Platinum group metal-supported catalyst column and carbon-carbon bond formation method

Abstract

To provide a platinum group metal-supported catalyst column enabling carbon-carbon bond formation reaction to be performed at a high yield even in aromatic bromide.SOLUTION: In a platinum group metal-supported catalyst column, a platinum group metal-supported catalyst includes at least one of platinum group metal nanoparticles, platinum group metal ions and platinum group metal complex ions supported on an ion exchanger; the ion exchanger consists of a continuous skeleton phase and a continuous hole phase; the thickness of a continuous skeleton is 1-100 μm; the average diameter of continuous holes is 1-1000 μm; the total pore volume is 0.5 - 50 mL / g; an ion exchange capacity per weight in a dry state is 1-9 mg equivalent / g; an ion exchange group is the non-particulate organic porous ion exchanger distributed in the ion exchanger; the amount of the supported platinum group metal nanoparticles, etc., is 0.004 wt.%-20 in a dry state; and a platinum group metal capturing material is installed in the latter part of the platinum group metal-supported catalyst.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a platinum group metal-supported catalyst column filled with a platinum group metal-supported catalyst, and a carbon-carbon bond formation method for performing a reaction for forming a carbon-carbon bond using the platinum group metal-supported catalyst column.

Background Art

[0002] Carbon-carbon bond formation reactions (coupling reactions) using platinum group metals such as palladium as catalysts, typified by Suzuki-Miyaura coupling, Sonogashira coupling, and Mizoroki-Heck coupling, have become increasingly important in recent years in the synthesis processes of high-functional materials such as pharmaceutical intermediates and organic ELs.

[0003] Conventionally, the above platinum group metal catalysts have often been used in a homogeneous system and have shown high catalytic activity. However, there have been problems such as difficulty in recovering the catalyst and contamination of the product with the metal that is the catalyst. Therefore, heterogeneous catalysts have been developed in which the above catalyst is supported on a carrier to facilitate recovery of the catalyst and reduce metal contamination of the product. In recent years, methods have also been developed for continuously forming carbon-carbon bonds through a reaction substrate solution with a heterogeneous catalyst.

[0004] For example, Patent Document 1 reports a method for continuously forming a carbon-carbon bond using a catalyst in which palladium is supported on a porous silica carrier, but no actual reaction examples are disclosed.

[0005] Patent Documents 2 and 3 disclose a method for forming a carbon-carbon bond using a catalyst in which a platinum group metal is supported on the wall surface of a microchannel having a width of 1 mm and a depth of 20 μm. However, although the reason is not clear, in the disclosed reaction examples, water is not used as a solvent, and the flow rate of the reaction substrate solution is only carried out at 1 μm / min, which causes problems in environmental load and production efficiency.

[0006] Non-Patent Document 1 reports a method of continuously forming carbon-carbon bonds using a column filled with a catalyst in which palladium is supported on an organic carrier. However, complex chemical conversions are required to obtain the organic carrier, and for some reason, it is necessary to mix a large amount of diatomaceous earth when using the catalyst supporting palladium.

[0007] On the other hand, the present inventors have developed a catalyst in which a platinum group metal is supported on a non-particulate organic ion exchanger having three-dimensionally continuous pores, and have reported in Patent Document 4 and Patent Document 5 that this catalyst exhibits high catalytic activity in an aqueous solvent in a carbon-carbon bond formation reaction.

[0008] According to the methods disclosed in Patent Document 4 and Patent Document 5, by using a platinum group metal-supported catalyst in which a platinum group metal is supported on a non-particulate organic ion exchanger as a catalyst, a carbon-carbon bond formation reaction can be carried out in a high yield in an aqueous solvent.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Documents

[0010]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0011] However, in the reaction examples of Patent Document 4 and Patent Document 5, it has been shown that the aromatic halide as a raw material can carry out a carbon-carbon bond formation reaction in a high yield only in a highly reactive aromatic iodide, but in the case of an aromatic bromide, the yield is insufficient and the available raw materials are limited.

[0012] An object of the present invention is to provide a platinum group metal-supported catalyst column filled with a platinum group metal-supported catalyst capable of carrying out a carbon-carbon bond formation reaction in a high yield even in an aromatic bromide, and a carbon-carbon bond formation method for carrying out a reaction for generating a carbon-carbon bond using the platinum group metal-supported catalyst column.

Means for Solving the Problems

[0013] The present invention relates to a platinum group metal-supported catalyst column in which a platinum group metal-supported catalyst is filled in a filling container. , for the carbon-carbon bond formation reaction The platinum group metal-supported catalyst column, wherein the platinum group metal-supported catalyst is a platinum group metal-supported catalyst in which at least one of platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions is supported on an ion exchanger, and the ion exchanger is composed of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and it is a non-particulate organic porous ion exchanger in which ion exchange groups are distributed in the ion exchanger, and the supported amount of at least one of the platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions is in the range of 0.004 to 20% by weight in the dry state, and a platinum group metal capturing material is installed behind the platinum group metal-supported catalyst. , and the platinum group metal capturing material consists of a continuous skeleton phase and a continuous pore phase. The thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 mg equivalent / g, and it is a non-particulate organic porous ion exchanger in which ion exchange groups are distributed in the ion exchanger The platinum group metal-supported catalyst column is as described above.

[0014] In the platinum group metal-supported catalyst column, it is preferable that the platinum group metal-supported catalyst is a platinum group metal-supported catalyst in which at least one of platinum group metal ions and platinum group metal complex ions is supported on the ion exchanger.

[0017] The present invention relates to a method for forming a carbon-carbon bond by performing a reaction of (1) an aromatic halide and an organoboron compound, (2) a reaction of an aromatic halide and a compound having an alkynyl group at the terminal, or (3) a reaction of an aromatic halide and a compound having an alkenyl group, wherein a raw material liquid (i) containing the aromatic halide and the organoboron compound, a raw material liquid (ii) containing the aromatic halide and the compound having an alkynyl group at the terminal, or a raw material liquid (iii) containing the aromatic halide and the compound having an alkenyl group is said A method for forming a carbon-carbon bond, which comprises passing a reaction liquid through a platinum group metal-supported catalyst column through an introduction path and discharging the reaction liquid from a discharge path to carry out a carbon-carbon bond formation reaction.

[0018] In the method for forming a carbon-carbon bond, it is preferable to carry out the carbon-carbon bond formation reaction in the presence of an inorganic base.

[0019] In the method for forming a carbon-carbon bond, the raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is an inorganic base-dissolved raw material liquid in which a raw material and an inorganic base are dissolved in water or a hydrophilic solvent, and it is preferable to carry out the carbon-carbon bond formation reaction by passing the inorganic base-dissolved raw material liquid through the platinum group metal-supported catalyst column through an introduction path and discharging the reaction liquid from a discharge path.

[0020] In the carbon-carbon bond formation method, it is preferable that the raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is a hydrophobic solvent raw material liquid in which a raw material is dissolved in a hydrophobic organic solvent, and a mixture of the hydrophobic solvent raw material liquid and an aqueous inorganic base solution in which an inorganic base is dissolved is passed through the platinum group metal-supported catalyst column through an introduction path, and the reaction liquid is discharged from a discharge path to carry out a carbon-carbon bond formation reaction.

Advantages of the Invention

[0021] According to the present invention, it is possible to provide a platinum group metal-supported catalyst column filled with a platinum group metal-supported catalyst capable of carrying out a carbon-carbon bond formation reaction with a high yield even in an aromatic bromide, and a carbon-carbon bond formation method for carrying out a reaction for generating a carbon-carbon bond using the platinum group metal-supported catalyst column.

Brief Description of the Drawings

[0022]

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Embodiments for Carrying Out the Invention

[0023] Embodiments of the present invention will be described below. This embodiment is an example of carrying out the present invention, and the present invention is not limited to this embodiment.

[0024] <Platinum Group Metal-Supported Catalyst Column> The platinum group metal-supported catalyst column according to the embodiment of the present invention is a platinum group metal-supported catalyst column in which a platinum group metal-supported catalyst is filled in a filling container. The platinum group metal-supported catalyst is a platinum group metal-supported catalyst in which at least one of platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions is supported on an ion exchanger. And this ion exchanger consists of a continuous skeleton phase and a continuous pore phase. The thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, and the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g. It is a non-particulate organic porous ion exchanger in which ion exchange groups are distributed in the ion exchanger.

[0025] In the platinum group metal-supported catalyst column according to this embodiment, the loading amount of at least one of platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions is in the range of 0.004 to 20% by weight in the dry state. Also, a platinum group metal scavenger is installed downstream of the platinum group metal-supported catalyst. Hereinafter, "at least one of platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions" may be referred to as "platinum group metals, etc."

[0026] As a result of intensive studies by the present inventor, when using a platinum group metal-supported catalyst column in which a platinum group metal scavenger is installed downstream of a platinum group metal-supported catalyst in which platinum group metals, etc. are supported on a non-particulate organic porous ion exchanger, it was found that the yield also increases when using an aromatic bromide as a raw material in a so-called fixed-bed continuous flow carbon-carbon bond reaction.

[0027] It is considered that the yield is improved because the catalyst metal flowing out from the packed bed of the platinum group metal-supported catalyst on the front stage side is captured by the platinum group metal capture material on the rear stage side, the amount of the catalyst metal in the entire catalyst column is maintained, and the catalyst metal captured by the platinum group metal capture material also functions as a catalyst.

[0028] [Non-particulate organic porous ion exchanger] In the platinum group metal-supported catalyst used in the platinum group metal-supported catalyst column according to the present embodiment, the carrier on which the platinum group metal and the like are supported is a non-particulate organic porous ion exchanger. The non-particulate organic porous ion exchanger is obtained by introducing an ion exchange group into a monolithic organic porous body having a continuous skeleton phase and a continuous pore phase. The monolithic organic porous body has a large number of communication pores serving as flow paths between the skeletons. In the present specification, the "monolithic organic porous body" is simply referred to as "monolith", the "monolithic organic porous ion exchanger" is simply referred to as "monolith ion exchanger", and the "monolithic organic porous intermediate" which is an intermediate (precursor) in the production of the monolith is also simply referred to as "monolith intermediate".

[0029] The structure of this non-particulate organic porous ion exchanger is disclosed in JP-A-2002-306976, JP-A-2009-007550, JP-A-2009-062512, JP-A-2009-067982, and JP-A-2009-108294.

[0030] The non-particulate organic porous ion exchanger is composed of a continuous skeleton phase and a continuous pore phase. The thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger. The continuous skeleton phase and the continuous pore phase are observed by SEM images.

[0031] The thickness of the continuous skeleton of the non-particulate organic porous ion exchanger in the dry state ranges from 1 to 100 μm. The thickness of the continuous skeleton of the non-particulate organic porous ion exchanger in the dry state is determined by SEM observation. When the thickness of this continuous skeleton is less than 1 μm, the ion exchange capacity per unit volume may decrease, or the mechanical strength may decrease. When filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, especially when passing the solution at a high flow rate, the non-particulate organic porous ion exchanger may be deformed. When the thickness of this continuous skeleton exceeds 100 μm, the skeleton may become too thick, and the pressure loss during the passage of the raw material solution may increase.

[0032] The average diameter of the continuous pores of the non-particulate organic porous ion exchanger in the dry state ranges from 1 to 1000 μm. The average diameter of the continuous pores of the non-particulate organic porous ion exchanger in the dry state is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. When the average diameter of this continuous pore is less than 1 μm, when filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, the pressure loss during the passage of the solution may increase. When the average diameter of this continuous pore exceeds 1000 μm, when filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, the contact between the reaction solution and the monolith ion exchanger may be insufficient, and the catalytic activity may decrease.

[0033] The total pore volume of the non-particulate organic porous ion exchanger in the dry state ranges from 0.5 to 50 mL / g. The total pore volume of the non-particulate organic porous ion exchanger in the dry state is measured by the mercury intrusion method. When this total pore volume is less than 0.5 mL / g, when filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, the pressure loss during the passage of the solution may increase. When this total pore volume exceeds 50 mL / g, the mechanical strength of the non-particulate organic porous ion exchanger decreases. When filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, especially when passing the solution at a high flow rate, the monolith ion exchanger may be deformed, and the pressure loss during the passage of the solution may increase.

