JP6178461B2 - Carbon-carbon bond formation method - Google Patents

Description

  The present invention relates to a carbon-carbon bond forming method for generating a carbon-carbon bond.

  The carbon-carbon formation reaction (coupling reaction) using platinum group metals such as palladium represented by Suzuki-Miyaura coupling, Sonogashira coupling, Mizorogi-Heck coupling as a catalyst is used for pharmaceutical intermediates and liquid crystals. In the process of synthesizing highly functional materials, in recent years it has become increasingly important.

  Conventionally, the platinum group metal catalyst is often used in a homogeneous system and has exhibited high catalytic activity. However, there are drawbacks in that it is difficult to recover the catalyst and the product is contaminated with the metal that is the catalyst. It was. In view of this, heterogeneous catalysts have been developed in which the catalyst is supported on a carrier to facilitate recovery of the catalyst and reduce metal contamination of the product. For example, Japanese Patent Application Laid-Open Nos. 2003-62468 and 2011-136329 disclose a catalyst using a particulate ion exchange resin as a carrier and supporting a platinum group metal.

JP 2003-62468 A (Claims) JP2011-136329A (Claims)

  However, since the particle size of the particulate ion exchange resin used as a carrier is usually as large as several hundred μm, it has a drawback that it takes time to diffuse the substrate and the reaction rate is slow.

  Accordingly, an object of the present invention is to provide a method for efficiently forming a carbon-carbon bond.

  In such a situation, the present inventors have conducted intensive studies, and as a result, platinum group metal-supported catalysts obtained by supporting a platinum group metal on a non-particulate organic porous ion exchanger include conventional palladium, platinum, etc. In the carbon-carbon bond forming reaction in which the platinum group metal functions as a catalyst, the present inventors have found that the catalyst activity is high, and therefore the reaction can be efficiently advanced, and the present invention has been completed.

That is, the present invention (1) comprises (1) a reaction between an aromatic halide and an organic boron compound in the presence of a platinum group metal supported catalyst, and (2) an aromatic halide and a compound having an alkynyl group at the terminal. Reaction, or (3) a carbon-carbon bond forming reaction in which an aromatic halide and a compound having an alkenyl group are reacted to form a carbon-carbon bond,
The platinum group metal supported catalyst is a platinum group metal supported catalyst in which platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported on a non-particulate organic porous ion exchanger. The ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 100 μm, the average diameter of the continuous pores is 1 to 1000 μm, and the total pore volume is 0.5 to 50 ml / g. Yes, the ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, the ion exchange groups are uniformly distributed in the organic porous ion exchanger, and the supported amount of the platinum group metal is , 0.004-20% by weight in a dry state,
The carbon-carbon bond formation reaction characterized by these is provided.

  Further, the present invention (2) is characterized in that the non-particulate organic porous ion exchanger has an open cell structure having a common pore (mesopore) having an average diameter of 1 to 1000 μm in the macropore and the macropore wall connected to each other. The total pore volume is 1 to 50 ml / g, the ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, and the ion exchange group is contained in the organic porous ion exchanger. The present invention provides the carbon-carbon bond forming reaction (1) characterized by being uniformly distributed.

  Further, in the present invention (3), the non-particulate organic porous ion exchanger is formed by agglomerating organic polymer particles having an average particle diameter of 1 to 50 μm to form a three-dimensionally continuous skeleton part. Having a three-dimensionally continuous pore having an average diameter of 20 to 100 μm, a total pore volume of 1 to 10 ml / g, and an ion exchange capacity per weight in a dry state of 1 to 6 mg equivalent / g The ion-exchange group is uniformly distributed in the organic porous ion exchanger, and the carbon-carbon bond forming reaction according to (1) is provided.

  Further, the present invention (4) is a continuous macropore structure in which the non-particulate organic porous ion exchanger has bubble-shaped macropores overlapped, and the overlapping portion has an opening having an average diameter of 30 to 300 μm. The pore volume is 0.5 to 10 ml / g, the ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, and the ion exchange groups are uniformly distributed in the organic porous ion exchanger. In addition, in the SEM image of the cut surface of the continuous macropore structure (dry body), the skeleton part area appearing in the cross section is 25 to 50% in the image region, (1) carbon-carbon bond It provides a formation reaction.

  In the invention (5), the non-particulate organic porous ion exchanger is an aromatic containing 0.1 to 5.0 mol% of a crosslinked structural unit in all the structural units into which an ion exchange group is introduced. A co-continuous structure composed of a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm made of vinyl polymer and three-dimensionally continuous pores having an average diameter of 10 to 200 μm between the skeletons. The total pore volume is 0.5 to 10 ml / g, the ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, and the ion exchange groups are uniform in the organic porous ion exchanger. The carbon-carbon bond forming reaction according to (1), characterized in that the carbon-carbon bond forming reaction is distributed.

  Further, in the present invention (6), the non-particulate organic porous ion exchanger is composed of a continuous skeleton phase and a continuous pore phase, and the skeleton is a large number of particles having a diameter of 4 to 40 μm fixed to the surface or The organic porous body has a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface, an average diameter of continuous pores of 10 to 200 μm, and a total pore volume of 0.5 to 10 ml / The ion exchange capacity per weight in a dry state is 1 to 6 mg equivalent / g, and the ion exchange groups are uniformly distributed in the organic porous ion exchanger (1 ) Of carbon-carbon bond formation.

  ADVANTAGE OF THE INVENTION According to this invention, the method of forming a carbon-carbon bond efficiently can be provided.

It is a SEM photograph of the example of the form of the 1st monolith. It is a SEM photograph of the example of the form of the 2nd monolith. It is a SEM photograph of the example of the form of the 3rd monolith. It is the figure which transcribe | transferred the frame | skeleton part which appears as a cross section of the SEM photograph of FIG. It is a SEM photograph of the example of the form of the 4th monolith. It is a schematic diagram of the co-continuous structure of a 4th monolith and a monolith ion exchanger. It is a SEM photograph of the example of a form of a monolith intermediate (4). It is typical sectional drawing of a protrusion. It is a SEM photograph of the example of a form of the 5-1 monolith. 2 is a SEM photograph of the monolith intermediate of Reference Example 1. 4 is a SEM photograph of the monolith of Reference Example 1. 3 is an EPMA analysis result of a monolith cation exchanger of Reference Example 1. 3 is an EPMA analysis result of a monolith cation exchanger of Reference Example 1. 4 is an EPMA analysis result of a platinum group metal supported catalyst of Reference Example 2. 4 is a TEM image of a platinum group metal supported catalyst of Reference Example 2. 4 is an EPMA analysis result of a monolith anion exchanger of Reference Example 4. 4 is an EPMA analysis result of a monolith anion exchanger of Reference Example 4. 7 is an EPMA analysis result of a platinum group metal supported catalyst of Reference Example 5. 6 is a TEM image of a platinum group metal supported catalyst of Reference Example 5.

The carbon-carbon bond forming reaction of the present invention comprises (1) a reaction between an aromatic halide and an organoboron compound in the presence of a platinum group metal-supported catalyst, and (2) a compound having an alkynyl group at the terminal with the aromatic halide. Or (3) a carbon-carbon bond forming reaction in which a reaction between an aromatic halide and a compound having an alkenyl group is performed to form a carbon-carbon bond,
The platinum group metal supported catalyst is a platinum group metal supported catalyst in which platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported on a non-particulate organic porous ion exchanger. The ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 100 μm, the average diameter of the continuous pores is 1 to 1000 μm, and the total pore volume is 0.5 to 50 ml / g. Yes, the ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, the ion exchange groups are uniformly distributed in the organic porous ion exchanger, and the supported amount of the platinum group metal is , 0.004-20% by weight in a dry state,
It is a carbon-carbon bond formation reaction characterized by these.

  In the platinum group metal supported catalyst according to the carbon-carbon bond forming reaction of the present invention, the support on which the platinum group metal is supported is a non-particulate organic porous ion exchanger. Is a monolithic organic porous ion exchanger. The monolithic organic porous body is a porous body having a skeleton formed of an organic polymer and a large number of communication holes serving as a flow path for a reaction solution between the skeletons. The monolithic organic porous ion exchanger is a porous body introduced so that ion exchange groups are uniformly distributed in the skeleton of the monolithic organic porous body. In the present specification, “monolithic organic porous material” is also simply referred to as “monolith”, and “monolithic organic porous ion exchanger” is also simply referred to as “monolith ion exchanger”, and is also an intermediate in the production of monoliths. The “monolithic organic porous intermediate” that is the body (precursor) is also simply referred to as “monolith intermediate”.

  The monolith ion exchanger related to the platinum group metal supported catalyst is obtained by introducing an ion exchange group into the monolith, and its structure is an organic porous body composed of a continuous skeleton phase and a continuous pore phase. The thickness of the continuous skeleton is 1 to 100 μm, the average diameter of the continuous pores is 1 to 1000 μm, and the total pore volume is 0.5 to 50 ml / g.

The thickness of the continuous skeleton in the dry state of the monolith ion exchanger according to the platinum group metal supported catalyst is 1 to 100 μm. When the thickness of the continuous skeleton of the monolith ion exchanger is less than 1 μm, the ion exchange capacity per volume decreases, and the mechanical strength decreases. Since the exchanger is greatly deformed, it is not preferable. Furthermore, the contact efficiency between the reaction solution and the monolith ion exchanger is lowered, and the catalytic activity is lowered, which is not preferable. On the other hand, if the thickness of the continuous skeleton of the monolith ion exchanger exceeds 100 μm, the skeleton becomes too thick, and it takes time to diffuse the substrate, which is not preferable. The thickness of the continuous skeleton is determined by SEM observation.

  The average diameter of the continuous pores in the dry state of the monolith ion exchanger related to the platinum group metal supported catalyst is 1-1000 μm. If the average diameter of the continuous pores of the monolith ion exchanger is less than 1 μm, it is not preferable because the pressure loss during liquid passage increases. On the other hand, if the average diameter of the continuous pores of the monolith ion exchanger exceeds 1000 μm, the contact between the reaction solution and the monolith ion exchanger becomes insufficient and the catalytic activity is lowered, which is not preferable. In addition, the average diameter of the continuous void | hole in the dry state of a monolith ion exchanger is measured by the mercury intrusion method, and points out the maximum value of the pore distribution curve obtained by the mercury intrusion method.

  The total pore volume in the dry state of the monolith ion exchanger according to the platinum group metal supported catalyst is 0.5 to 50 ml / g. If the total pore volume of the monolith ion exchanger is less than 0.5 ml / g, the pressure loss at the time of liquid passing is undesirably large, and further, the amount of permeate per unit cross-sectional area is small, This is not preferable because the processing amount decreases. On the other hand, if the total pore volume of the monolith ion exchanger exceeds 50 ml / g, the ion exchange capacity per volume decreases, the amount of platinum group metal nanoparticles supported decreases, and the catalytic activity decreases, which is not preferable. Further, the mechanical strength is lowered, and the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high speed, and the pressure loss at the time of the liquid passing increases rapidly. Furthermore, since the contact efficiency between the reaction solution and the monolith ion exchanger is reduced, the catalytic activity is significantly reduced. The total pore volume is measured by a mercury intrusion method.

  Examples of the structure of such a monolith ion exchanger are disclosed in Japanese Unexamined Patent Application Publication No. 2002-306976 and Japanese Unexamined Patent Application Publication No. 2009-62512, and Japanese Unexamined Patent Application Publication No. 2009-67982. Examples thereof include a co-continuous structure, a particle aggregation structure disclosed in JP2009-7550A, and a particle composite structure disclosed in JP2009-108294A.

  The ion exchange capacity per weight in the dry state of the monolith ion exchanger according to the platinum group metal supported catalyst is 1 to 6 mg equivalent / g. If the ion exchange capacity in the dry state of the monolithic ion exchanger is less than 1 mg equivalent / g, the amount of platinum group metal that can be supported will be reduced, while if it exceeds 6 mg equivalent / g, ion exchange groups are introduced. This is not preferable because the reaction becomes harsh and the oxidation deterioration of the monolith is remarkably advanced. When the monolith ion exchanger is a monolith anion exchanger, an anion exchange group is introduced into the monolith anion exchanger, and the anion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g. When the monolith ion exchanger is a monolith cation exchanger, a cation exchange group is introduced into the monolith cation exchanger, and the cation exchange capacity per weight in a dry state is 1 to 6 mg equivalent / g. is there. The ion exchange capacity of a porous material in which ion exchange groups are introduced only on the surface of the skeleton cannot be determined unconditionally depending on the type of the porous material or ion exchange groups, but is at most 500 μg equivalent / g.

  In the monolith ion exchanger related to the platinum group metal supported catalyst, the introduced ion exchange groups are uniformly distributed not only on the surface of the monolith but also inside the skeleton of the monolith. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution status of the ion exchange groups can be easily confirmed by using EPMA. In addition, if the ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the monolith, the physical and chemical properties of the surface and the interior can be made uniform, so that they are resistant to swelling and shrinkage. Improves.

  The ion exchange group introduced into the monolith ion exchanger related to the platinum group metal supported catalyst is a cation exchange group or an anion exchange group. Examples of the cation exchange group include a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric ester group. Examples of anion exchange groups include trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group, methyldihydroxyethylammonium group, quaternary ammonium group, tertiary sulfonium group, phosphonium group. Etc.

In the monolith ion exchanger according to the platinum group metal supported catalyst of the present invention, the material constituting the continuous skeleton is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material is not particularly limited, but it contains 0.1 to 30 mol%, preferably 0.1 to 20 mol% of crosslinkable structural units with respect to all structural units constituting the polymer material. Is preferred. If the cross-linking structural unit is less than 0.1 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 30 mol%, it may be difficult to introduce an ion exchange group. The type of the polymer material is not particularly limited, and examples thereof include aromatic vinyl polymers such as polystyrene, poly (α-methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, and polyvinyl naphthalene; polyolefins such as polyethylene and polypropylene; Poly (halogenated polyolefin) such as vinyl chloride and polytetrafluoroethylene; Nitrile-based polymer such as polyacrylonitrile; Cross-linking weight of (meth) acrylic polymer such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate Coalescence is mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, a cross-linked polymer of an aromatic vinyl polymer because of the ease of forming a continuous structure, the ease of introducing ion exchange groups and the high mechanical strength, and the high stability to acids or alkalis. In particular, styrene-divinylbenzene copolymer and vinylbenzyl chloride-divinylbenzene copolymer are preferable materials.

<Examples of Monolithic Organic Porous Material and Monolithic Organic Porous Ion Exchanger>
Examples of the monolith include the following first to fifth monoliths. Examples of the monolith ion exchanger include the following first to fifth monolith ion exchangers.

<Description of First Monolith and First Monolith Ion Exchanger>
In the platinum group metal-supported catalyst of the present invention, the first monolith ion exchanger serving as a support for the platinum group metal particles is a common one having an average diameter of 1 to 1000 μm in a dry state inside the macropore and the macropore wall connected to each other. It has an open cell structure with openings (mesopores), the total pore volume in the dry state is 1 to 50 ml / g, has ion exchange groups, and the ion exchange groups are uniformly distributed, It is a monolithic ion exchanger having an ion exchange capacity per weight in a dry state of 1 to 6 mg equivalent / g. The first monolith is a monolith before the ion exchange group is introduced, and has a common pore (mesopore) having an average diameter of 1 to 1000 μm in a dry state in the macropore and the macropore wall connected to each other. It is an organic porous body having an open cell structure and a total pore volume of 1 to 50 ml / g in a dry state.

In the first monolithic ion exchanger, bubble-shaped macropores overlap each other, and the overlapping portion is in a dry state with a common opening (mesopore) having an average diameter of 1 to 1000 μm, preferably 10 to 200 μm, particularly preferably 20 to 100 μm. A continuous macropore structure, most of which has an open pore structure. In the open pore structure, when water is flowed, the inside of bubbles formed by the macropores and the mesopores becomes a flow path. The number of overlapping macropores is 1 to 12 for one macropore, and 3 to 10 for many. FIG. 1 shows a scanning electron microscope (SEM) photograph of an embodiment of the first monolith ion exchanger. The first monolith ion exchanger shown in FIG. 1 has a large number of bubble-like macropores. The cell-shaped macropores overlap each other, and the overlapping portion is a continuous macropore structure having a common opening (mesopore), most of which has an open pore structure. If the average diameter in the dry state of the mesopores is less than 1 μm, the pressure loss at the time of passing the liquid becomes undesirably large, and if the average diameter in the dry state of the mesopores exceeds 1000 μm, the reaction solution and the monolithic ion The contact with the exchanger becomes insufficient, and the catalytic activity decreases, which is not preferable. When the structure of the first monolith ion exchanger is an open cell structure as described above, the macropore group and the mesopore group can be formed uniformly, and the particle aggregation as described in JP-A-8-252579 is also possible. The pore volume and specific surface area can be remarkably increased compared to the type porous body.

  In the present invention, the average diameter of the opening of the first monolith in the dry state and the average diameter of the opening of the first monolith ion exchanger in the dry state are measured by the mercury intrusion method, and are obtained by the mercury intrusion method. The maximum value of the pore distribution curve.

  The total pore volume per weight of the first monolith ion exchanger in the dry state is 1 to 50 ml / g, preferably 2 to 30 ml / g. If the total pore volume is less than 1 ml / g, it is not preferable because the pressure loss at the time of liquid passing increases, and further, the permeation amount per unit cross-sectional area decreases, and the processing capacity decreases. Absent. On the other hand, if the total pore volume exceeds 50 ml / g, the mechanical strength is lowered, and the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high flow rate. Furthermore, since the contact efficiency between the reaction solution, the monolith ion exchanger, and the platinum group metal particles supported thereon decreases, the catalytic effect also decreases, which is not preferable. In the conventional particulate porous ion exchange resin, the total pore volume is 0.1 to 0.9 ml / g at the most. Those having a specific surface area can be used.

  In the first monolith ion exchanger, the material constituting the skeleton is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. It is preferable. If the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, it may be difficult to introduce an ion exchange group.

