JP2009154074A - Catalyst immobilized reactor for carbon-carbon bond forming reaction - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst immobilized vessel or a catalyst immobilized tubular reactor of immobilizing a solid catalyst which can be used for carbon-carbon bond forming reaction between a compound having unsaturated bonds and a compound having active methylene or active methine onto an inner wall of the vessel or the tube. <P>SOLUTION: The reactor immobilizes the solid catalyst which is used for addition reaction or condensation reaction of forming carbon-carbon bond by using the compound (x1) having unsaturated bonds and the compound (x2) having active methylene or active methine, wherein the solid catalyst is a composite body prepared by covering a polymer (A) having a linear-chain polyethylene imine skeleton (a) with a metal oxide (B) and the composite body is immobilized onto the inner wall of the vessel or the tube. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a reactor in which a solid catalyst, which is an organic / inorganic complex used in a carbon-carbon bond forming reaction, is fixed to a reaction vessel, and more specifically, a compound having an unsaturated bond and a compound having active methylene or active methine. And a reaction in which a solid catalyst used for forming a carbon-carbon bond is fixed to the inner wall of a container or a tube.

  Reactions in which a compound having an unsaturated bond and a compound having active methylene or active methine undergo an addition reaction or condensation reaction to form a carbon-carbon bond are used in the chemical industry, particularly in the field of fine chemistry, production of pharmaceutical intermediates. It is an indispensable reaction, and a catalyst is always required for the reaction. Among the carbon-carbon bond forming reactions, the Knoevenagel reaction and the Michael reaction use a basic substance as a catalyst, and therefore, technical development relating to the catalyst is constantly being developed. Generally, an organic amine compound that exhibits basicity is often used as the catalyst for a long time, but it is difficult to completely remove the organic amine compound from the reaction system, so that the cost for the purification process tends to be high. Furthermore, the amount of waste generated in the refining process increases and the environmental load increases. Therefore, many developments of solid catalysts have been made from the viewpoint of separation of the catalyst and product and reuse of the catalyst. For example, an inorganic oxide catalyst having Lewis basicity (for example, see Non-patent Document 1), a catalyst in which an organic amine or an organic basic residue is fixed to a silica surface by a chemical bond (for example, Non-Patent Documents 2 and 3). Many solid catalysts have been proposed, such as a solid catalyst in which an amine residue is fixed in mesoporous silica (for example, see Non-Patent Document 4).

  In any case, the solid catalysts proposed in Non-Patent Documents 1 to 4 are characterized in that a part of the compound having a catalytic function is chemically bonded to the solid surface. When the solid catalyst is to be reused, the structure of the compound having a catalytic function that is bonded to the solid surface is likely to change. Therefore, the catalytic activity is inevitably lowered, and the amount of the solid catalyst to be used is increased. Is required. Therefore, industrialization with the basic solid catalyst proposed in Non-Patent Documents 1 to 4 is usually difficult.

  In contrast to fixing the catalyst to the solid surface, a method of confining the molecule of the compound functioning as the catalyst in the polymer capsule is also disclosed (for example, see Non-Patent Document 5). This method does not reduce the catalytic activity, but when repeated use is considered, operations such as recovery are not simpler than solid catalysts.

  In a carbon-carbon bond forming reaction involving a compound having an unsaturated bond and a compound having active methylene or active methine, when an organic amine compound showing basicity is used as a catalyst, the catalyst functions as a molecular catalyst. If it is confined in a solid, it is expected to bring many advantages such as improved catalyst activity, simplified separation and recovery, and improved recycling efficiency, which further reduces the environmental burden. This is thought to lead to cost reduction. However, the separation and recovery of the solid catalyst from the reaction solution is a technique that can be grasped even in a classic synthesis process, and a certain work process is required. To innovate the whole process of chemical synthesis, fix the composition having a catalytic function to the reaction vessel or reaction tube at the nano level, take out the reaction solution after the completion of the reaction, and introduce the next reactant into the reaction vessel or tube. Catalytic functional reactors are most desirable.

A. Corma et al. , J .; Catal. 1990, 126, 192. J. et al. L. Defreese et al. , Chem. Mater. 2005, 17: 6503. C. Paun et al. , J .; Mol. Cat. A: Chem. 2007, 269, 6 E. DeOliveira et al. , J .; Mol. Cat. A: Chem. , 2007, 271, 63 Sarah L. Poe et al. , J .; AM. CHEM. SOC. 2006, 128, 15586.

  In view of the above circumstances, the problem to be solved by the present invention is that a solid catalyst that can be used in a carbon-carbon bond forming reaction between a compound having an unsaturated bond and a compound having active methylene or active methine is used in a container or tube. It is an object to provide a catalyst-fixed vessel or a catalyst-fixed tubular reactor fixed to the inner wall of the catalyst.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composite formed by coating a metal oxide with a polymer having a linear polyethyleneimine skeleton is a container made of glass or plastic or the like. It can be fixed to the inner wall surface of the tube, and the composite can be suitably used as a basic solid catalyst used in the carbon-carbon bond forming reaction. Further, after the reaction is completed, the reaction solution is taken out. The present invention has been completed by finding that it can be used repeatedly by replacing a new reaction solution, and that there is no decrease in the catalytic activity even when it is reused.

  That is, in the present invention, the solid catalyst used in the addition reaction or condensation reaction in which a carbon-carbon bond is formed using the compound (x1) having an unsaturated bond and the compound (x2) having an active methylene or active methine is fixed. The solid catalyst is a complex formed by coating a polymer (A) having a linear polyethyleneimine skeleton (a) with a metal oxide (B), and the complex is a container. Alternatively, the present invention provides a catalyst-fixed reactor for carbon-carbon bond forming reaction, which is fixed to an inner wall of a pipe.

  In the catalyst-fixed reactor of the present invention, a complex having a very high specific surface area is formed on the inner wall surface of a container or tube, and a polymer having a linear polyethyleneimine skeleton functioning as a catalyst is confined in the complex. It is characterized by. Therefore, this reactor can be used as a catalyst in a carbon-carbon bond reaction. Such a catalyst-fixed reactor can renew the process for producing a useful compound in the chemical industry and a pharmaceutical intermediate. In particular, simplification of the overall synthesis process and dramatic improvement in catalyst efficiency can greatly contribute to reducing environmental impact.