[0034] The ion exchange capacity per weight of the non-particulate organic porous ion exchanger in the dry state is in the range of 1 to 9 meq / g. The ion exchange capacity per weight of the non-particulate organic porous ion exchanger in the dry state is measured by methods such as neutralization titration and precipitation titration. If this ion exchange capacity is less than 1 meq / g, the amount of platinum group metal ions or platinum group metal complex ions that can be supported may decrease. If this ion exchange capacity exceeds 9 meq / g, the ion exchange group introduction reaction becomes severe, and oxidative degradation of the monolith may progress significantly.

[0035] In the non-particulate organic porous ion exchanger, it is preferable that the introduced ion exchange groups are distributed not only on the surface of the monolith but also inside the skeleton of the monolith, that is, in the organic porous ion exchanger, and more preferably, they are uniformly distributed. "The ion exchange groups are uniformly distributed in the organic porous ion exchanger" means that the distribution of the ion exchange groups is distributed on the surface and inside the skeleton of the organic porous ion exchanger at least on the μm order. The distribution status of the ion exchange groups is confirmed by using an electron probe microanalyzer (EPMA). When the ion exchange groups are distributed not only on the surface of the monolith but also inside the skeleton of the monolith, the physical and chemical properties of the surface and inside of the monolith can be made almost uniform, so the durability against swelling and shrinkage is improved.

[0036] The ion exchange groups introduced into the non-particulate organic porous ion exchanger are cation exchange groups or anion exchange groups. Examples of the cation exchange groups include carboxylic acid groups, iminodiacetic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphate ester groups. Examples of the anion exchange groups include quaternary ammonium groups such as trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group, and methyldihydroxyethylammonium group, and tertiary sulfonium groups and phosphonium groups.

[0037] In the non-particulate organic porous ion exchanger, the material constituting the continuous skeleton is an organic polymer material having a crosslinked structure. It is preferable that the crosslinked structure units are contained in an amount of 0.1 to 30 mol% based on all the constituent units constituting the organic polymer material, and more preferably 0.1 to 20 mol%.

[0038] There is no particular limitation on the type of the organic polymer material. Examples thereof include crosslinked polymers such as aromatic vinyl polymers such as polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, and polyvinylnaphthalene; polyolefins such as polyethylene and polypropylene; poly(halogenated polyolefins) such as polyvinyl chloride and polytetrafluoroethylene; nitrile-based polymers such as polyacrylonitrile; and (meth)acrylic-based polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate. The organic polymer material may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more polymers. Among these organic polymer materials, a crosslinked polymer of an aromatic vinyl polymer is preferable from the viewpoints of ease of forming a continuous structure, ease of introducing an ion exchange group, high mechanical strength, and high stability to acids or alkalis. In particular, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are mentioned as preferable materials.

[0039] [First to Fifth Monolithic Ion Exchangers] As a more specific embodiment of the non-particulate organic porous ion exchanger, for example, the following first monolithic organic porous ion exchanger (monolithic ion exchanger) to fifth monolithic organic porous ion exchanger (monolithic ion exchanger) can be mentioned. In the following description, the description of the same configuration as that of the above non-particulate organic porous ion exchanger will be omitted.

[0040] (First Monolithic Ion Exchanger) The first monolithic ion exchanger has a continuous macroporous structure with macropores connected to each other and common openings (mesopores) with an average diameter in the range of 1 to 1000 μm within the walls of the macropores. The total pore volume is in the range of 1 to 50 mL / g, and the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g. The ion exchange groups are distributed in the organic porous ion exchanger, and it is a monolithic ion exchanger.

[0041] As shown in Fig. 1, the first monolithic ion exchanger is a continuous macroporous structure having continuous macropores (pores). The first monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2002-306976.

[0042] The first monolithic ion exchanger has macropores connected to each other and common openings (mesopores) located within the walls of the macropores. The mesopores have overlapping portions where the macropores overlap. The overlapping portion of the mesopores preferably has an average diameter in the range of 1 to 1000 μm in the dry state, more preferably in the range of 10 to 200 μm, and even more preferably in the range of 20 to 200 μm. The average diameter of the openings of the first monolith in the dry state is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method.

[0043] Most of such a first monolithic ion exchanger has an open pore structure in which the voids formed by macropores and mesopores serve as flow channels. If the average diameter of the overlapping part of the mesopores in the dry state is less than 1 μm, when a platinum group metal-supported catalyst is filled in a column and a reaction solution is passed through, the pressure loss during the liquid flow may become extremely large. If the average diameter of the overlapping part of the mesopores in the dry state exceeds 1000 μm, when a platinum group metal-supported catalyst is filled in a column and a reaction solution is passed through, the contact between the reaction solution and the monolithic ion exchanger may be insufficient, and the catalytic activity may decrease. The overlap of macropores and macropores is, for example, 1 to 12 in one macropore, and many are 3 to 10. Since the first monolithic ion exchanger is the above-described continuous macroporous structure, it can form groups of macropores and groups of common pores almost uniformly, and compared with the particle-aggregated porous body described in JP-A-8-252579 and the like, the pore volume and specific surface area can be significantly increased.

[0044] The total pore volume per unit weight of the first monolithic ion exchanger in the dry state is preferably in the range of 1 to 50 mL / g, and more preferably in the range of 2 to 30 mL / g. If the total pore volume per unit weight in the dry state is less than 1 mL / g, when a platinum group metal-supported catalyst is filled in a column and a reaction solution is passed through, the pressure loss during the liquid flow may increase, and furthermore, the permeation amount per unit cross-sectional area may decrease, and the processing capacity may decrease. If the total pore volume per unit weight in the dry state exceeds 50 mL / g, the mechanical strength may decrease, and when a platinum group metal-supported catalyst is filled in a column and a reaction solution is passed through, the monolithic ion exchanger may be deformed especially when the liquid is passed at a high flow rate.

[0045] The ion exchange capacity per unit weight in the dry state is as described above. Also, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0046] (Method for producing the first monolithic ion exchanger) The first monolithic ion exchanger can be produced, for example, by the following method.

[0047] For example, first, an oil-soluble monomer containing no ion-exchange group, a surfactant, water, and, if necessary, a polymerization initiator are mixed to obtain a water-in-oil emulsion. Next, this water-in-oil emulsion can be polymerized to form the first monolith.

[0048] The oil-soluble monomer containing no ion-exchange group used in the production of the first monolith refers to a monomer that contains no ion-exchange group, has low solubility in water, and is lipophilic. Such monomers include, for example, styrene, α-methylstyrene, vinylbenzyl chloride, ethylene, propylene, vinyl chloride, vinyl bromide, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, butanediol diacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, ethylene glycol dimethacrylate, etc. These monomers can be used alone or in combination of two or more. However, it is preferable to select at least one component of the oil-soluble monomer as a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate, and set its content in the total oil-soluble monomers in the range of, for example, 0.3 to 10 mol%, preferably in the range of 0.3 to 5 mol%. This is preferable in that an ion-exchange group can be quantitatively introduced in a later step and practically sufficient mechanical strength can be ensured.

[0049] The surfactant used in the production of the first monolith may be any surfactant that can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion-exchange group is mixed with water, and there are no particular restrictions. Surfactants include, for example, nonionic surfactants such as sorbitan monooleate, sorbitan monolaurate, polyoxyethylene nonylphenyl ether; anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, sodium dioctyl sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; and amphoteric surfactants such as lauryldimethylbetaine. These surfactants can be used alone or in combination of two or more. A water-in-oil emulsion refers to an emulsion in which the oil phase is the continuous phase and water droplets are dispersed therein. The addition amount of the surfactant may be, for example, in the range of about 2 to 70% with respect to the total amount of the oil-soluble monomer and the surfactant. In order to control the bubble shape and size of the monolith, alcohols such as methanol and stearyl alcohol; carboxylic acids such as stearic acid; hydrocarbons such as octane, dodecane, and toluene; and cyclic ethers such as tetrahydrofuran and dioxane can also coexist in the system.

[0050] In the production of the first monolith, when forming the monolith by polymerization, the polymerization initiator that is used as necessary is preferably a compound that generates radicals by heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and tetramethylthiuram disulfide. However, in some cases, there are systems in which polymerization proceeds only by heating or only by light irradiation without adding a polymerization initiator, and in such systems, it is not necessary to add a polymerization initiator.

[0051] In the production of the first monolith, various polymerization conditions for polymerizing the water-in-oil emulsion can be selected depending on the type of monomer, initiator system, etc. When azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, etc. are used as the polymerization initiator, for example, in a sealed container under an inert atmosphere, for example, at 30 to 100°C for 1 to 48 hours, the polymerization can be performed, for example, in a sealed container under an inert atmosphere, at 0 to 30°C for 1 to 48 hours. After the polymerization is completed, the contents are taken out and subjected to Soxhlet extraction with a solvent such as isopropanol to remove unreacted monomers and residual surfactants, to obtain the first monolith.

[0052] Methods for introducing ion exchange groups into the first monolith include, for example, the following methods (1) and (2). (1) Instead of a monomer that does not contain an ion exchange group, a monomer that contains an ion exchange group, for example, the oil-soluble monomer that does not contain an ion exchange group, is polymerized with a monomer to which an ion exchange group has been introduced, to produce a monolith ion exchanger in one step. (2) A monomer that does not contain an ion exchange group is polymerized to form the first monolith, and then an ion exchange group is introduced.

[0053] As a method for introducing an ion-exchange group into the first monolith, there are no particular restrictions, and known methods such as polymer reactions and graft polymerization can be used. For example, as a method for introducing a quaternary ammonium group, if the monolith is a styrene-divinylbenzene copolymer or the like, a method of introducing a chloromethyl group with chloromethyl methyl ether or the like and then reacting with a tertiary amine for introduction; a method of producing the monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine for introduction; a method of introducing a radical initiator or a chain transfer group into the monolith and graft-polymerizing N,N,N-trimethylammonium ethyl acrylate or N,N,N-trimethylammonium propyl acrylamide; similarly, a method of graft-polymerizing glycidyl methacrylate and then introducing a quaternary ammonium group by functional group conversion, etc. can be mentioned. For example, as a method for introducing a sulfonic acid group, if the monolith is a styrene-divinylbenzene copolymer or the like, a method of sulfonating with chlorosulfuric acid, concentrated sulfuric acid, or fuming sulfuric acid; a method of introducing a radical initiator or a chain transfer group onto the surface and inside of the skeleton of the monolith and graft-polymerizing sodium styrenesulfonate or acrylamide-2-methylpropanesulfonic acid; similarly, a method of graft-polymerizing glycidyl methacrylate and then introducing a sulfonic acid group by functional group conversion, etc. can be mentioned.

[0054] (The second monolith ion exchanger) The second monolith ion exchanger is a monolith ion exchanger in which organic polymer particles in the range of an average particle diameter of 1 to 50 μm are aggregated to form a three-dimensionally continuous skeleton portion, and three-dimensionally continuous pores in the range of an average diameter of 20 to 100 μm are present between the skeletons. The total pore volume is in the range of 1 to 10 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and the ion-exchange groups are distributed in the organic porous ion exchanger.

[0055] As shown in Fig. 2, the second monolith ion exchanger is a particle-aggregated structure in which particles are aggregated. The second monolith ion exchanger and its production method are disclosed in JP-A-2009-007550.