There is no restriction | limiting in particular in the kind of organic polymer material which comprises the frame | skeleton of a 1st monolith ion exchanger, For example, fragrances, such as a polystyrene, poly (alpha-methyl styrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene Acrylic vinyl polymers; Polyolefins such as polyethylene and polypropylene; Poly (halogenated polyolefins) such as polyvinyl chloride and polytetrafluoroethylene; Nitrile polymers such as polyacrylonitrile; Polymethyl methacrylate, Polyglycidyl methacrylate, Polyethyl acrylate And a crosslinked polymer such as a (meth) acrylic polymer. The organic polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or two or more kinds of polymers. It may be blended. Among these organic polymer materials, the cross-linking weight of the aromatic vinyl polymer is determined by the ease of forming a continuous macropore structure, the ease of introduction of ion exchange groups and the high mechanical strength, and the high stability to acids or alkalis. A styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.

The ion exchange group introduced into the first monolith ion exchanger is the same in the second monolith ion exchanger to the fifth monolith ion exchanger. The ion exchange group is a cation exchange group or an anion exchange group, and examples of the cation exchange group include a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric acid ester group. Exchange groups include quaternary ammonium groups such as trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group, methyldihydroxyethylammonium group, tertiary sulfonium group, phosphonium group, etc. Is mentioned.

  In the first monolith ion exchanger (the same applies to the second monolith ion exchanger to the fifth monolith ion exchanger), the introduced ion exchange group is not only the surface of the porous body but also the porous body. It is evenly distributed within the skeleton. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution state of the ion exchange groups is confirmed by using EPMA. In addition, if the ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and shrinkage can be achieved. The durability against is improved.

  The ion exchange capacity per weight in the dry state of the first monolith ion exchanger is 1 to 6 mg equivalent / g. When the ion exchange capacity per weight in the dry state is in the above range, the environment around the catalyst active point such as the pH inside the catalyst can be changed, thereby increasing the catalyst activity. When the first monolith ion exchanger is a monolith anion exchanger, anion exchange groups are introduced into the first monolith anion exchanger, and the anion exchange capacity per weight in the dry state is 1 to 6 mg. Equivalent / g. When the first monolith ion exchanger is a monolith cation exchanger, a cation exchange group is introduced into the first monolith cation exchanger, and the cation exchange capacity per weight in a dry state is 1 ~ 6 mg equivalent / g. Note that the ion exchange capacity of the porous body in which the ion exchange group is introduced only on the surface cannot be determined unconditionally depending on the kind of the porous body or the ion exchange group, but is at most 500 μg equivalent / g.

<Method for producing first monolith and first monolith ion exchanger>
Although it does not restrict | limit especially as a manufacturing method of a 1st monolith, An example of the manufacturing method according to the method of Unexamined-Japanese-Patent No. 2002-306976 is shown below. That is, the first monolith is prepared by mixing an oil-soluble monomer not containing an ion exchange group, a surfactant, water and a polymerization initiator as necessary to obtain a water-in-oil emulsion and polymerizing the emulsion. Is obtained. Such a manufacturing method of the first monolith is preferable in that the porous structure of the monolith can be easily controlled.

The oil-soluble monomer containing no ion exchange group used in the production of the first monolith does not contain any ion exchange group such as carboxylic acid group or sulfonic acid group and anion exchange group such as quaternary ammonium group, This refers to a lipophilic monomer that has a low solubility in water. Specific examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, 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, ethylene glycol dimethyl ester Acrylate, and the like. These monomers can be used singly or in combination of two or more. However, in the present invention, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and its content is preferably 0.3 to 10 mol% in the total oil-soluble monomer. Is preferably 0.3 to 5 mol% from the viewpoint of quantitatively introducing ion-exchange groups in a later step and securing a practically sufficient mechanical strength.

  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 an oil-soluble monomer containing no ion exchange group and water are mixed. There is no limitation, such as sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan monooleate Nonionic surfactants; Anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; lauryldimethylbetaine, etc. It can be used sex surfactant. These surfactants can be used singly or in combination of two or more. The water-in-oil emulsion refers to an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the surfactant added may vary depending on the type of oil-soluble monomer and the size of the target emulsion particles (macropores), but it cannot be generally stated, but the total amount of oil-soluble monomer and surfactant Can be selected within a range of about 2 to 70%. Moreover, although not necessarily essential, in order to control the bubble shape and size of the monolith, alcohols such as methanol and stearyl alcohol; carboxylic acids such as stearic acid; hydrocarbons such as octane, dodecane and toluene; tetrahydrofuran, dioxane and the like Cyclic ether can coexist in the system.

  In the production of the first monolith, when forming the monolith by polymerization, a compound that generates radicals by heat and light irradiation is suitably used as the polymerization initiator used as necessary. The polymerization initiator may be water-soluble or oil-soluble. For example, azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, persulfate Examples include potassium, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and tetramethylthiuram disulfide. However, in some cases, there is a system in which the polymerization proceeds only by heating or light irradiation without adding a polymerization initiator, and in such a system, the addition of the polymerization initiator is unnecessary.

In the production of the first monolith, the mixing method for mixing the oil-soluble monomer not containing an ion exchange group, a surfactant, water and a polymerization initiator to form a water-in-oil emulsion is not particularly limited. Without mixing each component at once, oil-soluble monomer, surfactant and oil-soluble polymerization initiator oil-soluble component and water or water-soluble polymerization initiator water-soluble component separately After uniformly dissolving, a method of mixing each component can be used. There is no particular limitation on the mixing apparatus for forming the emulsion, and ordinary mixers, homogenizers, high-pressure homogenizers, and objects to be treated are placed in a mixing container, and the mixing container is tilted and revolved around the revolution axis. While rotating, a so-called planetary stirring device that stirs and mixes the object to be processed can be used, and an appropriate device may be selected to obtain the desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily. Among these mixing apparatuses, the planetary stirring apparatus is preferably used because it can uniformly generate water droplets in the W / O emulsion and can arbitrarily set the average diameter within a wide range.

In the production of the first monolith, various polymerization conditions for polymerizing the water-in-oil emulsion thus obtained can be selected depending on the type of monomer and the initiator system. For example, when azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, or the like is used as a polymerization initiator, it can be heated and polymerized at 30 to 100 ° C. for 1 to 48 hours in a sealed container under an inert atmosphere. When hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, etc. are used as initiators, polymerization can be carried out at 0-30 ° C. for 1-48 hours in a sealed container under an inert atmosphere. That's fine. After completion of the polymerization, the content is taken out and subjected to Soxhlet extraction with a solvent such as isopropanol to remove the unreacted monomer and the remaining surfactant to obtain a first monolith.

  The method for producing the first monolith ion exchanger is not particularly limited. In the 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 ion An oil-soluble monomer that does not contain an exchange group is polymerized using a monomer into which an ion exchange group such as a carboxylic acid group or a sulfonic acid group is introduced to form a monolith ion exchanger in one step, including an ion exchange group For example, a method in which a monomer is polymerized to form a first monolith and then an ion exchange group is introduced. Among these methods, the method of polymerizing using a monomer not containing an ion exchange group to form the first monolith and then introducing the ion exchange group makes it easy to control the porous structure of the monolith ion exchanger. It is preferable because quantitative introduction of ion exchange groups is possible.

There is no restriction | limiting in particular as a method to introduce | transduce an ion exchange group into a 1st monolith, Well-known methods, such as a polymer reaction and graft polymerization, can be used. For example, as a method of introducing a quaternary ammonium group, if the monolith is a styrene-divinylbenzene copolymer or the like, a chloromethyl group is introduced with chloromethyl methyl ether or the like and then reacted with a tertiary amine for introduction; Monolith is produced by copolymerization of chloromethylstyrene and divinylbenzene and introduced by reacting with a tertiary amine; radical initiation group or chain transfer group is introduced into monolith, and N, N, N-trimethylammonium ethyl acrylate or N , N, N-trimethylammonium propylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. Among these methods, the method of introducing a quaternary ammonium group includes a method of introducing a chloromethyl group into a styrene-divinylbenzene copolymer with chloromethyl methyl ether and then reacting with a tertiary amine, or chloromethylstyrene. A method of producing a monolith by copolymerization with divinylbenzene and reacting with a tertiary amine is preferable in that the ion exchange groups can be introduced uniformly and quantitatively. Examples of anion exchange groups to be introduced include quaternary ammonium groups such as trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group, methyldihydroxyethylammonium group, and tertiary sulfonium. Group, phosphonium group and the like. Further, for example, as a method for introducing a sulfonic acid group, if the monolith is a styrene-divinylbenzene copolymer or the like, a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid, or fuming sulfuric acid; And a method of grafting sodium styrene sulfonate or acrylamido-2-methylpropane sulfonic acid by introducing a chain transfer group into the skeleton surface or inside the skeleton; Similarly, after graft polymerization of glycidyl methacrylate, the sulfonic acid group is converted by functional group conversion. The method etc. which introduce | transduce are mentioned. Among these methods, the method of introducing sulfonic acid into the styrene-divinylbenzene copolymer using chlorosulfuric acid is preferable in that the ion exchange groups can be introduced uniformly and quantitatively. Examples of the cation exchange group to be introduced include cation exchange groups such as a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric acid ester group.

<Description of Second Monolith and Second Monolith Ion Exchanger>
In the platinum group metal-supported catalyst of the present invention, the second monolith ion exchanger serving as a carrier for the platinum group metal particles is a particle aggregation type monolith, and an organic polymer particle having an average particle diameter of 1 to 50 μm in the dry state is aggregated. Thus, a three-dimensionally continuous skeleton portion is formed, and there are three-dimensionally continuous pores having an average diameter of 20 to 100 μm in the dry state between the skeletons, and the total pore volume in the dry state is 1 It is an organic porous body of 10 ml / g, has an ion exchange group, has an ion exchange capacity per weight in a dry state of 1 to 6 mg equivalent / g, and the ion exchange group is an organic porous material. It is a monolithic ion exchanger that is uniformly distributed in the ion exchanger. The second monolith is a monolith before the ion exchange group is introduced, and is a particle aggregation type monolith. The organic polymer particles having an average particle diameter of 1 to 50 μm in a dry state are aggregated to form a three-dimensional view. A continuous skeleton portion is formed, and the average diameter between the skeletons is three-dimensionally continuous pores of 20 to 100 μm in a dry state, and the total pore volume in the dry state is 1 to 10 ml / g. It is an organic porous body which is an organic porous body.

  The basic structure of the second monolith ion exchanger is that the organic polymer particles having an average particle diameter of 1 to 50 μm, preferably 1 to 30 μm in a dry state, having a crosslinked structural unit aggregate to form a three-dimensional continuous skeleton portion And a particle aggregation type structure having three-dimensionally continuous pores having an average diameter of 20 to 100 μm, preferably 20 to 90 μm in a dry state between the skeletons, and the three-dimensionally continuous pores are liquid Or a gas flow path. FIG. 2 shows an SEM photograph of a form example of the second monolith ion exchanger. The second monolith ion exchanger shown in FIG. 2 is a skeleton part in which organic polymer particles are aggregated to be three-dimensionally continuous. Is a particle aggregation type structure having three-dimensionally continuous pores between the skeletons. If the average particle size of the organic polymer particles is less than 1 μm in the dry state, the average diameter of the continuous pores between the skeletons becomes less than 20 μm in the dry state, which is not preferable. Contact with the monolith ion exchanger becomes insufficient, and as a result, the catalytic activity is lowered, which is not preferable. Further, if the average diameter of the three-dimensionally continuous pores existing between the skeletons is less than 20 μm in the dry state, it is not preferable because the pressure loss when the reaction solution is permeated increases. Exceeding this ratio is not preferable because the contact between the reaction solution and the monolith ion exchanger becomes insufficient and the catalytic activity is lowered.

  In addition, the average particle diameter in the dry state of the organic polymer particle which comprises the frame | skeleton part of a 2nd monolith and a 2nd monolith ion exchanger is simply measured by using SEM. Specifically, an SEM photograph of an arbitrarily extracted portion of the cross section of the second monolith ion exchanger in the dry state is taken, the diameters of the organic polymer particles of all the particles in the SEM photograph are measured, and the average of them is measured. The value is the average particle size.

  In addition, the average diameter of three-dimensionally continuous pores existing between the skeletons of the second monolith in the dry state or the three-dimensionally continuous voids existing between the skeletons of the second monolith ion exchanger in the dry state. The average diameter of the pores is obtained by the mercury intrusion method, and indicates the maximum value of the pore distribution curve obtained by the mercury intrusion method.

  The total pore volume per weight in the dry state of the second monolith ion exchanger is 1 to 10 ml / g. If the total pore volume is less than 1 ml / g, it is not preferable because the pressure loss at the time of liquid passing increases, and further, the permeation amount per unit cross-sectional area decreases, and the processing capacity decreases. Absent. On the other hand, if the total pore volume exceeds 10 ml / g, the mechanical strength is lowered, and this is not preferable in that the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high flow rate.

In the second monolith ion exchanger, the material of the skeleton portion is an organic polymer material having a crosslinked structural unit. That is, the organic polymer material has a constitutional unit composed of a vinyl monomer and a cross-linking agent structural unit having two or more vinyl groups in the molecule, and the polymer material comprises all the constitutions constituting the polymer material. It is preferable that 1 to 5 mol%, preferably 1 to 4 mol% of a crosslinked structural unit is contained with respect to the unit. When the cross-linking structural unit is less than 1 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, when it exceeds 5 mol%, the pore diameter that exists three-dimensionally continuously between the skeletons is reduced. Therefore, the pressure loss increases, which is not preferable.

The type of the polymer material constituting the skeleton of the second monolith ion exchanger is not particularly limited, and examples thereof include styrene 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 polymers such as polyacrylonitrile; (meth) acrylic polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate; styrene -A divinylbenzene copolymer, a vinylbenzyl chloride-divinylbenzene copolymer, etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single monomer and a crosslinking agent, or may be a polymer obtained by polymerizing a plurality of monomers and a crosslinking agent, and two or more kinds of polymers are blended. It may be a thing. Among these organic polymer materials, styrene-divinylbenzene copolymer is used because of its easy formation of particle aggregate structure, ease of ion exchange group introduction and high mechanical strength, and high stability against acid or alkali. Preferred materials include a polymer and a vinylbenzyl chloride-divinylbenzene copolymer.

  The ion exchange group introduced into the second monolith ion exchanger is the same as the ion exchange group introduced into the first monolith ion exchanger.

  In the second monolith ion exchanger, 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, as in the first monolith ion exchanger. Yes.

  The ion exchange capacity of the second monolith ion exchanger is 1 to 6 mg equivalent / g per weight in the dry state. The second monolith ion exchanger can significantly increase the ion exchange capacity per weight while keeping the pressure loss low. When the ion exchange capacity per weight in the dry state is in the above range, the environment around the catalyst active point such as the pH inside the catalyst can be changed, thereby increasing the catalyst activity. When the second monolith ion exchanger is a monolith anion exchanger, anion exchange groups are introduced into the second monolith anion exchanger, and the anion exchange capacity per weight in the dry state is 1 to 6 mg. Equivalent / g. When the second monolith ion exchanger is a monolith cation exchanger, a cation exchange group is introduced into the second monolith cation exchanger, and the cation exchange capacity per weight in a dry state is 1 ~ 6 mg equivalent / g.

<Method for Producing Second Monolith and Second Monolith Ion Exchanger>
As a method for producing the second monolith, a method of obtaining a second monolith by mixing a vinyl monomer, a specific amount of a crosslinking agent, an organic solvent and a polymerization initiator and polymerizing them in a stationary state can be mentioned. It is done.

The vinyl monomer used for the production of the second monolith is not particularly limited as long as it is a lipophilic monomer containing a polymerizable vinyl group in the molecule and having high solubility in an organic solvent. Specific examples of these vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyl toluene and vinyl benzyl chloride; α-olefins such as ethylene, propylene, 1-butene and isobutene; butadiene, isoprene and chloroprene. Diene monomers; 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; Methyl acrylate and Acrylic Ethyl acetate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate And (meth) acrylic monomers such as benzyl methacrylate and glycidyl methacrylate. These monomers are used singly or in combination of two or more. The vinyl monomer preferably used is a styrenic monomer such as styrene or vinyl benzyl chloride.

  The cross-linking agent used for the production of the second monolith preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents are used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of crosslinking agent used ({crosslinking agent / (vinyl monomer + crosslinking agent)} × 100) relative to the total amount of vinyl monomer and crosslinking agent is 1 to 5 mol%, preferably 1 to 4 mol%. The use amount of the crosslinking agent has a great influence on the porous structure of the resulting monolith, and if the use amount of the crosslinking agent exceeds 5 mol%, the size of the continuous pores formed between the skeletons is preferably reduced. Absent. On the other hand, when the amount of the crosslinking agent used is less than 1 mol%, the mechanical strength of the monolith is insufficient, and the monolith is greatly deformed during liquid passage or the monolith is destroyed, which is not preferable.

  The organic solvent used for the production of the second monolith is an organic solvent that dissolves the vinyl monomer and the cross-linking agent but does not dissolve the polymer produced by polymerization of the vinyl monomer, in other words, for the polymer produced by polymerization of the vinyl monomer. It is a poor solvent. Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, alcohols such as ethylene glycol, tetramethylene glycol, glycerin; chain ethers such as diethyl ether, ethylene glycol dimethyl ether; hexane, octane, decane, dodecane, etc. And the like. Among these, alcohols are preferable because the particle aggregation structure is easily formed by stationary polymerization and the three-dimensional continuous pores are increased. Moreover, even if it is a good solvent of polystyrene like benzene and toluene, it is used with the said poor solvent, and when the usage-amount is small, it is used as an organic solvent.

As the polymerization initiator used for the production of the second monolith, a compound that generates radicals by heat and light irradiation is preferable. 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). Nitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis (4-cyanovaleric acid), 1,1 ' -Azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide and the like. The amount of 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 about 0.01 to 5 mol%.

