Carbon-carbon bond formation method

Abstract

To provide a catalyst which makes it possible to perform a carbon-carbon bond formation process for forming a carbon-carbon bond to produce a desired compound in a fixed bed continuous flow manner and which enables the reactions to take place with high yield in various raw materials.SOLUTION: Provided is a catalyst having a platinum-group metal ion supported thereon, which comprises a platinum-group metal ion or a platinum-group metal complex ion supported on a non-particulate organic porous ion exchanger, the non-particulate organic porous ion exchanger is composed of a continuous backbone phase 1 and a continuous void phase 2, the thickness of the continuous backbone is 1 to 100 μm, the average diameter of the continuous voids is 1 to 1000 μm, the total pore volume is 0.5 to 50 ml / g, the ion exchange volume per dry weight is 1 to 9 mg equivalent / g, and ion exchange groups are distributed uniformly in the organic porous ion exchanger.SELECTED DRAWING: Figure 6

Description

[Technical Field]

[0001] The present invention relates to a carbon-carbon bond forming method in which a reaction to form a carbon-carbon bond is carried out by passing a raw material liquid for the reaction through a platinum group metal ion-supported catalyst, and to a platinum group metal ion-supported catalyst for carrying out the method. [Background technology]

[0002] Carbon-carbon formation reactions (coupling reactions) using platinum group metals such as palladium as catalysts, such as Suzuki-Miyaura coupling, Sonogashira coupling, and Mizoroki-Heck coupling, have recently become increasingly important in the synthesis of pharmaceutical intermediates, liquid crystals, and other highly functional materials.

[0003] Conventionally, the platinum group metal catalysts have often been used in homogeneous systems and have demonstrated high catalytic activity, but have drawbacks such as difficulty in recovering the catalyst and contamination of the product with the catalyst metal. Therefore, heterogeneous catalysts have been developed in which the catalyst is supported on a carrier, facilitating catalyst recovery and reducing metal contamination of the product. Recently, methods have also been developed for continuously forming carbon-carbon bonds by passing a reaction substrate solution through a heterogeneous catalyst. For example, Japanese Patent Publication No. 5638862 reports a method for continuously forming carbon-carbon bonds using a catalyst in which palladium is supported on a porous silica carrier, but does not disclose any actual reaction examples. In addition, Japanese Patent Publication No. 5255215 and Japanese Patent Application Laid-Open Publication No. 2008-212765 disclose a method for forming carbon-carbon bonds using a catalyst in which a platinum group metal is supported on the wall of a microchannel with a width of 1 mm and a depth of 20 μm. However, for reasons unknown, the disclosed reaction examples do not use water as a solvent, and the reaction substrate solution is only passed through at a rate of 1 μm / min, which creates problems with environmental impact and production efficiency. Furthermore, ChemCatChem, 2019, Vol. 11, p. 2427, reports a method for continuously forming carbon-carbon bonds in a column packed with a catalyst in which palladium is supported on an organic support. However, obtaining the organic support requires complex chemical conversion, and for reasons unknown, a large amount of diatomaceous earth must be mixed in when using a palladium-supported catalyst.

[0004] Meanwhile, we 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 reported in JP 2014-15420 A (Patent Document 4) or JP 2016-190853 A (Patent Document 5) that the catalyst exhibits high catalytic activity in an aqueous solvent in a carbon-carbon bond-forming reaction. According to the methods disclosed in Patent Documents 4 and 5, by using a platinum group metal ion-supported catalyst in which a platinum group metal is supported on a non-particulate organic ion exchanger as a catalyst, a carbon-carbon bond-forming reaction can be carried out in a high yield in an aqueous solvent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5638862 (Claims) [Patent Document 2] Patent No. 5255215 (Claims) [Patent Document 3] JP 2008-212765 A (Claims) [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-15420 [Patent Document 5] Japanese Patent Application Laid-Open No. 2016-190853 [Non-patent literature]

[0006] [Non-Patent Document 1] ChemCatChem, 2019, No. 11, p. 2427 Summary of the Invention [Problem to be solved by the invention]

[0007] From the viewpoint of production efficiency, a reaction method with a short reaction time is required, and a method for increasing production efficiency is to carry out the reaction in a fixed-bed continuous flow system.

[0008] However, in Suzuki-Miyaura coupling, Sonogashira coupling, and Mizoroki-Heck coupling, the reactivity varies depending on the reactants, and it is sometimes difficult to achieve the reaction in a short time. Therefore, there is a problem that carbon-carbon bond forming reactions such as Suzuki-Miyaura coupling, Sonogashira coupling, and Mizoroki-Heck coupling are difficult to achieve in the fixed-bed continuous flow system.

[0009] Therefore, an object of the present invention is to provide a catalyst that can be used in a fixed-bed continuous flow method for forming a carbon-carbon bond to obtain a desired compound, and that can carry out the reaction in high yield with various raw materials. [Means for solving the problem]

[0010] Under these circumstances, the present inventors have conducted extensive research and have found that a catalyst in which platinum group metal ions or platinum group metal complex ions are supported on a non-particulate organic porous ion exchanger, i.e., a catalyst in which a platinum group metal is supported in an ionic state on a non-particulate organic porous ion exchanger, can increase the yield in a so-called fixed-bed continuous flow carbon-carbon bond reaction even when an aromatic bromine compound is used as a raw material, thereby completing the present invention.

[0011] That is, the present invention (1) provides a platinum group metal ion-supported catalyst in which platinum group metal ions or platinum group metal complex ions are supported on a non-particulate organic porous ion exchanger, characterized in that the non-particulate organic porous ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the continuous skeleton thickness is 1 to 100 μm, the continuous pores have an average diameter of 1 to 1000 μm, the total pore volume is 0.5 to 50 ml / g, the ion exchange capacity per weight in a dry state is 1 to 9 mg equivalents / g, and the ion exchange groups are uniformly distributed throughout the organic porous ion exchanger.

[0012] The present invention (2) provides a platinum group metal ion-supported catalyst according to (1), characterized in that the non-particulate organic porous ion exchanger has an open-cell structure with interconnected macropores and common openings (mesopores) with an average diameter of 1 to 1000 μm within the walls of the macropores, a total pore volume of 1 to 50 ml / g, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and ion exchange groups are uniformly distributed throughout the organic porous ion exchanger.

[0013] The present invention (3) provides a platinum group metal ion-supported catalyst according to (1), characterized in that the non-particulate organic porous ion exchanger is composed of organic polymer particles having an average particle size of 1 to 50 μm aggregated to form a three-dimensionally continuous framework, and has three-dimensionally continuous pores having an average diameter of 20 to 100 μm between the frameworks, a total pore volume of 1 to 10 ml / g, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and ion exchange groups uniformly distributed throughout the organic porous ion exchanger.

[0014] The present invention (4) provides a platinum group metal ion-supported catalyst according to (1), characterized in that the non-particulate organic porous ion exchanger has a continuous macropore structure in which cellular macropores overlap each other and the overlapping portions form openings with an average diameter of 30 to 300 μm, a total pore volume of 0.5 to 10 ml / g, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, ion exchange groups are uniformly distributed throughout the organic porous ion exchanger, and in an SEM image of a cross section of the continuous macropore structure (dried body), the area of ​​the framework appearing in the cross section accounts for 25 to 50% of the image area.

[0015] The present invention (5) provides a platinum group metal ion-supported catalyst according to (1), characterized in that the non-particulate organic porous ion exchanger is a bicontinuous structure consisting of a three-dimensionally continuous skeleton with an average thickness of 1 to 60 μm, which is made of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of crosslinked structural units among all structural units having ion exchange groups introduced therein, and three-dimensionally continuous pores with an average diameter of 10 to 200 μm between the skeletons, the total pore volume being 0.5 to 10 ml / g, the ion exchange capacity per weight in a dry state being 1 to 9 mg equivalents / g, and the ion exchange groups being uniformly distributed throughout the organic porous ion exchanger.

[0016] The present invention (6) provides a platinum group metal ion-supported catalyst according to (1), characterized in that the non-particulate organic porous ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the skeleton having a large number of particles with a diameter of 4 to 40 μm adhered to the surface or a large number of protrusions with a size of 4 to 40 μm formed on the skeleton surface of the organic porous ion exchanger, the average diameter of the continuous pores being 10 to 200 μm, the total pore volume being 0.5 to 10 ml / g, the ion exchange capacity per weight in a dry state being 1 to 9 mg equivalents / g, and the ion exchange groups being uniformly distributed throughout the organic porous ion exchanger.

[0017] The present invention (7) also provides a platinum group metal ion-supported catalyst according to any one of (1) to (6), characterized in that the amount of the platinum group metal ion or the platinum group metal complex ion supported is 0.05 to 10.0 mass% in terms of platinum group metal atom.

[0018] The present invention (8) is a method for forming a carbon-carbon bond by (1) reacting an aromatic halide with an organoboron compound, (2) reacting an aromatic halide with a compound having a terminal alkynyl group, or (3) reacting an aromatic halide with a compound having an alkenyl group, a raw material liquid (i) containing an aromatic halide and an organoboron compound, a raw material liquid (ii) containing an aromatic halide and a compound having an alkynyl group at a terminal, or a raw material liquid (iii) containing an aromatic halide and a compound having an alkenyl group is introduced into a vessel filled with a platinum group metal ion-supported catalyst through an inlet path of the vessel, the raw material liquid is passed through the platinum group metal ion-supported catalyst, and a reaction liquid is discharged from a discharge path of the vessel, thereby carrying out a carbon-carbon bond forming reaction; the platinum group metal ion-supported catalyst is any one of the platinum group metal ion-supported catalysts (1) to (7); The present invention provides a method for forming a carbon-carbon bond, characterized by the following:

[0019] The present invention (9) also provides the method for forming a carbon-carbon bond according to (8), characterized in that the carbon-carbon bond-forming reaction is carried out in the presence of an inorganic base.

[0020] The present invention (10) also provides a method for producing a raw material solution (i) containing an aromatic halide and an organoboron compound, a raw material solution (ii) containing an aromatic halide and a compound having an alkynyl group at a terminal, or a raw material solution (iii) containing an aromatic halide and a compound having an alkenyl group, wherein the raw material solution (i) is an inorganic base-dissolved raw material solution in which a raw material and an inorganic base are dissolved in water or a hydrophilic solvent, introducing the inorganic base-dissolved raw material solution into a packed container filled with the platinum group metal ion-supported catalyst through an inlet path of the packed container, passing the inorganic base-dissolved raw material solution through the platinum group metal ion-supported catalyst, and discharging the reaction solution through a discharge path of the packed container, thereby carrying out a carbon-carbon bond forming reaction; The present invention also provides a method for forming a carbon-carbon bond according to (8) or (9), characterized in that:

[0021] The present invention (11) also provides a method for preparing a raw material solution (i) containing an aromatic halide and an organoboron compound, a raw material solution (ii) containing an aromatic halide and a compound having an alkynyl group at a terminal, or a raw material solution (iii) containing an aromatic halide and a compound having an alkenyl group, wherein the raw material solution is a hydrophobic solvent raw material solution in which raw materials are dissolved in a hydrophobic organic solvent; introducing a mixture of the hydrophobic solvent raw material liquid and the inorganic base aqueous solution into a container filled with the platinum group metal ion-supported catalyst through an inlet path of the container, passing the hydrophobic solvent-dissolved raw material liquid and the inorganic base aqueous solution through the platinum group metal ion-supported catalyst, and discharging the reaction solution through a discharge path of the container, thereby carrying out a carbon-carbon bond forming reaction; The present invention also provides a method for forming a carbon-carbon bond according to (8) or (9), characterized in that: [Effects of the Invention]

[0022] According to the present invention, it is possible to provide a catalyst that can be used in a fixed-bed continuous flow method for forming a carbon-carbon bond to obtain a desired compound, and that can carry out the reaction with various raw materials in high yields. [Brief explanation of the drawings]

[0023] [Figure 1] 1 is an SEM photograph of a first monolith morphology example. [Figure 2] 10 is an SEM photograph of a second monolith morphology example. [Figure 3] 10 is an SEM photograph of a third monolith morphology example. [Figure 4] This is a transfer of the skeleton portion that appears as a cross section of the SEM photograph in Figure 3. [Figure 5] 10 is an SEM photograph of a fourth monolith morphology example. [Figure 6] FIG. 1 is a schematic diagram of the co-continuous structure of a fourth monolith and a weakly basic monolith ion exchanger. [Figure 7] 1 is a SEM photograph of an example of the morphology of the monolith intermediate (4). [Figure 8] FIG. 2 is a schematic cross-sectional view of a protrusion. [Figure 9] 5-1 is an SEM photograph of an example of the monolith shape. [Figure 10] 1 is an SEM photograph of the monolith intermediate of Reference Example 1. [Figure 11] 1 is an SEM photograph of the monolith of Reference Example 1. [Figure 12] 1 shows the results of EPMA analysis of the platinum group metal ion supported catalyst of Example 1. [Figure 13] 1 is a Pd3d5 / 2 spectrum obtained by ESCA analysis of the platinum group metal ion supported catalyst of Example 1. [Figure 14] FIG. 1 is a flow diagram of an example of a reactor configuration illustrating a first embodiment of a carbon-carbon bond forming method of the present invention. [Figure 15] FIG. 2 is a flow diagram of an example of the configuration of a reaction apparatus showing a second embodiment of the carbon-carbon bond forming method of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] The platinum group metal ion-supported catalyst of the present invention is a platinum group metal ion-supported catalyst in which platinum group metal ions or platinum group metal complex ions are supported on a non-particulate organic porous ion exchanger. The non-particulate organic porous ion exchanger is composed of a continuous skeleton phase and a continuous pore phase, the continuous skeleton having a thickness of 1 to 100 μm, the continuous pores having an average diameter of 1 to 1000 μm, a total pore volume of 0.5 to 50 ml / g, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and ion exchange groups being uniformly distributed throughout the organic porous ion exchanger.

[0025] In the platinum group metal ion-supported catalyst of the present invention, the support on which platinum group metal ions or platinum group metal complex ions are supported is a non-particulate organic porous ion exchanger, and this non-particulate organic porous ion exchanger is an acidic monolithic organic porous cation exchanger or a basic monolithic organic porous anion exchanger. A monolithic organic porous material is a porous material whose skeleton is formed from an organic polymer and has a large number of interconnecting pores that serve as flow paths for the reaction solution. A monolithic organic porous ion exchanger is a porous material in which cation exchange groups or anion exchange groups are uniformly distributed within the skeleton of the monolithic organic porous material. In this specification, a "monolithic organic porous material" is also referred to simply as a "monolith," and a "monolithic organic porous ion exchanger" is also referred to simply as a "monolith ion exchanger." Furthermore, a "monolithic organic porous intermediate," which is an intermediate (precursor) in the production of a monolith, is also referred to simply as a "monolith intermediate."

[0026] The non-particulate organic porous ion exchanger for the platinum group metal ion-supported catalyst of the present invention is obtained by introducing ion exchange groups into a monolith, and has a structure of an organic porous material consisting of a continuous skeleton phase and a continuous pore phase, with the continuous skeleton having a thickness of 1 to 100 μm, the continuous pores having an average diameter of 1 to 1000 μm, and the total pore volume being 0.5 to 50 ml / g.

[0027] The continuous skeleton thickness of the non-particulate organic porous ion exchanger in the platinum group metal ion-supported catalyst of the present invention is 1 to 100 μm in a dry state. A continuous skeleton thickness of less than 1 μm is undesirable because it reduces the ion exchange capacity per volume and also reduces mechanical strength, resulting in significant deformation of the non-particulate organic porous ion exchanger, particularly when passing a liquid at a high flow rate. Furthermore, it is undesirable because it reduces the contact efficiency between the reaction liquid and the non-particulate organic porous ion exchanger and reduces catalytic activity. On the other hand, a continuous skeleton thickness of more than 100 μm is undesirable because the skeleton becomes too thick, requiring longer substrate diffusion times and reducing catalytic activity. The thickness of the continuous skeleton is determined by SEM observation.

[0028] The non-particulate organic porous ion exchanger for the platinum group metal ion-supported catalyst of the present invention has an average diameter of interconnected pores in a dry state of 1 to 1,000 μm. An average diameter of interconnected pores in the non-particulate organic porous ion exchanger of less than 1 μm is undesirable because it increases the pressure loss during liquid passage. On the other hand, an average diameter of interconnected pores in the non-particulate organic porous ion exchanger of more than 1,000 μm is undesirable because it results in insufficient contact between the reaction liquid and the non-particulate organic porous ion exchanger and reduces catalytic activity. The average diameter of interconnected pores in the non-particulate organic porous ion exchanger in a dry state is measured by mercury intrusion porosimetry and refers to the maximum value of the pore size distribution curve obtained by mercury intrusion porosimetry.

[0029] The total pore volume of the non-particulate organic porous ion exchanger for the platinum group metal ion-supported catalyst of the present invention in a dry state is 0.5 to 50 ml / g. A total pore volume of less than 0.5 ml / g is undesirable because it increases the pressure loss during liquid passage. Furthermore, the permeate volume per unit cross-sectional area decreases, resulting in a reduced throughput. On the other hand, a total pore volume of more than 50 ml / g is undesirable because it reduces the ion exchange capacity per volume, reduces the amount of platinum group metal ions supported, and reduces catalytic activity. Furthermore, the mechanical strength decreases, causing significant deformation of the non-particulate organic porous ion exchanger, especially when liquid is passed through at high speeds, resulting in a rapid increase in pressure loss during liquid passage. Furthermore, the contact efficiency between the reaction liquid and the non-particulate organic porous ion exchanger decreases, resulting in a significant decrease in catalytic activity. The total pore volume is measured by mercury intrusion porosimetry.

[0030] Examples of the structure of such non-particulate organic porous ion exchangers include the open-cell structure disclosed in JP-A-2002-306976 and JP-A-2009-62512, the bicontinuous structure disclosed in JP-A-2009-67982, the particle agglomeration structure disclosed in JP-A-2009-7550, and the particle composite structure disclosed in JP-A-2009-108294.

[0031] The non-particulate organic porous ion exchanger according to the present invention for supporting platinum group metal ions has an ion exchange capacity per unit weight in a dry state of 1 to 9 mg equivalents / g. A dry ion exchange capacity of less than 1 mg equivalent / g is undesirable because the amount of platinum group metal ions that can be supported is reduced. On the other hand, a dry ion exchange capacity of more than 9 mg equivalents / g is undesirable because the ion exchange group introduction reaction becomes harsh and oxidative degradation of the monolith progresses significantly. The dry ion exchange capacity of the non-particulate organic porous ion exchanger is 1 to 9 mg equivalents / g, preferably 1 to 8 mg equivalents / g, and particularly preferably 1 to 7 mg equivalents / g. The ion exchange capacity of a porous material in which ion exchange groups are introduced only on the framework surface cannot be determined in general terms depending on the porous material and the type of ion exchange group, but is at most 500 μg equivalents / g.

[0032] In the non-particulate organic porous ion exchanger for the platinum group metal ion-supported catalyst of the present invention, the introduced ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the monolith's skeleton. Here, "uniformly distributed ion exchange groups" refers to ion exchange groups being uniformly distributed on the surface and within the skeleton at least on the order of μm. The distribution of ion exchange groups can be easily confirmed using EPMA. Furthermore, uniform distribution of ion exchange groups not only on the surface of the monolith but also within the skeleton of the monolith can make the physical and chemical properties of the surface and the interior uniform, thereby improving resistance to swelling and shrinkage.

[0033] The cation exchange groups introduced into the non-particulate organic porous ion exchanger for the platinum group metal ion-supported catalyst of the present invention are strongly acidic cation exchange groups or weakly acidic cation exchange groups. Examples of strongly acidic cation exchange groups include sulfonic acid groups. Examples of weakly acidic cation exchange groups include carboxyl groups. The anion exchange groups introduced into the non-particulate organic porous ion exchanger for the platinum group metal ion-supported catalyst of the present invention are strongly basic anion exchange groups or weakly basic anion exchange groups. Examples of strongly basic anion exchange groups include quaternary ammonium groups such as trimethylammonium groups, triethylammonium groups, tributylammonium groups, dimethylhydroxyethylammonium groups, dimethylhydroxypropylammonium groups, and methyldihydroxyethylammonium groups. Examples of weakly basic anion exchange groups include tertiary amino groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, methylhydroxyethylamino, methylhydroxypropylamino, dicyclohexylamino, pyrrolidyl, piperidyl, 2,2,6,6-tetramethylpiperidyl, and morpholyl groups; secondary amino groups such as methylamino, ethylamino, propylamino, butylamino, hydroxyethylamino, and hydroxybutylamino groups; and primary amino groups.

[0034] In the non-particulate organic porous ion exchanger for the platinum group metal ion-supported catalyst of the present invention, the material constituting the continuous skeleton is an organic polymer material having a crosslinked structure. While the crosslink density of the polymer material is not particularly limited, it is preferable that the polymer material contains 0.1 to 30 mol %, preferably 0.1 to 20 mol %, of crosslinked structural units relative to the total structural units constituting the polymer material. A crosslinked structural unit content of less than 0.1 mol % is undesirable due to insufficient mechanical strength, while a content exceeding 30 mol % is undesirable due to difficulties in introducing ion exchange groups. The type of polymer material is not particularly limited, and examples 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 polymers such as polyacrylonitrile; and (meth)acrylic polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing multiple vinyl monomers and a crosslinking agent, or a blend of two or more polymers. Among these organic polymer materials, crosslinked polymers of aromatic vinyl polymers are preferred because of their ease of forming a continuous structure, ease of introducing ion exchange groups, high mechanical strength, and high stability against acids or alkalis. In particular, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred materials.

[0035] <Examples of the monolithic organic porous material and the monolithic organic porous ion exchanger> Examples of the monolith form include the first to fifth monoliths shown below. Furthermore, examples of the monolith ion exchanger include the first to fifth monolith ion exchangers shown below. In the first to fifth monolith ion exchangers, the ion exchange groups introduced into the monolith are strongly acidic cation exchange groups, weakly acidic cation exchange groups, strongly basic anion exchange groups, or weakly basic anion exchange groups.

[0036] <Description of the first monolith and the first monolith ion exchanger> In the platinum group metal ion-supported catalyst of the present invention, the first monolith ion exchanger serving as a support for platinum group metal ions or platinum group metal complex ions has an open-cell structure with interconnected macropores and common openings (mesopores) in the walls of the macropores having an average diameter of 1 to 1000 μm in a dry state, a total pore volume in the dry state of 1 to 50 ml / g, ion exchange groups that are uniformly distributed, and an ion exchange capacity per weight in the dry state of 1 to 9 mg / equivalent / g. The first monolith is a monolith before ion exchange groups are introduced, and is an organic porous material having an open-cell structure with interconnected macropores and common openings (mesopores) in the walls of the macropores having an average diameter of 1 to 1000 μm in a dry state, and a total pore volume in the dry state of 1 to 50 ml / g.