  An organic low molecular weight amine and a high molecular weight amine can be used as a carbon-carbon bond reaction catalyst in which a compound containing an active methylene (methine) is involved in a compound having an unsaturated carbon bond. However, in the case of low molecular amines, if the structure of the amine is modified, the catalyst is completely deactivated, and it is almost impossible to confine the low molecular amine in a solid at the molecular level. . For efficient confinement of the molecular catalyst, it is premised that a polymer polyamine is used. Since the polymer polyamine contains a large number of amines in the polymer chain, even if partial modification occurs in the amine structure, it is considered that catalyst deactivation basically does not occur. In polymeric polyamine systems, polyethyleneimine is known as an important basic molecular catalyst. Polyethyleneimine is effective as a catalyst for precipitating silica, but at the same time, it is hybridized with silica and easily becomes a polyimine-silica composite. In particular, when a polymer having a linear polyethyleneimine skeleton is used for silica precipitation, a nanocomposite having a structure in which an aggregate of the polymer is confined in the order of nanometers in silica can be obtained. This is exactly a nanocomposite in which a basic polymer having a linear polyethyleneimine skeleton is confined in a silica gel.

  The present inventors have already used a crystalline aggregate in which a polymer having a linear polyethyleneimine skeleton grows in an aqueous medium in a self-organizing manner as a reaction field, and hydrolyzes alkoxysilane on the surface of the aggregate in a solution. By condensing decomposingly and precipitating silica, complex nanosilica structures rich in shape change and methods for producing them were provided (Japanese Patent Laid-Open Nos. 2005-264421, 2005-336440, 2006). No. -063097, JP 2007-051056 A). The basic principle of this technique is to spontaneously grow a crystalline aggregate of a linear polyethyleneimine skeleton-containing polymer in a solution. Once a crystalline aggregate is formed, the crystalline aggregate is then simply used. A silica source is mixed in the dispersion liquid, and the deposition of the silica only on the surface of the crystalline aggregate is allowed to leave naturally (so-called sol-gel reaction). If the growth of the crystalline association of the polyethyleneimine skeleton-containing polymer in the solution proceeds on the surface of a solid substrate of an arbitrary shape and the layer of the crystalline association of the polymer can be formed on the substrate, the solid group It is considered that a nanostructure having a new interface in which silica and a polymer are combined on a material can be constructed. If this working model is further expanded, even if the layer formed on the solid substrate is not a polymer crystalline aggregate, but a stable layer composed of a non-crystalline molecular aggregate of a polymer having a polyethyleneimine skeleton. Similarly, it is considered that a new nanointerface in which the target silica and polymer are combined can be constructed.

  Therefore, the fundamental problem of solving the above problem is how to form a stable layer (film) of a self-assembled assembly of a polymer having a linear polyethyleneimine skeleton on the surface of a solid substrate, that is, the inner wall of a container or a tube. It will only be formed. An important feature of a polymer having a linear polyethyleneimine skeleton is that it is basic and has a very high polarity. Therefore, the polymer is a metal substrate, a glass substrate, an inorganic metal oxide substrate, a plastic substrate having a polar surface, a cellulose substrate, many electron acceptor substrates, Lewis acidic substrates, acidic groups It has a strong interaction force (adsorption force) with various surfaces such as materials, polar substrates, hydrogen bonding substrates and the like. Taking advantage of this characteristic of the polymer, the present inventors contacted (immersed) the inner wall surface of the container or the tube with a molecular solution of the polymer at a constant concentration and at a constant temperature so that the polymer in the solution is brought into contact with the surface. As a result, it has been found that a layer composed of molecular aggregates of the polymer can be easily formed over the entire surface of the contacted portion of the inner wall surface. Furthermore, by immersing the inner wall surface coated with the polymer layer thus obtained in a metal oxide source solution, a complex nano-interface structure composed of metal oxide / polymer composite can be constructed on the inner wall surface. The present inventors have found that a linear polyethyleneimine moiety confined in the inner wall can function as a catalyst for a carbon-carbon bond reaction. The present invention will be described in detail below.

[Container or tube]
The container or tube used in the present invention is not particularly limited as long as the polymer (A) having a linear polyethyleneimine skeleton (a) described later can be adsorbed. For example, glass, metal, metal oxide, etc. Inorganic material base material, resin (plastic), organic material base material such as cellulose, etc. Furthermore, glass, metal, metal oxide surface etched substrate, resin substrate surface plasma treatment, ozone treatment Etching-treated substrates can be used.

  Although it does not specifically limit as an inorganic material type glass substrate, For example, glass, such as heat resistant glass (borosilicate glass), soda-lime glass, crystal glass, optical glass which does not contain lead and arsenic, is used suitably. Can do. In the use of a glass substrate, the surface can be used by etching with an alkaline solution such as sodium hydroxide, if necessary.

  Although it does not specifically limit as an inorganic material type metal base material, For example, the base material which consists of iron, copper, aluminum, stainless steel, zinc, silver, gold | metal | money, platinum, or these alloys etc. can be used suitably.

  Although it does not specifically limit as an inorganic material type metal oxide base material, For example, ITO (indium tin oxide), a tin oxide, copper oxide, a titanium oxide, a zinc oxide, an alumina etc. can be used suitably.

  Examples of resin substrates include processed products of various polymers such as polyethylene, polypropylene, polycarbonate, polyester, polystyrene, polymethacrylate, polyvinyl chloride, polyethylene alcohol, polyvinyl acetate, polyimide, polyamide, polyurethane, epoxy resin, and cellulose. Can be used. In the use of various polymers, the surface may be treated with plasma or ozone, or treated with sulfuric acid or alkali, if necessary.

  The shape of the above equipment is not particularly limited, and is a tubular tube of a complex shape processed product, a spiral tube of a tubular tube, a microtube, or an arbitrary shape (for example, a spherical shape, a square shape, a triangular shape, a cylindrical shape, etc. ) Containers can also be suitably used.

[Polymer (A) having linear polyethyleneimine skeleton (a)]
In the present invention, it is essential to use a polymer (A) having a linear polyethyleneimine skeleton (a) having a high ability to form a crystalline aggregate for a polymer layer formed on the inner wall of a container or a tube. The polymer (A) may be a homopolymer having a linear, star-like or comb-like structure, or a copolymer having other repeating units. In the case of a copolymer, the molar ratio of the linear polyethyleneimine skeleton (a) in the polymer (A) is preferably 20% or more from the viewpoint that a stable polymer layer can be formed. A block copolymer having a repeating polyethyleneimine skeleton (a) having 10 or more repeating units is more preferable.

  As the linear polyethyleneimine skeleton (a), whether it is a homopolymer or a copolymer, the molecular weight corresponding to the polyethyleneimine skeleton portion is in the range of 500 to 1,000,000. This is preferable because a stable polymer layer can be formed on the inner wall of the container or tube. The polymer (A) having the linear polyethyleneimine skeleton (a) can be obtained from a commercially available product or a synthesis method already disclosed by the present inventors (see the above-mentioned patent document).