In the production of the second monolith, various conditions can be selected as polymerization conditions depending on the type of monomer and the type of initiator. For example, when 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as initiators In a sealed container under an inert atmosphere, heat polymerization may be performed at 30 to 100 ° C. for 1 to 48 hours. After completion of the polymerization, the contents are taken out and extracted with a solvent such as acetone to obtain a second monolith for the purpose of removing unreacted vinyl monomer and organic solvent.

  In the production of the second monolith, if the polymerization of the vinyl monomer dissolved in the organic solvent proceeds fast, organic polymer particles with an average particle diameter of 1 μm settle and aggregate to form a three-dimensional continuous skeleton. Can be made. The conditions under which the polymerization of the vinyl monomer proceeds rapidly vary depending on the vinyl monomer, the crosslinking agent, the polymerization initiator, the polymerization temperature, etc., but cannot be determined unconditionally, but increase the crosslinking agent, increase the monomer concentration, increase the temperature, etc. is there. Taking such polymerization conditions into consideration, the polymerization conditions for aggregating organic polymer particles having an average particle diameter of 1 to 50 μm may be appropriately determined. In addition, in order to form three-dimensionally continuous pores having an average diameter of 20 to 100 μm between the skeletons, as described above, the amount of crosslinking agent used should be a specific amount with respect to the total amount of vinyl monomer and crosslinking agent. That's fine. Moreover, in order to set the total pore volume of the monolith to 1 to 5 ml / g, depending on the vinyl monomer, the crosslinking agent, the polymerization initiator, the polymerization temperature, etc. If the amount of organic solvent used relative to the total amount used ({organic solvent / (organic solvent + monomer + crosslinking agent)} × 100) is polymerized under conditions such as 30 to 80% by weight, preferably 40 to 70% by weight Good.

  As a method for producing the second monolith ion exchanger, 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, a carboxylic acid group, a sulfonic acid group Polymerization using a monomer having an ion exchange group introduced therein to form a monolith ion exchanger in one step, polymerization using a vinyl monomer containing no ion exchange group to form a second monolith, And a method of introducing an ion exchange group.

  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.

<Description of Third Monolith and Third Monolith Ion Exchanger>
In the platinum group metal-supported catalyst of the present invention, the third monolith ion exchanger serving as a carrier for the platinum group metal particles has bubble-shaped macropores overlapped with each other, and the overlapping portion has an opening with an average diameter of 30 to 300 μm in a dry state. A continuous macropore structure having a total pore volume of 0.5 to 10 ml / g in a dry state, and a skeletal part appearing in a cross section in a SEM image of a cut surface of the continuous macropore structure (dry body) The area is 25 to 50% in the image area, has an ion exchange group, and the ion exchange capacity per weight in a dry state is 1 to 6 mg equivalent / g, and the ion exchange group is an organic porous ion. It is a monolithic ion exchanger that is uniformly distributed in the exchanger. The third monolith is a monolith before the ion exchange group is introduced, and is a continuous macropore structure in which bubble-like macropores overlap each other, and this overlapping portion becomes an opening having an average diameter of 30 to 300 μm in a dry state. Yes, the total pore volume in the dry state is 0.5 to 10 ml / g, and in the SEM image of the cut surface of the continuous macropore structure (dry body), the skeleton area shown in the cross section is in the image region. It is an organic porous body which is an organic porous body which is 25 to 50%.

In the third monolith ion exchanger, bubble-like macropores overlap each other, and the overlapping portion is a continuous state having an average diameter of 30 to 300 μm, preferably 30 to 200 μm, particularly preferably 40 to 100 μm in a dry state. Macropore structure. FIG. 3 shows an SEM photograph of an example of the third monolith ion exchanger. The third monolith ion exchanger shown in FIG. 3 has a large number of bubble-like macropores. The macropores overlap each other, and the overlapping portion is a continuous macropore structure in which a common opening (mesopore) is formed, and most of them have an open pore structure. If the average diameter of the openings in the dry state is less than 30 μm, the pressure loss at the time of passing the liquid increases, which is not preferable. If the average diameter of the openings in the dry state is too large, the reaction liquid and the monolith ion exchanger Further, the contact with the supported platinum group metal particles becomes insufficient, and as a result, the catalytic activity is lowered, which is not preferable.

  Incidentally, the average diameter of the opening of the third monolith in the dry state, the average diameter of the opening of the third monolith ion exchanger in the dry state, and the dry state obtained in step I of the production of the third monolith described below The average diameter of the opening of the third monolith intermediate (3) is measured by the mercury intrusion method and indicates the maximum value of the pore distribution curve obtained by the mercury intrusion method.

  In the third monolith ion exchanger, in the SEM image of the cut surface of the continuous macropore structure (dried body), the skeleton part area appearing in the cross section is 25 to 50%, preferably 25 to 45% in the image region. . When the area of the skeleton part shown in the cross section is less than 25% in the image region, the skeleton becomes a thin skeleton, the mechanical strength is lowered, and the monolith ion exchanger is greatly deformed particularly when liquid is passed at a high flow rate. Therefore, it is not preferable. Furthermore, the contact efficiency between the reaction liquid and the monolith ion exchanger and the platinum group metal particles supported on the reaction liquid is lowered, and the catalytic effect is lowered, which is not preferable. If it exceeds 50%, the skeleton becomes too thick and the liquid is passed through. This is not preferable because the pressure loss increases.

  The conditions for obtaining the SEM image may be any conditions as long as the skeleton part that appears in the cross section of the cut surface appears clearly. For example, the magnification is 100 to 600, and the photographic area is about 150 mm × 100 mm. The SEM observation is performed on three or more images, preferably five or more images, taken at arbitrary locations on an arbitrary cut surface of the third monolith ion exchanger excluding subjectivity and at different locations. Good. The third monolith ion exchanger to be cut is in a dry state for use in an electron microscope. The skeleton part of the cut surface in the SEM image will be described with reference to FIGS. FIG. 4 is a transcribed skeleton that appears as a cross section of the SEM photograph of FIG. In FIGS. 3 and 4, what is generally indeterminate and shown in cross section is the “skeleton part (reference numeral 12)” in the present invention, the circular hole shown in FIG. 3 is an opening (mesopore), and A relatively large curvature or curved surface is a macropore (reference numeral 13 in FIG. 4). The skeleton part area appearing in the cross section of FIG. 4 is 28% in the rectangular image region 11. Thus, the skeleton can be clearly determined.

  In the SEM image, the method for measuring the area of the skeletal part appearing in the cross section of the cut surface is not particularly limited, and after specifying the skeleton part by performing known computer processing, etc., calculation by automatic calculation or manual calculation by a computer or the like A method is mentioned. The manual calculation includes a method in which an indefinite shape is replaced with an aggregate such as a quadrangle, a triangle, a circle, or a trapezoid, and the areas are obtained by stacking them.

  Further, the total pore volume per weight in the dry state of the third monolith ion exchanger is 0.5 to 10 ml / g, preferably 0.8 to 8 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of liquid passing is increased, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area is reduced, and the processing capacity is reduced. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 10 ml / g, the mechanical strength is lowered, and the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high flow rate. Furthermore, since the contact efficiency between the reaction solution, the monolith ion exchanger, and the platinum group metal particles supported thereon decreases, the catalytic effect also decreases, which is not preferable.

In the third monolith ion exchanger, the material constituting the skeleton is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. It is preferable. If the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, it may be difficult to introduce an ion exchange group.

The type of the polymer material constituting the skeleton of the third monolith ion exchanger is not particularly limited. For example, the aromatic material such as polystyrene, poly (α-methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene, etc. Acrylic vinyl polymers; Polyolefins such as polyethylene and polypropylene; Poly (halogenated polyolefins) such as polyvinyl chloride and polytetrafluoroethylene; Nitrile polymers such as polyacrylonitrile; Polymethyl methacrylate, Polyglycidyl methacrylate, Polyethyl acrylate And a crosslinked polymer such as a (meth) acrylic polymer. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, it is easy to form a continuous macropore structure. Therefore, a crosslinked polymer of an aromatic vinyl polymer is preferable, and a styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.

  The ion exchange group introduced into the third monolith ion exchanger is the same as the ion exchange group introduced into the first monolith ion exchanger.

  In the third monolith ion exchanger, the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body.

  The third monolith ion exchanger has an ion exchange capacity per weight in the dry state of 1 to 6 mg equivalent / g. The third monolith ion exchanger can further increase the opening diameter and thicken the skeleton of the continuous macropore structure (thicken the skeleton wall), so that the pressure loss per volume can be kept low. The ion exchange capacity can be dramatically increased. When the ion exchange capacity per weight in the dry state is in the above range, the environment around the catalyst active point such as the pH inside the catalyst can be changed, thereby increasing the catalyst activity. When the third monolith ion exchanger is a monolith anion exchanger, an anion exchange group is introduced into the third monolith anion exchanger, and the anion exchange capacity per weight in the dry state is 1 to 6 mg. Equivalent / g. When the third monolith ion exchanger is a monolith cation exchanger, a cation exchange group is introduced into the third monolith cation exchanger, and the cation exchange capacity per weight in a dry state is 1 ~ 6 mg equivalent / g.

<Method for Producing Third Monolith and Third Monolith Ion Exchanger>
The third monolith prepares a water-in-oil emulsion by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion exchange groups, and then polymerizes the water-in-oil emulsion to form a total pore. Step I for obtaining a monolithic organic porous intermediate (hereinafter also referred to as monolith intermediate (3)) having a continuous macropore structure having a volume of 5 to 16 ml / g, vinyl monomer, at least two or more in one molecule Obtained in Steps II and II of preparing a mixture comprising an organic solvent and a polymerization initiator that dissolves the vinyl monomer and the vinyl monomer and the crosslinking agent, but does not dissolve the polymer formed by polymerization of the vinyl monomer. The mixture was allowed to stand and polymerized in the presence of the monolith intermediate (3) obtained in the step I, and the mixture had a skeleton thicker than the skeleton of the monolith intermediate (3). III to obtain a monolithic, obtained by performing.

  In the third method for producing a monolith, the step I may be performed according to the method described in JP-A-2002-306976.

  In the production of the monolith intermediate (3) in the step I according to the third monolith production method, examples of the oil-soluble monomer containing no ion exchange group include a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group. Examples thereof include an oleophilic monomer that does not contain an ion exchange group and has low solubility in water. Preferable examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, ethylene glycol dimethacrylate, and the like. These monomers can be used singly or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 10 mol% in the total oil-soluble monomer, preferably 0.3 to 5 mol% is preferable because the amount of ion-exchange groups can be quantitatively introduced when ion-exchange groups are introduced.

The surfactant used in step I according to the third monolith production method can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion exchange group and water are mixed. If it is a thing, there will be no restriction in particular, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonyl phenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan Nonionic surfactants such as monooleate; anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; lauryl dimethi Amphoteric surfactants such as rubetaine can be used. These surfactants can be used singly or in combination of two or more. The water-in-oil emulsion refers to an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the surfactant added may vary depending on the type of oil-soluble monomer and the size of the target emulsion particles (macropores), but it cannot be generally stated, but the total amount of oil-soluble monomer and surfactant Can be selected within a range of about 2 to 70%.

  Further, in the step I according to the third method for producing a monolith, a polymerization initiator may be used as necessary when forming the water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. For example, azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, persulfate Examples include potassium, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and tetramethylthiuram disulfide.

As the mixing method when forming the water-in-oil emulsion by mixing an oil-soluble monomer not containing an ion exchange group, a surfactant, water, and a polymerization initiator in the step I according to the third monolith production method. There is no particular limitation, a method of mixing each component at once, an oil-soluble monomer, a surfactant, an oil-soluble component that is an oil-soluble polymerization initiator, and water or a water-soluble polymerization initiator that is water-soluble For example, a method of mixing each component separately after uniformly dissolving the components can be used. There is no particular limitation on the mixing apparatus for forming the emulsion, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain the desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily.

The monolith intermediate (3) obtained in the step I according to the third monolith production method has a continuous macropore structure. When this coexists in the polymerization system, a porous structure having a thick skeleton with the structure of the monolith intermediate (3) as a mold is formed. The monolith intermediate (3) is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. In particular, when the total pore volume is as large as 10 to 16 ml / g, in order to maintain a continuous macropore structure, it is preferable to contain 2 mol% or more of cross-linked structural units. On the other hand, if it exceeds 10 mol%, it may be difficult to introduce ion exchange groups, which is not preferable.

  In the step I relating to the third method for producing a monolith, the type of the polymer material of the monolith intermediate (3) is not particularly limited, and examples thereof include the same as the polymer material of the first monolith described above. Thereby, the same polymer can be formed in the skeleton of the monolith intermediate (3), and the skeleton can be thickened to obtain a third monolith having a uniform skeleton structure.

  The total pore volume per weight in the dry state of the monolith intermediate (3) obtained in Step I according to the third monolith production method is 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 becomes too small, and the pressure loss during fluid permeation increases, which is not preferable. On the other hand, if the total pore volume is too large, the structure of the monolith obtained after polymerizing the vinyl monomer deviates from the continuous macropore structure, which is not preferable. In order to make the total pore volume of the monolith intermediate (3) within the above numerical range, the ratio of monomer to water may be set to approximately 1: 5 to 1:20.

  In addition, in the monolith intermediate (3) obtained in step I according to the third method for producing a monolith, the average diameter of openings (mesopores), which is an overlapping portion of macropores and macropores, is 20 to 200 μm in a dry state. If the average diameter of the opening in the dry state is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss during liquid passage becomes large, which is not preferable. On the other hand, if it exceeds 200 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, resulting in insufficient contact between the reaction solution and the monolith anion exchanger, resulting in a decrease in catalytic activity. Therefore, it is not preferable. The monolith intermediate (3) preferably has a uniform structure with uniform macropore size and opening diameter, but is not limited to this, and the nonuniform macropore larger than the uniform macropore size in the uniform structure. May be scattered.

  The II step relating to the third monolith production method includes a vinyl monomer, a cross-linking agent having at least two vinyl groups in one molecule, and a polymer formed by polymerization of the vinyl monomer while dissolving the vinyl monomer and the cross-linking agent. Is a step of preparing a mixture comprising an insoluble organic solvent and a polymerization initiator. In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

The vinyl monomer used in step II according to the third monolith production method is not particularly limited as long as it is a lipophilic vinyl monomer containing a polymerizable vinyl group in the molecule and having high solubility in an organic solvent. Although not, it is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate (3) that coexists in the polymerization system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyl toluene,
Aromatic vinyl monomers such as vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; Diene monomers such as butadiene, isoprene and chloroprene; Vinyl chloride, vinyl bromide and chloride Halogenated olefins such as vinylidene and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate , Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glyceryl methacrylate Gilles et al. (Meth) acrylic monomer. These monomers can be used singly or in combination of two or more. The vinyl monomer preferably used is an aromatic vinyl monomer such as styrene or vinyl benzyl chloride.

  The addition amount of the vinyl monomer used in Step II according to the third monolith production method is 3 to 50 times, preferably 4 to 40 times, by weight with respect to the monolith intermediate (3) that coexists during polymerization. . If the amount of vinyl monomer added is less than 3 times that of the monolith intermediate, the resulting monolith skeleton (thickness of the wall of the monolith skeleton) cannot be increased, and when an ion exchange group is introduced, Since the ion exchange capacity per volume becomes small, it is not preferable. On the other hand, when the addition amount of vinyl monomer exceeds 50 times, the opening diameter becomes small, and the pressure loss during liquid passage becomes large, which is not preferable.

  As the crosslinking agent used in Step II according to the third monolith production method, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of the crosslinking agent used is preferably from 0.3 to 10 mol%, particularly preferably from 0.3 to 5 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. When the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, the amount of ion-exchange groups introduced may decrease, which is not preferable. In addition, it is preferable to use the said crosslinking agent usage-amount so that it may become substantially equal to the crosslinking density of the monolith intermediate (3) coexisted at the time of vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion exchange group introduction reaction.

The organic solvent used in Step II of the third monolith production method is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, in other words, the vinyl monomer is polymerized. It is a poor solvent for the polymer produced. Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Alcohols such as hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, ethylene glycol, propylene glycol, tetramethylene glycol, glycerin; diethyl ether, ethylene glycol dimethyl ether, cellosolve, methyl cellosolve, butyl cellosolve, polyethylene glycol, polypropylene Chain (poly) ethers such as glycol and polytetramethylene glycol; hexane, heptane, octane, isooctane, decane, dode Chain saturated hydrocarbons such as down, ethyl acetate, isopropyl acetate, cellosolve acetate, esters such as ethyl propionate. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the vinyl monomer is 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered, 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, the polymerization may run away, which is not preferable.

As the polymerization initiator used in Step II according to the third method for producing a monolith, a compound that generates radicals by heat or light irradiation is preferably used. 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, tetramethylthiuram disulfide and the like. The amount of the polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in a range of about 0.01 to 5% with respect to the total amount of vinyl monomer and crosslinking agent.

  In step III according to the third method for producing a monolith, the mixture obtained in step II is allowed to stand, and polymerization is performed in the presence of the monolith intermediate (3) obtained in step I. This is a step of obtaining a third monolith having a skeleton thicker than the skeleton of the body (3). The monolith intermediate (3) used in Step III plays an extremely important role in creating the third monolith, and when the monolith intermediate (3) having a continuous macropore structure is present in the polymerization system, A third monolith is obtained.

In the third method for producing a monolith, the internal volume of the reaction vessel is not particularly limited as long as the monolith intermediate (3) is large enough to be present in the reaction vessel, and the monolith intermediate (3 ) May be any of those in which a gap is formed around the monolith in plan view and those in which the monolith intermediate (3) enters the reaction vessel without any gap. Of these, the thick monolith after polymerization is not pressed from the inner wall of the container and enters the reaction container without any gap, and the monolith is not distorted, and the reaction raw materials are not wasted and efficient. Even when the internal volume of the reaction vessel is large and there are gaps around the monolith after polymerization, the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate (3). A particle aggregate structure is not generated in the gap portion inside.
In step III according to the third method for producing a monolith, the monolith intermediate (3) is placed in a state impregnated with the mixture (solution) in the reaction vessel. As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate (3) is 3 to 50 times by weight, preferably 4 to 4 times by weight with respect to the monolith intermediate (3). It is preferable to blend so as to be 40 times. Thereby, it is possible to obtain a third monolith having a thick skeleton while having an appropriate opening diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that has been allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate (3).

