described in the reagent catalog of Aldrich can be used. Moreover, it can synthesize | combine and use suitably according to the objective.

  Examples of commercially available reagents include, for example, an ethylenediamine core third generation (product code 41422) of a polyamidoamine (PAMAM) dendrimer represented by the formula (3) and a formula (4) 4 generations (product code 41449), 1,6-diaminohexane core 4th generation (product code 596965) represented by formula (5), cystamine core 4th generation (product code 648043) represented by formula (6), Ethylenediamine core 4th generation (product code 477850) having a hydroxyl group terminal represented by formula (7), sodium salt of ethylenediamine core 3.5th generation having a carboxylic acid terminal represented by formula (8) (product code 41430) ), Polypropylene imine dendrimer first generation represented by formula (9) (product code 460) There are 99), and the like.

  The method for synthesizing the dendrimer (a1) having an amidoamine structure represented by the formula (1) is not particularly limited. For example, the methods described in JP-A-7-267879 and JP-A-11-140180 are used. be able to. First, 2 equivalents of methyl acrylate are allowed to act on the compound having a primary amino group as a core, and a compound having a nitrogen branch and having a methyl ester moiety is obtained by Michael addition reaction. Convert. Next, one of the diamine compounds having a primary amino group is reacted with the methyl ester moiety to form an amide bond, and the other primary amino group is left at the terminal. Thereafter, the Michael addition reaction and the amide bond formation reaction are alternately performed an arbitrary number of times, whereby an amidoamine-structured dendrimer (a1) can be synthesized.

  The method for synthesizing the propyleneimine structure dendrimer (a1) represented by the formula (2) is not particularly limited. For example, the methods described in WO-A93 / 14147 and WO-A95 / 2008 are used. Can be used. First, acrylonitrile is allowed to act on a compound having a primary amino group serving as a core to be cyanoethylated. Next, the nitrile group is reduced to a primary amino group using hydrogen or ammonia in the presence of a catalyst. Then, the propyleneimine structure dendrimer (a1) can be synthesized by alternately performing these cyanoethylation reaction and nitrile group reduction reaction an arbitrary number of times.

  The core structure of the dendrimer (a1) is not particularly limited, but the core structure using residues of ammonia, ethylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-diaminododecane, cystamine is used. preferable.

The reactive functional group (Q ₁ ) bonded to the end of the dendrimer is preferably bonded to the end. Then, by reacting with reactive functional groups contained in the compound (a3) having a vinyl group to be described later (Q _2), is not particularly limited as long as it can give a polymerizable compound having an amino group and a vinyl group and (a) Is preferably a primary or secondary amino group, hydroxyl group, or carboxy group. Of these, primary or secondary amino groups are particularly preferred because of their high chemical reactivity and variety of reactions.

  The molecular weight of the dendrimer (a1) is preferably 300 or more, particularly preferably 1000 to 100,000. When the organic-inorganic composite of the present invention is used as a catalyst, the molecular weight of 300 or less is disadvantageous for utilizing the space inside the dendrimer (a1).

  The polyethyleneimine (a2) used for the preparation of the organic-inorganic composite of the present invention may be linear or branched. The said polyethyleneimine (a2) can use what is marketed as a reagent. Moreover, according to the objective, the terminal group of the commercially available polyethyleneimine (a2) can be converted and used, or the polyethyleneimine (a2) can be synthesized and used. Although there is no restriction | limiting in particular in the synthesis method of a polyethyleneimine (a2), For example, the polymer which has an amide bond obtained by cationic polymerization of oxazolines in a repeating unit can be obtained by hydrolyzing.

The reactive functional group (Q ₁ ) of the polyethyleneimine (a2) is preferably bonded to the terminal. Then, by reacting with reactive functional groups contained in the compound (a3) having a vinyl group to be described later (Q _2), is not particularly limited as long as it can give a polymerizable compound having an amino group and a vinyl group and (a) Is preferably a primary or secondary amino group, hydroxyl group, or carboxy group. Of these, primary or secondary amino groups are particularly preferred because of their high chemical reactivity and variety of reactions.

  The weight average molecular weight of the polyethyleneimine (a2) is preferably 200 or more, particularly preferably 1000 to 100,000. When the organic polymer porous material of the present invention is used as a catalyst, if the weight average molecular weight is 200 or less, the space formed by the polyethyleneimine (a2) in the polymer becomes small, which is disadvantageous for performing a catalytic reaction. .

As the compound (a3) having a reactive functional group (Q ₂ ) capable of reacting with the reactive functional group (Q ₁ ) of the tertiary amino group-containing dendrimer (a1) or polyethyleneimine (a2) and a vinyl group, As long as it can give a polymerizable compound (a) having an amino group and a vinyl group by reacting with the dendrimer (a1) or the polyethyleneimine (a2), any polymer such as radical polymerizable, anionic polymerizable, or cationic polymerizable can be used. It may be a compound. However, among these, a compound having radical polymerizability is preferably used, and a (meth) acryloxy group, a (meth) acrylamide group, or a styryl group is preferably selected as the polymerizable group.

The compound (a3) having a reactive functional group (Q ₂ ) and a vinyl group used in the present invention includes an isocyanato group, an epoxy group, a primary or secondary amino group, a hydroxyl group, a carboxy group, or a carboxylic acid. And a compound (a3) having a vinyl group having a chloride unit. In particular, when reacting with a dendrimer (a1) or polyethyleneimine (a2) having a primary or secondary amino group as a reactive functional group (Q ₁ ), an isocyanate group, an epoxy group, and a vinyl group A compound (a3) having an isocyanato group and a vinyl group (a3) is preferably used because of its high reactivity.

  Examples of such a compound (a3) include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Compounds having an isocyanato group such as ethyl isocyanate, 4′-vinylphenyl isocyanate, compounds having an epoxy group such as glycidyl (meth) acrylate, 3-aminopropyl (meth) acrylamide, 2-aminoethyl (meth) acrylate, 4- Compounds having an amino group such as vinylaniline, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, compounds having a hydroxyl group such as 4-vinylphenol, 2- (meth) acryloyloxyethyl koha Acid, (meth) acrylic acid, 4 compounds having such carboxyl group of vinyl benzoate, and (meth) acrylic acid chloride, such as acid chlorides of 4-vinyl benzoic acid chloride and the like. These (meth) acrylates can be used alone or in combination of two or more.

  The reaction between the dendrimer (a1) or polyethyleneimine (a2) and the compound (a3) can be carried out, for example, by dissolving both the compounds used in the reaction in a solvent, and mixing and contacting them. A catalyst can be used as needed. When the reaction is performed without a catalyst, the reaction product can be used as it is for the preparation of the subsequent organic-inorganic composite without isolation from the solvent. When the reaction is carried out using a catalyst, the reaction product is purified and isolated, and then used for the preparation of an organic-inorganic composite.

In the said reaction, if the polymeric compound (a) obtained has an amino group and a vinyl group, the reactive functional group (Q contained in a dendrimer (a1) or a polyethyleneimine (a2) in arbitrary ratios. ₁ ) and the reactive functional group (Q ₂ ) contained in the compound (a3) having a vinyl group can be charged into the reaction solution. However, since the metal content in the polymer decreases when the number of amino groups acting as a metal-coordinating functional group is small, it is preferable to have 4 or more amino groups in one molecule of the polymerizable compound, and to have 8 or more amino groups. Is particularly preferred. Moreover, when there are many vinyl groups in 1 molecule of polymeric compounds, the quantity of the copolymerization component added to polymeric composition can be reduced, and, thereby, the relative amino group content in a polymer is increased. be able to. Therefore, it is preferable to have 4 or more vinyl groups in one molecule of the polymerizable compound, and it is particularly preferable to have 6 or more vinyl groups.