[0056] The second monolithic ion exchanger has a three-dimensionally continuous skeletal portion formed by aggregation of organic polymer particles having a crosslinked structural unit and having an average particle diameter preferably in the range of 1 to 50 μm, more preferably in the range of 1 to 30 μm in the dry state. The second monolithic ion exchanger has three-dimensionally continuous pores (continuous pores) having an average diameter preferably in the range of 20 to 100 μm, more preferably in the range of 20 to 90 μm in the dry state between the continuous skeletons. An SEM photograph of an arbitrarily extracted portion of the cross section of the second monolithic ion exchanger in the dry state is taken, the diameters of the organic polymer particles of all the particles in the SEM photograph are measured, and their average value is taken as the average particle diameter. The average diameter of the continuous pores in the dry state is determined by the mercury intrusion method, similar to the first monolithic ion exchanger.

[0057] When the average particle diameter of the organic polymer particles is less than 1 μm in the dry state, the average diameter of the continuous pores between the skeletons may become less than 20 μm in the dry state. When the average particle diameter of the organic polymer particles exceeds 50 μm, the pressure loss may increase when the platinum group metal-supported catalyst is packed in the column and the reaction liquid is passed through. Further, when the average diameter of the above-described continuous pores is less than 20 μm in the dry state, the pressure loss when the reaction liquid is permeated may increase when the platinum group metal-supported catalyst is packed in the column and the reaction liquid is passed through. When the average diameter of the above-described continuous pores exceeds 100 μm in the dry state, the contact between the reaction liquid and the monolithic ion exchanger may become insufficient when the platinum group metal-supported catalyst is packed in the column and the reaction liquid is passed through.

[0058] The total pore volume per unit weight of the second monolithic ion exchanger in the dry state is preferably in the range of 1 to 10 mL / g. When the total pore volume is less than 1 mL / g, when filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, the pressure loss during liquid passage may become large. Furthermore, the permeation amount per unit cross-sectional area may become small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, the monolithic ion exchanger may be deformed particularly when passing the liquid at a high flow rate.

[0059] The ion exchange capacity per unit weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0060] (Method for producing the second monolithic ion exchanger) The second monolithic ion exchanger can be produced, for example, by the following method.

[0061] For example, a vinyl monomer, a specific amount of a cross-linking agent, an organic solvent, and a polymerization initiator are mixed and polymerized in a stationary state to obtain a second monolith.

[0062] The vinyl monomer used for producing the second monolith is the same as the monomer used for producing the first monolith.

[0063] The crosslinking agent used for producing the second monolith preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Examples of the crosslinking agent include divinylbenzene, divinylbiphenyl, and ethylene glycol dimethacrylate. These crosslinking agents can be used alone or in combination of two or more. Preferred crosslinking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl in terms of high mechanical strength and stability against hydrolysis. The amount of the crosslinking agent used relative to the total amount of the vinyl monomer and the crosslinking agent ({crosslinking agent / (vinyl monomer + crosslinking agent)} × 100) is, for example, in the range of 1 to 5 mol%, preferably in the range of 1 to 4 mol%.

[0064] The organic solvent used for producing the second monolith is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but hardly dissolves the polymer formed by polymerization of the vinyl monomer. In other words, it is a poor solvent for the polymer formed by polymerization of the vinyl monomer. Examples of this organic solvent include alcohols such as methanol, butanol, and octanol when the vinyl monomer is styrene; chain ethers such as diethyl ether and ethylene glycol dimethyl ether; and chain saturated hydrocarbons such as hexane, octane, and decane.

[0065] The polymerization initiator used for the production of the second monolith is preferably a compound that generates radicals by heat and light irradiation. The polymerization initiator is preferably oil-soluble. Examples of the polymerization initiator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide, and the like. The amount of the polymerization initiator used relative to the total amount of the vinyl monomer and the crosslinking agent ({polymerization initiator / (vinyl monomer + crosslinking agent)} × 100) is, for example, in the range of about 0.01 to 5 mol%.

[0066] In the production of the second monolith, when, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as the polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be heated and polymerized at, for example, 30 to 100 °C for 1 to 48 hours. After the polymerization is completed, the content is taken out, and for the purpose of removing the unreacted vinyl monomer and the organic solvent, for example, it can be extracted with a solvent such as acetone to obtain the second monolith.

[0067] In the production of the second monolith, organic polymer particles with an average particle diameter of 1 to 50 μm can be aggregated by adjusting polymerization conditions such as increasing the crosslinking agent, increasing the monomer concentration, and raising the temperature. By setting the amount of the crosslinking agent used relative to the total amount of the vinyl monomer and the crosslinking agent to a specific amount, three-dimensionally continuous pores with an average diameter of 20 to 100 μm can be formed between the skeletons. By polymerizing under conditions such that the amount of the organic solvent used ({organic solvent / (organic solvent + monomer + crosslinking agent)} × 100) relative to the total amount of the organic solvent, monomer, and crosslinking agent used is, for example, in the range of 30 to 80% by weight, preferably in the range of 40 to 70% by weight, the total pore volume of the monolith can be made 1 to 5 mL / g.

[0068] The method for introducing an ion exchange group into the second monolith is the same as the method for introducing an ion exchange group into the first monolith.

[0069] (The third monolith ion exchanger) The third monolith ion exchanger is a continuous macroporous structure in which bubble-like macropores overlap with each other, and the overlapping part forms an opening in the range of an average diameter of 30 to 300 μm. The total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, the ion exchange groups are distributed in the organic porous ion exchanger, and in the SEM image of the cross-section of the continuous macroporous structure, the area of the skeleton part appearing in the cross-section is in the range of 25 to 50% in the image area. It is a monolith ion exchanger.

[0070] As shown in FIG. 3, the third monolith ion exchanger is a continuous macroporous structure, similar to the first monolith ion exchanger. The third monolith ion exchanger and its production method are disclosed in JP-A-2009-062512.

[0071] The continuous pores have overlapping portions where the macropores overlap each other. The overlapping portion preferably has an average diameter in the range of 30 to 300 μm, more preferably in the range of 30 to 200 μm, and even more preferably in the range of 40 to 100 μm in the dry state. This average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. If the average diameter of the openings in the dry state is less than 30 μm, when the platinum group metal-supported catalyst is packed in a column and the reaction liquid is passed through, the pressure loss during liquid passage may become large. If it exceeds 300 μm, the contact between the reaction liquid and the monolith ion exchanger may be insufficient.

[0072] In the third monolith ion exchanger, in the SEM image of the cross-section of the continuous macroporous structure in the dry state, the area of the skeleton portion appearing on the cross-section is in the range of, for example, 25 to 50% in the image area, preferably in the range of 25 to 45%. If the area of the skeleton portion appearing on the cross-section is less than 25% in the image area, the skeleton becomes thin and the mechanical strength decreases. When the platinum group metal-supported catalyst is packed in a column and the reaction liquid is passed through, especially when the liquid is passed at a high flow rate, the monolith ion exchanger may be deformed. If the area of the skeleton portion appearing on the cross-section exceeds 50% in the image area, the skeleton becomes too thick, and when the platinum group metal-supported catalyst is packed in a column and the reaction liquid is passed through, the pressure loss during liquid passage may increase.

[0073] The conditions for obtaining SEM images only need to be those under which the skeletal parts appearing on the cross-section of the cut surface are clearly shown. For example, the magnification is 100 - 600, and the photo area is approximately 150 mm × 100 mm. The SEM observation is preferably performed with three or more images taken at different cutting locations or shooting locations on an arbitrary cut surface of the third monolithic ion exchanger excluding subjectivity. The third monolithic ion exchanger to be cut is in a dry state. The skeletal parts on the cut surface in the SEM image will be described with reference to FIGS. 3 and 4. In FIGS. 3 and 4, those that are generally irregularly shaped and appear in cross-section are the "skeletal parts appearing in the cross-section (reference numeral 12)". The circular holes shown in FIG. 3 are openings (mesopores), and those with a relatively large curvature or curved surface are macropores (reference numeral 13 in FIG. 4). The area of the skeletal part appearing in the cross-section of FIG. 4 is 28% in the rectangular image area 11.

[0074] As a method for measuring the area of the skeletal parts appearing in the cross-section of the cut surface in the SEM image, after identifying the skeletal parts by performing known computer processing or the like, calculation methods by automatic calculation or manual calculation using a computer or the like can be mentioned. As manual calculation, a method of replacing an irregularly shaped object with an aggregate of quadrilaterals, triangles, circles, trapezoids, etc., and stacking them to obtain the area can be mentioned.

[0075] The total pore volume per unit weight of the third monolithic ion exchanger in the dry state is preferably in the range of 0.5 - 10 mL / g, more preferably in the range of 0.8 - 8 mL / g. When the total pore volume is less than 0.5 mL / g, when filling the column with the platinum group metal-supported catalyst and passing the reaction solution, the pressure loss during liquid passing may become large. Furthermore, the amount of permeating fluid per unit cross-sectional area may become small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when filling the column with the platinum group metal-supported catalyst and passing the reaction solution, especially when passing the liquid at a high flow rate, the monolithic ion exchanger may be deformed. Furthermore, the contact efficiency between the reaction solution and the monolithic ion exchanger may decrease.

[0076] The ion exchange capacity per weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0077] (Method for producing the third monolithic ion exchanger) The third monolithic ion exchanger can be produced, for example, by the following method.

[0078] For example, first, an oil-in-water emulsion is prepared by stirring a mixture of an oil-soluble monomer not containing an ion exchange group, a surfactant, and water. Next, the third monolith can be obtained by performing the following steps I, II, and III. In step I, the oil-in-water emulsion is polymerized to obtain a monolithic organic porous intermediate (hereinafter also referred to as the monolith intermediate (3)) having a continuous macroporous structure with a total pore volume in the range of 5 to 16 mL / g, for example. In step II, a mixture containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent dissolve but the polymer produced by the polymerization of the vinyl monomer does not dissolve, and a polymerization initiator is prepared. In step III, the mixture obtained in step II is polymerized under standing and in the presence of the monolith intermediate (3) obtained in step I to obtain a third monolith having a skeleton thicker than the skeleton of the monolith intermediate (3).

[0079] Step I is the same as the method for producing the first monolithic ion exchanger.

[0080] The monolith intermediate (3) obtained in step I has a continuous macroporous structure. When this is coexisted in the polymerization system, a porous structure having a thick skeleton can be formed using the structure of the monolith intermediate (3) as a mold. The crosslink density of the polymer material preferably contains crosslinked structural units in the range of, for example, 0.3 to 10 mol%, preferably 0.3 to 5 mol%, based on all the constituent units constituting the polymer material of the monolith intermediate (3).

[0081] The total pore volume per weight of the monolithic intermediate (3) obtained in Step I in the dry state is, for example, in the range of 5 to 16 mL / g, preferably in the range of 6 to 16 mL / g. To make the total pore volume of the monolithic intermediate (3) within the above numerical range, the ratio of monomer to water may be, for example, in the range of approximately 1:5 to 1:20.

[0082] The monolithic intermediate (3) obtained in Step I has an average diameter of openings (mesopores), which are the overlapping parts of macropores, in the dry state in the range of, for example, 20 to 200 μm.

[0083] Step II is a step of preparing a mixture containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent dissolve but the polymer formed by the polymerization of the vinyl monomer does not dissolve, and a polymerization initiator. Note that the order of Step I and Step II may be either one first.

[0084] The vinyl monomer used in Step II may be any lipophilic vinyl monomer containing a polymerizable vinyl group in the molecule and having high solubility in the organic solvent, and it is preferable to select a vinyl monomer that produces the same type or a similar polymer material as the monolithic intermediate (3) coexisting in the above polymerization system. Specific examples of these vinyl monomers are the same as those used in the production of the first monolith.

[0085] The addition amount of the vinyl monomer used in Step II is, based on the monolithic intermediate (3) coexisting during polymerization, in the range of, for example, 3 to 50 times by weight, preferably in the range of 4 to 40 times by weight.

[0086] The crosslinking agent used in Step II is the same as the crosslinking agent used in the production of the second monolith.

[0087] The organic solvent used in Step II is the same as the organic solvent used in the production of the second monolith. The amount of these organic solvents used is preferably such that the concentration of the above vinyl monomer is, for example, 30 to 80% by weight.

[0088] The polymerization initiator used in the II process is the same as the polymerization initiator used in the production of the second monolith.

