JP2022163531A - Ion exchanger and method for producing ion exchanger - Google Patents

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

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

Ion exchange reactions are important in the purification of water, sugar solutions, etc., synthesis processes of chemical products such as pharmaceutical intermediates, etc., and ion exchangers such as ion exchange resins are used. In recent years, there has been a demand for highly purified organic solvents, and methods for purifying organic solvents using ion exchangers have also been developed. describes a method of purifying by contacting an organic solvent such as 2-propanol containing polyvalent metal ions.

JP 2017-119233 A

However, as a result of examination by the present inventors, when an organic solvent is passed through a column filled with a monolithic organic porous ion exchanger in a water-wet state, the monolithic organic porous ion exchanger shrinks significantly, and the organic solvent is removed. It has been found that there is a problem of not efficiently contacting the monolithic organic porous ion exchanger.

SUMMARY OF THE INVENTION An object of the present invention is to provide an ion exchanger that shrinks less when it contacts with an organic solvent in a water-wet state, and a method for producing the ion exchanger.

（式中Ｒ^１は、置換されていてもよい炭素数４から２２のアルキル基；または、置換されていてもよい炭素数１から６のアルキル基、ハロゲン原子、置換されていてもよい炭素数１から６のアルコキシ基、置換されていてもよいアミノ基、シアノ基、もしくはニトロ基で置換されていてもよいベンジル基；を表し、Ｒ^２，Ｒ^３は、それぞれ独立して炭素数１から４のアルキル基を表し、Ｌは、リンカー部位を表し、Ｐｏｌｙｍｅｒは、高分子鎖を表す。）
で表される高分子鎖から構成される、イオン交換体である。 The present invention has the general formula (1)

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

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

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

In the ion exchanger, the ion exchanger is a 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, and the ion exchange capacity per weight in the dry state is 1 to 9 mg equivalent. /g, and the ion exchange groups are preferably distributed in the organic porous ion exchanger.

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

（式中Ｒ^１は、置換されていてもよい炭素数４から２２のアルキル基；または、置換されていてもよい炭素数１から６のアルキル基、ハロゲン原子、置換されていてもよい炭素数１から６のアルコキシ基、置換されていてもよいアミノ基、シアノ基、もしくはニトロ基で置換されていてもよいベンジル基；を表し、Ｒ^２，Ｒ^３は、それぞれ独立して炭素数１から４のアルキル基を表す。）
で表される第三級アミンと、
を反応させる、イオン交換体の製造方法である。 The present invention has the general formula (2)

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

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

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

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

In the method for producing an ion exchanger, the ion exchanger is a non-particulate organic porous ion exchanger, consists of a continuous skeleton phase and a continuous pore phase, and the thickness of the continuous skeleton is in the range of 1 to 100 μm. , the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, and the ion exchange capacity per weight in the dry state is 1 It is preferably in the range of ~9 mg equivalent/g, and the ion exchange groups are distributed in the organic porous ion exchanger.

ADVANTAGE OF THE INVENTION According to this invention, the ion exchanger which shrinks little when it contacts with the organic solvent in a water wet state, and the manufacturing method of the ion exchanger can be provided.

FIG. 4 is an SEM photograph of a first example monolith morphology; FIG. FIG. 4 is an SEM photograph of a second example monolith morphology; FIG. FIG. 11 is an SEM photograph of a third example monolith morphology; FIG. FIG. 4 is a diagram obtained by transferring a skeleton portion appearing as a cross section of the SEM photograph of FIG. 3 ; FIG. 4 is an SEM photograph of a fourth example monolith morphology; FIG. FIG. 4 is a schematic representation of the co-continuous structure of the fourth monolith and weakly basic monolith ion exchanger. FIG. 10 is an SEM photograph of an example morphology of monolith intermediate (4). FIG. FIG. 4 is a schematic cross-sectional view of a projection; FIG. 10 is a SEM photograph of a morphological example of a monolith of No. 5-1. FIG. 1 is a SEM photograph of a monolithic intermediate obtained in Example 1. FIG. 1 is an SEM photograph of a monolith obtained in Example 1. FIG. 4 is a graph showing the swelling rate (%) (length ratio) when the monolithic anion exchanger in a water-wet state is brought into contact with each organic solvent in Example 2 and Comparative Example 2. FIG.