  As will be described later, the polymer (A) can be used by dissolving in various solutions. At this time, in addition to the polymer (A) having a linear polyethyleneimine skeleton (a), the polymer (A) It can be used by mixing with other polymers that are compatible with. Examples of other polymers include polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, poly (N-isopropylacrylamide), polyhydroxyethyl acrylate, polymethyloxazoline, polyethyloxazoline, and polypropyleneimine. By using these other polymers, it is possible to easily adjust the thickness and the like of the solid catalyst layer made of the resulting composite.

[Metal oxide (B)]
The solid catalyst fixed to the reactor obtained in the present invention is a great feature that it is a composite composed of a polymer and a metal oxide. As a source necessary for depositing the metal oxide (B), for example, alkoxysilanes, water glass, hexafluorosilicon ammonium, tetrabutoxy titanium, tetraisopropoxy titanium, or titanium bis (ammonium stable in an aqueous medium) Lactate) dihydroxide aqueous solution, titanium bis (lactate) aqueous solution, titanium bis (lactate) propanol / water mixture, titanium (ethyl acetoacetate) diisopropoxide, titanium sulfate, hexafluorotitanium ammonium, etc. . Among these, the sol-gel reaction by the polymer (A) having the linear polyethyleneimine skeleton (a) proceeds rapidly, and a composite complexed in the nanometer order can be easily obtained, and industrially available. From the viewpoint of ease, alkoxysilanes are preferably used. That is, it is preferable that the solid catalyst fixed to the reactor of the present invention is a composite formed by coating the aforementioned polymer (A) with silica.

  As the alkoxysilanes, tetramethoxysilane, oligomers of methoxysilane condensates, tetraethoxysilane, oligomers of ethoxysilane condensates can be suitably used. Further, alkyl-substituted alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, etc., 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptotriethoxysilane, 3,3 -Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p -Chloromethylphenyltrimethoxysilane, p-chloromethylphenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane and the like can be used alone or in combination.

  In the reactor of the present invention, the inner wall of a vessel or tube is coated with a solid catalyst comprising a composite having the above-mentioned polymer (A) having a linear polyethyleneimine skeleton (a) and a metal oxide (B). However, due to the basicity and coordinating power of the polyethyleneimine skeleton, metal ions, metal nanoparticles, organic dye molecules, and the like can be stably incorporated into the complex. Since some metal ions and metal nanoparticles have a catalytic function during a chemical reaction, when performing various chemical reactions using the reactor of the present invention, the metal ions and metal nanoparticles are selected according to the purpose of controlling the reaction. Are preferably used. Further, when a compound exhibiting color developability and fluorescence such as organic dye molecules is used in combination, it can be suitably used for applications such as judgment of the lifetime of the reactor of the present invention and detection of the progress of chemical reaction.

  Since the polyethyleneimine skeleton (a) has a strong coordination ability with respect to metal ions, the metal ions coordinate with the ethyleneimine units in the skeleton to form a metal ion complex. The metal ion complex is obtained by coordination of a metal ion to an ethyleneimine unit. Unlike a process such as ionic bonding, the metal ion is coordinated to an ethyleneimine unit regardless of whether the metal ion is a cation or an anion. Can form a complex. Accordingly, the metal species of the metal ion is not limited as long as it can coordinate with the ethyleneimine unit in the polymer (A), and is not limited to alkali metal, alkaline earth metal, transition metal, metalloid, lanthanum metal, poly Any of metal compounds such as oxometalates may be used, and they may be used alone or in combination.

Examples of the alkali metal include Li, Na, K, Cs and the like, and examples of counter ions of the alkali metal ions include Cl, Br, I, NO ₃ , SO ₄ , PO ₄ , ClO ₄ , PF ₆ , Examples thereof include BF ₄ and F ₃ CSO ₃ .

  Examples of the alkaline earth metal include Mg, Ba, and Ca.

As a transition metal-based metal ion, even if it is a transition metal cation (M ^{n +} ), an acid group anion (MO _x ⁿ⁻ ) composed of a bond with oxygen, or an anion composed of a halogen bond ( ML _x ⁿ⁻ ) can also be suitably used. In the present specification, the transition metal refers to Sc, Y in Group 3 of the periodic table, and transition metal elements in Groups 4 to 12 in the 4th to 6th periods.

Examples of transition metal cations include cations of various transition metals (M ^{n +} ), such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, and Ag. , Cd, W, Os, Ir, Pt, Au, Hg, monovalent, divalent, trivalent or tetravalent cations. The counter anion of these metal cations may be any of Cl, NO ₃ , SO ₄ , polyoxometalates anions, or organic anions of carboxylic acids. However, for those that are easily reduced by the ethyleneimine skeleton, such as Ag, Au, and Pt, it is preferable to prepare an ionic complex by suppressing the reduction reaction, for example, by adjusting the pH to an acidic condition.

As transition metal anions, various transition metal anions (MO _x ⁿ⁻ ) such as M _n O ₄ , MoO ₄ , ReO ₄ , WO ₃ , RuO ₄ , CoO ₄ , CrO ₄ , VO ₃ , NiO ₄ , And an anion of UO ₂ .

  In addition, as the metal ion, a metal compound of polyoxometalates in which the transition metal anion is fixed in the metal oxide (B) through a metal cation coordinated to the ethyleneimine unit in the polymer (A). It may be a form. Specific examples of the polyoxometalates include molybdate, tungstate and vanadate in combination with a transition metal cation.

Further, anions (MLxn−) containing various metals, such as AuCl ₄ , PtCl ₆ , RhCl ₄ , ReF ₆ , NiF ₆ , CuF ₆ , RuCl ₆ , In ₂ Cl _6, etc., are coordinated to the halogen. The anion thus formed can also be suitably used for forming an ion complex.

  Further, examples of the metalloid ions include ions of Al, Ga, In, Tl, Ge, Sn, Pb, Sb, and Bi. Among them, ions of Al, Ga, In, Sn, Pb, and Tl are preferable.

  Examples of the lanthanum metal ions include trivalent cations such as La, Eu, Gd, Yb, and Eu.

  As described above, in the present invention, metal ions can be taken into the solid catalyst on the inner wall surface. Therefore, among these metal ions, metal ions that are easily reduced by a reduction reaction can be converted into metal nanoparticles, whereby the metal nanoparticles can be contained in the solid catalyst.

  Examples of the metal species of the metal nanoparticles include copper, silver, gold, platinum, palladium, manganese, nickel, rhodium, cobalt, ruthenium, rhenium, molybdenum, iron, and the like. One kind or two or more kinds of nanoparticles may be used. Among these metal species, silver, gold, platinum, and palladium are particularly preferable because the metal ions are spontaneously reduced at room temperature or in a heated state after being coordinated to the ethyleneimine unit.

  The size of the metal nanoparticles in the solid catalyst composed of the composite can be controlled in the range of 1 to 20 nm. The metal nanoparticles can be fixed to the inside or the outer surface of the nanostructure composite of the polymer (A) and the metal oxide (B).

