Ion exchanger and method for producing the same

Abstract

To provide: an ion exchanger which hardly shrinks when coming into contact with an organic solvent in a water-wet state; and a method for producing the ion exchanger.SOLUTION: Provided is 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

Technical Field

[0001] The present invention relates to an ion exchanger and a method for producing the ion exchanger.

Background Art

[0002] Ion exchange reactions are important in the purification of water, sugar solutions, etc., and the synthesis process of chemical products such as pharmaceutical intermediates, and ion exchangers including ion exchange resins are used. In recent years, due to the demand for high-purity organic solvents, a method for purifying organic solvents using an ion exchanger has also been developed. For example, Patent Document 1 describes a method of purifying an organic solvent such as 2-propanol containing a polyvalent metal ion by bringing it into contact with a column filled with a monolithic organic porous ion exchanger.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, when the present inventor studied, it was found that when an organic solvent was passed through a column filled with a water-wet monolithic organic porous ion exchanger, the monolithic organic porous ion exchanger shrank significantly, and there was a problem that the organic solvent did not efficiently contact the monolithic organic porous ion exchanger.

[0005] An object of the present invention is to provide an ion exchanger with less shrinkage when contacting an organic solvent in a water-wet state, and a method for producing the ion exchanger.

Means for Solving the Problems

[0006] The present invention provides a compound represented by the general formula (1)

Chemical Formula

[0007] In the ion exchanger, L in the general formula (1) is preferably a methylene group.)

[0008] In the ion exchanger, the polymer chain of the ion exchanger is preferably a styrene - divinylbenzene copolymer.)

[0010] The present invention relates to a general formula (2) [Chemical formula] (wherein L represents a linker moiety, Polymer represents a polymer chain, and X represents a halogen atom, an optionally substituted alkylsulfonyl group having 1 to 8 carbon atoms, or an optionally substituted benzenesulfonyl group.) a polymer chain represented by, and a general formula (3) [Chemical formula] (wherein R 1 represents an alkyl group having 6 to 20 carbon atoms; or a benzyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms; R 2 , R 3 each independently represents an alkyl group having 1 to 4 carbon atoms.) a tertiary amine represented by, and a method for producing an ion exchanger by reacting them.) The ion exchanger is a non-particulate organic porous ion exchanger, and it is a method for producing an ion exchanger. wherein the non-particulate organic porous ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton ranges from 1 to 100 μm, the average diameter of the continuous pores ranges from 1 to 1000 μm, the total pore volume ranges from 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state ranges from 1 to 9 mg equivalent / g, and the ion exchange groups are distributed in the organic porous ion exchanger

[0011] In the method for producing the ion exchanger, L in the general formula (1) is preferably a methylene group.

[0012] In the method for producing the ion exchanger, the polymer chain of the ion exchanger is preferably a styrene-divinylbenzene copolymer.

Advantages of the Invention

[0014] According to the present invention, it is possible to provide an ion exchanger with little shrinkage when contacted with an organic solvent in a water-wet state, and a method for producing the ion exchanger.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Mode for Carrying Out the Invention

[0016] The embodiments of the present invention will be described below. This embodiment is an example of carrying out the present invention, and the present invention is not limited to this embodiment.

[0017] <Ion Exchanger> The ion exchanger according to the embodiment of the present invention has the general formula (1)

Chemical Formula

[0018] The present inventor has found that the ion exchanger composed of the polymer chain represented by the above general formula (1) has little shrinkage when in contact with an organic solvent in a water-wet state. This ion exchanger can be filled in a column in a water-wet state and passed through an organic solvent, and the ion exchanger hardly shrinks, making it possible to efficiently contact the organic solvent with the ion exchanger. This is presumably because, as R 1 , the hydrophobicity increases by having the alkyl group having 4 to 22 carbon atoms or the benzyl group described above.

[0019] With the ion exchanger according to this embodiment, the shrinkage rate when it is brought into contact with an organic solvent in a water-wet state can be, for example, within ±10% compared to before contact with the organic solvent, preferably within ±8%. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol and 2-propanol, amide solvents such as N,N-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP), ether solvents such as diisopropyl ether and tetrahydrofuran (THF), aromatic solvents such as toluene and xylene, and hydrocarbon solvents such as pentane and hexane.

[0020] R in the general formula (1) 1 represents an optionally substituted alkyl group having 4 to 22 carbon atoms. Or, R 1 represents 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, a benzyl group optionally substituted with an optionally substituted alkoxy group having 1 to 6 carbon atoms, a benzyl group optionally substituted with an optionally substituted amino group, a benzyl group optionally substituted with a cyano group, or a benzyl group optionally substituted with a nitro group. The optionally substituted benzyl group is a benzyl group in which a substituent may be substituted on the phenyl group of the benzyl group.

[0021] 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 preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable, from the viewpoints of high reaction yield during production and easy availability of raw materials.

[0022] The alkyl group having 1 to 6 carbon atoms that 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 viewpoint of easy availability of raw materials.

[0023] Examples of the halogen atom which may be substituted for the benzyl group include a chlorine atom, a bromine atom, an iodine atom, etc. From the viewpoint of low cost of raw material production, etc., a chlorine atom is preferable.

[0024] The C1-C6 alkoxy group which may be substituted for the benzyl group may be linear, branched or cyclic. From the viewpoint of easy availability of raw materials, etc., a C1-C4 alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable.

[0025] Examples of the substituent in the case where the C4-C22 alkyl group, the C1-C6 alkyl group, or the C1-C6 alkoxy group is "optionally substituted" include a nitro group, a cyano group, a halogen atom, etc.

[0026] Examples of the substituent in the case where the amino group is "optionally substituted" include a C1-C8 alkyl group, a phenyl group, a C1-C4 fluoroalkyl group, etc.

[0027] The C1-C8 alkyl group which may be substituted for the amino group may be linear, branched or cyclic. From the viewpoint of high reaction yield during production, etc., a C1-C4 alkyl group is preferable, and a methyl group and an ethyl group are more preferable.

[0028] The C1-C4 fluoroalkyl group which may be substituted for the amino group may be linear, branched or cyclic. From the viewpoint of easy availability of raw materials, etc., a C1-C2 fluoroalkyl group is preferable, and a trifluoromethyl group and a 2,2,2-trifluoroethyl group are more preferable.

[0029] R in the general formula (1) 1 is preferably a C6-C20 alkyl group or a benzyl group which may be substituted with a C1-C4 alkyl group, and more preferably a dodecyl group or a benzyl group.

[0030] R in the general formula (1) 2 ,R3 Each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched or cyclic. As the alkyl group having 1 to 4 carbon atoms, a methyl group and an ethyl group are preferable, and a methyl group is more preferable, from the viewpoints such as high reaction yield during production.

[0031] In the general formula (1), L represents a linker moiety. Examples of the linker moiety include an alkylene group having 1 to 4 carbon atoms which may be substituted with an oxy group. From the viewpoints such as high reaction yield during production, a methylene group, an ethylene group, and a 1-oxyethylene group are preferable, and a methylene group is more preferable.

[0032] In the general formula (1), Polymer represents a polymer chain. Examples of the polymer chain include aromatic vinyl polymers such as polystyrene, poly(α-methylstyrene), polyvinylbenzyl chloride; polyolefins such as polyethylene, polypropylene; poly(halogenated polyolefins) such as polyvinyl chloride, polytetrafluoroethylene; nitrile-based polymers such as polyacrylonitrile; crosslinked polymers such as (meth)acrylic-based polymers such as polymethacrylate, polyacrylate. The above polymer chain may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or may be a blend of two or more polymers. Among these, a crosslinked polymer of an aromatic vinyl polymer is preferable from the viewpoints of ease of forming a continuous structure, ease of introducing an ion exchange group, high mechanical strength, and high stability against acids or alkalis. In particular, a styrene-divinylbenzene copolymer or a vinylbenzyl chloride-divinylbenzene copolymer is preferable, and a styrene-divinylbenzene copolymer is preferable.

[0033] The ion exchanger according to this embodiment may be a particulate ion exchanger or a non-particulate ion exchanger, and is preferably a non-particulate organic porous ion exchanger.

[0034] <Non-Particulate Organic Porous Ion Exchanger> The non-particulate organic porous ion exchanger is obtained by introducing an ion exchange group into a monolithic organic porous body having a continuous skeleton phase and a continuous pore phase. The non-particulate organic porous ion exchanger composed of the polymer chain represented by the general formula (1) above is a basic monolithic organic porous anion exchanger. The monolithic organic porous body has a large number of through-holes serving as flow paths between the skeletons. In this specification, the "monolithic organic porous body" is simply referred to as "monolith", the "monolithic organic porous ion exchanger" is simply referred to as "monolith ion exchanger", and the "monolithic organic porous intermediate" which is an intermediate (precursor) in the production of the monolith is also simply referred to as "monolith intermediate".