  Examples of the polymerizable compound (b) having an optionally branched alkylene group having 4 to 12 carbon atoms and two or more vinyl groups used in the present invention include radical polymerizable property, anionic polymerizable property, and cationic polymerizable property. Any compound may be used. Of these, compounds having radical polymerizability are preferably used, and a (meth) acryloxy group or a styryl group is preferably selected as the vinyl group. Especially, it is preferable that it is a compound which has a C4-C12 alkylene group and two or more (meth) acryloyl groups, A C4-C12 alkylene group and two or more (meth) acryloyl groups are included. A (meth) acrylic acid ester is particularly preferable. As carbon number, it is more preferable that it is 4-9, and it is especially preferable that it is 4-8.

  Since the polymerizable compound (b) is a cross-linkable polymerizable compound having two or more vinyl groups, it has a great influence on the strength after curing. Examples of the polymerizable compound (b) include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( Bifunctional monomers such as (meth) acrylate and dimethyloltricyclodecane di (meth) acrylate, trifunctional monomers such as trimethylolpropane tri (meth) acrylate and trimethylolethane tri (meth) acrylate; pentaerythritol tetra (meth) acrylate And tetrafunctional monomers such as dipentaerythritol hexa (meth) acrylate. These polymerizable compounds (b) can be used alone or in admixture of two or more. Among them, since the strength after curing is high and leakage of metals to the reaction system as a catalyst can be suppressed to a very low level, compounds having an alkylene group having 4 to 12 carbon atoms, particularly 1,6-hexanediol (Meth) acrylate is preferably used.

  The content of the amino group or urea bond of the organic-inorganic composite is preferably in the range of 0.01 mmol / g to 9.00 mmol / g, and in the range of 0.1 mmol / g to 9.0 mmol / g. Is particularly preferred. Therefore, in consideration of these contents, the polymerizable compound (a) having an amino group and a vinyl group or the polymerizable compound (b) having a urea bond and a vinyl group contained in the polymerizable composition (A). It is desirable to determine the amount.

  The amount of the polymerizable compound (b) having 4 to 12 carbon atoms which may be branched and 2 or more vinyl groups, which is contained in the polymerizable composition (A), is obtained as an organic compound. In order to effectively suppress the metal component leaking into the reaction system when the inorganic composite is used as a catalyst, it is preferably 25% by weight or more, more preferably 50% by weight or more of all the polymerizable compound components. It is particularly preferred.

  The metal nanoparticles contained in the organic-inorganic composite of the present invention are one or more selected from elements contained in any of the first transition element, the second transition element, the third transition element, or the fourth transition element. These particles are composed of these elements. However, particles composed of one or more elements selected from the elements included in the second transition element or the third transition element are preferable, and among these, palladium, platinum, ruthenium, rhodium, gold, silver, and rhenium are preferable. Particles composed of one or more selected elements are particularly preferred. The metal content in the organic-inorganic composite is preferably in the range of 0.01 mmol / g to 5.00 mmol / g, and particularly preferably in the range of 0.05 mmol / g to 5.00 mmol / g. The average particle diameter of the metal nanoparticles is preferably in the range of 0.1 to 100 nm, particularly preferably in the range of 0.5 to 10 nm.

When the organic-inorganic composite of the present invention is a porous body, the shape of the porous body is a structure such as an aggregated particle shape, a network shape, or a pore shape, and the average pore diameter is in the range of 0.001 to 10 μm. Things are desirable. Also, an inclined structure whose structure changes in the depth direction can be formed. In many fields of use, an inclined structure in which the hole diameter on the surface is large and the hole diameter decreases with increasing depth is preferred. The porous body is characterized in that its specific surface area is in the range of 5 to 2000 m ² / g, but when the porous body is used for the catalytic reaction, it is preferably in the range of 50 to 2000 m ² / g. .

  The organic-inorganic composite of the present invention can take a film form. In that case, the film thickness is preferably in the range of 1 to 100 μm, particularly preferably in the range of 3 to 50 μm. When the film thickness is thinner than 1 μm, when used as a catalyst, its performance tends to deteriorate, which is not preferable. In addition, the film thickness of an organic inorganic composite can be measured by microscopic observation of the cross section using a scanning electron microscope.

[Method for producing organic-inorganic composite]
The organic-inorganic composite of the present invention can be produced by the following four methods.

  The first method includes a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two A composition (X) in which a polymerizable composition (A) containing the above-described polymerizable compound (b) having a vinyl group, a metal compound (c), and a solvent (M) are mixed is prepared, and the composition ( This is a method for producing an organic-inorganic composite by polymerizing X) and simultaneously reducing the metal compound (c) to form metal nanoparticles, and then removing the solvent (M) (step (α-1) )).

  In the second method, after performing the step (α-1) shown in the first method, the organic-inorganic composite is brought into contact with the solution (H) containing the reducing agent (d), and then the organic-inorganic composite is used. In this method, the body is separated from the solution (H) (α-2).

In the third method, a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two A composition (Y) prepared by mixing a polymerizable composition (A) containing the above-described polymerizable compound (b) having a vinyl group and a solvent (M) was prepared, and the composition (Y) was polymerized. Thereafter, the step of removing the solvent (M) (α-3), the polymer (P _A ) is brought into contact with the solution (I) containing the metal compound (c), whereby the metal compound (c) is polymerized ( P _A ) is adsorbed, and then the polymer (P _A ) is separated from the solution (I) (α-4), and the polymer (P _A ) containing the metal compound (c) is reduced to the reducing agent (d The metal compound (c) is reduced by contacting with a solution (H) containing , Then separating the polymer containing the produced metal nanoparticles (P _A) from the solution (H) (α-5) , a method of performing.

The fourth method is a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two A composition in which a polymerizable composition (A) containing the above-described polymerizable compound (b) having a vinyl group, a metal compound (c), a reducing agent (d), and a solvent (Q) compatible with these are mixed. Preparing the product (Z), reducing the metal compound (c) in the composition to form metal nanoparticles (α-6), a composition containing the metal nanoparticles, and a compatibility therewith A composition (V) mixed with the solvent (R) is prepared, and the composition (V) is polymerized to produce a polymer (P _A ) containing metal nanoparticles, and then the solvents (Q) and ( This is a method of sequentially performing the step (α-7) of removing R). However, in this method, it is necessary that the mixed solvent in which the solvent (Q) and the solvent (R) are mixed does not dissolve or swell the polymer (P _A ) of the polymerizable composition (A).

  The first to fourth methods for producing the organic-inorganic composite will be described in detail.

In method 1, the composition (X) in the polymerizable composition polymer produced by polymerization of (A) by the degree of compatibility of (P _A) and a solvent (M), the obtained polymer (P _A) The microstructure is different. When the polymer (P _A ) and the solvent (M) are completely compatible, the polymer (P _A ) is swollen by the solvent (M), and after removing the solvent, the resulting organic-inorganic composite is nonporous. Become. On the other hand, when the polymer (P _A ) and the solvent (M) are partially compatible or incompatible, when the polymer (P _A ) and the solvent (M) are in a phase separated state , a state in which the solvent (M) is incorporated between the polymer _{(P a)} or inside the polymer _{(P a).} By removing this solvent (M), the region occupied by the solvent (M) becomes pores, and a porous organic-inorganic composite can be formed.

The polymerizable composition (A) is an alkylene group having 4 to 12 carbon atoms which may be branched with a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group. And a polymerizable compound (b) having only two or more vinyl groups, or a copolymer obtained by copolymerizing with the polymerizable compound (a) and the polymerizable compound (b). It comprises other polymerizable compounds (a ′) that can form (P _A ). A polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two or more vinyl groups The polymerizable compound (b) can be used alone or in combination of two or more. A polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two or more vinyl groups As the polymerizable compound (b), the aforementioned polymerizable compounds and the like can be used.

A polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two or more vinyl groups The other polymerizable compound (a ′) that can be copolymerized with the polymerizable compound (b) to form a copolymer (P _A ) is one that is polymerized in the presence or absence of a polymerization initiator. Those having a vinyl group are preferred, and among them, highly reactive (meth) acrylic compounds and styryl compounds are preferred. Moreover, since the intensity | strength after hardening can be made high, it is preferable that it is a compound which superposes | polymerizes and forms a crosslinked polymer. Therefore, a compound having two or more vinyl groups in one molecule is particularly preferable.