  In the present invention, the polyethyleneimine skeleton (a) in the solid catalyst comprising a composite covering the surface of the inner wall of the container or tube is composed of a compound having an amino group, a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, hydrogen A physical coupling structure can be constructed by coupling and / or electrostatic attraction. Therefore, organic dye molecules having these functional groups can be contained in the solid catalyst composed of the complex.

  As the organic dye molecule, a monofunctional acidic compound or a bifunctional or higher polyfunctional acidic compound can be suitably used.

  Specifically, for example, aromatic acids such as tetraphenylporphyrin tetracarboxylic acid and pyrene dicarboxylic acid, naphthalene disulfonic acid, pyrene disulfonic acid, pyrene tetrasulfonic acid, anthraquinone disulfonic acid, tetraphenyl porphyrin tetrasulfonic acid, phthalocyanine tetra Aromatic or aliphatic sulfonic acids such as sulfonic acid and pipes (PIPES), acid yellow, acid blue, acid red, direct blue, direct yellow, direct red series azo dyes and the like can be mentioned. In addition, a dye having a xanthene skeleton, for example, rhodamine, erythrosine, and eosin dyes can be used.

[Composite containing polymer (A) and metal oxide (B)]
The composite containing the polymer (A) and the metal oxide (B) is basically a composite nanofiber or composite nanoparticle assembly of the polymer (A) and the metal oxide (B). Various patterns or morphologies are formed while forming a state in which the aggregate covers the entire inner wall surface of the solid container or tube. For example, the composite nanofabric has a relatively long turf-like (nano turf) or fiber long axis where the long axis of the fiber grows in the vertical direction on the entire surface of the inner wall of the solid container or tube. Rice field (nano rice field), which has a tendency to fall more than the vertical direction, tatami shape (nano tatami mat) in which composite nanofibers lie down on the entire surface of the substrate, composite nanofibers or composite nanoparticles on the entire surface of the substrate A wide variety of hierarchical structures such as a sponge (nano sponge) forming a network can be formed.

  The thickness of the composite nanofiber of the basic unit in the higher-order structure such as the nano turf shape, the nano rice field shape, the nano tatami shape, or the nano sponge shape is in the range of 10 to 100 nm. The length (major axis direction) of the composite nanofiber in the nano turf shape or the nano rice field shape can be controlled in the range of 50 nm to 10 μm.

  When a network is formed on the inner wall of a solid container or tube, that is, when a three-dimensional network structure is constructed over the entire coating layer, the basic structure is composed only of the composite nanofiber. Alternatively, it may be composed only of composite nanoparticles, or may be formed by combining both. At this time, the average particle size of the composite nanoparticles is preferably controlled to 20 nm or less.

  The thickness from the solid surface when coating on the inner wall of the solid container or tube is related to the aggregate structure of the composite nanofiber and / or composite nanoparticle, but can be varied in the range of about 50 nm to 20 μm. In the nano-turf shape, the composite nanofibers tend to stand upright, the length of the fibers basically constitutes the thickness, and the lengths of the individual fibers are fairly uniform. . In the nano rice field, the composite nanofibers tend to extend obliquely, and the thickness of the coating layer is smaller than the length of the fibers. In addition, the thickness of the nano rice field-like layer is characterized in that it is determined by the overlaid state of the composite nanofibers. The thickness of the nanosponge-like layer is characterized in that it is determined by the degree to which the composite nanofiber swells with a complex entanglement having regularity. When a network is formed, the thickness is determined by the overlapping state, the existence ratio of the composite nanofiber and the composite nanoparticle, and the like.

  In the composite, the component of the polymer (A) can be adjusted at 5 to 30% by mass. By changing the content of the polymer (A) component, the aggregate structure (higher order structure) can be changed.

  In addition, when a metal ion, a metal nanoparticle, or an organic dye molecule is contained in the complex, it is possible to control the higher order structure depending on the type. Even in this case, the basic unit is a composite nanofiber and / or composite nanoparticle as described above, which are combined to form a complex shape.

  The amount of metal ions taken up when taking in metal ions is preferably adjusted in the range of 1/4 to 1/200 equivalent to 1 equivalent of ethyleneimine unit in polymer (A), and this ratio is changed. Can change the thickness of the coating layer. In addition, the coating layer at this time may develop color depending on the metal species.

  The amount of metal nanoparticles incorporated when incorporating metal nanoparticles is preferably prepared in the range of 1/4 to 1/200 equivalent per 1 equivalent of ethyleneimine unit in the polymer (A). By changing the thickness, the thickness of the coating layer can be changed. In addition, the coating layer at this time may develop color depending on the metal species.

  The organic dye molecule incorporation amount when incorporating the organic dye molecule is preferably prepared in the range of 1/2 to 1/1200 equivalent to 1 equivalent of the ethyleneimine unit in the polymer (A). By changing the thickness, the thickness and shape pattern of the coating layer can be changed.

  In addition, two or more kinds of metal ions, metal nanoparticles, and organic dye molecules can be simultaneously incorporated into the composite.

[Production method of reactor with catalyst fixed on the surface of a solid container or tubular inner wall]
The method for producing a reactor of the present invention comprises a solution of a polymer (A) having a linear polyethyleneimine skeleton (a), a mixed solution of a polymer (A) having a linear polyethyleneimine skeleton (a) and a metal ion, Mixed solution of polymer (A) having linear polyethyleneimine skeleton (a) and organic dye molecule, or mixing of polymer (A) having linear polyethyleneimine skeleton (a), metal ion and organic dye molecule After the solution is brought into contact with the inner wall surface of the solid container or tube, the polymer (A) having a linear polyethyleneimine skeleton (a) on these inner walls and the combined metal ions and / or organic dye molecules are used. The step (1) of obtaining a substrate on which the polymer layer is adsorbed, and the substrate adsorbed on the polymer layer and the metal oxide source liquid (B ′) are brought into contact with each other and adsorbed on the substrate surface. A step (2) of coating the substrate while forming a composite by depositing the metal oxide (B) by the catalytic function of the linear polyethyleneimine skeleton (a) in the polymer layer; and It is a manufacturing method which has this. By this method, the nano-interface consisting of polymer (A) and metal oxide (B), the nano-interface consisting of polymer (A) / metal ion / metal oxide (B), polymer (A) on the inner wall surface of the container or tube It is possible to easily form a nano-interface catalyst layer comprising / organic dye molecule / metal oxide (B).

  As the polymer (A) having the linear polyethyleneimine skeleton (a) used in the step (1), the aforementioned polymer can be used. In addition, the solvent that can be used for obtaining the solution of the polymer (A) is not particularly limited as long as the polymer (A) can be dissolved, and examples thereof include water, organic solvents such as methanol and ethanol, These mixed solvents can be used as appropriate.