[0037] The first monolithic ion exchanger has a continuous macropore structure in which cellular macropores overlap each other, forming common openings (mesopores) with an average diameter of 1 to 1,000 μm, preferably 10 to 200 μm, and particularly preferably 20 to 100 μm, in a dry state. The majority of these macropores have an open pore structure. When water flows through the open pore structure, the bubbles formed by the macropores and mesopores become flow paths. The number of overlapping macropores per macropore is 1 to 12, and in most cases, 3 to 10. Figure 1 shows a scanning electron microscope (SEM) photograph of an example of the first weakly basic monolithic anion exchanger. The first monolithic ion exchanger shown in Figure 1 has numerous cellular macropores. The cellular macropores overlap each other, forming a continuous macropore structure in which the overlapping macropores form common openings (mesopores), with the majority of these macropores having an open pore structure. If the average diameter of the mesopores in the dry state is less than 1 μm, the pressure loss during liquid passage will be significantly increased, which is undesirable, whereas if the average diameter of the mesopores in the dry state is more than 1000 μm, the contact between the reaction solution and the monolith ion exchanger will be insufficient, resulting in a decrease in catalytic activity, which is undesirable.The open-cell structure of the first monolith ion exchanger described above allows for the uniform formation of macropores and mesopores, and also allows for a significantly larger pore volume and specific surface area than particle-aggregate porous media such as those described in JP-A-8-252579.

[0038] In the present invention, the average diameter of the openings of the first monolith in a dry state and the average diameter of the openings of the first monolith ion exchanger in a dry state are measured by mercury intrusion porosimetry and refer to the maximum value of the pore size distribution curve obtained by mercury intrusion porosimetry.

[0039] The total pore volume per unit weight of the first monolith ion exchanger in a dry state is 1 to 50 ml / g, preferably 2 to 30 ml / g. A total pore volume of less than 1 ml / g is undesirable because it increases the pressure loss during liquid passage and reduces the permeation rate per unit cross-sectional area, resulting in a decrease in processing capacity. On the other hand, a total pore volume exceeding 50 ml / g is undesirable because it reduces the mechanical strength and significantly deforms the monolith ion exchanger, especially when liquid is passed through at a high flow rate. Furthermore, it reduces the contact efficiency between the reaction liquid and the monolith ion exchanger and the platinum group metal particles supported on it, resulting in a decrease in catalytic activity. While conventional particulate porous ion exchange resins have a total pore volume of at most 0.1 to 0.9 ml / g, unprecedented high pore volumes and high specific surface areas of 1 to 50 ml / g can be used.

[0040] In the first monolith ion exchanger, the material constituting the skeleton is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material is not particularly limited, but it is preferable that the crosslinked structural units are contained in an amount of 0.3 to 10 mol %, and more preferably 0.3 to 5 mol %, of the total structural units constituting the polymer material. If the crosslinked structural units are less than 0.3 mol %, the mechanical strength will be insufficient, which is undesirable. On the other hand, if the crosslinked structural units are more than 10 mol %, the introduction of ion exchange groups may become difficult, which is undesirable.

[0041] The organic polymer material constituting the skeleton of the first monolithic ion exchanger is not particularly limited by its type. Examples include 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 polymers such as polyacrylonitrile; and crosslinked polymers such as (meth)acrylic polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate. The organic polymer may be a polymer obtained by copolymerizing a single vinyl monomer with a crosslinking agent, a polymer obtained by polymerizing multiple vinyl monomers with a crosslinking agent, or a blend of two or more polymers. Among these organic polymer materials, crosslinked polymers of aromatic vinyl polymers are preferred due to their ease of forming a continuous macropore structure, ease of introducing ion exchange groups, high mechanical strength, and high stability against acids and alkalis. In particular, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred.

[0042] The ion exchange groups introduced into the first monolith ion exchanger are the same as those introduced into the second to fifth monolith ion exchangers. The cation exchange groups introduced into the monolith ion exchanger are strongly acidic cation exchange groups or weakly acidic cation exchange groups. Examples of strongly acidic cation exchange groups include sulfonic acid groups. Examples of weakly acidic cation exchange groups include carboxyl groups. The anion exchange groups introduced into the monolith ion exchanger are strongly basic anion exchange groups or weakly basic anion exchange groups. Examples of strongly basic anion exchange groups include quaternary ammonium groups such as trimethylammonium groups, triethylammonium groups, tributylammonium groups, dimethylhydroxyethylammonium groups, dimethylhydroxypropylammonium groups, and methyldihydroxyethylammonium groups. Examples of weakly basic anion exchange groups include tertiary amino groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, methylhydroxyethylamino, methylhydroxypropylamino, dicyclohexylamino, pyrrolidyl, piperidyl, 2,2,6,6-tetramethylpiperidyl, and morpholyl groups; secondary amino groups such as methylamino, ethylamino, propylamino, butylamino, hydroxyethylamino, and hydroxybutylamino groups; and primary amino groups.

[0043] In the first monolith ion exchanger (and the second to fifth monolith ion exchangers), the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also inside the skeleton of the porous body. Here, "uniform distribution of ion exchange groups" refers to the ion exchange groups being uniformly distributed on the surface and inside the skeleton at least on the order of μm. The distribution of ion exchange groups is confirmed using EPMA. Furthermore, if the ion exchange groups are uniformly distributed not only on the surface of the monolith but also inside the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, improving resistance to swelling and shrinkage.

[0044] The ion exchange capacity per weight of the first monolith ion exchanger in a dry state is 1 to 9 mg equivalents / g. By having the ion exchange capacity per weight in a dry state within the above range, it is possible to change the environment around the catalytic active sites, such as the pH inside the catalyst, thereby increasing catalytic activity. The ion exchange capacity per weight of the first monolith ion exchanger in a dry state is 1 to 9 mg equivalents / g, preferably 1 to 8 mg equivalents / g, and particularly preferably 1 to 7 mg equivalents / g. The ion exchange capacity of a porous material in which ion exchange groups are introduced only on the surface cannot be determined in general terms depending on the type of porous material and ion exchange groups, but is at most 500 μg equivalents / g.

[0045] <Method for producing the first monolith and the first monolith ion exchanger> The method for producing the first monolith is not particularly limited, but an example of a production method based on the method described in JP 2002-306976 A is shown below. That is, the first monolith is obtained by mixing an oil-soluble monomer not containing an ion exchange group, a surfactant, water, and, if necessary, a polymerization initiator to obtain a water-in-oil emulsion, which is then polymerized to form a monolith. This method for producing the first monolith is preferable in that it is easy to control the porous structure of the monolith.

[0046] The oil-soluble monomers not containing ion exchange groups used in the production of the first monolith refer to monomers that do not contain ion exchange groups such as carboxylic acid groups or sulfonic acid groups, or anion exchange groups such as quaternary ammonium groups, and that have low solubility in water and are lipophilic. Specific examples of these monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isobutene, butadiene, isoprene, chloroprene, vinyl chloride, vinyl bromide, vinylidene chloride, tetrafluoroethylene, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, trimethylolpropane triacrylate, butanediol diacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and ethylene glycol dimethacrylate. These monomers can be used alone or in combination of two or more. However, in the present invention, it is preferable to select a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate as at least one component of the oil-soluble monomers and set the content thereof to 0.3 to 10 mol %, preferably 0.3 to 5 mol %, of the total oil-soluble monomers, in order to quantitatively introduce ion-exchange groups in a later step and to ensure practically sufficient mechanical strength.

[0047] The surfactant used in the production of the first monolith is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when mixed with an oil-soluble monomer not containing an ion exchange group and water. Examples of suitable surfactants include nonionic surfactants such as sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, and polyoxyethylene sorbitan monooleate; anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyl dimethyl ammonium chloride; and amphoteric surfactants such as lauryl dimethyl betaine. These surfactants can be used alone or in combination. A water-in-oil emulsion is an emulsion in which the oil phase is the continuous phase and water droplets are dispersed within it. The amount of surfactant added varies greatly depending on the type of oil-soluble monomer and the size of the desired emulsion particles (macropores), so it cannot be generalized, but it can be selected from a range of approximately 2 to 70% of the total amount of oil-soluble monomer and surfactant. Furthermore, although not necessarily required, 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 be present in the system to control the shape and size of the monolith's cells.

[0048] Furthermore, in the production of the first monolith, when forming a monolith by polymerization, a polymerization initiator, if used as needed, is preferably a compound that generates radicals upon heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and examples 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, polymerization may proceed by heating or light irradiation alone without the addition of a polymerization initiator, and in such systems, the addition of a polymerization initiator is not necessary.

[0049] In the production of the first monolith, the oil-soluble monomer not containing an ion exchange group, the surfactant, water, and the polymerization initiator are mixed to form a water-in-oil emulsion. The mixing method is not particularly limited, and can include simultaneously mixing all the components at once, or separately dissolving the oil-soluble components (oil-soluble monomer, surfactant, and oil-soluble polymerization initiator) and the water-soluble components (water and water-soluble polymerization initiator) uniformly and then mixing the components. The mixing device used to form the emulsion is also not particularly limited, and can be a standard mixer, homogenizer, high-pressure homogenizer, or a planetary mixer, which mixes the material placed in a mixing container and rotates the container around its axis while tilting it, thereby stirring and mixing the material. Any suitable device can be used to achieve the desired emulsion particle size. Furthermore, the mixing conditions are not particularly limited, and the stirring speed and stirring time can be set as desired to achieve the desired emulsion particle size. Of these mixing devices, the planetary mixer is preferably used because it can generate uniform water droplets in the W / O emulsion and the average diameter of the droplets can be set arbitrarily within a wide range.

[0050] In producing the first monolith, the polymerization conditions for polymerizing the water-in-oil emulsion thus obtained can be selected from a variety of conditions depending on the type of monomer and initiator system. For example, when azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, or the like is used as the polymerization initiator, the polymerization can be carried out by heating in a sealed container under an inert atmosphere at 30 to 100°C for 1 to 48 hours. When hydrogen peroxide-ferrous chloride, sodium persulfate-sodium sulfite, or the like is used as the initiator, the polymerization can be carried out in a sealed container under an inert atmosphere at 0 to 30°C for 1 to 48 hours. After polymerization is complete, the contents are removed and subjected to Soxhlet extraction with a solvent such as isopropanol to remove unreacted monomer and residual surfactant, yielding the first monolith.

[0051] The method for producing the first monolith ion exchanger is not particularly limited, and examples include a method in which, in the above-mentioned first monolith production method, instead of the monomer not containing an ion exchange group, a monomer containing an ion exchange group, for example, the above-mentioned oil-soluble monomer not containing an ion exchange group, is polymerized with a monomer into which an ion exchange group has been introduced, to produce a monolith ion exchanger in one step, and a method in which a monomer not containing an ion exchange group is polymerized to form a first monolith, and then an ion exchange group is introduced. Of these methods, the method in which a monomer not containing an ion exchange group is polymerized to form a first monolith, and then an ion exchange group is introduced, is preferred because it makes it easy to control the porous structure of the monolith ion exchanger and enables quantitative introduction of ion exchange groups.

[0052] The method for introducing ion exchange groups into the first monolith is not particularly limited, and known methods such as polymer reactions and graft polymerization can be used. For example, methods for introducing strongly acidic cation exchange groups, such as sulfonic acid groups, include heating a styrene-divinylbenzene copolymer in concentrated sulfuric acid and reacting a styrene-divinylbenzene copolymer with chlorosulfonic acid. For example, methods for introducing weakly acidic cation exchange groups, such as carboxyl groups, include hydrolysis of an acrylic acid ester polymer. For example, methods for introducing strongly basic anion exchange groups, such as quaternary ammonium groups, include reacting a vinylbenzyl chloride-divinylbenzene copolymer with a tertiary amine. Examples of methods for introducing weakly basic anion exchange groups, such as amine groups, include: if the monolith is a styrene-divinylbenzene copolymer, for example, a method in which chloromethyl groups are introduced using chloromethyl methyl ether or the like, followed by reaction with a secondary amine; a method in which a monolith is produced by copolymerizing chloromethylstyrene and divinylbenzene, followed by reaction with a secondary amine; and a method in which a radical initiator group or a chain transfer group is introduced into a monolith, graft polymerized with glycidyl methacrylate, followed by reaction with a secondary amine. Examples of amine groups include weakly basic amine groups, such as tertiary amino groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, methylhydroxyethylamino, and methylhydroxypropylamino; secondary amino groups such as methylamino, ethylamino, propylamino, butylamino, hydroxyethylamino, and hydroxybutylamino; and primary amino groups.

[0053] <Description of the second monolith and the second monolith ion exchanger> In the platinum group metal ion-supported catalyst of the present invention, the second monolith ion exchanger that serves as a support for platinum group metal ions or platinum group metal complex ions is a particle-aggregation monolith, in which organic polymer particles having an average particle diameter of 1 to 50 μm in a dry state are aggregated to form a three-dimensionally continuous framework, and the framework has three-dimensionally continuous pores having an average diameter of 20 to 100 μm in a dry state between the skeletal components. The second monolith ion exchanger is an organic porous material with a total pore volume in a dry state of 1 to 10 ml / g, and contains ion exchange groups. The monolith ion exchanger has an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and the ion exchange groups are uniformly distributed throughout the organic porous ion exchanger. The second monolith is a monolith before ion exchange groups are introduced, and is a particle aggregation monolith in which organic polymer particles having an average particle diameter of 1 to 50 μm in a dry state are aggregated to form a three-dimensionally continuous skeleton, and between the skeletons there are three-dimensionally continuous pores having an average diameter of 20 to 100 μm in a dry state, and the organic porous body has a total pore volume in a dry state of 1 to 10 ml / g.

[0054] The basic structure of the second monolith ion exchanger is a particle agglomeration structure in which organic polymer particles having crosslinked structural units and an average particle diameter of 1 to 50 μm, preferably 1 to 30 μm, in a dry state are aggregated to form a three-dimensionally continuous skeleton, with three-dimensionally continuous voids having an average diameter of 20 to 100 μm, preferably 20 to 90 μm, in a dry state, between the skeletons. These three-dimensionally continuous voids serve as flow paths for liquids and gases. Figure 2 shows an SEM photograph of an example of the second monolith ion exchanger. The second monolith ion exchanger shown in Figure 2 has a particle agglomeration structure in which organic polymer particles are aggregated to form a three-dimensionally continuous skeleton, with three-dimensionally continuous voids between the skeletons. If the average particle diameter of the organic polymer particles is less than 1 μm in a dry state, the average diameter of the continuous voids between the skeletons will be small, less than 20 μm in a dry state, which is undesirable. If the average particle diameter of the organic polymer particles is more than 50 μm, contact between the reaction solution and the monolith ion exchanger will be insufficient, resulting in reduced catalytic activity, which is undesirable. Furthermore, if the average diameter of the three-dimensionally continuous pores present between the frameworks is less than 20 μm in a dry state, the pressure loss when the reaction liquid is passed through becomes large, which is undesirable. On the other hand, if it exceeds 100 μm, the contact between the reaction liquid and the monolith ion exchanger becomes insufficient, which reduces the catalytic activity, which is undesirable.

[0055] The average particle size in a dry state of the organic polymer particles constituting the framework of the second monolith and the second monolith ion exchanger can be easily measured using an SEM. Specifically, an SEM photograph is taken of an arbitrarily selected portion of the cross section of the second monolith ion exchanger in a dry state, the diameters of all the organic polymer particles in the SEM photograph are measured, and the average value is taken as the average particle size.

[0056] In addition, the average diameter of the three-dimensionally continuous pores present between the skeletons of the second monolith in a dry state or the average diameter of the three-dimensionally continuous pores present between the skeletons of the second monolith ion exchanger in a dry state is determined by mercury intrusion porosimetry and refers to the maximum value of the pore distribution curve obtained by mercury intrusion porosimetry.

[0057] The total pore volume per weight of the second monolith ion exchanger in a dry state is 1 to 10 ml / g. A total pore volume of less than 1 ml / g is undesirable because it increases the pressure loss during liquid passage and also reduces the permeation amount per unit cross-sectional area, resulting in a decrease in processing capacity. On the other hand, a total pore volume of more than 10 ml / g is undesirable because it reduces the mechanical strength and causes significant deformation of the monolith ion exchanger, especially when liquid is passed through at a high flow rate.

[0058] In the second monolith ion exchanger, the skeleton material is an organic polymer material having crosslinked structural units. That is, the organic polymer material has structural units consisting of vinyl monomers and crosslinker structural units having two or more vinyl groups in the molecule, and the polymer material preferably contains 1 to 5 mol %, and more preferably 1 to 4 mol %, of the crosslinked structural units relative to the total structural units constituting the polymer material. If the crosslinked structural units are less than 1 mol %, the mechanical strength will be insufficient, which is undesirable. On the other hand, if the crosslinked structural units are more than 5 mol %, the diameter of the three-dimensionally continuous pores existing between the skeletons will become small, which is undesirable because of increased pressure loss.

[0059] The polymer material constituting the skeleton of the second monolithic ion exchanger is not particularly limited, and examples thereof include styrene-based polymers such as polystyrene, poly(α-methylstyrene), and polyvinylbenzyl chloride; polyolefins such as polyethylene and polypropylene; poly(halogenated polyolefins) such as polyvinyl chloride and polytetrafluoroethylene; nitrile-based polymers such as polyacrylonitrile; (meth)acrylic polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate; styrene-divinylbenzene copolymers, vinylbenzyl chloride-divinylbenzene copolymers, and the like. The polymers may be polymers obtained by copolymerizing a single monomer and a crosslinking agent, polymers obtained by polymerizing multiple monomers and a crosslinking agent, or blends of two or more polymers. Among these organic polymer materials, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred due to their ease of forming particle aggregate structures, ease of ion-exchange group introduction, high mechanical strength, and high stability against acids and alkalis.

[0060] The anion exchange groups introduced into the second monolith ion exchanger are the same as the anion exchange groups introduced into the first monolith ion exchanger.

[0061] In the second monolith ion exchanger, the introduced ion exchange groups are distributed uniformly not only on the surface of the porous body but also inside the skeleton of the porous body, as in the first monolith ion exchanger.

[0062] The ion exchange capacity of the second monolith ion exchanger is 1 to 9 mg equivalents / g per weight in a dry state. The second monolith ion exchanger can significantly increase the ion exchange capacity per weight while maintaining low pressure loss. When the ion exchange capacity per weight in a dry state is within the above range, the environment around the catalytic active sites, such as the pH inside the catalyst, can be changed, thereby increasing catalytic activity. The ion exchange capacity per weight of the second monolith ion exchanger in a dry state is 1 to 9 mg equivalents / g, preferably 1 to 8 mg equivalents / g, and particularly preferably 1 to 7 mg equivalents / g.

[0063] <Method for producing second monolith and second monolith ion exchanger> A method for producing the second monolith includes mixing a vinyl monomer, a specific amount of a cross-linking agent, an organic solvent, and a polymerization initiator, and polymerizing the mixture in a static state to obtain the second monolith.

[0064] The vinyl monomer used in the production of the second monolith is not particularly limited as long as it contains a polymerizable vinyl group in the molecule and is a lipophilic monomer with high solubility in organic solvents. Specific examples of these vinyl monomers include styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzyl chloride; α-olefins such as ethylene, propylene, 1-butene, and isobutene; diene-based monomers such as butadiene, isoprene, and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride, and tetrafluoroethylene; nitrile-based monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; and (meth)acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and glycidyl methacrylate. These monomers may be used singly or in combination of two or more. The vinyl monomers preferably used are styrene-based monomers such as styrene and vinylbenzyl chloride.

[0065] The crosslinking agent used in the production of the second monolith preferably contains at least two polymerizable vinyl groups in the molecule and is highly soluble in organic solvents. Specific examples of crosslinking agents include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylate. These crosslinking agents may be used alone or in combination. Preferred crosslinking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl, due to their high mechanical strength and stability against hydrolysis. The amount of crosslinking agent used relative to the total amount of vinyl monomer and crosslinking agent ({crosslinking agent / (vinyl monomer + crosslinking agent)} × 100) is 1 to 5 mol%, preferably 1 to 4 mol%. The amount of crosslinking agent used significantly affects the porous structure of the resulting monolith. Using an amount of crosslinking agent exceeding 5 mol% is undesirable because it reduces the size of the interconnected pores formed between the skeletons. On the other hand, if the amount of crosslinking agent used is less than 1 mol %, the mechanical strength of the monolith will be insufficient, which may result in significant deformation or destruction of the monolith when a liquid is passed through it, which is undesirable.

[0066] The organic solvent used in the production of the second monolith dissolves vinyl monomers and crosslinkers but not the polymer produced by polymerization of the vinyl monomers. In other words, it is a poor solvent for the polymer produced by polymerization of the vinyl monomers. Because the type of organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general examples. For example, when the vinyl monomer is styrene, examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, ethylene glycol, tetramethylene glycol, and glycerin; chain ethers such as diethyl ether and ethylene glycol dimethyl ether; and chain saturated hydrocarbons such as hexane, octane, decane, and dodecane. Among these, alcohols are preferred because they facilitate the formation of particle aggregate structures by static polymerization and increase the size of three-dimensionally continuous pores. Furthermore, even good solvents for polystyrene, such as benzene and toluene, can be used as organic solvents when used in small amounts together with the poor solvent.

[0067] The polymerization initiator used in the production of the second monolith is preferably a compound that generates radicals upon heat and light irradiation. The polymerization initiator is preferably oil-soluble. Specific 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), 2,2'-azobisisobutyric acid dimethyl, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, and tetramethylthiuram disulfide. The amount of polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but the amount of polymerization initiator used relative to the total amount of vinyl monomer and crosslinking agent ({polymerization initiator / (vinyl monomer+crosslinking agent)}×100) is approximately 0.01 to 5 mol %.

[0068] In producing the second monolith, various polymerization conditions can be selected depending on the type of monomer and initiator. For example, when using 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, or the like as the initiator, the polymerization can be carried out by heating in a sealed container under an inert atmosphere at 30 to 100°C for 1 to 48 hours. After polymerization is complete, the contents are removed and extracted with a solvent such as acetone to remove unreacted vinyl monomer and organic solvent, yielding the second monolith.