  Examples of the (meth) acrylic compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, and 2,2 ′. -Bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, hydroxydipivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, N-methylene Bifunctional monomers such as bisacrylamide; and trifunctional monomers such as tris (acryloxyethyl) isocyanurate and caprolactone-modified tris (acryloxyethyl) isocyanurate.

  Examples of the polymerizable oligomer having a (meth) acryloyl group in the molecular chain include those having a weight average molecular weight of 500 to 50,000. For example, (meth) acrylic acid ester of epoxy resin, (meta) of polyether resin ) Acrylic acid ester, (meth) acrylic acid ester of polybutadiene resin, polyurethane resin having a (meth) acryloyl group at the molecular terminal.

  Examples of the styryl compound include 1,3-divinylbenzene and 1,3-dipropenylbenzene.

  These polymerizable compounds (a ′) can be used alone or in admixture of two or more. Further, for the purpose of adjusting the viscosity, it may be used by mixing with a polymerizable compound having one vinyl group, in particular, a (meth) acryl compound or styryl compound having one vinyl group.

  Examples of (meth) acrylic compounds having one vinyl group include methyl (meth) acrylate, alkyl (meth) acrylate, isobornyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, Phenoxypolyethylene glycol (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol acrylate methacrylate, butanediol mono (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl acrylate, Tylene oxide modified phthalic acid acrylate, w-carboxycaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2-acryloyloxypropyl hexahydrohydrogen phthalate, fluorine-substituted alkyl ( (Meth) acrylate, chlorine-substituted alkyl (meth) acrylate, sulfonic acid sodaethoxy (meth) acrylate, sulfonic acid-2-methylpropane-2-acrylamide, phosphoric ester group-containing (meth) acrylate, glycidyl (meth) acrylate, 2- Isocyanatoethyl (meth) acrylate, (meth) acryloyl chloride, (meth) acrylaldehyde, sulfonic acid ester group-containing (meth) acrylate , Silano group-containing (meth) acrylate, ((di) alkyl) amino group-containing (meth) acrylate, quaternary ((di) alkyl) ammonium group-containing (meth) acrylate, (N-alkyl) acrylamide, (N, N -Dialkyl) acrylamide, acryloylmorpholine and the like.

  Examples of the styryl compound having one vinyl group include styrene, propenylbenzene, 1-vinylnaphthalene, and 9-vinylanthracene.

  The metal compound (c) is a salt composed of an element contained in any of the first transition element, the second transition element, the third transition element, or the fourth transition element, for example, iodate, bromate, chlorine Acid salts, fluoride salts, nitrates, perchlorates, phosphates, sulfates, sulfites, acetates, acetylacetonates, oxalates, gluconates, p-toluenesulfonates, etc. are preferably used it can. Among them, a salt composed of an element included in the second transition element or the third transition element is preferable, and among them, a salt composed of an element selected from palladium, platinum, ruthenium, rhodium, gold, silver, and rhenium is particularly preferable. preferable. Further, chlorates, acetates and nitrates of these transition metals can be preferably used. These transition metal compounds can be used alone or in combination of two or more.

  In the composition (X) prepared by mixing the polymerizable composition (A) and the metal compound (c), the amino group or urea bond in the polymerizable composition (A) and the transition in the metal compound (c) The metal forms a coordination bond, and the metal compound (c) can be incorporated into the polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group.

  As a solvent (M), a uniform composition (X) should just be obtained with polymeric composition (A) and a metal compound (c). The solvent (M) may be a single solvent or a mixed solvent. In the case of a mixed solvent, the component alone is not compatible with the polymerizable composition (A) or the metal compound (c). It may be a thing. Examples of the solvent (M) include alkyl esters of fatty acids such as ethyl acetate, methyl decanoate, methyl laurate, and diisobutyl adipate, and ketones such as acetone, 2-butanone, isobutyl methyl ketone, and diisobutyl ketone. , Diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and other ethers, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Aprotic polar solvents, aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane and octane, dichloromethane, chloroform, and carbon tetrachloride. Halogenated hydrocarbons, methanol, ethanol, 2-propanol, 1-butanol, 1,1-dimethyl-1-ethanol, hexanol, alcohols such as decanol, and include a solvent such as water. Among these solvents, when used as a single solvent, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, Highly polar alcohols such as -propanol and 1,1-dimethyl-1-ethanol are branched from the polymerizable compound (a) having the amino group, imino group, urea bond or amide bond, and vinyl group. Since it is easy to be compatible with the polymerizable composition (A) containing the polymerizable compound (b) having an alkylene group having 4 to 12 carbon atoms and 2 or more vinyl groups, it is preferably used. Moreover, when obtaining a porous organic-inorganic composite, in order to control the specific surface area, a high amount of acetone, N, N-dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, 2-propanol or the like is used. A mixed solvent of a polar solvent and a medium polar solvent such as tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether compatible with them is also preferably used.

  The method for removing the solvent (M) after polymerizing the composition (X) is not particularly limited, but when the solvent (M) is a highly volatile solvent, it is dried by drying at normal pressure or reduced pressure. be able to. When the solvent (M) is a low volatility solvent, the polymer obtained by polymerizing the composition (X) is brought into contact with a high volatility solvent, the solvent is exchanged, and then dried at normal pressure or reduced pressure. Can be performed. Further, when the solvent (M) is removed, it branches off from the polymerizable compound (a) having an amino group, imino group, urea bond or amide bond and a vinyl group contained in the polymerizable composition (A). Among the polymerizable compounds (b) having 4 to 12 carbon atoms that may be present and a polymerizable compound (b) having two or more vinyl groups and other polymerizable compounds, for the purpose of removing unpolymerized components, It is also effective to perform washing and extraction using a solvent in which the compound dissolves. The extraction operation can also be performed using a Soxhlet extractor.

  When the obtained organic-inorganic composite is porous, the pore size and strength of the organic-inorganic composite vary depending on the content of the polymerizable composition (A) contained in the composition (X). As the content of the polymerizable composition (A) increases, the strength of the porous body improves, but the pore diameter tends to decrease. The preferable content of the polymerizable composition (A) is in the range of 15 to 50% by mass, more preferably in the range of 25 to 40% by mass. When the content of the polymerizable composition (A) is 15% by mass or less, the strength of the porous body is lowered, and when the content of the polymerizable composition (A) is 50% by mass or more, the pore size of the porous body. It becomes difficult to adjust.

  Various additives such as a polymerization initiator, a polymerization inhibitor, or a polymerization retarder may be added to the composition (X) in order to adjust the polymerization rate, the polymerization degree, and the like.

  The polymerization initiator is not particularly limited as long as it can polymerize the polymerizable composition (A), and a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and the like can be used. For example, 2,2′-azobisbutyronitrile, 2,2′-azobiscyclohexanecarbonitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyrate) Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyano) Valeric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2-methylpropionamidoxime), 2,2′-azobis (2- (2-imidazolin-2-yl) propane), 2, Azo initiators such as 2′-azobis (2,4,4-trimethylpentane), benzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene Peroxide initiators such as Roperuokishido the like. Moreover, as a polymerization initiator that functions by the action of active energy rays, p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Ketones such as acetophenones, benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin Benzoin ethers such as isobutyl ether, benzyl ketals such as benzyldimethyl ketal and hydroxycyclohexyl phenyl ketone, and N-azidosulfonylphenylmaleimide. Include the azide. A polymerizable ultraviolet polymerization initiator such as a maleimide compound can also be used. Further, disulfide initiators such as tetraethylthiilam disulfide, nitroxide initiators such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4,4′-di-t-butyl-2,2′- Living radical polymerization initiators such as bipyridine copper complex-methyl trichloroacetate complex and benzyldiethyldithiocarbamate can also be used.

