JP2010070751A - Porous organic polymer material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porous organic polymer material acting as a catalyst which has a large base-immobilizing capacity, a large specific surface area, and is excellent in durability to repeated nucleophilic addition reactions of an aldehyde compound or a ketone compound. <P>SOLUTION: There is provided the porous material formed from the polymer of a polymerizing composition (A) comprising a polymerizing compound (a) having two or more amino groups and two or more vinyl groups, characterized in that the polymerizing compound (a) is a compound obtained by reacting a dendrimer having at least an amino group as a reactive functional group or polyethylene imine having at least an amino group as a reactive functional group with a compound having a group capable of reacting with the reactive functional group and a vinyl group. Therein, the reactive functional group is a primary amino group, a secondary amino group, a hydroxyl group or a carboxyl group, and the group capable of reacting with the reactive functional group is an isocyanato group, an epoxy group, a primary amino group, a secondary amino group, a hydroxyl group, a carboxyl group or a halogenated acyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic polymer porous body, and more particularly to an organic polymer porous body that functions as an insoluble solid catalyst that can be used repeatedly, and a method for producing the same.

  The base-catalyzed nucleophilic addition reaction of aldehydes and ketones is recognized as one of the most important catalytic reactions in today's organic synthesis as a carbon-carbon bond formation reaction. A heterogeneous reaction system using a solid catalyst to which a basic functional group such as an amino group is immobilized is advantageous for repeated use because it is easy to separate and recover the catalyst from the solution after the reaction. Consideration has been made.

  In general, aldehydes and ketones are reduced in electron density on oxygen of carbonyl units contained in them by the action of proton acids, Lewis acids, and hydrogen-bonded proton donors, and the activity for nucleophilic addition reaction is improved. It has been known. Actually, in Non-Patent Document 1, silica gel in which a silane compound having an amino group (base) and a silane compound having a urea bond (hydrogen bondable proton donor) are simultaneously introduced into the surface is used for aldol reaction of aldehydes, etc. It has been shown to function as a highly active solid catalyst for nucleophilic addition reactions.

  The dendrimer (a1) represented by poly (amidoamine) dendrimer, poly (propyleneimine) dendrimer, and branched or linear polyethyleneimine (a2) are organic polymers containing amino groups, It is a useful molecule capable of arranging the amino groups of the above in high density. Dendrimers (a1) and polyethyleneimines (a2) immobilized on an insoluble carrier are known. For example, in Patent Documents 1 and 2, as physical property modifiers for cured coatings and as stabilizing capture agents for producing metal particles An applied example is shown. Patent Document 3 discloses an example in which a hydrogel formed by a polymer having a linear polyethyleneimine skeleton is used as a carrier for generating metal particles. However, there are no examples of using these as base catalysts for nucleophilic addition reactions of aldehydes and ketones.

JP 2000-63513 A WO2004 / 110930 Publication Japanese Unexamined Patent Publication No. 2006-22367

S. Huh et al., Angew. Chem. Int. Ed., 2005, 44, 1826-1830.

  The problem to be solved by the present invention relates to an organic polymer porous material having a large amount of base fixation and a large specific surface area. Another object of the present invention is to provide an organic polymer porous body that functions as a catalyst having excellent durability against nucleophilic addition reactions of aldehydes and ketones, and a method for producing the same. is there.

  As a result of various studies, the present inventors have found that an organic polymer porous body obtained from a polymer of a polymerizable composition containing a polymerizable compound having an amino group and a vinyl group can solve the above-mentioned problems, and has completed the present invention. I let you.

That is, the present invention is an organic polymer porous body formed by a polymer (P _A ) of a polymerizable composition (A) containing a polymerizable compound (a) having an amino group and a vinyl group,
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),
An organic polymer porous body characterized in that it is a compound obtained by reacting the above.

  The present invention also provides a catalyst characterized by using the above organic polymer porous material.

In the present invention, the polymerizable composition (A) containing the polymerizable compound (a) having an amino group and a vinyl group is compatible with the polymerizable composition (A). The organic polymer porous body-forming composition (X) mixed with the solvent (M) that does not dissolve or swell the polymer (P _A ) of (A) is polymerized, and then the solvent (M) is removed (step) (Α-1)) and a method for producing the above organic polymer porous body.

  The present invention provides a polymerizable compound (a) obtained by reacting a dendrimer (a1) or polyethyleneimine (a2) with a compound (a3) having a vinyl group capable of reacting with a reactive functional group contained therein. Therefore, it is possible to provide an organic polymer porous body having a large amount of fixed amino groups. In addition, since the dendrimer (a1) or the polyethyleneimine (a2) can arrange a plurality of amino groups in one molecule at a high density, an acid group or a hydrogen bondable proton donor is formed in the vicinity of the amino group by derivatization. It is also easy to introduce a group, and an organic polymer porous material having high catalytic activity can be provided for nucleophilic addition reaction of aldehydes and ketones.