[0069] In the production of the second monolith, if the conditions are such that the polymerization of the vinyl monomer dissolved in the organic solvent proceeds rapidly, organic polymer particles with an average particle size of approximately 1 μm can be precipitated and aggregated to form a three-dimensionally continuous skeleton. Conditions for rapid polymerization of the vinyl monomer vary depending on the vinyl monomer, crosslinking agent, polymerization initiator, and polymerization temperature, and cannot be determined in general terms. Examples include increasing the amount of crosslinking agent, increasing the monomer concentration, and increasing the temperature. Taking these polymerization conditions into consideration, the polymerization conditions for aggregating organic polymer particles with an average particle size of 1 to 50 μm can be appropriately determined. Furthermore, to form three-dimensionally continuous pores with an average diameter of 20 to 100 μm between the skeletons, as described above, the amount of crosslinking agent used relative to the total amount of vinyl monomer and crosslinking agent can be set to a specific amount. Furthermore, to achieve a total pore volume of 1 to 5 ml / g for the monolith, polymerization can be carried out under conditions such that the amount of organic solvent used relative to the total amount of organic solvent, monomer, and crosslinking agent ({organic solvent / (organic solvent + monomer + crosslinking agent)} × 100) is 30 to 80% by weight, preferably 40 to 70% by weight, although this cannot be determined in general as it varies depending on factors such as the vinyl monomer, crosslinking agent, polymerization initiator, and polymerization temperature.

[0070] Methods for producing the second monolith ion exchanger include a method in which, in the above-mentioned method for producing the second monolith, a monomer containing an ion exchange group, for example, a vinyl monomer not containing an ion exchange group, is polymerized with a monomer to which an ion exchange group such as a carboxylic acid group or a sulfonic acid group has been introduced, to produce a monolith ion exchanger in one step, and a method in which a vinyl monomer not containing an ion exchange group is polymerized to form a second monolith, and then an ion exchange group is introduced.

[0071] The method for introducing ion exchange groups into the second monolith is the same as the method for introducing ion exchange groups into the first monolith.

[0072] <Description of the third monolith and the third monolith ion exchanger> In the platinum group metal ion-supported catalyst of the present invention, the third monolith ion exchanger serving as a carrier for platinum group metal ions or platinum group metal complex ions is a monolith ion exchanger having a continuous macropore structure in which cellular macropores overlap each other, and these overlapping portions form openings with an average diameter of 30 to 300 μm in a dry state, a total pore volume in a dry state of 0.5 to 10 ml / g, and in an SEM image of a cut surface of the continuous macropore structure (dried body), the area of ​​the skeleton appearing in the cross section accounts for 25 to 50% of the image area, the monolith ion exchanger has ion exchange groups, and an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and the ion exchange groups are uniformly distributed throughout the organic porous ion exchanger. The third monolith is a monolith before ion exchange groups are introduced, and is an organic porous body having a continuous macropore structure in which bubble-like macropores overlap each other and these overlapping portions form openings with an average diameter of 30 to 300 μm in a dry state, a total pore volume in a dry state of 0.5 to 10 ml / g, and in an SEM image of a cut surface of the continuous macropore structure (dried body), the area of ​​the skeleton appearing in the cross section is 25 to 50% of the image area.

[0073] The third monolith ion exchanger has a continuous macropore structure in which cellular macropores overlap each other, forming openings (mesopores) with an average diameter of 30 to 300 μm, preferably 30 to 200 μm, and particularly preferably 40 to 100 μm in a dry state. Figure 3 shows an SEM photograph of an example of the third monolith ion exchanger. The third monolith ion exchanger shown in Figure 3 has numerous cellular macropores, and the cellular macropores overlap each other, forming common openings (mesopores) in the overlapping areas, forming a continuous macropore structure, the majority of which has an open pore structure. An average opening diameter of less than 30 μm in a dry state is undesirable because it increases the pressure loss during liquid flow. On the other hand, an opening diameter that is too large in a dry state is undesirable because it results in insufficient contact between the reaction solution and the monolith ion exchanger and the supported platinum group metal particles, resulting in reduced catalytic activity.

[0074] The average diameter of the openings of the dry third monolith, the average diameter of the openings of the dry third monolith ion exchanger, and the average diameter of the openings of the dry third monolith intermediate (3) obtained in step I of the production of the third monolith described below are measured by mercury intrusion porosimetry and refer to the maximum values ​​of the pore size distribution curve obtained by mercury intrusion porosimetry.

[0075] In the third monolith ion exchanger, in an SEM image of a cut surface of the continuous macropore structure (dried body), the area of ​​the skeleton appearing in the cross section is 25 to 50% of the image area, preferably 25 to 45%. If the area of ​​the skeleton appearing in the cross section is less than 25% of the image area, the skeleton becomes thin, reducing mechanical strength and causing significant deformation of the monolith ion exchanger, particularly when passing a liquid at a high flow rate, which is undesirable. Furthermore, this reduces the contact efficiency between the reaction liquid and the monolith ion exchanger and the platinum group metal particles supported thereon, thereby reducing the catalytic effect. If the area exceeds 50%, the skeleton becomes too thick, increasing pressure loss during liquid passage, which is undesirable.

[0076] The conditions for obtaining an SEM image may be any conditions that clearly show the skeleton portion in the cross section of the cut surface, such as a magnification of 100 to 600 and a photographic area of ​​approximately 150 mm × 100 mm. SEM observation is preferably performed using three or more, preferably five or more, images taken at different cut locations or photographed at different positions on any cut surface of the third monolith ion exchanger, eliminating subjective judgment. The third monolith ion exchanger to be cut is in a dry state for use in electron microscopy. The skeleton portion of the cut surface in the SEM image will be described with reference to FIGS. 3 and 4. FIG. 4 is a transfer of the skeleton portion appearing as the cross section of the SEM photograph in FIG. 3. In FIGS. 3 and 4, the roughly irregular shape and cross section represents the "skeleton portion appearing in the cross section (reference numeral 12)" of the present invention. The circular pores appearing in FIG. 3 are open pores (mesopores), and those with a relatively large curvature or curved surface are macropores (reference numeral 13 in FIG. 4). The area of ​​the skeleton that appears in the cross section of Figure 4 is 28% of the rectangular image area 11. In this way, the skeleton can be clearly identified.

[0077] The method for measuring the area of ​​the skeleton portion appearing in the cross section of the cut surface in an SEM image is not particularly limited, and examples include a method in which the skeleton portion is identified by known computer processing or the like, and then automatic calculation by a computer or manual calculation is performed. An example of manual calculation is a method in which irregularly shaped objects are replaced with aggregates of squares, triangles, circles, trapezoids, etc., and these are stacked to determine the area.

[0078] The total pore volume per unit weight of the third monolith ion exchanger in a dry state is 0.5 to 10 ml / g, preferably 0.8 to 8 ml / g. A total pore volume of less than 0.5 ml / g is undesirable because it increases the pressure loss during liquid passage, and also reduces the amount of permeating fluid per unit cross-sectional area, resulting in a decrease in processing capacity. On the other hand, a total pore volume of more than 10 ml / g is undesirable because it reduces the mechanical strength and significantly deforms the monolith ion exchanger, particularly when liquid is passed through at a high flow rate. Furthermore, the contact efficiency between the reaction liquid and the monolith ion exchanger and the platinum group metal ions supported on it decreases, resulting in a decrease in catalytic effect, which is undesirable.

[0079] In the third monolith ion exchanger, the material constituting the skeleton is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material is not particularly limited, but it is preferable that the crosslinked structural units are contained in an amount of 0.3 to 10 mol %, and more preferably 0.3 to 5 mol %, based on the total structural units constituting the polymer material. If the crosslinked structural units are less than 0.3 mol %, the mechanical strength will be insufficient, which is undesirable. On the other hand, if the crosslinked structural units are more than 10 mol %, the introduction of ion exchange groups may become difficult, which is undesirable.

[0080] The polymer material constituting the skeleton of the third monolithic ion exchanger is not particularly limited, and examples thereof include crosslinked polymers such as aromatic vinyl polymers (e.g., polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, and polyvinylnaphthalene); polyolefins (e.g., polyethylene and polypropylene); poly(halogenated polyolefins) (e.g., polyvinyl chloride and polytetrafluoroethylene); nitrile polymers (e.g., polyacrylonitrile); and (meth)acrylic polymers (e.g., polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate). The polymers may be polymers obtained by copolymerizing a single vinyl monomer with a crosslinking agent, polymers obtained by polymerizing multiple vinyl monomers with a crosslinking agent, or blends of two or more polymers. Among these organic polymer materials, crosslinked polymers of aromatic vinyl polymers are preferred because of their ease of forming a continuous macropore structure, their ease of introducing ion-exchange groups when ion-exchange groups are introduced, their high mechanical strength, and their high stability against acids and alkalis. In particular, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred.

[0081] The ion exchange groups introduced into the third monolith ion exchanger are the same as those introduced into the first monolith ion exchanger.

[0082] In the third monolithic ion exchanger, the introduced ion exchange groups are distributed uniformly not only on the surface of the porous body but also inside the skeleton of the porous body.

[0083] The third monolith ion exchanger has an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g. The third monolith ion exchanger can further increase the opening diameter and thicken the skeleton of the continuous macropore structure (thicken the walls of the skeleton), thereby dramatically increasing the ion exchange capacity per volume while maintaining low pressure loss. Having an ion exchange capacity per weight in the dry state within the above range allows for changes in the environment around the catalytic active sites, such as the pH inside the catalyst, thereby increasing catalytic activity. The ion exchange capacity per weight of the third monolith ion exchanger in a dry state is 1 to 9 mg equivalents / g, preferably 1 to 8 mg equivalents / g, and particularly preferably 1 to 7 mg equivalents / g.

[0084] <Method for producing the third monolith and the third monolith ion exchanger> The third monolith can be obtained by carrying out the following steps: Step I: preparing a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer that does not contain ion exchange groups, a surfactant, and water; then polymerizing the water-in-oil emulsion to obtain a monolithic organic porous intermediate (hereinafter also referred to as monolith intermediate (3)) with a continuous macropore structure and a total pore volume of 5 to 16 ml / g; Step II: preparing a mixture consisting of a vinyl monomer, a crosslinking agent having at least two vinyl groups per molecule, an organic solvent that dissolves the vinyl monomer and the crosslinking agent but not the polymer produced by polymerization of the vinyl monomer, and a polymerization initiator; and Step III: allowing the mixture obtained in Step II to stand and polymerizing it in the presence of the monolith intermediate (3) obtained in Step I to obtain a third monolith having a skeleton thicker than that of the monolith intermediate (3).

[0085] In the third monolith manufacturing method, step I may be carried out in accordance with the method described in Japanese Patent Application Laid-Open No. 2002-306976.

[0086] In the production of the monolith intermediate (3) in step I of the third monolith production method, examples of oil-soluble monomers that do not contain ion exchange groups include, for example, monomers that do not contain ion exchange groups such as carboxylic acid groups, sulfonic acid groups, or quaternary ammonium groups, have low solubility in water, and are lipophilic. Suitable examples of these monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isobutene, butadiene, and ethylene glycol dimethacrylate. These monomers can be used alone or in combination. However, it is preferable to select a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate as at least one component of the oil-soluble monomers and adjust its content to 0.3 to 10 mol%, preferably 0.3 to 5 mol%, of the total oil-soluble monomers, because this allows for quantitative introduction of ion exchange groups.

[0087] The surfactant used in step I of the third monolith production method is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when mixed with an oil-soluble monomer not containing ion exchange groups and water. Examples of suitable surfactants include nonionic surfactants such as sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, and polyoxyethylene sorbitan monooleate; anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyl dimethyl ammonium chloride; and amphoteric surfactants such as lauryl dimethyl betaine. These surfactants can be used alone or in combination. A water-in-oil emulsion is an emulsion in which the oil phase is the continuous phase and water droplets are dispersed within it. The amount of surfactant to be added cannot be generalized because it varies greatly depending on the type of oil-soluble monomer and the size of the desired emulsion particles (macropores), but it can be selected from the range of approximately 2 to 70% of the total amount of oil-soluble monomer and surfactant.

[0088] Furthermore, in step I of the third monolith manufacturing method, a polymerization initiator may be used as needed when forming the water-in-oil emulsion. A compound that generates radicals upon heat and light irradiation is preferably used as the polymerization initiator. The polymerization initiator may be water-soluble or oil-soluble, and examples include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-acidic sodium sulfite, and tetramethylthiuram disulfide.

[0089] In step I of the third monolith production method, the oil-soluble monomer not containing an ion exchange group, surfactant, water, and polymerization initiator are mixed to form a water-in-oil emulsion. The mixing method is not particularly limited, and can include simultaneously mixing all the components at once, or separately dissolving the oil-soluble components (oil-soluble monomer, surfactant, and oil-soluble polymerization initiator) and the water-soluble components (water and water-soluble polymerization initiator) uniformly and then mixing the components. The mixing device used to form the emulsion is also not particularly limited, and a standard mixer, homogenizer, high-pressure homogenizer, or other suitable device can be used. Select an appropriate device to achieve the desired emulsion particle size. The mixing conditions are also not particularly limited, and the stirring speed and stirring time can be set as desired to achieve the desired emulsion particle size.

[0090] The monolith intermediate (3) obtained in step I of the third monolith production method has a continuous macropore structure. When this monolith intermediate (3) is present in a polymerization system, a porous structure with a thick skeleton is formed based on the structure of the monolith intermediate (3). The monolith intermediate (3) is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material is not particularly limited, but it is preferable that the crosslinked structural units are contained in an amount of 0.3 to 10 mol %, preferably 0.3 to 5 mol %, based on the total structural units constituting the polymer material. If the crosslinked structural units are less than 0.3 mol %, mechanical strength will be insufficient, which is undesirable. In particular, when the total pore volume is large, such as 10 to 16 ml / g, it is preferable that the crosslinked structural units be contained in an amount of 2 mol % or more to maintain a continuous macropore structure. On the other hand, if the crosslinked structural units are contained in an amount exceeding 10 mol %, it may be difficult to introduce ion exchange groups, which is undesirable.

[0091] In step I of the third monolith manufacturing method, the type of polymer material for the monolith intermediate (3) is not particularly limited, and may be the same as the polymer material for the first monolith described above. This allows a similar polymer to be formed in the skeleton of the monolith intermediate (3), thickening the skeleton and obtaining a third monolith with a uniform skeleton structure.

[0092] The monolith intermediate (3) obtained in step I of the third monolith production method has a total pore volume per weight in a dry state of 5 to 16 ml / g, preferably 6 to 16 ml / g. If the total pore volume is too small, the total pore volume of the monolith obtained after polymerizing the vinyl monomer will be too small, which is undesirable because it increases the pressure loss during fluid permeation. On the other hand, if the total pore volume is too large, the structure of the monolith obtained after polymerizing the vinyl monomer will deviate from a continuous macropore structure, which is undesirable. To ensure that the total pore volume of the monolith intermediate (3) falls within the above numerical range, the ratio of monomer to water should be approximately 1:5 to 1:20.

[0093] Furthermore, the monolith intermediate (3) obtained in step I of the third monolith production method has an average diameter of openings (mesopores), which are the overlapping portions of macropores, of 20 to 200 μm in a dry state. If the average opening diameter in a dry state is less than 20 μm, the opening diameter of the monolith obtained after polymerization of the vinyl monomer will be small, resulting in a large pressure loss during liquid passage, which is undesirable. On the other hand, if the average opening diameter exceeds 200 μm, the opening diameter of the monolith obtained after polymerization of the vinyl monomer will be too large, resulting in insufficient contact between the reaction liquid and the monolith anion exchanger, which is undesirable as a result of reduced catalytic activity. The monolith intermediate (3) preferably has a uniform structure with uniform macropore size and opening diameter, but is not limited thereto. It may also have a uniform structure in which non-uniform macropores larger than the uniform macropore size are scattered.

[0094] Step II in the third monolith manufacturing method is a step of preparing a mixture consisting of a vinyl monomer, a crosslinking agent having at least two vinyl groups per molecule, an organic solvent that dissolves the vinyl monomer and the crosslinking agent but not the polymer produced by polymerization of the vinyl monomer, and a polymerization initiator. Note that there is no particular order for steps I and II; step II may be performed after step I, or step I may be performed after step II.

[0095] The vinyl monomer used in step II of the third monolith manufacturing method is not particularly limited as long as it contains a polymerizable vinyl group in the molecule and is a lipophilic vinyl monomer that is highly soluble in organic solvents, but it is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate (3) that is coexistent in the above polymerization system. Specific examples of these vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene; α-olefins such as ethylene, propylene, 1-butene, and isobutene; diene monomers such as butadiene, isoprene, and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride, and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; and (meth)acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and glycidyl methacrylate. These monomers can be used alone or in combination of two or more. Preferred vinyl monomers are aromatic vinyl monomers such as styrene and vinylbenzyl chloride.

[0096] The amount of vinyl monomer used in step II of the third monolith production method is 3 to 50 times, preferably 4 to 40 times, by weight relative to the monolith intermediate (3) coexisting during polymerization. If the amount of vinyl monomer added is less than 3 times the amount of monolith intermediate, the skeleton of the resulting monolith (the thickness of the monolith skeleton wall) cannot be made thicker, and when ion exchange groups are introduced, the ion exchange capacity per volume after introduction will be small, which is undesirable. On the other hand, if the amount of vinyl monomer added is more than 50 times, the opening diameter will be small, which is undesirable, and the pressure loss during liquid passage will be large.

[0097] The crosslinking agent used in step II of the third monolith production method preferably contains at least two polymerizable vinyl groups in the molecule and is highly soluble in organic solvents. Specific examples of crosslinking agents include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylate. These crosslinking agents can be used alone or in combination. Preferred crosslinking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl, due to their high mechanical strength and stability against hydrolysis. The amount of crosslinking agent used is preferably 0.3 to 10 mol %, particularly 0.3 to 5 mol %, based on the total amount of vinyl monomer and crosslinking agent. A crosslinking agent used in an amount less than 0.3 mol % is undesirable because the mechanical strength of the monolith is insufficient. On the other hand, a crosslinking agent used in an amount greater than 10 mol % is undesirable because the amount of ion-exchange groups introduced may decrease. The amount of crosslinking agent used is preferably approximately equal to the crosslink density of the monolith intermediate (3) that is coexistent during vinyl monomer / crosslinking agent polymerization. If the amounts of the two used are too different, the crosslink density distribution in the produced monolith will become uneven, making it more likely to crack during the ion exchange group introduction reaction.

[0098] The organic solvent used in step II of the third monolith production method dissolves vinyl monomers and crosslinking agents but not the polymers produced by polymerization of vinyl monomers—in other words, it is a poor solvent for the polymers produced by polymerization of vinyl monomers. Because the type of organic solvent varies significantly depending on the type of vinyl monomer, it is difficult to list general examples. For example, when the vinyl monomer is styrene, examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, ethylene glycol, propylene glycol, tetramethylene glycol, and glycerin; linear (poly)ethers such as diethyl ether, ethylene glycol dimethyl ether, cellosolve, methyl cellosolve, butyl cellosolve, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; linear saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, and dodecane; and esters such as ethyl acetate, isopropyl acetate, cellosolve acetate, and ethyl propionate. Furthermore, even good solvents for polystyrene, such as dioxane, THF, and toluene, can be used as organic solvents when used in small amounts together with the poor solvent. The amount of these organic solvents used is preferably such that the vinyl monomer concentration is 30 to 80% by weight. If the amount of organic solvent used deviates from the above range and the vinyl monomer concentration is less than 30% by weight, this is undesirable because the polymerization rate decreases and the monolith structure after polymerization deviates from the range of the third monolith. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, this is undesirable because the polymerization may go out of control.

[0099] The polymerization initiator used in step II of the third monolith manufacturing method is preferably a compound that generates radicals upon heat or light irradiation. The polymerization initiator is preferably oil-soluble. Specific 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, and tetramethylthiuram disulfide. The amount of polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in the range of about 0.01 to 5% based on the total amount of vinyl monomer and crosslinking agent.

[0100] Step III of the third monolith production method involves allowing the mixture obtained in Step II to stand and polymerizing it in the presence of the monolith intermediate (3) obtained in Step I to obtain a third monolith having a skeleton thicker than that of the monolith intermediate (3). The monolith intermediate (3) used in Step III plays an extremely important role in creating the third monolith, and the third monolith can be obtained by adding the monolith intermediate (3) with a continuous macropore structure to the polymerization system.

[0101] In the third monolith production method, the internal volume of the reaction vessel is not particularly limited as long as it is large enough to accommodate the monolith intermediate (3) within the reaction vessel. When the monolith intermediate (3) is placed within the reaction vessel, it may be either one in which there is a gap around the monolith in a plan view, or one in which the monolith intermediate (3) fits snugly within the reaction vessel. Among these, a reaction vessel in which the thick monolith after polymerization fits snugly within the reaction vessel without being pressed by the vessel's inner wall is efficient, with no distortion of the monolith and no waste of reaction raw materials. Even if the internal volume of the reaction vessel is large and gaps exist around the monolith after polymerization, the vinyl monomer and crosslinking agent are adsorbed and distributed to the monolith intermediate (3), so particle aggregate structures do not form in the gaps within the reaction vessel. In step III of the third monolith production method, the monolith intermediate (3) is placed in a reaction vessel in a state impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in step II to the monolith intermediate (3) is preferably such that the amount of vinyl monomer added is 3 to 50 times, preferably 4 to 40 times, by weight relative to the monolith intermediate (3). This makes it possible to obtain a third monolith having a suitable opening diameter and a thick skeleton. In the reaction vessel, the vinyl monomer and crosslinker in the mixture are adsorbed and distributed to the skeleton of the stationary monolith intermediate, and polymerization proceeds within the skeleton of the monolith intermediate (3).

[0102] In step III of the third monolith production method, the polymerization conditions vary depending on the type of monomer and initiator. For example, when using 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, or potassium persulfate as the initiator, the polymerization can be carried out by heating in a sealed container under an inert atmosphere at 30 to 100°C for 1 to 48 hours. During the thermal polymerization, the vinyl monomer and crosslinker adsorbed and distributed in the skeleton of the monolith intermediate (3) polymerize within the skeleton, thickening the skeleton. After polymerization is complete, the contents are removed and extracted with a solvent such as acetone to remove unreacted vinyl monomer and organic solvent, yielding the third monolith.

[0103] The third monolith ion exchanger can be obtained by carrying out step IV, in which ion exchange groups are introduced into the third monolith, which is a thick organic porous material obtained in step III.

[0104] The method for introducing ion exchange groups into the third monolith is the same as the method for introducing ion exchange groups into the first monolith.

[0105] Although the third monolith and the third monolith ion exchanger have a significantly larger opening diameter, they have a thick skeleton and therefore high mechanical strength.

[0106] <Description of the fourth monolith and the fourth monolith ion exchanger> In the platinum group metal ion-supported catalyst of the present invention, the fourth weakly basic monolith anion exchanger serving as a support for platinum group metal ions or platinum group metal complex ions is a monolith ion exchanger having a bicontinuous structure consisting of a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm in a dry state, which skeleton is made of an aromatic vinyl polymer containing 0.1 to 5.0 mol % of crosslinked structural units among all constituent units, and three-dimensionally continuous pores having an average diameter of 10 to 200 μm in a dry state, the monolith ion exchanger having a total pore volume of 0.5 to 10 ml / g in a dry state, ion exchange groups, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and the ion exchange groups being uniformly distributed within the organic porous ion exchanger. The fourth monolith is a monolith before ion exchange groups are introduced, and is an organic porous body having a bicontinuous structure consisting of a three-dimensionally continuous skeleton with an average thickness of 1 to 60 μm in a dry state, made of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of crosslinked structural units among all constituent units, and three-dimensionally continuous pores with an average diameter of 10 to 200 μm in a dry state between the skeletons, and a total pore volume in a dry state of 0.5 to 10 ml / g.