  The concentration of the polymer (A) in the solution is not particularly limited as long as the polymer layer can be formed on the inner wall surface of the container or the tube. Is preferably in the range of 0.5% by mass to 50% by mass, and more preferably in the range of 5% by mass to 50% by mass.

  In the solution of the polymer (A) having a linear polyethyleneimine skeleton (a), the above-mentioned other polymers that are soluble in the solvent and compatible with the polymer (A) can be mixed. The mixing amount of the other polymer may be higher or lower than the concentration of the polymer (A) having the linear polyethyleneimine skeleton (a).

  When forming the solid catalyst which consists of a composite_body | complex containing a metal ion, the said metal ion is mixed in the solution of the polymer (A) which has a linear polyethyleneimine frame | skeleton (a). The concentration of the metal ion is preferably adjusted to ¼ equivalent or less of the ethyleneimine unit in the linear polyethyleneimine skeleton (a).

  Moreover, when forming the solid catalyst which consists of a composite_body | complex containing an organic pigment | dye molecule | numerator, the said organic pigment | dye molecule | numerator is mixed in the solution of the polymer (A) which has a linear polyethyleneimine frame | skeleton (a). The concentration of the organic dye molecule is preferably adjusted to ½ equivalent or less of the ethyleneimine unit in the linear polyethyleneimine skeleton (a).

  Moreover, in order to produce a polymer layer in a process (1), the inner wall of a container or a pipe | tube is made to contact with the solution of a polymer (A). As the contact method, it is preferable to immerse the inner wall of a desired container or tube in the polymer (A) solution.

  In the dipping method, the base material and the solution can be brought into contact with each other by placing the polymer solution in a container or a tube. During the immersion, the temperature of the polymer (A) solution is preferably in a heated state, and a temperature of about 50 to 90 ° C. is suitable. The time for bringing the container or the tube into contact with the solution of the polymer (A) is not particularly limited, and it is preferable to select from several seconds to 1 hour according to these materials. If the material of the container or tube has a strong binding ability with polyethyleneimine, for example, it may be several seconds to several minutes for glass, metal, etc. If the material of the base material is weakly binding ability with polyethyleneimine, it will be tens of minutes to 1 hour But it ’s okay.

  After contacting the container or tube with the polymer (A) solution and then removing them from the polymer (A) solution and leaving them at room temperature (around 25 ° C.), the polymer (A) aggregate layer spontaneously forms the inner wall surface. Formed. Alternatively, after separating from the polymer (A) solution, the polymer (A) aggregate layer is spontaneously formed by placing it in distilled water at 4 to 30 ° C. or in an aqueous ammonia solution at room temperature to below freezing temperature. You may let them.

  In the step (2), the polymer layer formed in the step (1) is brought into contact with the source liquid (B ′) of the metal oxide to deposit the metal oxide (B) on the surface of the polymer layer. And a solid catalyst layer made of a composite containing metal oxide (B). Even when a metal ion and / or an organic dye molecule is contained in the polymer layer, the metal oxide (B) can be deposited by the same method to form a solid catalyst layer made of the target composite.

  As the source liquid (B ′) used at this time, the above-mentioned various metal oxide source aqueous solutions, alcohol solvents, for example, aqueous organic solvent solutions such as methanol, ethanol and propanol, or a mixture of these with water A solvent solution can be used. Moreover, the water glass aqueous solution which adjusted pH value to the range of 9-11 can also be used.

  Moreover, the alkoxysilane compound as a silica source can be used even in a solvent-free bulk liquid.

  As a method for bringing the container or tube on which the polymer layer is adsorbed into contact with the source liquid (B ′), an immersion method can be preferably used. It is sufficient that the immersion time is 5 to 60 minutes, but the time can be further increased as necessary. The temperature of the source liquid (B ′) may be room temperature or a heated state. In the case of heating, in order to regularly deposit the metal oxide (B) on the inner wall surface of the container or tube, it is desirable to set the temperature to 70 ° C. or lower.

  By selecting the type and concentration of the source of the metal oxide, the structure of the solid catalyst layer composed of the composite of the deposited metal oxide (B) and the polymer (A) can be adjusted. It is preferable to select an appropriate source type and concentration.

  Polyethyleneimine can reduce noble metal ions such as gold, platinum, silver, palladium, etc. to metal nanoparticles. Therefore, the precious metal ions are converted into metal nanoparticles in the composite through the step (3) of contacting the inner wall covered with the composite obtained in the above step with the aqueous solution of the precious metal ions. And a solid catalyst layer made of a composite having metal nanoparticles can be formed.

  In the step (3), a dipping method can be preferably used as the method of contacting with an aqueous solution of noble metal ions. As the aqueous solution of noble metal ions, aqueous solutions of chloroauric acid, sodium chloroaurate, chloroplatinic acid, sodium chloroplatinate, silver nitrate and the like can be suitably used, and the aqueous solution concentration of noble metal ions is 0.1 to 5 mol. % Is preferred.

  The temperature of the aqueous solution of noble metal ions is not particularly limited, and may be in the range of room temperature to 90 ° C. However, in order to promote the reduction reaction, it is preferable to use a heated aqueous solution of 50 to 90 ° C. Moreover, the time for immersing the structure in the aqueous solution of metal ions may be 0.5 to 3 hours, and about 30 minutes is sufficient when immersed in the heated aqueous solution.

  In the case of a metal ion that is difficult to reduce with polyethyleneimine alone, the metal ion in the solid catalyst layer made of the composite having the metal ion obtained above is used as a reducing agent, particularly a low molecular weight reducing agent solution or hydrogen gas. The solid catalyst layer made of the composite containing the metal nanoparticles can be formed by reducing the metal ions in combination with the step (4) of contacting with the catalyst.

  Examples of the reducing agent that can be used at this time include ascorbic acid, aldehyde, hydrazine, sodium borohydride, ammonium borohydride, hydrogen, and the like. When reducing metal ions using a reducing agent, the reaction can be carried out in an aqueous medium, and a method of immersing a complex containing metal ions in a reducing agent solution or leaving it in a hydrogen gas atmosphere. Can be used. At this time, the temperature of the reducing agent aqueous solution may be in the range of room temperature to 90 ° C., and the concentration of the reducing agent is preferably 1 to 5 mol%.

  Although it does not specifically limit as a metal seed | species of the metal ion which can be adapted to a process (4), From the point that a reductive reaction advances rapidly, it is preferable that they are copper, manganese, chromium, nickel, tin, vanadium, and palladium.

  When the composite is immersed in the reducing agent aqueous solution, the temperature of the reducing agent aqueous solution is suitable even at room temperature or in a heated state of 90 ° C. or less, and a concentration of the reducing agent of about 1 to 5% is sufficient.

  The various solid catalyst layers obtained by the above-described method can be left at room temperature (25 ° C.) to about 60 ° C. to remove the solvent and water, thereby forming the reactor of the present invention.