2 is a scanning electron micrograph of an organic polymer porous material [P-1] obtained in Example 1. FIG. 3 is a scanning electron micrograph of an organic polymer porous material [P-7] obtained in Example 7. FIG.

Hereafter, the principal part for implementing this invention is demonstrated.
[Structure of porous organic polymer]
The organic polymer porous body of the present invention is an organic polymer porous body formed of a polymer (P _A ) of a polymerizable compound (a) having an amino group and a vinyl group, and the polymerizable compound (a) but dendrimer (a1) having a tertiary amino group and a reactive functional group _{(Q 1),} or a polyethyleneimine having a reactive functional group _{(Q 1)} (a2), and the reactive functional group _{(Q 1)} An organic polymer porous body characterized by being a compound obtained by reacting a reactive functional group (Q ₂ ) capable of reacting with a compound (a3) having a vinyl 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 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 can be used. . 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. Then, an amidoamine-structured dendrimer can be synthesized by alternately performing these Michael addition reaction and amide bond formation reaction any number of times.

  Although there is no restriction | limiting in particular in the synthesis method of the dendrimer of the propylene imine structure represented by Formula (2), For example, using the method as described in WO-A93 / 14147 and WO-A95 / 2008 is used. it can. 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. Thereafter, a dendrimer having a propyleneimine structure 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 is not particularly limited, but a core structure using residues of ammonia, ethylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-diaminododecane, and cystamine is preferable.

The reactive functional group (Q ₁ ) bonded to the end of the dendrimer is preferably bonded to the end. And, reacts with the 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 is preferably 300 or more, particularly preferably 1000 to 100,000. When the organic polymer porous material 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.

  The polyethyleneimine (a2) used for the preparation of the organic polymer porous material 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. And, reacts with the 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 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. Among them, when reacting with a dendrimer (a1) or polyethyleneimine (a2) having a primary or secondary amino group as a reactive functional group (Q ₁ ), the compound (a3) having an isocyanato group and a vinyl group is: Since a urea bond can be produced | generated by reaction, it is used preferably. The urea bond can increase the reactivity as an auxiliary catalyst in the nucleophilic addition reaction of aldehydes or ketones by the action as a hydrogen bondable proton donor.

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

  The reaction between the dendrimer (a1) or the polyethyleneimine (a2) and the compound (a3) having a vinyl group can be carried out, for example, by dissolving both 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 subsequent preparation of the porous organic polymer without isolating the reaction product 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 polymer porous material.

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, when the organic polymer porous material is used as a catalyst in the nucleophilic addition reaction of aldehydes or ketones, the effect is reduced if the number of amino groups acting as a base is small. Therefore, in one molecule of the polymerizable compound (a) It preferably has 2 or more amino groups, more preferably 4 or more, and particularly preferably 8 or more. Moreover, when there are many vinyl groups in 1 molecule of polymeric compound (a), the quantity of the copolymerization component added in polymeric composition (A) can be reduced, and, thereby, in an organic polymer porous body The relative amino group content of can be increased. Therefore, it is preferable to have 2 or more vinyl groups in one molecule of the polymerizable compound (a), more preferably 4 or more, and particularly preferably 6 or more.

Further, as described above, a dendrimer (a1) or polyethyleneimine (a2) having a primary or secondary amino group as a reactive functional group (Q ₁ ), and a compound (a3) having an isocyanato group and a vinyl group In the case of the reaction, a urea bond that can act as an auxiliary catalyst can be generated by the reaction. In this case, the relative ratio of the primary or secondary amino group contained in the dendrimer (a1) or polyethyleneimine (a2) to the isocyanato group contained in the compound (a3) having a vinyl group is 1: 1/8. It is preferably in the range of ˜1: 1, particularly preferably in the range of 1: 1/4 to 1: 1/2.

The amino group content of the organic polymer porous material is preferably in the range of 0.010 mmol / g to 9.00 mmol / g, particularly preferably in the range of 0.10 mmol / g to 9.00 mmol / g. . The amino group in the polymer (P _A ) may be any of primary, secondary and tertiary amino groups.

The shape of the organic polymer porous body is a structure such as an aggregated particle shape, a network shape, or a pore shape, and an average pore diameter in the range of 0.001 to 10 μm is 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 organic polymer porous body of the present invention preferably has a specific surface area of 5 to 2000 m ² / g. When the organic polymer porous body is used for a catalytic reaction, the organic polymer porous body has a specific surface area of 50 to 2000 m ² / g. More preferably.