[0035] 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.

[0036] 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, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and it is preferable that the ion exchange groups are distributed in the organic porous ion exchanger. The continuous skeleton phase and the continuous pore phase are observed by SEM images.

[0037] The thickness of the continuous skeleton of the non-particulate organic porous ion exchanger in the dry state is preferably in the range of 1 to 100 μm. The thickness of the continuous skeleton of the non-particulate organic porous ion exchanger in the dry state is determined by SEM observation. When the thickness of this continuous skeleton is less than 1 μm, the ion exchange capacity per unit volume may decrease, or the mechanical strength may decrease. When the ion exchanger is packed in a column and the liquid to be treated is passed through, especially when passing the liquid at a high flow rate, the non-particulate organic porous ion exchanger may be deformed. When the thickness of this continuous skeleton exceeds 100 μm, the skeleton may become too thick, and the pressure loss during liquid passage may increase.

[0038] The average diameter of the continuous pores of the non-particulate organic porous ion exchanger in the dry state is preferably in the range of 1 to 1000 μm. The average diameter of the continuous pores of the non-particulate organic porous ion exchanger in the dry state is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. When the average diameter of this continuous pore is less than 1 μm, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may increase. When the average diameter of this continuous pore exceeds 1000 μm, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the contact between the liquid to be treated and the monolithic ion exchanger may be insufficient, and the ion exchange performance may decrease.

[0039] The total pore volume of the non-particulate organic porous ion exchanger in the dry state is preferably in the range of 0.5 to 50 mL / g. The total pore volume of the non-particulate organic porous ion exchanger in the dry state is measured by the mercury intrusion method. When this total pore volume is less than 0.5 mL / g, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may increase. When this total pore volume exceeds 50 mL / g, the mechanical strength of the non-particulate organic porous ion exchanger decreases. When the ion exchanger is packed in a column and the liquid to be treated is passed through, especially when passing the liquid at a high flow rate, the ion exchanger may be deformed and the pressure loss during liquid passage may increase.

[0040] The ion exchange capacity per weight of the non-particulate organic porous ion exchanger in the dry state is preferably in the range of 1 to 9 meq / g. The ion exchange capacity per weight of the non-particulate organic porous ion exchanger in the dry state is measured by a method such as neutralization titration. If this ion exchange capacity is less than 1 meq / g, the amount of ions that can be exchanged and supported may be reduced. If this ion exchange capacity exceeds 9 meq / g, the ion exchange group introduction reaction becomes severe, and oxidative degradation of the monolith may progress significantly.

[0041] 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, and more preferably uniformly distributed. "The ion exchange groups are uniformly distributed in the organic porous ion exchanger" means that the distribution of the ion exchange groups is distributed on the surface and inside the skeleton of the organic porous ion exchanger at least on the μm order. The distribution status of the ion exchange groups is confirmed by using an electron probe microanalyzer (EPMA). When the ion exchange groups are distributed not only on the surface of the monolith but also inside the skeleton of the monolith, the physical and chemical properties of the surface and inside of the monolith can be made substantially uniform, so the durability against swelling and shrinkage is improved.

[0042] 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 part in the general formula (1). It preferably contains 0.1 to 30 mol% of crosslinked structure units, and more preferably 0.1 to 20 mol% of crosslinked structure units, based on all the constituent units constituting the polymer material.

[0043] <The 1st to 5th monolith ion exchangers> As a more specific embodiment of the non-particulate organic porous ion exchanger, for example, the following first monolithic organic porous ion exchanger (monolithic ion exchanger) to fifth monolithic organic porous ion exchanger (monolithic ion exchanger) can be mentioned. In the following description, the description of the same configuration as the above non-particulate organic porous ion exchanger will be omitted.

[0044] <First monolithic ion exchanger> The first monolithic ion exchanger has a continuous macropore structure having common openings (mesopores) with an average diameter in the range of 1 to 1000 μm in the macropores and the walls of the macropores that are connected to each other. The total pore volume is in the range of 1 to 50 mL / g, and the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g. It is a monolithic ion exchanger in which ion exchange groups are distributed in the organic porous ion exchanger.

[0045] As shown in FIG. 1, the first monolithic ion exchanger is a continuous macroporous structure having continuous macropores (pores). The first monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2002-306976.

[0046] The first monolithic ion exchanger has common openings (mesopores) located in the macropores and the walls of the macropores that are connected to each other. The mesopores have overlapping portions where the macropores overlap. The overlapping portion of these mesopores preferably has an average diameter in the range of 1 to 1000 μm in the dry state, more preferably in the range of 10 to 200 μm, and even more preferably in the range of 20 to 200 μm. The average diameter of the openings of the first monolith in the dry state is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method.

[0047] Most of such a first monolithic ion exchanger has an open pore structure in which the voids formed by macropores and mesopores serve as flow paths. If the average diameter of the overlapping part of the mesopores in the dry state is less than 1 μm, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may become extremely large. If the average diameter of the overlapping part of the mesopores in the dry state exceeds 1000 μm, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the contact between the liquid to be treated and the monolithic ion exchanger may be insufficient, and the ion exchange performance may decrease. The overlap of macropores and macropores is, for example, 1 to 12 in one macropore, and many are 3 to 10. Since the first monolithic ion exchanger is the above-mentioned continuous macroporous structure, it is possible to form groups of macropores and groups of common pores almost uniformly, and compared with the particle-aggregated porous body described in JP-A-8-252579 and the like, the pore volume and specific surface area can be significantly increased.

[0048] The total pore volume per unit weight of the first monolithic ion exchanger in the dry state is preferably in the range of 1 to 50 mL / g, and more preferably in the range of 2 to 30 mL / g. If the total pore volume per unit weight in the dry state is less than 1 mL / g, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may increase, and furthermore, the permeation amount per unit cross-sectional area may decrease, and the treatment 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 ion exchanger is packed in a column and the liquid to be treated is passed through, the monolithic ion exchanger may be deformed especially when passing the liquid at a high flow rate.

[0049] The ion exchange capacity per unit weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0050] <Manufacturing Method of the First Monolithic Ion Exchanger> The first monolithic ion exchanger can be produced, for example, by the following method.

[0051] For example, first, an oil-soluble monomer containing no ion-exchange group, a surfactant, water, and, if necessary, a polymerization initiator are mixed to obtain a water-in-oil emulsion. Next, this water-in-oil emulsion can be polymerized to form the first monolith.

[0052] The oil-soluble monomer containing no ion-exchange group used in the production of the first monolith refers to a monomer that does not contain an ion-exchange group, has low solubility in water, and is lipophilic. Such monomers include, for example, styrene, α-methylstyrene, vinylbenzyl chloride, ethylene, propylene, vinyl chloride, vinyl bromide, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, butanediol diacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, ethylene glycol dimethacrylate, etc. These monomers can be used alone or in combination of two or more. However, it is preferable to select at least one component of the oil-soluble monomer as a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate, and set its content in the total oil-soluble monomers in the range of, for example, 0.3 to 10 mol%, preferably in the range of 0.3 to 5 mol%, because it is possible to quantitatively introduce an ion-exchange group in a subsequent step and ensure practically sufficient mechanical strength.

[0053] The surfactant used in the production of the first monolith may be any surfactant that can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion-exchange group is mixed with water, and there are no particular restrictions. Examples of the surfactant include nonionic surfactants such as sorbitan monooleate, sorbitan monolaurate, and polyoxyethylene nonylphenyl ether; anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, and sodium dioctyl sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; and amphoteric surfactants such as lauryldimethylbetaine. These surfactants can be used alone or in combination of two or more. A water-in-oil emulsion refers to an emulsion in which the oil phase is the continuous phase and water droplets are dispersed therein. The addition amount of the surfactant may be, for example, in the range of about 2 to 70% with respect to the total amount of the oil-soluble monomer and the surfactant. In order to control the bubble shape and size of the monolith, alcohols such as methanol and stearyl alcohol; carboxylic acids such as stearic acid; hydrocarbons such as octane, dodecane, and toluene; and cyclic ethers such as tetrahydrofuran and dioxane can also coexist in the system.