  Polymerization retarders and polymerization inhibitors can be used mainly during polymerization by active energy rays, and vinyls having a low polymerization rate such as α-methylstyrene and 2,4-diphenyl-4-methyl-1-pentene. And hindant phenols such as tert-butylphenol.

  The soluble polymer can be used without limitation as long as it gives a uniform composition as the composition (X) and is soluble in the solvent (M) alone. By being soluble in the solvent (M), it can be easily removed from the cured coating film by an operation of removing the solvent (M) after the composition (X) is cured.

  The polymerization reaction may be a known method such as a thermal polymerization method and an active energy ray polymerization method performed by irradiation with ultraviolet rays or electron beams. For example, an organic-inorganic composite can be produced by reacting with the above-described thermal polymerization initiator at 40 to 100 ° C., preferably 60 to 80 ° C. for 10 minutes to 72 hours, preferably 6 to 24 hours. Moreover, an organic-inorganic composite can be manufactured by making it react for 1 second-2 hours, preferably 10 seconds-30 minutes at room temperature in the output of 250-3000W using various mercury lamps and metal halide lamps.

  In the first method for producing an organic-inorganic composite, when the composition (X) is polymerized, the metal compound (c) is simultaneously reduced to produce metal nanoparticles (step (α-1)). The metal compound (c) is reduced by the reducing action of radicals at the ends of the growing polymer chain generated during the polymerization reaction of the polymerizable composition (A), and converted into metal nanoparticles. This method is preferably used because metal nanoparticles having a crystal face with excellent catalytic properties can be easily formed. Further, the metal may be reduced by the reducing action of the amino group contained in the polymerizable compound (a). In the case of active energy ray polymerization, the benzyl ketal polymerization initiator is preferably used because the ketyl radical generated by irradiation with active energy rays has a reducing action on the metal compound (b).

  In the second method for producing the organic-inorganic composite, after performing the step (α-1) shown in the first method, the organic-inorganic composite is brought into contact with the solution (H) containing the reducing agent (d). Thereafter, the step (α-2) of separating the organic-inorganic composite from the solution (H) is performed. By performing this step, if the metal compound (c) remains after performing the first method, it is possible to reduce all of the metal compound (c) and promote the generation of metal nanoparticles.

  As the reducing agent (d), a hydride-based reducing agent such as sodium borohydride, potassium borohydride, tetrabutylammonium borohydride or the like, and a known and conventional reducing agent such as hydrazine or ascorbic acid can be used. Alcohols such as methanol, ethanol, 2-propanol, and 1-hexanol can also be used as the reducing agent. The solvent used for preparing the solution (H) can be used without limitation as long as it can dissolve the reducing agent to be used and does not react with the polymer. For example, an organic-inorganic composite can be produced by performing a reduction reaction at 0 to 80 ° C., preferably at room temperature to 40 ° C. for 1 second to 24 hours, preferably 10 seconds to 6 hours.

In the step of the third method for producing the organic-inorganic composite, the step (α-3) of polymerizing the composition (Y) has been described in the method 1 except that the metal compound (c) is not allowed to coexist. According to the method of the step (α-1) for polymerizing the composition (X), polymerization can be carried out to prepare a polymer (P _A ).

Subsequently, the polymer (P _A ) is brought into contact with the solution (I) containing the metal compound (c) to adsorb the metal compound (c) to the polymer (P _A ), and then the polymer (P _A ) Is separated from the solution (I) (α-4). The metal compound (c) is as described above. The solvent used for the preparation of the solution (I) can be used without limitation as long as it can dissolve the metal compound to be used and does not react with the polymer (P _A ). The metal compound (c) can be adsorbed to the polymer (P _A ) by reacting at 0 to 80 ° C., preferably at room temperature to 40 ° C. for 10 minutes to 24 hours, preferably 30 minutes to 6 hours.

In the step (α-5), the polymer (P _A ) on which the metal compound is adsorbed is brought into contact with the solution (H) containing the reducing agent (d), and then the polymer containing the produced metal nanoparticles is used. This is a step of separating (P _A ) from the solution (H). This step can be performed according to the method shown in the second method.
In the fourth method for producing the organic-inorganic composite, before the polymerizable composition (A) is polymerized to form the polymer (P _A ), the metal compound (A) is present in the presence of the polymerizable composition (A). It is a method for producing an organic-inorganic composite by reducing metal c) to form metal nanoparticles, and then polymerizing a solution containing the obtained metal nanoparticles to form a polymer (P _A ). .

The polymerizable composition (A), metal compound (c), and reducing agent (d) used in this method are the same as described above. It is a necessary condition that the solvent (Q) is compatible with the polymerizable composition (A), the metal compound (c), and the reducing agent (d). The solvent (Q) may be a single solvent or a mixed solvent. In addition, it is a necessary condition that the solvent (R) is compatible with the composition obtained by reducing the metal compound (c) in the composition (Z). The solvent (R) may be a single solvent or a mixed solvent. However, what is important in producing a porous organic-inorganic composite is that the mixed solvent in which the solvent (Q) and the solvent (R) are mixed is a polymer of the polymerizable composition (A) ( P _A ) is not dissolved or swollen. As such solvents (Q) and (R), for example, the solvents mentioned in the description of the solvent (M) can be selected and used.

  In this method, the reduction reaction of the composition (Z) is a reduction reaction method using the reducing agent (d), the polymerization reaction of the composition (V) is a polymerization reaction of the composition (X), and The method for removing the solvent (Q) and (R) after the polymerization reaction can be carried out in accordance with the method for removing the solvent (M).

[Method for producing film-like organic-inorganic composite]
In the case of an organic-inorganic composite having a film-like form, known and commonly used surfactants, thickeners, modifiers, catalysts, and the like can be added for the purpose of improving coatability and smoothness.

  The support that can be used in producing the organic-inorganic composite having a film-like form is not substantially affected by the composition (X), (Y), or (Z), and can be dissolved, decomposed, or the like. Any material that does not occur and does not substantially invade the composition (X), (Y), or (Z) may be used. Examples of such a support include resins, crystals such as glass and quartz, ceramics, semiconductors such as silicon, metals, and the like. Among these, the transparency is high and the cost is low. , Resin or glass is preferred. The resin used for the support may be a homopolymer, a copolymer, a thermoplastic polymer, or a thermosetting polymer. The support may be composed of a polymer blend or a polymer alloy, or may be a laminate or other complex. Further, the support may contain additives such as a modifier, a colorant, a filler, and a reinforcing material.

  The shape of the support is not particularly limited, and an arbitrary shape can be used according to the purpose of use. For example, a sheet shape (including a film shape, a ribbon shape, a belt shape), a plate shape, a roll shape, a spherical shape, and the like can be mentioned, and the composition (X), (Y), or (Z) is formed thereon. From the viewpoint of easy application, it is preferable that the coated surface has a planar shape or a quadric surface shape.

  The support may be surface-treated both in the case of resin and other materials. The surface treatment is for the purpose of preventing dissolution of the support by the composition (X), (Y), or (Z), improving the wettability of the composition (X), (Y), or (Z) and organic The thing for the purpose of the adhesive improvement of an inorganic composite is mentioned.

  The surface treatment method of the support is arbitrary, for example, a treatment in which an arbitrary polymerizable composition is applied to the surface of the support and cured by a polymerization reaction, corona treatment, plasma treatment, flame treatment, acid or alkali treatment, sulfone. For example, a primer treatment with a fluorination treatment, a fluorination treatment, a silane coupling agent or the like, a surface graft polymerization, a coating with a surfactant or a release agent, or a physical treatment such as rubbing or sandblasting. Moreover, the method of reacting with the reactive functional group which the raw material of an organic inorganic composite has, or the reactive functional group introduce | transduced by the said surface treatment method, and reacting the compound fixed on the surface is mentioned. Among these, when glass or quartz is used as the support, for example, a method of treating with a silane coupling agent such as trimethoxysilylpropyl (meth) acrylate or triethoxysilylpropyl (meth) acrylate is used as these. Since the polymerizable group of the silane coupling agent can be copolymerized with the composition (X), (Y), or (Z), it is useful for improving the adhesion of the organic-inorganic composite onto the support.