  The organic polymer porous body of the present invention can be in the form of a film. In that case, the thickness of the organic polymer porous body is preferably in the range of 1 to 100 μm, particularly preferably in the range of 3 to 50 μm. When the thickness of the organic polymer porous body is less than 1 μm, when used as a catalyst, the performance tends to decrease, which is not preferable. In addition, the thickness of the organic polymer porous body can be measured by microscopic observation of the cross section using a scanning electron microscope.

[Method for producing organic polymer porous body]
The organic polymer porous body of the present invention is compatible with the polymerizable composition (A) containing the polymerizable compound (a) having an amino group and a vinyl group, and the polymerizable composition (A). polymerizable composition (a) of the polymer (P _a) dissolved or solvent which does not swell (M) and an organic polymer porous material-forming composition comprising a mixture of (X) is polymerized, after which the solvent (M) It can manufacture by removing (process ((alpha) -1)).

In this method, the polymer (P _A ) produced by the polymerization of the polymerizable composition (A) becomes incompatible with the solvent (M), and the polymer (P _A ) and the solvent (M) undergo phase separation. occurs, a state where a solvent (M) is incorporated between the polymer _{(P a)} or inside the polymer _{(P a).} By removing the solvent (M), the region occupied by the solvent (M) becomes pores, and an organic polymer porous body can be formed.

The polymerizable composition (A) comprises only a polymerizable compound (a) having an amino group and a vinyl group, or, together with the polymerizable compound (a), the polymerizable compound (a) and a copolymer. It contains other polymerizable compounds that can form the structure. The polymerizable compound (a) can be used alone or in combination of two or more.
The other polymerizable compound capable of forming a copolymer with the polymerizable compound (a) is one that is polymerized in the presence or absence of a polymerization initiator, and preferably has a vinyl group. 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, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 2,2. '-Bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, hydroxydipivalate neopentyl glycol di (meth) acrylate, Bifunctional monomers such as dicyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, N-methylenebisacrylamide; trimethylolpropane tri (meth) acrylate, trimethylo Trifunctional monomers such as ethanetri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; dipentaerythritol hexa (meta) ) Hexafunctional monomers such as acrylate.

  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 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.

As the solvent (M), a solvent that is compatible with the polymerizable composition (A) but does not dissolve or swell the polymer (P _A ) of the polymerizable composition (A) is used. The degree of compatibility between the solvent (M) and the polymerizable composition (A) may be such that a uniform organic polymer porous body-forming composition (X) can be obtained. The solvent (M) may be a single solvent or a mixed solvent. In the case of a mixed solvent, the component alone may not be compatible with the polymerizable composition (A), or the polymerizable composition. The polymer (P _A ) of the product ( _A ) may be dissolved. 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 preferably used because they are easily compatible with the polymerizable composition (A) containing the polymerizable compound (a). In addition, in order to control the specific surface area of the obtained organic polymer porous body, a highly polar solvent such as acetone, N, N-dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, 2-propanol, A mixed solvent with a neutral solvent such as compatible tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether and the like is also preferably used.

  The method for removing the solvent (M) after polymerizing the organic polymer porous body-forming composition (X) is not particularly limited, but when the solvent (M) is a highly volatile solvent, It can be performed by drying under reduced pressure. 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. Moreover, when removing the solvent (M), for the purpose of removing the components remaining unpolymerized among the polymerizable compound (a) and other polymerizable compounds contained in the polymerizable composition (A), 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.

  Depending on the content of the polymerizable composition (A) contained in the organic polymer porous body-forming composition (X), the pore diameter and strength of the obtained organic polymer porous body vary. As the content of the polymerizable composition (A) is increased, the strength of the organic polymer porous body is improved, but the pore diameter tends to be reduced. 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 organic polymer porous body is lowered, and when the content of the polymerizable composition (A) is 50% by mass or more, the porous body is obtained. It becomes difficult to adjust the hole diameter.

  The organic polymer porous body-forming composition (X) includes a polymerization initiator, a polymerization inhibitor, a polymerization retarder, a soluble polymer, etc. in order to adjust the polymerization rate, polymerization degree, pore size distribution, etc. Various additives may be added.

  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 photopolymerization 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 organic polymer porous body-forming composition (X) and is soluble in the solvent (M) alone. By being soluble in the solvent (M), it can be easily removed from the polymer when the solvent (M) is removed from the polymer obtained by polymerization of the composition (X).