[0054] In the production of the first monolith, when forming the monolith by polymerization, the polymerization initiator that is used as needed is preferably a compound that generates radicals by heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and tetramethylthiuram disulfide. However, in some cases, there are systems in which polymerization proceeds only by heating or only by light irradiation without adding a polymerization initiator, and in such systems, it is not necessary to add a polymerization initiator.

[0055] 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, initiator system, etc. When using, for example, azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, etc. as the polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be heated and polymerized at, for example, 30 to 100 °C for 1 to 48 hours. When using hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, etc. as the polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be polymerized at, for example, 0 to 30 °C for 1 to 48 hours. After the polymerization is completed, the contents are taken out and extracted by Soxhlet extraction with a solvent such as isopropanol to remove unreacted monomers and residual surfactants, and the first monolith can be obtained.

[0056] As methods for introducing an ion exchange group into the first monolith, for example, there are the following methods (1) and (2). (1) Instead of using a monomer that does not contain an ion exchange group, a monomer that contains an ion exchange group, for example, a monomer in which an ion exchange group is introduced into the above-mentioned oil-soluble monomer that does not contain an ion exchange group, can be used for polymerization to obtain a monolith ion exchanger in one step. (2) Polymerization is carried out using a monomer that does not contain an ion exchange group to form the first monolith, and then an ion exchange group can be introduced.

[0057] As methods for introducing an ion exchange group into the first monolith, known methods such as polymer reactions and graft polymerization can be used. For example, there are the following methods (1) to (3). In the method (1), if the monolith is a styrene-divinylbenzene copolymer, etc., a chloromethyl group can be introduced by using chloromethyl methyl ether, etc., and then reacted with a desired tertiary amine for introduction. In the method (2), the monolith is produced by copolymerization of chloromethylstyrene and divinylbenzene, and can be reacted with a desired tertiary amine for introduction. In the method (3), a radical initiating group or a chain transfer group is introduced into the monolith, glycidyl methacrylate is graft polymerized, and then reacted with a desired tertiary amine for introduction.

[0058] For example, general formula (2)

Chem.

Chem.

[0059] In this method for producing an ion exchanger, the definitions of L and Polymer in general formula (2) and R 1 , R 2 , R 3 in general formula (3) are the same as the definitions of L, Polymer, R 1 , R 2 , R 3 in general formula (1), respectively.

[0060] X in general formula (2) represents a halogen atom, an optionally substituted alkylsulfonyl group having 1 to 8 carbon atoms, or an optionally substituted benzenesulfonyl group.

[0061] Examples of the halogen atom of X include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferred in view of the low cost of production raw materials and the like.

[0062] 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 in view of easy availability of raw materials, high reaction yield during production, and the like.

[0063] 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, and a halogen atom is preferred, and a fluorine atom is more preferred in view of high reaction yield and the like.

[0064] 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 in view of easy availability of raw materials and the like.

[0065] 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, for example, by mixing them in an organic solvent such as tetrahydrofuran, DMF, or toluene and heating at a temperature of, for example, 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 or water.

[0066] <The second monolithic ion exchanger> The second monolithic ion exchanger is a monolithic ion exchanger in which organic polymer particles in the range of an average particle diameter of 1 to 50 μm aggregate to form a three-dimensionally continuous skeleton portion, and three-dimensionally continuous pores in the range of an average diameter of 20 to 100 μm are provided between the skeletons, the total pore volume is in the range of 1 to 10 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger.

[0067] As shown in Fig. 2, the second monolithic ion exchanger is a particle-aggregated structure in which particles are aggregated. The second monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-007550.

[0068] The second monolithic ion exchanger has a three-dimensionally continuous skeleton portion formed by aggregation of organic polymer particles having a crosslinked structural unit and having an average particle diameter preferably in the range of 1 to 50 μm, more preferably in the range of 1 to 30 μm in the dry state. The second monolithic ion exchanger has three-dimensionally continuous pores (continuous pores) having an average diameter preferably in the range of 20 to 100 μm, more preferably in the range of 20 to 90 μm in the dry state between the continuous skeletons. An SEM photograph of an arbitrarily extracted portion of the cross section of the second monolithic ion exchanger in the dry state is taken, and the diameters of the organic polymer particles of all the particles in the SEM photograph are measured, and the average value thereof is taken as the average particle diameter. The average diameter of the continuous pores in the dry state is determined by the mercury intrusion method, similarly to the first monolithic ion exchanger.

[0069] When the average particle diameter of the organic polymer particles is less than 1 μm in the dry state, the average diameter of the continuous pores between the skeletons may become less than 20 μm in the dry state. When the average particle diameter of the organic polymer particles exceeds 50 μm, the pressure loss may increase when the ion exchanger is packed in a column and the liquid to be treated is passed through. Further, when the average diameter of the above-described continuous pores is less than 20 μm in the dry state, the pressure loss when the liquid to be treated is permeated may increase when the ion exchanger is packed in a column and the liquid to be treated is passed through. When the average diameter of the above-described continuous pores exceeds 100 μm in the dry state, the contact between the liquid to be treated and the monolithic ion exchanger may become insufficient when the ion exchanger is packed in a column and the liquid to be treated is passed through.

[0070] The total pore volume per unit weight of the second monolithic ion exchanger in the dry state is preferably in the range of 1 to 10 mL / g. If the total pore volume is less than 1 mL / g, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may become large. Furthermore, the permeation amount per unit cross-sectional area may become small, and the treatment capacity may decrease. If the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when the ion exchanger is packed in a column and the liquid to be treated is passed through, the monolithic ion exchanger may deform particularly when passing the liquid at a high flow rate.

[0071] The ion exchange capacity per unit weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0072] <Manufacturing Method of the Second Monolithic Ion Exchanger> The second monolithic ion exchanger can be manufactured, for example, by the following method.

[0073] For example, a second monolith can be obtained by mixing a vinyl monomer, a specific amount of a crosslinking agent, an organic solvent, and a polymerization initiator and polymerizing this in a stationary state.

[0074] The vinyl monomer used for the production of the second monolith is the same as the monomer used for the production of the first monolith.

[0075] The crosslinking agent used for manufacturing the second monolith preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Examples of the crosslinking agent include divinylbenzene, divinylbiphenyl, and ethylene glycol dimethacrylate. These crosslinking agents can be used alone or in combination of two or more. Preferred crosslinking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl from the viewpoints of high mechanical strength and stability against hydrolysis. The amount of the crosslinking agent used relative to the total amount of the vinyl monomer and the crosslinking agent ({crosslinking agent / (vinyl monomer + crosslinking agent)} × 100) is, for example, in the range of 1 to 5 mol%, preferably in the range of 1 to 4 mol%.

[0076] The organic solvent used for manufacturing the second monolith is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but hardly dissolves the polymer formed by polymerization of the vinyl monomer. In other words, it is a poor solvent for the polymer formed by polymerization of the vinyl monomer. Examples of this organic solvent include alcohols such as methanol, butanol, and octanol when the vinyl monomer is styrene; chain ethers such as diethyl ether and ethylene glycol dimethyl ether; and chain saturated hydrocarbons such as hexane, octane, and decane.

[0077] The polymerization initiator used for the production of the second monolith is preferably a compound that generates radicals by heat and light irradiation. The polymerization initiator is preferably oil-soluble. The polymerization initiator is, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide, etc. The amount of the polymerization initiator used relative to the total amount of the vinyl monomer and the crosslinking agent ({polymerization initiator / (vinyl monomer + crosslinking agent)} × 100) is, for example, in the range of about 0.01 to 5 mol%.

[0078] In the production of the second monolith, when, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as the polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be heated and polymerized at, for example, 30 to 100 °C for 1 to 48 hours. After the polymerization is completed, the contents are taken out, and for the purpose of removing unreacted vinyl monomer and organic solvent, for example, extraction with a solvent such as acetone can be carried out to obtain the second monolith.

[0079] In the production of the second monolith, organic polymer particles with an average particle diameter of 1 to 50 μm can be aggregated by adjusting polymerization conditions such as increasing the crosslinking agent, increasing the monomer concentration, and raising the temperature. By setting the amount of the crosslinking agent used to a specific amount relative to the total amount of the vinyl monomer and the crosslinking agent, three-dimensionally continuous pores with an average diameter of 20 to 100 μm can be formed between the skeletons. By polymerizing under conditions such that the amount of the organic solvent used ({organic solvent / (organic solvent + monomer + crosslinking agent)} × 100) relative to the total amount of the organic solvent, monomer, and crosslinking agent used is, for example, in the range of 30 to 80% by weight, preferably in the range of 40 to 70% by weight, the total pore volume of the monolith can be made 1 to 5 mL / g.