[0089] In the III process, for example, the mixture obtained in the II process is polymerized under standing and in the presence of the monolith intermediate (3) obtained in the I process, and a third monolith having a skeleton thicker than the skeleton of the monolith intermediate (3) can be obtained. When the monolith intermediate (3) with a continuous macroporous structure is present in the polymerization system, a third monolith can be obtained.

[0090] In the III process, for example, in a reaction vessel, the monolith intermediate (3) is placed in a state impregnated with the mixture (solution). The mixing ratio of the mixture obtained in the II process and the monolith intermediate (3) may be adjusted, for example, so that the addition amount of the vinyl monomer is in the range of 3 to 50 times by weight, preferably 4 to 40 times by weight, based on the monolith intermediate (3). In the reaction vessel, the vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the standing monolith intermediate, and polymerization proceeds within the skeleton of the monolith intermediate (3).

[0091] In the III process, various polymerization conditions are selected depending on the type of monomer, the type of polymerization initiator, etc. For example, when 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as the polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be heated and polymerized at 30 to 100 °C for 1 to 48 hours. By heat polymerization, the vinyl monomer and the cross-linking agent adsorbed and distributed on the skeleton of the monolith intermediate (3) polymerize within the skeleton, and the skeleton can be thickened. After the polymerization is completed, the content is taken out, and for the purpose of removing unreacted vinyl monomer and organic solvent, it can be extracted with a solvent such as acetone to obtain the third monolith.

[0092] The third monolithic ion exchanger can be obtained, for example, by performing a step IV of introducing an ion exchange group into the third monolith obtained in step III. The method of introducing an ion exchange group into the third monolith is the same as the method of introducing an ion exchange group into the first monolith.

[0093] (The fourth monolithic ion exchanger) The fourth monolithic ion exchanger is a co-continuous structure composed of a three-dimensionally continuous skeleton with a thickness in the range of 1 to 60 μm of a continuous skeleton composed of an aromatic vinyl polymer containing a crosslinked structural unit in the range of 0.1 to 5.0 mol% among all the structural units into which an ion exchange group is introduced, and three-dimensionally continuous pores with an average diameter in the range of 10 to 200 μm between the skeletons. The total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and it is a monolithic ion exchanger in which the ion exchange groups are distributed in the organic porous ion exchanger.

[0094] As shown in FIGS. 5 and 6, the fourth monolithic ion exchanger has a continuous skeleton phase 1 (continuous skeleton) and a continuous pore phase 2 (continuous pores), and they are intertwined to form a co-continuous structure 10 that is three-dimensionally continuous together. The pore phase 2 has higher continuity and almost no bias in its size compared to the first and second monoliths described above. The fourth monolithic ion exchanger is considered to have high mechanical strength because its skeleton is thick. The fourth monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-067982.

[0095] The continuous skeleton is composed of a vinyl polymer (such as an aromatic vinyl polymer) containing a crosslinked structural unit in the range of 0.1 to 5.0 mol% among all the constituent units into which an ion exchange group is introduced, and the thickness of the continuous skeleton is three-dimensionally continuous in the range of, for example, 1 to 60 μm, preferably 3 to 58 μm in the dry state. If the crosslinked structural unit is less than 0.1 mol%, the mechanical strength may be insufficient. If it exceeds 5.0 mol%, the structure of the porous body may easily deviate from the co-continuous structure. If the thickness of the continuous skeleton is less than 1 μm in the dry state, when the platinum group metal-supported catalyst is filled in the column and the reaction liquid is passed through, the monolith ion exchanger may be deformed especially when passing through at a high flow rate. If the thickness of the continuous skeleton exceeds 60 μm in the dry state, the skeleton becomes too thick, and when the platinum group metal-supported catalyst is filled in the column and the reaction liquid is passed through, the pressure loss during liquid passage may increase.

[0096] The continuous pores are three-dimensionally continuous between the continuous skeletons in the range of, for example, an average diameter of 10 to 200 μm, preferably 15 to 180 μm in the dry state. If the average diameter of the continuous pores is less than 10 μm in the dry state, when the platinum group metal-supported catalyst is filled in the column and the reaction liquid is passed through, the pressure loss during liquid passage may become large. If the average diameter exceeds 200 μm, when the platinum group metal-supported catalyst is filled in the column and the reaction liquid is passed through, the contact between the reaction liquid and the monolith ion exchanger may be insufficient.

[0097] The above-mentioned average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. The thickness of the continuous skeleton in the dry state is determined by SEM observation of the fourth monolith ion exchanger in the dry state. Specifically, SEM observation of the fourth monolith ion exchanger in the dry state is performed at least three times, the thickness of the skeleton in the obtained images is measured, and their average value is taken as the thickness of the continuous skeleton. Note that the skeleton is rod-shaped and has a circular cross-sectional shape, but those with an elliptical cross-sectional shape or other non-uniform cross-sectional shapes may also be included. In this case, the thickness is the average of the minor axis and the major axis.

[0098] The total pore volume per weight of the fourth monolithic ion exchanger in the dry state is, for example, in the range of 0.5 to 10 mL / g. If the total pore volume is less than 0.5 mL / g, when filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, the pressure loss during liquid passing may become large, and furthermore, the amount of permeating fluid per unit cross-sectional area may become small, resulting in a decrease in processing capacity. If the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when filling a column with a platinum group metal-supported catalyst and passing a reaction solution through it, the monolithic ion exchanger may be deformed especially when passing the liquid at a high flow rate. Furthermore, the contact efficiency between the reaction solution and the monolithic ion exchanger may decrease.

[0099] The vinyl polymer (aromatic vinyl polymer) constituting the continuous skeleton includes, for example, polystyrene, poly(α-methylstyrene), polyvinylbenzyl chloride, and the like. The above polymers may be polymers obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or polymers obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or may be a blend of two or more polymers. Among these organic polymer materials, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred in terms of the ease of forming a co-continuous structure, the ease of introducing ion exchange groups, high mechanical strength, and high stability against acids or alkalis.

[0100] The ion exchange capacity per weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0101] (Method for Producing the Fourth Monolithic Ion Exchanger) The fourth monolithic ion exchanger can be produced, for example, by the following method.

[0102] For example, the fourth monolith can be obtained by performing the following steps I to III after adjusting the water-in-oil emulsion. In step I, for example, the water-in-oil emulsion is polymerized to obtain a monolithic organic porous intermediate (hereinafter referred to as monolith intermediate (4)) having a continuous macroporous structure with a total pore volume of more than, for example, 16 mL / g and 30 mL / g or less. In step II, for example, a mixture containing an aromatic vinyl monomer, a crosslinking agent in the range of, for example, 0.3 to 5 mol% in a fully oil-soluble monomer having at least two or more vinyl groups in one molecule, an organic solvent in which the aromatic vinyl monomer and the crosslinking agent dissolve but the polymer formed by polymerization of the aromatic vinyl monomer does not dissolve, and a polymerization initiator is prepared. In step III, for example, the mixture obtained in step II is polymerized under standing in the presence of the monolith intermediate (4) obtained in step I to obtain the fourth monolith.

[0103] Step I in the method for producing the fourth monolith is the same as the method for producing the first monolith ion exchanger.

[0104] The monolith intermediate (4) obtained in step I is, for example, an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. The crosslinking density of this polymer material contains crosslinked structure units in the range of, for example, 0.1 to 5 mol%, preferably 0.3 to 3 mol% with respect to all the constituent units constituting the polymer material.

[0105] The type of the polymer material of the monolith intermediate (4) is the same as the type of the polymer material of the monolith intermediate (3) in the method for producing the third monolith.

[0106] The total pore volume per weight of the monolith intermediate (4) obtained in step I in the dry state is more than, for example, 16 mL / g and 30 mL / g or less, preferably more than 16 mL / g and 25 mL / g or less. As shown in FIG. 7, the monolith intermediate (4) has a skeleton close to a rod shape. When this is allowed to coexist in the polymerization system, a porous body having a co-continuous structure can be formed using the structure of the monolith intermediate (4) as a mold.

[0107] The monolithic intermediate (4) obtained in step I has an average diameter of the openings (mesopores), which are the overlapping parts of macropores, in the range of, for example, 5 to 100 μm in the dry state.

[0108] Step II in the method for producing the fourth monolith is, for example, a step of preparing a mixture containing an aromatic vinyl monomer, a crosslinking agent in the range of, for example, 0.3 to 5 mol% in all oil-soluble monomers having at least two or more vinyl groups in one molecule, an organic solvent in which the aromatic vinyl monomer and the crosslinking agent are soluble but the polymer formed by polymerization of the aromatic vinyl monomer is insoluble, and a polymerization initiator. The order of step I and step II may be either one first.

[0109] The aromatic vinyl monomer used in step II is not particularly limited as long as it contains a polymerizable vinyl group in the molecule and is a lipophilic aromatic vinyl monomer having high solubility in the organic solvent. However, it is preferable to select a vinyl monomer that produces the same type or a similar polymer material as the monolithic intermediate (4) coexisting in the above polymerization system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, vinylnaphthalene, and the like. These monomers can be used alone or in combination of two or more. Preferred aromatic vinyl monomers used are styrene, vinylbenzyl chloride, and the like.

[0110] The addition amount of the aromatic vinyl monomer used in step II is in the range of, for example, 5 to 50 times by weight, preferably 5 to 40 times by weight, based on the monolithic intermediate (4) coexisting during polymerization.

[0111] The crosslinking agent used in the II process preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent used is, for example, in the range of 0.3 to 5 mol%, particularly in the range of 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the crosslinking agent (total oil-soluble monomers). It is preferable that the amount of the crosslinking agent used is substantially equal to the crosslinking density of the monolith intermediate (4) coexisting during the vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too far apart, a deviation in the crosslinking density distribution may occur in the produced monolith, and when introducing an ion exchange group, cracks may easily occur during the ion exchange group introduction reaction.

[0112] The organic solvent used in the II process is, for example, an organic solvent that dissolves aromatic vinyl monomers and crosslinking agents but does not dissolve the polymers produced by the polymerization of aromatic vinyl monomers. In other words, it is a poor solvent for the polymers produced by the polymerization of aromatic vinyl monomers. For example, when the aromatic vinyl monomer is styrene, the organic solvent can be alcohols such as methanol, butanol, and octanol; chain (poly)ethers such as diethyl ether, polyethylene glycol, and polypropylene glycol; chain saturated hydrocarbons such as hexane, heptane, and octane; esters such as ethyl acetate, isopropyl acetate, and ethyl propionate. Also, even if it is a good solvent for polystyrene such as dioxane, THF, or toluene, it can be used as an organic solvent when used together with the above poor solvent and the amount used is small. The amount of these organic solvents used can be such that the concentration of the above aromatic vinyl monomer is, for example, 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the concentration of the aromatic vinyl monomer is less than 30% by weight, the polymerization rate may decrease, or the monolith structure after polymerization may deviate from the range of the fourth monolith. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may proceed too far.

[0113] The polymerization initiator used in the II process in the method for producing the fourth monolith is the same as the polymerization initiator used in the II process in the method for producing the third monolith.

[0114] The III process in the method for producing the fourth monolith is, for example, a process in which the mixture obtained in the II process is polymerized under standing and in the presence of the monolith intermediate (4) obtained in the I process, changing the continuous macroporous structure of the monolith intermediate (4) to a co-continuous structure to obtain the fourth monolith, which is a co-continuous structure monolith.

[0115] In the III process, for example, in a reaction vessel, the monolith intermediate (4) is placed in a state of being impregnated with a mixture (solution). As described above, the mixing ratio of the mixture obtained in the II process and the monolith intermediate (4) should be adjusted so that the addition amount of the aromatic vinyl monomer is, for example, in the range of 5 to 50 times by weight, preferably 5 to 40 times by weight, with respect to the monolith intermediate (4). Thereby, a fourth monolith with a co-continuous structure can be obtained in which pores of appropriate size are three-dimensionally continuous and a thick skeleton is three-dimensionally continuous. In the reaction vessel, the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the stationary monolith intermediate (4), and polymerization proceeds within the skeleton of the monolith intermediate (4).