  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 polymer porous body 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 polymer porous body can be produced by reacting various mercury lamps and metal halide lamps at a power of 250 to 3000 W at room temperature for 1 second to 2 hours, preferably 10 seconds to 30 minutes. .

  In the case of an organic polymer porous body having a film-like form, a known and commonly used surfactant, thickener, modifier, catalyst, etc. may be added for the purpose of improving coatability and smoothness. You can also.

  The support that can be used for producing the organic polymer porous body having a film-like form is not substantially affected by the organic polymer porous body-forming composition (X), and, for example, dissolution and decomposition occur. And the organic polymer porous body-forming composition (X) is not substantially affected. 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. Examples of the shape include a sheet shape (including a film shape, a ribbon shape, and a belt shape), a plate shape, a roll shape, and a spherical shape. A composition for forming an organic polymer porous body (X) is applied thereon. From the viewpoint of ease, 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 the dissolution of the support by the organic polymer porous body-forming composition (X), improving the wettability of the organic polymer porous body-forming composition (X), and the organic polymer porous body. And the like for the purpose of improving the adhesion.

  The surface treatment method of the support is arbitrary, for example, a treatment in which an arbitrary polymerizable composition (A) is applied to the surface of the support and cured by a polymerization reaction, corona treatment, plasma treatment, flame treatment, acid or alkali Examples include treatment, sulfonation treatment, fluorination treatment, primer treatment with a silane coupling agent, surface graft polymerization, application of a surfactant, a release agent, etc., physical treatment such as rubbing and sandblasting. Moreover, the method of reacting with the reactive functional group which the raw material of an organic polymer porous body and the reactive functional group introduce | transduced by the said surface treatment method react with the compound fixed to 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 organic polymer porous body-forming composition (X), it is useful for improving the adhesion of the organic polymer porous body to the support.

  The coating method of the organic polymer porous body-forming composition (X) on the support may be any known method as long as it is a publicly known method. For example, a coating method using a coater or spraying is preferred.

  According to the method for producing an organic polymer porous material shown here, polymer particles having a diameter of about 0.1 μm to 1 μm are aggregated with each other, and the gap between the particles becomes pores. Or a polymer porous body having a three-dimensional network structure in which polymers are aggregated in a network.

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

[Catalytic reaction using organic polymer porous material]
The catalytic reaction using the organic polymer porous material of the present invention will be described.
The organic polymer porous body of the present invention is an organic polymer porous body containing a polymer (P _A ) of a polymerizable compound (a) having two or more amino groups and two or more vinyl groups. Therefore, it can be used for catalytic reactions involving amino groups. Especially, it is preferable to use for the catalytic reaction using an amino group as a base, and it is especially preferable to use in the nucleophilic addition reaction of aldehydes or ketones as a base catalyst. Examples of preferred reactions include Aldol reaction, Knoevenagel reaction, Henry (Nitroaldol) reaction, cyanosilylation reaction and the like.

  When the organic polymer porous material 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 polymer porous material 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 polymer porous body 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.

  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
[Synthesis of Polymerizable Compound (a)]
570 mg (4.0 μmol) 4th generation (G4) polyamidoamine (PAMAM) dendrimer having a primary amino group as a reactive functional group (10% by weight methanol solution, manufactured by Aldrich, molecular weight: 14214.4, product code: 4124949) , terminal primary amine equivalent: 2.60X10 to ² [mu] mol), 2-isocyanatoethyl methacrylate (manufactured by Showa Denko KK, product name: Karenz MOI) 40 mg of (2.56x10 ² μmol) was added, using a magnetic stirrer, room temperature For 1 day. Thereafter, the solvent was distilled off to obtain the target polymerizable compound (a) [a-1]. The polymerizable compound [a-1] 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 porous organic polymer]
Polymerizable compound (a) [a-1] 97 mg, ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical, product name: Light Ester M) (hereinafter abbreviated as “EGDMA”) 870 mg, azobisisobuty as a polymerization initiator Ronitrile (hereinafter abbreviated as “AIBN”) 13 mg, diethylene glycol dimethyl ether (hereinafter abbreviated as “diglyme”) 4.0 mL, and methanol 1.0 mL were mixed to form a composition for forming an organic polymer porous material [X -1] was prepared.
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 white solid from the polymerization tube, the organic polymer porous material [P-1] is removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). Prepared.
Yield: 950 mg, yield: 97%.
Amino group content: 0.25 mmol / g (tertiary amino group).
Specific surface area (BET simplified method): 450 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 Morphological observation: Scanning electron micrograph is shown in FIG.
Apparatus: Real surface view microscope VE-9800 (Keyence)

[Catalytic reaction test using porous organic polymer]
A reaction solution (Y1) was prepared by uniformly mixing 0.72 mmol of malononitrile, 0.60 mmol of benzaldehyde, and 2 mL of toluene. To this, 20 mg (amine equivalent: 5.06 μmol) of the organic polymer porous material [P-1] was added and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that the target benzalmalononitrile was produced at a reaction rate of 98% or more.
The organic polymer porous material [P-1] filtered from the reaction solution was washed with ethanol and toluene, dried, and then subjected to the same catalytic reaction test 5 times as described above, the reaction rate also decreased. It was confirmed that the product could be obtained without doing so.

