JP2022163532A - Platinum group metal ion supported catalyst and carbon-carbon bond forming method - Google Patents

Abstract

To provide a platinum group metal ion supported catalyst which enables a carbon-carbon bond forming reaction to be performed in high yield even in an aromatic bromide.SOLUTION: Provided is a platinum group metal ion supported catalyst in which at least one of platinum group metal ions and platinum group metal complex ions is supported by an ion exchanger comprising a polymer chain represented by a general formula (1). (In the formula, R1 represents a C4-22 alkyl group which may be substituted or a benzyl group which may be substituted with a C1-6 alkyl group which may be substituted, with a halogen atom, with a C1-6 alkoxy group which may be substituted, with an amino group which may be substituted, with a cyano group, or with a nitro group; R2 and R3 represent each independently a C1-4 alkyl group; L represents a linker site; and Polymer represents a polymer chain).SELECTED DRAWING: None

Description

The present invention relates to a platinum group metal ion-supported catalyst and a carbon-carbon bond forming method for carrying out a reaction for forming a carbon-carbon bond using the platinum group metal ion-supported catalyst.

Carbon-carbon formation reactions (coupling reactions) using platinum group metals such as palladium as catalysts, typified by Suzuki-Miyaura coupling, Sonogashira coupling, and Mizorogi-Heck coupling, are used for pharmaceutical intermediates, organic EL, etc. In recent years, it has become more and more important in the synthesis process of high-performance materials.

Conventionally, the above platinum group metal catalysts have often been used in a homogeneous system and have exhibited high catalytic activity, but there are problems such as the difficulty of recovering the catalyst and the contamination of the product with the metal that is the catalyst. rice field. Therefore, a heterogeneous catalyst has been developed in which the catalyst is supported on a carrier to facilitate the recovery of the catalyst and reduce the metal contamination of the product. - Methods for forming carbon bonds have also been developed.

For example, Patent Document 1 reports a method of continuously forming carbon-carbon bonds using a catalyst in which palladium is supported on a porous silica carrier, but does not disclose an actual reaction example.

Patent Documents 2 and 3 disclose a method of forming a carbon-carbon bond using a catalyst in which a platinum group metal is supported on the wall surface of a microchannel having a width of 1 mm and a depth of 20 μm. Although it is not clear, in the disclosed reaction example, water is not used as a solvent, and the reaction substrate solution is passed only at a flow rate of 1 μm / min, which poses problems in terms of environmental load and production efficiency. .

Non-Patent Document 1 reports a method of continuously forming carbon-carbon bonds in a column filled with a catalyst in which palladium is supported on an organic carrier, but requires complex chemical transformations to obtain an organic carrier. In addition, although the reason is not clear, it is necessary to mix a large amount of diatomaceous earth when using a palladium-supported catalyst.

On the other hand, the present inventors have developed a catalyst in which a platinum group metal is supported on a non-particulate organic ion exchanger having three-dimensionally continuous pores. It has been reported that it exhibits high catalytic activity in aqueous solvents in carbon-carbon bond forming reactions.

According to the methods disclosed in Patent Documents 4 and 5, by using a platinum group metal-supported catalyst in which a platinum group metal is supported on a non-particulate organic ion exchanger as a catalyst, in an aqueous solvent, Carbon-carbon bond forming reactions can be carried out in high yields.

Japanese Patent No. 5638862 Japanese Patent No. 5255215 JP 2008-212765 A JP 2014-015420 A JP 2016-190853 A

ChemCatChem, 2019, No. 11, p.2427

However, in the reaction examples of Patent Documents 4 and 5, only highly reactive aromatic iodides can be used as raw material aromatic halides to carry out the carbon-carbon bond forming reaction in high yields. However, for aromatic bromides, the yields are poor and the raw materials available are limited.

An object of the present invention is to provide a platinum group metal ion-supported catalyst capable of carrying out a carbon-carbon bond forming reaction in a high yield even in aromatic bromides, and a carbon-carbon bond-forming method using the platinum group metal ion-supported catalyst. to provide.

（式中Ｒ^１は、置換されていてもよい炭素数４から２２のアルキル基；または、置換されていてもよい炭素数１から６のアルキル基、ハロゲン原子、置換されていてもよい炭素数１から６のアルコキシ基、置換されていてもよいアミノ基、シアノ基、もしくはニトロ基で置換されていてもよいベンジル基；を表し、Ｒ^２，Ｒ^３は、それぞれ独立して炭素数１から４のアルキル基を表し、Ｌは、リンカー部位を表し、Ｐｏｌｙｍｅｒは、高分子鎖を表す。）
で表される高分子鎖から構成されるイオン交換体に、白金族金属イオンおよび白金族金属錯イオンのうち少なくとも１つが担持されている、白金族金属イオン担持触媒である。 The present invention has the general formula (1)

(In the formula, R ¹ is an optionally substituted alkyl group having 4 to 22 carbon atoms; or an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, or an optionally substituted carbon number 1 to ⁶ alkoxy groups, optionally substituted amino groups, cyano groups ^, or benzyl groups optionally substituted with nitro groups; 4 represents an alkyl group, L represents a linker moiety, and Polymer represents a polymer chain.)
At least one of platinum group metal ions and platinum group metal complex ions is supported on an ion exchanger composed of a polymer chain represented by the platinum group metal ion supported catalyst.

In the platinum group metal ion-supported catalyst, the ion exchanger consists of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, and the average diameter of the continuous pores is 1 ~1000 μm, the total pore volume ranges from 0.5 to 50 mL/g, the dry weight ion exchange capacity ranges from 1 to 9 mg equivalent/g, and the ion exchange It is preferably a non-particulate organic porous ion exchanger in which the groups are distributed throughout said ion exchanger.

In the platinum group metal ion-supported catalyst, the non-particulate organic porous ion exchanger has macropores connected to each other and a continuous macropore structure having common openings with an average diameter in the range of 1 to 1000 μm in the walls of the macropores. The total pore volume is in the range of 1 to 50 mL / g, the ion exchange capacity per weight in a dry state is in the range of 1 to 9 mg equivalent / g, and the ion exchange group is the organic porous It is preferably distributed in the ion exchanger.

In the platinum group metal ion-supported catalyst, the non-particulate organic porous ion exchanger has an average particle size of 1 to 50 μm, in which organic polymer particles aggregate to form a three-dimensionally continuous skeleton portion. It has three-dimensionally continuous pores with an average diameter in the range of 20 to 100 μm between the skeletons, the total pore volume is in the range of 1 to 10 mL / g, and the ion exchange capacity per weight in a dry state is in the range of 1 to 9 mg equivalent/g, and the ion exchange groups are preferably distributed in the organic porous ion exchanger.

In the platinum group metal ion-supported catalyst, the non-particulate organic porous ion exchanger is a continuous macropore structure in which bubble-like macropores overlap each other, and the overlapped portions are openings having an average diameter of 30 to 300 μm. , the total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per weight in a dry state is in the range of 1 to 9 mg equivalent / g, and the ion exchange groups are in the organic porous It is distributed in the ion exchanger, and in the SEM image of the cross section of the continuous macropore structure, the skeleton portion area appearing in the cross section is preferably in the range of 25 to 50% of the image area.

In the platinum group metal ion-supported catalyst, the non-particulate organic porous ion exchanger contains crosslinked structural units in the range of 0.1 to 5.0 mol% in all structural units into which ion exchange groups are introduced. A three-dimensionally continuous skeleton having a thickness in the range of 1 to 60 μm, and three-dimensionally continuous pores having an average diameter in the range of 10 to 200 μm between the skeletons. The total pore volume is in the range of 0.5 to 10 mL / g, and the ion exchange capacity per weight in the dry state is in the range of 1 to 9 mg equivalent / g It is preferable that the ion exchange groups are distributed in the organic porous ion exchanger.

In the platinum group metal ion-supported catalyst, the non-particulate organic porous ion exchanger consists of a continuous skeleton phase and a continuous pore phase, and the skeleton consists of a plurality of particles with a diameter in the range of 4 to 40 μm fixed to the surface. a plurality of projections with a size in the range of 4 to 40 μm formed on the surface of the skeleton of the body or the organic porous body, and the average diameter of the continuous pores is in the range of 10 to 200 μm. The pore volume is in the range of 0.5 to 10 mL/g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 mg equivalent/g, and the ion exchange groups are in the organic porous ion exchanger. preferably distributed in the

In the platinum group metal ion-supported catalyst, the supported amount of at least one of the platinum group metal ions and platinum group metal complex ions is in the range of 0.01 to 10.0% by mass in terms of platinum group metal atoms. preferable.

In the platinum group metal ion-supported catalyst, R ¹ in the general formula (1) is an alkyl group having 6 to 20 carbon atoms, or a benzyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms. is preferred.

In the platinum group metal ion-supported catalyst, R ¹ in general formula (1) is preferably a dodecyl group or a benzyl group.

In the platinum group metal ion-supported catalyst, R ² and R ³ in general formula (1) are each independently preferably a methyl group or an ethyl group.

In the platinum group metal ion-supported catalyst, R ² and R ³ in general formula (1) are preferably methyl groups.

In the platinum group metal ion-supported catalyst, L in general formula (1) is preferably a methylene group.

In the platinum group metal ion-supported catalyst, the polymer chain of the ion exchanger is preferably a styrene-divinylbenzene copolymer.

The present invention provides (1) a reaction between an aromatic halide and an organic boron compound, (2) a reaction between an aromatic halide and a compound having a terminal alkynyl group, or (3) a reaction between an aromatic halide and an alkenyl group. A carbon-carbon bond forming method for forming a carbon-carbon bond by reacting with a compound having a raw material liquid (i) containing the aromatic halide and the organic boron compound, the aromatic halide and a compound having an alkynyl group at the end thereof (ii), or a raw material solution (iii) containing the aromatic halide and the compound having an alkenyl group, a platinum group metal ion-supported catalyst By introducing into the filled container from the introduction route of the filled container, passing the raw material solution through the platinum group metal ion-supported catalyst, and discharging the reaction solution from the discharge route of the filled container, A method for forming a carbon-carbon bond, wherein a reaction for forming a carbon-carbon bond is carried out, and the supported platinum group metal ion catalyst is the supported platinum group metal ion catalyst according to any one of claims 1 to 8.

In the carbon-carbon bond forming method, the carbon-carbon bond forming reaction is preferably carried out in the presence of an inorganic base.

In the carbon-carbon bond forming method, the raw material solution (i), the raw material solution (ii), or the raw material solution (iii) is an inorganic base in which the raw material and the inorganic base are dissolved in water or a hydrophilic solvent. The raw material solution for dissolution of an inorganic base, which is a raw material solution for dissolution, is introduced into the filled container through an introduction route of the filled container filled with the platinum group metal ion-supported catalyst, and is introduced into the platinum group metal ion-supported catalyst. It is preferable that the carbon-carbon bond forming reaction is carried out by passing the inorganic base-dissolved raw material solution and discharging the reaction solution from the discharge path of the filling container.

In the carbon-carbon bond forming method, the raw material solution (i), the raw material solution (ii), or the raw material solution (iii) is a hydrophobic solvent raw material solution in which raw materials are dissolved in a hydrophobic organic solvent. A mixture of the hydrophobic solvent raw material liquid and the inorganic base aqueous solution in which the inorganic base is dissolved is introduced into the filled container through the introduction route of the filled container filled with the platinum group metal ion-supported catalyst. , passing the hydrophobic solvent raw material solution and the inorganic base aqueous solution through the platinum group metal ion-supported catalyst, and discharging the reaction solution from the discharge route of the filled container, thereby forming a carbon-carbon bond formation reaction It is preferable to

According to the present invention, a platinum group metal ion-supported catalyst capable of performing a carbon-carbon bond forming reaction in a high yield even in aromatic bromides, and a carbon-carbon bond-forming method using the platinum group metal ion-supported catalyst are provided. can provide.

FIG. 4 is an SEM photograph of a first example monolith morphology; FIG. FIG. 4 is an SEM photograph of a second example monolith morphology; FIG. FIG. 11 is an SEM photograph of a third example monolith morphology; FIG. FIG. 4 is a diagram obtained by transferring a skeleton portion appearing as a cross section of the SEM photograph of FIG. 3 ; FIG. 4 is an SEM photograph of a fourth example monolith morphology; FIG. FIG. 4B is a schematic diagram of the co-continuous structure of the fourth monolith. FIG. 10 is an SEM photograph of an example morphology of monolith intermediate (4). FIG. FIG. 4 is a schematic cross-sectional view of a projection; FIG. 10 is a SEM photograph of a morphological example of a monolith of No. 5-1. FIG. 1 is a SEM photograph of a monolithic intermediate obtained in Example 1. FIG. 1 is an SEM photograph of a monolith obtained in Example 1. FIG.

An embodiment of the present invention will be described below. This embodiment is an example of implementing the present invention, and the present invention is not limited to this embodiment.