In the step III according to the third monolith production method, various conditions are selected as the polymerization conditions depending on the type of monomer and the type of initiator. For example, when 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as initiators In a sealed container under an inert atmosphere, heat polymerization may be performed at 30 to 100 ° C. for 1 to 48 hours. By the heat polymerization, the vinyl monomer adsorbed and distributed on the skeleton of the monolith intermediate (3) and the crosslinking agent are polymerized in the skeleton to thicken the skeleton. After completion of the polymerization, the content is taken out and extracted with a solvent such as acetone to obtain a third monolith for the purpose of removing unreacted vinyl monomer and organic solvent.

  The third monolith ion exchanger is obtained by performing an IV step of introducing an ion exchange group into the third monolith, which is a thick organic porous material obtained in the step III.

  The method for introducing an ion exchange group into the third monolith is the same as the method for introducing an ion exchange group into the first monolith.

  The third monolith and the third monolith ion exchanger have high mechanical strength because they have a thick bone skeleton despite the remarkably large opening diameter.

<Description of Fourth Monolith and Fourth Monolith Ion Exchanger>
In the platinum group metal-supported catalyst of the present invention, the fourth monolith ion exchanger serving as a carrier for the platinum group metal particles is an aromatic vinyl containing 0.1 to 5.0 mol% of a crosslinked structural unit in all the structural units. Co-continuous consisting of a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm in a dry state and a three-dimensionally continuous pore having an average diameter of 10 to 200 μm in the dry state between the skeletons A structure having a total pore volume in a dry state of 0.5 to 10 ml / g, an ion exchange group, and an ion exchange capacity per weight in a dry state of 1 to 6 mg equivalent / g, a monolithic ion exchanger in which the ion exchange groups are uniformly distributed in the organic porous ion exchanger. The fourth monolith is a monolith before the ion exchange group is introduced, and the average thickness of the aromatic monolithic polymer containing 0.1 to 5.0 mol% of the crosslinked structural unit among all the structural units. Is a co-continuous structure comprising a three-dimensionally continuous skeleton of 1 to 60 μm in a dry state and three-dimensionally continuous pores having an average diameter of 10 to 200 μm between the skeletons, An organic porous body having a total pore volume of 0.5 to 10 ml / g in a dry state.

  The fourth monolith ion exchanger has a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm, preferably 3 to 58 μm in a dry state, and an average diameter between the skeletons of 10 to 200 μm in a dry state, preferably Is a co-continuous structure composed of three-dimensionally continuous pores of 15 to 180 μm, particularly preferably 20 to 150 μm. In FIG. 5, the SEM photograph of the example of a form of the 4th monolith ion exchanger is shown, and the schematic diagram of the co-continuous structure of a 4th monolith ion exchanger is shown in FIG. As shown in the schematic diagram of FIG. 6, the co-continuous structure is a structure 10 in which a continuous skeleton phase 1 and a continuous vacancy phase 2 are intertwined and each of them is three-dimensionally continuous. The continuous pores 2 have higher continuity of the pores than the conventional open-cell type monolith and the particle aggregation type monolith, and the size thereof is not biased. Moreover, since the skeleton is thick, the mechanical strength is high.

  If the average diameter of the three-dimensionally continuous pores is less than 10 μm in the dry state, the pressure loss at the time of liquid passage increases, which is not preferable. If the average diameter exceeds 200 μm, the reaction liquid and the monolith ion exchanger are not suitable. The contact is insufficient, and as a result, the catalytic activity becomes insufficient, which is not preferable. Moreover, when the average thickness of the skeleton is less than 1 μm in a dry state, the monolith ion exchanger is greatly deformed when the liquid is passed at a high flow rate, which is not preferable. Furthermore, the contact efficiency between the reaction solution and the monolith ion exchanger is lowered, and the catalytic effect is lowered. On the other hand, if the thickness of the skeleton exceeds 60 μm, the skeleton becomes too thick, and the pressure loss during liquid passage increases, which is not preferable.

The average diameter of the opening of the fourth monolith in the dry state, the average diameter of the opening of the fourth monolith ion exchanger in the dry state, and the fourth of the dry state obtained in Step I of the production of the fourth monolith described below. The average diameter of the openings of the monolith intermediate (4) is measured by the mercury intrusion method, and indicates the maximum value of the pore distribution curve obtained by the mercury intrusion method. The average thickness of the skeleton of the fourth monolith ion exchanger in the dry state can be obtained by SEM observation of the fourth monolith ion exchanger in the dry state. Specifically, SEM observation of the fourth monolith ion exchanger in the dry state is performed at least three times, the thickness of the skeleton in the obtained image is measured, and the average value thereof is taken as the average thickness. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

The total pore volume per weight in the dry state of the fourth monolith ion exchanger is 0.5 to
10 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of liquid passing is increased, which is not preferable. Further, the permeation amount per unit cross-sectional area is decreased, and the processing amount is decreased. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 10 ml / g, the mechanical strength is lowered, and the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high flow rate. Furthermore, since the contact efficiency between the reaction solution and the monolith ion exchanger decreases, the catalyst efficiency also decreases, which is not preferable. If the three-dimensionally continuous pore size and total pore volume are within the above ranges, the contact with the reaction solution is extremely uniform, the contact area is large, and the solution can be passed under a low pressure loss. .

In the fourth monolith ion exchanger, the material constituting the skeleton is an aromatic containing 0.1 to 5 mol%, preferably 0.5 to 3.0 mol% of a crosslinked structural unit in all the structural units. It is a vinyl polymer and is hydrophobic. If the cross-linking structural unit is less than 0.1 mol%, the mechanical strength is insufficient, which is not preferable. There is no restriction | limiting in particular in the kind of aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, a styrene-divinylbenzene copolymer is used because of its ease of forming a co-continuous structure, ease of introduction of ion-exchange groups, high mechanical strength, and high stability against acids or alkalis. And vinylbenzyl chloride-divinylbenzene copolymer is preferred.

  The ion exchange group introduced into the fourth monolith ion exchanger is the same as the ion exchange group introduced into the first monolith ion exchanger.

  In the fourth monolith ion exchanger, the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body.

  The fourth monolith ion exchanger has an ion exchange capacity of 1 to 6 mg equivalent / g by weight in the dry state. Since the fourth monolith ion exchanger has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, it is possible to dramatically increase the ion exchange capacity per volume while keeping the pressure loss low. When the ion exchange capacity per weight is in the above range, the environment around the catalyst active point such as the pH inside the catalyst can be changed, and thereby the catalyst activity is increased. When the fourth monolith ion exchanger is a monolith anion exchanger, an anion exchange group is introduced into the fourth monolith anion exchanger, and the anion exchange capacity per weight in the dry state is 1 to 6 mg. Equivalent / g. When the fourth monolith ion exchanger is a monolith cation exchanger, a cation exchange group is introduced into the fourth monolith cation exchanger, and the cation exchange capacity per weight in a dry state is 1 ~ 6 mg equivalent / g.

<Method for Manufacturing Fourth Monolith and Fourth Monolith Inion Exchanger>
The fourth monolith prepares a water-in-oil emulsion by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion exchange groups, and then polymerizes the water-in-oil emulsion to form a total pore. Step I for obtaining a monolithic organic porous intermediate (hereinafter also referred to as monolith intermediate (4)) having a continuous macropore structure having a volume of more than 16 ml / g and 30 ml / g or less, an aromatic vinyl monomer, one In all oil-soluble monomers having at least two vinyl groups in the molecule, 0.3 to 5 mol% of the crosslinking agent, aromatic vinyl monomer and crosslinking agent are dissolved, but the aromatic vinyl monomer is polymerized to form. Preparation of a mixture consisting of an organic solvent in which the polymer does not dissolve and a polymerization initiator, Step II, Monolith intermediate obtained in Step I while the mixture obtained in Step II is allowed to stand ( Present operating polymerization under the), III to obtain a fourth monolith organic porous material is a co-continuous structure, obtained by performing.

  In the step I relating to the fourth method for producing a monolith, the step I for obtaining the monolith intermediate (4) may be performed according to the method described in JP-A-2002-306976.

That is, in the step I according to the fourth method for producing a monolith, as the oil-soluble monomer containing no ion exchange group, for example, ion exchange such as a carboxylic acid group, a sulfonic acid group, a tertiary amino group, a quaternary ammonium group, etc. Examples thereof include a lipophilic monomer which does not contain a group and has low solubility in water. Specific examples of these monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; butadiene Diene monomers 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 Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
Examples include (meth) acrylic monomers such as benzyl methacrylate and glycidyl methacrylate. Among these monomers, preferred are aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene and the like. These monomers can be used singly or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and its content is 0.3 to 5 mol%, preferably 0.3 to the total oil-soluble monomer. 3 mol% is preferable because it is advantageous for forming a co-continuous structure.

  The surfactant used in step I according to the fourth monolith production method is the same as the surfactant used in step I according to the third monolith production method, and the description thereof is omitted.

Further, in the step I according to the fourth method for producing a monolith, a polymerization initiator may be used as necessary when forming the water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat or light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis ( 4-cyanovaleric acid), 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide, hydrogen peroxide-ferrous chloride Sodium persulfate-sodium acid sodium sulfite and the like.

  As the mixing method for forming a water-in-oil emulsion by mixing an oil-soluble monomer that does not contain an ion exchange group, a surfactant, water, and a polymerization initiator in Step I according to the fourth method for producing a monolith. Is the same as the mixing method in the step I according to the third method for producing a monolith, and the description thereof is omitted.

The monolith intermediate (4) obtained in step I according to the fourth method for producing a monolith is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.1 to 5 mol%, preferably 0.3 to 3 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the monolith tends to deviate from the co-continuous structure, which is not preferable. In particular, when the total pore volume is 16 to 20 ml / g, the cross-linking structural unit is preferably less than 3 mol% in order to form a co-continuous structure.

  In step I according to the fourth monolith production method, the type of the polymer material of the monolith intermediate (4) is the same as the type of the polymer material of the monolith intermediate (4) according to the third monolith production method. The description is omitted.

  The total pore volume per weight in the dry state of the monolith intermediate (4) obtained in step I according to the fourth method for producing a monolith is more than 16 ml / g and not more than 30 ml / g, preferably 16 ml / g. g and 25 ml / g or less. That is, this monolith intermediate (4) is basically a continuous macropore structure, but the opening (mesopore) that is the overlapping portion of the macropore and the macropore is remarkably large, so that the skeleton constituting the monolith structure is two-dimensional. It has a structure that is almost as close as possible to a one-dimensional rod-like skeleton from the wall surface. FIG. 7 shows an SEM photograph of a form example of the monolith intermediate (4), which has a skeleton close to a rod shape. When this coexists in the polymerization system, a porous body having a co-continuous structure is formed using the structure of the monolith intermediate (4) as a mold. If the total pore volume is too small, the structure of the monolith obtained after polymerizing the vinyl monomer is not preferable because it changes from a co-continuous structure to a continuous macropore structure. On the other hand, if the total pore volume is too large, When the mechanical strength of the monolith obtained after polymerizing the vinyl monomer is reduced or an ion exchange group is introduced, the ion exchange capacity per volume is lowered, which is not preferable. In order to make the total pore volume of the monolith intermediate (4) within the above range, the ratio of monomer to water may be about 1:20 to 1:40.

  Moreover, as for the monolith intermediate body (4) obtained at the I process which concerns on the manufacturing method of the 4th monolith, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is 5-100 micrometers in a dry state. When the average diameter of the openings is less than 5 μm in the dry state, the opening diameter of the monolith obtained after polymerizing the vinyl monomer is reduced, and the pressure loss during fluid permeation is increased, which is not preferable. On the other hand, if it exceeds 100 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, resulting in insufficient contact between the reaction liquid and the monolith ion exchanger, resulting in a decrease in the catalytic activity. Therefore, it is not preferable. The monolith intermediate (4) preferably has a uniform structure with a uniform macropore size and opening diameter, but is not limited to this, and the nonuniform macropore larger than the uniform macropore size in the uniform structure. May be scattered.

  Step II according to the fourth method for producing a monolith includes an aromatic vinyl monomer, a total oil-soluble monomer having at least two vinyl groups in one molecule, 0.3 to 5 mol% of a crosslinking agent, aromatic This is a step of preparing a mixture of an organic solvent and a polymerization initiator that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer. In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

The aromatic vinyl monomer used in Step II according to the fourth method for producing a monolith is an oleophilic aromatic vinyl monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. Although there is no particular limitation, it is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate (4) to be coexisted in the polymerization system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl, vinyl naphthalene and the like. These monomers can be used singly or in combination of two or more. Aromatic vinyl monomers preferably used are styrene, vinyl benzyl chloride and the like.

  The addition amount of the aromatic vinyl monomer used in Step II according to the fourth monolith production method is 5 to 50 times by weight, preferably 5 to 40 times by weight, relative to the monolith intermediate (4) to be coexisted during the polymerization. It is. If the amount of the aromatic vinyl monomer added is less than 5 times that of the monolith intermediate (4), the rod-like skeleton cannot be made thick, and when ion exchange groups are introduced, ions per volume after introduction of the ion exchange groups This is not preferable because the exchange capacity becomes small. On the other hand, if the amount of the aromatic vinyl monomer added exceeds 50 times, the diameter of the continuous pores becomes small, and the pressure loss during liquid passage becomes large, which is not preferable.

  As the crosslinking agent used in Step II according to the fourth method for producing a monolith, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of the 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 monomer). When the amount of the crosslinking agent used is less than 0.3 mol%, it is not preferable because the mechanical strength of the monolith is insufficient. On the other hand, when the amount is too large, it is difficult to quantitatively introduce the ion exchange group when introducing the ion exchange group. Since it may become, it is not preferable. In addition, it is preferable to use the said crosslinking agent usage-amount so that it may become substantially equal to the crosslinking density of the monolith intermediate (4) coexisted at the time of vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too large, the crosslink density distribution will be biased in the produced monolith, and when ion exchange groups are introduced, cracks are likely to occur during the ion exchange group introduction reaction.

The organic solvent used in Step II according to the fourth monolith production method is an organic solvent that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by the polymerization of the aromatic vinyl monomer. It is a poor solvent for a polymer produced by polymerization of an aromatic vinyl monomer. Since organic solvents vary greatly depending on the type of aromatic vinyl monomer, it is difficult to list general specific examples. For example, when the aromatic vinyl monomer is styrene, the organic solvents include methanol, ethanol, and propanol. , Butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol and other alcohols; Poly) ethers; chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane, etc .; ethyl acetate, isopropyl acetate, cellosolve acetate, propionic acid Examples include esters such as chill. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the aromatic vinyl monomer is 30 to 80% by weight. When the amount of the organic solvent deviates from the above range and the aromatic vinyl monomer concentration is less than 30% by weight, it is preferable because the polymerization rate decreases or the monolith structure after polymerization deviates from the range of the fourth monolith. Absent. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may run away, which is not preferable.

  The polymerization initiator used in Step II according to the fourth monolith production method is the same as the polymerization initiator used in Step II according to the third monolith production method, and the description thereof is omitted.

  In step III according to the fourth method for producing a monolith, the mixture obtained in step II is allowed to stand and polymerize in the presence of the monolith intermediate (4) obtained in step I. This is a step of changing the continuous macropore structure of the body (4) to a co-continuous structure to obtain a fourth monolith that is a co-continuous structure monolith. The monolith intermediate (4) used in the step III plays an extremely important role in creating a monolith having a novel structure of the present invention. As disclosed in JP-A-7-501140 and the like, when a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of the monolith intermediate (4), a particle aggregation type monolith shape is obtained. An organic porous body is obtained. On the other hand, when a monolith intermediate (4) having a specific continuous macropore structure is present in the polymerization system as in the case of the fourth monolith, the structure of the monolith after the polymerization changes dramatically and the particle aggregation structure disappears. Thus, the fourth monolith having the above-described co-continuous structure is obtained. The reason for this has not been elucidated in detail, but when the monolith intermediate (4) does not exist, the crosslinked polymer produced by polymerization precipitates and precipitates in the form of particles to form a particle aggregate structure. On the other hand, when a porous body (intermediate) having a large total pore volume exists in the polymerization system, the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization is performed in the porous body. It is considered that the skeleton constituting the monolith structure progresses to change from a two-dimensional wall surface to a one-dimensional rod-like skeleton, thereby forming a fourth monolith having a co-continuous structure.

  In the fourth monolith manufacturing method, the internal volume of the reaction vessel is the same as the description of the internal volume of the reaction vessel according to the third monolith manufacturing method, and the description thereof is omitted.

  In step III according to the fourth method for producing a monolith, the monolith intermediate (4) is placed in a state impregnated with the mixture (solution) in the reaction vessel. The blending ratio of the mixture obtained in Step II and the monolith intermediate (4) is, as described above, 5 to 50 times the weight of the aromatic vinyl monomer added to the monolith intermediate (4), preferably It is suitable to mix 5 to 40 times. Thereby, it is possible to obtain a fourth monolith having a co-continuous structure in which pores of an appropriate size are three-dimensionally continuous and a thick skeleton is three-dimensionally continuous. In the reaction vessel, the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate (4) that is allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate (4).

  The polymerization conditions of the III step according to the fourth monolith production method are the same as the explanation of the polymerization conditions of the III step according to the third monolith production method, and the description thereof is omitted. By performing step III, a fourth monolith is obtained.

  The fourth monolith ion exchanger is obtained by performing an IV step for introducing an ion exchange group into the fourth monolith obtained in the step III.

  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.