[0080] The method for introducing an ion exchange group into the second monolith is the same as the method for introducing an ion exchange group into the first monolith.

[0081] <The third monolith ion exchanger> The third monolith ion exchanger is a continuous macroporous structure in which bubble-like macropores overlap with each other, and the overlapping part forms an opening with an average diameter in the range of 30 to 300 μm. The total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, the ion exchange groups are distributed in the organic porous ion exchanger, and in the SEM image of the cross-section of the continuous macroporous structure, the cross-sectional skeletal area appearing in the cross-section is in the range of 25 to 50% of the image area. It is a monolith ion exchanger.

[0082] As shown in FIG. 3, the third monolith ion exchanger is a continuous macroporous structure similar to the first monolith ion exchanger. The third monolith ion exchanger and its production method are disclosed in JP-A-2009-062512.

[0083] The continuous pores have overlapping portions where the macropores overlap each other. The overlapping portion preferably has an average diameter in the range of 30 to 300 μm, more preferably in the range of 30 to 200 μm, and even more preferably in the range of 40 to 100 μm in the dry state. This average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. If the average diameter of the openings in the dry state is less than 30 μm, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may become large. If it exceeds 300 μm, the contact between the liquid to be treated and the monolithic ion exchanger may be insufficient.

[0084] In the third monolithic ion exchanger, in the SEM image of the cross-section of the continuous macroporous structure in the dry state, the area of the skeleton part appearing on the cross-section is in the range of, for example, 25 to 50% in the image area, preferably in the range of 25 to 45%. If the area of the skeleton part appearing on the cross-section is less than 25% in the image area, the skeleton becomes thin and the mechanical strength decreases. When the ion exchanger is packed in a column and the liquid to be treated is passed through, especially when passing the liquid at a high flow rate, the monolithic ion exchanger may be deformed. If the area of the skeleton part appearing on the cross-section exceeds 50% in the image area, the skeleton becomes too thick, and when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may increase.

[0085] The conditions for obtaining SEM images only need to be those under which the skeletal parts appearing on the cross-section of the cut surface are clearly shown. For example, the magnification is 100 - 600, and the photo area is approximately 150 mm × 100 mm. The SEM observation is preferably carried out with three or more images taken at different cutting locations or shooting locations on an arbitrary cut surface of the third monolithic ion exchanger excluding subjectivity. The third monolithic ion exchanger to be cut is in a dry state. The skeletal parts on the cut surface in the SEM image will be described with reference to FIGS. 3 and 4. In FIGS. 3 and 4, those that are generally irregularly shaped and appear in cross-section are the "skeletal parts appearing in the cross-section (reference numeral 12)". The circular holes shown in FIG. 3 are openings (mesopores), and those with relatively large curvatures or curved surfaces are macropores (reference numeral 13 in FIG. 4). The area of the skeletal part appearing in the cross-section of FIG. 4 is 28% in the rectangular image area 11.

[0086] As a method for measuring the area of the skeletal part appearing in the cross-section of the cut surface in the SEM image, after identifying the skeletal part by performing known computer processing or the like, calculation methods by automatic calculation or manual calculation using a computer or the like can be mentioned. As manual calculation, a method of replacing an irregularly shaped object with an aggregate of quadrilaterals, triangles, circles, trapezoids, etc., and stacking them to obtain the area can be mentioned.

[0087] The total pore volume per unit weight of the third monolithic ion exchanger in the dry state is preferably in the range of 0.5 - 10 mL / g, more preferably in the range of 0.8 - 8 mL / g. When the total pore volume is less than 0.5 mL / g, when filling the ion exchanger into a column and passing the liquid to be treated, the pressure loss during liquid passage may become large. Furthermore, the amount of permeating fluid per unit cross-sectional area may become small, and the treatment capacity may decrease. When the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when filling the ion exchanger into a column and passing the liquid to be treated, especially when passing the liquid at a high flow rate, the monolithic ion exchanger may be deformed. Furthermore, the contact efficiency between the liquid to be treated and the monolithic ion exchanger may decrease.

[0088] The ion exchange capacity per unit weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0089] <Method for Producing a Third Monolithic Ion Exchanger> The third monolithic ion exchanger can be produced, for example, by the following method.

[0090] For example, first, an oil-in-water emulsion is prepared by stirring a mixture of an oil-soluble monomer not containing an ion exchange group, a surfactant, and water. Next, the third monolith can be obtained by performing the following steps I, II, and III. In step I, the oil-in-water emulsion is polymerized to obtain a monolithic organic porous intermediate (hereinafter also referred to as monolith intermediate (3)) having a continuous macropore structure with a total pore volume in the range of, for example, 5 to 16 mL / g. In step II, a mixture containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent dissolve but the polymer formed by polymerization of the vinyl monomer does not dissolve, and a polymerization initiator is prepared. In step III, the mixture obtained in step II is polymerized in the presence of the monolith intermediate (3) obtained in step I under static conditions to obtain a third monolith having a skeleton thicker than the skeleton of the monolith intermediate (3).

[0091] Step I is the same as the method for producing the first monolithic ion exchanger.

[0092] The monolith intermediate (3) obtained in step I has a continuous macropore structure. When this is coexisted in the polymerization system, a porous structure having a thick skeleton can be formed using the structure of the monolith intermediate (3) as a mold. The crosslinking density of the polymer material preferably contains crosslinked structural units in the range of, for example, 0.3 to 10 mol%, preferably 0.3 to 5 mol%, based on all the constituent units constituting the polymer material of the monolith intermediate (3).

[0093] The total pore volume per weight of the monolithic intermediate (3) obtained in Step I in the dry state is, for example, in the range of 5 to 16 mL / g, preferably in the range of 6 to 16 mL / g. To make the total pore volume of the monolithic intermediate (3) within the above numerical range, the ratio of the monomer to water may be, for example, in the range of approximately 1:5 to 1:20.

[0094] The monolithic intermediate (3) obtained in Step I has an average diameter of the openings (mesopores), which are the overlapping parts of the macropores, in the dry state in the range of, for example, 20 to 200 μm.

[0095] Step II is a step of preparing a mixture containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent are soluble but the polymer produced by the polymerization of the vinyl monomer is insoluble, and a polymerization initiator. Note that the order of Step I and Step II may be either one first.

[0096] The vinyl monomer used in Step II may be any lipophilic vinyl monomer containing a polymerizable vinyl group in the molecule and having high solubility in the organic solvent, and it is preferable to select a vinyl monomer that produces the same type or a similar polymer material as the monolithic intermediate (3) coexisting in the above polymerization system. Specific examples of these vinyl monomers are the same as those used in the production of the first monolith.

[0097] The addition amount of the vinyl monomer used in Step II is, with respect to the monolithic intermediate (3) coexisting during the polymerization, in the range of, for example, 3 to 50 times by weight, preferably in the range of 4 to 40 times by weight.

[0098] The crosslinking agent used in Step II is the same as the crosslinking agent used in the production of the second monolith.

[0099] The organic solvent used in Step II is the same as the organic solvent used in the production of the second monolith. The amount of these organic solvents used is preferably such that the concentration of the above vinyl monomer is, for example, 30 to 80% by weight.

[0100] The polymerization initiator used in the II process is the same as the polymerization initiator used in the production of the second monolith.

[0101] In the III process, for example, the mixture obtained in the II process is polymerized under standing and in the presence of the monolith intermediate (3) obtained in the I process, and a third monolith having a skeleton thicker than that of the monolith intermediate (3) can be obtained. When the monolith intermediate (3) having a continuous macroporous structure is present in the polymerization system, a third monolith can be obtained.

[0102] In the III process, for example, in a reaction vessel, the monolith intermediate (3) is placed in a state of being impregnated with a mixture (solution). The mixing ratio of the mixture obtained in the II process and the monolith intermediate (3) may be adjusted, for example, so that the addition amount of the vinyl monomer is in the range of 3 to 50 times by weight, preferably 4 to 40 times by weight, based on the monolith intermediate (3). In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the standing monolith intermediate, and polymerization proceeds within the skeleton of the monolith intermediate (3).

[0103] In the III process, various polymerization conditions are selected depending on the type of monomer, the type of polymerization initiator, etc. For example, when 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as the polymerization initiator, for example, in a sealed container under an inert atmosphere, heating polymerization may be carried out at, for example, 30 to 100 °C for 1 to 48 hours. By heating polymerization, the vinyl monomer and the crosslinking agent adsorbed and distributed on the skeleton of the monolith intermediate (3) polymerize within the skeleton, and the skeleton can be thickened. After the polymerization is completed, the contents are taken out, and for the purpose of removing unreacted vinyl monomer and organic solvent, for example, extraction with a solvent such as acetone can be carried out to obtain a third monolith.