（式中Ｒ^１は、置換されていてもよい炭素数４から２２のアルキル基；または、置換されていてもよい炭素数１から６のアルキル基、ハロゲン原子、置換されていてもよい炭素数１から６のアルコキシ基、置換されていてもよいアミノ基、シアノ基、もしくはニトロ基で置換されていてもよいベンジル基；を表し、Ｒ^２，Ｒ^３は、それぞれ独立して炭素数１から４のアルキル基を表し、Ｌは、リンカー部位を表し、Ｐｏｌｙｍｅｒは、高分子鎖を表す。）
で表される高分子鎖から構成されるイオン交換体に、白金族金属イオンおよび白金族金属錯イオンのうち少なくとも１つが担持されている触媒である。 <Platinum group metal ion-supported catalyst>
[Ion exchanger]
The platinum group metal ion-supported catalyst according to the embodiment of the present invention has the general formula (1)

(In the formula, R ¹ is an optionally substituted alkyl group having 4 to 22 carbon atoms; or an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, or an optionally substituted carbon number 1 to ⁶ alkoxy groups, optionally substituted amino groups, cyano groups ^, or benzyl groups optionally substituted with nitro groups; 4 represents an alkyl group, L represents a linker moiety, and Polymer represents a polymer chain.)
It is a catalyst in which at least one of platinum group metal ions and platinum group metal complex ions is supported on an ion exchanger composed of a polymer chain represented by.

As a result of intensive studies by the present inventors, at least one of platinum group metal ions and platinum group metal complex ions was supported on an ion exchanger composed of a polymer chain represented by the general formula (1). The catalyst, that is, the catalyst in which the platinum group metal in the state of ions is supported on the ion exchanger composed of the polymer chain represented by the general formula (1), is a carbon- It has been found that carbon bond forming reactions can be carried out. In particular, the inventors have found that the yield is increased even when an aromatic bromide is used as a starting material in a fixed-bed continuous flow carbon-carbon bonding reaction.

This is because the ion exchanger composed of the polymer chain represented by the general formula (1) has, as R ¹ , the alkyl group having 4 to 22 carbon atoms or the benzyl group, so that the lipophilicity is increased. This is believed to be due to efficient contact between the organic phase and the aqueous phase on the surface of the ion exchanger in carbon-carbon bonding reactions such as fixed-bed continuous flow systems.

R ¹ in general formula (1) represents an optionally substituted alkyl group having 4 to 22 carbon atoms. Alternatively, R ¹ is a benzyl group optionally substituted with an optionally substituted alkyl group having 1 to 6 carbon atoms, a benzyl group optionally substituted with a halogen atom, or optionally substituted carbon number a benzyl group optionally substituted with 1 to 6 alkoxy groups, a benzyl group optionally substituted with an amino group optionally substituted, a benzyl group optionally substituted with a cyano group, or a nitro group; It represents an optionally substituted benzyl group. An optionally substituted benzyl group is a benzyl group in which the phenyl group of the benzyl group may be substituted with a substituent.

The alkyl group having 4 to 22 carbon atoms may be linear, branched or cyclic. An alkyl group having 6 to 20 carbon atoms is preferred, and an alkyl group having 6 to 18 carbon atoms is more preferred, from the viewpoints of high reaction yield during production, easy availability of raw materials, and good performance.

The alkyl group having 1 to 6 carbon atoms which may be substituted on the benzyl group may be linear, branched or cyclic. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable, from the viewpoints of easy availability of raw materials and good performance.

The halogen atom which may be substituted on the benzyl group includes a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom is preferable from the viewpoints of inexpensive starting material production and easy availability of the starting material. .

The alkoxy group having 1 to 6 carbon atoms which may be substituted on the benzyl group may be linear, branched or cyclic. An alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group and an ethoxy group are more preferable from the viewpoints of easy availability of raw materials and good performance.

Examples of substituents when "optionally substituted" with an alkyl group having 4 to 22 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms include a nitro group, a cyano group, and a halogen atom. etc.

Examples of the substituent when the amino group is "optionally substituted" include an alkyl group having 1 to 8 carbon atoms, a phenyl group, a fluoroalkyl group having 1 to 4 carbon atoms, and the like.

The alkyl group having 1 to 8 carbon atoms which may be substituted on the amino group may be linear, branched or cyclic. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable, because the reaction yield during production is high.

The fluoroalkyl group having 1 to 4 carbon atoms which may be substituted on the amino group may be linear, branched or cyclic. A fluoroalkyl group having 1 to 2 carbon atoms is preferable, and a trifluoromethyl group and a 2,2,2-trifluoroethyl group are more preferable, in terms of availability of raw materials.

R ¹ in the general formula (1) is preferably an alkyl group having 6 to 20 carbon atoms or a benzyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, and is preferably a dodecyl group or a benzyl group. It is more preferable to have

R ² and R ³ in general formula (1) each independently represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched or cyclic. The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, more preferably a methyl group, from the viewpoint of high reaction yield during production.

L in general formula (1) represents a linker site. Examples of the linker moiety include an alkylene group having 1 to 4 carbon atoms which may be substituted with an oxy group. An ethylene group is preferred, and a methylene group is more preferred.

Polymer in general formula (1) represents a polymer chain. Examples of polymer chains include aromatic vinyl 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; crosslinked polymers such as (meth)acrylic polymers such as polymethacrylic acid esters and polyacrylic acid esters. The polymer chain may be a polymer obtained by copolymerizing a single vinyl monomer and a cross-linking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a cross-linking agent. may be blended. Among these, crosslinked polymers of aromatic vinyl polymers are preferred because of the ease of forming a continuous structure, the ease of introducing ion-exchange groups, high mechanical strength, and high stability against acids or alkalis. In particular, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred, and styrene-divinylbenzene copolymers are preferred.

The ion exchanger according to the present embodiment may be either a particulate ion exchanger or a non-particulate ion exchanger. It is preferably a non-particulate organic porous ion exchanger.

[Nonparticulate organic porous ion exchanger]
The non-particulate organic porous ion exchanger is obtained by introducing ion exchange groups into a monolithic organic porous material having a continuous skeleton phase and a continuous pore phase. The non-particulate organic porous ion exchanger composed of the polymer chains represented by the general formula (1) is a basic monolithic organic porous anion exchanger. A monolithic organic porous body has a large number of communicating pores serving as channels between skeletons. In the present specification, "monolithic organic porous material" is simply referred to as "monolith", and "monolithic organic porous ion exchanger" is simply referred to as "monolithic ion exchanger". The "monolithic organic porous intermediate" which is the body (precursor) is also simply referred to as "monolithic intermediate".

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

The non-particulate organic porous ion exchanger consists of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, and the average diameter of the continuous pores is in the range of 1 to 1000 μm. , the total pore volume is in the range of 0.5 to 50 mL/g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 mg equivalent/g, and the ion exchange group is an organic porous preferably distributed throughout the ion exchanger. A continuous skeleton phase and a continuous pore phase are observed by SEM images.

The thickness of the continuous skeleton of the non-particulate organic porous ion exchanger in a dry state is preferably in the range of 1 to 100 μm. The thickness of the continuous framework in the dry state of the non-particulate organic porous ion exchanger is determined by SEM observation. If the thickness of the continuous skeleton is less than 1 μm, the ion exchange capacity per volume may be reduced, or the mechanical strength may be reduced. In some cases, the non-particulate organic porous ion exchanger may be deformed, particularly when the liquid is passed at a high flow rate. If the thickness of the continuous skeleton exceeds 100 μm, the skeleton becomes too thick, and the pressure loss during passage of the raw material liquid may increase.

The average diameter of continuous pores in the non-particulate organic porous ion exchanger in a dry state is preferably in the range of 1 to 1000 μm. The average diameter of continuous pores in the dry state of the non-particulate organic porous ion exchanger is measured by mercury porosimetry and refers to the maximum value of the pore distribution curve obtained by mercury porosimetry. If the average diameter of the continuous pores is less than 1 μm, when the platinum group metal ion-supported catalyst is packed in a column and the reaction solution is passed through, the pressure loss during the passing of the solution may increase. . If the average diameter of the continuous pores exceeds 1000 μm, when the platinum group metal ion-supported catalyst is packed in a column and the reaction solution is passed through, the contact between the reaction solution and the monolithic ion exchanger becomes insufficient, resulting in insufficient catalyst Activity may decrease.

The total pore volume in the dry state of the nonparticulate organic porous ion exchanger is preferably in the range of 0.5 to 50 mL/g. The total dry pore volume of the non-particulate organic porous ion exchanger is measured by mercury porosimetry. If the total pore volume is less than 0.5 mL/g, when the platinum group metal ion-supported catalyst is packed in a column and the reaction solution is passed through, the pressure loss during the passing of the solution may increase. There is If the total pore volume exceeds 50 mL/g, the mechanical strength of the non-particulate organic porous ion exchanger decreases, and when the platinum group metal ion-supported catalyst is packed in a column and the reaction liquid is passed through, In particular, when the liquid is passed at a high flow rate, the monolithic ion exchanger may be deformed, resulting in an increase in pressure loss when the liquid is passed.

The ion exchange capacity per weight of the nonparticulate organic porous ion exchanger in a dry state is preferably in the range of 1 to 9 mg equivalent/g. The ion exchange capacity per unit weight of the non-particulate organic porous ion exchanger in a dry state is measured by a method such as neutralization titration or precipitation titration. If the ion exchange capacity is less than 1 mg equivalent/g, the amount of platinum group metal ions or platinum group metal complex ions that can be supported may decrease. If the ion exchange capacity exceeds 9 mg equivalent/g, the conditions for introducing reaction of ion exchange groups become severe, and oxidative deterioration of the monolith may proceed remarkably.

In the non-particulate organic porous ion exchanger, the introduced ion exchange groups are preferably distributed not only on the surface of the monolith but also inside the skeleton of the monolith, that is, in the organic porous ion exchanger. , more preferably uniformly distributed. "The ion-exchange groups are uniformly distributed in the organic porous ion-exchanger" means that the ion-exchange groups are distributed on the surface and inside the skeleton of the organic porous ion-exchanger at least on the order of μm. point to The distribution of ion exchange groups is confirmed by using an electron probe microanalyzer (EPMA). If the ion-exchange groups are distributed not only on the surface of the monolith but also on the inside of the monolith skeleton, the physical and chemical properties of the surface and inside of the monolith can be made almost uniform, which improves the resistance to swelling and shrinkage. do.

In the non-particulate organic porous ion exchanger, the material constituting the continuous skeleton is an organic polymer material having a crosslinked structure, which is the polymer moiety in the general formula (1). It preferably contains 0.1 to 30 mol% of the crosslinked structural unit, more preferably 0.1 to 20 mol% of the crosslinked structural unit, based on the total structural units constituting the polymer material. .

[First to Fifth Monolithic Ion Exchangers]
As a more specific embodiment of the non-particulate organic porous ion exchanger, for example, first monolithic organic porous ion exchanger (monolithic ion exchanger) to fifth monolithic organic porous ion exchanger shown below Exchangers (monolithic ion exchangers) may be mentioned. In the following description, descriptions of the same configurations as those of the non-particulate organic porous ion exchanger are omitted.

(First monolithic ion exchanger)
The first monolithic ion exchanger has a continuous macropore structure with interconnecting macropores and common openings (mesopores) in the walls of the macropores with an average diameter ranging from 1 to 1000 μm, and a total pore volume of 1 ~50 mL/g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 mg equivalent/g, and the ion exchange groups are distributed in the organic porous ion exchanger. It is an exchanger.

The first monolithic ion exchanger is a continuous macropore structure with continuous macropores, as shown in FIG. A first monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2002-306976.

The first monolithic ion exchanger has macropores that are interconnected and common openings (mesopores) located in the walls of the macropores. Mesopores have overlapping portions where macropores overlap. The overlapping portion of the mesopores preferably has an average diameter of 1 to 1000 μm, more preferably 10 to 200 μm, even more preferably 20 to 200 μm in a dry state. The average diameter of the openings of the dry first monolith is measured by mercury porosimetry and refers to the maximum of the pore distribution curve obtained by mercury porosimetry.

Most of such first monolithic ion exchangers have an open pore structure in which the voids formed by macropores and mesopores serve as channels. If the average diameter of the overlapping portions of the mesopores in the dry state is less than 1 μm, when the reaction solution is passed through a column filled with the platinum group metal ion-supported catalyst, the pressure loss at the time of passing the solution is significantly increased. may be lost. If the average diameter of the overlapping mesopores exceeds 1000 μm in a dry state, contact between the reaction liquid and the monolithic ion exchanger is impeded when the platinum group metal ion-supported catalyst is packed in a column and the reaction liquid is passed through. sufficient, and the catalytic activity may decrease. The number of overlapping macropores is, for example, 1 to 12 per macropore, and 3 to 10 in most cases. Since the first monolithic ion exchanger has the above-described continuous macropore structure, it is possible to form a group of macropores and a group of common pores almost uniformly, as described in JP-A-8-252579. The pore volume and specific surface area can be remarkably increased compared to the particle aggregation type porous material.