  The fourth monolith and the fourth monolith ion exchanger have high mechanical strength because they have a thick bone skeleton even though the size of three-dimensionally continuous pores is extremely large. Further, since the fourth monolith ion exchanger has a thick skeleton, the ion exchange capacity per volume in a dry state can be increased, and the reaction solution can be passed for a long time at a low pressure and a large flow rate. .

<Description of Fifth Monolith and Fifth Monolith Ion Exchanger>
In the platinum group metal-supported catalyst of the present invention, the fifth monolith ion exchanger serving as a support for the platinum group metal particles includes an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a skeleton of the organic porous body. A composite structure comprising a large number of particles having a diameter of 4 to 40 μm in a dry state adhering to the surface or a large number of protrusions having a size of 4 to 40 μm in a dry state formed on the skeleton surface of the organic porous material. The average pore diameter in the dry state is 10 to 200 μm, and the total pore volume in the dry state is 0.5 to
10 ml / g, having ion exchange groups, 1-6 mg equivalent / g of ion exchange capacity per weight in a dry state, and uniform distribution of ion exchange groups in organic porous ion exchanger Monolith ion exchanger. The fifth monolith is a monolith before the ion exchange group is introduced, and is an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a dry state that is fixed to the skeleton surface of the organic porous body. A composite structure of a large number of particles having a diameter of 4 to 40 μm or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous material in a dry state. Is an organic porous body having an average diameter of 10 to 200 μm and a total pore volume in a dry state of 0.5 to 10 ml / g.

  The fifth monolith ion exchanger includes an organic porous body composed 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 fixed to the skeleton surface of the organic porous body, It is a composite structure with many protrusions having a size of 4 to 40 μm in a dry state formed on the skeleton surface of the organic porous body. In the present specification, “particle bodies” and “projections” may be collectively referred to as “particle bodies”.

  The continuous skeleton phase and the continuous pore phase of the fifth monolith ion exchanger are observed by the SEM image. The basic structure of the fifth monolith ion exchanger includes a continuous macropore structure and a co-continuous structure. The skeletal phase of the fifth monolith ion exchanger appears as a columnar continuum, a concave wall continuum, or a composite thereof, and has a shape that is clearly different from a particle shape or a protrusion shape.

  As a preferred structure of the fifth monolithic ion exchanger, bubble-shaped macropores overlap each other, and the overlapping portion is a dry macropore and has a continuous macropore structure (hereinafter referred to as “5-1-1”) having an average diameter of 10 to 120 μm. A monolithic ion exchanger ”), and a three-dimensional continuous skeleton having an average thickness of 0.8 to 40 μm in a dry state, and a three-dimensional three-dimensional structure having an average diameter of 8 to 80 μm in a dry state between the skeletons. A co-continuous structure (hereinafter also referred to as “5-2 monolithic ion exchanger”). Further, as the fifth monolith, in the 5-1 monolith ion exchanger, the monolith before the ion exchange group is introduced (hereinafter also referred to as “5-1 monolith”), and the 5-th monolith. In the second monolith ion exchanger, a monolith before the ion exchange group is introduced (hereinafter also referred to as “second monolith”) is preferable.

  In the case of the 5-1 monolith ion exchanger, the 5-1 monolith ion exchanger has bubble-like macropores overlapped with each other, and the overlapping portion has an average diameter of 20 to 150 μm, preferably 30 to 150 μm in a dry state. Particularly preferably, it is a continuous macropore structure that becomes an opening (mesopore) of 35 to 150 μm, and the inside of bubbles formed by the macropore and the opening (mesopore) is a flow path. The continuous macropore structure is preferably a uniform structure having the same macropore size and aperture diameter, but is not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do. If the average diameter of the opening in the dry state of the 5-1 monolith ion exchanger is less than 20 μm, it is not preferable because the pressure loss at the time of liquid passage increases, and the average diameter of the opening in the dry state is not preferable. If it exceeds 150 μm, contact between the reaction solution, the monolith ion exchanger and the supported platinum group metal particles becomes insufficient, and as a result, the catalytic activity is lowered, which is not preferable.

  In addition, the average diameter of the opening of the fifth monolith in the dry state, the average diameter of the opening of the fifth monolith ion exchanger in the dry state, and the dry state obtained in Step I of the production of the fifth monolith described below. The average diameter of the opening of the monolith intermediate (5) refers to the maximum value of the pore distribution curve obtained by the mercury intrusion method.

In the case of the 5-2 monolith ion exchanger, the 5-2 monolith ion exchanger has a three-dimensional continuous skeleton having an average thickness of 1 to 50 μm, preferably 5 to 50 μm in a dry state, It is a co-continuous structure having three-dimensionally continuous pores having an average diameter of 10 to 100 μm, preferably 10 to 90 μm in a dry state between the skeletons. If the average diameter in the dry state of the three-dimensionally continuous pores of the 5-2 monolith ion exchanger is less than 10 μm, it is not preferable because the pressure loss at the time of liquid passage becomes large, and 100 μm. Exceeding this ratio is not preferable because the contact between the reaction solution, the monolith ion exchanger, and the supported platinum group metal particles becomes insufficient, and as a result, the catalytic activity decreases. Further, when the average thickness of the skeleton of the 5-2 monolith ion exchanger is less than 1 μm in a dry state, the mechanical strength is lowered, and the monolith ion exchanger is particularly large when liquid is passed at a high flow rate. Since it will deform | transform, it is not preferable. On the other hand, when the average thickness of the skeleton of the 5-2 monolith ion exchanger exceeds 50 μm in a dry state, the skeleton becomes too thick, and the pressure loss at the time of liquid passage increases, which is not preferable.

  The average thickness of the skeleton of the 5-2 monolith ion exchanger in the dry state can be obtained by SEM observation of the dry 5-2 monolith ion exchanger. Specifically, SEM observation of the dried 5-2 monolith ion exchanger is performed at least three times, the thickness of the skeleton in the obtained image is measured, and the average value thereof is defined as the average thickness. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

  The average diameter of the pores of the fifth monolith ion exchanger in the dry state is 10 to 200 μm. In the case of the 5-1 monolith ion exchanger, the preferred value of the pore diameter in the dry state of the 5-1 monolith ion exchanger is 30 to 150 μm, and in the case of the 5-2 monolith ion exchanger The preferable value of the pore diameter in the dry state of the 5-2 monolith ion exchanger is 10 to 90 μm.

  In the fifth monolith ion exchanger, the particle diameter and the protrusion size in the dry state are 4 to 40 μm, preferably 4 to 30 μm, and particularly preferably 4 to 20 μm. In the present invention, both the particles and the protrusions are observed as protrusions on the surface of the skeleton, and the particles observed are referred to as particles, and the protrusions that are not granular are protrusions. Called the body. FIG. 8 shows a schematic cross-sectional view of the protrusion. As shown in FIGS. 8A to 8E, the protrusions protruding from the skeleton surface 21 are protrusions 22, and the protrusions 22 are like protrusions 22a shown in FIG. The shape close | similar to a granular shape, a hemispherical thing like the protrusion 22b shown to (B), the thing like the rise | swell of the skeleton surface like the protrusion 22c shown to (C), etc. are mentioned. In addition, the protrusion 22 has a shape that is longer in the direction perpendicular to the skeleton surface 21 than in the plane direction of the skeleton surface 21 as in the protrusion 22d shown in FIG. There is a thing of the shape which protruded in the several direction like the protrusion 22e shown to (E). Further, the size of the protrusions is determined by the SEM image when observed by SEM, and indicates the length of the portion where the width of each protrusion is the largest in the SEM image. In addition, FIG. 9 shows an SEM photograph of an example of the fifth monolith ion exchanger. A large number of protrusions are formed on the skeleton surface of the organic porous body.

In the fifth monolith ion exchanger, the proportion of 4 to 40 μm particles in the dry state in all particles is 70% or more, preferably 80% or more. In addition, the ratio which 4-40 micrometers particle bodies etc. occupy in the dry state in all the particle bodies etc. points out the number ratio of 4-40 micrometers particle bodies etc. in the dry state which occupies the number of all particle bodies. Further, the surface of the skeletal phase is covered by 40% or more, preferably 50% or more by the whole particles. In addition, the coverage ratio of the surface of the skeleton layer with all particles and the like refers to an area ratio on the SEM image when the surface is observed by SEM, that is, an area ratio when the surface is viewed in plan. If the size of the particle covering the wall surface or the skeleton deviates from the above range, the effect of improving the contact efficiency between the fluid and the skeleton surface of the monolith ion exchanger and the inside of the skeleton tends to be small. In addition, all the particle bodies etc. are all the particle bodies formed on the surface of the skeleton layer, including all the particle bodies and protrusions in the size range other than the particle bodies of 4 to 40 μm in the dry state, Refers to a protrusion.

  The diameter or size of the particles attached to the skeleton surface of the fifth monolith ion exchanger in the dry state is the diameter of the particles obtained by observing the SEM image of the fifth monolith ion exchanger in the dry state. Or size. Then, the diameter or size of all particles observed in the SEM image of the fifth monolith ion exchanger in the dry state is measured, and based on the value, all particles in the SEM image of one field of view Calculate the diameter or size of the body in a dry state. The SEM observation of the fifth monolith ion exchanger in the dry state is performed at least three times, and the diameter or size in the dry state of all particles in the SEM image is calculated in the entire field of view. Is confirmed to be observed in the entire field of view, the diameter or size is 4 in a dry state on the skeleton surface of the fifth monolith ion exchanger. It is determined that a particle body or the like at ˜40 μm is formed. In addition, the diameter or size in the dry state of all particles in the SEM image is calculated for each visual field in accordance with the above, and the particle size of 4 to 40 μm in the dry state occupying the total particles in each visual field. When the proportion of 4 to 40 μm particles in the dry state in all particles is 70% or more in all fields of view, the surface of the skeleton of the fifth monolith ion exchanger It is determined that the proportion of 4 to 40 μm particles in the dry state in all formed particles is 70% or more. Further, according to the above, the coverage ratio of the surface of the skeletal layer with all particles in the SEM image was determined for each field of view, and the coverage ratio of the surface of the skeleton layer with all particles in all fields was 40% or more. In this case, it is determined that the ratio of the surface of the skeleton layer of the fifth monolith ion exchanger covered with all the particulates is 40% or more.

  In the fifth monolith ion exchanger, when the coverage of the surface of the skeleton phase by the particulates or the like is less than 40%, the effect of improving the contact efficiency between the reaction solution and the inside of the skeleton of the monolith ion exchanger and the skeleton surface is small. Easy to be. Examples of the method for measuring the coverage with the above-mentioned particle body and the like include an image analysis method using an SEM image of the fifth monolith ion exchanger.

  The total pore volume per weight of the fifth monolith ion exchanger in the dry state is 0.5 to 10 ml / g, preferably 0.8 to 8 ml / g. If the total pore volume of the monolith ion exchanger is less than 0.5 ml / g, the pressure loss during liquid passage is increased, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area is decreased, and processing is performed. This is not preferable because the ability is reduced. On the other hand, if the total pore volume of the monolith ion exchanger exceeds 10 ml / g, the mechanical strength is lowered, and the monolith ion exchanger is greatly deformed particularly when it is passed at a high flow rate. Furthermore, since the contact efficiency between the reaction solution, the monolith ion exchanger, and the platinum group metal particles supported thereon decreases, the catalytic effect also decreases, which is not preferable.

  In the fifth monolith ion exchanger, the material constituting the skeleton phase of the continuous pore structure is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. It is preferable. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, when it exceeds 10 mol%, when an ion exchange group is introduced, it is difficult to introduce the ion exchange group, Since the introduction amount may decrease, it is not preferable.

There is no restriction | limiting in particular in the kind of polymer material used by manufacture of a 5th monolith, For example, aromatic vinyl polymers, such as a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene; Polyolefins such as polyethylene and polypropylene; poly (halogenated polyolefins) such as polyvinyl chloride and polytetrafluoroethylene; nitrile polymers such as polyacrylonitrile; poly (methyl methacrylate, polyglycidyl methacrylate, poly (ethyl acrylate), etc. ) Crosslinked polymers such as acrylic polymers. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, the cross-linking of aromatic vinyl polymers is facilitated by the ease of forming a continuous pore structure, the ease of introducing ion-exchange groups and the high mechanical strength, and the high stability to acids and alkalis. A polymer is preferable, and a styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.

  In the fifth monolith ion exchanger, the material constituting the skeletal phase of the organic porous body and the particles formed on the surface of the skeletal phase are made of the same material in which the same structure is continuous, or the same structure. The thing of the material from which a continuous mutually differs is mentioned. For materials with different structures with different continuous structures, such as materials with different types of vinyl monomers, materials with different blending ratios even if the types of vinyl monomers and crosslinking agents are the same, etc. Is mentioned.

  The ion exchange group introduced into the fifth monolith ion exchanger is the same as the ion exchange group introduced into the first monolith ion exchanger.

  In the fifth monolith ion exchanger, the introduced ion exchange groups are uniformly distributed not only on the surface of the organic porous body but also within the skeleton of the organic porous body. When the ion exchange groups are uniformly distributed not only on the surface of the fifth monolith ion exchanger but also inside the skeleton, the physical and chemical properties of the surface and the inside can be made uniform, so that the swelling and shrinkage The durability against is improved.

  The fifth monolith ion exchanger has an ion exchange capacity per weight in a dry state of 1 to 6 mg equivalent / g, preferably 2 to 5 mg equivalent / g. When the ion exchange capacity per weight of the fifth monolith ion exchanger is in the above range, the environment around the catalyst active point such as the pH inside the catalyst can be changed, thereby increasing the catalyst activity. When the fifth monolith ion exchanger is a monolith anion exchanger, an anion exchange group is introduced into the fifth monolith anion exchanger, and the anion exchange capacity per weight in the dry state is 1 to 6 mg. Equivalent / g. When the fifth monolith ion exchanger is a monolith cation exchanger, a cation exchange group is introduced into the fifth monolith cation exchanger, and the cation exchange capacity per weight in a dry state is 1 ~ 6 mg equivalent / g.

  The fifth monolith ion exchanger has a thickness of 1 mm or more, and is distinguished from a membrane-like porous body. If the thickness is less than 1 mm, the ion exchange capacity per porous body is extremely low, which is not preferable. The thickness of the fifth monolith ion exchanger is preferably 3 to 1000 mm. The fifth monolith ion exchanger has high mechanical strength because the basic structure of the skeleton is a continuous pore structure.

<The manufacturing method of a 5th monolith and a 5th monolith ion exchanger>
The fifth monolith prepares 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, and then polymerizes the water-in-oil emulsion to form a total pore. Step I to obtain a monolithic organic porous intermediate having a continuous macropore structure with a volume of 5 to 30 ml / g (hereinafter also referred to as monolith intermediate (5)), vinyl monomer, at least two or more in one molecule Obtained in Steps II and II of preparing a mixture comprising an organic solvent and a polymerization initiator that dissolves the vinyl monomer and the vinyl monomer and the crosslinking agent, but does not dissolve the polymer formed by polymerization of the vinyl monomer. A fifth monolith which is a composite monolith having a composite structure, wherein the mixture is allowed to stand for polymerization in the presence of the monolith intermediate (5) obtained in Step I. Obtaining step III, obtained by performing.

  What is necessary is just to perform I process which concerns on the manufacturing method of 5th monolith based on the method of Unexamined-Japanese-Patent No. 2002-306976.

  In the production of the monolith intermediate (5) of the step I according to the fifth monolith production method, examples of the oil-soluble monomer not containing an ion exchange group include a carboxylic acid group, a sulfonic acid group, a tertiary amino group, Examples thereof include an oleophilic monomer which does not contain an ion exchange group such as a quaternary ammonium group and has low solubility in water. Preferable examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, ethylene glycol dimethacrylate, and the like. These monomers can be used singly or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 10 mol% in the total oil-soluble monomer, preferably 0.3 to When introducing an ion exchange group in a later step, it is preferable to set the amount to 5 mol% because the amount of ion exchange group can be quantitatively introduced.

  The surfactant used in Step I according to the fifth monolith production method can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion exchange group and water are mixed. If it is a thing, there will be no restriction in particular, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonyl phenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan Nonionic surfactants such as monooleate; Anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, dioctyl sodium sulfosuccinate; Cationic surfactants such as distearyldimethylammonium chloride; Lauryl dimethyl It can be used an amphoteric surfactant such as Rubetain. These surfactants can be used singly or in combination of two or more. In addition, a water-in-oil emulsion refers to an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the surfactant added is not unclear because it varies greatly depending on the type of oil-soluble monomer and the size of the target emulsion particles (macropores), but the total amount of oil-soluble monomer and surfactant Can be selected within a range of about 2 to 70%.

Moreover, in I process which concerns on the manufacturing method of a 5th monolith, you may use a polymerization initiator as needed in the case of water-in-oil type emulsion formation. As the polymerization initiator, a compound that generates radicals by heat or light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis ( 4-cyanovaleric acid), 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate- Examples include acidic sodium sulfite.

As the mixing method when forming the water-in-oil emulsion by mixing an oil-soluble monomer that does not contain an ion exchange group, a surfactant, water, and a polymerization initiator in Step I according to the fifth monolith production method. There is no particular limitation, a method of mixing each component at once, an oil-soluble monomer, a surfactant, an oil-soluble component that is an oil-soluble polymerization initiator, and a water-soluble component that is water or a water-soluble polymerization initiator And the like can be separately dissolved, and then the respective components can be mixed. The mixing apparatus for forming the emulsion is not particularly limited, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain a desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily.

  The monolith intermediate (5) obtained in step I according to the fifth method for producing a monolith has a continuous macropore structure. When this coexists in the polymerization system, particles or the like are formed on the surface of the skeleton phase of the continuous macropore structure using the structure of the monolith intermediate (5) as a template, or particles or the like are formed on the surface of the skeleton phase of the co-continuous structure. Or form. The monolith intermediate (5) is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, the flexibility of the porous material is lost, and when an ion exchange group is introduced, it may be difficult to introduce the ion exchange group.