[0104] The third monolithic ion exchanger can be obtained, for example, by performing a step IV of introducing an ion exchange group into the third monolith obtained in step III. The method of introducing an ion exchange group into the third monolith is the same as the method of introducing an ion exchange group into the first monolith.

[0105] <The fourth monolithic ion exchanger> The fourth monolithic ion exchanger is a co-continuous structure comprising a three-dimensionally continuous skeleton with a thickness in the range of 1 to 60 μm of a continuous skeleton composed of an aromatic vinyl polymer containing a crosslinked structural unit in the range of 0.1 to 5.0 mol% among all the structural units into which an ion exchange group is introduced, and three-dimensionally continuous pores with an average diameter in the range of 10 to 200 μm between the skeletons. The total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and it is a monolithic ion exchanger in which the ion exchange groups are distributed in the organic porous ion exchanger.

[0106] As shown in FIGS. 5 and 6, the fourth monolithic ion exchanger has a continuous skeleton phase 1 (continuous skeleton) and a continuous pore phase 2 (continuous pores), and they are intertwined to form a co-continuous structure 10 that is three-dimensionally continuous together. The pore phase 2 has higher continuity and almost no bias in its size compared to the first and second monoliths described above. The fourth monolithic ion exchanger is considered to have high mechanical strength because its skeleton is thick. The fourth monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-067982.

[0107] The continuous skeleton is composed of a vinyl polymer (such as an aromatic vinyl polymer) containing a cross-linked structural unit in the range of 0.1 to 5.0 mol% among all the constituent units into which an ion-exchange group is introduced, and the thickness of the continuous skeleton is three-dimensionally continuous in the range of, for example, 1 to 60 μm, preferably 3 to 58 μm in the dry state. If the cross-linked 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 the dry state, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the monolithic ion exchanger may be deformed particularly when passing through at a high flow rate. If the thickness of the continuous skeleton exceeds 60 μm in the dry state, the skeleton becomes too thick, and when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may increase.

[0108] The continuous pores are three-dimensionally continuous between the continuous skeletons in the range of, for example, an average diameter of 10 to 200 μm, preferably 15 to 180 μm in the dry state. If the average diameter of the continuous pores is less than 10 μm in the dry state, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may become large. If the average diameter exceeds 200 μm, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the contact between the liquid to be treated and the monolithic ion exchanger may be insufficient.

[0109] The aforementioned average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. The thickness of the continuous skeleton in the dry state is determined by SEM observation of the fourth monolithic ion exchanger in the dry state. Specifically, SEM observation of the fourth monolithic ion exchanger in the dry state is performed at least three times, the thickness of the skeleton in the obtained images is measured, and their average value is taken as the thickness of the continuous skeleton. Although the skeleton is rod-shaped and has a circular cross-sectional shape, those with an elliptical cross-sectional shape or other non-uniform cross-sectional shapes may be included. In this case, the thickness is the average of the minor axis and the major axis.

[0110] The total pore volume per weight of the fourth monolithic ion exchanger in the dry state is, for example, in the range of 0.5 to 10 mL / g. If the total pore volume is less than 0.5 mL / g, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may become large. Furthermore, the amount of permeating fluid per unit cross-sectional area may become small, and the processing capacity may decrease. If the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when the ion exchanger is packed in a column and the liquid to be treated is passed through, the monolithic ion exchanger may deform particularly when passing the liquid at a high flow rate. Furthermore, the contact efficiency between the liquid to be treated and the monolithic ion exchanger may decrease.

[0111] The vinyl polymer (aromatic vinyl polymer) constituting the continuous skeleton includes, for example, polystyrene, poly(α-methylstyrene), polyvinylbenzyl chloride, and the like. The above polymers may be polymers obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or polymers obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or may be a blend of two or more polymers. Among these organic polymer materials, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred in terms of the ease of forming a co-continuous structure, the ease of introducing ion exchange groups, high mechanical strength, and high stability to acids or alkalis.

[0112] The ion exchange capacity per weight in the dry state is as described above. Also, the fact that "ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0113] <Manufacturing Method of the Fourth Monolithic Ion Exchanger> The fourth monolithic ion exchanger can be produced, for example, by the following method.

[0114] For example, the fourth monolith can be obtained by performing the following steps I to III after adjusting the water-in-oil emulsion. In step I, for example, the water-in-oil emulsion is polymerized to obtain a monolithic organic porous intermediate (hereinafter referred to as monolith intermediate (4)) having a continuous macroporous structure with a total pore volume of more than, for example, 16 mL / g and 30 mL / g or less. In step II, for example, a mixture containing an aromatic vinyl monomer, a crosslinking agent in the range of, for example, 0.3 to 5 mol% in a fully oil-soluble monomer having at least two or more vinyl groups in one molecule, an organic solvent in which the aromatic vinyl monomer and the crosslinking agent dissolve but the polymer formed by polymerization of the aromatic vinyl monomer does not dissolve, and a polymerization initiator is prepared. In step III, for example, the mixture obtained in step II is polymerized in the presence of the monolith intermediate (4) obtained in step I under static conditions to obtain the fourth monolith.

[0115] Step I in the method for producing the fourth monolith is the same as that in the method for producing the first monolith ion exchanger.

[0116] The monolith intermediate (4) obtained in step I is, for example, an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. The crosslink density of this polymer material includes crosslinked structure units in the range of, for example, 0.1 to 5 mol%, preferably 0.3 to 3 mol% with respect to all the constituent units constituting the polymer material.

[0117] The type of the polymer material of the monolith intermediate (4) is the same as that of the polymer material of the monolith intermediate (3) in the method for producing the third monolith.

[0118] The total pore volume per weight of the monolith intermediate (4) obtained in step I in the dry state is more than, for example, 16 mL / g and 30 mL / g or less, preferably more than 16 mL / g and 25 mL / g or less. As shown in FIG. 7, the monolith intermediate (4) has a skeleton close to a rod shape. When this is made to coexist in the polymerization system, a porous body having a co-continuous structure can be formed using the structure of the monolith intermediate (4) as a mold.

[0119] The average diameter of the openings (mesopores), which are the overlapping parts of macropores in the monolithic intermediate (4) obtained in Step I, is in the range of, for example, 5 to 100 μm in the dry state.

[0120] Step II in the method for producing the fourth monolith is, for example, a step of preparing a mixture containing an aromatic vinyl monomer, a crosslinking agent in the range of, for example, 0.3 to 5 mol% in all oil-soluble monomers having at least two or more vinyl groups in one molecule, an organic solvent in which the aromatic vinyl monomer and the crosslinking agent dissolve but the polymer produced by the polymerization of the aromatic vinyl monomer does not dissolve, and a polymerization initiator. Note that the order of Step I and Step II may be either one first.

[0121] The aromatic vinyl monomer used in Step II is not particularly limited as long as it contains a polymerizable vinyl group in the molecule and is a lipophilic aromatic vinyl monomer having high solubility in the organic solvent. However, it is preferable to select a vinyl monomer that produces the same type or a similar polymer material as the monolithic intermediate (4) coexisting in the above polymerization system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, vinylnaphthalene, and the like. These monomers can be used alone or in combination of two or more. Preferred aromatic vinyl monomers are styrene, vinylbenzyl chloride, and the like.

[0122] The addition amount of the aromatic vinyl monomer used in Step II is in the range of, for example, 5 to 50 times by weight, preferably 5 to 40 times by weight, based on the monolithic intermediate (4) coexisting during the polymerization.

[0123] The crosslinking agent used in the II process preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent used is, for example, in the range of 0.3 to 5 mol%, particularly in the range of 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the crosslinking agent (total oil-soluble monomers). It is preferable that the amount of the crosslinking agent used is substantially equal to the crosslinking density of the monolith intermediate (4) coexisting during the vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too far apart, a deviation in the crosslinking density distribution may occur in the produced monolith, and when introducing an ion exchange group, cracks may easily occur during the ion exchange group introduction reaction.

[0124] The organic solvent used in the II process is, for example, an organic solvent that can dissolve aromatic vinyl monomers and crosslinking agents but cannot dissolve the polymer formed by the polymerization of aromatic vinyl monomers. In other words, it is a poor solvent for the polymer formed by the polymerization of aromatic vinyl monomers. The organic solvent is, 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 such as hexane, heptane, and octane; esters such as ethyl acetate, isopropyl acetate, and ethyl propionate. Also, even if it is a good solvent for polystyrene such as dioxane, THF, or toluene, it can be used as an organic solvent when used together with the above poor solvent and the amount used is small. The amount of these organic solvents used can be such that the concentration of the above aromatic vinyl monomer is, for example, 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the concentration of the aromatic vinyl monomer is less than 30% by weight, the polymerization rate may decrease, or the monolith structure after polymerization may deviate from the range of the fourth monolith. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may proceed too far.