The total pore volume per weight of the first monolithic ion exchanger is preferably in the range of 1 to 50 mL/g, more preferably in the range of 2 to 30 mL/g. If the total pore volume per unit weight in a dry state is less than 1 mL/g, when the platinum group metal ion-supported catalyst is packed in a column and the reaction solution is passed through, the pressure loss during the passing of the solution is large. Furthermore, the permeation amount per unit cross-sectional area becomes small, and the processing capacity may decrease. If the total pore volume per unit weight in the dry state exceeds 50 mL / g, the mechanical strength decreases, and when the catalyst supported on platinum group metal ions is packed in a column and the reaction solution is passed through, it is particularly high. The monolithic ion exchanger may be deformed when the liquid is passed at the flow rate.

The ion exchange capacity per weight in the dry state is as described above. Further, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

(Method for manufacturing the first monolithic ion exchanger)
The first monolithic ion exchanger can be produced, for example, by the following method.

For example, first, an oil-soluble monomer containing no ion-exchange group, a surfactant, water, and optionally a polymerization initiator are mixed to obtain a water-in-oil emulsion. This water-in-oil emulsion can then be polymerized to form a first monolith.

The oil-soluble monomer containing no ion-exchange group used in the production of the first monolith refers to a monomer containing no ion-exchange group, low solubility in water, and lipophilicity. This monomer is, for example, styrene, α-methylstyrene, vinylbenzyl chloride, ethylene, propylene, vinyl chloride, vinyl bromide, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate. , butanediol diacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, ethylene glycol dimethacrylate, 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 preferably in the range of, for example, 0.3 to 10 mol% of the total oil-soluble monomer. The range of 0.3 to 5 mol % is preferable in that the ion exchange groups can be quantitatively introduced in the subsequent step and sufficient mechanical strength for practical use can be ensured.

The surfactant used in the production of the first monolith should be capable of forming a water-in-oil (W/O) emulsion when an oil-soluble monomer containing no ion-exchange group is mixed with water. , there are no particular restrictions. Surfactants include, for example, nonionic surfactants such as sorbitan monooleate, sorbitan monolaurate, polyoxyethylene nonylphenyl ether; anionic surfactants such as potassium oleate, sodium dodecylbenzene sulfonate, dioctyl sodium sulfosuccinate; active agents; cationic surfactants such as distearyldimethylammonium chloride; amphoteric surfactants such as lauryldimethylbetaine. These surfactants can be used singly or in combination of two or more. 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 surfactant added may be, for example, in the range of about 2 to 70% of the total amount of the oil-soluble monomer and surfactant. Alcohols such as methanol and stearyl alcohol; carboxylic acids such as stearic acid; hydrocarbons such as octane, dodecane and toluene; cyclic ethers such as tetrahydrofuran and dioxane; You can also let

In the production of the first monolith, a compound that generates radicals by heat and light irradiation is preferably used as a polymerization initiator that is optionally used when the monolith is formed by polymerization. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, peroxide. Potassium sulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, tetramethylthiuram disulfide and the like. However, depending on the case, there are systems in which polymerization proceeds only by heating or light irradiation without adding a polymerization initiator.

In the production of the first monolith, the polymerization conditions for polymerizing the water-in-oil emulsion can be selected from various conditions depending on the type of monomer, the initiator system, and the like. When, for example, azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, or the like is used as the polymerization initiator, for example, in a sealed container under an inert atmosphere, for example, heating is performed at 30 to 100° C. for 1 to 48 hours. polymerize it. When hydrogen peroxide-ferrous chloride, sodium persulfate-sodium sulfite, or the like is used as the polymerization initiator, polymerization is carried out, for example, at 0 to 30° C. for 1 to 48 hours in a sealed container under an inert atmosphere. All you have to do is After completion of the polymerization, the content is taken out and, for example, Soxhlet extraction is performed with a solvent such as isopropanol to remove unreacted monomers and residual surfactant, whereby a first monolith can be obtained.

Methods of introducing ion exchange groups into the first monolith include, for example, the following methods (1) and (2). (1) Polymerizing a monomer containing an ion-exchange group instead of a monomer containing no ion-exchange group, for example, a monomer in which an ion-exchange group is introduced into the oil-soluble monomer containing no ion-exchange group, It can be made into a monolithic ion exchanger in one step. (2) monomers that do not contain ion-exchange groups can be polymerized to form a first monolith and then introduced with ion-exchange groups;

As a method for introducing ion exchange groups into the first monolith, known methods such as polymer reaction and graft polymerization can be used. Methods for introducing a strongly basic anion exchange group (quaternary ammonium group) include, for example, the following methods (1) to (3). In method (1), if the monolith is a styrene-divinylbenzene copolymer or the like, chloromethyl groups can be introduced by introducing chloromethyl methyl ether or the like, followed by reaction with a desired tertiary amine. In method (2), a monolith can be prepared by copolymerizing chloromethylstyrene and divinylbenzene, reacted with the desired tertiary amine and introduced. In the method (3), a radical initiation group or a chain transfer group can be introduced into the monolith, followed by graft polymerization of glycidyl methacrylate, followed by reaction with a desired tertiary amine.

（式中Ｌは、リンカー部位を表し、Ｐｏｌｙｍｅｒは、高分子鎖を表し、Ｘは、ハロゲン原子、置換されていてもよい炭素数１から８のアルキルスルホニル基、または置換されていてもよいベンゼンスルホニル基を表す。）
で表される高分子鎖と、
一般式（３）

（式中Ｒ^１は、置換されていてもよい炭素数４から２２のアルキル基；または、置換されていてもよい炭素数１から６のアルキル基、ハロゲン原子、置換されていてもよい炭素数１から６のアルコキシ基、置換されていてもよいアミノ基、シアノ基、もしくはニトロ基で置換されていてもよいベンジル基；を表し、Ｒ^２，Ｒ^３は、それぞれ独立して炭素数１から４のアルキル基を表す。）
で表される第三級アミンと、
を反応させることによって、第１のモノリスイオン交換体を製造することができる。 For example, general formula (2)

(In the formula, L represents a linker site, Polymer represents a polymer chain, X represents a halogen atom, an optionally substituted alkylsulfonyl group having 1 to 8 carbon atoms, or an optionally substituted benzene represents a sulfonyl group.)
A polymer chain represented by
General formula (3)

(In the formula, R ¹ is an optionally substituted alkyl group having 4 to 22 carbon atoms; or an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, or an optionally substituted carbon number 1 to ⁶ alkoxy groups, optionally substituted amino groups, cyano groups ^, or benzyl groups optionally substituted with nitro groups; represents the alkyl group of 4.)
A tertiary amine represented by
A first monolithic ion exchanger can be produced by reacting

In this method for producing an ion exchanger, the definitions of L and Polymer in general formula (2) and the definitions of R ¹ , R ² and R ³ in general formula (3) are the same as L, Polymer, The definitions of R ¹ , R ² and R ³ are the same as those of R 1 , R 2 and R 3 .

X in the general formula (2) represents a halogen atom, an optionally substituted alkylsulfonyl group having 1 to 8 carbon atoms, or an optionally substituted benzenesulfonyl group.

Examples of the halogen atom for X include a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom is preferable from the viewpoint of inexpensive production raw materials.

The alkyl group in the alkylsulfonyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. A methylsulfonyl group and an ethylsulfonyl group are preferred from the viewpoints of easy availability of raw materials, high reaction yield during production, and the like.

The alkylsulfonyl group having 1 to 8 carbon atoms may be substituted with a cyano group, a nitro group, a halogen atom or the like, preferably a halogen atom, more preferably a fluorine atom, from the viewpoint of high reaction yield.

The benzenesulfonyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, a halogen atom or the like, and a methyl group is preferred from the viewpoint of easy availability of starting materials.

The reaction between the polymer chain represented by the general formula (2) and the tertiary amine represented by the general formula (3) is carried out by mixing them in an organic solvent such as tetrahydrofuran, DMF, toluene, etc. For example, it is carried out by heating at a temperature of 20 to 130° C. for 4 to 60 hours. After the reaction, it may be washed with an organic solvent such as methanol or tetrahydrofuran, water, or the like.

(Second monolithic ion exchanger)
In the second monolithic ion exchanger, organic polymer particles with an average particle size of 1 to 50 μm are aggregated to form a three-dimensionally continuous skeleton portion, and an average diameter of 20 to 100 μm is formed between the skeletons. It has three-dimensionally continuous pores, the total pore volume is in the range of 1 to 10 mL / g, and the ion exchange capacity per weight in a dry state is in the range of 1 to 9 mg equivalent / g. , is a monolithic ion exchanger in which the ion exchange groups are distributed in an organic porous ion exchanger.

The second monolithic ion exchanger, as shown in FIG. 2, is a particle-aggregated structure in which particles are aggregated. A second monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-007550.

In the second monolithic ion exchanger, organic polymer particles having a crosslinked structural unit and having an average particle size in a dry state of preferably in the range of 1 to 50 μm, more preferably in the range of 1 to 30 μm are aggregated and three-dimensionally continuous. It has a skeletal part. The second monolithic ion exchanger has three-dimensionally continuous pores (continuous pores) having an average diameter in a dry state of preferably in the range of 20 to 100 μm, more preferably in the range of 20 to 90 μm between the continuous skeletons. have A SEM photograph of an arbitrarily extracted portion of the cross section of the second monolithic ion exchanger in a dry state is taken, the diameters of the organic polymer particles of all particles in the SEM photograph are measured, and the average value thereof is calculated as the average particle diameter. and The average diameter of the continuous pores in the dry state is determined by the mercury porosimetry method as in the case of the first monolithic ion exchanger.

If the average particle size of the organic polymer particles is less than 1 μm in a dry state, the average diameter of continuous pores between skeletons may be as small as less than 20 μm in a dry state. If the average particle size of the organic polymer particles exceeds 50 μm, pressure loss may increase when the platinum group metal ion-supported catalyst is packed in a column and the reaction liquid is passed through the column. Further, when the average diameter of the continuous pores is less than 20 μm in a dry state, when the catalyst supported on platinum group metal ions is filled in the column and the reaction liquid is passed through, the pressure when the reaction liquid is passed through The loss may become large. If the average diameter of the above-mentioned continuous pores exceeds 100 μm in a dry state, contact between the reaction solution and the monolithic ion exchanger is impeded when the platinum group metal ion-supported catalyst is packed in a column and the reaction solution is passed through. may be sufficient.

The total pore volume per dry weight of the second monolithic ion exchanger is preferably in the range of 1 to 10 mL/g. If the total pore volume is less than 1 mL/g, pressure loss may increase when the platinum group metal ion-supported catalyst is packed in a column and the reaction solution is passed through. Furthermore, the permeation amount per unit cross-sectional area becomes small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when the reaction solution is passed through a column filled with a platinum group metal ion-supported catalyst, especially at a high flow rate. The monolithic ion exchanger may be deformed.

The ion exchange capacity per weight in the dry state is as described above. Further, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

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

For example, a second monolith can be obtained by mixing a vinyl monomer, a specific amount of a cross-linking agent, an organic solvent and a polymerization initiator, and allowing the mixture to polymerize under static conditions.

The vinyl monomers used to make the second monolith are similar to the monomers used to make the first monolith.

The cross-linking agent used to prepare the second monolith preferably contains at least two polymerizable vinyl groups in the molecule and is highly soluble in organic solvents. Cross-linking agents are, for example, divinylbenzene, divinylbiphenyl, ethylene glycol dimethacrylate. These cross-linking 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 in terms of high mechanical strength and stability against hydrolysis. The amount of cross-linking agent used relative to the total amount of vinyl monomer and cross-linking agent ({cross-linking agent/(vinyl monomer+cross-linking agent)}×100) is, for example, in the range of 1 to 5 mol %, preferably in the range of 1 to 4 mol %. is.

The organic solvent used in the production of the second monolith dissolves the vinyl monomer and the cross-linking agent, but hardly dissolves the polymer produced by polymerizing the vinyl monomer.In other words, the polymer produced by polymerizing the vinyl monomer. It is a poor solvent for For example, when the vinyl monomer is styrene, the organic solvent includes alcohols such as methanol, butanol and octanol; chain ethers such as diethyl ether and ethylene glycol dimethyl ether; chain saturated hydrocarbons such as hexane, octane and decane. etc.

The polymerization initiator used for producing the second monolith is preferably a compound that generates radicals by heat and light irradiation. The polymerization initiator is preferably oil-soluble. Polymerization initiators include, 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), 2,2′-azobisdimethyl isobutyrate, 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 relative to the total amount of vinyl monomer and cross-linking agent ({polymerization initiator/(vinyl monomer+cross-linking agent)}×100) is, for example, in the range of about 0.01 to 5 mol %.