[Carbon-carbon bond-forming reaction using a glass container or tube as a catalytic reactor]
The carbon-carbon bond forming reaction referred to in the present invention refers to a reaction involving a compound (x1) having an unsaturated bond and a compound (x2) having active methylene or active methine. For example, methylene or methine binds to a strong electron-withdrawing group to a compound containing an unsaturated carbon atom such as aldehyde or ketone, or a compound containing a structure in which a C═C bond is conjugated to an aldehyde, ketone, ester or amide group. It is a reaction in which a carbon-carbon bond is formed by the reaction of a compound having active methylene or active methine, which is known as a Knoevenagel reaction or a Michael reaction.

  The aldehydes are not limited to aliphatic and aromatic, and can be used if the compound contains an aldehyde group. The ketones are not limited to aliphatic and aromatic, and can be used as long as the compound contains a ketone group.

The compound (x2) having active methylene or active methine is required to have a strong electron-withdrawing group bonded to the methylene or methine. For example, —CN, —NO ₂ , —COOH, —CO (O _{) CH 3, -CO (O)} C 2 H 5, -C (O) NH 2, -C (O) NHCH 3, -C (O) N (CH 3) 2, -S (O 2) OPh like It can be preferably used if it is a compound in which the functional groups are singly or in combination of two and bonded to methylene carbon.

  Hereinafter, the compound (x1) having an unsaturated bond such as the aldehydes and ketones is defined as an electron acceptor, while the compound (x2) having active methylene or active methine is defined as an electron donor.

  The compound as the acceptor is, for example, one in which a substituted or unsubstituted aliphatic, cycloaliphatic, heteroaliphatic, heterocycloaliphatic, aromatic, or heteroaromatic group is bonded to an aldehyde or a ketone. Specifically, examples of the aliphatic group include alkyl groups such as methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Can be mentioned. Further, it may be an alkenyl group such as propenyl, isopropenyl, isobutenyl, 2-butenyl, 3-butenyl, n-2-pentenyl, n-2-octenyl and the like. Examples of the aliphatic group having a substituent include hydroxymethyl, hydroxyethyl, 1-hydroxy-n-propyl, 1-hydroxy-i-propyl, 1-hydroxy-n-propyl, 1-hydroxy-n-butyl, Examples thereof include hydroxyalkyl groups of various isomers such as 1-hydroxy-i-butyl and 2-hydroxy-n-butyl. Furthermore, as a substituted aliphatic group, an aliphatic group having a halogen group, for example, methyl fluoride, 2-ethyl fluoride, chloromethyl, 2-fluoroethyl, 2-chloroethyl, difluoromethyl, trifluoromethyl, dichloro Methyl, trichloromethyl, 2,2,2-trichloroethyl, and i-propyl, n-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, substituted with chloro, fluoro, bromo, An alkyl group such as octyl, nonyl, decyl and the like can be mentioned. Examples of the cyclic aliphatic group include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Heteroaliphatic groups include those where the aliphatic group contains one or more heteroatoms, such as O, S, N, P, and the like. As the heterocycloaliphatic group, the heterocyclic group has 4 or 5 carbon atoms, and the cyclic structure includes one or two heteroatoms such as O, S, N, for example, oxirane, Examples include azirine, 1,2-oxathiolane, pyrazoline, pyrrolidone, piperidine, morpholine, tetrahydrofuran, and tetrahydrothiophene.

  In the case of an aromatic group, there can be mentioned, for example, phenyl, pentaline, indene, naphthalene, anthracene, etc. having 6 to 10 carbon atoms. In the case of heteroaromatic, the carbon atom is 4 or 5, and the cyclic structure includes one of heteroatoms such as O, S, and N, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine , Pyrazine, indole, purine, quinoline and the like.

Moreover, as a compound as a donor, following Structural formula (1),
YCH ₂ Y (1)
[Wherein Y is CN, COOR, COOH, NO ₂ , CONH ₂ , CONHR, COR, or —SO ₂ R (where R is a C _{1 to} C ₁₂ alkyl group, phenyl group, or naphthyl group) .)]
The following structural formula (2),
XCH ₂ Y (2)
[Wherein, Y is as defined above, X is a C _{1 to} C ₆ alkyl group, or a phenyl group or naphthyl group which may have a substituent, and the substituent includes Cl, Br, F, OH, CN, COOR ′, COOH, CONH ₂ , NO ₂ , OCH ₃ , OC ₂ H ₅ , SO ₂ R ′, PO ₃ R ′ (R ′ is a C ₁ -C ₆ alkyl group). ]
The following structural formula (3),
YCHZY (3)
Wherein, Y is as defined above, Z is alkyl, phenyl, or naphthyl group of C ₁ -C _6. ]
Or the following structural formula (4)
XCHZY
[Wherein, X, Y and Z are as defined above. ]
The compound represented by these can be mentioned.

  The reaction between the acceptor and the donor is a reaction using the complex in the present invention as a catalyst. At this time, the reaction temperature, the reaction solvent, the amount of catalyst used, and the like affect the reaction efficiency.

  When the donor is an active methylene compound, when two electron-withdrawing groups (for example, two CN groups) are bonded to the methylene, the reaction activity is increased. Therefore, when the acceptor reacts with such a donor, the reaction can be allowed to proceed at room temperature or in the range of 30 ° C. When the reaction activity of the donor is relatively weak, it is desirable to raise the temperature slightly, and for example, it can be set to 50 to 150 ° C.

  The catalyst of the present invention can be used without a solvent or in the presence of a solvent. In particular, when the compound used as a raw material is a liquid, the catalytic activity can be sufficiently exerted without using a solvent.

  In particular, when the raw material compound has crystallinity, or when the product has crystallinity, it is preferably carried out in a polar solvent when the reaction is carried out using the solid catalyst of the present invention. The polar solvent is preferably a solvent that easily undergoes solvation with the polymer (A) having the linear polyethyleneimi skeleton (a) contained in the solid catalyst, particularly methanol, ethanol, propanol, Alcohol solvents such as ethylene dialcohol can be preferably used. These alcohol solvents can also be used by mixing with other solvents. Examples of other solvents include polar solvents such as acetonitrile, dimethylformamide, acetamide, dimethylacetamide, and dimethylsulfone oxide.

  The inner wall composite interface of the catalyst-fixed reactor in the present invention contains a linear polyethyleneimine skeleton polymer that functions as a molecular catalyst inside, so that the catalytic activity is high and the reaction can be carried out even if the amount used is considerably small. Can be advanced. In general, the molar ratio of an acceptor to a donor used in a carbon-carbon bond reaction involving an aldehyde or a ketone often uses 5/100 to 10/100 equivalents of the acceptor while using a large excess of the donor. In the case of using the solid catalyst in the present invention, the acceptor and the donor are each equivalent, and the catalyst amount (equivalent to the ethyleneimine unit in the polyethyleneimine contained in the solid catalyst) is in the range of 1/1000 to 1/100 equivalent. Can be used.