[0116] The polymerization conditions in the III process in the production method of the fourth monolith are the same as the description of the polymerization conditions in the III process in the production method of the third monolith. The fourth monolith ion exchanger can be obtained by performing a step IV of introducing an ion exchange group into the fourth monolith obtained in the III process. The method of introducing an ion exchange group into the fourth monolith is the same as the method of introducing an ion exchange group into the first monolith.

[0117] (The fifth monolith ion exchanger) The fifth monolith ion exchanger consists of a continuous skeleton phase and a continuous pore phase. The skeleton has a plurality of protrusions with a size in the range of 4 to 40 μm formed on the surface of a plurality of particulate bodies or organic porous bodies with a diameter in the range of 4 to 40 μm fixed on the surface. The average diameter of the continuous pores is in the range of 10 to 200 μm, the total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 mg equivalent / g, and the ion exchange groups are distributed in the organic porous ion exchanger, which is a monolith ion exchanger.

[0118] The fifth monolithic ion exchanger is a composite structure having an organic porous body with a continuous skeletal phase and a continuous pore phase, and further having a plurality of particulate bodies or a plurality of protrusions, and is a composite structure having a large number of particulate bodies or a large number of protrusions. The fifth monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-108294.

[0119] The plurality of particulate bodies are fixed to the skeletal surface of the organic porous body, and their diameter is, for example, in the range of 4 to 40 μm. The plurality of protrusions are formed on the skeletal surface of the organic porous body, and their size is, for example, in the range of 4 to 40 μm in the dry state. The diameter of the particulate body or the size of the protrusion is preferably in the range of 4 to 30 μm, and more preferably in the range of 4 to 20 μm. In the present specification, the "particulate body" and the "protrusion" are collectively referred to as "particulate bodies etc.".

[0120] The average diameter of the continuous pores in the dry state is preferably in the range of 10 to 200 μm.

[0121] The continuous skeletal phase and the continuous pore phase of the fifth monolithic ion exchanger are observed by SEM images. Examples of the basic structure of the fifth monolithic ion exchanger include a continuous macropore structure and a co-continuous structure. The skeletal phase of the fifth monolithic ion exchanger appears as a columnar continuum, a concave wall continuum, or a composite thereof, and has a shape clearly different from that of particulate or protrusion shapes.

[0122] The fifth monolithic ion exchanger includes a fifth-1 monolithic ion exchanger or a fifth-2 monolithic ion exchanger. The fifth-1 monolithic ion exchanger is a continuous macroporous structure in which bubble-like macropores overlap with each other, and the overlapping part forms an opening with an average diameter in the range of, for example, 10 to 120 μm in the dry state. The fifth-2 monolithic ion exchanger is a co-continuous structure composed of a three-dimensionally continuous skeleton with a thickness of the continuous skeleton in the dry state in the range of, for example, 0.8 to 40 μm, and three-dimensionally continuous pores with an average diameter in the range of, for example, 8 to 80 μm between the skeletons in the dry state. The monoliths before the ion exchange groups are introduced into the fifth-1 and fifth-2 monolithic ion exchangers are called the fifth-1 and fifth-2 monoliths. The average diameter and the thickness of the continuous skeleton in the dry state described above are determined by the same measurement method as that of the fourth monolithic ion exchanger.

[0123] As shown in (A) to (E) in Fig. 8, the protruding projections from the skeleton surface 21 are the projections 22a to 22e. As shown in (A), the projection 22a has a shape close to granular. As shown in (B), the projection 22b is hemispherical. As shown in (C), the projection 22c has a shape like a bulge on the skeleton surface. As shown in (D), the length of the projection 22d in the planar direction of the skeleton surface 21 is longer than the length in the direction perpendicular to the skeleton surface 21 of the projection 22d. As shown in (E), the projection 22e has a shape protruding in a plurality of directions. The size of the projection is the length of the part where the width in the SEM image of each individual projection is the largest. As shown in Fig. 9, in the fifth monolithic ion exchanger, a plurality of projections are formed on the skeleton surface of the organic porous body.

[0124] In the fifth monolithic ion exchanger, in the whole particle body etc., the proportion occupied by particle bodies etc. in the range of 4 to 40 μm in the dry state is, for example, 70% or more, preferably 80% or more. The proportion occupied by the aforementioned particle bodies etc. refers to the number ratio of particle bodies etc. of a specific size in the dry state to the number of the whole particle body etc. Also, the surface of the skeletal phase is coated, for example, by 40% or more, preferably 50% or more, with the whole particle body etc. Note that the coating ratio of the surface of the skeletal layer by the whole particle body etc. refers to the area ratio on the SEM image when observing the surface by SEM, that is, the area ratio when the surface is viewed in plan view. When the size of the particles covering the wall surface and the skeleton deviates from the above range, the effect of improving the contact efficiency between the fluid and the skeletal surface and the inside of the monolithic ion exchanger may be likely to become small.

[0125] Perform SEM observation of the fifth monolithic ion exchanger in the dry state at least three times, calculate the diameter or size in the dry state of all particle bodies etc. in the SEM image in the whole field of view, and confirm whether particle bodies etc. with a diameter or size in the range of, for example, 4 to 40 μm are observed. If it is confirmed in the whole field of view, it is determined that particle bodies etc. with a diameter or size in the range of, for example, 4 to 40 μm in the dry state are formed on the skeletal surface of the fifth monolithic ion exchanger. Also, calculate the diameter or size in the dry state of all particle bodies etc. in the SEM image for each field of view according to the above, obtain the proportion of particle bodies etc. in the range of, for example, 4 to 40 μm in the dry state in all particle bodies etc. for each field of view, and when the proportion occupied by particle bodies etc. in the range of, for example, 4 to 40 μm in the dry state in all particle bodies etc. is 70% or more in the whole field of view, it is determined that the proportion occupied by particle bodies etc. in the range of, for example, 4 to 40 μm in the dry state in all particle bodies etc. formed on the skeletal surface of the fifth monolithic ion exchanger is 70% or more. Also, obtain the coating ratio of the surface of the skeletal layer by all particle bodies etc. in the SEM image for each field of view according to the above, and when the coating ratio of the surface of the skeletal layer by all particle bodies etc. is 40% or more in the whole field of view, it is determined that the ratio of the surface of the skeletal layer of the fifth monolithic ion exchanger coated by all particle bodies etc. is 40% or more.

[0126] In the fifth monolithic ion exchanger, if the coverage rate of the surface of the skeleton phase by particulate matter or the like is less than 40%, the effect of improving the contact efficiency between the reaction solution and the inside and surface of the skeleton of the monolithic ion exchanger may be likely to be small. As a method for measuring the coverage rate by the particulate matter or the like, an image analysis method using a SEM image of the fifth monolithic ion exchanger can be mentioned.

[0127] The total pore volume per unit weight of the fifth monolithic ion exchanger in the dry state is, for example, in the range of 0.5 to 10 mL / g, preferably in the range of 0.8 to 8 mL / g. If the total pore volume is less than 0.5 mL / g, when a platinum group metal-supported catalyst is filled in a column and a reaction solution is passed through, the pressure loss during the liquid passage may become large. Furthermore, the amount of permeated fluid per unit cross-sectional area may become small, and the processing capacity may decrease. If the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when a platinum group metal-supported catalyst is filled in a column and a reaction solution is passed through, the monolithic ion exchanger may be deformed particularly when the liquid is passed at a high flow rate. Furthermore, the contact efficiency between the reaction solution and the monolithic ion exchanger may decrease.

[0128] In the fifth monolithic ion exchanger, the crosslinking density of the polymer material constituting the skeleton may contain crosslinked structural units in the range of, for example, 0.3 to 10 mol%, preferably 0.3 to 5 mol% with respect to all the constituent units constituting the polymer material. The organic polymer material constituting the skeleton of the fifth monolithic ion exchanger is the same as that of the first monolithic ion exchanger.

[0129] In the fifth monolithic ion exchanger, the material constituting the skeleton phase of the organic porous body and the particulate matter or the like formed on the surface of the skeleton phase may include those of the same material with continuous same tissue, those of different materials with continuous different tissues, etc. Examples of those of different materials with continuous different tissues include cases where the types of vinyl monomers are different from each other, and cases where the types of vinyl monomers and crosslinking agents are the same but the blending ratios are different from each other.

[0130] The fifth monolithic ion exchanger has a thickness of, for example, 1 mm or more and is distinguished from a membrane-like porous body. The thickness of the fifth monolithic ion exchanger is preferably in the range of 3 to 1000 mm.

[0131] The ion exchange capacity per weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0132] (Method for producing the fifth monolithic ion exchanger) The fifth monolithic ion exchanger can be produced, for example, by the following method.

[0133] The fifth monolith can be obtained, for example, by preparing a water-in-oil emulsion and then performing the following steps I to III. In step I, for example, the water-in-oil emulsion is polymerized to obtain a monolithic organic porous intermediate (hereinafter referred to as monolith intermediate (5)) having a continuous macroporous structure with a total pore volume in the range of, for example, 5 to 30 mL / g. In step II, for example, a mixture containing a vinyl monomer, a crosslinking agent having at least 2 or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent dissolve but the polymer formed by polymerization of the vinyl monomer does not dissolve, and a polymerization initiator is prepared. In step III, for example, the mixture obtained in step II is polymerized under static conditions and in the presence of the monolith intermediate (5) obtained in step I to obtain the fifth monolith.

[0134] Step I in the method for producing the fifth monolith is the same as step I in the method for producing the third monolith.

[0135] In Process I, when forming an oil-in-water droplet emulsion, a polymerization initiator may be used as necessary. As the polymerization initiator, a compound that generates radicals by heat or light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. Examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and the like.

[0136] The monolith intermediate (5) obtained in Process I has a continuous macroporous structure. When this is allowed to coexist in the polymerization system, particles or the like are formed on the surface of the skeletal phase of the continuous macroporous structure using the structure of the monolith intermediate (5) as a template, or particles or the like are formed on the surface of the skeletal phase of the co-continuous structure. Further, the monolith intermediate (5) is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material includes crosslinked structural units in the range of, for example, 0.3 to 10 mol%, preferably 0.3 to 5 mol%, based on all the constituent units constituting the polymer material.

[0137] The type of the polymer material of the monolith intermediate (5) is the same as the type of the polymer material of the monolith intermediate (3) in the method for producing the third monolith.

[0138] The total pore volume per weight of the monolith intermediate (5) obtained in Process I in the dry state is in the range of, for example, 5 to 30 mL / g, preferably in the range of 6 to 28 mL / g. To make the total pore volume of the monolith intermediate (5) within the above numerical range, the ratio (by weight) of the monomer to water may be, for example, approximately 1:5 to 1:35.

[0139] In the I step, if the ratio of this monomer to water is approximately 1:5 to 1:20, a monolith intermediate (5) with a continuous macropore structure having a total pore volume of, for example, 5 to 16 mL / g can be obtained, and the monolith obtained through the III step becomes the 5-1 monolith. On the other hand, if the ratio of the monomer to water is approximately 1:20 to 1:35, a monolith intermediate (5) with a total pore volume exceeding, for example, 16 mL / g and not exceeding 30 mL / g and having a continuous macropore structure can be obtained, and the monolith obtained through the III step becomes the 5-2 monolith.

[0140] In the monolith intermediate (5) obtained in the I step in the method for producing the fifth monolith, the average diameter in the dry state of the opening (mesopore), which is the overlapping part of the macropores, is, for example, 20 to 200 μm.

[0141] The II step in the method for producing the fifth monolith is the same as the II step in the method for producing the third monolith. In the III step in the method for producing the fifth monolith, for example, the mixture obtained in the II step is polymerized while standing and in the presence of the monolith intermediate (5) obtained in the I step to obtain the fifth monolith.