(Example 2)
[Synthesis of Polymerizable Compound (a)]
In the same manner as in Example 1, polymerizable compound (a) [a-1] was obtained.
[Preparation of porous organic polymer]
Polymerizable compound (a) [a-1] 194 mg, AIBN 6 mg, diglyme 1.6 mL, and methanol 1.1 mL were mixed to prepare organic polymer porous body-forming composition [X-2].

Next, the composition [X-2] was charged into a polymerization tube, and nitrogen gas was blown for 30 minutes, and then sealed and heat-treated at 70 ° C. for 12 hours. After removing the formed white solid from the polymerization tube, the organic polymer porous material [P-2] is removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). Prepared.
Yield: 190 mg, yield: 95%.
Amino group content: 2.5 mmol / g (tertiary amino group).
Specific surface area (BET simplified method): 224 m ² / g.
The measuring apparatus, sample amount, and pretreatment method are as described in Example 1.

[Catalytic reaction test using porous organic polymer]
In the same manner as in Example 1, 15 mg (amine equivalent: 37.4 μmol) of the organic polymer porous material [P-2] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that the target benzalmalononitrile was produced at a reaction rate of 98% or more.
The organic polymer porous material [P-2] filtered from the reaction solution was washed with ethanol and toluene, dried, and then subjected to the same catalytic reaction test 5 times as described above, the reaction rate also decreased. It was confirmed that the product could be obtained without doing so.

(Example 3)
[Synthesis of Polymerizable Compound (a)]
A polymerizable compound (a) [a-2] is obtained in the same manner as in Example 1 except that 10 mg (64.4 μmol) is used instead of 40 mg (2.56 × 10 ² μmol) of 2-isocyanatoethyl methacrylate. It was. The polymerizable compound [a-2] has 62 tertiary amino groups, 48 primary amino groups, and 16 vinyl groups in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.91-1.95, 2.35-2.37, 2.57-2.59, 2.78-2.80, 3.25 -3.35, 3.42, 4.16, 5.62-5.66 (vinyl group), 6.01-6.14 (vinyl group).

[Preparation of porous organic polymer]
Polymeric compound (a) [a-2] 134 mg, EGDMA 1.21 g, AIBN 18 mg, diglyme 5.5 mL, and methanol 1.3 mL were mixed to prepare an organic polymer porous body forming composition [X-3]. .

Next, the composition [X-3] was charged into a polymerization tube, and nitrogen gas was blown for 30 minutes, and then sealed and heat-treated at 70 ° C. for 12 hours. After removing the formed white solid from the polymerization tube, the organic polymer porous material [P-3] is removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). Prepared.
Yield: 1.30 g, yield: 96%.
Amino group content: 0.37 mmol / g (tertiary amino group), 0.28 mmol / g (primary amino group).
Specific surface area (BET simplified method): 339 m ² / g.
The measuring apparatus, sample amount, and pretreatment method are as described in Example 1.

[Catalytic reaction test using porous organic polymer]
In the same manner as in Example 1, 20 mg (amine equivalent: 5.66 μmol) of the organic polymer porous material [P-3] was added to the reaction solution (Y1), and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that the target benzalmalononitrile was produced at a reaction rate of 98% or more.
The organic polymer porous material [P-3] filtered from the reaction solution was washed with ethanol and toluene, dried, and then subjected to the same catalytic reaction test 5 times as described above, the reaction rate also decreased. It was confirmed that the product could be obtained without doing so.

Example 4
[Synthesis of Polymerizable Compound (a)]
The polymerizable compound (a) [a-3] was prepared in the same manner as in Example 1 except that 5.0 mg (32.2 μmol) of 2-isocyanatoethyl methacrylate was used instead of 40 mg (2.56 × 10 ² μmol). ] Was obtained. The polymerizable compound [a-3] has 62 tertiary amino groups, 56 primary amino groups, and 8 vinyl groups in the molecule.
¹ H-NMR (300 MHz, CD ₃ OD): δ / ppm 1.91-1.95, 2.35-2.39, 2.58-2.60, 2.70-2.81, 3.23 -3.35, 3.42, 3.55-3.60, 4.16, 5.62-5.65 (vinyl group), 6.07-6.11 (vinyl group).