In the production of the second monolith, polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide When potassium persulfate or the like is used, it may be polymerized by heating at 30 to 100° C. for 1 to 48 hours, for example, in a sealed container under an inert atmosphere. After completion of the polymerization, the content is taken out and extracted with a solvent such as acetone for the purpose of removing the unreacted vinyl monomer and the organic solvent to obtain a second monolith.

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

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.

(Third monolithic ion exchanger)
The third monolithic ion exchanger has a continuous macropore structure in which bubble-like macropores overlap each other, and the overlapping portions are openings with an average diameter of 30 to 300 μm, and the total pore volume is 0.5 to 10 mL. / g, the ion exchange capacity per weight in a dry state is in the range of 1 to 9 mg equivalent / g, the ion exchange groups are distributed in the organic porous ion exchanger, and the continuous macropores In the SEM image of the cross section of the structure, it is a monolithic ion exchanger in which the skeleton area appearing in the cross section is in the range of 25 to 50% of the image area.

The third monolithic ion exchanger is a continuous macropore structure, similar to the first monolithic ion exchanger, as shown in FIG. A third monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-062512.

Continuous pores have overlapping portions where macropores overlap. The overlapping portion preferably has a dry average diameter of 30 to 300 μm, more preferably 30 to 200 μm, and even more preferably 40 to 100 μm. This average diameter is measured by mercury porosimetry and refers to the maximum value of the pore distribution curve obtained by mercury porosimetry. If the average diameter of the openings in a dry state is less than 30 μm, when the catalyst supported on platinum group metal ions is packed in a column and the reaction solution is passed through, the pressure loss during the passing of the solution may increase. If it exceeds 300 μm, the contact between the reaction solution and the monolithic ion exchanger may be insufficient.

In the third monolithic ion exchanger, in the SEM image of the cut surface of the continuous macropore structure in the dry state, the skeleton area appearing in the cross section is, for example, 25 to 50% of the image area, preferably It is in the range of 25-45%. If the area of the skeleton appearing in the cross section is less than 25% of the image area, the skeleton becomes thin and the mechanical strength decreases. In addition, the monolithic ion exchanger may be deformed, especially when the liquid is passed at a high flow rate. If the area of the skeleton appearing in the cross section exceeds 50% of the image area, the skeleton becomes too thick, and when the reaction liquid is passed through a column filled with a platinum group metal ion-supported catalyst, the reaction liquid is passed. Pressure loss may increase.

The conditions for obtaining the SEM image may be any conditions as long as the skeletal portion appearing in the cross section of the cut surface is clearly visible, for example, the magnification is 100 to 600, and the photographic area is about 150 mm×100 mm. The SEM observation is preferably performed using three or more images of different cut points and photographed points taken at arbitrary positions on arbitrary cut surfaces of the third monolithic ion exchanger, excluding subjectivity. The third monolithic ion exchanger that is cleaved is in a dry state. The skeletal portion of the cut surface in the SEM image will be described with reference to FIGS. 3 and 4. FIG. In FIGS. 3 and 4, what appears in the cross section having a generally irregular shape is the “skeleton part (reference numeral 12) appearing in the cross section”, and the circular pores appearing in FIG. 3 are openings (mesopores) and have relatively large curvatures Those with curved surfaces are macropores (reference numeral 13 in FIG. 4). The skeleton area appearing in the cross section of FIG. 4 is 28% of the rectangular image area 11 .

In the SEM image, as a method for measuring the area of the skeletal part appearing in the cross section of the cut surface, there is a method of calculating the skeletal part by performing known computer processing or the like to specify it, and then calculating it automatically or manually by a computer or the like. As manual calculation, there is a method of replacing an irregularly shaped object with a set of squares, triangles, circles, trapezoids, etc., and stacking them to determine the area.

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

The ion exchange capacity per weight in the dry state is as described above. Further, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

(Third manufacturing method of monolithic ion exchanger)
A third monolithic ion exchanger can be produced, for example, by the following method.

For example, first, a water-in-oil emulsion is prepared by stirring a mixture of an oil-soluble monomer containing no ion-exchange groups, a surfactant and water. Then, a third monolith can be obtained by performing the following steps I, II, and III. In step I, a water-in-oil emulsion is polymerized to obtain, for example, a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume in the range of 5 to 16 mL/g (hereinafter also referred to as monolith intermediate (3). ) can be obtained. In step II, a vinyl monomer, a cross-linking agent having at least two vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the cross-linking agent are dissolved but the polymer produced by polymerization of the vinyl monomer is not dissolved, and a polymerization initiator. Prepare a mixture containing In step III, the mixture obtained in step II is allowed to stand and polymerized in the presence of the monolithic intermediate (3) obtained in step I to obtain a monolithic intermediate (3) having a thicker skeleton than that of the monolithic intermediate (3). A third monolith can be obtained.

Step I is the same as the first monolithic ion exchanger manufacturing method.

The monolithic intermediate (3) obtained in step I has a continuous macropore structure. When this is allowed to coexist in the polymerization system, a porous structure having a thick skeleton can be formed using the structure of the monolithic intermediate (3) as a mold. The crosslink density of the polymer material is, for example, in the range of 0.3 to 10 mol%, preferably in the range of 0.3 to 5 mol%, based on the total structural units constituting the polymer material of the monolithic intermediate (3). It preferably contains a structural unit.

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

In the monolithic intermediate (3) obtained in step I, the average diameter of the openings (mesopores), which are the overlapping portions of macropores, ranges from 20 to 200 μm in a dry state, for example.

In step II, a vinyl monomer, a cross-linking agent having at least two vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the cross-linking agent are dissolved but the polymer produced by polymerization of the vinyl monomer is not dissolved, and a polymerization initiator. It is a step of preparing a mixture containing It should be noted that either step I or step II may be performed first.

The vinyl monomer used in step II may be any lipophilic vinyl monomer that contains a polymerizable vinyl group in the molecule and is highly soluble in organic solvents. ) is preferably selected to produce a polymeric material of the same type or similar. Specific examples of these vinyl monomers are the same as the vinyl monomers used in the production of the first monolith.

The amount of the vinyl monomer added in step II is, for example, 3 to 50 times, preferably 4 to 40 times, the weight of the monolithic intermediate (3) coexisting during polymerization.

The cross-linking agent used in step II is similar to the cross-linking agent used in the production of the second monolith.

The organic solvent used in step II is similar to the organic solvent used in the production of the second monolith. The amount of these organic solvents used is preferably such that the concentration of the vinyl monomer is, for example, 30 to 80% by weight.

The polymerization initiator used in step II is the same as the polymerization initiator used in the production of the second monolith.

In step III, for example, the mixture obtained in step II is allowed to stand and polymerized in the presence of the monolithic intermediate (3) obtained in step I to obtain a thicker skeleton than the monolithic intermediate (3). A third monolith with a skeleton can be obtained. A third monolith can be obtained by allowing the continuous macropore structure monolith intermediate (3) to exist in the above polymerization system.

In step III, for example, the monolithic intermediate (3) is left impregnated with the mixture (solution) in a reaction vessel. The blending ratio of the mixture obtained in Step II and the monolithic intermediate (3) is, for example, that the amount of the vinyl monomer added is in the range of 3 to 50 times the weight of the monolithic intermediate (3), preferably 4 to 50 times. It suffices to mix so that the range is 40 times. In the reaction vessel, the vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the monolithic intermediate (3) which is left standing, and the polymerization proceeds within the skeleton of the monolithic intermediate (3).

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

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

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

The fourth monolithic ion exchanger has a continuous framework phase 1 (continuous framework) and a continuous pore phase 2 (continuous pore), which are intertwined and together, as shown in FIGS. It is a co-continuous structure 10 that is three-dimensionally continuous. The void phase 2 has higher continuity than the above-described first and second monoliths, and there is almost no deviation in size. The fourth monolithic ion exchanger is considered to have high mechanical strength due to its thick skeleton. A fourth monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-067982.

The continuous skeleton is composed of a vinyl polymer (aromatic vinyl polymer, etc.) containing crosslinked structural units in the range of 0.1 to 5.0 mol% in all structural units into which ion exchange groups are introduced, and a continuous skeleton is three-dimensionally continuous with a dry thickness of, for example, 1 to 60 μm, preferably 3 to 58 μm. If the crosslinked structural unit is less than 0.1 mol%, the mechanical strength may be insufficient, and if it exceeds 5.0 mol%, the structure of the porous body may easily deviate from the co-continuous structure. . If the thickness of the continuous skeleton is less than 1 μm in a dry state, the monolithic ion exchanger deforms when the platinum group metal ion-supported catalyst is packed in a column and the reaction solution is passed through, especially when the solution is passed at a high flow rate. It may happen. If the thickness of the continuous skeleton exceeds 60 μm in a dry state, the skeleton becomes too thick, and when the reaction solution is passed through a column filled with a platinum group metal ion-supported catalyst, the pressure loss increases during the passage. Sometimes.

The continuous pores are three-dimensionally continuous between the continuous skeletons in a dry state, for example, having an average diameter in the range of 10 to 200 μm, preferably 15 to 180 μm. If the average diameter of the continuous pores is less than 10 μm in a dry state, the pressure loss at the time of passing the reaction liquid will increase when filling the column with the platinum group metal ion-supported catalyst and passing the reaction liquid. Sometimes. If the average diameter exceeds 200 μm, when the platinum group metal ion-supported catalyst is packed in a column and the reaction liquid is passed through, the contact between the reaction liquid and the monolithic ion exchanger may be insufficient.

The aforementioned average diameter is measured by mercury porosimetry and refers to the maximum value of the pore distribution curve obtained by mercury porosimetry. The thickness of the continuous skeleton in a dry state is determined by SEM observation of the fourth monolithic ion exchanger in a dry state. Specifically, the SEM observation of the fourth monolithic ion exchanger in a dry state is performed at least three times, the thickness of the skeleton in the obtained images is measured, and the average value thereof is taken as the thickness of the continuous skeleton. The skeleton is rod-shaped and has a circular cross-sectional shape, but may include 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 dry weight of the fourth monolithic ion exchanger is, for example, in the range of 0.5 to 10 mL/g. If the total pore volume is less than 0.5 mL/g, when the platinum group metal ion-supported catalyst is packed in a column and the reaction solution is passed through, the pressure loss during the passing of the solution may increase. Furthermore, the amount of permeating fluid per unit cross-sectional area becomes small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when the reaction solution is passed through a column filled with a platinum group metal ion-supported catalyst, especially at a high flow rate. The monolithic ion exchanger may be deformed. Furthermore, the contact efficiency between the reaction liquid and the monolithic ion exchanger may decrease.

Examples of the vinyl polymer (aromatic vinyl polymer) constituting the continuous skeleton include polystyrene, poly(α-methylstyrene), polyvinylbenzyl chloride and the like. The above polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a cross-linking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a cross-linking agent, or a blend of two or more types of polymers. may have been Among these organic polymer materials, styrene-divinylbenzene-based co-polymers are preferred because of their ease of formation of co-continuous structures, ease of introduction of ion-exchange groups, high mechanical strength, and high stability against acids and alkalis. Polymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred.

The ion exchange capacity per weight in the dry state is as described above. Further, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

(Fourth method for producing a monolithic inion exchanger)
A fourth monolithic ion exchanger can be produced, for example, by the following method.

For example, a fourth monolith can be obtained by preparing a water-in-oil emulsion and then carrying out the following steps I to III. In step I, for example, a water-in-oil emulsion is polymerized to obtain a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume of, for example, more than 16 mL/g and 30 mL/g or less (hereinafter referred to as a monolith intermediate). (4)) can be obtained. In step II, for example, an aromatic vinyl monomer, a cross-linking agent in the range of 0.3 to 5 mol% of all oil-soluble monomers having at least two or more vinyl groups in one molecule, an aromatic vinyl monomer or cross-linking A mixture containing an organic solvent and a polymerization initiator is prepared in which the agent is dissolved but the polymer formed by polymerization of the aromatic vinyl monomer is not dissolved. In step III, for example, the mixture obtained in step II is allowed to stand and polymerized in the presence of the monolith intermediate (4) obtained in step I to obtain a fourth monolith.

Step I in the fourth monolith manufacturing method is the same as the first monolith ion exchanger manufacturing method.

The monolithic intermediate (4) obtained in step I is, for example, an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. The crosslink density of the polymer material is, for example, in the range of 0.1 to 5 mol%, preferably in the range of 0.3 to 3 mol%, based on the total structural units constituting the polymer material. there is

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

The total pore volume per weight of the monolithic intermediate (4) obtained in step I is, for example, greater than 16 mL/g and less than or equal to 30 mL/g, preferably greater than 16 mL/g and 25 mL/g. It is below. As shown in FIG. 7, the monolithic intermediate (4) has a nearly rod-like skeleton. When this is allowed to coexist in the polymerization system, a porous body having a co-continuous structure can be formed using the structure of the monolithic intermediate (4) as a mold.