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

（式中Ｒ^１は、置換されていてもよい炭素数４から２２のアルキル基；または、置換されていてもよい炭素数１から６のアルキル基、ハロゲン原子、置換されていてもよい炭素数１から６のアルコキシ基、置換されていてもよいアミノ基、シアノ基、もしくはニトロ基で置換されていてもよいベンジル基；を表し、Ｒ^２，Ｒ^３は、それぞれ独立して炭素数１から４のアルキル基を表し、Ｌは、リンカー部位を表し、Ｐｏｌｙｍｅｒは、高分子鎖を表す。）
で表される高分子鎖から構成される。 <Ion exchanger>
An ion exchanger according to an embodiment of the present invention has the general formula (1)

(In the formula, R ¹ is an optionally substituted alkyl group having 4 to 22 carbon atoms; or an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, or an optionally substituted carbon number 1 to ⁶ alkoxy groups, optionally substituted amino groups, cyano groups ^, or benzyl groups optionally substituted with nitro groups; 4 represents an alkyl group, L represents a linker moiety, and Polymer represents a polymer chain.)
Consists of a polymer chain represented by

The present inventors have found that the ion exchanger composed of the polymer chains represented by the above general formula (1) shrinks little when in contact with an organic solvent in a water-wet state. Even when the ion exchanger is packed in a column in a water-wet state and an organic solvent is passed through the ion exchanger, the ion exchanger hardly shrinks and the organic solvent can be brought into contact with the ion exchanger efficiently. It is considered that this is because the presence of the alkyl group having 4 to 22 carbon atoms or the benzyl group as R ¹ increases the hydrophobicity.

With the ion exchanger according to the present embodiment, the shrinkage rate when contacted with an organic solvent in a water-wet state can be, for example, within ±10% compared to before contact with an organic solvent, preferably within ± It can be 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), and diisopropyl ether. , tetrahydrofuran (THF) and the like, aromatic solvents such as toluene and xylene, and hydrocarbon solvents such as pentane and hexane.

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

The alkyl group having 4 to 22 carbon atoms may be linear, branched or cyclic. An alkyl group having 6 to 20 carbon atoms is 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.

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

The halogen atom which may be substituted on the benzyl group includes a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom is preferable from the viewpoint of low cost of raw material production.

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

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

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

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

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

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

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

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

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

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

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

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

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

The thickness of the continuous skeleton of the non-particulate organic porous ion exchanger in a dry state is preferably in the range of 1 to 100 μm. The thickness of the continuous framework in the dry state of the non-particulate organic porous ion exchanger is determined by SEM observation. If the thickness of the continuous skeleton is less than 1 μm, the ion exchange capacity per volume is lowered, or the mechanical strength is lowered, so that when the ion exchanger is packed in a column and the liquid to be treated is passed through, it is difficult. Especially when the liquid is passed at a high flow rate, the non-particulate organic porous ion exchanger may be deformed. When the thickness of the continuous skeleton exceeds 100 μm, the skeleton becomes too thick, and the pressure loss during liquid passage may increase.

The average diameter of continuous pores in the non-particulate organic porous ion exchanger in a dry state is preferably in the range of 1 to 1000 μm. The average diameter of continuous pores in the dry state of the non-particulate organic porous ion exchanger is measured by mercury porosimetry and refers to the maximum value of the pore distribution curve obtained by mercury porosimetry. If the average diameter of the continuous pores is less than 1 μm, when the ion exchanger is packed in a column and the liquid to be treated is passed through the column, the pressure loss during the passage of the liquid may become large. If the average diameter of the continuous pores 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 monolith ion exchanger becomes insufficient, resulting in ion exchange. Performance may degrade.

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

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

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

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

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

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

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

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

Most of such first monolithic ion exchangers have an open pore structure in which the voids formed by macropores and mesopores serve as channels. If the average diameter of the overlapping portions of the mesopores in the dry state is less than 1 μm, when the ion exchanger is filled in the column and the liquid to be treated is passed through the column, the pressure loss during the passage of the liquid becomes remarkably large. Sometimes. If the average diameter of the overlapping portions of mesopores in a dry state exceeds 1000 μm, the contact between the liquid to be treated and the monolithic ion exchanger is insufficient when the liquid to be treated is passed through a column packed with the ion exchanger. As a result, the ion exchange performance may decrease. The number of overlapping macropores is, for example, 1 to 12 per macropore, and 3 to 10 in most cases. Since the first monolithic ion exchanger has the above-described continuous macropore structure, it is possible to form a group of macropores and a group of common pores almost uniformly, as described in JP-A-8-252579. The pore volume and specific surface area can be remarkably increased compared to the particle aggregation type porous material.