[Preparation of porous organic polymer]
Polymerizable compound (a) [a-3] 124 mg, EGDMA 1.12 g, AIBN 17 mg, diglyme 5.1 mL, and methanol 1.3 mL were mixed to prepare an organic polymer porous body-forming composition [X-4]. .

Next, the composition [X-4] was charged into a polymerization tube, and nitrogen gas was blown for 30 minutes, and then sealed and heat-treated at 70 ° C. for 12 hours. After removing the formed white solid from the polymerization tube, the organic polymer porous material [P-4] is removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). Prepared.
Yield: 1.21 g, yield: 96%.
Amino group content: 0.39 mmol / g (tertiary amino group), 0.36 mmol / g (primary amino group).
Specific surface area (BET simplified method): 377 m ² / g.
The measuring apparatus, sample amount, and pretreatment method are as described in Example 1.

[Catalytic reaction test using porous organic polymer]
In the same manner as in Example 1, 20 mg (amine equivalent: 7.12 μmol) of the organic polymer porous material [P-4] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that the target benzalmalononitrile was produced at a reaction rate of 98% or more.
The organic polymer porous material [P-4] filtered from the reaction solution was washed with ethanol and toluene, dried, and then subjected to the same catalytic reaction test 5 times as described above, the reaction rate also decreased. It was confirmed that the product could be obtained without doing so.

(Example 5)
[Synthesis of Polymerizable Compound (a)]
4th generation (G4) polyamidoamine (PAMAM) dendrimer having a hydroxyl group as a reactive functional group ((10% by mass methanol solution, Aldrich, molecular weight: 14277.4, product code: 477850) 570 mg (4.0 μmol, terminal) primary amine equivalent:. to 2.60x10 ² μmol), 2- isocyanatoethyl methacrylate 40mg (2.56x10 ² μmol) was added, using a magnetic stirrer and stirred for 1 day at room temperature then evaporated The target polymerizable compound (a) [a-4] was obtained, and 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 porous organic polymer]
Polymerizable compound (a) [a-4] 97 mg, EGDMA 870 mg, AIBN 3 mg, diglyme 0.8 mL, and methanol 0.6 mL were mixed to prepare an organic polymer porous body-forming composition [X-5].

Next, the composition [X-5] was charged into a polymerization tube, and nitrogen gas was blown for 30 minutes, and then sealed and heat-treated at 70 ° C. for 12 hours. After removing the formed white solid from the polymerization tube, the organic polymer porous material [P-5] is removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). Prepared.
Yield: 950 mg, yield: 98%.
Amino group content: 0.26 mmol / g (tertiary amino group).
Specific surface area (BET simplified method): 423 m ² / g.
The measuring apparatus, sample amount, and pretreatment method are as described in Example 1.

[Catalytic reaction test using porous organic polymer]
In the same manner as in Example 1, 47 mg (amine equivalent: 12.1 mmol) of the organic polymer porous material [P-5] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that the target benzalmalononitrile was produced at a reaction rate of 98% or more.
The organic polymer porous material [P-5] filtered from the reaction solution was washed with ethanol and toluene, dried, and then subjected to the same catalytic reaction test five times as described above, the reaction rate also decreased. It was confirmed that the product could be obtained without doing so.

(Example 6)
[Synthesis of Polymerizable Compound (a)]
The polymerizable compound (a) [a] [a] was used in the same manner as in Example 1 except that 36 mg (2.56 × 10 ² μmol) of glycidyl methacrylate was used instead of 40 mg (2.56 × 10 ² μmol) of 2-isocyanatoethyl methacrylate. −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 porous organic polymer]
Polymerizable compound (a) [a-5] 93 mg, EGDMA 870 mg, AIBN 12 mg, diglyme 4.0 mL, and methanol 1.0 mL were mixed to prepare organic polymer porous body-forming composition [X-6].

Next, the composition [X-6] was charged into a polymerization tube, and nitrogen gas was blown for 30 minutes, and then sealed and heat-treated at 70 ° C. for 12 hours. After removing the formed white solid from the polymerization tube, the organic polymer porous material [P-6] is removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). Prepared.
Yield: 926 mg, yield: 95%.
Amino group content: 0.25 mmol / g (tertiary amino group), 0.26 mmol / g (secondary amino group).
Specific surface area (BET simplified method): 466 m ² / g.
The measuring apparatus, sample amount, and pretreatment method are as described in Example 1.