  In the reaction using the catalyst-fixed reactor in the present invention, after the reaction is completed, the reaction solution can be taken out and subsequently the next reactant is charged and the reaction can be repeated one after another.

  In the repeated use of the catalyst-fixed reactor, the reaction solution can be taken out after completion of the reaction, and the inside of the reactor can be washed with a solvent, and then used for the next reaction through the drying step or without the drying step.

  The catalyst-fixed reactor of the present invention can be used as a catalyst-type reactor for carbon-carbon bond reaction, and is composed of a “nano turf” -like composite having a high specific surface area at the inner wall interface of the reactor, Each formed composite nanofiber or composite nanoparticle has a structure in which polyethyleneimine acting as a catalyst is confined. Therefore, since this catalyst can actually function as a molecular catalyst in the reaction solution, it is greatly different from the conventional supported catalyst in which the amine residue is bound to the solid powder surface. It is also considered that polyethyleneimine can be used as a catalyst for other organic reactions involving the catalyst.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “%” represents “mass%”.

[Shape analysis of solid catalyst composed of composites by scanning electron microscope]
The solid catalyst composed of the isolated and dried composite was fixed to a sample support with a double-sided tape, and observed with a surface observation device VE-9800 manufactured by Keyence.

Synthesis example 1
<Synthesis of linear polyethyleneimine (L-PEI)>
3 g of commercially available polyethyloxazoline (number average molecular weight 50,000, average polymerization degree 5,000, manufactured by Aldrich) was dissolved in 15 mL of 5 mol / L hydrochloric acid. The solution was heated to 90 ° C. in an oil bath and stirred at that temperature for 10 hours. Acetone 50 mL was added to the reaction solution to completely precipitate the polymer, which was filtered and washed three times with methanol to obtain a white polyethyleneimine powder. When the obtained powder was identified by ¹ H-NMR (heavy water, manufactured by JEOL Ltd., AL300, 300 MHz), the peak derived from the side chain ethyl group of polyethyloxazoline was 1.2 ppm (CH ₃ ) and 2. It was confirmed that 3 ppm (CH ₂ ) disappeared completely. That is, it was shown that polyethyloxazoline was completely hydrolyzed and converted to polyethyleneimine.

  The powder was dissolved in 5 mL of distilled water, and 50 mL of 15% aqueous ammonia was added dropwise to the solution while stirring. The mixture was allowed to stand overnight, and then the precipitated polymer aggregate powder was filtered, and the polymer aggregate powder was washed three times with cold water. The crystal powder after washing was dried in a desiccator at room temperature to obtain linear polyethyleneimine (L-PEI). The yield was 2.2 g (including crystal water). In polyethyleneimine obtained by hydrolysis of polyoxazoline, only the side chain reacts and the main chain does not change. Therefore, the polymerization degree of L-PEI is the same as 5,000 before hydrolysis.

Synthesis example 2
<Synthesis of star-shaped polyethyleneimine (B-PEI) centered on benzene ring>
Jin, J .; Mater. Chem. , 13, 672-675 (2003), a star-shaped polymethyloxazoline in which six polymethyloxazoline arms were bonded to the center of the benzene ring as a precursor polymer was synthesized as follows.

Put 0.021 g (0.033 mmol) of hexakis (bromomethyl) benzene as a polymerization initiator in a test tube set with a magnetic stirrer, attach a three-way cock to the test tube, and then put it in a vacuum state. Was replaced with nitrogen. Under a nitrogen stream, 2.0 ml (24 mmol) of 2-methyl-2-oxazoline and 4.0 ml of N, N-dimethylacetamide were sequentially added from the inlet of the three-way cock using a syringe. When the test tube was heated to 60 ° C. on an oil bath and kept for 30 minutes, the mixture became transparent. The transparent mixture was further heated to 100 ° C. and stirred at that temperature for 20 hours to obtain a precursor polymer. From the ¹ H-NMR measurement of this mixture, the monomer conversion was 98 mol% and the yield was 1.8 g. When the average degree of polymerization of the polymer was estimated based on this conversion, the average degree of polymerization of each arm was 115. Moreover, in the molecular weight measurement by GPC, the mass average molecular weight of the polymer was 22,700, and the molecular weight distribution was 1.6.

Using this precursor polymer, polymethyloxazoline was hydrolyzed in the same manner as in Synthesis Example 1 to obtain star-shaped polyethyleneimine B-PEI in which 6 polyethyleneimines were bonded to the benzene ring core. ^{As a result of 1} H-NMR (TMS external standard, heavy water) measurement, it was confirmed that the peak of 1.98 ppm derived from the side chain methyl of the precursor polymer before hydrolysis completely disappeared.

  The powder was dissolved in 5 mL of distilled water, and 50 mL of 15% aqueous ammonia was added dropwise to the solution while stirring. The mixture was allowed to stand overnight, and then the precipitated crystal powder was filtered, and the crystal powder was washed three times with cold water. The washed crystal powder was dried in a desiccator at room temperature (25 ° C.) to obtain star-shaped polyethyleneimine (B-PEI) in which six polyethyleneimines were bonded to the benzene ring core. The yield was 1.3 g (including crystal water).

Example 1
<Reaction of benzaldehyde with malononitrile in a fixed catalyst glass reactor>
[Preparation of Reactor A with Glass Test Tube Inner Wall Coated with Solid Catalyst Composed of Polymer / Silica Composite]
Polymer L-PEI obtained in Synthesis Example 1 was added to distilled water and heated to 90 ° C. to prepare 15 mL of 4% aqueous solution. The heated aqueous polymer solution was added to a soda-lime glass test tube (trade name: AR-GLAS, manufactured by DURAN, inner diameter: 2 cm, length: 15 cm), and allowed to stand for 30 seconds. Discharged by law. By this operation, an L-PEI polymer layer was formed on the inner wall of the glass tube. A silica source solution (0.5% tetramethoxysilane in ethanol) was added to the test tube and held for 10 minutes. After removing the solution from the glass tube and washing the inner wall of the glass tube with ethanol, it was dried at room temperature. The inner wall surface of the test tube was coated with approximately 5 mg of the composite nanostructure. Five reactors A were produced by this working method. FIG. 1 shows an SEM photograph observed from a fragment of the produced reactor.

[Reaction of benzaldehyde with malononitrile using reactor A]
In the reactor A purged with nitrogen, 1.06 g (10 mmol) of benzaldehyde, 0.66 g (10 mmol) of malononitrile and 10 mL of methanol were mixed. The reaction solution was heated to 30 ° C. and allowed to stand at that temperature for 4 hours, after which the reaction solution was taken out a little and the conversion rate of the reaction product was measured by ¹ H-NMR. From the disappearance of the aldehyde peak derived from benzaldehyde at around 10 ppm, it was confirmed that the conversion rate was 100%.