In the monolithic intermediate (4) obtained in step I, the average diameter of openings (mesopores), which are the overlapping portions of macropores, is in the range of 5 to 100 μm in a dry state, for example.

In step II in the fourth method for producing a monolith, for example, an aromatic vinyl monomer, in all oil-soluble monomers having at least two or more vinyl groups in one molecule, for example, cross-linking in the range of 0.3 to 5 mol% It is a step of preparing a mixture containing an organic solvent in which an agent, an aromatic vinyl monomer and a cross-linking agent are dissolved but a polymer formed by polymerization of the aromatic vinyl monomer is not dissolved, and a polymerization initiator. It should be noted that either step I or step II may be performed first.

The aromatic vinyl monomer used in step II is not particularly limited as long as it contains a polymerizable vinyl group in the molecule and is highly soluble in an organic solvent. It is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolithic intermediate (4) coexisting in the system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl and vinylnaphthalene. These monomers can be used singly or in combination of two or more. Preferred aromatic vinyl monomers are styrene, vinylbenzyl chloride, and the like.

The amount of the aromatic vinyl monomer added in Step II is, for example, 5 to 50 times, preferably 5 to 40 times, the weight of the monolithic intermediate (4) coexisting during polymerization.

The cross-linking agent used in step II preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in organic solvents. Examples of cross-linking agents include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These cross-linking agents can be used singly or in combination of two or more. The amount of cross-linking agent used is, for example, in the range of 0.3 to 5 mol %, particularly in the range of 0.3 to 3 mol %, based on the total amount of vinyl monomer and cross-linking agent (total oil-soluble monomer). The amount of the cross-linking agent to be used is preferably used so as to be approximately equal to the cross-linking density of the monolithic intermediate (4) coexisting during vinyl monomer/cross-linking agent polymerization. If the amounts of the two used are too different, the resulting monolith will have a biased crosslink density distribution, and when ion-exchange groups are introduced, cracks may easily occur during the ion-exchange group-introducing reaction.

The organic solvent used in Step II is, for example, an organic solvent that dissolves the aromatic vinyl monomer and the cross-linking agent but does not dissolve the polymer produced by polymerizing the aromatic vinyl monomer. It is a poor solvent for the resulting polymer. Organic solvents include, for example, when the aromatic vinyl monomer is styrene, alcohols such as methanol, butanol and octanol; chain (poly)ethers such as diethyl ether, polyethylene glycol and polypropylene glycol; chain saturated hydrocarbons; esters such as ethyl acetate, isopropyl acetate, and ethyl propionate; Even good solvents for polystyrene, such as dioxane, THF, and toluene, can be used as organic solvents when they are used together with the above-described poor solvents and in small amounts. These organic solvents can be used in an amount such that the concentration of the aromatic vinyl monomer is, for example, 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the aromatic vinyl monomer concentration becomes less than 30% by weight, the polymerization rate may decrease or the monolith structure after polymerization may deviate from the range of the fourth monolith. be. On the other hand, if the aromatic vinyl monomer concentration exceeds 80% by weight, polymerization may proceed excessively.

The polymerization initiator used in step II in the fourth monolith manufacturing method is the same as the polymerization initiator used in step II in the third monolith manufacturing method.

In step III in the fourth method for producing a monolith, for example, the mixture obtained in step II is allowed to stand and polymerized in the presence of the monolith intermediate (4) obtained in step I to obtain a monolith intermediate. This is the step of changing the continuous macropore structure of (4) to a co-continuous structure to obtain a fourth monolith which is a co-continuous structure monolith.

In step III, for example, the monolithic intermediate (4) is left impregnated with the mixture (solution) in a reaction vessel. The blending ratio of the mixture obtained in step II and the monolithic intermediate (4) is, as described above, such that the amount of the aromatic vinyl monomer added is, for example, 5 to 50 times the weight of the monolithic intermediate (4). , preferably in the range of 5 to 40 times. As a result, it is possible to obtain a fourth monolith having a co-continuous structure in which the pores of appropriate size are three-dimensionally continuous and the bone 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 monolithic intermediate (4) which is left still, and polymerization proceeds within the skeleton of the monolithic intermediate (4).

The polymerization conditions for Step III in the fourth method for producing a monolith are the same as the polymerization conditions for Step III in the third method for producing a monolith. A fourth monolith ion exchanger can be obtained by carrying out step IV for introducing ion exchange groups into the fourth monolith obtained in 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.

(Fifth monolithic ion exchanger)
The fifth monolithic ion exchanger consists of a continuous skeleton phase and a continuous pore phase. having a plurality of projections with a size in the range of 4 to 40 μm, an average diameter of continuous pores in the range of 10 to 200 μm, and a total pore volume in the range of 0.5 to 10 mL/g. It is a monolithic ion exchanger in which the ion exchange capacity per weight in a dry state is in the range of 1 to 9 mg equivalent/g, and the ion exchange groups are distributed in the organic porous ion exchanger.

The fifth monolithic ion exchanger is a composite structure having an organic porous body having a continuous skeleton phase and a continuous pore phase, and further having a plurality of particles or a plurality of projections, and a large number of particles or A composite structure having a large number of protrusions. A fifth monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-108294.

A plurality of particles are adhered to the skeleton surface of the organic porous material, and have diameters in the range of 4 to 40 μm, for example. A plurality of protrusions are formed on the skeleton surface of the organic porous material, and the size thereof ranges from 4 to 40 μm in a dry state, for example. The diameter of the particles or the size of the projections is preferably in the range of 4-30 μm, more preferably in the range of 4-20 μm. In this specification, "particles" and "projections" are collectively referred to as "particles and the like".

The average diameter of the open pores in the dry state is preferably in the range of 10-200 μm.

The continuous skeleton phase and continuous pore phase of the fifth monolithic ion exchanger are observed by SEM images. The basic structure of the fifth monolithic ion exchanger includes continuous macropore structures and co-continuous structures. The skeletal phase of the fifth monolithic ion exchanger appears as a continuum of columns, a continuum of concave wall surfaces, or a composite of these, and has a shape clearly different from that of particles and protrusions.

The fifth monolith ion exchanger includes a 5-1 monolith ion exchanger or a 5-2 monolith ion exchanger. The 5-1 monolithic ion exchanger is a continuous macropore structure in which cellular macropores are overlapped with each other, and the overlapped portions form openings having an average diameter of 10 to 120 μm in a dry state. The 5-2 monolithic ion exchanger has a three-dimensionally continuous skeleton having a thickness of, for example, 0.8 to 40 μm in a dry state, and an average diameter of, for example, 8 to 8 in a dry state between the skeletons. It is a co-continuous structure consisting of three-dimensionally continuous pores in the range of 80 μm. The monoliths before the ion exchange groups of the 5-1 and 5-2 monolith ion exchangers are introduced are called 5-1 and 5-2 monoliths. The aforementioned average diameter and dry thickness of the continuous skeleton are determined by the same measurement method as for the fourth monolithic ion exchanger.

As shown in (A) to (E) in FIG. 8, projections 22a to 22e protrude from the skeleton surface 21. As shown in FIG. As shown in (A), the protrusion 22a has a nearly granular shape. As shown in (B), the protrusion 22b is hemispherical. As shown in (C), the protrusion 22c has a shape like a bulge on the skeleton surface. As shown in (D), the length in the plane direction of the skeleton surface 21 of the projection 22d is longer in the direction perpendicular to the skeleton surface 21 of the projection 22d. As shown in (E), the protrusion 22e has a shape that protrudes in a plurality of directions. The size of the protrusions is the length of the widest part of each protrusion in the SEM image. As shown in FIG. 9, the fifth monolithic ion exchanger has a plurality of protrusions formed on the skeleton surface of the organic porous material.

In the fifth monolithic ion exchanger, the ratio of particles having a diameter of 4 to 40 μm in a dry state to all particles is, for example, 70% or more, preferably 80% or more. The ratio of the above-described particles or the like refers to the ratio of the number of particles or the like having a specific size in a dry state to the total number of particles or the like. In addition, the surface of the skeleton phase is covered with, for example, 40% or more, preferably 50% or more, of all the particles or the like. In addition, the coverage ratio of the surface of the skeleton layer with all the particles or the like refers to the area ratio on the SEM image when the surface is observed by SEM, that is, the area ratio when the surface is viewed in plan. If the size of the particles covering the wall surface or the skeleton deviates from the above range, the effect of improving the efficiency of contact between the fluid and the skeleton surface and the inside of the skeleton of the monolithic ion exchanger tends to decrease.

SEM observations of the fifth monolithic ion exchanger in the dry state were performed at least three times, and in all fields of view, the diameter or size in the dry state of all particles, etc. in the SEM image was calculated, and the diameter or size was For example, it is confirmed whether particles in the range of 4 to 40 μm are observed. For example, it is determined that particles having a size of 4 to 40 μm are formed. In addition, according to the above, the diameter or size in the dry state of all the particles, etc. in the SEM image is calculated for each field of view, and for each field of view, the diameter or size of the dry state, for example, in the range of 4 to 40 μm in the total particles, etc. The ratio of particles, etc. is obtained, and when the ratio of particles, etc. in the dry state of, for example, 4 to 40 μm in the total particles, etc. in the entire field of view is 70% or more, the fifth monolithic ion It is judged that the ratio of particles having a diameter of 4 to 40 μm in a dry state to all the particles formed on the skeleton surface of the exchanger is 70% or more. Further, according to the above, the coverage ratio of the surface of the skeletal layer with all particles, etc. in the SEM image was obtained for each field of view, and the coverage ratio of the surface of the skeleton layer with all particles, etc. was 40% or more in all fields of view. In this case, it is judged that the proportion of the surface of the skeleton layer of the fifth monolithic ion exchanger covered with all particles and the like is 40% or more.

In the fifth monolithic ion exchanger, if the coverage of the surface of the skeleton phase with particles or the like is less than 40%, the effect of improving the contact efficiency between the reaction liquid and the skeleton inside and the skeleton surface of the monolithic ion exchanger is small. There are times when it is easy to As a method for measuring the coverage rate of the particles, etc., there is an image analysis method using an SEM image of the fifth monolithic ion exchanger.

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

In the fifth monolithic ion exchanger, the crosslink density of the polymer material constituting the skeleton is, for example, in the range of 0.3 to 10 mol%, preferably 0.3, based on the total structural units constituting the polymer material. It suffices if the crosslinked structural unit is contained in a range of up to 5 mol %. The organic polymeric material constituting the skeleton of the fifth monolithic ion exchanger is the same as that of the first monolithic ion exchanger.

In the fifth monolithic ion exchanger, the material constituting the skeleton phase of the organic porous body and the particles formed on the surface of the skeleton phase are made of the same material with the same continuous structure, and the structure is not the same. Examples include continuous ones made of different materials. Examples of materials with different continuous non-same textures include materials with different types of vinyl monomers, materials with the same types of vinyl monomers and cross-linking agents but different blending ratios, etc. is mentioned.

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

The ion exchange capacity per weight in the dry state is as described above. Further, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

(Fifth manufacturing method of monolithic ion exchanger)
A fifth monolithic ion exchanger can be produced, for example, by the following method.

A fifth monolith can be obtained, for example, by preparing a water-in-oil emulsion and then carrying out the following steps I to III. In step I, for example, a water-in-oil emulsion is polymerized to obtain a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume in the range of, for example, 5 to 30 mL/g (hereinafter, monolith intermediate (5) ) can be obtained. In step II, for example, a vinyl monomer, a cross-linking agent having at least two vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the cross-linking agent are soluble but the polymer produced by polymerization of the vinyl monomer is not soluble, and polymerization. A mixture containing an initiator is prepared. In step III, for example, the mixture obtained in step II is allowed to stand and polymerized in the presence of the monolith intermediate (5) obtained in step I to obtain a fifth monolith.

Step I in the fifth monolith manufacturing method is the same as step I in the third monolith manufacturing method.

In step I, 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. Polymerization initiators may be water-soluble or oil-soluble, such as 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2 , 2'-azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis dimethyl isobutyrate, 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- and sodium acid sulfite.

The monolithic intermediate (5) obtained in step I has a continuous macropore structure. When this is allowed to coexist in the polymerization system, particles or the like are formed on the surface of the skeleton phase with a continuous macropore structure using the structure of the monolithic intermediate (5) as a template, or particles or the like are formed on the surface of the skeleton phase with a co-continuous structure. is formed. Also, the monolithic intermediate (5) is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material is, for example, in the range of 0.3 to 10 mol %, preferably in the range of 0.3 to 5 mol %, of crosslinked structural units relative to the total structural units constituting the polymer material.