  Any method may be used for applying the composition (X), (Y), or (Z) to the support as long as it is a known and commonly used method. For example, a coating method using a coater, spraying, or the like is preferable.

  As mentioned above, although demonstrated regarding manufacture of an organic inorganic composite, the manufacturing method of the organic inorganic composite which can be used by this invention is not limited to the said illustration.

[Catalytic reaction using organic-inorganic composite]
The catalytic reaction using the organic-inorganic composite of the present invention will be described.

  The organic-inorganic composite of the present invention can be used for catalytic reactions involving metal nanoparticles. Among these, it is preferably used for a catalytic reaction using nanoparticles of palladium, platinum, ruthenium, rhodium, gold, silver, or rhenium, and particularly preferably used for a catalytic reaction using nanoparticles of palladium or platinum. Examples of the catalytic reaction include a cross coupling reaction, a hydrogenation reaction, and an oxidation reaction. Among them, the cross-coupling reaction of aryl halides is preferable, and examples of the reaction include Susuki-Miyaura (Suzuki-Miyaura) reaction, Sonogashira (Soto) reaction, Heck reaction, Stille reaction, Buchwald-Hartwig reaction and the like. Other preferred reaction examples include an allylic rearrangement reaction.

  When the organic-inorganic composite is used for the catalytic reaction, it is only necessary to dissolve or disperse the reaction raw material in a solvent and to contact the organic-inorganic composite in a heterogeneous system. A cocatalyst and an additive can coexist as needed. As the solvent used for the reaction, water, an organic solvent, and a mixed solvent thereof can be appropriately selected according to the type of reaction.

  The organic-inorganic composite of the present invention can provide a catalyst excellent in repeated use stability. The catalyst having excellent use stability mentioned here means that it can be used repeatedly 5 times or more without changing the catalyst ability in the catalyst test at 80 ° C. for 24 hours. It can be used repeatedly more than once.

  Moreover, the organic-inorganic composite of the present invention can effectively suppress leakage of the immobilized metal component into the reaction system. The metal component leaking into the reaction system can be suppressed to a level of at least 300 ppb or less, and further can be suppressed to 100 ppb or less.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to the range of a following example.

Example 1
[Preparation of organic-inorganic composite]
150 mg of dimethylaminoethyl methacrylate (product name: Light Ester DM, manufactured by Kyoeisha Chemical Co., Ltd.), which is a polymerizable compound having a tertiary amino group, is added to 1.40 mL of N, N-dimethylformamide (hereinafter abbreviated as “DMF”). Dissolved. To this, 1.60 mL (Pd ²⁺ equivalent: 320 μmol) of a DMF solution of palladium acetate (0.2 mol·L ⁻¹ ) was added, and the mixture was stirred at room temperature for 30 minutes using a magnetic stirrer. Subsequently, 1,6-hexanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: light ester 1.6HX) (hereinafter abbreviated as “HX”) 1.74 g, azobisiso 20 mg of butyronitrile (hereinafter abbreviated as “AIBN”), 4.0 mL of diethylene glycol dimethyl ether (hereinafter abbreviated as “diglyme”), and 6.0 mL of DMF were added to prepare Composition [X-1].

  Next, the composition [X-1] was charged into a polymerization tube and nitrogen gas was blown in for 30 minutes, and then sealed and heat-treated at 70 ° C. for 12 hours. After removing the formed pale yellow solid from the polymerization tube, the organic-inorganic composite [P-1] is removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). Prepared.

Yield: 1.83 g, yield: 97%.
Specific surface area (BET simplified method): 0.69 m ² / g.
Measuring device: Flow soap type II flow type specific surface area automatic measuring device (Shimadzu Corporation)
Sample amount: about 0.01 to 0.03 g
Pretreatment: heated in carrier gas (N ₂ / He mixed gas) at 100 ° C. for 30 minutes Metal content: 0.16 mmol / g.
Measuring device: Differential thermal thermogravimetric simultaneous measurement device EXSTAR6000TG / DTA
Sample amount: about 0.05g
Measurement temperature range: 30-1000 ° C
Average particle size of metal nanoparticles (transmission electron microscope analysis): 2.5 nm
Apparatus: Transmission electron microscope JEM-2200FS (JEOL)
Accelerating voltage: 200kV
Image analysis type particle size distribution measurement software: Macview
Number of particles to be analyzed: 100 or more

[Catalytic reaction test using organic-inorganic composite]
4-Bromoacetophenone 0.65 mmol, phenylboronic acid 0.86 mmol, potassium carbonate 2.0 mmol, and water 3 mL were mixed to prepare a reaction solution (Y1). 41.0 mg (Pd equivalent: 6.5 μmol) of the organic-inorganic composite [P-1] (classified size: 75 to 300 μm) was added thereto, and reacted at 80 ° C. for 4 hours. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.

  After filtering the organic-inorganic composite [P-1] from the reaction solution, the filtrate was evaluated using an inductively coupled plasma emission spectrometer ICP-AES (Perkin Elmer Optima 3300DV). It was confirmed that the leaked Pd component was an amount below the detection limit (<300 ppb). The organic / inorganic composite [P-1] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 2)
(Synthesis of polymerizable compound)
A THF solution of 2-isocyanatoethyl methacrylate (product name: Karenz MOI) 5.0 g (32.2 mol) in 16.1 mL (32.2 mmol) of a 2.0 mol / L tetrahydrofuran (THF) solution of ethylamine. (40 mL) was added, and the mixture was stirred at room temperature for 1 day using a magnetic stirrer. Thereafter, the solvent was distilled off to obtain the target polymerizable compound [a-1]. The polymerizable compound [a-1] has a urea bond and a vinyl group in the molecule.

¹ H-NMR (300 MHz, CDCl ₃ ): δ / ppm 1.12, 1.94, 3.19, 3.48, 4.22, 4.89, 5.12, 5.58 (vinyl group), 6.11 (vinyl group).

[Preparation of organic-inorganic composite]
A composition [X-2] was prepared in the same manner as in Example 1 except that 155 mg of the polymerizable compound [a-1] was used instead of using 150 mg of the light ester DM.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-2] was used to prepare an organic-inorganic composite [P-2]. .
Yield: 1.81 g, yield: 96%.
Specific surface area (BET simplified method): 0.55 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 2.8 nm
The measurement apparatus and measurement conditions are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-2] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After filtering the organic-inorganic complex [P-2] from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-2] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 3)
(Synthesis of polymerizable compound)
To a DMF solution (10 mL) of 4.6 g (5.0 mmol) of N, N-dimethylethylenediamine was added 7.8 g (5.0 mmol) of 2-isocyanatoethyl methacrylate, and the mixture was stirred at room temperature for 1 day using a magnetic stirrer. did. Thereafter, the solvent was distilled off to obtain the target polymerizable compound [a-2]. The polymerizable compound [a-2] has a tertiary amino group, a urea bond, and a vinyl group in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.93, 2.25, 2.42, 3.24, 3.42, 4.16, 5.63 (vinyl group), 6.12 (Vinyl group).