[0107] The fourth monolith ion exchanger has a bicontinuous structure consisting of a three-dimensionally continuous skeleton having an average diameter of 1 to 60 μm, preferably 3 to 58 μm, in a dry state, and three-dimensionally continuous pores having an average diameter of 10 to 200 μm, preferably 15 to 180 μm, and particularly preferably 20 to 150 μm, in a dry state. Fig. 5 shows an SEM photograph of an example of the fourth monolith ion exchanger, and Fig. 6 shows a schematic diagram of the bicontinuous structure of the fourth monolith ion exchanger. As shown in the schematic diagram of Fig. 6, the bicontinuous structure is a structure 10 in which a continuous skeleton phase 1 and a continuous pore phase 2 are intertwined and are three-dimensionally continuous. These continuous pores 2 have higher pore continuity and no size bias compared to conventional open-cell monoliths or particle-aggregation monoliths. Furthermore, the thick skeleton provides high mechanical strength.

[0108] If the average diameter of the three-dimensionally continuous pores is less than 10 μm in a dry state, the pressure loss during liquid passage is undesirable, and if it exceeds 200 μm, the contact between the reaction solution and the monolith ion exchanger is insufficient, resulting in insufficient catalytic activity. Furthermore, if the average skeleton thickness is less than 1 μm in a dry state, the monolith ion exchanger is significantly deformed when liquid is passed through it at a high flow rate, which is undesirable. Furthermore, the contact efficiency between the reaction solution and the monolith ion exchanger is reduced, resulting in a reduced catalytic effect, which is undesirable. On the other hand, if the skeleton thickness exceeds 60 μm, the skeleton becomes too thick, which increases the pressure loss during liquid passage, which is undesirable.

[0109] The average diameter of the openings of the fourth monolith in a dry state, the average diameter of the openings of the fourth monolith ion exchanger in a dry state, and the average diameter of the openings of the fourth monolith intermediate (4) in a dry state obtained in step I of the fourth monolith production described below are measured by mercury intrusion porosimetry and refer to the maximum value of the pore size distribution curve obtained by mercury intrusion porosimetry. The average thickness of the skeleton of the fourth monolith ion exchanger in a dry state is determined by SEM observation of the fourth monolith ion exchanger in a dry state. Specifically, SEM observation of the fourth monolith ion exchanger in a dry state is performed at least three times, the skeleton thickness in the obtained images is measured, and the average value is taken as the average thickness. The skeleton is rod-shaped and has a circular cross-sectional shape, but may also have a cross-section with a different diameter, such as an elliptical cross-section. In this case, the thickness is the average of the minor and major diameters.

[0110] The fourth monolith ion exchanger has a total pore volume per weight in a dry state of 0.5 to 10 ml / g. A total pore volume of less than 0.5 ml / g is undesirable because the pressure loss during liquid passage increases, and the permeation volume per unit cross-sectional area decreases, resulting in a reduced throughput. On the other hand, a total pore volume exceeding 10 ml / g is undesirable because the mechanical strength decreases, causing the monolith ion exchanger to deform significantly, particularly when liquid is passed through at a high flow rate. Furthermore, the contact efficiency between the reaction liquid and the monolith ion exchanger decreases, resulting in a reduced catalytic efficiency. When the size and total pore volume of the three-dimensionally continuous pores are within the above ranges, contact with the reaction liquid is extremely uniform, the contact area is large, and liquid passage with low pressure loss is possible.

[0111] In the fourth monolithic ion exchanger, the skeleton is made of a hydrophobic aromatic vinyl polymer containing 0.1 to 5 mol %, preferably 0.5 to 3.0 mol %, of crosslinked structural units relative to the total structural units. A crosslinked structural unit content of less than 0.1 mol % is undesirable due to insufficient mechanical strength, while a content exceeding 5 mol % tends to cause the porous structure to deviate from a co-continuous structure. The type of aromatic vinyl polymer is not particularly limited, and examples include polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, and polyvinylnaphthalene. The polymer may be obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or by polymerizing multiple vinyl monomers and crosslinking agents, 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 due to their ease of forming a co-continuous structure, ease of introducing ion exchange groups, high mechanical strength, and high stability against acids and alkalis.

[0112] The ion exchange groups introduced into the fourth monolith ion exchanger are the same as those introduced into the first monolith ion exchanger.

[0113] In the fourth monolithic ion exchanger, the introduced ion exchange groups are distributed uniformly not only on the surface of the porous body but also inside the skeleton of the porous body.

[0114] The fourth monolith ion exchanger has an ion exchange capacity per weight of 1 to 9 mg equivalents / g in a dry state. Because the fourth monolith ion exchanger has high continuity and uniformity of three-dimensionally connected pores, reducing the total pore volume does not significantly increase pressure loss. Therefore, it is possible to dramatically increase the ion exchange capacity per volume while maintaining low pressure loss. Having an ion exchange capacity per weight within the above range allows for changes in the environment around the catalytic active sites, such as the pH inside the catalyst, thereby increasing catalytic activity. The ion exchange capacity per weight of the fourth monolith ion exchanger in a dry state is 1 to 9 mg equivalents / g, preferably 1 to 8 mg equivalents / g, and particularly preferably 1 to 7 mg equivalents / g.

[0115] <Method for producing the fourth monolith and the fourth monolith ion exchanger> The fourth monolith can be obtained by carrying out the following steps: (1) preparing a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer that does not contain an ion exchange group, a surfactant, and water; (2) polymerizing the water-in-oil emulsion to obtain a monolithic organic porous intermediate (hereinafter also referred to as monolith intermediate (4)) with a continuous macropore structure and a total pore volume of more than 16 ml / g and not more than 30 ml / g; (2) preparing a mixture of an aromatic vinyl monomer, 0.3 to 5 mol% of a crosslinking agent in all oil-soluble monomers having at least two vinyl groups per molecule, an organic solvent that dissolves the aromatic vinyl monomer and the crosslinking agent but not the polymer produced by polymerization of the aromatic vinyl monomer, and a polymerization initiator; and (3) polymerizing the mixture obtained in step II while standing in the presence of the monolith intermediate (4) obtained in step I to obtain the fourth monolith, which is an organic porous body with a co-continuous structure.

[0116] In step I of the fourth monolith production method, step I for obtaining the monolith intermediate (4) may be carried out in accordance with the method described in JP-A-2002-306976.

[0117] That is, in step I of the fourth monolith manufacturing method, examples of oil-soluble monomers that do not contain ion exchange groups include, for example, monomers that do not contain ion exchange groups such as carboxylic acid groups, sulfonic acid groups, tertiary amino groups, and quaternary ammonium groups, have low solubility in water, and are lipophilic. Specific examples of these monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene; α-olefins such as ethylene, propylene, 1-butene, and isobutene; diene monomers such as butadiene, isoprene, and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride, and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; and (meth)acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and glycidyl methacrylate. Among these monomers, preferred are aromatic vinyl monomers, such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, and divinylbenzene. These monomers can be used alone or in combination of two or more. However, it is preferable to select a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate as at least one component of the oil-soluble monomers and to set the content of this monomer to 0.3 to 5 mol %, preferably 0.3 to 3 mol %, of the total oil-soluble monomers, because this is advantageous for the formation of a co-continuous structure.

[0118] The surfactant used in step I of the fourth monolith production method is the same as the surfactant used in step I of the third monolith production method, and therefore a description thereof will be omitted.

[0119] Furthermore, in step I of the fourth monolith manufacturing method, a polymerization initiator may be used as needed when forming the water-in-oil emulsion. A compound that generates radicals upon heat or light irradiation is preferably used as the polymerization initiator. The polymerization initiator may be water-soluble or oil-soluble, and 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), 2,2'-azobisisobutyric acid dimethyl, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium sulfite, and the like.

[0120] In step I of the fourth monolith manufacturing method, the oil-soluble monomer not containing an ion exchange group, surfactant, water and polymerization initiator are mixed to form a water-in-oil emulsion, and the mixing method is the same as the mixing method in step I of the third monolith manufacturing method, so its explanation is omitted.

[0121] The monolith intermediate (4) obtained in step I of the fourth monolith production method is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. The crosslink density of the polymer material is not particularly limited, but it is preferable that the crosslinked structural units are contained in an amount of 0.1 to 5 mol %, preferably 0.3 to 3 mol %, based on the total structural units constituting the polymer material. A crosslinked structural unit content of less than 0.3 mol % is undesirable because it results in insufficient mechanical strength. On the other hand, a content of more than 5 mol % is undesirable because it tends to cause the monolith structure to deviate from the co-continuous structure. In particular, when the total pore volume is 16 to 20 ml / g, it is preferable that the crosslinked structural units be less than 3 mol % in order to form a co-continuous structure.

[0122] In step I of the fourth monolith manufacturing method, the type of polymer material of the monolith intermediate (4) is the same as the type of polymer material of the monolith intermediate (4) of the third monolith manufacturing method, and therefore its explanation is omitted.

[0123] The monolith intermediate (4) obtained in step I of the fourth monolith production method has a total pore volume per weight in a dry state of more than 16 ml / g and not more than 30 ml / g, preferably more than 16 ml / g and not more than 25 ml / g. That is, although this monolith intermediate (4) basically has a continuous macropore structure, the openings (mesopores) where the macropores overlap are significantly larger, so the skeleton constituting the monolith structure has a structure that is very close to a one-dimensional rod-like skeleton rather than a two-dimensional wall surface. Figure 7 shows an SEM photograph of an example of the morphology of the monolith intermediate (4), which has a skeleton that is close to a rod-like skeleton. When this is present in a polymerization system, a porous body with a co-continuous structure is formed using the structure of the monolith intermediate (4) as a template. If the total pore volume is too small, the structure of the monolith obtained after polymerizing the vinyl monomer will change from a bicontinuous structure to a continuous macropore structure, which is undesirable, while if the total pore volume is too large, the mechanical strength of the monolith obtained after polymerizing the vinyl monomer will decrease, and if ion exchange groups are introduced, the ion exchange capacity per volume will decrease, which is undesirable. To keep the total pore volume of the monolith intermediate (4) within the above range, the ratio of monomer to water should be approximately 1:20 to 1:40.

[0124] Furthermore, the monolith intermediate (4) obtained in step I of the fourth monolith production method has an average diameter of openings (mesopores), which are the overlapping portions of macropores, of 5 to 100 μm in a dry state. If the average opening diameter is less than 5 μm in a dry state, the monolith obtained after polymerization of the vinyl monomer will have a small opening diameter, which is undesirable because it increases the pressure loss during fluid permeation. On the other hand, if the average opening diameter exceeds 100 μm, the monolith obtained after polymerization of the vinyl monomer will have an excessively large opening diameter, which results in insufficient contact between the reaction solution and the weakly basic monolith anion exchanger and, as a result, reduced catalytic activity. The monolith intermediate (4) preferably has a uniform structure with uniform macropore size and opening diameter, but is not limited thereto. It may also have a uniform structure in which non-uniform macropores larger than the uniform macropore size are scattered.

[0125] Step II in the fourth monolith manufacturing method is a step of preparing a mixture consisting of an aromatic vinyl monomer, 0.3 to 5 mol % of a crosslinking agent in total oil-soluble monomers having at least two vinyl groups per molecule, an organic solvent that dissolves the aromatic vinyl monomer and the crosslinking agent but not the polymer produced by polymerization of the aromatic vinyl monomer, and a polymerization initiator. Note that there is no particular order for steps I and II; step II may be performed after step I, or step I may be performed after step II.

[0126] The aromatic vinyl monomer used in step II of the fourth monolith production method is not particularly limited as long as it contains a polymerizable vinyl group in the molecule and is lipophilic and highly soluble in organic solvents. However, it is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate (4) that is coexisted in the polymerization system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, vinylnaphthalene, etc. These monomers can be used alone or in combination of two or more. Preferred aromatic vinyl monomers include styrene, vinylbenzyl chloride, etc.

[0127] The amount of aromatic vinyl monomer used in step II of the fourth monolith production method is 5 to 50 times, preferably 5 to 40 times, by weight relative to the monolith intermediate (4) coexisting during polymerization. If the amount of aromatic vinyl monomer added is less than 5 times the amount of monolith intermediate (4), the rod-shaped skeleton cannot be made thicker, and when ion exchange groups are introduced, the ion exchange capacity per volume after introduction of the ion exchange groups becomes small, which is undesirable. On the other hand, if the amount of aromatic vinyl monomer added exceeds 50 times, the diameter of the interconnected pores becomes small, which is undesirable because it increases the pressure loss during liquid passage.

[0128] The crosslinking agent used in step II of the fourth monolith production method preferably contains at least two polymerizable vinyl groups in the molecule and is highly soluble in organic solvents. Specific examples of crosslinking agents include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylate. These crosslinking agents can be used alone or in combination. Preferred crosslinking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl, due to their high mechanical strength and stability against hydrolysis. The amount of crosslinking agent used is 0.3 to 5 mol %, particularly 0.3 to 3 mol %, based on the total amount of vinyl monomer and crosslinking agent (total oil-soluble monomers). Using an amount of crosslinking agent less than 0.3 mol % is undesirable because the mechanical strength of the monolith is insufficient. On the other hand, using an amount that is too high is undesirable because quantitative introduction of ion-exchange groups may be difficult. The amount of crosslinking agent used is preferably approximately equal to the crosslink density of the monolith intermediate (4) that is coexistent during vinyl monomer / crosslinking agent polymerization. If the amounts of the two used are too different, the crosslink density distribution in the produced monolith will become uneven, and if ion exchange groups are introduced, cracks will easily occur during the ion exchange group introduction reaction.

[0129] The organic solvent used in step II of the fourth monolith production method dissolves the aromatic vinyl monomer and the crosslinking agent but not the polymer produced by polymerization of the aromatic vinyl monomer—in other words, it is a poor solvent for the polymer produced by polymerization of the aromatic vinyl monomer. Because the organic solvent varies greatly depending on the type of aromatic vinyl monomer, it is difficult to list general examples. For example, when the aromatic vinyl monomer is styrene, examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, and tetramethylene glycol; linear (poly)ethers such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; linear saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, and dodecane; and esters such as ethyl acetate, isopropyl acetate, cellosolve acetate, and ethyl propionate. Furthermore, even good solvents for polystyrene, such as dioxane, THF, and toluene, can be used as organic solvents when used in small amounts together with the poor solvent. The amount of these organic solvents used is preferably such that the concentration of the aromatic vinyl monomer is 30 to 80% by weight. If the amount of organic solvent used deviates from the above range and the aromatic vinyl monomer concentration becomes less than 30% by weight, this is undesirable because the polymerization rate decreases and the monolith structure after polymerization deviates from the range of the fourth monolith. On the other hand, if the aromatic vinyl monomer concentration exceeds 80% by weight, this is undesirable because the polymerization may go out of control.

[0130] The polymerization initiator used in step II of the fourth monolith production method is the same as the polymerization initiator used in step II of the third monolith production method, and therefore a description thereof will be omitted.

[0131] In step III of the fourth monolith production method, the mixture obtained in step II is polymerized while standing in the presence of the monolith intermediate (4) obtained in step I, thereby converting the continuous macropore structure of the monolith intermediate (4) into a bicontinuous structure, thereby obtaining a fourth monolith, a bicontinuous structure monolith. The monolith intermediate (4) used in step III plays an extremely important role in creating the monoliths with the novel structure of the present invention. As disclosed in JP-A-7-501140, the static polymerization of a vinyl monomer and a crosslinker in a specific organic solvent in the absence of the monolith intermediate (4) produces a particle-aggregated monolithic organic porous material. In contrast, when a specific continuous macropore structure monolith intermediate (4) is present in the polymerization system, as in the fourth monolith, the structure of the monolith after polymerization changes dramatically, the particle-aggregated structure disappears, and the fourth monolith with the above-mentioned bicontinuous structure is obtained. The reason for this has not been elucidated in detail, but it is thought that in the absence of the monolith intermediate (4), the crosslinked polymer produced by polymerization precipitates and settles in the form of particles, forming a particle aggregate structure. On the other hand, in the presence of a porous body (intermediate) with a large total pore volume in the polymerization system, the vinyl monomer and crosslinking agent are adsorbed or distributed from the liquid phase into the skeleton of the porous body, polymerization proceeds within the porous body, and the skeleton constituting the monolith structure changes from a two-dimensional wall surface to a one-dimensional rod-like skeleton, forming a fourth monolith with a bicontinuous structure.

[0132] In the fourth monolith production method, the internal volume of the reaction vessel is the same as that of the third monolith production method, and therefore the description thereof will be omitted.

[0133] In step III of the fourth monolith production method, the monolith intermediate (4) is placed in a reaction vessel in a state impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in step II to the monolith intermediate (4) is preferably such that the amount of aromatic vinyl monomer added is 5 to 50 times, preferably 5 to 40 times, by weight relative to the monolith intermediate (4). This allows for the production of a fourth monolith with a bicontinuous structure in which pores of appropriate size are three-dimensionally connected and a thick skeleton is three-dimensionally connected. In the reaction vessel, the aromatic vinyl monomer and crosslinker in the mixture are adsorbed and distributed to the skeleton of the stationary monolith intermediate (4), and polymerization proceeds within the skeleton of the monolith intermediate (4).

[0134] The polymerization conditions for step III in the fourth monolith production method are the same as those for step III in the third monolith production method, and therefore the explanation thereof will be omitted. By carrying out step III, the fourth monolith is obtained.

[0135] The fourth monolith ion exchanger can be obtained by carrying out step IV in which ion exchange groups are introduced into the fourth monolith obtained in step III.

[0136] The method for introducing ion exchange groups into the fourth monolith is the same as the method for introducing ion exchange groups into the first monolith.

[0137] The fourth monolith and the fourth monolith ion exchanger have a thick skeleton, which gives them high mechanical strength despite their significantly larger three-dimensionally connected pores. Furthermore, the fourth monolith ion exchanger has a thick skeleton, which allows for a large ion exchange capacity per unit volume in a dry state, and also allows for the flow of reaction liquid at low pressure and at a large flow rate for a long period of time.

[0138] <Description of the fifth monolith and the fifth monolith ion exchanger> In the platinum group metal ion-supported catalyst of the present invention, the fifth monolith ion exchanger serving as a support for platinum group metal ions or platinum group metal complex ions is a composite structure comprising an organic porous material consisting of a continuous skeletal phase and a continuous porous phase, and a large number of particles having a diameter of 4 to 40 μm in a dry state that are adhered to the skeletal surface of the organic porous material, or a large number of protrusions having a size of 4 to 40 μm in a dry state that are formed on the skeletal surface of the organic porous material, the monolith ion exchanger having an average pore diameter of 10 to 200 μm in a dry state and a total pore volume of 0.5 to 10 ml / g in a dry state, containing ion exchange groups, and an ion exchange capacity per weight of 1 to 9 mg equivalents / g in a dry state, with the ion exchange groups being uniformly distributed throughout the organic porous ion exchanger. The fifth monolith is a monolith before ion exchange groups are introduced, and is a composite structure of an organic porous material consisting of a continuous skeletal phase and a continuous pore phase, and a large number of particles having a diameter of 4 to 40 μm in a dry state that are adhered to the skeletal surface of the organic porous material, or a large number of protrusions having a size of 4 to 40 μm in a dry state that are formed on the skeletal surface of the organic porous material, and having an average pore diameter of 10 to 200 μm in a dry state and a total pore volume of 0.5 to 10 ml / g in a dry state.

[0139] The fifth monolith ion exchanger is a composite structure comprising an organic porous material consisting of a continuous skeleton phase and a continuous pore phase, and a large number of particles having a diameter of 4 to 40 μm in a dry state that are adhered to the skeleton surface of the organic porous material, or a large number of protrusions having a diameter of 4 to 40 μm in a dry state that are formed on the skeleton surface of the organic porous material. Note that in this specification, "particles" and "protrusions" are sometimes collectively referred to as "particles, etc."

[0140] The continuous skeletal phase and continuous pore phase of the fifth monolith ion exchanger are observed in SEM images. The basic structure of the fifth monolith ion exchanger includes a continuous macropore structure and a bicontinuous structure. The skeletal phase of the fifth monolith ion exchanger appears as a continuous columnar structure, a continuous concave wall structure, or a composite of these, and is clearly different in shape from particulates or protrusions.

[0141] Preferred structures of the fifth monolith ion exchanger include a continuous macropore structure in which cellular macropores overlap, and the overlapping portions form openings with an average diameter of 10 to 120 μm in a dry state (hereinafter also referred to as the "5-1 monolith ion exchanger"); and a co-continuous structure consisting of a three-dimensionally continuous skeleton with an average diameter of 0.8 to 40 μm in a dry state and three-dimensionally continuous pores with an average diameter of 8 to 80 μm between the skeletons in a dry state (hereinafter also referred to as the "5-2 monolith ion exchanger"). Furthermore, preferred fifth monoliths include the monolith of the 5-1 monolith ion exchanger before ion exchange groups are introduced (hereinafter also referred to as the "5-1 monolith") and the monolith of the 5-2 monolith ion exchanger before ion exchange groups are introduced (hereinafter also referred to as the "5-2 monolith").

[0142] In the case of the monolith ion exchanger No. 5-1, the monolith ion exchanger No. 5-1 has a continuous macropore structure in which cellular macropores overlap each other, and the overlapping portions form openings (mesopores) with an average diameter of 20 to 150 μm, preferably 30 to 150 μm, and particularly preferably 35 to 150 μm in a dry state, and the interior of the cells formed by the macropores and the openings (mesopores) serves as a flow path. The continuous macropore structure is preferably a uniform structure in which the macropores have a uniform size and opening diameter, but is not limited thereto, and may also have a uniform structure in which non-uniform macropores larger than the uniform macropores are scattered throughout. If the average diameter of the openings of the monolith ion exchanger No. 5-1 in the dry state is less than 20 μm, the pressure loss during liquid passage will be large, which is undesirable. On the other hand, if the average diameter of the openings in the dry state exceeds 150 μm, the contact between the reaction liquid and the monolith ion exchanger and the supported platinum group metal ions will be insufficient, resulting in a decrease in catalytic activity, which is undesirable.

[0143] The average diameter of the openings of the dry fifth monolith, the average diameter of the openings of the dry fifth monolith ion exchanger, and the average diameter of the openings of the dry monolith intermediate (5) obtained in step I of the production of the fifth monolith described below refer to the maximum values ​​of the pore size distribution curve obtained by mercury intrusion porosimetry.