  In the step I relating to the fifth monolith production method, the type of the polymer material of the monolith intermediate (5) is not particularly limited, and examples thereof include the same as the polymer material of the fifth monolith described above. Thereby, the same polymer is formed in the skeleton of the monolith intermediate (5), and the fifth monolith which is a monolith having a composite structure can be obtained.

  The total pore volume per weight in the dry state of the monolith intermediate (5) obtained in step I according to the fifth monolith production method is 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 becomes too small, and the pressure loss during fluid permeation increases, which is not preferable. 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 tends to be non-uniform, which may cause structural collapse in some cases. In order to set the total pore volume of the monolith intermediate (5) in the above numerical range, the ratio (weight) of the monomer to water may be set to approximately 1: 5 to 1:35.

In Step I according to the fifth method for producing a monolith, if the ratio of the monomer to water is approximately 1: 5 to 1:20, the total pore volume of the monolith intermediate (5) is 5 to 16 ml / g having a continuous macropore structure is obtained, and the monolith obtained through the step III is the 5-1 monolith. Further, if the blending ratio is approximately 1:20 to 1:35, the monolith intermediate (5) has a total pore volume of more than 16 ml / g and a continuous macropore structure of 30 ml / g or less. The monolith obtained through the step III becomes the 5-2 monolith.

  In addition, the monolith intermediate (5) obtained in Step I according to the fifth method for producing a monolith has an average diameter of 20 to 200 μm in the dry state of the opening (mesopore) that is the overlapping portion of the macropore and the macropore. When the average diameter of the opening in the dry state of the monolith intermediate is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer is decreased, and the pressure loss during liquid passage is increased, which is preferable. Absent. On the other hand, when the average diameter of the opening in the dry state of the monolith intermediate exceeds 200 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the reaction liquid and the monolith ion exchanger is Insufficient and, as a result, the catalytic activity is lowered, which is not preferable. The monolith intermediate (5) is preferably of a uniform structure with a uniform macropore size and opening diameter, but is not limited to this, and the nonuniform macropore is larger than the uniform macropore size in the uniform structure. May be scattered.

  The II step relating to the fifth monolith production method comprises a vinyl monomer, a second crosslinking agent having at least two vinyl groups in one molecule, a vinyl monomer and a second crosslinking agent are dissolved, but the vinyl monomer is polymerized. This is a step of preparing a mixture comprising an organic solvent and a polymerization initiator that do not dissolve the polymer produced. In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

The vinyl monomer used in Step II according to the fifth monolith production method is not particularly limited as long as it is a lipophilic vinyl monomer containing a polymerizable vinyl group in the molecule and having high solubility in an organic solvent. Absent. Specific examples of these vinyl monomers include styrene, α-
Aromatic vinyl monomers such as 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, tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, acrylic (Meth) acrylic monomers such as butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate Is mentioned. These monomers can be used alone or in combination of two or more. The vinyl monomer preferably used is an aromatic vinyl monomer such as styrene or vinyl benzyl chloride.

  The addition amount of the vinyl monomer used in Step II according to the fifth monolith production method is 3 to 50 times, preferably 4 to 40 times, by weight with respect to the monolith intermediate (5) to be coexisted during the polymerization. . If the amount of vinyl monomer added is less than 3 times that of the porous body, particles cannot be formed on the skeleton of the produced monolith, and when ion exchange groups are introduced, the volume per volume after introduction of ion exchange groups This is not preferable because the ion exchange capacity is reduced. On the other hand, when the addition amount of vinyl monomer exceeds 50 times, the opening diameter becomes small, and the pressure loss during liquid passage becomes large, which is not preferable.

  As the crosslinking agent used in Step II according to the fifth monolith production method, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of the crosslinking agent used is preferably 0.3 to 20 mol%, particularly preferably 0.3 to 10 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. When the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it exceeds 20 mol%, the brittleness of the monolith proceeds and the flexibility is lost, and when introducing an ion exchange group, the introduction amount of the ion exchange group may decrease, which is not preferable. .

The organic solvent used in Step II of the fifth monolith production method is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, in other words, the vinyl monomer is polymerized. It is a poor solvent for the polymer produced. Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Hexanol, cyclohexanol,
Alcohols such as octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol; chain (poly) ethers such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; hexane, heptane , Octane, isooctane, decane, dodecane, and other chain saturated hydrocarbons; and esters such as ethyl acetate, isopropyl acetate, cellosolve acetate, and ethyl propionate. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the vinyl monomer is 5 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 5% by weight, the polymerization rate is lowered, which is not preferable. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, the polymerization may run away, which is not preferable.

As the polymerization initiator used in Step II according to the fifth method for producing a monolith, a compound that generates radicals by heat or light irradiation is suitably used. 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, tetramethylthiuram disulfide and the like. The amount of the polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in a range of about 0.01 to 5% with respect to the total amount of vinyl monomer and crosslinking agent.

  In step III according to the fifth monolith production method, the mixture obtained in step II is allowed to stand and polymerization is carried out in the presence of the monolith intermediate (5) obtained in step I. It is the process of obtaining. The monolith intermediate (5) used in the step III plays an extremely important role in creating the fifth monolith. As disclosed in JP-A-7-501140 and the like, when a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of the monolith intermediate (5), a particle aggregation type monolith shape is obtained. An organic porous body is obtained. On the other hand, when the monolith intermediate (5) having a continuous macropore structure is present in the polymerization system as in the present invention, the structure of the composite monolith after the polymerization changes dramatically, not the particle aggregation structure. A fifth monolith having a specific skeletal structure is obtained. The internal volume of the reaction vessel is not particularly limited as long as it is large enough to allow the monolith intermediate (5) to be present in the reaction vessel, and when the monolith intermediate (5) is placed in the reaction vessel, the plan view In this case, the monolith may have a gap around the monolith or the monolith intermediate (5) may enter the reaction vessel without any gap. Of these, the fifth monolith after polymerization does not receive any pressure from the inner wall of the vessel and enters the reaction vessel without any gap, so that the fifth monolith is not distorted, and there is no waste of reaction raw materials and the like. Is. Even when the internal volume of the reaction vessel is large and a gap exists around the fifth monolith after polymerization, the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate (5). In addition, a particle aggregate structure is not generated in a gap portion in the reaction vessel.

  In step III according to the fifth method for producing a monolith, the monolith intermediate (5) is placed in a state impregnated with the mixture (solution) in the reaction vessel. As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate (5) is 3 to 50 times, preferably 4 to 4 times, by weight with respect to the monolith intermediate (5). It is preferable to blend so as to be 40 times. As a result, a fifth monolith that is a composite monolith having a specific skeleton while having an appropriate opening diameter can be obtained. In the reaction vessel, the vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate (5) that is allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate (5).

In step III according to the fifth monolith production method, various polymerization conditions can be selected depending on the type of monomer and the type of initiator. For example, when 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, or the like is used as an initiator, an inert atmosphere What is necessary is just to heat-polymerize at 20-100 degreeC for 1 to 48 hours in the lower sealed container. By the heat polymerization, the vinyl monomer adsorbed and distributed on the skeleton of the monolith intermediate (5) and the crosslinking agent are polymerized in the skeleton to form the specific skeleton structure. After completion of the polymerization, the contents are taken out and extracted with a solvent such as acetone for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a fifth monolith that is a composite monolith having a specific skeleton structure.

When the above-mentioned fifth monolith is produced, if the II step or the III step is performed under the conditions satisfying at least one of the following conditions (1) to (5), the characteristic structure of the fifth monolith is obtained. A monolith having a particle body or the like formed on the surface of the skeleton can be produced.
(1) The polymerization temperature in step III is a temperature that is at least 5 ° C. lower than the 10-hour half-life temperature of the polymerization initiator.
(2) The mole% of the crosslinking agent used in Step II is at least twice the mole% of the crosslinking agent used in Step I.
(3) The vinyl monomer used in step II is a vinyl monomer having 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 of Step II.

(Description of (1) above)
The 10-hour half temperature is a characteristic value of the polymerization initiator, and if the polymerization initiator to be used is determined, the 10-hour half temperature can be known. Moreover, if there exists desired 10-hour half temperature, the polymerization initiator applicable to it can be selected. In step III, the polymerization rate is lowered by lowering the polymerization temperature, and particles and the like can be formed on the surface of the skeleton phase. The reason for this is that the monomer concentration drop inside the skeleton phase of the monolith intermediate becomes gradual, and the monomer distribution rate from the liquid phase part to the monolith intermediate decreases, so the surplus monomer is on the surface of the skeleton layer of the monolith intermediate. It is thought that it was concentrated in the vicinity and polymerized in situ.

  In Step III according to the fifth monolith production method, a preferable polymerization temperature is a temperature that is at least 10 ° C. lower than the 10-hour half-life temperature of the polymerization initiator used. Although the lower limit of the polymerization temperature is not particularly limited, the polymerization rate decreases as the temperature decreases, and the polymerization time becomes unacceptably long. Therefore, the polymerization temperature is 5 to 20 ° C. with respect to the 10-hour half temperature. It is preferable to set to a low range.

(Explanation of (2) above)
When the mol% of the cross-linking agent used in the step II according to the fifth monolith production method is set to be 2 times or more of the mol% of the cross-linking agent used in the I step, a monolith having a composite structure is obtained. The reason for this is that the compatibility between the monolith intermediate and the polymer produced by impregnation polymerization is reduced and phase separation proceeds, so the polymer produced by impregnation polymerization is excluded in the vicinity of the surface of the skeleton phase of the monolith intermediate, It is considered that irregularities such as particles are formed on the surface. In addition, mol% of a crosslinking agent is a crosslinking density mol%, Comprising: The crosslinking agent amount (mol%) with respect to the total amount of a vinyl monomer and a crosslinking agent is said.

The upper limit of the cross-linking agent mol% used in Step II according to the fifth monolith production method is not particularly limited, but when the cross-linking agent mol% is remarkably large, cracks occur in the monolith after polymerization.
Since monolithic embrittlement progresses and flexibility is lost, and when ion exchange groups are introduced, the amount of ion exchange groups introduced may decrease, which is not preferable. The preferred multiple of the crosslinker mol% is 2 to 10 times. On the other hand, even if the crosslinker mol% used in Step I is set to be twice or more the crosslinker mol% used in Step II, the formation of particles on the surface of the skeleton phase does not occur, and the fifth monolith Was not obtained.

(Description of (3) above)
If the vinyl monomer used in step II according to the fifth monolith production method is a vinyl monomer having a structure different from that of the oil-soluble monomer used in step I, the fifth monolith is obtained. For example, if the structures of vinyl monomers are slightly different, such as styrene and vinyl benzyl chloride, a composite monolith having particles or the like formed on the surface of the skeleton phase is generated. In general, two types of homopolymers obtained from two types of monomers that are slightly different in structure are not compatible with each other. Therefore, when a monomer having a structure different from that used for forming the monolith intermediate used in Step I is used in Step II and polymerization is performed in Step III, the monomer used in Step II is uniformly distributed to the monolith intermediate. Although impregnation occurs, when the polymerization proceeds to produce a polymer, the produced polymer is not compatible with the monolith intermediate, so phase separation proceeds, and the produced polymer is near the surface of the skeleton phase of the monolith intermediate. It is considered that irregularities such as particles are formed on the surface of the skeleton phase.

(Explanation of (4) above)
A 5th monolith is obtained when the organic solvent used by II process concerning the manufacturing method of a 5th monolith is a polyether with a molecular weight of 200 or more. Polyethers have a relatively high affinity with monolith intermediates, especially low molecular weight cyclic polyethers are good solvents for polystyrene, and low molecular weight chain polyethers are not good solvents but have considerable affinity. . However, as the molecular weight of the polyether increases, the affinity with the monolith intermediate dramatically decreases and shows little affinity with the monolith intermediate. When such a solvent having poor affinity is used as the organic solvent, diffusion of the monomer into the skeleton of the monolith intermediate is inhibited, and as a result, the monomer is polymerized only near the surface of the skeleton of the monolith intermediate. It is considered that particles and the like are formed on the phase surface and irregularities are formed on the skeleton surface.

  The upper limit of the molecular weight of the polyether used in Step II according to the fifth monolith production method is not particularly limited 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 is high. Therefore, it is not preferable because it is difficult to impregnate the monolith intermediate. The molecular weight of the preferred polyether is 200 to 100,000, particularly preferably 200 to 10,000. The terminal structure of the polyether may be an unmodified hydroxyl group, etherified with an alkyl group such as a methyl group or an ethyl group, or esterified with acetic acid, oleic acid, lauric acid, stearic acid, or the like. It may be made.

(Description of (5) above)
The fifth monolith is obtained when the concentration of the vinyl monomer used in step II according to the fifth monolith production method is 30% by weight or less in the mixture in step II. By reducing the monomer concentration in the step II, the polymerization rate is reduced, and for the same reason as the above (1), particles and the like can be formed on the surface of the skeleton phase, and irregularities can be formed on the surface of the skeleton phase. . Although the lower limit of the monomer concentration is not particularly limited, the polymerization rate decreases as the monomer concentration decreases and the polymerization time becomes unacceptably long, so the monomer concentration may be set to 10 to 30% by weight. preferable.

As a preferable structure of the fifth monolith thus obtained, bubble-shaped macropores overlap each other, and the overlapping portion is a continuous macropore structure (“5-1th” in which openings have an average diameter of 10 to 120 μm in a dry state. Monolith ") and an average thickness in a dry state of 0.8 to
Co-continuous structure consisting of three-dimensionally continuous skeletons of 40 μm and three-dimensionally continuous pores with a diameter of 8 to 80 μm between the skeletons (“5-2 monolith”) Is mentioned.

  When the fifth monolith is the 5-1 monolith, the 5-1 monolith has bubble-like macropores that overlap each other, and the overlapping portion has an average diameter of 10 to 120 μm, preferably 20 to 120 μm, especially in a dry state. Preferably, it is a continuous macropore structure which becomes an opening (mesopore) of 25 to 120 μm, and the inside of bubbles formed by the macropore and the opening (mesopore) is a flow path. The continuous macropore structure is preferably a uniform structure having the same macropore size and aperture diameter, but is not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do. When the average diameter of the opening in the dry state of the 5-1 monolith is less than 10 μm, it is not preferable because the pressure loss at the time of liquid passing increases, and the average diameter of the opening in the dry state is 120 μm. If exceeding, contact between the reaction solution, the monolith ion exchanger and the supported platinum group metal particles becomes insufficient, and as a result, the catalytic activity is lowered, which is not preferable.

  In the case of the 5-2 monolith, the 5-2 monolith has a three-dimensional continuous skeleton having an average thickness of 0.8 to 40 μm in a dry state, and an average diameter in a dry state between the skeletons. Is a co-continuous structure having three-dimensionally continuous pores of 8 to 80 μm. If the average diameter in the dry state of the three-dimensionally continuous pores of the 5-2 monolith is less than 8 μm, it is not preferable because the pressure loss at the time of passing liquid becomes large, and if it exceeds 80 μm The contact between the reaction solution, the monolith or the monolith ion exchanger and the supported platinum group metal particles becomes insufficient, and as a result, the catalytic activity is lowered, which is not preferable. Further, when the average thickness in the dry state of the skeleton of the 5-2 monolith is less than 0.8 μm, when ion exchange groups are introduced, the ion exchange capacity per volume of the monolith ion exchanger decreases. In addition to the disadvantages, the mechanical strength is reduced, and the monolith or the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high flow rate. 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 not preferable.

  The fifth monolith ion exchanger is obtained by performing an IV step for introducing an ion exchange group into the fifth monolith obtained in the step III.

  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.

  The platinum group metal supported catalyst according to the carbon-carbon bond forming method of the present invention comprises a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 100 μm, the average diameter of the continuous pores is 1-1000 μm, The pore volume is 0.5 to 50 ml / g, the ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, and the ion exchange groups are uniformly distributed in the organic porous ion exchanger. A platinum group metal-supported catalyst in which platinum group metal particles having an average particle diameter of 1 to 100 nm are supported on the non-particulate organic porous ion exchanger (the monolithic organic porous ion exchanger), The supported amount of the platinum group metal particles is 0.004 to 20% by weight in a dry state.

  The platinum group metal-supported catalyst according to the present invention has an average particle diameter of 1 to 100 nm in any of the above monolithic organic porous ion exchangers, for example, any one of the first monolith ion exchanger to the fifth monolith ion exchanger. This is a platinum group metal-supported catalyst in which the platinum group metal particles are supported.

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, and more than one metal may be used as an alloy. Among these,
Platinum, palladium, and platinum / palladium alloys have high catalytic activity and are preferably used.

  The average particle diameter of the platinum group metal particles supported on the platinum group metal catalyst is 1 to 100 nm, preferably 1 to 50 nm, more preferably 1 to 20 nm. If the average particle diameter is less than 1 nm, the possibility that the platinum group metal particles will be detached from the carrier increases, which is not preferable. On the other hand, if the average particle diameter exceeds 100 nm, the surface area per unit mass of the metal decreases. This is not preferable because the catalytic effect cannot be obtained efficiently. In the present invention, the average particle diameter of the platinum group metal particles is determined by image analysis of a TEM image obtained by transmission electron microscope (TEM) analysis. Specifically, first, the surface of the platinum group metal supported catalyst is subjected to TEM analysis. Next, in the obtained TEM image, one visual field in which the number of particles is 200 or more is arbitrarily selected, and the TEM image of the visual field is image-analyzed to measure the particle diameter of all particles in the visual field. When the number of platinum group metal particles carried in one field is less than 200, two or more fields of view are arbitrarily selected, and the particle size of all particles in the selected two or more fields of view is Measure. Next, the average particle diameter of the platinum group metal particles is expressed by the following formula: “average particle diameter of platinum group metal particles (nm) = total particle diameter of all measured particles (nm) / number of measured particles (pieces)” To calculate.