[Preparation of organic-inorganic composite]
A composition [X-3] was prepared in the same manner as in Example 1 except that 170 mg of the polymerizable compound [a-2] was used instead of using 150 mg of the light ester DM.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-3] was used to prepare an organic-inorganic composite [P-3]. .
Yield: 1.80 g, yield: 95%.
Specific surface area (BET simplified method): 0.72 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.0 nm
The measurement apparatus and measurement conditions are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-3] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic complex [P-3] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-3] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

Example 4
(Synthesis of polymerizable compound)
4.14th generation (G4) polyamidoamine (PAMAM) dendrimer having a primary amino group as a reactive functional group (10% by mass methanol solution, manufactured by Aldrich, molecular weight: 14214.4, product code: 41249) .02Myumol, terminal primary amine equivalent: 5.13X10 to ² [mu] mol), 2-isocyanatoethyl methacrylate 79.6mg (5.13x10 ^{2 μmol)} was added, using a magnetic stirrer and stirred at room temperature for 1 day. Thereafter, the solvent was distilled off to obtain the target polymerizable compound [a-3]. The polymerizable compound [a-3] has 62 tertiary amino groups and 64 vinyl groups in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.92, 2.35-2.37, 2.57-2.59, 2.78-2.80, 3.25-3.35 3.42, 4.16, 5.63 (vinyl group), 6.11 (vinyl group).

[Preparation of organic-inorganic composite]
A composition [X-4] was prepared in the same manner as in Example 1 except that 194 mg of the polymerizable compound [a-3] was used instead of using 150 mg of the light ester DM.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-4] was used to prepare an organic-inorganic composite [P-4]. .
Yield: 1.89 g, yield: 97%.
Specific surface area (BET simplified method): 0.79 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 2.5 nm
A transmission electron micrograph is shown in Fig. 1.
Morphological observation: Fig. 2 shows a scanning electron micrograph.
Apparatus: Real surface view microscope VE-9800 (Keyence)
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-4] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-4] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES, and the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-4] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 5)
(Synthesis of polymerizable compound)
570 mg (4.0 μmol, terminal hydroxyl group) 4th generation (G4) polyamidoamine (PAMAM) dendrimer having a hydroxyl group as a reactive functional group (10 mass% methanol solution, manufactured by Aldrich, molecular weight: 14277.4, product code: 477850) Equivalent: 2.60 × 10 ² μmol), 2-isocyanatoethyl methacrylate 40 mg (2.56 × 10 ² μmol) was added, and the mixture was stirred at room temperature for 1 day using a magnetic stirrer. Thereafter, the solvent was distilled off to obtain the target polymerizable compound [a-4]. The polymerizable compound [a-4] has 62 tertiary amino groups and 64 vinyl groups in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.93, 2.36-2.40, 2.59-2.61, 2.77-2.81, 3.28-3.41 3.62, 4.17, 5.62 (vinyl group), 6.11 (vinyl group).

[Preparation of organic-inorganic composite]
A composition [X-5] was prepared in the same manner as in Example 1 except that 194 mg of the polymerizable compound [a-4] was used instead of using 150 mg of the light ester DM.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-5] was used to prepare an organic-inorganic composite [P-5]. .
Yield: 1.88 g, yield: 97%.
Specific surface area (BET simplified method): 0.65 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.5 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic / inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic / inorganic composite [P-5] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-5] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES, and the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-5] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 6)
(Synthesis of polymerizable compound)
2-isocyanatoethyl methacrylate in place of using 79.6mg (5.13x10 ² μmol), except for using 72mg glycidyl methacrylate (5.13x10 ² μmol), in the same manner as in Example 4, the polymerizable compound [a- 5] was obtained. The polymerizable compound [a-5] has 62 tertiary amino groups and 64 vinyl groups in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.92, 2.35-2.37, 2.57-2.59, 2.78-2.80, 3.25-3.35 3.42, 4.16, 5.63 (vinyl group), 6.11 (vinyl group).

[Preparation of organic-inorganic composite]
A composition [X-6] was prepared in the same manner as in Example 1 except that 186 mg of the polymerizable compound [a-5] was used instead of using 150 mg of the light ester DM.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-6] was used to prepare an organic-inorganic composite [P-6]. .
Yield: 1.85 g, yield: 95%.
Specific surface area (BET simplified method): 0.70 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.2 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-6] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-6] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-6] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 7)
(Synthesis of polymerizable compound)
2-isocyanatoethyl was added to 0.20 g (primary amine equivalent: 1.16 mmol, secondary amine equivalent: 2.33 mmol) of polyethyleneimine (average molecular weight 10,000, manufactured by Wako Pure Chemicals, product code: 167-147821). 0.54 g (3.49 mmol) of methacrylate was added, and the mixture was stirred at room temperature for 1 day using a magnetic stirrer. Thereafter, the solvent was distilled off to obtain the target polymerizable compound [a-6]. The polymerizable compound [a-6] has, on average, 58 tertiary amino groups and 174 vinyl groups in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.92, 2.63, 3.22-3.42, 4.15-4.22, 5.62 (vinyl group), 6.11 (Vinyl group).

[Preparation of organic-inorganic composite]
A composition [X-7] was prepared in the same manner as in Example 1 except that 153 mg of the polymerizable compound [a-6] was used instead of 150 mg of the light ester DM.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-7] was used to prepare an organic-inorganic composite [P-7]. .
Yield: 1.36 g, yield: 97%.
Specific surface area (BET simplified method): 0.58 m ² / g.
Metal content: 0.11 mmol / g.
Average particle diameter of metal nanoparticles (transmission electron microscope analysis): 3.6 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-7] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-7] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-7] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 8)
(Synthesis of polymerizable compound)
To a DMF solution (5.0 mL) of 0.73 g (5.0 mmol) of tris (2-aminoethyl) amine, 0.23 g (15.0 mmol) of 2-isocyanatoethyl methacrylate was added, and a magnetic stirrer was used. For 1 day. Thereafter, the solvent was distilled off to obtain the target polymerizable compound [a-7]. The polymerizable compound [a-7] has one tertiary amino group, three urea bonds, and three vinyl groups in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.92, 2.55, 3.15, 3.42, 4.16, 5.62 (vinyl group), 6.12 (vinyl group) .

[Preparation of organic-inorganic composite]
A composition [X-8] was prepared in the same manner as in Example 1 except that 174 mg of the polymerizable compound [a-7] was used instead of using 150 mg of the light ester DM.
Next, instead of using the composition [X-1], a polymerization reaction was carried out in the same manner as in Example 1 except that the composition [X-8] was used to prepare an organic-inorganic composite [P-8]. .
Yield: 1.83 g, yield: 96%.
Specific surface area (BET simplified method): 0.60 m ² / g.
Metal content: 0.16 mmol / g.
Average particle diameter of metal nanoparticles (transmission electron microscope analysis): 3.4 nm
The measurement apparatus and measurement conditions are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-8] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic complex [P-8] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-8] separated by filtration was washed with water and diethyl ether alternately 4 times each, dried, and then subjected to the same catalytic reaction test 5 times as described above. It was confirmed that the product was obtained without lowering.

Example 9
(Synthesis of polymerizable compound)
First generation (G1) polyamidoamine (PAMAM) dendrimer having a primary amino group as a reactive functional group (20% by mass methanol solution, manufactured by Aldrich, molecular weight: 1429.8, product code: 413844) 0.59 g (82 .5Myumol, terminal primary amine equivalent: 6.63X10 to ² [mu] mol), 2-isocyanatoethyl methacrylate 103mg (6.63x10 ^{2 μmol)} was added, using a magnetic stirrer and stirred at room temperature for 1 day. Thereafter, the solvent was distilled off to obtain the target polymerizable compound [a-8]. The polymerizable compound [a-8] has 6 tertiary amino groups, 8 urea bonds, and 8 vinyl groups in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.92, 2.34-2.36, 2.57-2.60, 2.78-2.81, 3.25-3.35 3.44, 4.17, 5.62 (vinyl group), 6.11 (vinyl group).

[Preparation of organic-inorganic composite]
A composition [X-9] was prepared in the same manner as in Example 1 except that 192 mg of the polymerizable compound [a-8] was used instead of using 150 mg of the light ester DM.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-9] was used to prepare an organic-inorganic composite [P-9]. .
Yield: 1.88 g, yield: 97%.
Specific surface area (BET simplified method): 0.66 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.0 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-9] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-9] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). Even when the organic-inorganic composite [P-9] separated by filtration was washed with water and diethyl ether alternately four times each and dried, and the catalytic reaction test similar to the above was repeated five times, the reaction rate It was confirmed that the product was obtained without lowering.