[0144] The monolith ion exchanger No. 5-2 has a bicontinuous structure, with a three-dimensionally continuous skeleton having an average diameter of 1 to 50 μm, preferably 5 to 50 μm, in the dry state, and three-dimensionally continuous pores having an average diameter of 10 to 100 μm, preferably 10 to 90 μm, in the dry state. If the average diameter of the three-dimensionally continuous pores in the monolith ion exchanger No. 5-2 in the dry state is less than 10 μm, this is undesirable because it increases the pressure loss during liquid passage. On the other hand, if the average diameter exceeds 100 μm, this is undesirable because it reduces the contact between the reaction solution and the monolith ion exchanger and the supported platinum group metal ions, resulting in reduced catalytic activity. Furthermore, if the average skeleton diameter of the monolith ion exchanger No. 5-2 in the dry state is less than 1 μm, this is undesirable because it reduces the mechanical strength and causes significant deformation of the monolith ion exchanger, especially when liquid is passed through it at a high flow rate. On the other hand, if the average skeleton thickness of the monolithic ion exchanger No. 5-2 exceeds 50 μm in a dry state, the skeleton becomes too thick, which is undesirable because it increases the pressure loss during liquid passage.

[0145] The average thickness of the skeleton of the monolith ion exchanger No. 5-2 in the dry state is determined by SEM observation of the monolith ion exchanger No. 5-2 in the dry state. Specifically, SEM observation of the monolith ion exchanger No. 5-2 in the dry state is performed at least three times, the thickness of the skeleton in the obtained images is measured, and the average value is taken as the average thickness. Note that the skeleton is rod-shaped and has a circular cross-sectional shape, but it may also have a cross-section with a different diameter, such as an elliptical cross-sectional shape. In this case, the thickness is the average of the minor axis and the major axis.

[0146] The average pore diameter of the fifth monolith ion exchanger in a dry state is 10 to 200 μm. In the case of the fifth monolith ion exchanger, the preferred pore diameter of the fifth monolith ion exchanger in a dry state is 30 to 150 μm, and in the case of the fifth monolith ion exchanger, the preferred pore diameter of the fifth monolith ion exchanger in a dry state is 10 to 90 μm.

[0147] In the fifth monolith ion exchanger, the diameter of the particles and the size of the protrusions in a dry state are 4 to 40 μm, preferably 4 to 30 μm, and particularly preferably 4 to 20 μm. In the present invention, both particles and protrusions are observed as protrusions on the skeleton surface. Those observed as granular are referred to as particles, and those not considered granular are referred to as protrusions. Figure 8 shows schematic cross-sectional views of protrusions. As shown in (A) to (E) in Figure 8, protrusions 22 protrude from the skeleton surface 21. Examples of protrusions 22 include those with a nearly granular shape, such as protrusion 22a shown in (A), those with a hemispherical shape, such as protrusion 22b shown in (B), and those that resemble protrusions on the skeleton surface, such as protrusion 22c shown in (C). In addition, the protrusions 22 may have a shape such as protrusion 22d shown in (D) that is longer in the direction perpendicular to the skeleton surface 21 than in the planar direction of the skeleton surface 21, or may have a shape such as protrusion 22e shown in (E) that protrudes in multiple directions. The size of the protrusions is determined from an SEM image observed with an SEM and refers to the length of the widest part of each protrusion in the SEM image. Figure 9 shows an SEM photograph of an example of the fifth monolith ion exchanger, in which numerous protrusions are formed on the skeleton surface of the organic porous material.

[0148] In the fifth monolith ion exchanger, the proportion of particles having a size of 4 to 40 μm in a dry state among all particles is 70% or more, preferably 80% or more. The proportion of particles having a size of 4 to 40 μm in a dry state among all particles refers to the proportion of particles having a size of 4 to 40 μm in a dry state among all particles. The surface of the skeletal phase is covered by all particles at 40% or more, preferably 50% or more. The coverage of the surface of the skeletal layer by all particles refers to the area ratio on an SEM image obtained by surface observation using an SEM, i.e., the area ratio when the surface is viewed from above. If the size of the particles covering the wall surface or skeleton deviates from the above range, the effect of improving the contact efficiency between the fluid and the skeleton surface and interior of the monolith ion exchanger is likely to be reduced. The term "all particles, etc." refers to all particles and protrusions formed on the surface of the skeleton layer, including particles and protrusions in a size range other than particles, etc., of 4 to 40 μm in a dry state.

[0149] The diameter or size of the particles, etc., in a dry state attached to the skeleton surface of the fifth monolith ion exchanger is the diameter or size of the particles, etc., obtained by observing an SEM image of the fifth monolith ion exchanger in a dry state. Then, the diameter or size of all particles, etc., observed in the SEM image of the dry fifth monolith ion exchanger is measured, and the diameter or size of all particles, etc., in one field of view of the SEM image is calculated based on the measured diameter or size. This dry fifth monolith ion exchanger is observed under SEM at least three times, and the diameter or size of all particles, etc., in the dry state in the SEM image is calculated to confirm whether particles, etc., with a diameter or size of 4 to 40 μm are observed in the entire field of view. If particles, etc., with a diameter or size of 4 to 40 μm in a dry state are observed in the entire field of view, it is determined that particles, etc., with a diameter or size of 4 to 40 μm in a dry state are formed on the skeleton surface of the fifth monolith ion exchanger. Furthermore, the diameter or size of all particles in the SEM image in a dry state is calculated for each field of view according to the above, the proportion of particles in the 4-40 μm range in a dry state to all particles in each field of view is determined, and if the proportion of particles in the 4-40 μm range in a dry state to all particles in the entire field of view is 70% or more, it is determined that the proportion of particles in the 4-40 μm range in a dry state to all particles formed on the skeleton surface of the fifth monolith ion exchanger is 70% or more. Furthermore, the proportion of the surface coverage of the skeleton layer by all particles in the SEM image is determined for each field of view according to the above, and if the proportion of the surface coverage of the skeleton layer by all particles in the entire field of view is 40% or more, it is determined that the proportion of the surface of the skeleton layer covered by all particles is 40% or more.

[0150] In the fifth monolith ion exchanger, if the coverage of the skeletal phase surface with particles or the like is less than 40%, the effect of improving the contact efficiency between the reaction solution and the interior and surface of the skeletal structure of the monolith ion exchanger is likely to be small. The coverage of particles or the like can be measured by image analysis of SEM images of the fifth monolith ion exchanger.

[0151] The total pore volume per unit weight of the fifth monolith ion exchanger in a dry state is 0.5 to 10 ml / g, preferably 0.8 to 8 ml / g. A monolith ion exchanger having a total pore volume of less than 0.5 ml / g is undesirable because it increases the pressure loss during liquid passage, and also reduces the amount of permeating fluid per unit cross-sectional area, thereby reducing processing capacity. On the other hand, a monolith ion exchanger having a total pore volume exceeding 10 ml / g is undesirable because it reduces the mechanical strength and significantly deforms the monolith ion exchanger, particularly when liquid is passed through it at a high flow rate. Furthermore, it is undesirable because it reduces the contact efficiency between the reaction liquid and the monolith ion exchanger and the platinum group metal ions supported on it, thereby reducing the catalytic effect.

[0152] In the fifth monolith ion exchanger, the material constituting the skeleton phase of the interconnected pore structure is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material is not particularly limited, but it is preferable that the polymer material contains 0.3 to 10 mol %, and more preferably 0.3 to 5 mol %, of crosslinked structural units relative to the total structural units constituting the polymer material. A crosslinked structural unit content of less than 0.3 mol % is undesirable because mechanical strength is insufficient. On the other hand, a content of more than 10 mol % is undesirable because, when ion exchange groups are introduced, it becomes difficult to introduce ion exchange groups, which may result in a reduced amount of introduction.

[0153] The polymer material used in the production of the fifth monolith is not particularly limited, and examples thereof include crosslinked polymers such as aromatic vinyl polymers (e.g., polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, and polyvinylnaphthalene); polyolefins (e.g., polyethylene and polypropylene); poly(halogenated polyolefins) (e.g., polyvinyl chloride and polytetrafluoroethylene); nitrile polymers (e.g., polyacrylonitrile); and (meth)acrylic polymers (e.g., polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate). The polymers may be polymers obtained by copolymerizing a single vinyl monomer with a crosslinking agent, polymers obtained by polymerizing multiple vinyl monomers with a crosslinking agent, or blends of two or more polymers. Among these organic polymer materials, crosslinked polymers of aromatic vinyl polymers are preferred due to their ease of forming a continuous pore structure, ease of introducing ion exchange groups, high mechanical strength, and high stability against acids and alkalis. In particular, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred.

[0154] In the fifth monolith ion exchanger, the material constituting the skeletal phase of the organic porous material and the particles formed on the surface of the skeletal phase may be the same material with a continuous structure of the same kind, or different materials with a continuous structure of different kinds. Examples of different materials with a continuous structure of different kinds include materials containing different types of vinyl monomers, and materials containing the same types of vinyl monomers and crosslinkers but in different proportions.

[0155] The ion exchange groups introduced into the fifth monolith ion exchanger are the same as those introduced into the first monolith ion exchanger.

[0156] In the fifth monolith ion exchanger, the introduced ion exchange groups are uniformly distributed not only on the surface of the organic porous material but also inside the skeleton of the organic porous material. Uniform distribution of the ion exchange groups not only on the surface of the fifth monolith ion exchanger but also inside the skeleton makes it possible to make the physical and chemical properties of the surface and the interior uniform, thereby improving resistance to swelling and shrinkage.

[0157] The fifth monolith ion exchanger has an ion exchange capacity per weight of 1 to 9 mg equivalents / g in a dry state. By having the ion exchange capacity per weight of the fifth monolith ion exchanger within the above range, it is possible to change the environment around the catalytic active sites, such as the pH inside the catalyst, thereby increasing catalytic activity. The ion exchange capacity per weight of the fifth monolith ion exchanger in a dry state is 1 to 9 mg equivalents / g, preferably 1 to 8 mg equivalents / g, and particularly preferably 1 to 7 mg equivalents / g.

[0158] The fifth monolith ion exchanger has a thickness of 1 mm or more and is distinguished from a membrane-like porous material. A thickness of less than 1 mm is undesirable because the ion exchange capacity per porous material becomes extremely low. The thickness of the fifth monolith ion exchanger is preferably 3 to 1000 mm. Furthermore, the fifth monolith ion exchanger has a basic skeleton structure of an interconnected pore structure, and therefore has high mechanical strength.

[0159] <Production method of fifth monolith and fifth monolith ion exchanger> The fifth monolith can be obtained by carrying out the following steps: Step I: preparing a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer not containing an ion exchange group, a surfactant, and water; then polymerizing the water-in-oil emulsion to obtain a monolithic organic porous intermediate (hereinafter also referred to as monolith intermediate (5)) with a continuous macropore structure and a total pore volume of 5 to 30 ml / g; Step II: preparing a mixture consisting of a vinyl monomer, a crosslinking agent having at least two vinyl groups per molecule, an organic solvent that dissolves the vinyl monomer and the crosslinking agent but not the polymer produced by polymerization of the vinyl monomer, and a polymerization initiator; and Step III: polymerizing the mixture obtained in Step II while standing and in the presence of the monolith intermediate (5) obtained in Step I to obtain the fifth monolith, which is a composite monolith with a composite structure.

[0160] Step I of the fifth monolith manufacturing method may be carried out in accordance with the method described in Japanese Patent Application Laid-Open No. 2002-306976.

[0161] In the production of the monolith intermediate (5) in step I of the fifth monolith production method, examples of oil-soluble monomers that do not contain ion exchange groups include, for example, monomers that do not contain ion exchange groups such as carboxylic acid groups, sulfonic acid groups, tertiary amino groups, and quaternary ammonium groups, have low solubility in water, and are lipophilic. Suitable examples of these monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isobutene, butadiene, and ethylene glycol dimethacrylate. These monomers can be used alone or in combination. However, it is preferable to select a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate as at least one component of the oil-soluble monomers and adjust its content to 0.3 to 10 mol%, preferably 0.3 to 5 mol%, of the total oil-soluble monomers, because this allows for quantitative introduction of ion exchange groups in a subsequent step.

[0162] The surfactant used in step I of the fifth monolith production method is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when mixed with an oil-soluble monomer not containing an ion exchange group and water. Examples of suitable surfactants include nonionic surfactants such as sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, and polyoxyethylene sorbitan monooleate; anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyl dimethyl ammonium chloride; and amphoteric surfactants such as lauryl dimethyl betaine. These surfactants can be used alone or in combination. A water-in-oil emulsion is an emulsion in which the oil phase is the continuous phase and water droplets are dispersed within it. The amount of surfactant to be added cannot be generalized because it varies greatly depending on the type of oil-soluble monomer and the size of the desired emulsion particles (macropores), but it can be selected from the range of approximately 2 to 70% of the total amount of oil-soluble monomer and surfactant.

[0163] Furthermore, in step I of the fifth monolith production method, a polymerization initiator may be used as needed when forming the water-in-oil emulsion. A compound that generates radicals upon heat or light irradiation is preferably used as the polymerization initiator. The polymerization initiator may be water-soluble or oil-soluble, and 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), 2,2'-azobisisobutyric acid dimethyl, 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 sulfite, and the like.

[0164] In step I of the fifth monolith production method, the oil-soluble monomer not containing an ion exchange group, surfactant, water, and polymerization initiator are mixed to form a water-in-oil emulsion. The mixing method is not particularly limited, and can include simultaneously mixing all the components at once, or separately dissolving the oil-soluble components (oil-soluble monomer, surfactant, and oil-soluble polymerization initiator) and the water-soluble components (water and water-soluble polymerization initiator) uniformly and then mixing the components. The mixing device used to form the emulsion is also not particularly limited, and a standard mixer, homogenizer, high-pressure homogenizer, or other suitable device can be used. Select an appropriate device to achieve the desired emulsion particle size. The mixing conditions are also not particularly limited, and the stirring speed and stirring time can be set as desired to achieve the desired emulsion particle size.

[0165] The monolith intermediate (5) obtained in step I of the fifth monolith production method has a continuous macropore structure. When this monolith intermediate (5) is present in a polymerization system, particles and the like are formed on the surface of the skeletal phase of the continuous macropore structure, or particles and the like are formed on the surface of the skeletal phase of the co-continuous structure, using the structure of the monolith intermediate (5) as a template. The monolith intermediate (5) is also an organic polymer material having a crosslinked structure. The crosslink density of the polymer material is not particularly limited, but it is preferable that the polymer material contains 0.3 to 10 mol %, preferably 0.3 to 5 mol %, of crosslinked structural units relative to the total structural units constituting the polymer material. A crosslinked structural unit content of less than 0.3 mol % is undesirable because it results in insufficient mechanical strength. On the other hand, a content of more than 10 mol % is undesirable because it can cause the porous body to lose flexibility or, if ion exchange groups are to be introduced, can make the introduction of ion exchange groups difficult.

[0166] In step I of the fifth monolith manufacturing method, the type of polymer material for the monolith intermediate (5) is not particularly limited, and may be the same as the polymer material for the fifth monolith described above. This allows a similar polymer to be formed in the skeleton of the monolith intermediate (5), resulting in a fifth monolith that is a monolith with a composite structure.

[0167] The monolith intermediate (5) obtained in step I of the fifth monolith production method has a total pore volume per weight in a dry state of 5 to 30 ml / g, preferably 6 to 28 ml / g. If the total pore volume of the monolith intermediate is too small, the total pore volume of the monolith obtained after polymerizing the vinyl monomer will be too small, which is undesirable because it increases the pressure loss during fluid permeation. On the other hand, if the total pore volume of the monolith intermediate is too large, the structure of the monolith obtained after polymerizing the vinyl monomer is likely to be nonuniform, and in some cases, this is undesirable because it may cause structural collapse. To ensure that the total pore volume of the monolith intermediate (5) falls within the above numerical range, the ratio (by weight) of monomer to water may be approximately 1:5 to 1:35.

[0168] In step I of the fifth monolith production method, if the ratio of this monomer to water is approximately 1:5 to 1:20, a monolith intermediate (5) with a continuous macropore structure and a total pore volume of 5 to 16 ml / g is obtained, and the monolith obtained through step III is a monolith No. 5-1. Furthermore, if the blending ratio is approximately 1:20 to 1:35, a monolith intermediate (5) with a continuous macropore structure and a total pore volume of more than 16 ml / g but not more than 30 ml / g is obtained, and the monolith obtained through step III is a monolith No. 5-2.

[0169] Furthermore, the monolith intermediate (5) obtained in step I of the fifth monolith production method has an average diameter of 20 to 200 μm in the dry state of the openings (mesopores) where macropores overlap. If the average diameter of the openings in the monolith intermediate in the dry state is less than 20 μm, the opening diameter of the monolith obtained after polymerization of the vinyl monomer will be small, resulting in increased pressure loss during liquid passage, which is undesirable. On the other hand, if the average diameter of the openings in the monolith intermediate in the dry state exceeds 200 μm, the opening diameter of the monolith obtained after polymerization of the vinyl monomer will be too large, resulting in insufficient contact between the reaction solution and the weakly basic monolith anion exchanger, which in turn reduces catalytic activity, which is undesirable. The monolith intermediate (5) is preferably one with a uniform structure in which the macropores are uniform in size and diameter, but is not limited thereto. It may also be one in which non-uniform macropores larger than the uniform macropores are scattered throughout the uniform structure.

[0170] Step II in the fifth monolith manufacturing method is a step of preparing a mixture consisting of a vinyl monomer, a second crosslinking agent having at least two vinyl groups per molecule, an organic solvent that dissolves the vinyl monomer and the second crosslinking agent but not the polymer produced by polymerization of the vinyl monomer, and a polymerization initiator. Note that there is no particular order for steps I and II; step II may be performed after step I, or step I may be performed after step II.

[0171] The vinyl monomer used in step II in the fifth monolith production method is not particularly limited as long as it contains a polymerizable vinyl group in the molecule and is lipophilic and highly soluble in organic solvents. Specific examples of these vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene; α-olefins such as ethylene, propylene, 1-butene, and isobutene; diene monomers such as butadiene, isoprene, and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride, and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; and (meth)acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and glycidyl methacrylate. These monomers can be used alone or in combination of two or more. Preferred vinyl monomers are aromatic vinyl monomers such as styrene and vinylbenzyl chloride.

[0172] The amount of vinyl monomer used in step II of the fifth monolith production method is 3 to 50 times, preferably 4 to 40 times, by weight relative to the monolith intermediate (5) that is present during polymerization. If the amount of vinyl monomer added is less than 3 times the amount of porous material, particles cannot be formed in the skeleton of the resulting monolith, and when ion exchange groups are introduced, the ion exchange capacity per volume after introduction of the ion exchange groups will be small, which is undesirable. On the other hand, if the amount of vinyl monomer added is more than 50 times, the opening diameter will be small, which is undesirable, and the pressure loss during liquid passage will be large.

[0173] The crosslinking agent used in step II of the fifth monolith production method preferably contains at least two polymerizable vinyl groups in its molecule and is highly soluble in organic solvents. Specific examples of crosslinking agents include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylate. These crosslinking agents can be used alone or in combination. Preferred crosslinking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl, due to their high mechanical strength and stability against hydrolysis. The amount of crosslinking agent used is preferably 0.3 to 20 mol %, particularly 0.3 to 10 mol %, based on the total amount of vinyl monomer and crosslinking agent. An amount of crosslinking agent less than 0.3 mol % is undesirable because the monolith will have insufficient mechanical strength. On the other hand, an amount exceeding 20 mol % is undesirable because the monolith will become embrittled and lose flexibility. Furthermore, if ion-exchange groups are introduced, the amount of ion-exchange groups introduced may be reduced.

[0174] The organic solvent used in step II of the fifth monolith production method dissolves vinyl monomers and crosslinking agents but not the polymers produced by polymerization of vinyl monomers—in other words, it is a poor solvent for the polymers produced by polymerization of vinyl monomers. Because the type of organic solvent varies significantly depending on the type of vinyl monomer, it is difficult to list general examples. For example, when the vinyl monomer is styrene, examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, and tetramethylene glycol; linear (poly)ethers such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; linear saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, and dodecane; and esters such as ethyl acetate, isopropyl acetate, cellosolve acetate, and ethyl propionate. Furthermore, even good solvents for polystyrene, such as dioxane, THF, and toluene, can be used as organic solvents when used in small amounts together with the poor solvent. The amount of these organic solvents used is preferably such that the vinyl monomer concentration is 5 to 80% by weight. If the amount of organic solvent used falls outside the above range and the vinyl monomer concentration is less than 5% by weight, this is undesirable because the polymerization rate decreases. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, this is undesirable because runaway polymerization may occur.

[0175] The polymerization initiator used in step II of the fifth monolith production method is preferably a compound that generates radicals upon heat or light irradiation. It is preferable that the polymerization initiator be oil-soluble. Specific examples of polymerization initiators 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, and tetramethylthiuram disulfide. The amount of polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in the range of approximately 0.01 to 5% of the total amount of vinyl monomer and crosslinker.

[0176] Step III of the fifth monolith production method involves polymerization of the mixture obtained in Step II while standing in the presence of the monolith intermediate (5) obtained in Step I to obtain a fifth monolith. The monolith intermediate (5) used in Step III plays an extremely important role in creating the fifth monolith. As disclosed in JP-A-7-501140, etc., static polymerization of a vinyl monomer and a crosslinker in a specific organic solvent in the absence of the monolith intermediate (5) produces a particle-aggregated monolithic organic porous material. In contrast, when the monolith intermediate (5) with a continuous macropore structure is present in the polymerization system as in the present invention, the structure of the composite monolith after polymerization changes dramatically, resulting in a fifth monolith with the specific skeletal structure described above, rather than a particle-aggregated structure. The internal volume of the reaction vessel is not particularly limited as long as it is large enough to accommodate the monolith intermediate (5) within the reaction vessel. When the monolith intermediate (5) is placed within the reaction vessel, it may be either one in which there is a gap around the monolith in a plan view, or one in which the monolith intermediate (5) fits snugly within the reaction vessel. Among these, a reaction vessel in which the fifth monolith after polymerization fits snugly within the reaction vessel without being pressed by the vessel's inner wall prevents distortion of the fifth monolith and results in no waste of reaction raw materials, making it efficient. Even if the reaction vessel has a large internal volume and gaps exist around the fifth monolith after polymerization, the vinyl monomer and crosslinking agent are adsorbed and distributed to the monolith intermediate (5), preventing particle aggregate structures from forming in the gaps within the reaction vessel.