The total pore volume per weight of the first monolithic ion exchanger is preferably in the range of 1 to 50 mL/g, more preferably in the range of 2 to 30 mL/g. If the total pore volume per unit weight in a dry state is less than 1 mL/g, pressure loss increases when the liquid to be treated is passed through a column packed with the ion exchanger. Furthermore, the permeation amount per unit cross-sectional area becomes small, and the throughput may decrease. If the total pore volume per unit weight in the dry state exceeds 50 mL/g, the mechanical strength is reduced, and when the ion exchanger is packed in a column and the liquid to be treated is passed through, especially at a high flow rate. The monolithic ion exchanger may be deformed when liquid is passed through it.

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

<Method for producing first monolithic ion exchanger>
The first monolithic ion exchanger can be produced, for example, by the following method.

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

The oil-soluble monomer containing no ion-exchange group used in the production of the first monolith refers to a monomer containing no ion-exchange group, low solubility in water, and lipophilicity. This monomer is, for example, styrene, α-methylstyrene, vinylbenzyl chloride, ethylene, propylene, vinyl chloride, vinyl bromide, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate. , butanediol diacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, ethylene glycol dimethacrylate, and the like. These monomers can be used singly or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is preferably in the range of, for example, 0.3 to 10 mol% of the total oil-soluble monomer. The range of 0.3 to 5 mol % is preferable in that the ion exchange groups can be quantitatively introduced in the subsequent step and sufficient mechanical strength for practical use can be ensured.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

If the average particle size of the organic polymer particles is less than 1 μm in a dry state, the average diameter of continuous pores between skeletons may be as small as less than 20 μm in a dry state. If the average particle size of the organic polymer particles exceeds 50 μm, the pressure loss may increase when the ion exchanger is packed in a column and the liquid to be treated is passed through the column. In addition, when the average diameter of the continuous pores is less than 20 μm in a dry state, when the ion exchanger is packed in a column and the liquid to be treated is passed through, the pressure loss when the liquid to be treated permeates may become large. If the average diameter of the above-mentioned continuous pores exceeds 100 μm in a dry state, the contact between the liquid to be treated and the monolithic ion exchanger is insufficient when the ion exchanger is packed in a column and the liquid to be treated is passed through. may be.

The total pore volume per dry weight of the second monolithic ion exchanger is preferably in the range of 1 to 10 mL/g. If the total pore volume is less than 1 mL/g, when the ion exchanger is packed in a column and the liquid to be treated is passed through the column, the pressure loss during the passage of the liquid may increase. The permeation amount per unit cross-sectional area becomes small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL/g, the mechanical strength decreases, and monolithic ion The exchange body may be deformed.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The dry weight total pore volume of the third monolithic ion exchanger is preferably in the range of 0.5 to 10 mL/g, more preferably in the range of 0.8 to 8 mL/g. If the total pore volume is less than 0.5 mL/g, when the ion exchanger is packed in a column and the liquid to be treated is passed through the column, the pressure loss during the passage of the liquid may increase. Furthermore, the amount of permeating fluid per unit cross-sectional area becomes small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL/g, the mechanical strength decreases, and monolithic ion The exchange body may be deformed. Furthermore, the contact efficiency between the liquid to be treated and the monolithic ion exchanger may decrease.

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

<Method for producing third monolithic ion exchanger>
A third monolithic ion exchanger can be produced, for example, by the following method.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The continuous skeleton is composed of a vinyl polymer (aromatic vinyl polymer, etc.) containing crosslinked structural units in the range of 0.1 to 5.0 mol% in all structural units into which ion exchange groups are introduced, and a continuous skeleton is three-dimensionally continuous with a dry thickness of, for example, 1 to 60 μm, preferably 3 to 58 μm. If the crosslinked structural unit is less than 0.1 mol%, the mechanical strength may be insufficient, and if it exceeds 5.0 mol%, the structure of the porous body may easily deviate from the co-continuous structure. . If the thickness of the continuous skeleton is less than 1 μm in a dry state, the monolithic ion exchanger deforms when the ion exchanger is packed in a column and the liquid to be treated is passed through, especially when the liquid is passed at a high flow rate. may be lost. When the thickness of the continuous skeleton exceeds 60 μm in a 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 the passage of the liquid may increase. be.