(Example 10)
(Synthesis of polymerizable compound)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.

[Preparation of organic-inorganic composite]
Instead of using 1.74 g of light ester HX, the composition [Example 4] was used in the same manner as in Example 4 except that 1.74 g of 1,4-butanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: light ester 1.6BG) was used. X-10] was prepared.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-10] was used to prepare an organic-inorganic composite [P-10]. .
Yield: 1.87 g, yield: 96%.
Specific surface area (BET simplified method): 24 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.7 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-10] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-10] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES, and the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The filtered organic / inorganic composite [P-10] was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 11)
(Synthesis of polymerizable compound)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.

[Preparation of organic-inorganic composite]
Instead of using 1.74 g of light ester HX, the composition [X-11] was prepared in the same manner as in Example 4 except that 1.74 g of neopentyl glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: light ester NP) was used. Prepared.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-11] was used to prepare an organic-inorganic composite [P-11]. .
Yield: 1.84 g, yield: 95%.
Specific surface area (BET simplified method): 11 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.7 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-11] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-11] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES, and the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). Even when the organic-inorganic composite [P-11] separated by filtration was washed four times with water and diethyl ether alternately and dried, and the catalytic reaction test similar to the above was repeated five times, the reaction rate It was confirmed that the product was obtained without lowering.

(Example 12)
(Synthesis of polymerizable compound)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.

[Preparation of organic-inorganic composite]
In place of using 1.74 g of light ester HX, the same procedure as in Example 4 was conducted except that 1.74 g of 1,9-nonanediol dimethacrylate (product of Kyoeisha Chemical Co., product name: light ester 1.9ND) was used. X-12] was prepared.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-12] was used to prepare an organic-inorganic composite [P-12]. .
Yield: 1.88 g, yield: 97%.
Specific surface area (BET simplified method): 0.55 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.7 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-12] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-12] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-12] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 13)
(Synthesis of polymerizable compound)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.

[Preparation of organic-inorganic composite]
Instead of using 1.74 g of light ester HX, composition [X-13] was prepared in the same manner as in Example 4 except that 1.74 g of trimethylolpropane trimethacrylate (product name: Light Ester TMP) was used. Prepared.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-13] was used to prepare an organic-inorganic composite [P-13]. .
Yield: 1.85 g, yield: 95%.
Specific surface area (BET simplified method): 42 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.7 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-13] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-13] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-13] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test five times as described above. It was confirmed that the product was obtained without lowering.

(Example 14)
(Synthesis of polymerizable compound)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.

[Preparation of organic-inorganic composite]
Instead of using 1.74 g of light ester HX, a composition [X-14] was prepared in the same manner as in Example 4 except that 1.74 g of pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light acrylate PE-4A) was used. Was prepared.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-14] was used to prepare an organic-inorganic composite [P-14]. .
Yield: 1.82 g, yield: 93%.
Specific surface area (BET simplified method): 7.2 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.7 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-14] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic complex [P-14] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES, and the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). Even when the organic-inorganic composite [P-14] separated by filtration was washed with water and diethyl ether alternately four times each, dried and then subjected to the same catalytic reaction test five times as described above, the reaction rate It was confirmed that the product was obtained without lowering.

(Example 15)
(Synthesis of polymerizable compound)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.

[Preparation of organic-inorganic composite]
Instead of using 1.74 g of light ester HX, a composition [X-15 was prepared in the same manner as in Example 4 except that 1.74 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light acrylate DPE-6A) was used. Was prepared.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-15] was used to prepare an organic-inorganic composite [P-15]. .
Yield: 1.80 g, yield: 92%.
Specific surface area (BET simplified method): 14 m ² / g.
Metal content: 0.16 mmol / g.
Average particle size of metal nanoparticles (transmission electron microscope analysis): 3.7 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-15] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic complex [P-15] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES, and the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). Even when the organic-inorganic composite [P-15] separated by filtration was washed with water and diethyl ether alternately four times each and dried, and the catalytic reaction test similar to the above was repeated five times, the reaction rate It was confirmed that the product was obtained without lowering.

(Example 16)
(Synthesis of polymerizable compound)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.

[Preparation of organic-inorganic composite]
Instead of using 1.74 g of light ester HX, 1.57 g of light ester HX and ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: light ester EG) (hereinafter abbreviated as “EG”) were used except 0.17 g. In the same manner as in Example 4, composition [X-16] was prepared.
Next, instead of using the composition [X-1], a polymerization reaction was carried out in the same manner as in Example 1 except that the composition [X-16] was used to prepare an organic-inorganic composite [P-16]. .
Yield: 1.87 g, yield: 96%.
Specific surface area (BET simplified method): 1.1 m ² / g.
Metal content: 0.16 mmol / g.
Average particle diameter of metal nanoparticles (transmission electron microscope analysis): 3.4 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.

[Catalytic reaction test using organic-inorganic composite]
Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-16] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-16] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-16] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test as described above five times. It was confirmed that the product was obtained without lowering.

(Example 17)
(Synthesis of polymerizable compound)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.

[Preparation of organic-inorganic composite]
Composition [X-17] was prepared in the same manner as in Example 4 except that 1.31 g of light ester HX and 0.43 g of light ester EG were used instead of using 1.74 g of light ester HX.
Next, instead of using the composition [X-1], a polymerization reaction was performed in the same manner as in Example 1 except that the composition [X-17] was used to prepare an organic-inorganic composite [P-17]. .
Yield: 1.85 g, yield: 95%.
Specific surface area (BET simplified method): 25 m ² / g.
Metal content: 0.16 mmol / g.
Average particle diameter of metal nanoparticles (transmission electron microscope analysis): 3.4 nm
The measurement apparatus and measurement conditions not described are as described in Example 1.
[Catalytic reaction test using organic-inorganic composite]

Instead of using the organic-inorganic composite [P-1] (classification size: 75 to 300 μm), the same procedure as in Example 1 was used except that the organic-inorganic composite [P-17] (classification size: 75 to 300 μm) was used. The catalytic reaction was carried out. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95% or more.
After the organic-inorganic composite [P-17] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the amount of Pd component leaked into the reaction system was below the detection limit (<300 ppb ). The organic / inorganic composite [P-17] separated by filtration was washed with water and diethyl ether alternately four times each, dried, and then subjected to the same catalytic reaction test as described above five times. It was confirmed that the product was obtained without lowering.

(Comparative Example 1)
In the same manner as in Example 3, a polymerizable compound [a-2] having a tertiary amino group, a urea bond, and a vinyl group in the molecule was obtained.
Subsequently, a comparative organic-inorganic composite [CP-1] was prepared in the same manner as in Example 3 except that 1.74 g of light ester EG was used instead of 1.74 g of light ester HX (metal content: 0 .16 mmol / g).
In the same manner as in Example 1, 41.0 mg (Pd equivalent: 6.5 μmol) of an organic-inorganic composite for comparison [CP-1] (classification size: 75 to 300 μm) was added to the reaction solution (Y1), and the mixture was heated to 80 ° C. For 4 hours. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 95%.
However, after the comparative organic-inorganic composite [CP-1] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES, and the Pd component leaked into the reaction system was 3.5 ppm. It was confirmed that there was. In this comparative example, the polymerizable composition does not contain a polymerizable compound (b) having a C 4-12 alkylene group and two or more vinyl groups, which may be branched. Therefore, it is surmised that many metal leaks into the reaction system were confirmed in the catalytic reaction.

  From the above results, the organic-inorganic composite obtained by the method shown in Example 3 is 4-bromo compared to the comparative organic-inorganic composite [CP-1] obtained by the method shown in this Comparative Example. It is clear that it is an excellent catalyst capable of suppressing metal leakage into the reaction system for the coupling reaction of acetophenone.