[0125] The polymerization initiator used in the II process in the manufacturing method of the fourth monolith is the same as the polymerization initiator used in the II process in the manufacturing method of the third monolith.

[0126] The III process in the manufacturing method of the fourth monolith is, for example, a process in which the mixture obtained in the II process is polymerized under standing and in the presence of the monolith intermediate (4) obtained in the I process, changing the continuous macroporous structure of the monolith intermediate (4) to a co-continuous structure to obtain the fourth monolith which is a co-continuous structure monolith.

[0127] In the III process, for example, in a reaction vessel, the monolith intermediate (4) is placed in a state of being impregnated with a mixture (solution). As described above, the mixing ratio of the mixture obtained in the II process and the monolith intermediate (4) may be adjusted such that the addition amount of the aromatic vinyl monomer is, for example, in the range of 5 to 50 times by weight, preferably 5 to 40 times by weight, with respect to the monolith intermediate (4). Thereby, a fourth monolith having a co-continuous structure in which pores of an appropriate size are three-dimensionally continuous and a thick skeleton is three-dimensionally continuous can be obtained. In the reaction vessel, the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the stationary monolith intermediate (4), and polymerization proceeds within the skeleton of the monolith intermediate (4).

[0128] The polymerization conditions in the III process in the method for producing the fourth monolith are the same as the description of the polymerization conditions in the III process in the method for producing the third monolith. The fourth monolith ion exchanger can be obtained by performing a step IV of introducing an ion exchange group into the fourth monolith obtained in the III process. The method for introducing an ion exchange group into the fourth monolith is the same as the method for introducing an ion exchange group into the first monolith.

[0129] <The fifth monolith ion exchanger> The fifth monolith ion exchanger consists of a continuous skeleton phase and a continuous pore phase. The skeleton has a plurality of protrusions with a size in the range of 4 to 40 μm formed on the surface of the skeleton of a plurality of particulate bodies or organic porous bodies with a diameter in the range of 4 to 40 μm fixed on the surface. The average diameter of the continuous pores is in the range of 10 to 200 μm, the total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger.

[0130] The fifth monolithic ion exchanger has an organic porous body having a continuous skeletal phase and a continuous pore phase, and is a composite structure further having a plurality of particulate bodies or a plurality of protrusions, and is a composite structure having a large number of particulate bodies or a large number of protrusions. The fifth monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-108294.

[0131] The plurality of particulate bodies are fixed to the skeletal surface of the organic porous body, and their diameter is, for example, in the range of 4 to 40 μm. The plurality of protrusions are formed on the skeletal surface of the organic porous body, and their size is, for example, in the range of 4 to 40 μm in the dry state. The diameter of the particulate body or the size of the protrusion is preferably in the range of 4 to 30 μm, and more preferably in the range of 4 to 20 μm. In the present specification, the "particulate body" and the "protrusion" are collectively referred to as "particulate bodies and the like".

[0132] The average diameter of the continuous pores in the dry state is preferably in the range of 10 to 200 μm.

[0133] The continuous skeletal phase and the continuous pore phase of the fifth monolithic ion exchanger are observed by SEM images. Examples of the basic structure of the fifth monolithic ion exchanger include a continuous macroporous structure and a co-continuous structure. The skeletal phase of the fifth monolithic ion exchanger appears as a columnar continuum, a continuum of concave walls, or a composite thereof, and has a shape clearly different from particulate or protrusion shapes.

[0134] The fifth monolithic ion exchanger includes a fifth-1 monolithic ion exchanger or a fifth-2 monolithic ion exchanger. The fifth-1 monolithic ion exchanger is a continuous macroporous structure in which bubble-like macropores overlap with each other, and the overlapping part forms an opening with an average diameter in the range of, for example, 10 to 120 μm in the dry state. The fifth-2 monolithic ion exchanger is a co-continuous structure composed of a three-dimensionally continuous skeleton with a thickness of the continuous skeleton in the dry state in the range of, for example, 0.8 to 40 μm, and three-dimensionally continuous pores with an average diameter in the range of, for example, 8 to 80 μm between the skeletons in the dry state. The monoliths before the introduction of the ion exchange groups of the fifth-1 and fifth-2 monolithic ion exchangers are called the fifth-1 and fifth-2 monoliths. The average diameter and the thickness of the continuous skeleton in the dry state described above are determined by the same measurement method as that of the fourth monolithic ion exchanger.

[0135] As shown in (A) to (E) in FIG. 8, the protruding projections from the skeleton surface 21 are the projections 22a to 22e. As shown in (A), the projection 22a has a shape close to a granular shape. As shown in (B), the projection 22b is hemispherical. As shown in (C), the projection 22c has a shape like a bulge on the skeleton surface. As shown in (D), the length of the projection 22d in the plane direction of the skeleton surface 21 is longer than the length in the direction perpendicular to the skeleton surface 21 of the projection 22d. As shown in (E), the projection 22e has a shape protruding in a plurality of directions. The size of the projection is the length of the part where the width in the SEM image of each individual projection is the largest. As shown in FIG. 9, in the fifth monolithic ion exchanger, a plurality of projections are formed on the skeleton surface of the organic porous body.

[0136] In the fifth monolithic ion exchanger, in the whole particle body or the like, the proportion of the particle body or the like in the range of 4 to 40 μm in the dry state is, for example, 70% or more, preferably 80% or more. The proportion occupied by the aforementioned particle body or the like refers to the proportion of the number of particle bodies or the like of a specific size in the dry state in the total number of all particle bodies or the like. Further, the surface of the skeleton phase is coated with, for example, 40% or more, preferably 50% or more, by all the particle bodies or the like. Note that the coating ratio of the surface of the skeleton layer by all the particle bodies or the like refers to the area ratio on the SEM image when observing the surface by SEM, that is, the area ratio when the surface is viewed in plan view. When the size of the particles covering the wall surface and the skeleton deviates from the above range, the effect of improving the contact efficiency between the fluid and the skeleton surface and the inside of the monolithic ion exchanger may be easily reduced.

[0137] Perform SEM observation of the fifth monolithic ion exchanger in the dry state at least three times. Calculate the diameter or size of all particle bodies or the like in the dry state in the SEM image in the entire field of view, and confirm whether particle bodies or the like with a diameter or size in the range of, for example, 4 to 40 μm are observed. If confirmed in the entire field of view, it is determined that particle bodies or the like with a diameter or size in the range of, for example, 4 to 40 μm in the dry state are formed on the skeleton surface of the fifth monolithic ion exchanger. Also, calculate the diameter or size of all particle bodies or the like in the dry state in the SEM image for each field of view according to the above, and for each field of view, obtain the proportion of particle bodies or the like in the range of, for example, 4 to 40 μm in the dry state in all particle bodies or the like. If the proportion of particle bodies or the like in the range of, for example, 4 to 40 μm in the dry state in all particle bodies or the like is 70% or more in the entire field of view, it is determined that the proportion of particle bodies or the like in the range of, for example, 4 to 40 μm in the dry state in all the particle bodies or the like formed on the skeleton surface of the fifth monolithic ion exchanger is 70% or more. Also, obtain the coating ratio of the surface of the skeleton layer by all the particle bodies or the like in the SEM image for each field of view according to the above. If the coating ratio of the surface of the skeleton layer by all the particle bodies or the like is 40% or more in the entire field of view, it is determined that the ratio of the surface of the skeleton layer of the fifth monolithic ion exchanger coated by all the particle bodies or the like is 40% or more.

[0138] In the fifth monolithic ion exchanger, if the coverage rate of the surface of the skeleton phase by particulate materials or the like is less than 40%, the effect of improving the contact efficiency between the liquid to be treated and the inside and surface of the skeleton of the monolithic ion exchanger may be likely to be reduced. Examples of the method for measuring the coverage rate by the particulate materials or the like include an image analysis method using a SEM image of the fifth monolithic ion exchanger.