[Catalytic reaction test using porous organic polymer]
In the same manner as in Example 1, 20 mg (amine equivalent: 10.3 μmol) of the organic polymer porous material [P-6] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that the target benzalmalononitrile was produced at a reaction rate of 98% or more.

  The organic polymer porous material [P-6] filtered from the reaction solution was washed with ethanol and toluene, dried, and then subjected to the same catalytic reaction test 5 times as described above, the reaction rate also decreased. It was confirmed that the product could be obtained without doing so.

(Example 7)
[Synthesis of Polymerizable Compound (a)]
To 0.20 g (primary amine equivalent: 1.16 mmol, secondary amine equivalent: 2.33 mmol) of polyethyleneimine (a2) (average molecular weight 10,000, manufactured by Wako Pure Chemicals, product code: 164-17721), 2- 0.54 g (3.49 mmol) of isocyanatoethyl methacrylate (manufactured by Showa Denko, product name: Karenz MOI) 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) [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 porous organic polymer]
Polymeric compound (a) [a-6] 150 mg, EGDMA 1.24 g, AIBN 16 mg, diglyme 5.5 mL, and methanol 1.5 mL were mixed to prepare an organic polymer porous body-forming composition [X-7]. .

  Next, the composition [X-7] 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 white solid from the polymerization tube, the organic polymer porous material [P-7] is removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). Prepared.

Yield: 1.36 g, yield: 97%.
Amino group content: 0.17 mmol / g (tertiary amino group).
Specific surface area (BET simplified method): 401 m ² / g.
The measuring apparatus, sample amount, and pretreatment method are as described in Example 1.
Morphological observation: Fig. 2 shows a scanning electron micrograph.
The apparatus is as described in Example 1.

[Catalytic reaction test using porous organic polymer]
In the same manner as in Example 1, 30 mg (amine equivalent: 5.02 μmol) of the organic polymer porous material [P-7] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that the target benzalmalononitrile was produced at a reaction rate of 98% or more.
The organic polymer porous material [P-7] filtered from the reaction solution was washed with ethanol and toluene, dried, and then subjected to the same catalytic reaction test five times as described above, the reaction rate also decreased. It was confirmed that the product could be obtained without doing so.

(Comparative Example 1)
Polypropylene imine dendrimer having a primary amino group as a reactive functional group (manufactured by Aldrich, molecular weight: 316, product code: 460699), 2-hydroxyethyl according to the method described in the patent document (Japanese Patent Laid-Open No. 2000-63513) A polymerizable compound composed of acrylate and 2-isocyanatoethyl methacrylate (raw material composition: 1/8/8 (molar ratio)) was synthesized (viscosity: 4.4 Pa · s). This polymerizable compound has two tertiary amino groups and four vinyl groups in the molecule. This was mixed with AIBN (0.01 molar equivalents relative to the vinyl group in the polymerizable compound), charged into a polymerization tube, blown with nitrogen gas for 30 minutes, sealed, and 12 ° C. at 70 ° C. A colorless transparent non-porous comparative polymer [CP-1] was prepared by carrying out heat treatment for a period of time (amino group content: 2.6 mmol / g).

In the same manner as in Example 1, 10 mg (amine equivalent: 25.7 μmol) of the polymer [CP-1] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that benzalmalononitrile was produced at a reaction rate of 32%.
The polymer was filtered from the reaction solution, washed with toluene and diethyl ether, and then subjected to the same catalytic reaction test as described above, it was confirmed that benzalmalononitrile was produced at a reaction rate of 29%.
From the above results, the organic polymer porous material obtained by the methods shown in Examples 1 to 7 was more benzaldehyde than the non-porous polymer [CP-1] obtained by the method shown in Comparative Example 1. It is clear that it is an excellent catalyst for nucleophilic addition reactions.

(Comparative Example 2)
A polymerizable compound comprising a polypropyleneimine dendrimer having a primary amino group as a reactive functional group, 2-hydroxyethyl acrylate, and 2-isocyanatoethyl methacrylate (raw material composition: 1/8/8 (molar ratio)) is used. Instead, a comparative example except that a polymerizable compound composed of the polypropylene imine dendrimer and PEG # 200 dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: light ester 4EG) (raw material composition: 1/6 (molar ratio)) is used. In the same manner as in Example 1, a colorless and transparent non-porous comparative polymer [CP-2] was prepared (amino group content: 2.8 mmol / g).
In the same manner as in Example 1, 10 mg (amine equivalent: 27.9 μmol) of the polymer [CP-2] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that benzalmalononitrile was produced at a reaction rate of 24%.
The polymer was filtered from the reaction solution, washed with toluene and diethyl ether, and then subjected to the same catalytic reaction test as described above, it was confirmed that benzalmalononitrile was produced at a reaction rate of 19%.
From the above results, the organic polymer porous material obtained by the method shown in Examples 1 to 7 was more benzaldehyde than the non-porous polymer [CP-2] obtained by the method shown in Comparative Example 2. It is clear that it is an excellent catalyst for nucleophilic addition reactions.