[0142] Here, as disclosed in Japanese Patent Application Laid-Open No. Hei 7-501140, etc., when a vinyl monomer and a crosslinking agent are polymerized while standing in a specific organic solvent in the absence of the monolith intermediate (5), a particulate-aggregation type monolithic organic porous body can be obtained. On the other hand, when the monolith intermediate (5) having a continuous macropore structure is present in the above polymerization system, the structure of the composite monolith after polymerization changes dramatically, and a fifth monolith having the above-described specific skeletal structure can be obtained instead of a particulate-aggregation structure.

[0143] In the III process in the method for manufacturing the fifth monolith, the internal volume of the reaction vessel is not particularly limited as long as it is large enough to accommodate the monolith intermediate (5) in the reaction vessel. When the monolith intermediate (5) is placed in the reaction vessel, it may be either one where a gap is formed around the monolith in plan view or one where the monolith intermediate (5) fits into the reaction vessel with almost no gap. Among these, the one where the fifth monolith after polymerization hardly receives pressure from the inner wall of the container and fits into the reaction vessel with almost no gap is efficient with almost no waste of reaction raw materials, etc., and hardly any distortion occurs in the fifth monolith. Even when the internal volume of the reaction vessel is large and there is a gap around the fifth monolith after polymerization, since the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate (5), hardly any particle aggregation structure is generated in the gap portion in the reaction vessel.

[0144] In this III process, for example, in the reaction vessel, the monolith intermediate (5) is placed in a state of being impregnated with a mixture (solution). As described above, the mixing ratio of the mixture obtained in the II process and the monolith intermediate (5) may be adjusted so that the addition amount of the vinyl monomer is in the range of, for example, 3 to 50 times, preferably 4 to 40 times, by weight with respect to the monolith intermediate (5). Thereby, it is possible to obtain the fifth monolith, which is a composite monolith having a specific skeleton while having an appropriate pore diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the stationary monolith intermediate (5), and polymerization proceeds within the skeleton of the monolith intermediate (5).

[0145] In the III process in the method for manufacturing the fifth monolith, the polymerization conditions are almost the same as those in the III process in the method for manufacturing the third monolith.

[0146] When manufacturing the above-mentioned fifth monolith, when performing the II process or the III process under at least one of the following conditions (1) to (5), it is possible to manufacture a monolith having particle bodies, etc. formed on the skeleton surface. (1) The polymerization temperature in the III process is at least 5 °C lower than the 10-hour half-life temperature of the polymerization initiator. (2) The molar percentage of the crosslinking agent used in the II process is 2 times or more the molar percentage of the crosslinking agent used in the I process. (3) The vinyl monomer used in the II process is a vinyl monomer having a structure different from the oil-soluble monomer used in the I process. (4) The organic solvent used in the II process is a polyether having a molecular weight of 200 or more. (5) The concentration of the vinyl monomer used in the II process is 30% by weight or less in the mixture of the II process.

[0147] Preferred structures of the fifth monolith thus obtained include a continuous macroporous structure (the "fifth-1 monolith") in which bubble-like macropores overlap and the overlapping part becomes an opening in the range of, for example, an average diameter of 10 to 120 μm in the dry state, and a co-continuous structure (the "fifth-2 monolith") composed of a three-dimensionally continuous skeleton with a thickness of the continuous skeleton in the dry state in the range of, for example, 0.8 to 40 μm and three-dimensionally continuous pores with a diameter in the range of, for example, 8 to 80 μm between the skeletons. Note that the method of introducing an ion exchange group into the fifth monolith is the same as the method of introducing an ion exchange group into the first monolith.

[0148] [Platinum group metal-supported catalyst] The platinum group metal-supported catalyst used in the platinum group metal-supported catalyst column according to this embodiment is a catalyst in which at least one of platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions is supported on the above non-particulate organic porous ion exchanger, for example, any one of the first monolith ion exchanger to the fifth monolith ion exchanger. That is, in the platinum group metal-supported catalyst, the platinum group metal is supported on the above non-particulate organic porous ion exchanger in the state of nanoparticles or ions. For example, the platinum group metal-supported catalyst is a catalyst in which platinum group metal ions or platinum group metal complex ions are bonded to the quaternary ammonium groups in the ion exchanger by ionic bonds or coordination bonds.

[0149] The platinum group metals are ruthenium, rhodium, palladium, osmium, iridium, and platinum. These platinum group metals may be a single type alone, a combination of two or more metals, or two or more metals may be used as an alloy. Among these, platinum, palladium, and platinum / palladium alloys are preferable in terms of high catalytic activity.

[0150] The average particle diameter of the platinum group metal nanoparticles is, for example, in the range of 1 to 100 nm, preferably in the range of 1 to 50 nm, and more preferably in the range of 1 to 20 nm. When the average particle diameter of the platinum group metal nanoparticles is less than 1 nm, the platinum group metal particles may detach from the carrier, and when it exceeds 100 nm, the surface area per unit mass of the metal may decrease and the catalytic effect may not be efficiently obtained.

[0151] The average particle diameter of the platinum group metal nanoparticles is determined by image analysis of a TEM image obtained by transmission electron microscope (TEM) analysis. Specifically, first, the surface of the platinum group metal-supported catalyst is analyzed by TEM. Next, in the obtained TEM image, an arbitrary field of view with 200 or more particles is selected, and the TEM image of that field of view is analyzed by image analysis to measure the particle diameters of all the particles in the field of view. When the number of platinum group metal particles supported in a single field of view is less than 200, two or more fields of view are arbitrarily selected, and the particle diameters of all the particles in the two or more selected fields of view are measured. Then, the average particle diameter of the platinum group metal nanoparticles is calculated by the formula "Average particle diameter of platinum group metal particles (nm) = Total of measured particle diameters of all particles (nm) / Number of measured particles (pieces)".

[0152] The platinum group metal ions are ions of the above platinum group metals, and the valence of the platinum group metal ions varies depending on the type of platinum group metal. These platinum group metal ions may be a single type alone or a combination of two or more metals. Among these, platinum ions and palladium ions are preferable in terms of high catalytic activity.

[0153] The platinum group metal complex ions are complex ions of the above platinum group metals, and examples thereof include palladium complex ions, platinum complex ions, iridium complex ions, etc. These platinum group metal complex ions may be a single type alone or a combination of two or more metals. Among these, platinum complex ions and palladium complex ions are preferable in terms of high catalytic activity.

[0154] In the platinum group metal-supported catalyst, the fact that platinum group metals, etc. are supported can be confirmed by performing transmission electron microscope (TEM) observation.

[0155] The supported amount of platinum group metals, etc. in the platinum group metal-supported catalyst ((weight in terms of platinum group metal atoms / weight of the platinum group metal-supported catalyst in the dry state) × 100) is in the range of 0.004 to 20% by weight in the dry state, preferably in the range of 0.005 to 15% by weight. When the supported amount of platinum group metals, etc. is less than 0.004% by weight in the dry state, the catalytic activity may become insufficient, and when it exceeds 20% by weight, metal elution into water may be observed. The quantification of platinum group metal atoms in the platinum group metal-supported catalyst is performed using an ICP emission spectroscopic analyzer.

[0156] There is no particular limitation on the method for producing the platinum group metal-supported catalyst, and a platinum group metal-supported catalyst can be obtained by supporting platinum group metals, etc. on a monolith ion exchanger by a known method. For example, a dry monolith ion exchanger is immersed in an organic solution such as methanol of a platinum group metal compound such as palladium acetate at a predetermined temperature for a predetermined time, and platinum group metal ions are adsorbed on the monolith ion exchanger by ion exchange, and then a method of contacting with a reducing agent to support platinum group metal nanoparticles on the monolith ion exchanger, or a method of immersing the monolith ion exchanger in an aqueous solution of a platinum group metal complex compound such as tetraamminepalladium complex at a predetermined temperature for a predetermined time, and platinum group metal ions are adsorbed on the monolith ion exchanger by ion exchange, and then a method of contacting with a reducing agent to support platinum group metal nanoparticles on the monolith ion exchanger, etc. can be mentioned.

[0157] The loading of platinum group metals or the like onto the monolithic ion exchanger may be carried out batchwise or continuously, without any particular limitation.

[0158] As the platinum group metal compound used in the method for producing the platinum group metal-supported catalyst, either organic salts or inorganic salts may be used, and examples include halides, sulfates, nitrates, phosphates, organic acid salts, inorganic complex salts, etc. Specific examples of the platinum group metal compound include palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, tetraamminepalladium chloride, tetraamminepalladium nitrate, platinum chloride, tetraammineplatinum chloride, tetraammineplatinum nitrate, chlorotriammineplatinum chloride, hexaammineplatinum chloride, hexaammineplatinum sulfate, chloropentammineplatinum chloride, cis-tetrachlorodiammineplatinum chloride, trans-tetrachlorodiammineplatinum chloride, rhodium chloride, rhodium acetate, hexaammine rhodium chloride, hexaammine rhodium bromide, hexaammine rhodium sulfate, pentaammineaquarhodium chloride, pentaammineaquarhodium nitrate, cis-dichlorotetraammine rhodium chloride, trans-dichlorotetraammine rhodium chloride, ruthenium chloride, hexaammine ruthenium chloride, hexaammine ruthenium bromide, hexaammine ruthenium iodide, chloropentammine ruthenium chloride, cis-dichlorotetraammine ruthenium chloride, trans-dichlorotetraammine rhodium chloride, iridium(III) chloride, iridium(IV) chloride, hexaammine iridium chloride, hexaammine iridium nitrate, chloropentammine iridium chloride, chloropentammine iridium bromide, hexaammine osmium chloride, hexaammine osmium bromide, hexaammine osmium iodide, etc. The usage amount of these compounds is, for example, 0.005 to 30% by weight in terms of metal relative to the monolithic ion exchanger as the carrier.

[0159] When supporting platinum group metals and the like, platinum group metal compounds are usually dissolved in a solvent and used. As the solvent, water; alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol; ketones such as acetone, methyl ethyl ketone; nitriles such as acetonitrile; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and mixtures thereof are used. Further, in order to enhance the solubility of the platinum group metal compound in the solvent, acids such as hydrochloric acid, sulfuric acid, nitric acid, and bases such as sodium hydroxide, tetramethylammonium hydroxide may be added.

[0160] There is no particular limitation on the reducing agent used in the method for producing a platinum group metal-supported catalyst either. Reducing gases such as hydrogen, carbon monoxide, ethylene; alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol; carboxylic acids such as formic acid, ammonium formate, oxalic acid, citric acid, sodium citrate, ascorbic acid, calcium ascorbate and their salts; ketones such as acetone, methyl ethyl ketone; aldehydes such as formaldehyde and acetaldehyde; hydrazines such as hydrazine, methylhydrazine, ethylhydrazine, butylhydrazine, allylhydrazine, phenylhydrazine; hypophosphites such as sodium hypophosphite, potassium hypophosphite acid salts; sodium borohydride and the like can be mentioned.

[0161] There are also no particular restrictions on the reaction conditions of the reduction reaction. For example, the reaction is carried out at a temperature of -20°C to 150°C for 1 minute to 20 hours to reduce the platinum group metal compound to a zero-valent platinum group metal.

[0162] In the platinum group metal-supported catalyst, there is no particular limitation on the ionic form of the monolith ion exchanger that is the carrier of the platinum group metal nanoparticles. In the case of a monolith cation exchanger, it may be in a salt form in which the counter ion is replaced by a sodium ion, a calcium ion, etc., or it may be in a regenerated form in which the counter ion is a hydrogen ion. Also, in the case of a monolith anion exchanger, it may be in a salt form in which the counter ion is replaced by a chloride ion, a nitrate ion, etc., or it may be in a regenerated form in which the counter ion is a hydroxide ion.

[0163] [Platinum group metal capturing material] The platinum group metal capturing material used in the platinum group metal-supported catalyst column according to this embodiment may be any material that can support at least one of platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions. Examples include ion exchangers, silica gels, metal removal filters, and the like. Among these, ion exchangers are preferred, and non-particulate organic porous ion exchangers are more preferred in terms of high capturing performance for various metals.