[0139] The total pore volume per unit weight of the fifth monolithic ion exchanger in the dry state is, for example, in the range of 0.5 to 10 mL / g, preferably in the range of 0.8 to 8 mL / g. If the total pore volume is less than 0.5 mL / g, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss during liquid passage may become large. Furthermore, the amount of permeated fluid per unit cross-sectional area may become small, and the processing capacity may decrease. If the total pore volume exceeds 10 mL / g, the mechanical strength may decrease, and when the ion exchanger is packed in a column and the liquid to be treated is passed through, the monolithic ion exchanger may be deformed particularly when passing the liquid at a high flow rate. Furthermore, the contact efficiency between the liquid to be treated and the monolithic ion exchanger may decrease.

[0140] In the fifth monolithic ion exchanger, the crosslinking density of the polymer material constituting the skeleton may include crosslinked structural units in the range of, for example, 0.3 to 10 mol%, preferably in the range of 0.3 to 5 mol% with respect to all the constituent units constituting the polymer material. The organic polymer material constituting the skeleton of the fifth monolithic ion exchanger is the same as that of the first monolithic ion exchanger.

[0141] In the fifth monolithic ion exchanger, examples of the material constituting the skeleton phase of the organic porous body and the particulate materials or the like formed on the surface of the skeleton phase include those of the same material with continuous same tissue, and those of different materials with continuous different tissues. Examples of those of different materials with continuous different tissues include cases where the types of vinyl monomers are different from each other, and cases where the types of vinyl monomers and crosslinking agents are the same but the blending ratios are different from each other.

[0142] The fifth monolithic ion exchanger has a thickness of, for example, 1 mm or more and is distinguished from a membrane-like porous body. The thickness of the fifth monolithic ion exchanger is preferably in the range of 3 to 1000 mm.

[0143] The ion exchange capacity per unit weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0144] <Manufacturing Method of the Fifth Monolithic Ion Exchanger> The fifth monolithic ion exchanger can be manufactured, for example, by the following method.

[0145] The fifth monolith can be obtained, for example, by preparing a water-in-oil emulsion and then performing the following steps I to III. In step I, for example, the water-in-oil emulsion is polymerized to obtain a monolithic organic porous intermediate (hereinafter referred to as monolith intermediate (5)) having a continuous macroporous structure with a total pore volume in the range of, for example, 5 to 30 mL / g. In step II, for example, a mixture containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent are soluble but the polymer formed by polymerization of the vinyl monomer is insoluble, and a polymerization initiator is prepared. In step III, for example, the mixture obtained in step II is polymerized under standing in the presence of the monolith intermediate (5) obtained in step I to obtain the fifth monolith.

[0146] Step I in the manufacturing method of the fifth monolith is the same as step I in the manufacturing method of the third monolith.

[0147] In Step I, when forming an oil-in-water droplet type emulsion, a polymerization initiator may be used as necessary. As the polymerization initiator, a compound that generates radicals by heat or light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. Examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and the like.

[0148] The monolith intermediate (5) obtained in Step I has a continuous macroporous structure. When this is allowed to coexist in the polymerization system, a particulate material or the like is formed on the surface of the skeletal phase of the continuous macroporous structure using the structure of the monolith intermediate (5) as a template, or a particulate material or the like is formed on the surface of the skeletal phase of the co-continuous structure. Further, the monolith intermediate (5) is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material includes crosslinked structure units in the range of, for example, 0.3 to 10 mol%, preferably 0.3 to 5 mol%, based on all the constituent units constituting the polymer material.

[0149] The type of the polymer material of the monolith intermediate (5) is the same as the type of the polymer material of the monolith intermediate (3) in the method for producing the third monolith.

[0150] The total pore volume per weight of the monolith intermediate (5) obtained in Step I in the dry state is in the range of, for example, 5 to 30 mL / g, preferably in the range of 6 to 28 mL / g. To make the total pore volume of the monolith intermediate (5) within the above numerical range, the ratio (by weight) of the monomer to water may be, for example, approximately 1:5 to 1:35.

[0151] In Step I, if the ratio of this monomer to water is approximately 1:5 to 1:20, a monolith intermediate (5) with a continuous macropore structure having a total pore volume of, for example, 5 to 16 mL / g can be obtained, and the monolith obtained through Step III becomes the Monolith No. 5-1. On the other hand, if the ratio of the monomer to water is approximately 1:20 to 1:35, a monolith intermediate (5) with a total pore volume exceeding, for example, 16 mL / g and not more than 30 mL / g and having a continuous macropore structure can be obtained, and the monolith obtained through Step III becomes the Monolith No. 5-2.

[0152] In the monolith intermediate (5) obtained in Step I in the method for producing the fifth monolith, the average diameter in the dry state of the openings (mesopores), which are the overlapping parts of the macropores, is, for example, 20 to 200 μm.

[0153] Step II in the method for producing the fifth monolith is the same as Step II in the method for producing the third monolith. In Step III in the method for producing the fifth monolith, for example, the mixture obtained in Step II can be polymerized while standing and in the presence of the monolith intermediate (5) obtained in Step I to obtain the fifth monolith.

[0154] Here, as disclosed in Japanese Patent Publication No. 7-501140 and the like, when a vinyl monomer and a crosslinking agent are allowed to stand and polymerize in a specific organic solvent in the absence of the monolith intermediate (5), a particulate-aggregation type monolithic organic porous body can be obtained. In contrast, when a monolith intermediate (5) having a continuous macropore structure is present in the above polymerization system, the structure of the composite monolith after polymerization changes dramatically, and a fifth monolith having the above-described specific skeletal structure rather than a particulate-aggregation structure can be obtained.

[0155] In the III step of the method for producing the fifth monolith, the internal volume of the reaction vessel is not particularly limited as long as it is large enough to accommodate the monolith intermediate (5) in the reaction vessel. When the monolith intermediate (5) is placed in the reaction vessel, it may be either a case where a gap is formed around the monolith in a plan view or a case where the monolith intermediate (5) fits into the reaction vessel with almost no gap. Among these, a case where the fifth monolith after polymerization enters the reaction vessel with almost no gap and is hardly pressed by the inner wall of the vessel is efficient with almost no waste of reaction raw materials and the like, and hardly causes distortion in the fifth monolith. Even when the internal volume of the reaction vessel is large and there is a gap around the fifth monolith after polymerization, since the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate (5), hardly any particle agglomeration structure is generated in the gap portion in the reaction vessel.

[0156] In this III step, for example, in the reaction vessel, the monolith intermediate (5) is placed in a state of being impregnated with a mixture (solution). As described above, the mixing ratio of the mixture obtained in the II step and the monolith intermediate (5) may be adjusted so that the addition amount of the vinyl monomer is in the range of, for example, 3 to 50 times by weight, preferably 4 to 40 times by weight, with respect to the monolith intermediate (5). Thereby, a fifth monolith, which is a composite monolith having a specific skeleton while having an appropriate pore diameter, can be obtained. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the stationary monolith intermediate (5), and polymerization proceeds within the skeleton of the monolith intermediate (5).

[0157] In the III step of the method for producing the fifth monolith, the polymerization conditions are almost the same as those in the III step of the method for producing the third monolith.

[0158] When producing the above-described fifth monolith, if the II step or the III step is carried out under conditions satisfying at least one of the following conditions (1) to (5), a monolith having particle bodies or the like formed on the surface of the skeleton can be produced. (1) The polymerization temperature in the III process is at least 5 °C lower than the 10-hour half-life temperature of the polymerization initiator. (2) The molar percentage of the crosslinking agent used in the II process is 2 times or more the molar percentage of the crosslinking agent used in the I process. (3) The vinyl monomer used in the II process is a vinyl monomer having a structure different from that of the oil-soluble monomer used in the I process. (4) The organic solvent used in the II process is a polyether having a molecular weight of 200 or more. (5) The concentration of the vinyl monomer used in the II process is 30% by weight or less in the mixture of the II process.

[0159] Preferred structures of the fifth monolith obtained in this way include a continuous macroporous structure in which bubble-like macropores overlap and the overlapping part becomes an opening in the range of, for example, an average diameter of 10 to 120 μm in the dry state ("the fifth-1 monolith"), and a three-dimensionally continuous skeleton with a thickness of the continuous skeleton in the dry state in the range of, for example, 0.8 to 40 μm, and three-dimensionally continuous pores with a diameter in the range of, for example, 8 to 80 μm in the dry state between the skeletons, a co-continuous structure ("the fifth-2 monolith"). Note that the method for introducing an ion-exchange group into the fifth monolith is the same as the method for introducing an ion-exchange group into the first monolith.

[0160] <Ion exchange method using an ion exchanger> Ion exchange (anion exchange) can be performed using the ion exchanger according to this embodiment. For ion exchange, the liquid to be treated and the ion exchanger may be brought into contact at a temperature of, for example, 0 to 100 °C. For example, ion exchange can be performed by passing the liquid to be treated through a column filled with the ion exchanger at a temperature of 0 to 100 °C.