(Comparative Example 3)
From 570 mg of 4th generation (G4) polyamidoamine (PAMAM) dendrimer having a primary amino group as a reactive functional group (10% by weight methanol solution, manufactured by Aldrich, molecular weight: 14214.4, product code: 4124949) Distilled off to obtain 57 mg of solid G4 (PAMAM) dendrimer.
A porous comparative polymer [CP-3] was prepared in the same manner as in Example 1 except that 57 mg of the G4 (PAMAM) dendrimer was used instead of 97 mg of the polymerizable compound [a-1]. Since the G4 (PAMAM) dendrimer has no vinyl group, it was mostly extracted by Soxhlet extraction, and it was confirmed that only about 20% of the charged amount of G4 (PAMAM) dendrimer remained in CP-3 ( Yield: 850 mg, amino group content: 0.05 mmol / g (tertiary amino group)).

In the same manner as in Example 1, 100 mg (amine equivalent: 5.02 μmol) of the polymer [CP-3] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that benzalmalononitrile was produced at a reaction rate of 33%.
The polymer was filtered from the reaction solution, washed with toluene and diethyl ether, and then subjected to the same catalytic reaction test as described above, it was confirmed that benzalmalononitrile was produced at a reaction rate of 30%.
Based on the above results, the porous organic polymer obtained by the methods shown in Examples 1 to 7 was found to have a higher benzaldehyde content than the porous polymer [CP-3] obtained by the method shown in Comparative Example 3. It is clear that it is an excellent catalyst for the nucleation reaction.

(Comparative Example 4)
A composition for polymerization was prepared by mixing 40 mg of dimethylaminoethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Ester DM), 920 mg of EGDMA, 12 mg of AIBN, 4.0 mL of diglyme, and 1.0 mL of methanol. Next, this composition was charged into a polymerization tube, and nitrogen gas was blown for 30 minutes, and then sealed and heat-treated at 70 ° C. for 12 hours. After the formed white solid was taken out from the polymerization tube, a porous comparative polymer [CP-4] was removed by removing unpolymerized components and the solvent using a Soxhlet extractor (solvent: tetrahydrofuran and methanol). (Amino group content: 0.26 mmol / g (tertiary amino group)).

In the same manner as in Example 1, 20 mg (amine equivalent: 5.04 μmol) of the polymer [CP-4] was added to the reaction solution (Y1) and reacted at room temperature for 3 hours. As a result of analysis by gas chromatography, it was confirmed that benzalmalononitrile was produced at a reaction rate of 55%.
The polymer was filtered from the reaction solution, washed with toluene and diethyl ether, and then subjected to the same catalytic reaction test as described above, it was confirmed that benzalmalononitrile was produced at a reaction rate of 36%.
From the above results, the organic polymer porous material obtained by the methods shown in Examples 1 to 7 was found to have benzaldehyde as compared with the porous polymer [CP-4] obtained by the method shown in Comparative Example 4. It is clear that it is an excellent catalyst for the nucleation reaction.

Claims (8)

An organic polymer porous body formed from a polymer (P _A ) of a polymerizable composition (A) containing a polymerizable compound (a) having an amino group and a vinyl group,
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),
An organic polymer porous material, 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 polymer porous body according to claim 1, 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 polymer porous body according to claim 1, wherein the structure represented by the formula is a repeating unit. The organic polymer porous body according to any one of claims 1 to 3, wherein an amino group content in the polymer (P _A ) is in a range of 0.010 mmol / g to 9.00 mmol / g. The organic polymer porous body according to any one of claims 1 to 4, wherein the specific surface area is in the range of 5 to 2000 m ² / g. A catalyst using the porous organic polymer according to any one of claims 1 to 5. The catalyst according to claim 6, which is used in a nucleophilic addition reaction of aldehydes or ketones. A polymerizable composition (A) containing a polymerizable compound (a) having an amino group and a vinyl group is compatible with the polymerizable composition (A), but a polymer of the polymerizable composition (A). The organic polymer porous body-forming composition (X) mixed with the solvent (M) that does not dissolve or swell (P _A ) is polymerized, and then the solvent (M) is removed (step (α-1)). The manufacturing method of the organic polymer porous body in any one of Claims 1-5 characterized by the above-mentioned.

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