[0177] In step III of the fifth monolith production method, the monolith intermediate (5) is placed in a reaction vessel in a state impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in step II to the monolith intermediate (5) is preferably such that the amount of vinyl monomer added is 3 to 50 times, preferably 4 to 40 times, by weight relative to the monolith intermediate (5). This makes it possible to obtain the fifth monolith, which is a composite monolith having a specific skeleton and an appropriate opening diameter. In the reaction vessel, the vinyl monomer and crosslinker in the mixture are adsorbed and distributed to the skeleton of the stationary monolith intermediate (5), and polymerization proceeds within the skeleton of the monolith intermediate (5).

[0178] In step III of the fifth monolith production method, various polymerization conditions can be selected depending on the type of monomer and initiator. For example, when using 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, or the like as the initiator, thermal polymerization can be carried out in a sealed container under an inert atmosphere at 20 to 100°C for 1 to 48 hours. Through thermal polymerization, the vinyl monomer and crosslinker adsorbed and distributed within the skeleton of the monolith intermediate (5) polymerize within the skeleton, forming the specific skeleton structure. After polymerization is complete, the contents are removed, and the contents are extracted with a solvent such as acetone to remove unreacted vinyl monomer and organic solvent, yielding a composite monolith with a specific skeleton structure, the fifth monolith.

[0179] When producing the above-mentioned fifth monolith, if step II or step III is carried out under conditions that satisfy at least one of the following conditions (1) to (5), a monolith having particles or the like formed on the skeleton surface, which is a characteristic structure of the fifth monolith, can be produced. (1) The polymerization temperature in step III is at least 5° C. lower than the 10-hour half-life temperature of the polymerization initiator. (2) The mol % of the crosslinking agent used in step II is at least twice the mol % of the crosslinking agent used in step I. (3) The vinyl monomer used in step II has a structure different from that of the oil-soluble monomer used in step I. (4) The organic solvent used in step II is a polyether having a molecular weight of 200 or more. (5) The concentration of the vinyl monomer used in step II is 30% by weight or less in the mixture in step II.

[0180] (Explanation of (1) above) The 10-hour half-life temperature is a characteristic value of the polymerization initiator, and once the polymerization initiator to be used is determined, the 10-hour half-life temperature can be determined. Furthermore, if a desired 10-hour half-life temperature is known, a polymerization initiator corresponding to that temperature can be selected. In step III, lowering the polymerization temperature reduces the polymerization rate, allowing particles to form on the surface of the skeletal phase. This is thought to be because the decrease in monomer concentration inside the skeletal phase of the monolith intermediate becomes more gradual, slowing the rate of monomer distribution from the liquid phase to the monolith intermediate. As a result, excess monomer is concentrated near the surface of the skeletal layer of the monolith intermediate and polymerizes in situ.

[0181] In step III of the fifth monolith production method, the polymerization temperature is preferably at least 10°C lower than the 10-hour half-life temperature of the polymerization initiator used. Although there are no particular restrictions on the lower limit of the polymerization temperature, the polymerization rate decreases as the temperature decreases, and the polymerization time becomes unacceptably long for practical purposes. Therefore, it is preferable to set the polymerization temperature in the range of 5 to 20°C lower than the 10-hour half-life temperature.

[0182] (Explanation of (2) above) In the fifth monolith manufacturing method, when the mol % of the crosslinking agent used in step II is set to at least twice the mol % of the crosslinking agent used in step I, a monolith with a composite structure is obtained. The reason for this is thought to be that the compatibility between the monolith intermediate and the polymer produced by impregnation polymerization decreases, causing phase separation, and the polymer produced by impregnation polymerization is excluded near the surface of the skeletal phase of the monolith intermediate, forming irregularities such as particles on the skeletal phase surface. The mol % of the crosslinking agent refers to the crosslink density mol %, which is the amount of crosslinking agent (mol %) relative to the total amount of vinyl monomer and crosslinking agent.

[0183] Although there is no particular upper limit to the mol% of crosslinker used in step II of the fifth monolith production method, a significantly high mol% of crosslinker is undesirable because it can cause cracks in the monolith after polymerization, cause the monolith to become increasingly embrittled and lose flexibility, and, when ion-exchange groups are introduced, can result in a reduced amount of ion-exchange groups being introduced. A preferred multiple of the mol% of crosslinker is 2 to 10 times. On the other hand, even if the mol% of crosslinker used in step I was set to more than twice the mol% of crosslinker used in step II, no particles or the like were formed on the skeletal phase surface, and the fifth monolith was not obtained.

[0184] (Explanation of (3) above) The fifth monolith can be obtained by using a vinyl monomer with a different structure from the oil-soluble monomer used in step I in the fifth monolith production method. For example, even slight differences in the structure of the vinyl monomer, such as between styrene and vinylbenzyl chloride, can result in the formation of a composite monolith with particles or the like formed on the surface of the skeletal phase. Generally, two homopolymers obtained from two monomers with even slight structural differences are incompatible with each other. Therefore, if a monomer with a different structure from the monomer used to form the monolith intermediate in step I is used in step II and polymerization is performed in step III, the monomer used in step II is uniformly distributed and impregnated into the monolith intermediate. However, as the polymerization progresses and a polymer is produced, the produced polymer is incompatible with the monolith intermediate, leading to phase separation. The produced polymer is then removed to the surface of the skeletal phase of the monolith intermediate, forming irregularities such as particles on the surface of the skeletal phase.

[0185] (Explanation of (4) above) The fifth monolith can be obtained by using a polyether with a molecular weight of 200 or more as the organic solvent used in step II of the fifth monolith production method. Polyethers have a relatively high affinity with the monolith intermediate. Low-molecular-weight cyclic polyethers are particularly good solvents for polystyrene, while low-molecular-weight linear polyethers, while not good solvents, have considerable affinity. However, as the molecular weight of the polyether increases, its affinity with the monolith intermediate dramatically decreases, and it no longer exhibits much affinity with the monolith intermediate. When such a solvent with poor affinity is used as the organic solvent, the diffusion of the monomer into the monolith intermediate's skeleton is hindered. As a result, the monomer polymerizes only near the surface of the monolith intermediate's skeleton, resulting in the formation of particles and other particles on the skeleton surface, creating irregularities on the skeleton surface.

[0186] There is no particular upper limit to the molecular weight of the polyether used in step II of the fifth monolith production method, as long as it is 200 or more. However, if the molecular weight is too high, the viscosity of the mixture prepared in step II increases, making it difficult to impregnate the interior of the monolith intermediate, which is undesirable. The molecular weight of the polyether is preferably 200 to 100,000, and particularly preferably 200 to 10,000. Furthermore, the terminal structure of the polyether may be an unmodified hydroxyl group, or may be etherified with an alkyl group such as a methyl group or an ethyl group, or may be esterified with acetic acid, oleic acid, lauric acid, stearic acid, or the like.

[0187] (Explanation of (5) above) The fifth monolith can be obtained by using a vinyl monomer in step II of the fifth monolith production method at a concentration of 30% by weight or less in the mixture in step II. Lowering the monomer concentration in step II reduces the polymerization rate, and for the same reason as in (1) above, particles or the like can be formed on the skeletal phase surface, resulting in the formation of irregularities on the skeletal phase surface. While there is no particular lower limit for the monomer concentration, the lower the monomer concentration, the lower the polymerization rate, resulting in an unacceptably long polymerization time. Therefore, it is preferable to set the monomer concentration to 10 to 30% by weight.

[0188] Preferred structures of the fifth monolith obtained in this manner include a continuous macropore structure ("5-1 monolith") in which bubble-like macropores overlap each other and these overlapping portions form openings with an average diameter of 10 to 120 μm in the dry state, and a co-continuous structure ("5-2 monolith") consisting of a three-dimensionally continuous skeleton with an average thickness of 0.8 to 40 μm in the dry state and three-dimensionally continuous pores with a diameter of 8 to 80 μm in the dry state between the skeletons.

[0189] When the fifth monolith is monolith No. 5-1, monolith No. 5-1 has a continuous macropore structure in which cellular macropores overlap each other, and these overlapping portions form openings (mesopores) with an average diameter of 10 to 120 μm, preferably 20 to 120 μm, and particularly preferably 25 to 120 μm in a dry state, and the interior of the cells formed by the macropores and the openings (mesopores) forms flow paths. The continuous macropore structure is preferably a uniform structure in which the macropores are of uniform size and opening diameter, but is not limited thereto, and may also be a uniform structure in which non-uniform macropores larger than the uniform macropores are scattered throughout. If the average diameter of the openings in the 5-1 monolith in a dry state is less than 10 μm, the pressure loss during liquid passage will be large, which is undesirable. On the other hand, if the average diameter of the openings in a dry state exceeds 120 μm, the contact between the reaction liquid and the monolith ion exchanger and the supported platinum group metal particles will be insufficient, resulting in a decrease in catalytic activity, which is undesirable.

[0190] In the case of monolith No. 5-2, the monolith No. 5-2 has a bicontinuous structure with a three-dimensionally continuous skeleton having an average dry diameter of 0.8 to 40 μm and three-dimensionally continuous pores having an average dry diameter of 8 to 80 μm between the skeletons. If the average dry diameter of the three-dimensionally continuous pores of monolith No. 5-2 is less than 8 μm, the pressure loss during liquid passage is undesirable. On the other hand, if the average dry diameter exceeds 80 μm, the contact between the reaction solution and the monolith or weakly basic monolith anion exchanger and the supported platinum group metal particles is insufficient, resulting in reduced catalytic activity. Furthermore, if the average dry width of the skeleton of monolith No. 5-2 is less than 0.8 μm, when ion exchange groups are introduced, the ion exchange capacity per volume of the monolith ion exchanger is reduced. Furthermore, the mechanical strength is reduced, which is undesirable, leading to significant deformation of the monolith or monolith ion exchanger, especially when liquid is passed through at high flow rates. On the other hand, if the average thickness of the skeleton in a dry state exceeds 80 μm, the pressure loss during liquid passage increases, which is undesirable.

[0191] The fifth monolith ion exchanger can be obtained by carrying out step IV, in which ion exchange groups are introduced into the fifth monolith obtained in step III.

[0192] The method for introducing ion exchange groups into the fifth monolith is the same as the method for introducing ion exchange groups into the first monolith.

[0193] In the platinum group metal ion-supported catalyst of the present invention, platinum group metal ions or platinum group metal complex ions are supported on a non-particulate organic porous monolith ion exchanger (monolith ion exchanger). That is, in the platinum group metal ion-supported catalyst of the present invention, the platinum group metal is supported in an ionic state on the monolith ion exchanger. For example, the platinum group metal ion-supported catalyst of the present invention may be a catalyst in which platinum group metal ions or platinum group metal complex ions are bonded to weakly basic anion exchange groups in the monolith ion exchanger, such as tertiary amino groups such as dimethylamino groups or diethylamino groups, via ionic or coordinate bonds, thereby supporting platinum group metal ions on the weakly basic monolith anion exchanger groups. Examples of the platinum group metal ion-supported catalyst of the present invention include catalysts in which platinum group metal ions are supported on strongly acidic cation exchange groups or weakly acidic cation exchange groups by ionic bonds to strongly acidic cation exchange groups, such as sulfonic acid groups or weakly acidic cation exchange groups, such as carboxyl groups, in a monolith ion exchanger. Also, examples of the catalysts include catalysts in which platinum group metal ions are supported on strongly basic monolith anion exchange groups by ionic bonds to strongly basic anion exchange groups, such as quaternary ammonium groups, in a monolith ion exchanger.

[0194] In the platinum group metal ion supported catalyst of the present invention, the platinum group metal is ruthenium, rhodium, palladium, osmium, iridium, or platinum. These platinum group metals may be used alone or in combination of two or more metals. The platinum group metal ions are ions of the above platinum group metals.

[0195] The presence of platinum group metal ions or platinum group metal complex ions on the supported platinum group metal catalyst of the present invention can be confirmed by observation with a transmission electron microscope (TEM).

[0196] The amount of platinum group metal ions or platinum group metal complex ions supported in the platinum group metal ion-supported catalyst of the present invention ((mass converted into platinum group metal atoms / mass of platinum group metal ion-supported catalyst in a dry state)×100) is 0.01 to 10.0 mass%, preferably 0.10 to 5.0 mass%, in atomic terms. When the amount of platinum group metal ions or platinum group metal complex ions supported is within the above range, the catalyst functions as such and is inexpensive from the viewpoint of raw materials. In the present invention, the platinum group metal atoms in the platinum group metal ion-supported catalyst are quantified using an ICP atomic emission spectrometer.

[0197] The method for producing the platinum group metal ion-supported catalyst of the present invention is not particularly limited, and the platinum group metal ion-supported catalyst can be obtained by supporting platinum group metal ions or platinum group metal complex ions on a monolith ion exchanger by a known method, such as a method of immersing a dry monolith ion exchanger in an organic solution of a platinum group metal compound to adsorb the platinum group metal ions onto the monolith ion exchanger by ion exchange, or a method of immersing a monolith ion exchanger in an aqueous solution of a platinum group metal complex compound such as a tetraamminepalladium complex to adsorb and support the platinum group metal ions onto the monolith ion exchanger by ion exchange.

[0198] Palladium ions may be introduced into the monolithic ion exchanger by either a batch method or a flow method, and there are no particular limitations.

[0199] The platinum group metal compound used in the method for producing a platinum group metal ion-supported catalyst may be either an organic salt or an inorganic salt, and examples thereof 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, chloropentaammineplatinum chloride, cis-tetrachlorodiammineplatinum chloride, trans-tetrachlorodiammineplatinum chloride, rhodium chloride, rhodium acetate, hexaamminerhodium chloride, hexaamminerhodium bromide, hexaamminerhodium sulfate, pentaammineaquarhodium chloride, pentaammineaquarhodium nitrate, cis-di ... Examples of the tetraamminerhodium chloride include trans-dichlorotetraamminerhodium chloride, ruthenium chloride, hexaammineruthenium chloride, hexaammineruthenium bromide, hexaammineruthenium iodide, chloropentaammineruthenium chloride, cis-dichlorotetraammineruthenium chloride, trans-dichlorotetraamminerhodium chloride, iridium(III) chloride, iridium(IV) chloride, hexaammineiridium chloride, hexaammineiridium nitrate, chloropentaammineiridium chloride, chloropentaammineiridium bromide, hexaammineosmium chloride, hexaammineosmium bromide, and hexaammineosmium iodide.

[0200] When supporting platinum group metal ions or platinum group metal complex ions, the platinum group metal compound is usually dissolved in a solvent before use. Examples of the solvent include water; alcohols such as methanol, ethanol, propanol, butanol, and benzyl alcohol; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and mixtures thereof. In addition, to increase the solubility of the platinum group metal compound in the solvent, an acid such as hydrochloric acid, sulfuric acid, or nitric acid, or a base such as sodium hydroxide or tetramethylammonium hydroxide may be added.

[0201] The carbon-carbon bond forming method of the present invention is a carbon-carbon bond forming method that involves (1) reacting an aromatic halide with an organoboron compound, (2) reacting an aromatic halide with a compound having an alkynyl group at a terminal, or (3) reacting an aromatic halide with a compound having an alkenyl group to form a carbon-carbon bond, a raw material liquid (i) containing an aromatic halide and an organoboron compound, a raw material liquid (ii) containing an aromatic halide and a compound having an alkynyl group at a terminal, or a raw material liquid (iii) containing an aromatic halide and a compound having an alkenyl group is introduced into a vessel filled with a platinum group metal ion-supported catalyst through an inlet path of the vessel, the raw material liquid is passed through the platinum group metal ion-supported catalyst, and a reaction liquid is discharged from a discharge path of the vessel, thereby carrying out a carbon-carbon bond forming reaction; the platinum group metal ion-supported catalyst is the platinum group metal ion-supported catalyst of the present invention; The carbon-carbon bond forming method is characterized by the following.

[0202] The carbon-carbon bond forming method of the present invention is a carbon-carbon bond forming method in which a raw material liquid for the reaction, i.e., raw material liquid (i), raw material liquid (ii), or raw material liquid (iii), is passed through the platinum group metal ion-supported catalyst of the present invention to bring the raw material liquid into contact with the platinum group metal ion-supported catalyst of the present invention, thereby carrying out a carbon-carbon bond forming reaction. In the carbon-carbon bond forming method of the present invention, when the carbon-carbon bond forming reaction is (1) a reaction between an aromatic halide and an organoboron compound, the raw material liquid is raw material liquid (i) containing the aromatic halide and the organoboron compound. In the carbon-carbon bond forming method of the present invention, when the carbon-carbon bond forming reaction is (2) a reaction between an aromatic halide and a compound having a terminal alkynyl group, the raw material liquid is raw material liquid (ii) containing the aromatic halide and the compound having a terminal alkynyl group. Furthermore, in the carbon-carbon bond forming method of the present invention, when the carbon-carbon bond forming reaction is (3) a reaction between an aromatic halide and a compound having an alkenyl group, the raw material liquid is raw material liquid (iii) containing an aromatic halide and a compound having an alkenyl group. Note that, hereinafter, the aromatic halide and an organoboron compound, the aromatic halide and a compound having an alkynyl group at its terminal, or the aromatic halide and an alkenyl group may also be referred to as raw materials.

[0203] In the carbon-carbon bond forming method of the present invention, the platinum group metal ion supported catalyst of the present invention is packed in a packed container. A raw material liquid is introduced into the packed container through an inlet path of the packed container filled with the platinum group metal ion supported catalyst of the present invention, and the raw material liquid is passed through the platinum group metal ion supported catalyst. The reaction liquid is then discharged through a discharge path of the packed container. The reaction raw material liquid passes through the continuous pores of the porous structure of the platinum group metal ion supported catalyst of the present invention, and at this time, the platinum group metal in the continuous pores of the porous structure of the platinum group metal ion supported catalyst of the present invention comes into contact with the reaction raw material liquid, causing a carbon-carbon bond forming reaction by the platinum group metal. In other words, the carbon-carbon bond forming method of the present invention is a fixed-bed continuous flow reaction system.

[0204] A flow diagram of a first embodiment of a reaction apparatus for carrying out the carbon-carbon bond forming method of the present invention is shown in Fig. 14. In Fig. 14, a carbon-carbon bond forming reaction apparatus 50a comprises a cylindrical packed vessel 51a filled with the platinum group metal ion-supported catalyst of the present invention, a raw material vessel 53a for containing raw material liquid 52a for the reaction, a raw material liquid supply pump 54a for supplying raw material liquid 52a to packed vessel 51a, a reaction liquid receiver 56a for containing reaction liquid 55a discharged from packed vessel 51a, a raw material liquid inlet pipe 57a connecting raw material vessel 53a and packed vessel 51a and serving as a raw material liquid introduction path, a reaction liquid outlet pipe 59a connecting packed vessel 51a and reaction liquid receiver 56a and having a switch valve 58a attached thereto, and a circulation pipe 60a branching from reaction liquid outlet pipe 59a at switch valve 58a and connected to raw material liquid inlet pipe 57a. Furthermore, a heating member or heating device for heating the inside of filling container 51a is attached to filling container 51a as needed.

[0205] In the carbon-carbon bond forming reaction apparatus 50a, a raw material liquid 52a is continuously supplied from a raw material container 53a to a packed container 51a by a raw material liquid supply pump 54a. The raw material liquid supplied to the packed container 51a passes through the platinum group metal ion-supported catalyst according to the present invention packed in the packed container 51a, specifically through the continuous pores of the organic porous material. This allows the raw material liquid to continuously contact the platinum group metal ion-supported catalyst according to the present invention, causing the raw materials in the raw material liquid to react and form carbon-carbon bonds. Next, a reaction liquid 55a after carbon-carbon bond formation is sent to a reaction liquid receiver 56a via a reaction liquid discharge pipe 59a. Alternatively, the reaction liquid 55a after carbon-carbon bond formation is returned to the raw material container 53a via a circulation pipe 60a branching from the reaction liquid discharge pipe 59a. Note that a switching valve 58a switches between sending the reaction liquid 55a to the reaction liquid receiver 56a and returning it to the raw material container 53a. Furthermore, by switching between sending the reaction liquid 55a to the reaction liquid receiver 56a and returning it to the raw material container 53a, the reaction can be carried out by passing the reaction liquid through the layer of the platinum group metal ion-supported catalyst according to the present invention only once, or by passing the reaction liquid through the catalyst layer two or more times.

[0206] A flow diagram of a second embodiment of a reaction apparatus for carrying out the carbon-carbon bond forming method of the present invention is shown in Figure 15. In Figure 15, carbon-carbon bond forming reaction apparatus 50b comprises: cylindrical packed vessel 51b filled with the platinum group metal ion supported catalyst of the present invention; raw material vessel 531b for containing raw material liquid 521b for the reaction; raw material vessel 532b for containing aqueous inorganic base solution 522b; raw material liquid supply pump 541b for supplying raw material liquid 521b to packed vessel 51b; raw material liquid supply pump 542b for supplying aqueous inorganic base solution 522b to packed vessel 51b; reaction liquid receiver 56b for containing reaction liquid 55b discharged from packed vessel 51b; and raw material liquid inlet pipe 57b extending from raw material vessel 531b and raw material vessel 532b, joining midway, connecting to packed vessel 51a, and serving as an introduction path for the raw material liquid and aqueous inorganic base solution. Furthermore, a heating member or heating device for heating the inside of filling container 51b is attached to filling container 51b as needed.

[0207] In carbon-carbon bond forming reaction apparatus 50b, raw material liquid 521b is continuously supplied from raw material container 531b to filling container 51b by raw material liquid supply pump 541b, and inorganic base aqueous solution 522b is continuously supplied from raw material container 532b to filling container 51b by raw material liquid supply pump 542b. Raw material liquid 521b and inorganic base aqueous solution 521b are mixed at the confluence, and the resulting mixture is supplied to filling container 51b. The mixture of raw material liquid and inorganic base aqueous solution supplied to filling container 51b passes through the platinum group metal ion supported catalyst of the present invention filled in filling container 51b, specifically through the continuous pores of the organic porous material. As a result, the raw material liquid and inorganic base aqueous solution come into continuous contact with the platinum group metal ion supported catalyst of the present invention, and the raw materials in the raw material liquid react to form carbon-carbon bonds. Next, the reaction liquid 55b after carbon-carbon bond formation is sent to a reaction liquid receiver 56b via a reaction liquid discharge pipe 59b.

[0208] In the carbon-carbon bond forming method of the present invention, the size of the packed vessel, the thickness of the catalyst packed layer, the flow rate of the solvent and reaction raw materials, the type of solvent, the direction of flow of the solution and hydrogen (upward, downward, or sideways), and the like are appropriately selected depending on the type of reaction or reaction conditions. In the carbon-carbon bond forming method of the present invention, the raw material liquid may be passed through the platinum group metal ion-supported catalyst of the present invention only once, or the raw material liquid may be passed through the platinum group metal ion-supported catalyst of the present invention, and then the resulting reaction liquid may be passed through the platinum group metal ion-supported catalyst of the present invention again. When the raw material liquid is passed through the platinum group metal ion-supported catalyst of the present invention and then the resulting reaction liquid is passed through the platinum group metal ion-supported catalyst of the present invention again, the reaction liquid may be passed through the platinum group metal ion-supported catalyst of the present invention again as is, or the raw material liquid may be mixed with the reaction liquid and the mixed liquid may be passed through the platinum group metal ion-supported catalyst of the present invention.