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

The total pore volume per weight of the monolithic intermediate (5) obtained in step I is, for example, in the range of 5-30 mL/g, preferably in the range of 6-28 mL/g. In order to make the total pore volume of the monolithic intermediate (5) within the above numerical range, the ratio (weight) of the monomer and water may be, for example, approximately 1:5 to 1:35.

In step I, if the ratio of this monomer to water is approximately 1:5 to 1:20, the monolith intermediate (5) has a continuous macropore structure with a total pore volume of, for example, 5 to 16 mL/g. The resulting monolith obtained through step III is the 5-1 monolith. On the other hand, if the monomer to water ratio is approximately 1:20 to 1:35, the total pore volume of the monolith intermediate (5) is, for example, more than 16 mL/g and a continuous macropore structure of 30 mL/g or less. , and the monolith obtained through the III step becomes the No. 5-2 monolith.

In the monolith intermediate (5) obtained in step I in the fifth monolith production method, the average diameter of the openings (mesopores), which are the overlapping portions of the macropores, is 20 to 200 μm in a dry state, for example.

Step II in the fifth method for manufacturing a monolith is the same as step II in the third method for manufacturing a monolith. In step III in the fifth method for producing a monolith, for example, the mixture obtained in step II is allowed to stand and in the presence of the monolith intermediate (5) obtained in step I, polymerization is performed to obtain the fifth You can get a monolith.

Here, as disclosed in JP-T-7-501140 and the like, static polymerization of a vinyl monomer and a cross-linking agent in a specific organic solvent in the absence of the monolithic intermediate (5) results in particle aggregation type of the monolithic organic porous body can be obtained. On the other hand, when the monolith intermediate (5) with a continuous macropore structure is allowed to exist in the polymerization system, the structure of the composite monolith after polymerization changes dramatically, and it has the above-mentioned specific skeleton structure instead of the particle aggregation structure. A fifth monolith can be obtained.

In step III of the fifth method for producing a monolith, 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 exist in the reaction vessel. When the monolith intermediate (5) is placed in the reaction vessel, either a gap is formed around the monolith in plan view or the monolith intermediate (5) enters the reaction vessel with almost no gap. . Of these, the fifth monolith after polymerization is hardly pressed by the inner wall of the vessel and enters the reaction vessel with almost no gap. efficient. Even if the inner volume of the reaction vessel is large and there is a gap around the fifth monolith after polymerization, the vinyl monomer and the cross-linking agent are adsorbed and distributed to the monolith intermediate (5). , particle aggregate structures are hardly formed in the gaps in the reaction vessel.

In this step III, for example, the monolithic intermediate (5) is left impregnated with the mixture (solution) in a reaction vessel. The blending ratio of the mixture obtained in step II and the monolithic intermediate (5) is, as described above, preferably such that the amount of the vinyl monomer added is in the range of, for example, 3 to 50 times the weight of the monolithic intermediate (5). may be blended so as to be in the range of 4 to 40 times. This makes it possible to obtain a fifth monolith, which is a composite monolith having a specific skeleton while having an appropriate aperture diameter. In the reaction vessel, the vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the monolithic intermediate (5) which is left standing, and the polymerization proceeds within the skeleton of the monolithic intermediate (5).

In step III in the fifth monolith manufacturing method, the polymerization conditions are almost the same as in step III in the third monolith manufacturing method.

When step II or step III is performed under conditions that satisfy at least one of the following conditions (1) to (5) when manufacturing the fifth monolith, particles and the like are formed on the surface of the skeleton. monoliths can be produced.
(1) The polymerization temperature in step III is at least 5°C lower than the 10-hour half-life temperature of the polymerization initiator.
(2) The mol % of the cross-linking agent used in step II is at least twice the mol % of the cross-linking agent used in step I.
(3) The vinyl monomer used in step II has a structure different from that of the oil-soluble monomer used in step I.
(4) The organic solvent used in step II is polyether having a molecular weight of 200 or more.
(5) The concentration of the vinyl monomer used in step II is 30% by weight or less in the mixture in step II.

A preferable structure of the fifth monolith obtained in this way is a continuous macropore structure ("second 5-1 monolith”), and a three-dimensionally continuous skeleton having a thickness in a dry state of, for example, 0.8 to 40 μm, and a diameter between the skeletons in a dry state of, for example, 8 to 80 μm. and a co-continuous structure (“No. 5-2 monolith”) consisting of three-dimensionally continuous pores in the range of . 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.

[Platinum group metal ion-supported catalyst]
The platinum group metal ion-supported catalyst according to the present embodiment is a catalyst in which at least one of platinum group metal ions and platinum group metal complex ions is supported on the ion exchanger. That is, in the platinum group metal ion-supported catalyst, the platinum group metal is supported in the form of ions on the ion exchanger. For example, platinum group metal ion-supported catalysts are catalysts supported by binding platinum group metal ions or platinum group metal complex ions to quaternary ammonium groups in the ion exchanger by ionic bonds or coordinate bonds. be. The platinum group metal ion-supported catalyst according to the present embodiment preferably includes platinum The catalyst supports at least one of group metal ions and platinum group metal complex ions.

Platinum group metals are ruthenium, rhodium, palladium, osmium, iridium and platinum. The platinum group metal ion is an ion of the platinum group metal, and the valence of the platinum group metal ion varies depending on the type of platinum group metal. These platinum group metal ions may be used singly or in combination of two or more metals. Among these, platinum ions and palladium ions are preferred because they have high catalytic activity.

The platinum group metal complex ions are complex ions of the above platinum group metals, and include, for example, palladium complex ions, platinum complex ions, iridium complex ions, and the like. These platinum group metal complex ions may be used singly or in combination of two or more metals. Among these, platinum complex ions and palladium complex ions are preferable because they have high catalytic activity.

It is confirmed by observation with a transmission electron microscope (TEM) that platinum group metal ions or platinum group metal complex ions are supported on the platinum group metal ion-supported catalyst.

The supported amount of platinum group metal ions or platinum group metal complex ions in the platinum group metal ion-supported catalyst ((mass in terms of platinum group metal atoms/mass of platinum group metal ion-supported catalyst in dry state) x 100) is, for example, In terms of atoms, it is in the range of 0.01 to 10.0 mass %, preferably in the range of 0.1 to 5.0 mass %. When the amount of platinum group metal ions or platinum group metal complex ions supported is within the above range, it easily functions as a catalyst for the carbon-carbon bond formation reaction, and is inexpensive from the viewpoint of raw materials. The amount of platinum group metal atoms in the platinum group metal ion-supported catalyst is determined using an ICP emission spectrometer.

There is no particular limitation on the method for producing the platinum group metal ion-supported catalyst, and by a known method, at least one of platinum group metal ions and platinum group metal complex ions is supported on an ion exchanger to obtain platinum group metal ions. A supported catalyst is obtained. For example, the monolithic ion exchanger in a dry state is immersed in an organic solution of a platinum group metal compound at a predetermined temperature for a predetermined time, and platinum group metal ions are adsorbed on the monolithic ion exchanger by ion exchange. A method in which the exchanger is immersed in an aqueous solution of a platinum group metal complex compound such as a tetraamminepalladium complex at a predetermined temperature for a predetermined time, and platinum group metal ions are adsorbed and supported on the monolithic ion exchanger by ion exchange. .

The loading of platinum group metal ions or platinum group metal complex ions on monolithic ion exchangers may be carried out either batchwise or in flow, without any particular limitation.

The platinum group metal compound used in the method for producing a platinum group metal ion-supported catalyst may be either an organic salt or an inorganic salt, and examples include halides, sulfates, nitrates, phosphates, organic acid salts, inorganic complex salts, and the like. be done. Specific examples of platinum group metal compounds include palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, tetraamminepalladium chloride, tetraamminepalladium nitrate, platinum chloride, tetraammineplatinum chloride, tetraammineplatinum nitrate, chlorotriammineplatinum chloride, Hexaammineplatinum chloride, hexaammineplatinum sulfate, chloropentammineplatinum chloride, cis-tetrachlorodiammineplatinum chloride, trans-tetrachlorodiammineplatinum chloride, rhodium chloride, rhodium acetate, hexaamminerhodium chloride, hexa ammine rhodium bromide, hexaammine rhodium sulfate, pentaammine aquarodium chloride, pentaammine aquarodium nitrate, cis-dichlorotetraammine rhodium chloride, trans-dichlorotetraammine rhodium chloride, ruthenium chloride, hexaammineruthenium chloride, hexaammine ruthenium bromide, hexaammineruthenium iodide, chloropentaammineruthenium chloride, cis-dichlorotetraammineruthenium chloride, trans-dichlorotetraamminerhodium chloride, iridium (III) chloride, iridium (IV) chloride, hexaammineiridium chloride, hexaammineiridium nitrate, chloropentammineiridium chloride, chloropentaammineiridium bromide, hexaammineosmium chloride, hexaammineosmium bromide, hexaammineosmium iodide and the like. The amount of these compounds used is, for example, 0.005 to 30% by weight in terms of metal relative to the monolithic ion exchanger as the carrier.

When supporting platinum group metal ions or platinum group metal complex ions, the platinum group metal compound is usually used by dissolving it in a solvent. Water; alcohols such as methanol, ethanol, propanol, butanol, and benzyl alcohol; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile; is used. In order to increase the solubility of the platinum group metal compound in the solvent, an acid such as hydrochloric acid, sulfuric acid, or nitric acid, or a base such as sodium hydroxide or tetramethylammonium hydroxide may be added.

<Method for Forming Carbon-Carbon Bond>
The method for forming a carbon-carbon bond according to an embodiment of the present invention includes, for example, (1) a reaction between an aromatic halide and an organic boron compound in the presence of the platinum group metal ion-supported catalyst, (2) an aromatic halide and a compound having an alkynyl group at the end thereof, or (3) an aromatic halide and a compound having an alkenyl group are reacted to form a carbon-carbon bond.

A first form of the carbon-carbon bond-forming method (hereinafter also referred to as a carbon-carbon bond-forming method (1)) is an aromatic halide and an organic boron compound in the presence of the platinum group metal ion-supported catalyst. is reacted to form a carbon-carbon single bond by coupling.

The organic boron compound used in the carbon-carbon bond forming method (1) is
^R4 -B(OH) ₂
(R ⁴ is an organic group, and is not particularly limited as long as it is an organic group. Examples include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aromatic carbocyclic group, an aromatic heterocyclic and the like, and these groups include methyl group, ethyl group, nitro group, amino group, methoxy group, ethoxy group, carboxyl group, acetyl group, etc., as long as they do not impair the effects of the present embodiment. It is an organoboron compound represented by.

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

In formula (I), examples of aromatic carbocyclic or aromatic heterocyclic groups for Ar ¹ include phenyl, naphthyl, biphenyl, anthranyl, pyridyl, pyrimidyl, indolyl, benz imidazolyl group, quinolyl group, benzofuranyl group, indanyl group, indenyl group, dibenzofuranyl group and the like. There are no particular restrictions on the position at which boron bonds to the aromatic carbocyclic group or aromatic heterocyclic group, and boron can be bonded to any position. In addition, one or more substituents may be introduced into the aromatic carbocyclic group or aromatic heterocyclic group. Examples of substituents 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, propoxy group and butoxy group; Nilmethoxycarbonyl group, butoxycarbonyl group, benzyloxycarbonyl group, nitro group and the like.

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

Examples of the aromatic carbocyclic group or aromatic heterocyclic group for Ar ² in formula (II) are the same as those for Ar ¹ . There are no particular restrictions on the position at which the halogen atom is bonded to the aromatic carbocyclic group or aromatic heterocyclic group, and the halogen atom can be bonded at any position. In addition, one or more substituents may be introduced into the aromatic carbocyclic group or aromatic heterocyclic group. Examples of substituents 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, propoxy group and butoxy group; Nilmethoxycarbonyl 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.

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

The usage ratio of the aromatic boron compound and the aromatic halide used in the carbon-carbon bond forming method (1) is not particularly limited, but for example, the molar ratio of the aromatic boron compound: aromatic halide = 0.5 to 2:1 range and may be used in equimolar amounts.

The second form of the carbon-carbon bond forming method (hereinafter also referred to as the carbon-carbon bond forming method (2)) is, in the presence of the platinum group metal ion-supported catalyst, an aromatic halide and an alkynyl group at the end It is a reaction to form a carbon-carbon single bond by reacting with a compound having

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

The compound having a terminal alkynyl group used in the carbon-carbon bond forming method (2) is, for example, the compound represented by formula (IV).
HC≡CR ⁵ (IV)
(Wherein, R ⁵ is a hydrogen atom, an optionally substituted C 6-18 aromatic carbocyclic group, an optionally substituted C 6-18 aromatic a heterocyclic group, an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, an optionally substituted alkenyl group having 2 to 18 carbon atoms, or having a substituent is an alkynyl group having 2 to 10 carbon atoms that may be

In formula (IV), R ⁵ is an optionally substituted aromatic carbocyclic group having 6 to 18 carbon atoms or an optionally substituted aromatic carbocyclic group having 6 to 18 carbon atoms Examples of heterocyclic groups are the same as Ar ¹ and Ar ² in formulas (I) and (II).