[0164] The non-particulate organic porous ion exchanger used as the platinum group metal capturing material consists of a continuous skeleton phase and a continuous pore phase. The thickness of the continuous skeleton ranges from 1 to 100 μm, the average diameter of the continuous pores ranges from 1 to 1000 μm, the total pore volume ranges from 0.5 to 50 mL / g, and the ion exchange capacity per unit weight in the dry state ranges from 1 to 9 mg-equiv / g. It is preferably a non-particulate organic porous ion exchanger in which ion exchange groups are distributed in the ion exchanger.

[0165] The non-particulate organic porous ion exchanger used as the platinum group metal capturing material is the same as the non-particulate organic porous ion exchanger as the above ion exchanger, and the description thereof is omitted.

[0166] In the platinum group metal-supported catalyst column, the platinum group metal capturing material is installed at the rear stage of the platinum group metal-supported catalyst. The platinum group metal capturing material may be filled in the rear stage within the filling container filled with the platinum group metal-supported catalyst, or may be filled in another filling container at the rear stage of the filling container filled with the platinum group metal-supported catalyst.

[0167] The filling amount of the platinum group metal capturing material may be, for example, in the range of the amount (vol) of the platinum group metal-supported catalyst: the amount (vol) of the platinum group metal capturing material = 1:0.5 to 1:50.

[0168] [Carbon-carbon bond formation method] The carbon-carbon bond formation method according to the embodiment of the present invention uses the above-mentioned platinum group metal-supported catalyst column to perform, for example, (1) a reaction between an aromatic halide and an organic boron compound, (2) a reaction between an aromatic halide and a compound having an alkynyl group at the terminal, or (3) a reaction between an aromatic halide and a compound having an alkenyl group to form a carbon-carbon bond.

[0169] The first form of the carbon-carbon bond formation method (hereinafter, also referred to as the carbon-carbon bond formation method (1)) is a reaction in which an aromatic halide and an organic boron compound are reacted and coupled using the above-mentioned platinum group metal-supported catalyst column to generate a carbon-carbon single bond.

[0170] The organic boron compound used in the carbon-carbon bond formation method (1) is R 1 -B(OH)2 (R 1 is an organic group and is not particularly limited as long as it is an organic group. For example, it is a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aromatic carbocyclic group, an aromatic heterocyclic group, etc. As long as the effects of the present embodiment are not inhibited, these groups may be introduced with a methyl group, an ethyl group, a nitro group, an amino group, a methoxy group, an ethoxy group, a carboxyl group, an acetyl group, etc.).) is an organic boron compound represented by

[0171] The organic boron compound used in the carbon-carbon bond formation method (1) is, for example, an aromatic boron compound represented by the following general formula (I). Ar 1 -B(OH)2 (I) (In the formula, Ar 1 is an aromatic carbocyclic group or an aromatic heterocyclic group having 6 to 18 carbon atoms.)

[0172] In formula (I), Ar 1Examples of the aromatic carbocyclic group or aromatic heterocyclic group include a phenyl group, naphthyl group, biphenyl group, anthranyl group, pyridyl group, pyrimidyl group, indolyl group, benzimidazolyl group, quinolyl group, benzofuranyl group, indanyl group, indenyl group, dibenzofuranyl group, and the like. There is no particular limitation on the position where boron binds to the aromatic carbocyclic group or aromatic heterocyclic group, and it can bind to any position. Further, one or more substituents may be introduced into the aromatic carbocyclic group or aromatic heterocyclic group. Examples of the substituent include hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, benzyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; 9-fluorenylmethoxycarbonyl group, butoxycarbonyl group, benzyloxycarbonyl group, nitro group, and the like.

[0173] The aromatic halide used in the carbon-carbon bond forming method (1) is, for example, an aromatic halide represented by the following general formula (II). Ar 2 -X (II) (In the formula, Ar 2 is an aromatic carbocyclic group or aromatic heterocyclic group having 6 to 18 carbon atoms, and X is a halogen atom.)

[0174] In formula (II), examples of the aromatic carbocyclic group or aromatic heterocyclic group where Ar 2 is the same as those of Ar 1 There is no particular limitation on the position where the halogen atom binds to the aromatic carbocyclic group or aromatic heterocyclic group, and it can bind to any position. Further, one or more substituents may be introduced into the aromatic carbocyclic group or aromatic heterocyclic group. Examples of the substituent include hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, benzyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; 9-fluorenylmethoxycarbonyl group, butoxycarbonyl group, benzyloxycarbonyl group, nitro group, carboxyl group, amino group, and the like.

[0175] X is a halogen atom, specifically a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0176] The formation of a carbon-carbon bond by the carbon-carbon bond formation method (1) means that a carbon-carbon bond is formed between an organic group from which a functional group containing boron has been eliminated from an organoboron compound and an aromatic residue from which a halogen has been eliminated from an aromatic halide. For example, when the organoboron compound is an aromatic boron compound represented by the formula (I) and the aromatic halide is an aromatic halide represented by the formula (II), the resulting coupling product is a compound represented by the formula (III). Ar 1 -Ar 2 (III) (In the formula, Ar 1 and Ar 2 are the same as those in the above formulas (I) and (II).)

[0177] The usage ratio of the aromatic boron compound and the aromatic halide used in the carbon-carbon bond formation method (1) is not particularly limited. For example, the molar ratio of the aromatic boron compound:aromatic halide = 0.5 to 2:1, and they may be used in equimolar amounts.

[0178] The second form of the carbon-carbon bond formation method (hereinafter also referred to as the carbon-carbon bond formation method (2)) is a reaction for forming a carbon-carbon single bond by reacting an aromatic halide with a compound having an alkynyl group at the terminal using the above platinum group metal-supported catalyst column.

[0179] The aromatic halide used in the carbon-carbon bond formation method (2) is, for example, the aromatic halide represented by the above formula (II).

[0180] The compound having an alkynyl group at the terminal used in the carbon-carbon bond formation method (2) is, for example, a compound represented by the formula (IV). HC≡C-R 2 (IV) (In the formula, R 2is a hydrogen atom, an optionally substituted aromatic carbocyclic group having 6 to 18 carbon atoms, an optionally substituted aromatic heterocyclic group having 6 to 18 carbon atoms, an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, an optionally substituted alkenyl group having 2 to 18 carbon atoms, or an optionally substituted alkynyl group having 2 to 10 carbon atoms.)

[0181] In formula (IV), R 2 Examples of the optionally substituted aromatic carbocyclic group having 6 to 18 carbon atoms or the optionally substituted aromatic heterocyclic group having 6 to 18 carbon atoms which is, are the same as Ar 1 and Ar 2 in formulas (I) and (II).

[0182] In formula (IV), R 2 Examples of the optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms which is, include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, an octadecyl group and the like.

[0183] In formula (IV), R 2 Examples of the optionally substituted alkenyl group having 2 to 18 carbon atoms which is, include a vinyl group, an allyl group, a methallyl group, a propenyl group, a butenyl group, a hexenyl group, an octenyl group, a decenyl group, an octadecenyl group and the like.

[0184] In formula (IV), R 2 Examples of the optionally substituted alkynyl group having 2 to 10 carbon atoms which is, include an ethynyl group, a propynyl group, a hexynyl group, an octenyl group and the like.

[0185] Examples of the optionally substitutable groups that these aromatic carbocyclic groups, aromatic heterocyclic groups, aliphatic hydrocarbon groups, alkenyl groups, and alkynyl groups may have include, for example, a hydroxyl group, a hydrocarbon group such as a phenyl group, a heteroatom-containing hydrocarbon group such as a methoxy group and a trifluoromethoxy group, and the like.

[0186] In the carbon-carbon bond formation method (2), using the above-mentioned platinum group metal-supported catalyst column, for example, an aromatic halide represented by the formula (II) and a compound represented by the formula (IV) react to obtain a product of the formula (V). Ar 2 -C≡C-R 2 (V) (In the formula, Ar 2 and R 2 are the same as those in the formulas (II) and (IV).)

[0187] The usage ratio of the aromatic halide and the compound having an alkynyl group at the terminal used in the carbon-carbon bond formation method (2) is not particularly limited. For example, the molar ratio of the aromatic halide: the compound having an alkynyl group at the terminal = 0.5 to 3:1, and they may be used in equimolar amounts.

[0188] The third form of the carbon-carbon bond formation method (hereinafter, also referred to as the carbon-carbon bond formation method (3)) is a reaction for forming a carbon-carbon single bond by reacting an aromatic halide and a compound having an alkenyl group using the above-mentioned platinum group metal-supported catalyst column.

[0189] The aromatic halide used in the carbon-carbon bond formation method (3) is, for example, the aromatic halide represented by the above formula (II).

[0190] The compound having an alkenyl group used in the carbon-carbon bond formation method (3) is, for example, the compound represented by the formula (VI). R 3 HC=CR 4 R 5 (VI) (In the formula, R 3 , R 4 , R 5 are each independently a hydrogen atom, an aromatic carbocyclic group having 6 to 18 carbon atoms which may have a substituent, an aromatic heterocyclic group having 6 to 18 carbon atoms which may have a substituent, an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, a carboxylic acid derivative, an acid amide derivative, or a cyano group.)

[0191] In formula (VI), R 3 , R 4 , R 5 is an optionally substituted aromatic carbocyclic group having 6 to 18 carbon atoms, an optionally substituted aromatic heterocyclic group having 6 to 18 carbon atoms, and an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms. Examples of the aliphatic hydrocarbon group are the same as R 2 in formula (IV).

[0192] In formula (VI), R 3 , R 4 , R 5 Examples of the carboxylic acid derivative include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl.

[0193] In formula (VI), R 3 , R 4 , R 5 Examples of the acid amide derivative include carbamoyl groups such as N-methylcarbamoyl group and N,N-dimethylcarbamoyl group.

[0194] In the carbon-carbon bond forming method (3), using the above-mentioned platinum group metal-supported catalyst column, the aromatic halide represented by formula (II) reacts with the compound represented by formula (VI) to obtain the product of formula (VII). R 3 Ar 2 C=CR 4 R 5 (VII) (Wherein Ar 2 , R 3 , R 4 , R 5 is the same as in the above formula (II) and the above formula (VI).)

[0195] The usage ratio of the aromatic halide and the compound having an alkenyl group used in the carbon-carbon bond forming method (3) is not particularly limited. For example, the molar ratio of the aromatic halide: the compound having an alkenyl group = 0.5 to 2:1, and they may be used in equimolar amounts.

[0196] In the carbon-carbon bond formation reactions (1) to (3), the amount of the platinum group metal-supported catalyst used is, for example, in the range of 0.01 to 20 mol% in terms of the platinum group metal relative to the aromatic halide.

[0197] In the carbon-carbon bond formation method, examples of the solvent used in the coupling reaction include water, organic solvents, and mixtures thereof. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, and glycerin; cyclic ethers such as tetrahydrofuran and dioxane.

[0198] The atmosphere in which the carbon-carbon bond formation method is carried out may be in air, but an inert gas atmosphere such as nitrogen or argon is preferably used. The reaction temperature is not particularly limited and is arbitrarily set, for example, in the range of -20°C to 150°C, and the reaction time is not particularly limited and is set, for example, in the range of 1 minute to 24 hours.

[0199] In the carbon-carbon bond formation reaction, it is preferable to have a base present, and it is more preferable to have an inorganic base present. Examples of the base used include inorganic bases such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium acetate, sodium phosphate, potassium phosphate, and barium hydroxide; and organic bases such as potassium phenolate, sodium methoxide, sodium ethoxide, potassium butoxide, trimethylamine, and triethylamine. The amount of these bases used is set, for example, in the range of 50 to 300 mol% relative to the aromatic halide.

[0200] In the carbon-carbon bond formation method according to this embodiment, a reaction for generating a carbon-carbon bond is carried out by passing the raw material liquid of the reaction through the platinum group metal-supported catalyst column.