[0209] A first embodiment of the carbon-carbon bond forming method of the present invention (hereinafter also referred to as carbon-carbon bond forming method (1)) is a reaction in which a raw material liquid (i) containing an aromatic halide and an organoboron compound is passed through the platinum group metal ion-supported catalyst according to the present invention to react the aromatic halide with the organoboron compound, thereby producing a carbon-carbon single bond.

[0210] The organoboron compounds used in the carbon-carbon bond forming method (1) are organoboron compounds represented by the general formulae (I) to (III).

[0211] [ka]

[0212] [ka]

[0213] [ka]

[0214] In the formula, R is any organic group, and is not particularly limited as long as it is an organic group. Examples include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aromatic carbocyclic group, and an aromatic heterocyclic group. An amino group, a methoxy group, an ethoxy group, a carboxyl group, an acetyl group, a nitro group, a cyano group, and the like may be introduced into these organic groups R, as long as the effects of the present invention are not impaired.

[0215] The organic boron compound used in the carbon-carbon bond forming method (1) is preferably an aromatic boron compound represented by the following general formulas (IV) to (VI).

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] (In the formula, Ar 1 are each an aromatic carbocyclic group or an aromatic heterocyclic group having 6 to 18 carbon atoms.

[0220] In formulas (IV) to (VI), Ar 1Examples of aromatic carbocyclic groups or aromatic heterocyclic groups according to the above formula (1) include a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group, a pyridyl group, a pyrimidyl group, an indolyl group, a benzimidazolyl group, a quinolyl group, a benzofuranyl group, an indanyl group, an indenyl group, and a dibenzofuranyl group. The position at which boron is bonded to the aromatic carbocyclic group or aromatic heterocyclic group is not particularly limited, and it can be bonded to any position. In addition, 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 a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a benzyl group; alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; a 9-fluorenylmethoxycarbonyl group, a butoxycarbonyl group, a benzyloxycarbonyl group, a nitro group, and a cyano group.

[0221] The aromatic halide used in the carbon-carbon bond forming method (1) is an aromatic halide represented by the following general formula (VII). Ar 2 -X (VII) (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.

[0222] In formula (VII), Ar 2Examples of the aromatic carbocyclic group or aromatic heterocyclic group include a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group, a pyridyl group, a pyrimidyl group, an indolyl group, a benzimidazolyl group, a quinolyl group, a benzofuranyl group, an indanyl group, an indenyl group, and a dibenzofuranyl group. The position at which the halogen atom is bonded to the aromatic carbocyclic group or aromatic heterocyclic group is not particularly limited, and the halogen atom can be bonded to any position. The aromatic carbocyclic group or aromatic heterocyclic group may also have one or more substituents introduced therein. Examples of the substituent include hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a benzyl group; alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; a 9-fluorenylmethoxycarbonyl group, a butoxycarbonyl group, a benzyloxycarbonyl group, a nitro group, a cyano group, a carboxyl group, and an amino group optionally substituted with an organic group. Here, X is a halogen atom, specifically a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0223] The formation of a carbon-carbon bond by the carbon-carbon bond forming method (1) refers to the formation of a carbon-carbon bond between an organic group obtained by eliminating a boron-containing functional group from an organoboron compound and an aromatic residue obtained by eliminating a halogen from an aromatic halide. For example, when the organoboron compound is an aromatic boron compound represented by any of formulas (IV) to (VI) and the aromatic halide is an aromatic halide represented by formula (VII), the resulting coupling product is a compound represented by formula (VIII). Ar 1 -Ar 2 (VIII) (In the formula, Ar 1 and Ar 2 is the same as in the formulas (IV) to (VII).

[0224] The aromatic boron compound and aromatic halide used in the carbon-carbon bond forming method (1) are preferably used in equimolar amounts, but as long as the molar ratio of aromatic boron compound:aromatic halide is in the range of 0.5 to 2:1, they can be used in the reaction without any problems.

[0225] A second embodiment of the carbon-carbon bond forming method of the present invention (hereinafter also referred to as carbon-carbon bond forming method (2)) is a reaction in which a raw material liquid (ii) containing an aromatic halide and a compound having an alkynyl group at a terminal is passed through the platinum group metal ion-supported catalyst according to the present invention to react the aromatic halide with the compound having an alkynyl group at a terminal, thereby producing a carbon-carbon single bond.

[0226] The aromatic halide used in the carbon-carbon bond forming method (2) is an aromatic halide represented by formula (VII).

[0227] The compound having an alkynyl group at its terminal, which is used in the carbon-carbon bond forming method (2), is a compound represented by formula (IX). HC≡CR 1 (IX) (In the formula, R 1 is a hydrogen atom, an aromatic carbocyclic group or 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, an alkenyl group having 2 to 18 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, or a silyl group having 1 to 18 carbon atoms which may have a substituent.

[0228] In formula (IX), R 1 Examples of the aromatic carbocyclic group or aromatic heterocyclic group having 6 to 18 carbon atoms and optionally having a substituent include Ar groups represented by formulae (IV) to (VII). 1 and Ar 2 In addition, in formula (IX), R 1 Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms, which may have a substituent, include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, and an octadecyl group. 1Examples of the alkenyl group having 2 to 18 carbon atoms and optionally having a substituent 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, and an octadecenyl group. 1 Examples of the alkynyl group having 2 to 10 carbon atoms and which may have a substituent include an ethynyl group, a propynyl group, a hexynyl group, and an octenyl group. Examples of the substituents of these aliphatic hydrocarbon groups, alkenyl groups, and alkynyl groups include a hydroxyl group, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Examples of the silyl group having 1 to 18 carbon atoms and which may have a substituent include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl group.

[0229] In the carbon-carbon bond forming method (2), an aromatic halide represented by formula (VII) and a compound represented by formula (IX) are reacted in the presence of a platinum group metal ion-supported catalyst according to the present invention to give a product represented by formula (X). Ar 2 -C≡CR 1 (X) (In the formula, Ar 2 and R 1 is the same as in formulas (VII) and (IX).

[0230] The aromatic halide and the compound having an alkynyl group at a terminal are preferably used in an equimolar ratio in the carbon-carbon bond forming method (2), but a molar ratio of aromatic halide:compound having an alkynyl group at a terminal within the range of 0.5 to 3:1 can be used in the reaction without any problems.

[0231] A third embodiment of the carbon-carbon bond forming method of the present invention (hereinafter also referred to as carbon-carbon bond forming method (3)) is a reaction in which a raw material liquid (iii) containing an aromatic halide and a compound having an alkenyl group is passed through the platinum group metal ion-supported catalyst according to the present invention to react the aromatic halide with the compound having an alkenyl group, thereby producing a carbon-carbon single bond.

[0232] The aromatic halide used in the carbon-carbon bond forming method (3) is an aromatic halide represented by formula (VII).

[0233] The compound having an alkenyl group used in the carbon-carbon bond forming method (3) is a compound represented by formula (XI). R 2 HC=CR 3 R 4 (XI) (In the formula, R 2 , R 3 , R 4 are each independently a hydrogen atom, an aromatic carbocyclic group or 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.

[0234] In formula (XI), R 2 , R 3 and R 4 Examples of the aromatic carbocyclic group or aromatic heterocyclic group having 6 to 18 carbon atoms which may have a substituent and the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, include R 1 In addition, in formula (XI), R 2 , R 3 and R 4 Examples of the carboxylic acid derivatives include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl. 2 , R 3 and R 4Examples of the acid amide derivatives include carbamoyl groups such as N-methylcarbamoyl and N,N-dimethylcarbamoyl.

[0235] In the carbon-carbon bond forming method (3), an aromatic halide represented by formula (VII) reacts with a compound represented by formula (XI) in the presence of a platinum group metal ion-supported catalyst according to the present invention to give a product represented by formula (XII). R 2 Ar 2 C=CR 3 R 4 (XII) (In the formula, Ar 2 , R 2 , R 3 and R 4 is the same as in formulas (VII) and (XI).

[0236] The ratio of the aromatic halide to the compound having an alkynyl group at a terminal used in the carbon-carbon bond forming method (3) is not particularly limited, but the reaction can proceed without any problems as long as the molar ratio of aromatic halide to compound having an alkenyl group is in the range of 0.5 to 2:1.

[0237] In the carbon-carbon bond forming reactions (1) to (3) of the present invention, the amount of the platinum group metal ion supported catalyst according to the present invention used is 0.01 to 20 mol % in terms of platinum group metal atoms relative to the aromatic halide.

[0238] In the carbon-carbon bond forming method of the present invention, the carbon-carbon bond forming reaction may be carried out in the absence of a solvent, or may be carried out using a solvent.

[0239] In the carbon-carbon bond forming method of the present invention, an example of a method for performing a carbon-carbon bond forming reaction without a solvent is to add liquid raw material liquid 53a to reaction raw material liquid 52a in a reaction apparatus 50a shown in FIG. 14, introduce liquid raw material liquid 53a into filled container 51a filled with the platinum group metal ion-supported catalyst of the present invention through an inlet path of filled container 51a, pass liquid raw material liquid 53a through the platinum group metal ion-supported catalyst of the present invention, and discharge reaction liquid 59a from the outlet path of filled container 51a, thereby performing a carbon-carbon bond forming reaction.

[0240] In the carbon-carbon bond forming method of the present invention, when the carbon-carbon bond forming reaction is carried out using a solvent, the solvent to be used is not particularly limited as long as it does not inhibit the carbon-carbon bond forming reaction, and examples thereof include hydrocarbon solvents such as hexane and heptane; aromatic solvents such as toluene and xylene; ether solvents such as diisopropyl ether, tetrahydrofuran, dioxane, and 4-methyltetrahydropyran; ester solvents such as ethyl acetate, propyl acetate, and ethyl propionate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, and glycerin; and water. One solvent selected from these may be used alone, or two or more solvents may be used in combination. In terms of low cost and high yield, toluene, xylene, tetrahydrofuran, 4-methyltetrahydropyran, N-methylpyrrolidone, 2-propanol, propylene glycol, water, a mixed solvent of toluene and water, a mixed solvent of xylene and water, a mixed solvent of tetrahydrofuran and water, a mixed solvent of 4-methyltetrahydropyran and water, a mixed solvent of N-methylpyrrolidone and water, a mixed solvent of 2-propanol and water, and a mixed solvent of propylene glycol and water are preferred, and toluene, 4-methyltetrahydropyran, N-methylpyrrolidone, 2-propanol, water, a mixed solvent of toluene and water, a mixed solvent of 4-methyltetrahydropyran and water, a mixed solvent of N-methylpyrrolidone and water, and a mixed solvent of 2-propanol and water are more preferred.

[0241] In the carbon-carbon bond forming method of the present invention, an example of a method for performing a carbon-carbon bond forming reaction using a solvent is to add raw material solution 53a, in which raw materials are dissolved in an organic solvent, to raw material reaction solution 52a of reactor 50a shown in FIG. 14, introduce raw material solution 52a, in which raw materials are dissolved in an organic solvent, into filled container 51a filled with the platinum group metal ion-supported catalyst of the present invention through an inlet path of filled container 51a, pass raw material solution 52a, in which raw materials are dissolved in an organic solvent, through the platinum group metal ion-supported catalyst of the present invention, and discharge reaction solution 59a from the outlet path of filled container 51a, thereby performing a carbon-carbon bond forming reaction.

[0242] In the carbon-carbon bond forming reaction of the present invention, it is preferable to carry out the carbon-carbon bond forming reaction in the presence of an inorganic base. Examples of the inorganic base that can be used include sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium acetate, sodium phosphate, potassium phosphate, potassium phenoxide, barium hydroxide, sodium methoxide, sodium ethoxide, potassium butoxide, trimethylamine, triethylamine, etc. The amount of these inorganic bases used is set in the range of 50 to 300 mol% based on the aromatic halide.

[0243] In a first embodiment of the method for carrying out the carbon-carbon bond forming reaction of the present invention, the raw material solution (i), the raw material solution (ii), or the raw material solution (iii) is an inorganic base-dissolved raw material solution in which raw materials (an aromatic halide and an organoboron compound, an aromatic halide and a compound having an alkynyl group at a terminal, or an aromatic halide and an alkenyl group) and an inorganic base are dissolved in water or a hydrophilic solvent, introducing the inorganic base-dissolved raw material solution into a packed container filled with the platinum group metal ion-supported catalyst of the present invention through an inlet path of the packed container, passing the inorganic base-dissolved raw material solution through the platinum group metal ion-supported catalyst, and discharging the reaction solution through a discharge path of the packed container, thereby carrying out a carbon-carbon bond forming reaction; The carbon-carbon bond forming method is characterized by the following.

[0244] A method for carrying out the first embodiment of the method for carrying out a carbon-carbon bond forming reaction of the present invention may include, for example, a method in which raw material solution (i), raw material solution (ii), or raw material solution (iii) in which an inorganic base is dissolved, i.e., inorganic base-dissolved raw material solution 52a in which raw materials (aromatic halide and an organoboron compound, aromatic halide and a compound having an alkynyl group at a terminal, or aromatic halide and an alkenyl group) and an inorganic base are dissolved in water or a hydrophilic solvent, is placed in reaction vessel 53a of reaction apparatus 50a shown in FIG. 14, and inorganic base-dissolved raw material solution 52a is introduced into packed vessel 51a filled with the platinum group metal ion-supported catalyst of the present invention through an inlet path of packed vessel 51a, and inorganic base-dissolved raw material solution 52a is passed through the platinum group metal ion-supported catalyst of the present invention, and reaction solution 59a is discharged from the outlet path of packed vessel 51a, thereby carrying out a carbon-carbon bond forming reaction.

[0245] In addition, as a method for carrying out the first embodiment of the method for carrying out a carbon-carbon bond forming reaction of the present invention, for example, raw material liquid (i), raw material liquid (ii), or raw material liquid (iii) in which raw materials (an aromatic halide and an organoboron compound, an aromatic halide and a compound having an alkynyl group at a terminal, or an aromatic halide and an alkenyl group) are dissolved in a hydrophilic organic solvent is placed in reaction vessel 531b of reaction apparatus 50b shown in FIG. 14, and inorganic base aqueous solution 522b is placed in raw material vessel 532b, and raw material liquid 521b in which raw materials are dissolved in a hydrophilic organic solvent and inorganic base aqueous solution 522b are supplied toward filling vessel 51a filled with the platinum group metal ion-supported catalyst of the present invention. Then, at the confluence, raw material liquid 521b and inorganic base aqueous solution 522b are mixed, and the resulting mixture, i.e., an inorganic base-dissolved raw material liquid in which raw materials (aromatic halide and organoboron compound, aromatic halide and compound having an alkynyl group at a terminal, or aromatic halide and alkenyl group) and an inorganic base are dissolved in water or a hydrophilic solvent, is introduced into filling container 51b through an inlet path of filling container 51b, and the inorganic base-dissolved raw material liquid is passed through the platinum group metal ion-supported catalyst of the present invention, and reaction liquid 59b is discharged from a discharge path of filling container 51b, thereby carrying out a carbon-carbon bond formation reaction.

[0246] A first example of the mode of carrying out the carbon-carbon bond forming reaction of the present invention is a homogeneous reaction mode using water or a hydrophilic organic solvent as a solvent, in which an inorganic base raw material solution obtained by dissolving a raw material and an inorganic base in water or a hydrophilic organic solvent is passed through the platinum group metal ion supported catalyst of the present invention.

[0247] In a first embodiment of the method for carrying out the carbon-carbon bond forming reaction of the present invention, both the raw material and the inorganic base may be dissolved in water or a hydrophilic organic solvent in advance to prepare an inorganic base-dissolved raw material solution, and this may be passed through the platinum group metal ion-supported catalyst of the present invention; alternatively, a raw material solution in which the raw material is dissolved in water or a hydrophilic organic solvent, and an aqueous solution of the inorganic base may be prepared separately and placed in separate containers, and the raw material solution and the aqueous solution of the inorganic base may be supplied from each container to an introduction path for supplying the reaction raw materials to the platinum group metal ion-supported catalyst of the present invention, and the raw material solution and the aqueous solution of the inorganic base may be mixed in the introduction path to prepare a uniform organic base-dissolved raw material solution, which may be passed through the platinum group metal ion-supported catalyst of the present invention.

[0248] As a second example of the implementation mode of the carbon-carbon bond forming reaction of the present invention, 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 raw materials are dissolved in a hydrophobic solvent, a mixture of the hydrophobic solvent raw material liquid and the inorganic base aqueous solution is introduced into a container filled with the platinum group metal ion-supported catalyst of the present invention through an inlet path of the container, the hydrophobic solvent-dissolved raw material liquid and the inorganic base aqueous solution are passed through the platinum group metal ion-supported catalyst, and the reaction solution is discharged through a discharge path of the container, thereby carrying out a carbon-carbon bond forming reaction; A method for forming a carbon-carbon bond, comprising:

[0249] As a method for carrying out the second embodiment of the method for carrying out the carbon-carbon bond forming reaction of the present invention, for example, a method may be mentioned in which raw material liquid (i), raw material liquid (ii), or raw material liquid (iii), in which raw materials (an aromatic halide and an organoboron compound, an aromatic halide and a compound having an alkynyl group at a terminal, or an aromatic halide and an alkenyl group) are dissolved in a hydrophobic organic solvent, is placed in reaction vessel 53a of reaction apparatus 50a shown in FIG. 15, i.e., the hydrophobic solvent raw material liquid and an aqueous solution of an inorganic base are charged, and the raw materials are mixed in reaction vessel 53a to form a suspension. The resulting suspension is introduced into packed vessel 51a, which is filled with the platinum group metal ion-supported catalyst of the present invention, through an inlet path of packed vessel 51a, and the suspension of the hydrophobic solvent raw material liquid and the aqueous solution of an inorganic base is passed through the platinum group metal ion-supported catalyst of the present invention, and reaction liquid 59a is discharged from the outlet path of packed vessel 51a, thereby carrying out the carbon-carbon bond forming reaction.

[0250] In addition, as a method for carrying out the second embodiment of the method for carrying out a carbon-carbon bond forming reaction of the present invention, for example, raw material liquid (i), raw material liquid (ii), or raw material liquid (iii) in which raw materials (an aromatic halide and an organoboron compound, an aromatic halide and a compound having an alkynyl group at a terminal, or an aromatic halide and an alkenyl group) are dissolved in a hydrophobic organic solvent is charged into reaction vessel 531b of reaction apparatus 50b shown in FIG. 15 as raw material liquid 521b, and also, inorganic base aqueous solution 522b is charged into raw material vessel 532b, and hydrophobic solvent raw material liquid 521b and inorganic base aqueous solution 522b are supplied toward filling vessel 51a filled with the platinum group metal ion supported catalyst of the present invention. Then, at the confluence, hydrophobic solvent raw material liquid 521b and inorganic base aqueous solution 522b are mixed, and the resulting mixture is introduced into filling vessel 51b through the inlet path of filling vessel 51b, and the hydrophobic solvent raw material liquid and inorganic base aqueous solution are passed through the platinum group metal ion supported catalyst of the present invention, and reaction liquid 59b is discharged from the outlet path of filling vessel 51b, thereby carrying out a carbon-carbon bond forming reaction.

[0251] A second example of the method for carrying out the carbon-carbon bond forming reaction of the present invention is a heterogeneous reaction method using a hydrophobic organic solvent as a solvent, in which a mixture of a raw material solution obtained by dissolving raw materials in a hydrophobic organic solvent and an aqueous solution of an inorganic base is passed through the platinum group metal ion supported catalyst of the present invention.

[0252] In a second embodiment of the method for carrying out the carbon-carbon bond forming reaction of the present invention, a hydrophobic solvent feedstock solution in which raw materials are dissolved in a hydrophobic organic solvent and an aqueous inorganic base solution may be mixed in advance in a container to prepare a mixture, and this mixture may be passed through the platinum group metal ion supported catalyst of the present invention; alternatively, a hydrophobic solvent feedstock solution in which raw materials are dissolved in a hydrophobic organic solvent and an aqueous inorganic base solution may be prepared separately and placed in separate containers, and the hydrophobic solvent feedstock solution and the aqueous inorganic base solution may be supplied from each container to an introduction path for supplying the reaction raw materials to the platinum group metal ion supported catalyst of the present invention, and the hydrophobic solvent feedstock solution and the aqueous inorganic base solution may be mixed in the introduction path to obtain a heterogeneous mixture, which may be passed through the platinum group metal ion supported catalyst of the present invention.

[0253] The carbon-carbon bond forming method of the present invention may be carried out in air, but is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The reaction temperature is not particularly limited, but may be set arbitrarily in the range of -20°C to 150°C, preferably 0°C to 120°C, and particularly preferably 20°C to 100°C. In the carbon-carbon bond forming reaction of the present invention, the reaction solution is fed at a rate of SV=0.1 h. -1 ~10000h -1 However, from the viewpoint of increasing the yield, SV=0.5h -1 ~2000h -1 It is preferable that SV=1h -1 ~1000h -1 It is particularly preferred that:

[0254] The concentration of raw materials in the reaction solution in the carbon-carbon bond forming method of the present invention is not particularly limited, but the carbon-carbon bond forming reaction of the present invention can be carried out in high yield even at a high raw material concentration of, for example, 0.40 to 1.00 mol / L, preferably 0.40 to 0.80 mol / L. Note that the carbon-carbon bond forming method of the present invention can also carry out a carbon-carbon bond forming reaction satisfactorily even when the raw material concentration is lower than the above range.

[0255] In the carbon-carbon bond forming method of the present invention, the filled container is a container filled with the platinum group metal ion-supported catalyst of the present invention, and has an inlet path for a raw material liquid, which serves as a path for delivering the raw material liquid to one end side of the platinum group metal ion-supported catalyst of the present invention, and an outlet path for a reaction liquid, which serves as a path for delivering the reaction liquid discharged to the other end side of the platinum group metal ion-supported catalyst of the present invention, to the outside of the filled container. The shape of the filled container is not particularly limited, and examples of the cross-sectional shape when cut along a plane perpendicular to the direction of liquid flow include a circle, a rectangle, and a hexagon. In the carbon-carbon bond forming method of the present invention, it is preferable that the gap between the filled container and the platinum group metal ion-supported catalyst is as small as possible, since this allows the raw material liquid to selectively flow through the continuous pores in the platinum group metal ion-supported catalyst of the present invention.

[0256] In the carbon-carbon bond forming method of the present invention, a container is filled with the platinum group metal ion-supported catalyst of the present invention, and a raw material solution is passed through the platinum group metal ion-supported catalyst of the present invention. This causes the carbon-carbon bond forming reaction to occur selectively within the open pores of the platinum group metal ion-supported catalyst of the present invention, and also makes it possible to uniformize the contact time and state of the catalyst and the raw material solution, thereby increasing the selectivity for the target product.