In formula (IV), examples of the optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, which is R ⁵ , include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. , octyl group, dodecyl group, octadecyl group and the like.

Examples of optionally substituted alkenyl groups having 2 to 18 carbon atoms, which are R ⁵ in formula (IV), include a vinyl group, an allyl group, a methallyl group, a propenyl group, a butenyl group and a hexenyl group. , octenyl group, decenyl group, octadecenyl group and the like.

Examples of the optionally substituted alkynyl group having 2 to 10 carbon atoms, which is R ⁵ in formula (IV), include an ethynyl group, a propynyl group, a hexynyl group and an octenyl group.

Examples of substituents that these aromatic carbocyclic groups, aromatic heterocyclic groups, aliphatic hydrocarbon groups, alkenyl groups, and alkynyl groups may have include hydrocarbon groups such as a hydroxyl group and a phenyl group, heteroatom-containing hydrocarbon groups such as methoxy group and trifluoromethoxy group;

In the carbon-carbon bond forming method (2), in the presence of the platinum group metal ion-supported catalyst, for example, the aromatic halide represented by the formula (II) and the compound represented by the formula (IV) react, The product of formula (V) is obtained.
Ar ² —C≡C—R ⁵ (V)
(wherein Ar ² and R ⁵ are the same as in formulas (II) and (IV).)

The ratio of the aromatic halide used in the carbon-carbon bond forming method (2) and the compound having an alkynyl group at the terminal is not particularly limited, but for example, the molar ratio of the aromatic halide: having an alkynyl group at the terminal The compound ratio ranges from 0.5 to 3:1 and may be used in equimolar amounts.

A third form of the carbon-carbon bond-forming method (hereinafter also referred to as the carbon-carbon bond-forming method (3)) has an aromatic halide and an alkenyl group in the presence of the platinum group metal ion-supported catalyst. It is a reaction that forms a carbon-carbon single bond by reacting with a compound.

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

A compound having an alkenyl group used in the carbon-carbon bond forming method (3) is, for example, a compound represented by formula (VI).
R6HC= ^{CR7R8 ( VI} )
(wherein R ⁶ , R ⁷ and R ⁸ each independently have a hydrogen atom, an optionally substituted aromatic carbocyclic group having 6 to 18 carbon atoms, a substituent an aromatic heterocyclic group having 6 to 18 carbon atoms which may be substituted, an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, a carboxylic acid derivative, an acid amide derivative or a cyano group. )

In formula (VI), R ⁶ , R ⁷ and R ⁸ , optionally substituted aromatic carbocyclic groups having 6 to 18 carbon atoms, optionally substituted carbon atoms Examples of aliphatic hydrocarbon groups such as 6 to 18 aromatic heterocyclic groups and optionally substituted groups having 1 to 18 carbon atoms are the same as R ¹ in formula (IV).

Examples of carboxylic acid derivatives represented by R ⁶ , R ⁷ and R ⁸ in formula (VI) include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl.

Examples of acid amide derivatives represented by R ⁶ , R ⁷ and R ⁸ in formula (VI) include carbamoyl groups such as N-methylcarbamoyl group and N,N-dimethylcarbamoyl group.

In the carbon-carbon bond formation method (3), the compound represented by the formula (VI) reacts with the aromatic halide represented by the formula (II) in the presence of the platinum group metal ion-supported catalyst to form the formula ( The product of VII) is obtained.
^{R6Ar2C = CR7R8} ( ^VII )
(In the formula, Ar ² , R ⁶ , R ⁷ and R ⁸ are the same as those in formula (II) and formula (VI) above.)

The proportion of the aromatic halide and the alkenyl group-containing compound used in the carbon-carbon bond forming method (3) is not particularly limited, but for example, the molar ratio of the aromatic halide to the alkenyl group-containing compound=0. It ranges from 5 to 2:1 and may be used in equimolar amounts.

In the carbon-carbon bond forming reactions (1) to (3), the amount of platinum group metal ion-supported catalyst used is, for example, 0.01 to 20 mol% in terms of platinum group metal with respect to the aromatic halide. Range.

In the carbon-carbon bond forming method, the coupling reaction may be carried out using a solvent or without solvent. Solvents used include water, organic solvents, and mixtures thereof. Examples of organic solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol and glycerin; cyclic ethers such as tetrahydrofuran and dioxane.

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

In the carbon-carbon bond forming reaction, the presence of a base is preferred, and the presence of an inorganic base is more preferred. Examples of bases used include inorganic bases such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium acetate, sodium phosphate, potassium phosphate, barium hydroxide; potassium phenolate, sodium methoxide, sodium ethoxylate; organic bases such as sodium chloride, potassium butoxide, trimethylamine and triethylamine. The amount of these bases to be used is set, for example, in the range of 50 to 300 mol % relative to the aromatic halide.

In the method for forming carbon-carbon bonds according to the present embodiment, the reaction for forming carbon-carbon bonds may be performed by passing the raw material solution for the reaction through a platinum group metal catalyst.

In the carbon-carbon bond forming method according to the present embodiment, the carbon-carbon bond forming reactions (1) to (3) are performed by, for example, a raw material solution (i) containing the aromatic halide and the organic boron compound. , the raw material solution (ii) containing the aromatic halide and the compound having an alkynyl group at the terminal, or the raw material solution (iii) containing the aromatic halide and the compound having an alkenyl group, is added to platinum Introduce into the filled container from the introduction route of the packed container filled with the group metal ion-supported catalyst, pass the raw material solution through the platinum group metal ion-supported catalyst, and discharge the reaction solution from the discharge route of the packed container. It is preferable to carry out the carbon-carbon bond forming reaction by.

In the carbon-carbon bond forming method, for example, the raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is an inorganic base-dissolving raw material in which the raw material and the inorganic base are dissolved in water or a hydrophilic solvent. It is a liquid, and the raw material solution for dissolving an inorganic base is introduced into the filled container through the introduction route of the packed container filled with the platinum group metal ion-supported catalyst, and the inorganic base-dissolved raw material solution is passed through the platinum group metal ion-supported catalyst. Then, the carbon-carbon bond formation reaction may be carried out by discharging the reaction solution from the discharge channel of the filled container.

Further, in the carbon-carbon bond forming method, for example, the raw material solution (i), the raw material solution (ii), or the raw material solution (iii) is a hydrophobic solvent raw material solution in which the raw material is dissolved in a hydrophobic organic solvent. A mixture of a hydrophobic solvent raw material solution and an inorganic base aqueous solution in which an inorganic base is dissolved is introduced into the filled container through the introduction route of the packed container filled with a platinum group metal ion-supported catalyst, and platinum The carbon-carbon bond formation reaction may be performed by passing the hydrophobic solvent raw material liquid and the inorganic base aqueous solution through the group metal ion-supported catalyst and discharging the reaction liquid from the discharge channel of the filled container.

The carbon-carbon bond forming method according to the present embodiment can form a carbon-carbon bond to obtain a desired compound, and can obtain a target product in high yield. In particular, the carbon-carbon bond forming reaction can be carried out in high yield even with aromatic bromides. In addition, the desired product can be obtained in a short reaction time and in a high yield. According to the carbon-carbon bond forming method according to the present embodiment, the carbon-carbon bond forming method for forming a carbon-carbon bond to obtain a desired compound can be performed in a fixed bed continuous flow system, Carbon-carbon bonding reactions can be carried out with high yields on a variety of starting materials. Moreover, from the viewpoint of production efficiency, a high-concentration raw material solution can be used.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

<Example 1>
A monolith was manufactured according to the fifth method for manufacturing a monolithic ion exchanger, and ion exchange groups were introduced into the obtained monolith.

(Production of monolithic intermediate (I step))
9.28 g of styrene as a monomer, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) as a surfactant, and 0.25 g of 2,2'-azobis(isobutyronitrile) as a polymerization initiator were mixed and dissolved until uniform. Next, this styrene/divinylbenzene/SMO/2,2′-azobis(isobutyronitrile) mixture was added to 180 g of pure water, and a planetary stirring device, a vacuum agitation defoaming mixer (manufactured by E.M.E. Co., Ltd.) was added. was stirred under reduced pressure to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel, sealed, and allowed to stand still at 60° C. for 24 hours for polymerization. After completion of the polymerization, the content was taken out, extracted with methanol, and dried under reduced pressure to produce a monolithic intermediate having a continuous macropore structure. The internal structure of the monolithic intermediate (dried body) thus obtained was observed by SEM. A SEM image is shown in FIG. 10. Although the walls that separate two adjacent macropores are extremely thin and rod-shaped, they have a continuous macropore structure, and the openings at the portions where the macropores overlap each other measured by the mercury intrusion method. The average diameter of (mesopores) was 40 μm, and the total pore volume was 18.2 mL/g.

(Manufacturing of Monolith (Step II))
Then, 216.6 g of styrene as a monomer, 4.4 g of divinylbenzene as a cross-linking agent, 220 g of 1-decanol as an organic solvent, and 0.8 g of 2,2′-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator are mixed. and dissolved uniformly (step II).

(Manufacturing of monolith (III step))
The above monolithic intermediate is then placed in a reaction vessel and immersed in this 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 stand at 50° C. for 24 hours to polymerize. After completion of the polymerization, the contents were taken out, subjected to Soxhlet extraction with acetone, and dried under reduced pressure (Step III).

FIG. 11 shows the result of SEM observation of the internal structure of the monolith (dry body) containing 1.2 mol % of the cross-linking component of the styrene/divinylbenzene copolymer thus obtained. As is clear from FIG. 11, this monolith had a co-continuous structure in which the skeleton and the pores were three-dimensionally continuous and consisted of a continuous skeleton phase and a continuous pore phase, and both phases were intertwined. Moreover, the thickness of the continuous skeleton measured from the SEM image was 20 μm. The three-dimensionally continuous pores of this monolith had an average diameter of 70 μm and a total pore volume of 4.4 mL/g, as measured by mercury porosimetry. The average pore diameter was obtained from the maximum value of the pore distribution curve obtained by the mercury porosimetry.

(Production of chloromethylated monolith)
The produced monolith was placed in a column reactor, and a solution containing 1,600 g of chlorosulfonic acid, 400 g of tin tetrachloride, and 2,500 mL of dimethoxymethane was circulated and allowed to react at 30° C. for 5 hours to introduce chloromethyl groups. After completion of the reaction, the chloromethylated monolith was washed with a mixed solvent of THF/water=2/1 (vol) and further washed with THF to obtain a chloromethylated monolith.

（式中、Ｐｏｌｙｍｅｒは、スチレン―ジビニルベンゼン共重合体を表す。） (Production of monolithic ion exchanger)
390 mL of THF and 30 mL of N,N-dimethylbenzylamine as a tertiary amine were added to 20 g of the chloromethylated monolith, 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 monolithic ion exchanger composed of polymer chains represented by the following formula (4).

(In the formula, Polymer represents a styrene-divinylbenzene copolymer.)

The anion exchange capacity of the obtained monolithic ion exchanger was 2.9 mg equivalent/g in a dry state, confirming that the quaternary ammonium groups were introduced quantitatively. As is clear from FIG. 11, the monolithic cation exchanger had a co-continuous structure in which the skeleton and pores were three-dimensionally continuous and both phases were entangled. In addition, the thickness of the skeleton in the dry state measured from the SEM image was 20 μm, and the average diameter of the three-dimensionally continuous pores of this monolith anion exchanger in the dry state obtained from the measurement by the mercury intrusion method was 70 μm and the total pore volume in the dry state was 4.4 mL/g.

(Production of platinum group metal ion-supported catalyst)
The monolithic ion exchanger produced was dried under reduced pressure. The weight of the monolithic ion exchanger after drying was 8.7 g. This dry monolithic ion exchanger was immersed in dilute hydrochloric acid in which 146 mg of palladium chloride was dissolved at 25° C. for 24 hours to support tetrachloropalladate ions. After completion of the immersion, it was washed several times with pure water to prepare a monolithic ion exchanger supporting Pd ions. When the amount of palladium carried in the Pd ion-carrying monolithic ion exchanger thus obtained was determined with an ICP emission spectrometer (manufactured by Hitachi High-Tech Science, PS3520UVDDII type), the amount of palladium carried was 1.0% by weight.

The platinum group metal ion-supported catalyst obtained in Example 1 is hereinafter referred to as "Pd ion-supported monolithic ion exchanger".