(Comparative Example 2)
A comparative organic-inorganic composite [CP-2] was prepared in the same manner as in Example 3 except that 63 mg of N, N-dimethylethylenediamine was used instead of 170 mg of the polymerizable compound [a-2] (metal-containing composition) Amount: 0.17 mmol / g).
In the same manner as in Example 1, 38.0 mg (Pd equivalent: 6.5 μmol) of an organic-inorganic composite for comparison [CP-2] (classification size: 75 to 300 μm) was added to the reaction solution (Y1) at 80 ° C. For 4 hours. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 65%.
However, when the comparative organic-inorganic composite [CP-2] filtered from the reaction solution was washed four times with water and diethyl ether alternately, dried, and then subjected to the same catalytic reaction test as described above. It was confirmed that 4-acetylbiphenyl was produced at a reaction rate of 10%. In this comparative example, since the comparative organic-inorganic composite [CP-2] was prepared using an amino group-containing compound having no vinyl group, the amino group-containing compound was not fixed in the composite by a covalent bond. Not in. Therefore, it was confirmed that about 80% of the initially charged amino group-containing compound and accompanyingly about 70% of palladium were eliminated from the complex by the first catalytic reaction and the subsequent washing operation. It was. This is presumed to be the cause of the decrease in the reaction rate in the second catalytic reaction.
From the above results, the organic-inorganic composite obtained by the method shown in Example 3 is 4-bromo compared with the comparative organic-inorganic composite [CP-2] obtained by the method shown in this Comparative Example. It is clear that it is an excellent catalyst capable of suppressing metal leakage into the reaction system for the coupling reaction of acetophenone.

(Comparative Example 3)
In the same manner as in Example 4, polymerizable compound [a-3] was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 64 urea bonds, and 64 vinyl groups in the molecule.
Subsequently, a comparative organic-inorganic composite was prepared in the same manner as in Example 17 except that 1.31 g of 2-ethylhexyl methacrylate (product name: Light Ester EH) was used instead of using 1.31 g of light ester HX. [CP-3] was prepared (metal content: 0.16 mmol / g).

  In the same manner as in Example 1, 39.0 mg (Pd equivalent: 6.5 μmol) of an organic-inorganic composite for comparison [CP-3] (classification size: 75 to 300 μm) was added to the reaction solution (Y1) at 80 ° C. For 4 hours. As a result of analysis by gas chromatography, it was confirmed that the desired 4-acetylbiphenyl was produced at a reaction rate of 90%.

  However, after the organic / inorganic composite for comparison [CP-3] was filtered from the reaction solution, the filtrate was evaluated using ICP-AES. As a result, the Pd component leaked into the reaction system was 5.5 ppm. It was confirmed that there was. In this comparative example, the polymerizable composition does not include the polymerizable compound (b) having 4 to 12 carbon atoms that may be branched and two or more vinyl groups, which may be branched. Although it contains an alkylene group having 4 to 12 carbon atoms which may be branched, it only contains a polymerizable compound containing only one vinyl group. Therefore, it is surmised that many metal leaks into the reaction system were confirmed in the catalytic reaction.

  From the above results, the organic-inorganic composite obtained by the method shown in Example 17 was 4-bromo compared with the comparative organic-inorganic composite [CP-3] obtained by the method shown in this Comparative Example. It is clear that it is an excellent catalyst capable of suppressing metal leakage into the reaction system for the coupling reaction of acetophenone.

Claims (13)

Polymer of the polymerizable composition (A) a complex with (P _A) and the metal nanoparticles, the polymerizable composition (A) is,
(1) a polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group;
(2) a polymerizable compound (b) having an optionally branched alkylene group having 4 to 12 carbon atoms and two or more vinyl groups;
An organic-inorganic composite comprising: The polymerizable compound (a) is
(1) a dendrimer (a1) having a tertiary amino group and a reactive functional group (Q ₁ ), or a polyethyleneimine (a2) having a reactive functional group (Q ₁ );
And (2) the reactive functional group _{(Q 1)} capable of reacting with the reactive functional group _{(Q 2),} a compound having a vinyl group and (a3),
The organic-inorganic composite according to claim 1, which is a compound obtained by reacting The reactive functional group (Q ₁ ) is a primary amino group, a secondary amino group, a hydroxyl group or a carboxy group, and the reactive functional group (Q ₂ ) is an isocyanato group, an epoxy group, a primary amino group, The organic-inorganic composite according to claim 2, which is a secondary amino group, a hydroxyl group, a carboxy group or an acyl halide group. The dendrimer (a1) is
Formula (1)

(In Formula (1), x is an integer of 1-10.)
Or formula (2)

(In formula (2), y is an integer of 1 to 10.)
The organic-inorganic composite according to any one of claims 1 to 3, wherein the structure represented by the formula is a repeating unit. The organic-inorganic composite according to any one of claims 1 to 4, wherein the polymerizable compound (b) is a compound having an alkylene group having 4 to 12 carbon atoms and two or more (meth) acryloyl groups. The organic-inorganic composite according to any one of claims 1 to 5, wherein the metal is a metal composed of one or more selected from palladium, platinum, ruthenium, rhodium, gold, silver, and rhenium. The organic-inorganic composite according to any one of claims 1 to 6, which has a porous structure. A catalyst using the organic-inorganic composite according to any one of claims 1 to 7. The catalyst according to claim 8, which is used in a cross-coupling reaction. (1) A polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two or more vinyl groups A composition (X) in which a polymerizable composition (A) containing a polymerizable compound (b) having a hydrogen atom, a metal compound (c) and a solvent (M) are mixed is prepared, and the composition (X) is polymerized. The metal compound (c) is reduced at the same time to form metal nanoparticles, and then the step (α-1) of removing the solvent (M) is included. A method for producing an organic-inorganic composite. After performing the step (α-1), the organic-inorganic composite obtained in the step (α-1) is brought into contact with a solution (H) containing a reducing agent (d), and then the organic-inorganic composite The manufacturing method of the organic inorganic composite of Claim 10 which performs the process ((alpha) -2) which isolate | separates a body from a solution (H). (1) A polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two or more vinyl groups A composition (Y) obtained by mixing a polymerizable composition (A) containing a polymerizable compound (b) having a solvent and a solvent (M) was prepared. After the composition (Y) was polymerized, the solvent (M ) Is removed (α-3),
(2) The polymer (P _A ) is brought into contact with the solution (I) containing the metal compound (c) to adsorb the metal compound (c) to the polymer (P _A ), and then the polymer (P A _A ) separating the solution (I) from the solution (I) (α-4),
(3) The metal compound (c) is reduced by bringing the polymer (P _A ) containing the metal compound (c) into contact with the solution (H) containing the reducing agent (d) to produce metal nanoparticles. Then, the step (α-5) of separating the polymer (P _A ) containing the generated metal nanoparticles from the solution (H) is sequentially performed.
The method for producing an organic-inorganic composite according to any one of claims 1 to 7. (1) A polymerizable compound (a) having an amino group, an imino group, a urea bond or an amide bond, and a vinyl group, an alkylene group having 4 to 12 carbon atoms which may be branched, and two or more vinyl groups A composition (Z) obtained by mixing a polymerizable composition (A) containing a polymerizable compound (b) having the following: a metal compound (c), a reducing agent (d), and a solvent (Q) compatible with these. Preparing and reducing the metal compound (c) in the composition to produce metal nanoparticles (α-6),
(2) A composition (V) prepared by mixing the composition containing the metal nanoparticles and a solvent (R) compatible with the composition is prepared, and the composition (V) is polymerized to contain the metal nanoparticles. _A method for producing an organic-inorganic composite in which a polymer (P _A ) is produced and then the steps (α-7) of removing the solvents (Q) and (R) are sequentially performed,
The mixed solvent in which the solvent (Q) and the solvent (R) are mixed does not dissolve or swell the polymer (P _A ) of the polymerizable composition (A). A method for producing the organic-inorganic composite according to 1.

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