  The amount of platinum group metal particles supported in the platinum group metal supported catalyst ((platinum group metal particles / platinum group metal supported catalyst in dry state) × 100) is 0.004 to 20% by weight, preferably 0.005 to 15%. % By weight. If the supported amount of platinum group metal particles is less than 0.004% by weight, the catalytic activity becomes insufficient, such being undesirable. On the other hand, when the amount of platinum group metal particles is more than 20% by weight, metal elution into water is observed, which is not preferable.

  The method for producing the platinum group metal supported catalyst is not particularly limited, and the platinum group metal supported catalyst can be obtained by supporting the platinum group metal nanoparticles on the monolith ion exchanger by a known method. For example, a monolith ion exchanger in a dry state is immersed in a methanol solution of a platinum group metal compound such as palladium acetate, and palladium ions are adsorbed on the monolith ion exchanger by ion exchange, and then contacted with a reducing agent to form palladium metal nano-particles. A method of supporting particles on a monolith ion exchanger, a monolith ion exchanger is immersed in an aqueous solution of a platinum group metal compound such as a tetraammine palladium complex, and palladium ions are adsorbed on the monolith ion exchanger by ion exchange, and then a reducing agent For example, a method in which palladium metal nanoparticles are supported on a monolith ion exchanger by contacting them.

  The introduction of palladium ions into the monolith ion exchanger and the loading of palladium metal nanoparticles may be batch-type or flow-type, and are not particularly limited.

The platinum group metal compound used in the method for producing a platinum group metal supported catalyst may be either an organic salt or an inorganic salt, and halides, sulfates, nitrates, phosphates, organic acid salts, inorganic complex salts, and the like can be used. . Specific examples of the platinum group metal compound include palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, tetraammine palladium chloride, tetraammine palladium nitrate, platinum chloride, tetraammine platinum chloride, tetraammine platinum nitrate, chlorotriammine platinum chloride, Hexaammine platinum chloride, hexaammine platinum sulfate, chloropentaammine platinum chloride, cis-tetrachlorodiammine platinum chloride, trans-tetrachlorodiammine platinum chloride, rhodium chloride, rhodium acetate, hexaammine rhodium chloride, hexa Ammine rhodium bromide, hexaammine rhodium sulfate, pentaammine aquadium chloride, pentaammine aquadium nitrate, cis-dichlorotetraammine rhodium chloride, trans-dichloro Rhotetraammine rhodium chloride, ruthenium chloride, hexaammineruthenium chloride, hexaammineruthenium bromide, hexaammineruthenium iodide, chloropentammineruthenium chloride, cis-
Dichlorotetraammine ruthenium chloride, trans-dichlorotetraammine rhodium chloride, iridium chloride (III), iridium chloride (IV), hexaammine iridium chloride, hexaammine iridium nitrate, chloropentammine iridium chloride, chloropentammine iridium bromide, Examples include hexaammine osmium chloride, hexaammine osmium bromide, and hexaammine osmium iodide. The usage-amount of these compounds is 0.005-30 weight% with respect to the monolith ion exchanger which is a support | carrier in metal conversion.

  The platinum group metal compound is usually used after being dissolved in a solvent. Solvents 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. Is used. In order to enhance the solubility of the platinum group metal compound in a 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.

  There are no particular restrictions on the reducing agent used in the method for producing a platinum group metal supported catalyst, and reducing gases such as hydrogen, carbon monoxide, and ethylene; alcohols such as methanol, ethanol, propanol, butanol, and benzyl alcohol; formic acid and formic acid Carboxylic acids such as ammonium, oxalic acid, citric acid, sodium citrate, ascorbic acid, calcium ascorbate and salts thereof; ketones such as acetone and methyl ethyl ketone; aldehydes such as formaldehyde and acetaldehyde; hydrazine, methyl hydrazine, ethyl hydrazine, butyl hydrazine Hydrazines such as allyl hydrazine and phenyl hydrazine; hypophosphorous step salts such as sodium hypophosphite and potassium hypophosphite; sodium borohydride and the like.

  Although there is no restriction | limiting in particular also about the reaction conditions of a reductive reaction, Usually, reaction is performed at -20 degreeC to 150 degreeC for 1 minute to 20 hours, and a platinum group metal compound is reduced to a zerovalent platinum group metal.

  In the platinum group metal supported catalyst, there is no particular limitation on the ion form of the monolith ion exchanger that is the carrier of the platinum group metal nanoparticles, and in the case of the monolith cation exchanger, a salt in which the counter ion is replaced with sodium ion, calcium ion, or the like. In the case of a monolith anion exchanger, a salt form in which the counter ion is substituted with chloride ion, nitrate ion, or the like may be used. A regenerated form in which the ions are hydroxide ions may be used.

  The carbon-carbon bond forming method of the present invention comprises (1) an aromatic halide and an organoboron compound in the presence of the platinum group metal-supported catalyst according to the present invention. Carbon-carbon bond formation by forming a carbon-carbon bond by reacting a halide with a compound having an alkynyl group at the end, or (3) reacting an aromatic halide with a compound having an alkenyl group Is the method.

  The first form of the carbon-carbon bond forming method of the present invention (hereinafter also referred to as carbon-carbon bond forming method (1)) is an aromatic halogen in the presence of the platinum group metal supported catalyst according to the present invention. This is a reaction in which a chemical compound and an organic boron compound are reacted and coupled to form a carbon-carbon single bond.

The organic boron compound used in the carbon-carbon bond forming method (1) is R—B (OH) ₂ (R is an organic group and is not particularly limited as long as it is an organic group. A branched alkyl group, a cyclic alkyl group, an aromatic carbocyclic group, an aromatic heterocyclic group, etc., and these groups include a methyl group, an ethyl group, and the like as long as they do not impair the effects of the present invention. Group, nitro group, amino group, methoxy group, ethoxy group, carboxyl group, acetyl group, etc. may be introduced). And as an organic boron compound used by the carbon-carbon bond formation method (1), the aromatic boron compound shown by the following general formula (I) is preferable.
Ar ¹ -B (OH) ₂ (I)
(In the formula, Ar ¹ is an aromatic carbocyclic group or aromatic heterocyclic group having 6 to 18 carbon atoms.)

In the formula (I), examples of the aromatic carbocyclic group or aromatic heterocyclic group according to Ar ¹ include phenyl group, naphthyl group, biphenyl group, anthranyl group, pyridyl group, pyrimidyl group, indolyl group, benzine. Examples include imidazolyl group, quinolyl group, benzofuranyl group, indanyl group, indenyl group, dibenzofuranyl group and the like. The position at which boron is bonded to the aromatic carbocyclic group or aromatic heterocyclic group is not particularly limited, and can be bonded to any position. One or more substituents may be introduced into the aromatic carbocyclic group or aromatic heterocyclic group. Examples of the substituent include hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and benzyl group; alkoxy groups such as methoxy group, ethoxy group, pulloxy group and butoxy group; 9-fluorene Examples include nylmethoxycarbonyl group, butoxycarbonyl group, benzyloxycarbonyl group, nitro group and the like.

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

In the formula (II), examples of the aromatic carbocyclic group or aromatic heterocyclic group related to Ar ² include phenyl group, naphthyl group, biphenyl group, anthranyl group, pyridyl group, pyrimidyl group, indolyl group, benzine. Examples include imidazolyl group, quinolyl group, benzofuranyl group, indanyl group, indenyl group, dibenzofuranyl group and the like. The position at which the halogen atom is bonded to the aromatic carbocyclic group or aromatic heterocyclic group is not particularly limited, and can be bonded to any position. One or more substituents may be introduced into the aromatic carbocyclic group or aromatic heterocyclic group. Examples of the substituent include hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and benzyl group; alkoxy groups such as methoxy group, ethoxy group, pulloxy group and butoxy group; 9-fluorene Examples include nylmethoxycarbonyl group, butoxycarbonyl group, benzyloxycarbonyl group, nitro group, carboxyl group, amino group and the like. X is a halogen atom, specifically a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Carbon-carbon bond formation by the carbon-carbon bond formation method (1) includes an organic group in which a functional group containing boron is eliminated from an organic boron compound, and an aromatic residue in which halogen is eliminated from an aromatic halide. Between carbon atoms and carbon atoms. For example, when the organic boron compound is an aromatic boron compound represented by the formula (I) and the aromatic halide is an aromatic halide represented by the formula (II), the resulting coupling product is represented by the formula (I III).
Ar ¹ -Ar ² (III)
(In the formula, Ar ¹ and Ar ² are the same as those in the formulas (I) and (II).)

  The use ratio of the aromatic boron compound and aromatic halide used in the carbon-carbon bond forming method (1) is preferably used in an equimolar ratio, but the aromatic boron compound: aromatic halide = 0 in molar ratio. If it is the range of 0.5-2: 1, it can use for a reaction without a problem.

  A second form of the carbon-carbon bond forming method of the present invention (hereinafter also referred to as carbon-carbon bond forming method (2)) is an aromatic halogen in the presence of the platinum group metal supported catalyst according to the present invention. This is a reaction in which a carbon-carbon single bond is formed by reacting a compound with a compound having an alkynyl group at the terminal.

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

The compound having an alkynyl group at the terminal used in the carbon-carbon bond forming method (2) is a compound represented by the formula (IV).
HC≡C-R ¹ (IV)
(In the formula, R ¹ has a hydrogen atom, an aromatic carbocyclic group or an aromatic heterocyclic group optionally having a substituent having 6 to 18 carbon atoms, and a substituent having 1 to 18 carbon atoms. An aliphatic hydrocarbon group that may be present, an alkenyl group that may have a substituent having 2 to 18 carbon atoms, and an alkynyl group that may have a substituent having 2 to 10 carbon atoms.)

Examples of the aromatic carbocyclic group or aromatic heterocyclic group which may have a substituent having 6 to 18 carbon atoms according to R ¹ in formula (IV) include formulas (I) and (II The same as Ar ¹ and Ar ^{2 according} to). In the formula (IV), examples of the aliphatic hydrocarbon group which may have a substituent having 1 to 18 carbon atoms according to R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Group, octyl group, dodecyl group, octadecyl group and the like. Furthermore, Formula (IV), examples of the alkenyl group which may have a substituent group having 2 to 18 carbon atoms according to R ¹ is a vinyl group, an allyl group, a methallyl group, a propenyl group, butenyl group, hexenyl group Octenyl group, decenyl group, octadecenyl group and the like. In the formula (IV), examples of the alkynyl group which may have a substituent having 2 to 10 carbon atoms according to R ¹ include ethynyl group, propynyl group, hexynyl group, octenyl group and the like. Examples of the substituent for the aliphatic hydrocarbon group, alkenyl group, and alkynyl group include a hydroxyl group, a hydrocarbon group, and a heteroatom-containing hydrocarbon group.

In the carbon-carbon bond forming method (2), the aromatic halide represented by the formula (II) reacts with the compound represented by the formula (IV) in the presence of the platinum group metal-supported catalyst according to the present invention, and the formula The product of (V) is given.
Ar ² —C≡C—R ¹ (V)
(In the formula, Ar ² and R ¹ are the same as those in the formulas (II) and (IV).)

  The use ratio of the aromatic halide used in the carbon-carbon bond forming method (2) and the compound having an alkynyl group at the end is preferably used in an equimolar ratio, but the aromatic halide: alkynyl at the end is used in a molar ratio. If it is the compound which has group = 0.5-3: 1, it can use for reaction without a problem.

  The third form of the carbon-carbon bond forming method of the present invention (hereinafter also referred to as carbon-carbon bond forming method (3)) is an aromatic halide in the presence of the platinum group metal supported catalyst according to the present invention. And a compound having an alkenyl group are reacted to form a carbon-carbon single bond.

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

The compound having an alkenyl group used in the carbon-carbon bond forming method (3) is represented by the formula (VI
).
R ² HC = CR ³ R ⁴ (VI)
(Wherein R ² , R ³ and R ⁴ are each independently a hydrogen atom, an aromatic carbocyclic group or an aromatic heterocyclic group optionally having a substituent having 6 to 18 carbon atoms, (It is an aliphatic hydrocarbon group, carboxylic acid derivative, acid amide derivative or cyano group which may have a substituent having 1 to 18 carbon atoms.)

In formula (VI), an aromatic carbocyclic group or aromatic heterocyclic group which may have a substituent having 6 to 18 carbon atoms according to R ² , R ³ and R ⁴ , and Examples of the aliphatic hydrocarbon group which may have 18 substituents are the same as those for R ^{1 according} to formula (IV). In addition, examples of the carboxylic acid derivative according to R ² , R ^3, and R ⁴ in formula (VI) include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl. Examples of the acid amide derivative according to R ² , R ³ and R ⁴ in formula (VI) include carbamoyl groups such as N-methylcarbamoyl group and N, N-dimethylcarbamoyl group.

In the carbon-carbon bond forming method (3), the aromatic halide represented by the formula (II) reacts with the compound represented by the formula (VI) in the presence of the platinum group metal-supported catalyst according to the present invention, and the formula The product of (VII) is given.
R ² Ar ² C═CR ³ R ⁴ (VII)
(In the formula, Ar ² , R ² , R ³ and R ⁴ are the same as those in the formulas (II) and (VI).)

  The ratio of the aromatic halide used in the carbon-carbon bond forming method (3) and the compound having an alkynyl group at the end is not particularly limited, but the aromatic halide: the compound having an alkenyl group in a molar ratio = 0. If it is the range of 5-2: 1, it can use for reaction without a problem.

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

  In the carbon-carbon bond forming method of the present invention, the coupling reaction may be performed using a solvent or may be performed in the absence of a solvent. Examples of the solvent used include water, organic solvents, and mixtures thereof. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, and glycerin; and cyclic ethers such as tetrahydrofuran and dioxane.

  The atmosphere in which the carbon-carbon bond forming method of the present invention is performed may be in air, but is preferably an inert gas atmosphere such as nitrogen or argon. The reaction temperature is not particularly limited, but is arbitrarily set in the range of −20 ° C. to 150 ° C., and the reaction time is not particularly limited, but is set in the range of 1 minute to 24 hours.

  In the carbon-carbon bond forming reaction of the present invention, a base is preferably present. Examples of bases used include sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, potassium acetate, sodium phosphate, potassium phosphate, potassium phenolate, barium hydroxide, sodium methoxide, sodium ethoxide, potassium butoxide , Trimethylamine, triethylamine and the like. The usage-amount of these bases is set in 50-300 mol% with respect to an aromatic halide.

(Example)
Next, the present invention will be specifically described by way of examples, but this is merely an example and does not limit the present invention.

Reference Example 1 Production of Monolith Cation Exchanger (Production of Monolith Intermediate (Step 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 pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co.) as a planetary stirring device. Was stirred under reduced pressure to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel and allowed to polymerize at 60 ° C. for 24 hours in a static state after sealing. After completion of the polymerization, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The internal structure of the monolith intermediate (dry body) thus obtained was observed by SEM. The SEM image is shown in FIG. 10, although the wall portion that divides two adjacent macropores is extremely thin and has a rod shape, but has an open cell structure, and the opening of the portion where the macropores and macropores measured by mercury porosimetry overlap (Mesopore) had an average diameter of 40 μm and a total pore volume of 18.2 ml / g.

(Manufacture of monoliths)
Next, 216.6 g of styrene, 4.4 g of divinylbenzene, 220 g of 1-decanol
0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was mixed and dissolved uniformly (step II). Next, the above monolith intermediate is placed in a reaction vessel, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and degassed in a vacuum chamber. The reaction vessel was sealed and allowed to polymerize at 50 ° C. for 24 hours. After completion of the polymerization, the content was taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure (step III).
The crosslinking component comprising the styrene / divinylbenzene copolymer thus obtained is
FIG. 11 shows the result of observing the internal structure of the monolith (dried body) containing 2 mol% by SEM. As is clear from FIG. 11, the monolith has a co-continuous structure in which the skeleton and the vacancies are three-dimensionally continuous, and both phases are intertwined. Moreover, the average thickness of the skeleton measured from the SEM image was 20 μm. Further, the average diameter of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 70 μm, and the total pore volume was 4.4 ml / g. The average diameter of the pores was determined from the maximum value of the pore distribution curve obtained by the mercury intrusion method.

(Production of monolith cation exchanger)
The monolith produced by the above method was put into a column reactor, and a solution consisting of 500 g of chlorosulfonic acid and 4 L of dichloromethane was passed through and reacted at 20 ° C. for 3 hours. After the reaction is complete
Methanol was added to the system to deactivate unreacted chlorosulfonic acid, and the product was taken out by washing with methanol. Finally, it was washed with pure water to obtain a monolith cation exchanger.
The obtained monolith cation exchanger had a cation exchange capacity of 4.7 mg equivalent / g in a dry state, and it was confirmed that sulfonic acid groups were quantitatively introduced. As is clear from FIG. 11, the monolith cation exchanger had a co-continuous structure in which the skeleton and the vacancies were three-dimensionally continuous and the two phases were intertwined. The average thickness of the skeleton in the dry state measured from the SEM image is 20 μm, and the average in the dry state of the three-dimensional continuous pores of the monolith cation exchanger determined from the measurement by the mercury intrusion method. The diameter was 70 μm, and the total pore volume in the dry state was 4.4 ml / g.
Subsequently, in order to confirm the distribution state of the sulfonic acid group in the monolith cation exchanger, the distribution state of sulfur was observed by EPMA. The distribution state of sulfur on the surface of the monolith cation exchanger is shown in FIG. 12, and the distribution state of sulfur in the skeleton cross section is shown in FIG. 13. Sulfur is uniformly distributed not only on the skeleton surface of the monolith cation exchanger but also inside the skeleton. It was confirmed that the sulfonic acid group was uniformly introduced into the monolith cation exchanger.