芳香族ハロゲン化物として２－ブロモベンゾニトリル（５．８２ｇ、３２．０ｍｍｏｌ）と有機ホウ素化合物として４－メチルフェニルボロン酸（４．７８ｇ、３５．２ｍｍｏｌ）の４－メチルテトラヒドロピラン（４－ＭＴＨＰ）／エタノール（３２ｍＬ，１：１（ｖｏｌ））溶液に、無機塩基として水酸化ナトリウム（３５．２ｍｍｏｌ）の水（２２ｍＬ）溶液を加え撹拌した。この溶液を、Ｐｄイオン担持モノリスイオン交換体（φ４．６×３０ｍｍ）を充填して８０℃に加熱したＳＵＳ製カラム内に流速０．３ｍＬ／分で通液し、飽和塩化アンモニウム水溶液を蓄えたフラスコに回収した。得られた液の有機層をＧＣ（島津製作所社製、ＧＣ－２０１０型）で分析した結果、転化率８０％で２－シアノ－４’－メチルビフェニルを得た。 <Example 2>
(Carbon-carbon bond formation reaction using Pd ion-supporting monolithic ion exchanger)

4-methyltetrahydropyran (4-MTHP) of 2-bromobenzonitrile (5.82 g, 32.0 mmol) as the aromatic halide and 4-methylphenylboronic acid (4.78 g, 35.2 mmol) as the organoboron compound A solution of sodium hydroxide (35.2 mmol) in water (22 mL) as an inorganic base was added to a solution of /ethanol (32 mL, 1:1 (vol)) and stirred. This solution was passed through a SUS column filled with a monolithic ion exchanger (φ4.6×30 mm) supporting Pd ions and heated to 80° C. at a flow rate of 0.3 mL/min, and a saturated ammonium chloride aqueous solution was stored. Collected in a flask. As a result of analyzing the organic layer of the obtained liquid by GC (manufactured by Shimadzu Corporation, Model GC-2010), 2-cyano-4'-methylbiphenyl was obtained with a conversion rate of 80%.

芳香族ハロゲン化物として４－ブロモベンゾトリフルオリド（１０．８ｇ、４８．０ｍｍｏｌ）と有機ホウ素化合物としてフェニルボロン酸（６．４４ｇ、５２．８ｍｍｏｌ）の４－ＭＴＨＰ／エタノール（４８ｍＬ，１：１（ｖｏｌ））溶液に、無機塩基として水酸化ナトリウム（５２．８ｍｍｏｌ）の水（３３ｍＬ）溶液を加え撹拌した。この溶液を、Ｐｄイオン担持モノリスイオン交換体（φ４．６×３０ｍｍ）を充填して８０℃に加熱したＳＵＳ製カラム内に流速０．３ｍＬ／分で通液し、飽和塩化アンモニウム水溶液を蓄えたフラスコに回収した。得られた液の有機層をＧＣで分析した結果、転化率７１％で４－（トリフルオロメチル）ビフェニルを得た。 <Example 3>

4-MTHP/ethanol (48 mL, 1:1 ( vol)) solution was added with a solution of sodium hydroxide (52.8 mmol) in water (33 mL) as an inorganic base and stirred. This solution was passed through a SUS column filled with a monolithic ion exchanger (φ4.6×30 mm) supporting Pd ions and heated to 80° C. at a flow rate of 0.3 mL/min, and a saturated ammonium chloride aqueous solution was stored. Collected in a flask. As a result of analyzing the organic layer of the obtained liquid by GC, 4-(trifluoromethyl)biphenyl was obtained with a conversion rate of 71%.

芳香族ハロゲン化物として２－ブロモニトロベンゼン（６．４６ｇ、３２．０ｍｍｏｌ）と有機ホウ素化合物としてフェニルボロン酸（４．２９ｇ、３５．２ｍｍｏｌ）の４－ＭＴＨＰ／エタノール（３２ｍＬ，１：１（ｖｏｌ））溶液に、無機塩基として水酸化ナトリウム（３５．２ｍｍｏｌ）の水（２２ｍＬ）溶液を加え撹拌した。この溶液を、Ｐｄイオン担持モノリスイオン交換体（φ４．６×３０ｍｍ）を充填して８０℃に加熱したＳＵＳ製カラム内に流速０．３ｍＬ／分で通液し、飽和塩化アンモニウム水溶液を蓄えたフラスコに回収した。得られた液の有機層をＧＣで分析した結果、転化率８１％で２－ニトロビフェニルを得た。 <Example 4>

2-bromonitrobenzene (6.46 g, 32.0 mmol) as an aromatic halide and phenylboronic acid (4.29 g, 35.2 mmol) as an organoboron compound in 4-MTHP/ethanol (32 mL, 1:1 (vol) ) solution, a solution of sodium hydroxide (35.2 mmol) in water (22 mL) as an inorganic base was added and stirred. This solution was passed through a SUS column filled with a monolithic ion exchanger (φ4.6×30 mm) supporting Pd ions and heated to 80° C. at a flow rate of 0.3 mL/min, and a saturated ammonium chloride aqueous solution was stored. Collected in a flask. As a result of analyzing the organic layer of the resulting liquid by GC, 2-nitrobiphenyl was obtained with a conversion rate of 81%.

（式中、Ｐｏｌｙｍｅｒは、スチレン―ジビニルベンゼン共重合体を表す。） <Comparative Example 1>
400 mL of THF and 56 mL of a 30% trimethylamine aqueous solution as a tertiary amine were added to 25.1 g of the chloromethyl monolith obtained in Example 1, and the mixture was reacted at 40° C. for 3 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a monolithic strong base anion exchanger composed of polymer chains represented by the following formula (5).

(In the formula, Polymer represents a styrene-divinylbenzene copolymer.)

The anion exchange capacity of the obtained monolithic anion exchanger was 4.6 mg equivalent/g in a dry state, confirming that the quaternary ammonium groups were introduced quantitatively. In addition, the thickness of the skeleton in the dry state measured from the SEM image is 20 μm, and the average diameter of the three-dimensionally continuous pores of the monolithic anion exchanger in the dry state obtained from the measurement by the mercury intrusion method is 70 μm. , the total pore volume in the dry state was 4.4 mL/g.

The resulting monolithic strong base anion exchanger was dried under reduced pressure. The weight of the monolithic strong base anion exchanger after drying was 18.0 g. This dry monolith was immersed in dilute hydrochloric acid in which 1.80 g of palladium chloride was dissolved at 25° C. for 24 hours to support tetrachloropalladate ions. After completion of the immersion, it was washed several times with pure water to prepare a monolithic ion exchanger supporting Pd ions. When the amount of palladium carried in the monolithic ion exchanger carrying Pd ions thus obtained was determined by ICP emission spectrometry, the amount of palladium carried was 4.8% by weight.

The platinum group metal ion-supported catalyst obtained in Comparative Example 1 is hereinafter referred to as "Pd ion-supported monolith strong base anion exchanger".

<Comparative Example 2>

A solution of 4-bromoacetophenone (0.796 g, 4.0 mmol) in toluene (2.0 mL) as the aromatic halide at 0.1 mL/min, and phenylboronic acid (0.536 g, 4.4 mmol) as the organoboron compound. And a solution of sodium hydroxide (4.4 mmol) in water (4.0 mL) as an inorganic base is fed at a rate of 0.2 mL/min, and the respective solutions are combined at a joint. The combined liquid was passed through a SUS column filled with the Pd ion-supporting monolithic strong base anion exchanger (φ4.6 × 30 mm) produced in Comparative Example 1 and heated to 80 ° C., saturated ammonium chloride It was collected in a flask containing an aqueous solution. As a result of analyzing the organic layer of the resulting liquid by GC, 4-acetylbiphenyl was obtained with a conversion rate of 33%.

<Comparative Example 3>
The procedure of Example 2 was repeated except that the Pd ion-supporting monolithic ion exchanger was changed to a Pd ion-supporting monolithic strong base anion exchanger. As a result, 2-cyano-4'-methylbiphenyl was obtained with a conversion rate of 14%.

As described above, by using the platinum group metal ion-supported catalyst of the example, the carbon-carbon bond forming reaction could be carried out in high yield even with aromatic bromides.

1 skeletal phase, 2 vacant phase, 10 bicontinuous structure, 11 rectangular image area, 12 skeletal portion, 13 macropores, 21 skeletal surface, 22a, 22b, 22c, 22d, 22e projections.

Claims (12)

General formula (1)

(In the formula, R ¹ is an optionally substituted alkyl group having 4 to 22 carbon atoms; or an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, or an optionally substituted carbon number 1 to ⁶ alkoxy groups, optionally substituted amino groups, cyano groups ^, or benzyl groups optionally substituted with nitro groups; 4 represents an alkyl group, L represents a linker moiety, and Polymer represents a polymer chain.)
A catalyst supported on platinum group metal ions, wherein at least one of platinum group metal ions and platinum group metal complex ions is supported on an ion exchanger composed of a polymer chain represented by: The platinum group metal ion-supported catalyst according to claim 1,
The ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, The pore volume is in the range of 0.5 to 50 mL/g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 mg equivalent/g, and the ion exchange groups are distributed in the ion exchanger. A platinum group metal ion-supported catalyst, which is a non-particulate organic porous ion exchanger. The platinum group metal ion-supported catalyst according to claim 1 or 2,
A supported platinum group metal ion catalyst, wherein the supported amount of at least one of the platinum group metal ions and platinum group metal complex ions is in the range of 0.01 to 10.0% by mass in terms of platinum group metal atoms. . The platinum group metal ion-supported catalyst according to any one of claims 1 to 3,
R ¹ in the general formula (1) is an alkyl group having 6 to 20 carbon atoms, or a benzyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms Supporting a platinum group metal ion catalyst. The platinum group metal ion-supported catalyst according to any one of claims 1 to 3,
A platinum group metal ion-supported catalyst, wherein R ¹ in the general formula (1) is a dodecyl group or a benzyl group. The platinum group metal ion-supported catalyst according to any one of claims 1 to 5,
A platinum group metal ion-supported catalyst, wherein R ² and R ³ in general formula (1) are each independently a methyl group or an ethyl group. The platinum group metal ion-supported catalyst according to any one of claims 1 to 6,
A platinum group metal ion-supported catalyst, wherein L in the general formula (1) is a methylene group. The platinum group metal ion-supported catalyst according to any one of claims 1 to 7,
A platinum group metal ion-supported catalyst, wherein the polymer chain of the ion exchanger is a styrene-divinylbenzene copolymer. (1) a reaction between an aromatic halide and an organic boron compound, (2) a reaction between an aromatic halide and a compound having an alkynyl group at its terminal, or (3) a reaction between an aromatic halide and a compound having an alkenyl group. A carbon-carbon bond forming method for conducting a reaction to form a carbon-carbon bond, comprising:
Raw material liquid (i) containing the aromatic halide and the organoboron compound, raw material liquid (ii) containing the aromatic halide and the compound having an alkynyl group at the terminal, or the aromatic halide and the compound having an alkenyl group, the raw material liquid (iii) is introduced into the filled container from the introduction route of the filled container filled with the platinum group metal ion-supported catalyst, and the platinum group metal ion-supported By passing the raw material liquid through the catalyst and discharging the reaction liquid from the discharge path of the filling container, a carbon-carbon bond forming reaction is performed,
A method for forming a carbon-carbon bond, wherein the platinum group metal ion-supported catalyst is the platinum group metal ion-supported catalyst according to any one of claims 1 to 8. The carbon-carbon bond forming method according to claim 9,
A method for forming a carbon-carbon bond, characterized in that the carbon-carbon bond-forming reaction is carried out in the presence of an inorganic base. The carbon-carbon bond forming method according to claim 9 or 10,
The raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is an inorganic base-dissolved raw material liquid in which the raw material and the inorganic base are dissolved in water or a hydrophilic solvent,
The raw material solution for dissolving an inorganic base is introduced into the filled container through an introduction route of the filled container filled with the platinum group metal ion-supported catalyst, and the raw material solution for dissolving the inorganic base is introduced into the platinum group metal ion-supported catalyst. and discharging the reaction liquid from the discharge path of the filling vessel to carry out a carbon-carbon bond forming reaction. The carbon-carbon bond forming method according to claim 9 or 10,
the raw material liquid (i), the raw material liquid (ii), or the raw material liquid (iii) is a hydrophobic solvent raw material liquid in which the raw material is dissolved in a hydrophobic organic solvent;
A mixture of the hydrophobic solvent raw material liquid and the inorganic base aqueous solution in which the inorganic base is dissolved is introduced into the filled container through the introduction route of the filled container filled with the platinum group metal ion-supported catalyst. Then, the hydrophobic solvent raw material liquid and the inorganic base aqueous solution are passed through the platinum group metal ion-supported catalyst, and the reaction liquid is discharged from the discharge route of the filled container, thereby performing a carbon-carbon bond formation reaction. A method for forming a carbon-carbon bond, characterized by:

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