Example 2
<Repetitive use of fixed catalyst reactor A>
The reactor A used in Example 1 was washed with methanol and then dried at room temperature, and used for the same reaction as in Example 1. After reacting at 30 ° C. for 4 hours, the entire reaction solution was taken out, and the inside of the reactor was washed twice with methanol. Then, the same reactant was added and reacted at 30 ° C. for 4 hours. Such an operation was repeated 9 times, and the reaction conversion rate at each time was measured by ¹ H-NMR in the same manner as in Example 1. The results are shown in Table 1.

  The results of Example 1 and Example 2 were combined, and it was found that the reaction progressed quantitatively with no decrease in catalytic activity even after a total of 10 reuses.

Example 3
<Reaction of benzaldehyde and malononitrile in a catalyst fixed plastic reactor>
[Preparation of Reactor B with Plastic Test Tube Inner Wall Coated with Solid Catalyst Composed of Polymer / Silica Composite]
Polymer L-PEI obtained in Synthesis Example 1 was added to distilled water and heated to 90 ° C. to prepare a 4% aqueous solution. The polymer aqueous solution was added to a polystyrene plastic test tube (inner diameter: 2 cm, length: 10 cm, and the inner surface of the test tube was etched with 85% sulfuric acid for 10 minutes) and allowed to stand for 30 seconds. Drained by the gradient method. By this operation, an L-PEI polymer layer was formed on the inner wall of the glass tube. The test tube was allowed to stand at room temperature for 5 minutes, and then a silica source solution (0.5% tetramethoxysilane ethanol solution) was added to the test tube and held for 10 minutes. After removing the solution from the glass tube and washing the inner wall of the glass tube with ethanol, it was dried at room temperature. The inner wall surface of the test tube was coated with approximately 5 mg of the composite nanostructure. Five reactors B were produced by this working method. FIG. 2 shows an SEM photograph observed from a fragment of the produced plastic reactor.

[Reaction of benzaldehyde with malononitrile using reactor B]
In the reactor B purged with nitrogen, 0.63 g of benzaldehyde, 0.40 g of malononitrile, and 7 mL of methanol were mixed. The reaction was heated to 30 ° C. and left at that temperature for 4 hours. A small amount of the reaction solution was taken out, and the conversion rate of the reaction product was measured by ¹ H-NMR. From the disappearance of the aldehyde peak derived from benzaldehyde at around 10 ppm, it was confirmed that the conversion rate was 100%.

Example 4
[Reaction of cyclohexenone with nitroethane using reactor A]
In the reactor A, 0.49 g (5 mmol) of cyclohexenone, 0.75 g (10 mmol) of nitroethane, and 3 mL of ethanol were mixed. The mixture was reacted at 30 ° C. for 2 hours. The reaction solution was taken out, and the conversion rate of the reaction product was measured by ¹ H-NMR. As a result, it was confirmed that the peak derived from CH═CH of cyclohexenone completely disappeared and the desired nitroethane adduct was produced. . The reaction proceeded quantitatively with a conversion of 100 mol%.

Example 5
[Reaction of cyclohexenone with phenylacetonitrile using reactor A]
In the reactor A, 0.98 g (10 mmol) of cyclohexenone, 1.17 g (10 mmol) of phenylacetonitrile and 5 mL of ethanol were mixed. The mixture was reacted at 30 ° C. for 2 hours. The reaction solution was taken out, and the conversion rate of the reaction product was measured by ¹ H-NMR. As a result, it was confirmed that the peak derived from CH═CH of cyclohexenone completely disappeared and the target adduct of phenylacetonitrile was formed. It was. The reaction proceeded quantitatively with a conversion of 100 mol%.

Example 6
<Reaction of benzaldehyde with malononitrile in a fixed catalyst glass reactor>
[Preparation of Reactor C with Glass Test Tube Inner Wall Coated with Solid Catalyst Composed of Polymer / Silica Composite]
A reactor C was produced in the same manner as in Example 1 except that the polymer B-PEI obtained in Synthesis Example 2 was used.

[Reaction of benzaldehyde with malononitrile using reactor C]
In the reactor C purged with nitrogen, 1.06 g (10 mmol) of benzaldehyde, 0.66 g (10 mmol) of malononitrile, and 10 mL of methanol were mixed. The reaction solution was heated to 30 ° C. and allowed to stand at that temperature for 4 hours, after which the reaction solution was taken out a little and the conversion rate of the reaction product was measured by ¹ H-NMR. From the disappearance of the aldehyde peak derived from benzaldehyde at around 10 ppm, it was confirmed that the conversion rate was 100%.

Example 7
[Reaction of cyclohexenone and phenylacetonitrile using reactor C]
After the inside of the reactor C used in Example 6 was washed with methanol, 0.98 g (10 mmol) of cyclohexenone, 1.17 g (10 mmol) of phenylacetonitrile and 5 mL of ethanol were added to the reactor. The mixture was reacted at 30 ° C. for 2 hours. The reaction solution was taken out, and the conversion rate of the reaction product was measured by ¹ H-NMR. As a result, it was confirmed that the peak derived from CH═CH of cyclohexenone completely disappeared and the target adduct of phenylacetonitrile was formed. It was. The reaction proceeded quantitatively with a conversion of 100 mol%.

Photo of reactor A with inner wall coated with composite (a1) Before coating (a2) After coating. SEM photograph of inner surface of glass tube fragment: (b) low magnification; (c) 5000 times; (d) 25000 times; (e) cross section (nano turf on glass surface, thickness is about 2 μm). Photo (a) of reactor B with inner wall coated with composite. SEM photograph of cracked reactor B fragment inner wall surface: (b) low magnification; (c) 25000 times; (d) cross section (nano turf on plastic surface).

Claims (3)

A reactor in which a solid catalyst used for an addition reaction or a condensation reaction for forming a carbon-carbon bond using a compound (x1) having an unsaturated bond and a compound (x2) having an active methylene or active methine is fixed. The solid catalyst is a composite formed by coating a polymer (A) having a linear polyethyleneimine skeleton (a) with a metal oxide (B), and the composite is fixed to the inner wall of a container or a tube. A catalyst-fixed reactor for carbon-carbon bond forming reaction. The catalyst-fixed reactor for carbon-carbon bond forming reaction according to claim 1, wherein the metal oxide (B) is silica. The catalyst-fixed reactor for carbon-carbon bond forming reaction according to claim 1 or 2, wherein the addition reaction or condensation reaction for forming the carbon-carbon bond is a Kunafener gel reaction or a Michael reaction.