[0201] In the carbon-carbon bond formation method according to this embodiment, the carbon-carbon bond formation reactions (1) to (3) are carried out, for example, by passing a raw material liquid (i) containing the aromatic halide and the organoboron compound, a raw material liquid (ii) containing the aromatic halide and the compound having an alkynyl group at the terminal, or a raw material liquid (iii) containing the aromatic halide and the compound having an alkenyl group, through the platinum group metal-supported catalyst column from the introduction path and discharging the reaction liquid from the discharge path, thereby carrying out the carbon-carbon bond formation reaction.

[0202] In the carbon-carbon bond formation method, for example, the raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is an inorganic base-dissolved raw material liquid in which the raw materials and the inorganic base are dissolved in water or a hydrophilic solvent. The carbon-carbon bond formation reaction may be carried out by passing the inorganic base-dissolved raw material liquid through the platinum group metal-supported catalyst column from the introduction path and discharging the reaction liquid from the discharge path.

[0203] Further, in the carbon-carbon bond formation method, for example, the raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is a hydrophobic solvent raw material liquid in which the raw material is dissolved in a hydrophobic organic solvent. The carbon-carbon bond formation reaction may be carried out by passing a mixture of the hydrophobic solvent raw material liquid and an aqueous solution of an inorganic base in which the inorganic base is dissolved through the platinum group metal-supported catalyst column from the introduction path and discharging the reaction liquid from the discharge path.

[0204] The carbon-carbon bond formation method according to this embodiment can form a carbon-carbon bond to obtain a desired compound, and can obtain the target product in a high yield. In particular, the carbon-carbon bond formation reaction can be carried out in a high yield even in the case of aromatic bromides. Further, the reaction time is short and the target product can be obtained in a high yield. According to the carbon-carbon bond formation method according to this embodiment, the carbon-carbon bond formation method for forming a carbon-carbon bond to obtain a desired compound can be carried out in a fixed bed continuous flow type, and the carbon-carbon bond reaction can be carried out in a high yield in various raw materials. Further, from the viewpoint of production efficiency, a high-concentration raw material solution can be used.

Example

[0205] Hereinafter, examples and comparative examples will be given to describe the present invention more specifically and in detail. However, the present invention is not limited to the following examples.

[0206] <Example 1> According to the manufacturing method of the fifth monolithic ion exchanger, a monolith was manufactured, and an ion exchange group was introduced into the obtained monolith.

[0207] (Manufacture of Monolith Intermediate (Step I)) 9.28 g of styrene as a monomer, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) as a surfactant, and 0.25 g of 2,2'-azobis(isobutyronitrile) as a polymerization initiator were mixed and dissolved uniformly. Next, this styrene / divinylbenzene / SMO / 2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water, and stirred under reduced pressure using a vacuum stirring and defoaming mixer (manufactured by EMI Co., Ltd.), which is a planetary stirring device, to obtain a water-in-oil droplet type emulsion. This emulsion was quickly transferred to a reaction vessel, sealed, and polymerized at 60°C for 24 hours under static conditions. After the polymerization was completed, the content was taken out, extracted with methanol, and then dried under reduced pressure to manufacture a monolith intermediate having a continuous macroporous structure. The internal structure of the thus obtained monolith intermediate (dry body) was observed by SEM. The SEM image is shown in Fig. 10. Although the wall portion partitioning two adjacent macropores is extremely thin and rod-shaped, it has a continuous macroporous structure. The average diameter of the opening (mesopore) of the portion where the macropores overlap measured by mercury intrusion porosimetry was 40 μm, and the total pore volume was 18.2 mL / g.

[0208] (Manufacture of Monolith (Step II)) Next, 216.6 g of styrene as a monomer, 4.4 g of divinylbenzene as a crosslinking agent, 220 g of 1-decanol as an organic solvent, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator were mixed and dissolved uniformly (Step II).

[0209] (Production of Monolith (Step III)) Next, the above monolith intermediate was placed in a reaction vessel, immersed in this styrene / divinylbenzene / 1-decanol / 2,2'-azobis(2,4-dimethylvaleronitrile) mixture, defoamed in a vacuum chamber, then the reaction vessel was sealed and polymerized at 50 °C for 24 hours under static conditions. After the polymerization was completed, the contents were taken out, Soxhlet extracted with acetone, and then dried under reduced pressure (Step III).

[0210] The results of observing the internal structure of the monolith (dry body) containing 1.2 mol% of the crosslinked component composed of the styrene / divinylbenzene copolymer thus obtained by SEM are shown in Fig. 11. As is clear from Fig. 11, this monolith has a continuous three-dimensional structure consisting of a continuous skeletal phase and a continuous pore phase with the skeleton and pores being three-dimensionally continuous respectively, and the two phases are intertwined in a co-continuous structure. Also, the thickness of the continuous skeleton measured from the SEM image was 20 μm. Further, the average diameter of the three-dimensionally continuous pores of this monolith measured by the mercury intrusion method was 70 μm, and the total pore volume was 4.4 mL / g. The average diameter of the pores was determined from the maximum value of the pore size distribution curve obtained by the mercury intrusion method.

[0211] (Production of Chloromethylated Monolith) The produced monolith was placed in a column reactor, and a solution containing 1600 g of thionyl chloride, 400 g of tin tetrachloride, and 2500 mL of dimethoxymethane was circulated and passed through to react at 30 °C for 5 hours to introduce chloromethyl groups. After the reaction was completed, the chloromethylated monolith was washed with a mixed solvent of THF / water = 2 / 1 (vol), and further washed with THF to obtain a chloromethylated monolith.

[0212] (Production of Weakly Basic Monolith Anion Exchanger) Next, the chloromethylated monolith was dried under reduced pressure. The weight of the dried chloromethylated monolith was 8.4 g. This chloromethylated monolith was placed in a separable flask containing a stir bar, and a solution containing 56 mL of a 50% aqueous solution of dimethylamine as a secondary amine and 180 mL of THF was introduced into the separable flask, and the mixture was stirred under reflux for 10 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a weakly basic monolith anion exchanger.

[0213] The total anion exchange capacity of the obtained dried weakly basic monolith anion exchanger was 4.7 meq / g, and the weak anion exchange capacity was 4.3 meq / g. Also, the thickness of the skeleton in the dried state measured from the SEM image was 25 μm.

[0214] Hereinafter, the obtained weakly basic monolith anion exchanger is referred to as the "monolith weak anion exchanger".

[0215] (Production of Platinum Group Metal-Supported Catalyst) The produced weakly basic monolith anion exchanger was dried under reduced pressure. The weight of the dried weakly basic monolith anion exchanger was 8.7 g. This dried weakly basic monolith anion exchanger was placed in a separable flask containing a stir bar, and an ethyl acetate solution of 190 mg of palladium acetate was further introduced, and the mixture was stirred at room temperature (25 ± 5°C) for 5 days to support palladium ions on the monolith anion exchanger. This monolith anion exchanger was washed with methanol and then with pure water. The obtained Pd ion-supported monolith anion exchanger was washed several times with pure water and then dried by drying under reduced pressure. When the palladium loading amount in the obtained Pd ion-supported monolith anion exchanger was determined using an ICP emission spectrometer (manufactured by Hitachi High-Technologies Corporation, model PS3520UVDDII), the palladium loading amount was 1 wt%.

[0216] Hereinafter, the obtained platinum group metal-supported catalyst is referred to as the "Pd monolith weak anion exchanger".

[0217] (Preparation of Platinum Group Metal-Supported Catalyst Column) The fabricated Pd monolith weak anion exchanger was formed into a shape of φ4.6×30 mm and filled into a column made of φ4.6×150 mm SUS. Then, the monolith weak anion exchanger fabricated above as a platinum group metal capturing material was formed into a shape of φ4.6×120 mm and filled into the SUS column filled with the Pd monolith weak anion exchanger to fabricate a platinum group metal supported catalyst column.

[0218] Hereinafter, the platinum group metal supported catalyst column obtained in Example 1 is referred to as "Catalyst Column 1".

[0219] <Example 2> (Carbon-carbon bond formation reaction using a platinum group metal supported catalyst column)

Chemical formula

[0220] <Comparative Example 1> (Fabrication of a platinum group metal supported catalyst column) The Pd monolith weak anion exchanger fabricated in Example 1 was formed into a shape of φ4.6×30 mm and filled into a column made of φ4.6×30 mm SUS to fabricate a platinum group metal supported catalyst column.

[0221] Hereinafter, the platinum group metal supported catalyst column obtained in Comparative Example 1 is referred to as "Catalyst Column 2".

[0222] <Comparative Example 2> The carbon-carbon bond formation reaction was carried out in the same manner as in Example 2 except that Catalyst Column 1 was changed to Catalyst Column 2, and as a result, 2-cyano-4'-methylbiphenyl was obtained with a conversion rate of 37%.

[0223] Thus, by using the platinum group metal-supported catalyst column of the example, the carbon-carbon bond formation reaction could be carried out in high yield even for aromatic bromides.

Explanation of Signs

[0224] 1 Skeletal phase, 2 Pore phase, 10 Co-continuous structure, 11 Rectangular image region, 12 Skeletal part, 13 Macropore, 21 Skeletal surface, 22a, 22b, 22c, 22d, 22e Protrusion.

Claims

1. A platinum group metal-supported catalyst column for carbon-carbon bond formation reaction, in which a platinum group metal-supported catalyst is filled in a filling container, wherein the platinum group metal-supported catalyst is a platinum group metal-supported catalyst in which at least one of platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions is supported on an ion exchanger, the ion exchanger consists of a continuous skeletal phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and it is a non-particulate organic porous ion exchanger in which ion exchange groups are distributed in the ion exchanger, the supported amount of at least one of the platinum group metal nanoparticles, platinum group metal ions, and platinum group metal complex ions is in the range of 0.004 to 20% by weight in the dry state, a platinum group metal scavenger is installed downstream of the platinum group metal-supported catalyst, the platinum group metal scavenger consists of a continuous skeletal phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and it is a non-particulate organic porous ion exchanger in which ion exchange groups are distributed in the ion exchanger. A platinum group metal-supported catalyst column characterized by this.

2. The platinum group metal-supported catalyst column according to Claim 1, wherein the platinum group metal-supported catalyst is a platinum group metal-supported catalyst in which at least one of platinum group metal ions and platinum group metal complex ions is supported on the ion exchanger. A platinum group metal-supported catalyst column characterized by this.

3. A carbon-carbon bond formation method for forming a carbon-carbon bond by performing (1) a reaction between an aromatic halide and an organic boron compound, (2) a reaction between an aromatic halide and a compound having an alkynyl group at the terminal, or (3) a reaction between an aromatic halide and a compound having an alkenyl group, A method for forming a carbon-carbon bond, comprising passing a raw material liquid (i) containing the aromatic halide and the organoboron compound, a raw material liquid (ii) containing the aromatic halide and the compound having an alkynyl group at the terminal, or a raw material liquid (iii) containing the aromatic halide and the compound having an alkenyl group through a platinum group metal-supported catalyst column according to claim 1 or 2 via an introduction path, and discharging the reaction liquid from a discharge path to effect the carbon-carbon bond formation reaction.

4. The method for forming a carbon-carbon bond according to claim 3, characterized in that the carbon-carbon bond formation reaction is carried out in the presence of an inorganic base.

5. The method for forming a carbon-carbon bond according to claim 3 or 4, wherein the raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is an inorganic base-dissolved raw material liquid in which a raw material and an inorganic base are dissolved in water or a hydrophilic solvent, and the carbon-carbon bond formation reaction is carried out by passing the inorganic base-dissolved raw material liquid through a platinum group metal-supported catalyst column via an introduction path and discharging the reaction liquid from a discharge path.

6. The method for forming a carbon-carbon bond according to claim 3 or 4, wherein the raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is a hydrophobic solvent raw material liquid in which a raw material is dissolved in a hydrophobic organic solvent, and the carbon-carbon bond formation reaction is carried out by passing a mixture of the hydrophobic solvent raw material liquid and an aqueous inorganic base solution in which an inorganic base is dissolved through a platinum group metal-supported catalyst column via an introduction path and discharging the reaction liquid from a discharge path.

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