Reference Example 2 Preparation of Platinum Group Metal-Supported Catalyst The monolith cation exchanger of Reference Example 1 was dried under reduced pressure, and the dried monolith cation exchanger was chopped with a knife into small pieces of about 3 mm. 1.5 g of this small piece was dispersed in 30 ml of methanol, 160 mg of palladium acetate was further added, and the mixture was stirred at room temperature for 6 days to support palladium ions on the monolith cation exchanger. Subsequently, the monolith cation exchanger was taken out by solid-liquid separation, dispersed in 50 ml of pure water, and reduced by adding 10 mmol of hydrazine monohydrate. The sample that was yellow when palladium ions were supported on the monolith cation exchanger turned black after reduction, suggesting the formation of palladium nanoparticles. The sample after the reduction was washed several times with pure water and then dried by pressure detection drying.
When the amount of palladium supported was determined by ICP emission spectroscopy, the amount of palladium supported was 4.0.
% By weight. In order to confirm the distribution state of palladium supported on the monolith cation exchanger, the distribution state of palladium was observed by EPMA. FIG. 14 shows the distribution state of palladium in the skeleton cross section of the monolith cation exchanger. Palladium is distributed not only on the skeleton surface of the monolith cation exchanger but also on the inside of the skeleton. It was confirmed that the distribution was relatively uniform. In order to measure the average particle diameter of the supported palladium particles, observation with a transmission electron microscope (TEM) was performed. The obtained TEM image is shown in FIG. The average particle diameter of the palladium nanoparticles was 10 nm.

(Example 1) Reaction of 4-nitro-1-bromobenzene and phenylboronic acid Using the palladium-supported catalyst prepared in Reference Example 2, 4-nitro-1-bromobenzene and phenylboronic acid were reacted. 101 mg (0.50 mmol) of 4-nitro-1-bromobenzene and 67.1 mg (0.55 mmol) of phenylboronic acid were added to 2 ml of a mixed solvent of water / isopropanol (1/1), and then prepared in Reference Example 2. 5.3 mg of the supported palladium catalyst (palladium was 0.5 mol% with respect to 4-nitro-1-bromobenzene) was added. Furthermore, 665 mg of sodium phosphate dodecahydrate as a base (3.5 to 4-nitro-1-bromobenzene)
(Double equivalent) was added and allowed to react at room temperature for 6 hours. The conversion of 4-nitro-1-bromobenzene after the reaction was measured by GCMS and found to be 100%. The yield of the reaction product, 4-nitro-biphenyl, was 92%.

(Example 2) Reaction of 4-methoxy-1-bromobenzene and phenylboronic acid
The reaction was carried out under the same conditions as in Example 1, except that 93.5 mg (0.50 mmol) of 4-methoxy-1-bromobenzene was used instead of 4-nitro-1-bromobenzene. The conversion of 4-methoxy-1-bromobenzene after the reaction for 19 hours was 100%, and the yield of the reaction product 4-methoxy-biphenyl was 97%.

(Example 3) Reaction of 4'-iodoacetophenone and ethynylbenzene Using the palladium-supported catalyst prepared in Reference Example 2, 4'-iodoacetophenone and ethynylbenzene were reacted. 123 mg (0.50 mmol) of 4′-iodoacetophenone and 65.9 μl (0.60 mmol) of ethynylbenzene were added to 2 ml of a mixed solvent of water / isopropanol (1/1), and then the palladium-supported catalyst prepared in Reference Example 2 4.2 mg (palladium was 0.4 mol% with respect to 4'-iodoacetophenone) was added. Further, 380 mg of sodium phosphate dodecahydrate (2 equivalents relative to 4′-iodoacetophenone) was added as a base and reacted at 80 ° C. for 1 hour. The yield of the reaction product was 100%.

(Example 4) Reaction of iodobenzene and butyl acrylate Using the palladium-supported catalyst prepared in Reference Example 2, the reaction of iodobenzene and butyl acrylate was performed. 55.8 μl (0.50 mmol) of iodobenzene and 85.4 μl (0.60 mmol) of butyl acrylate were added to 2 ml of dimethylacetamide, and then 2.1 mg of palladium-supported catalyst prepared in Reference Example 2 (palladium represents iodobenzene). 0.2 mol%) was added. Further, 131 μl of tributylamine (1.1 times equivalent to iodobenzene) was added as a base and reacted at 100 ° C. for 3 hours. The yield of the reaction product was 91%.

(Reference Example 3) Preparation of a platinum group metal-supported catalyst using a monolith having no ion exchange group introduced thereon as a carrier The monolith before introduction of the cation exchange group produced in Reference Example 1 was dried under reduced pressure and chopped with a knife. A small piece of about 3 mm was used. 2.0 g of this small piece was dispersed in 40 ml of methanol, 210 mg of palladium acetate was further added, and the mixture was stirred at room temperature for 6 days. After the reaction, the sample turned black after reduction, suggesting the formation of palladium nanoparticles. The obtained sample was washed several times with pure water, and then dried by pressure detection drying. The amount of palladium supported was determined by ICP emission spectrometry, and the amount of palladium supported was 4.8% by weight.

(Comparative Example 1)
The same reaction as in Example 1 was carried out except that the palladium supported catalyst prepared in Reference Example 3 was used instead of the palladium supported catalyst prepared in Reference Example 2. In Example 1, the yield reached 92% in the reaction for 6 hours, whereas in the case of using the catalyst of Reference Example 3 (using a monolith having no ion exchange group as a support), the reaction was performed for 24 hours. The yield was only 2%.

(Comparative Example 2)
The same reaction as in Example 2 was performed except that the palladium-supported catalyst prepared in Reference Example 3 was used instead of the palladium-supported catalyst prepared in Reference Example 2. In Example 3, the yield reached 97% after 19 hours of reaction, whereas in the case of using the catalyst of Reference Example 3 (using a monolith having no ion exchange group as a support), the reaction was performed for 24 hours. The yield was 31%.

Reference Example 4 Production of monolith anion exchanger (production of monolith anion exchanger)
The monolith produced in Reference Example 1 was placed in a column reactor, and a solution consisting of 1600 g of chlorosulfonic acid, 400 g of tin tetrachloride and 2500 ml of dimethoxymethane was circulated and passed through, and reacted at 30 ° C. for 5 hours to give a chloromethyl group. Was introduced. After completion of the reaction, the chloromethylated monolith was washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1600 ml of THF and 1400 ml of 30% aqueous solution of trimethylamine were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a monolith anion exchanger.
The resulting monolith anion exchanger had an anion exchange capacity of 4.2 mg equivalent /
g, and it was confirmed that quaternary ammonium groups were quantitatively introduced. The average thickness of the skeleton in the dry state measured from the SEM image is 20 μm, and the average in the dry state of the three-dimensional continuous pores of the monolith anion exchanger determined from the measurement by mercury porosimetry. The diameter was 70 μm, and the total pore volume in the dry state was 4.4 ml / g.
Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chloride ions was observed by EPMA. . The distribution state of chloride ions on the surface of the monolith anion exchanger is shown in FIG. 16, and the distribution state of chloride ions in the skeleton cross section is shown in FIG. 17. The chloride ions are not limited to the skeleton surface of the monolith anion exchanger. It was uniformly distributed inside, and it was confirmed that quaternary ammonium groups were uniformly introduced into the monolith anion exchanger.

(Reference Example 5) Production of platinum group metal supported catalyst The monolith anion exchanger of Reference Example 4 was ion-exchanged into Cl form, cut into a cylindrical shape in a dry state, and dried under reduced pressure. The weight of the monolith anion exchanger after drying was 1.2 g. This dried monolith anion exchanger was immersed in dilute hydrochloric acid in which 100 mg of palladium chloride was dissolved for 24 hours, and ion-exchanged to the palladium chloride acid form. After completion of the immersion, the monolith anion exchanger was washed several times with pure water, and immersed in an aqueous hydrazine solution for 24 hours for reduction treatment. The chloropalladium acid form monolith anion exchanger was brown, whereas the monolith anion exchanger after the reduction treatment was colored black, suggesting the formation of palladium nanoparticles. The sample after the reduction was washed several times with pure water and then dried by pressure detection drying.
When the amount of palladium supported was determined by ICP emission spectroscopy, the amount of palladium supported was 3.9.
% By weight. In order to confirm the distribution state of palladium supported on the monolith anion exchanger, the distribution state of palladium was observed by EPMA. Although the distribution state of palladium in the skeleton cross section of the monolith anion exchanger is shown in FIG. It was confirmed that the distribution was relatively uniform. In order to measure the average particle diameter of the supported palladium particles, observation with a transmission electron microscope (TEM) was performed. The obtained TEM image is shown in FIG. The average particle diameter of the palladium nanoparticles was 8 nm.

(Example 5) Reaction of 4-methoxy-1-bromobenzene and phenylboronic acid Using the palladium-supported catalyst prepared in Reference Example 5, 4-methoxy-1-bromobenzene and phenylboronic acid were reacted. 4-methoxy-1-bromobenzene 93.5 mg (0.50
Mmol) and 67.1 mg (0.55 mmol) of phenylboronic acid in 2 ml of a mixed solvent of water / isopropanol (1/1), and then the palladium-supported catalyst prepared in Reference Example 5.
8 mg (palladium was 0.5 mol% with respect to 4-methoxy-1-bromobenzene) was added. Further, 665 mg of sodium phosphate dodecahydrate (3.5 times equivalent to 4-methoxy-1-bromobenzene) was added as a base, and the mixture was reacted at room temperature for 24 hours. The conversion of 4-methoxy-1-bromobenzene after the reaction was measured by GCMS and found to be 97%. The yield of 4-methoxy-biphenyl as a reaction product was 76%.

Example 6 Reaction of 4-bromoaniline with phenylboronic acid
The reaction was carried out under the same conditions as in Example 5, except that 86.0 mg (0.50 mmol) of 4-bromoaniline was used instead of 4-methoxy-1-bromobenzene, and the reaction temperature was 80 ° C. It was. The reaction was completed in only 30 minutes, the conversion rate was 100%, and the yield was 95%.

(Example 7) Reaction of 4'-iodoacetophenone and ethynylbenzene Using the palladium-supported catalyst prepared in Reference Example 5, 4'-iodoacetophenone and ethynylbenzene were reacted. 123 mg (0.50 mmol) of 4′-iodoacetophenone and 65.9 μl (0.60 mmol) of ethynylbenzene were added to 2 ml of a mixed solvent of water / isopropanol (1/1), and then the palladium supported catalyst prepared in Reference Example 5 was used. 5.5 mg (palladium was 0.4 mol% with respect to 4'-iodoacetophenone) was added. Further, 380 mg of sodium phosphate dodecahydrate (2 times equivalent to 4′-iodoacetophenone) was added as a base and reacted at 80 ° C. for 1 hour. The yield of the reaction product was 99%.

(Example 8) Reaction of iodobenzene and butyl acrylate Using the palladium-supported catalyst prepared in Reference Example 5, reaction of iodobenzene and butyl acrylate was performed. 55.8 μl (0.50 mmol) of iodobenzene and 85.4 μl (0.60 mmol) of butyl acrylate were added to 2 ml of dimethylacetamide, and then 2.8 mg of palladium-supported catalyst prepared in Reference Example 5 (palladium represents iodobenzene). 0.2 mol%) was added. Furthermore, 131 μl of tributylamine (1.1 equivalents relative to iodobenzene) was added as a base and reacted at 100 ° C. for 4 hours. The yield of the reaction product is 100
%Met.

DESCRIPTION OF SYMBOLS 1 Skeletal phase 2 Pore phase 10 Monolith 11 Image area 12 Skeletal part 13 shown in cross section Macropore 21 Skeletal surface 22 Projection body 30 Monolith (monolith ion exchanger)
31 Macropore 32 Opening 33 Inner layer portion 34 Surface layer portion 35 Gas phase portion (bubble portion)
36 Wall (skeleton)
37 pores

Claims (12)

In the presence of a platinum group metal supported catalyst, (1) reaction between an aromatic halide and an organic boron compound, (2) reaction between an aromatic halide and a compound having an alkynyl group at the end, or (3) aromatic halogen A carbon-carbon bond forming method of reacting a compound with a compound having an alkenyl group to form a carbon-carbon bond,
The platinum group metal supported catalyst is a platinum group metal supported catalyst in which platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported on a non-particulate organic porous anion exchanger, and the non-particulate organic porous catalyst The anion exchanger is composed of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 100 μm, the average diameter of the continuous pores is 1 to 1000 μm, and the total pore volume is 0.5 to 50 ml / g. The anion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, the anion exchange groups are uniformly distributed in the organic porous anion exchanger, and the supported amount of the platinum group metal is , 0.004-20% by weight in a dry state,
A carbon-carbon bond forming method characterized by the above. The non-particulate organic porous anion exchanger has an open cell structure having a common pore (mesopore) having an average diameter of 1 to 1000 μm in a macropore and a macropore wall connected to each other, and the total pore volume is 1 to 50 ml / g, anion exchange capacity per weight in a dry state is 1 to 6 mg equivalent / g, and anion exchange groups are uniformly distributed in the organic porous anion exchanger The carbon-carbon bond forming method according to claim 1. The non-particulate organic porous anion exchanger aggregates organic polymer particles having an average particle diameter of 1 to 50 μm to form a three-dimensional continuous skeleton part, and a tertiary having an average diameter of 20 to 100 μm between the skeletons. Originally having continuous pores, the total pore volume is 1 to 10 ml / g, the anion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, and the anion exchange group is the organic 2. The carbon-carbon bond forming method according to claim 1, wherein the carbon-carbon bond is uniformly distributed in the porous anion exchanger. The non-particulate organic porous anion exchanger is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion is an opening having an average diameter of 30 to 300 μm, and the total pore volume is 0.5 to 10 ml. / G, the anion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, the anion exchange groups are uniformly distributed in the organic porous anion exchanger, and the continuous macropore structure ( 2. The carbon-carbon bond forming method according to claim 1, wherein in the SEM image of the cut surface of the dried body, the area of the skeleton part appearing in the cross section is 25 to 50% in the image region. The non-particulate organic porous anion exchanger has an average thickness of 1 consisting of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of a crosslinked structural unit among all the structural units into which an anion exchange group has been introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton of ˜60 μm and three-dimensionally continuous pores having an average diameter of 10 to 200 μm between the skeletons, and the total pore volume is 0.5 10 ml / g, an anion exchange capacity per weight in a dry state is 1 to 6 mg equivalent / g, and an anion exchange group is uniformly distributed in the organic porous anion exchanger The carbon-carbon bond forming method according to claim 1. The non-particulate organic porous anion exchanger comprises a continuous skeleton phase and a continuous pore phase, and the skeleton is a large number of particles having a diameter of 4 to 40 μm fixed on the surface or the skeleton surface of the organic porous body. Having a large number of protrusions having a size of 4 to 40 μm, an average diameter of continuous pores of 10 to 200 μm, a total pore volume of 0.5 to 10 ml / g, and a weight in a dry state 2. The carbon-carbon bond forming method according to claim 1, wherein the anion exchange capacity per unit is 1 to 6 mg equivalent / g, and the anion exchange groups are uniformly distributed in the organic porous anion exchanger. . A platinum group metal-supported catalyst for carbon-carbon bond forming reaction in which nanoparticles of platinum group metal having an average particle diameter of 1 to 100 nm are supported on a non-particulate organic porous anion exchanger,
  The non-particulate organic porous anion exchanger comprises a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 100 μm, the average diameter of the continuous pores is 1 to 1000 μm, and the total pore volume is 0.5. ˜50 ml / g, the anion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, and the anion exchange groups are uniformly distributed in the organic porous anion exchanger,
  The supported amount of the platinum group metal is 0.004 to 20% by weight in a dry state;
A platinum group metal supported catalyst for carbon-carbon bond forming reaction. The non-particulate organic porous anion exchanger has an open cell structure having a common pore (mesopore) with an average diameter of 1 to 1000 μm in the walls of the macropores and the macropores connected to each other, and the total pore volume is 1 to 50 ml / g, anion exchange capacity per weight in a dry state is 1 to 6 mg equivalent / g, and anion exchange groups are uniformly distributed in the organic porous anion exchanger The platinum group metal supported catalyst for carbon-carbon bond forming reaction according to claim 7. The non-particulate organic porous anion exchanger aggregates organic polymer particles having an average particle diameter of 1 to 50 μm to form a three-dimensional continuous skeleton part, and a tertiary having an average diameter of 20 to 100 μm between the skeletons. Originally having continuous pores, the total pore volume is 1 to 10 ml / g, the anion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, and the anion exchange group is the organic The platinum group metal supported catalyst for carbon-carbon bond forming reaction according to claim 7, wherein the catalyst is uniformly distributed in the porous anion exchanger. The non-particulate organic porous anion exchanger is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion is an opening having an average diameter of 30 to 300 μm, and the total pore volume is 0.5 to 10 ml. / G, the anion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, the anion exchange groups are uniformly distributed in the organic porous anion exchanger, and the continuous macropore structure ( The platinum group metal-supported catalyst for carbon-carbon bond forming reaction according to claim 7, wherein the area of the skeleton part shown in the cross section in the SEM image of the cut surface of the dried body) is 25 to 50% in the image region . The non-particulate organic porous anion exchanger has an average thickness of 1 consisting of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of a crosslinked structural unit among all the structural units into which an anion exchange group has been introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton of ˜60 μm and three-dimensionally continuous pores having an average diameter of 10 to 200 μm between the skeletons, and the total pore volume is 0.5 10 ml / g, an anion exchange capacity per weight in a dry state is 1 to 6 mg equivalent / g, and an anion exchange group is uniformly distributed in the organic porous anion exchanger The platinum group metal supported catalyst for carbon-carbon bond forming reaction according to claim 7. The non-particulate organic porous anion exchanger comprises a continuous skeleton phase and a continuous pore phase, and the skeleton is a large number of particles having a diameter of 4 to 40 μm fixed on the surface or the skeleton surface of the organic porous body. Having a large number of protrusions having a size of 4 to 40 μm, an average diameter of continuous pores of 10 to 200 μm, a total pore volume of 0.5 to 10 ml / g, and a weight in a dry state The carbon-carbon bond forming reaction according to claim 7, wherein the permeation anion exchange capacity is 1 to 6 mg equivalent / g, and the anion exchange groups are uniformly distributed in the organic porous anion exchanger. Platinum group metal supported catalyst.