[0257] On the other hand, when a batchwise reaction method is used in which a raw material liquid is mixed and contacted with the platinum group metal ion-supported catalyst according to the present invention in a reaction vessel, the contact time between the catalyst and the raw material liquid becomes long, and particularly when heating is required during the reaction, the heating time of the raw material liquid also becomes long, making it impossible to control side reactions, resulting in low selectivity to the target product.

[0258] The platinum group metal ion-supported catalyst of the present invention can carry out a carbon-carbon bond-forming reaction in high yield, whether the raw material is an aromatic iodine compound having high reactivity or an aromatic bromine compound having lower reactivity than that of an aromatic iodine compound. Furthermore, when the reaction is carried out in the presence of an inorganic base, the platinum group metal ion-supported catalyst of the present invention can carry out a carbon-carbon bond-forming reaction in high yield both in a homogeneous system using an inorganic base-dissolved raw material solution in which the raw material and the inorganic base are dissolved in water or a hydrophilic organic solvent, and in a heterogeneous system using a hydrophobic organic solvent as a solvent for dissolving the raw material and a hydrophobic solvent raw material solution in which the raw material is dissolved in the hydrophobic organic solvent, and an aqueous solution of an inorganic base.

[0259] Next, the present invention will be described in detail with reference to examples, but these are merely illustrative and do not limit the present invention. [Example]

[0260] (Reference Example 1) Production of a weakly basic monolithic anion exchanger (Manufacturing of monolith intermediate (Process I)) 9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO), and 0.25 g of 2,2'-azobis(isobutyronitrile) were mixed and uniformly dissolved. Next, the styrene / divinylbenzene / SMO / 2,2'-azobis(isobutyronitrile) mixture was added to 180 g of purified water and stirred under reduced pressure using a planetary stirring device, a vacuum stirring / degassing mixer (manufactured by EME Corporation), to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel, sealed, and allowed to polymerize at 60°C for 24 hours. After polymerization, the contents were removed, extracted with methanol, and dried under reduced pressure to produce a monolith intermediate with a continuous macropore structure. The internal structure of the monolith intermediate (dried product) obtained in this manner was observed by SEM. An SEM image is shown in Figure 10. Although the wall separating two adjacent macropores is extremely thin and rod-like, it has an open-cell structure. The average diameter of the openings (mesopores) where the macropores overlap, as measured by mercury intrusion porosimetry, was 40 μm, and the total pore volume was 18.2 ml / g.

[0261] (Monolith manufacturing) Next, 216.6 g of styrene, 4.4 g of divinylbenzene, 220 g of 1-decanol, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (Step II). Next, the monolith intermediate was placed in a reaction vessel and immersed in the styrene / divinylbenzene / 1-decanol / 2,2'-azobis(2,4-dimethylvaleronitrile) mixture. After degassing in a vacuum chamber, the reaction vessel was sealed and allowed to polymerize at 50°C for 24 hours. After polymerization was completed, the contents were removed, extracted with acetone using a Soxhlet extractor, and then dried under reduced pressure (Step III). The internal structure of the monolith (dried body) thus obtained, containing 1.2 mol% of a crosslinking component made of styrene / divinylbenzene copolymer, was observed by SEM and the results are shown in Figure 11. As is clear from Figure 11, the monolith had a bicontinuous structure in which the skeleton and pores were three-dimensionally continuous and the two phases were entangled. Furthermore, the average skeleton diameter measured from the SEM image was 20 μm. Furthermore, the average diameter of the three-dimensionally continuous pores of the monolith, measured by mercury intrusion porosimetry, was 70 μm, and the total pore volume was 4.4 ml / g. The average pore diameter was determined from the maximum value of the pore distribution curve obtained by mercury intrusion porosimetry.

[0262] (Production of Weakly Basic Monolithic Anion Exchanger) The monolith produced above was placed in a columnar reactor, and a solution consisting of 1600 g of thionyl chloride, 400 g of tin tetrachloride, and 2500 ml of dimethoxymethane was circulated and passed through, causing a reaction 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, and then further washed with THF to obtain a chloromethylated monolith. The chloromethylated monolith was then dried under reduced pressure. The weight of the dried chloromethylated monolith was 8.4 g. The chloromethylated monolith was placed in a separable flask containing a stirrer, and a solution consisting of 56 ml of a 50% aqueous solution of dimethylamine and 180 ml of THF was introduced into the separable flask and stirred under reflux for 10 hours. After the reaction was completed, the product was washed with methanol and then washed again to obtain a weakly basic monolith anion exchanger. The dry anion exchange capacity of the resulting weakly basic monolithic anion exchanger was 4.7 mg / g, the dry anion exchange capacity was 4.3 mg / g, and the average skeleton diameter in the dry state measured from SEM images was 25 μm.

[0263] Example 1 The weakly basic monolith anion exchanger prepared in Reference Example 1 was dried under reduced pressure. The weight of the dried weakly basic monolith anion exchanger was 8.7 g. This dried monolith was treated with hydrochloric acid in methanol and then immersed in dilute hydrochloric acid containing 146 mg of palladium chloride for 24 hours to attach tetrachloropalladate ions. After immersion, the monolith was washed several times with pure water to prepare a Pd ion-supported weakly basic monolith anion exchanger. The amount of palladium supported in the obtained Pd ion-supported weakly basic monolith anion exchanger was determined by ICP emission spectroscopy, and the palladium support amount was 1.0 wt%. The results of EPMA (Electron Probe Micro Analyzer) and ESCA (Electron Spectroscopy for Chemical Analysis) analysis of the obtained Pd ion-supported weakly basic monolith anion exchanger are shown in Figures 12 and 13, respectively. Hereinafter, the platinum group metal ion-supported catalyst obtained in Example 1 will be referred to as a "Pd ion-supported weakly basic monolith anion exchanger."

[0264] Example 2

[0265] [ka]

[0266] A solution of 4-bromoacetophenone (0.796 g, 4.0 mmol) and phenylboronic acid (0.536 g, 4.4 mmol) in toluene (2.0 mL) was added to 1.1 M aqueous sodium hydroxide (4.0 mL, 4.4 mmol) and stirred. This suspension was passed through an ETFE column packed with Pd ion-supported weakly basic monolithic anion exchanger (φ2.0 × 150 mm) and heated to 80 °C at a flow rate of 0.3 mL / min, and collected in a flask containing saturated aqueous ammonium chloride. GC analysis of the organic layer of the resulting solution revealed 4-acetylbiphenyl at a conversion of 83%.

[0267] Example 3

[0268] [ka]

[0269] A solution of 4-bromoacetophenone (0.796 g, 4.0 mmol) in toluene (2.0 mL) was pumped at 0.1 mL / min, and a solution of phenylboronic acid (0.536 g, 4.4 mmol) and sodium hydroxide (4.4 mmol) in water (4.0 mL) was pumped at 0.2 mL / min, respectively, and the solutions were combined at a joint. The combined solution was passed through an ETFE column packed with Pd ion-supported weakly basic monolithic anion exchanger (φ2.0 × 150 mm) heated to 80 °C and collected in a flask containing saturated aqueous ammonium chloride. The organic layer of the resulting solution was analyzed by GC, revealing 4-acetylbiphenyl at a conversion of 78%.

[0270] Example 4

[0271] [ka]

[0272] A solution of 4-bromoacetophenone (0.995 g, 5.0 mmol) and phenylboronic acid (0.671 g, 5.5 mmol) in NMP (10 mL) was pumped at 0.5 mL / min, and 0.55 M sodium hydroxide (10 mL, 5.5 mmol) was pumped at 0.2 mL / min, respectively, and the solutions were combined at a joint. The combined solution was passed through an ETFE column packed with Pd ion-loaded weakly basic monolithic anion exchanger (φ2.0 × 150 mm) heated to 80 °C and collected in a flask containing saturated aqueous ammonium chloride. GC analysis of the organic layer of the resulting solution revealed 4-acetylbiphenyl with a conversion of 94%.

[0273] Example 5

[0274] [ka]

[0275] A solution of 2-bromobenzonitrile (0.728 g, 4.0 mmol) and 4-methylphenylboronic acid (0.598 g, 4.4 mmol) in toluene (1.0 mL) was added to 1.0 M aqueous sodium hydroxide (4.0 mL, 4.0 mmol) and stirred. This suspension was passed through an ETFE column packed with Pd ion-supported weakly basic monolithic anion exchanger (φ2.0 × 150 mm) and heated to 80 °C at a flow rate of 0.5 mL / min, and the mixture was collected in a flask containing saturated aqueous ammonium chloride. GC analysis of the organic layer of the resulting solution revealed 2-cyano-4'-methylbiphenyl with a conversion of 97%.

[0276] Example 6

[0277] [ka]

[0278] A solution of 2-bromobenzonitrile (0.728 g, 4.0 mmol) in toluene (2.0 mL) was pumped at 0.1 mL / min, and a solution of 4-methylphenylboronic acid (0.598 g, 4.4 mmol) in sodium hydroxide (4.4 mmol) in water (4.0 mL) was pumped at 0.4 mL / min, respectively, and the solutions were combined at a joint. The combined solution was passed through an ETFE column packed with Pd ion-loaded weakly basic monolithic anion exchanger (φ2.0 × 150 mm) and heated to 80 °C, and collected in a flask containing saturated aqueous ammonium chloride. The organic layer of the resulting solution was analyzed by GC, revealing 2-cyano-4'-methylbiphenyl at a conversion of 95%.

[0279] (Reference Example 2) Preparation of a Strongly Acidic Monolithic Cation Exchanger (Manufacturing of monolith intermediate (Process I)) 9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO), and 0.25 g of 2,2'-azobis(isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2'-azobis(isobutyronitrile) mixture was added to 180 g of purified water and stirred under reduced pressure using a planetary stirring device, a vacuum stirring / degassing mixer (manufactured by EME Corporation), to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel, sealed, and allowed to polymerize at 60°C for 24 hours. After polymerization, the contents were removed, extracted with methanol, and dried under reduced pressure to produce a monolith intermediate with a continuous macropore structure. When the internal structure of the monolith intermediate (dried body) obtained in this way was observed using SEM, it was found that the walls separating two adjacent macropores were extremely thin and rod-shaped, but had an open-cell structure.The average diameter of the openings (mesopores) where the macropores overlapped, measured by mercury intrusion porosimetry, was 40 μm, and the total pore volume was 18.2 ml / g.

[0280] (Monolith manufacturing) Next, 216.6 g of styrene, 4.4 g of divinylbenzene, 220 g of 1-decanol, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (Step II). Next, the monolith intermediate was placed in a reaction vessel and immersed in the styrene / divinylbenzene / 1-decanol / 2,2'-azobis(2,4-dimethylvaleronitrile) mixture. After degassing in a vacuum chamber, the reaction vessel was sealed and allowed to polymerize at 50°C for 24 hours. After polymerization was completed, the contents were removed, extracted with acetone using a Soxhlet extractor, and then dried under reduced pressure (Step III). The internal structure of the monolith (dried body) thus obtained, containing 1.2 mol% of a crosslinking component made of styrene / divinylbenzene copolymer, was observed by SEM. The monolith's skeleton and pores were each three-dimensionally continuous, forming a bicontinuous structure in which the two phases were intertwined. The average skeleton diameter measured from the SEM image was 20 μm. Mercury intrusion porosimetry measurements revealed that the average diameter of the three-dimensionally continuous pores of the monolith was 70 μm, and the total pore volume was 4.4 ml / g. The average pore diameter was determined from the maximum value of the pore distribution curve obtained by mercury intrusion porosimetry.

[0281] (Production of Strongly Acidic Monolithic Cation Exchanger) The monolith produced above was placed in a columnar reactor, and a solution consisting of 500 g of chlorosulfonic acid and 1,000 ml of dichloroethane was circulated and passed through, causing a reaction for 3 hours at 30° C. After completion of the reaction, the chloromethylated monolith was washed with dichloroethane and then with methanol to obtain a strongly acidic monolith cation exchanger. The dry total anion exchange capacity of the resulting strongly acidic monolithic cation exchanger was 4.7 mg / g, the strong cation exchange capacity was 4.3 mg / g, and the average skeleton diameter in the dry state measured from SEM images was 25 μm.

[0282] Example 7 The strongly acidic monolith cation exchanger produced in Reference Example 2 was dried under reduced pressure. After drying, 7.5 g of the dried monolith was immersed in methanol containing 800 mg of palladium acetate dissolved therein under a nitrogen atmosphere at room temperature to load palladium ions onto the strongly acidic monolith cation exchanger. The strongly acidic monolith cation exchanger was then removed and washed several times with pure water to prepare a Pd ion-loaded strongly acidic monolith cation exchanger. The amount of palladium loaded in the resulting Pd ion-loaded strongly acidic monolith cation exchanger was determined by ICP emission spectroscopy, and was found to be 4.6 wt%. Hereinafter, the platinum group metal ion-supported catalyst obtained in Example 7 will be referred to as "Pd ion-supported strongly acidic monolithic cation exchanger."

[0283] Example 8

[0284] [ka]

[0285] A toluene (1.0 mL) solution of 2-bromobenzonitrile (0.728 g, 4.0 mmol) and 4-methylphenylboronic acid (0.598 g, 4.4 mmol) was mixed with 1.0 M aqueous sodium hydroxide (4.0 mL, 4.0 mmol) and stirred. This suspension was passed through a stainless steel column packed with a Pd ion-supported strongly acidic monolithic cation exchanger (φ4.6 × 30 mm) heated to 80 °C, and the mixture was collected in a flask containing saturated aqueous ammonium chloride. GC analysis of the organic layer of the resulting solution revealed that 2-cyano-4'-methylbiphenyl was obtained with a conversion of 24%.

[0286] (Comparative Example 1) The Pd ion-supported weakly basic monolith anion exchanger prepared in Example 1 was immersed in a hydrazine aqueous solution for 24 hours to reduce the Pd ions. After immersion, the material was washed several times with pure water to prepare a Pd nanoparticle-supported weakly basic monolith anion exchanger.

[0287] (Comparative Example 2)

[0288] [ka]

[0289] A solution of 4-bromoacetophenone (0.796 g, 4.0 mmol) in toluene (2.0 mL) was pumped at 0.1 mL / min, and a solution of phenylboronic acid (0.536 g, 4.4 mmol) and sodium hydroxide (4.4 mmol) in water (4.0 mL) was pumped at 0.2 mL / min, respectively, and the solutions were combined at a joint. The combined solution was passed through an ETFE column packed with the Pd nanoparticle-supported weakly basic monolithic anion exchanger (φ2.0 × 150 mm) prepared in Comparative Example 1 and heated to 80 °C, and collected in a flask containing saturated aqueous ammonium chloride. The organic layer of the resulting solution was analyzed by GC, revealing that 4-acetylbiphenyl was obtained with a conversion of 53%.

[0290] (Comparative Example 3) Weakly basic anion exchange resin (Amberlite TM A21) 10 g of dry weight was treated with hydrochloric acid in methanol, and then immersed in dilute hydrochloric acid containing 170 mg of palladium chloride for 24 hours to attach tetrachloropalladate ions. After immersion, the resin was washed several times with pure water to prepare a Pd ion-supported weakly basic anion exchange resin.

[0291] Comparative Example 4

[0292] [ka]

[0293] A solution of 4-bromoacetophenone (0.796 g, 4.0 mmol) in toluene (2.0 mL) was fed at 0.1 mL / min, and a solution of phenylboronic acid (0.536 g, 4.4 mmol) and sodium hydroxide (4.4 mmol) in water (4.0 mL) was fed at 0.2 mL / min, respectively, and the solutions were combined at a joint. The combined solution was passed through a SUS column packed with the Pd ion-supported weakly basic anion exchange resin (0.5 mL) prepared in Comparative Example 3 and heated to 80 °C, and collected in a flask containing saturated aqueous ammonium chloride. The organic layer of the resulting solution was analyzed by GC, revealing that 4-acetylbiphenyl was obtained at a conversion rate of 28%. [Explanation of symbols]

[0294] 1 Skeletal phase 2 vacancy phase 10. Monolith 11 Image Area 12 Skeletal structure shown in cross section 13 Macropores 21 Skeletal Surface 22 Protrusion 30 Monolith (monolith ion exchanger) 31 Macropore 32 Aperture 33 Inner layer 34 Surface layer 35 Gas phase (bubble) 36 Wall (skeleton) 37 pores 50a, 50b Carbon-carbon bond forming reactor 51a, 51b Filling container 52a, 521b Raw material liquid 53a, 531b, 532b Raw material container 54a, 541b, 542b Raw material liquid supply pump 55a, 55b Reaction solution 56a, 56b Reaction liquid receiver 57a, 57b Raw material liquid introduction pipe 58a Switching valve 59a Reaction liquid discharge pipe 60a circulation pipe 522b Aqueous solutions of inorganic bases

Claims

1. A carbon-carbon bond forming method in which a carbon-carbon bond is formed by (1) reacting an aromatic halide with an organoboron compound, (2) reacting an aromatic halide with a compound having an alkynyl group at a terminal, or (3) reacting an aromatic halide with a compound having an alkenyl group, a raw material liquid (i) containing an aromatic halide and an organoboron compound, a raw material liquid (ii) containing an aromatic halide and a compound having an alkynyl group at a terminal, or a raw material liquid (iii) containing an aromatic halide and a compound having an alkenyl group is introduced into a container filled with a platinum group metal ion-supported catalyst for a carbon-carbon bond-forming reaction through an inlet path of the container, the raw material liquid is passed through the platinum group metal ion-supported catalyst, and the reaction liquid is discharged from a discharge path of the container, thereby carrying out a carbon-carbon bond-forming reaction; the supported platinum group metal ion catalyst for carbon-carbon bond-forming reactions is a platinum group metal ion-supported catalyst for carbon-carbon bond-forming reactions in which platinum group metal ions or platinum group metal complex ions are supported on a non-particulate organic porous ion exchanger, the non-particulate organic porous ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the continuous skeleton having a thickness of 1 to 100 μm, the continuous pores having an average diameter of 1 to 1000 μm, a total pore volume of 0.5 to 50 ml / g, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and ion exchange groups being uniformly distributed throughout the organic porous ion exchanger; A method for forming a carbon-carbon bond, comprising:

2. The method for forming a carbon-carbon bond according to claim 1, wherein the non-particulate organic porous ion exchanger has an open-cell structure with interconnected macropores and common openings (mesopores) with an average diameter of 1 to 1000 μm in the walls of the macropores, a total pore volume of 1 to 50 ml / g, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and ion exchange groups are uniformly distributed in the organic porous ion exchanger.

3. 2. The method for forming a carbon-carbon bond according to claim 1, wherein the non-particulate organic porous ion exchanger is formed by agglomeration of organic polymer particles having an average particle size of 1 to 50 μm to form a three-dimensionally continuous skeleton portion, and has three-dimensionally continuous pores having an average diameter of 20 to 100 μm between the skeletons, a total pore volume of 1 to 10 ml / g, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, and ion exchange groups uniformly distributed in the organic porous ion exchanger.

4. The carbon-carbon bond formation method according to claim 1, wherein the non-particulate organic porous ion exchanger has a continuous macropore structure in which bubble-like macropores overlap each other and the overlapping portions form openings with an average diameter of 30 to 300 μm, a total pore volume of 0.5 to 10 ml / g, an ion exchange capacity per weight in a dry state of 1 to 9 mg equivalents / g, ion exchange groups are uniformly distributed throughout the organic porous ion exchanger, and in an SEM image of a cross section of the continuous macropore structure (dried product), the area of ​​the skeleton appearing in the cross section accounts for 25 to 50% of the image area.

5. The method for forming a carbon-carbon bond according to claim 1, wherein the non-particulate organic porous ion exchanger is a bicontinuous structure consisting of a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm and made of an aromatic vinyl polymer containing 0.1 to 5.0 mol % of crosslinked structural units among all structural units having ion exchange groups introduced therein, and three-dimensionally continuous pores having an average diameter of 10 to 200 μm between the skeletons, the total pore volume being 0.5 to 10 ml / g, the ion exchange capacity per weight in a dry state being 1 to 9 mg equivalents / g, and the ion exchange groups being uniformly distributed in the organic porous ion exchanger.

6. 2. The method for forming a carbon-carbon bond according to claim 1, wherein the non-particulate organic porous ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the skeleton having a large number of particles with a diameter of 4 to 40 μm adhered to the surface or a large number of protrusions with a size of 4 to 40 μm formed on the skeleton surface of the organic porous ion exchanger, the average diameter of the continuous pores being 10 to 200 μm, the total pore volume being 0.5 to 10 ml / g, the ion exchange capacity per weight in a dry state being 1 to 9 mg equivalents / g, and the ion exchange groups being uniformly distributed in the organic porous ion exchanger.

7. 7. The carbon-carbon bond forming method according to claim 1, wherein the amount of the platinum group metal ions or the platinum group metal complex ions supported is 0.01 to 10.0 mass% in terms of platinum group metal atoms.

8. 8. The method for forming a carbon-carbon bond according to claim 1, wherein the carbon-carbon bond forming reaction is carried out in the presence of an inorganic base.

9. the raw material liquid (i) containing the aromatic halide and the organoboron compound, the raw material liquid (ii) containing the aromatic halide and the compound having an alkynyl group at a terminal, or the raw material liquid (iii) containing the aromatic halide and the compound having an alkenyl group 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, introducing the inorganic base-dissolved raw material solution into a container filled with a platinum group metal ion-supported catalyst for the carbon-carbon bond forming reaction through an inlet path of the container, passing the inorganic base-dissolved raw material solution through the platinum group metal ion-supported catalyst for the carbon-carbon bond forming reaction, and discharging the reaction solution through a discharge path of the container, thereby carrying out a carbon-carbon bond forming reaction; The method for forming a carbon-carbon bond according to any one of claims 1 to 8,

10. the raw material liquid (i) containing the aromatic halide and the organoboron compound, the raw material liquid (ii) containing the aromatic halide and the compound having an alkynyl group at a terminal, or the raw material liquid (iii) containing the aromatic halide and the compound having an alkenyl group is a hydrophobic solvent raw material liquid in which raw materials are dissolved in a hydrophobic organic solvent; introducing a mixture of the hydrophobic solvent raw material liquid and the inorganic base aqueous solution into a container filled with a platinum group metal ion-supported catalyst for the carbon-carbon bond forming reaction through an inlet path of the container, passing the hydrophobic solvent-dissolved raw material liquid and the inorganic base aqueous solution through the platinum group metal ion-supported catalyst for the carbon-carbon bond forming reaction, and discharging the reaction liquid through a discharge path of the container, thereby carrying out a carbon-carbon bond forming reaction; The method for forming a carbon-carbon bond according to any one of claims 1 to 8,

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