[0161] The ion exchange method using the ion exchanger according to this embodiment can be used, for example, in the purification of water, sugar solutions, organic solvents, etc., in the synthesis process of chemical products such as pharmaceutical intermediates, and as a packing material for ion chromatography for analysis.

[0162] By using the ion exchanger according to the present embodiment, even when an organic solvent is passed through a column filled with the ion exchanger in a water-wet state, the shrinkage of the ion exchanger is small, and the organic solvent can be efficiently brought into contact with the ion exchanger.

Example

[0163] Hereinafter, examples and comparative examples will be given to describe the present invention more specifically and in detail. However, the present invention is not limited to the following examples.

[0164] <Example 1> According to the method for producing the fifth monolithic ion exchanger, a monolith was produced, and an ion exchange group was introduced into the obtained monolith.

[0165] (Production of Monolith Intermediate (Step I)) 9.28 g of styrene as a monomer, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) as a surfactant, and 0.25 g of 2,2'-azobis(isobutyronitrile) as a polymerization initiator were mixed and dissolved uniformly. Next, this styrene / divinylbenzene / SMO / 2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water, and stirred under reduced pressure using a vacuum stirring and degassing mixer (manufactured by EMI Co., Ltd.), which is a planetary stirring device, to obtain a water-in-oil droplet type emulsion. This emulsion was quickly transferred to a reaction vessel, sealed, and polymerized at 60°C for 24 hours under standing. After the polymerization was completed, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macroporous structure. The internal structure of the thus obtained monolith intermediate (dry body) was observed by SEM. The SEM image is shown in FIG. 10. Although the wall portion partitioning two adjacent macropores is extremely thin and rod-shaped, it has a continuous macroporous structure. The average diameter of the opening (mesopore) of the portion where the macropores overlap measured by mercury intrusion porosimetry was 40 μm, and the total pore volume was 18.2 mL / g.

[0166] (Production of Monolith (Step II)) Next, 216.6 g of styrene as a monomer, 4.4 g of divinylbenzene as a crosslinking agent, 220 g of 1-decanol as an organic solvent, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator were mixed and dissolved uniformly (Step II).

[0167] (Production of Monolith (Step III)) Next, the above monolith intermediate was placed in a reaction vessel, immersed in the styrene / divinylbenzene / 1-decanol / 2,2'-azobis(2,4-dimethylvaleronitrile) mixture, defoamed in a vacuum chamber, and then the reaction vessel was sealed and polymerized at 50 °C for 24 hours under static conditions. After the polymerization was completed, the contents were taken out, Soxhlet extracted with acetone, and then dried under reduced pressure (Step III).

[0168] The results of observing the internal structure of the monolith (dry body) containing 1.2 mol% of the crosslinked component composed of the styrene / divinylbenzene copolymer thus obtained by SEM are shown in Fig. 11. As is clear from Fig. 11, this monolith had a continuous skeletal phase and a continuous pore phase in which the skeleton and pores were three-dimensionally continuous, respectively, and had a co-continuous structure in which both phases were intertwined. Also, the thickness of the skeleton measured from the SEM image was 20 μm. Further, the average diameter of the three-dimensionally continuous pores of this monolith measured by mercury intrusion porosimetry was 70 μm, and the total pore volume was 4.4 mL / g. The average diameter of the pores was determined from the maximum value of the pore size distribution curve obtained by mercury intrusion porosimetry.

[0169] (Production of Chloromethylated Monolith) The produced monolith was placed in a column reactor, and a solution containing 1600 g of chlorosulfonic acid, 400 g of tin tetrachloride, and 2500 mL of dimethoxymethane was circulated and passed through to react at 30 °C for 5 hours to introduce chloromethyl groups. After the reaction was completed, the chloromethylated monolith was washed with a mixed solvent of THF / water = 2 / 1 (vol), and further washed with THF to obtain a chloromethylated monolith.

[0170] (Production of Monolith Ion Exchanger) To 20 g of the chloromethylated monolith, 390 mL of THF and 30 mL of N,N-dimethylbenzylamine as a tertiary amine were added, and the mixture was reacted at 60 °C for 6 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a monolith ion exchanger composed of a polymer chain represented by the following formula (4).

Chemical formula

[0171] The anion exchange capacity of the obtained monolith ion exchanger was 2.9 meq / g in the dry state, and it was confirmed that the quaternary ammonium groups were quantitatively introduced. As is clear from Fig. 11, the monolith anion exchanger had a co-continuous structure in which the skeleton and pores were three-dimensionally continuous and the two phases were intertwined. Also, the thickness of the skeleton in the dry state measured from the SEM image was 20 μm, the average diameter of the three-dimensionally continuous pores of this monolith anion exchanger in the dry state determined by mercury intrusion porosimetry was 70 μm, and the total pore volume in the dry state was 4.4 mL / g.

[0172] Hereinafter, the monolith ion exchanger obtained in Example 1 will be referred to as "benzyl-type monolith anion exchanger".

[0173] <Comparative Example 1> The procedure of Example 1 was repeated except that 30% aqueous trimethylamine solution was used instead of N,N-dimethylbenzylamine as the tertiary amine to obtain a monolith ion exchanger composed of a polymer chain represented by the following formula (5).

Chemical formula

[0174] Hereinafter, the monolith ion exchanger obtained in Comparative Example 1 will be referred to as "trimethyl-type monolith anion exchanger".

[0175] <Example 2> The benzyl-type monolith anion exchanger obtained in Example 1 was cut into a size of 600 mm × 150 mm × 100 mm. After immersing this in 300 mL of water at room temperature (25 ± 2°C) for 30 minutes to make it in a water-wet state, it was washed three times with 150 mL each of methanol, 2-propanol, N-methyl-2-pyrrolidone (NMP), and tetrahydrofuran (THF) as organic solvents. After sufficiently performing the substitution of moisture, the size was measured, and the swelling ratio (%) (length ratio) from the water-wet state was estimated. The results are shown in FIG. 12.

[0176] <Comparative Example 2> It was carried out in the same manner as in Example 2 except that the benzyl-type monolith anion exchanger was made into a trimethyl-type monolith anion exchanger. The results are shown in FIG. 12.

[0177] Thus, the ion exchanger of the example had less shrinkage when contacted with the organic solvent in the water-wet state compared to the ion exchanger of the comparative example.

Explanation of Signs

[0178] 1 Skeletal phase, 2 Pore phase, 10 Co-continuous structure, 11 Rectangular image region, 12 Skeletal part, 13 Macropore, 21 Skeletal surface, 22a, 22b, 22c, 22d, 22e Protrusions.

Claims

1. An ion exchanger composed of a polymer chain represented by the general formula (1), 【Chemical 1】 (wherein R １ represents an alkyl group having 6 to 20 carbon atoms; or a benzyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms; R ２ , R ３ each independently represents an alkyl group having 1 to 4 carbon atoms, L represents a linker moiety, and Polymer represents a polymer chain.) wherein the ion exchanger is a non-particulate organic porous ion exchanger, 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, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger. An ion exchanger characterized by this.

2. The ion exchanger according to Claim 1, wherein L in the general formula (1) is a methylene group. An ion exchanger characterized by this.

3. The ion exchanger according to Claim 1 or 2, wherein the polymer chain of the ion exchanger is a styrene - divinylbenzene copolymer. An ion exchanger characterized by this.

4. A method for producing an ion exchanger by reacting a polymer chain represented by the general formula (2), (wherein L represents a linker site, Polymer represents a polymer chain, and X represents a halogen atom, an optionally substituted alkylsulfonyl group having 1 to 8 carbon atoms, or an optionally substituted benzenesulfonyl group.) 【Chemical 2】 with a tertiary amine represented by the general formula (3), wherein the ion exchanger is a non-particulate organic porous ion exchanger, 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, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger. A method for producing an ion exchanger characterized by this. 【Chemical Formula 3】 (wherein R １ represents an alkyl group having 6 to 20 carbon atoms; or a benzyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms; and R ２ , R ３ each independently represents an alkyl group having 1 to 4 carbon atoms.)

5. The method for producing an ion exchanger according to Claim 4, wherein L in the general formula (1) is a methylene group. A method for producing an ion exchanger characterized by this.

6. The method for producing an ion exchanger according to Claim 4 or 5, wherein the polymer chain of the ion exchanger is a styrene - divinylbenzene copolymer. A method for producing an ion exchanger characterized by this. ​ ​ ​ ​

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