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

The aforementioned average diameter is measured by mercury porosimetry and refers to the maximum value of the pore distribution curve obtained by mercury porosimetry. The thickness of the continuous skeleton in a dry state is determined by SEM observation of the fourth monolithic ion exchanger in a dry state. Specifically, the SEM observation of the fourth monolithic ion exchanger in a dry state is performed at least three times, the thickness of the skeleton in the obtained images is measured, and the average value thereof is taken as the thickness of the continuous skeleton. The skeleton is rod-shaped and has a circular cross-sectional shape, but may include a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

The total pore volume per dry weight of the fourth monolithic ion exchanger is, for example, in the range of 0.5 to 10 mL/g. If the total pore volume is less than 0.5 mL/g, when the ion exchanger is packed in a column and the liquid to be treated is passed through the column, the pressure loss during the passage of the liquid may increase. Furthermore, the amount of permeating fluid per unit cross-sectional area becomes small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL/g, the mechanical strength decreases, and monolithic ion The exchange body may be deformed. Furthermore, the contact efficiency between the liquid to be treated and the monolithic ion exchanger may decrease.

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

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

<Method for producing fourth monolithic inion exchanger>
A fourth monolithic ion exchanger can be produced, for example, by the following method.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the fifth monolithic ion exchanger, when the coverage of the surface of the skeleton phase with the particles 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 is obtained. It can easily become smaller. As a method for measuring the coverage rate of the particles, etc., there is an image analysis method using an SEM image of the fifth monolithic ion exchanger.

The total pore volume per weight in the dry state of the fifth monolithic ion exchanger is, for example, in the range of 0.5 to 10 mL/g, preferably in the range of 0.8 to 8 mL/g. If the total pore volume is less than 0.5 mL/g, when the ion exchanger is packed in a column and the liquid to be treated is passed through the column, the pressure loss during the passage of the liquid may increase. Furthermore, the amount of permeating fluid per unit cross-sectional area becomes small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL/g, the mechanical strength decreases, and monolithic ion The exchange body may be deformed. Furthermore, the contact efficiency between the liquid to be treated and the monolithic ion exchanger may decrease.

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

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

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

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

<Manufacturing Method of Fifth Monolithic Ion Exchanger>
A fifth monolithic ion exchanger can be produced, for example, by the following method.

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

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

In step I, a polymerization initiator may be used as necessary when forming the water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat or light irradiation is preferably used. Polymerization initiators may be water-soluble or oil-soluble, such as 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2 , 2'-azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis dimethyl isobutyrate, 4,4'-azobis ( 4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate- and sodium acid sulfite.

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

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

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

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

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

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

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

In step III of the fifth method for producing a monolith, the internal volume of the reaction vessel is not particularly limited as long as it is large enough to allow the monolith intermediate (5) to exist in the reaction vessel. When the monolith intermediate (5) is placed in the reaction vessel, either a gap is formed around the monolith in plan view or the monolith intermediate (5) enters the reaction vessel with almost no gap. . Of these, the fifth monolith after polymerization is hardly pressed by the inner wall of the vessel and enters the reaction vessel with almost no gap. efficient. Even if the inner volume of the reaction vessel is large and there is a gap around the fifth monolith after polymerization, the vinyl monomer and the cross-linking agent are adsorbed and distributed to the monolith intermediate (5). , particle aggregate structures are hardly formed in the gaps in the reaction vessel.

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

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

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

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

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

The ion exchange method using the ion exchanger according to the present embodiment includes, for example, purification of water, sugar solutions, organic solvents, etc., synthesis processes of chemical products such as pharmaceutical intermediates, fillers for ion chromatography for analysis, etc. can be used in

By using the ion exchanger according to the present embodiment, even when an organic solvent is passed through a column filled with an ion exchanger in a water-wet state, the ion exchanger shrinks little, and the organic solvent is efficiently converted into an ion exchanger. can be brought into direct contact.

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

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

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

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

(Manufacturing of monolith (III step))
The above monolithic intermediate is then placed in a reaction vessel and immersed in this styrene/divinylbenzene/1-decanol/2,2′-azobis(2,4-dimethylvaleronitrile) mixture and degassed in a vacuum chamber. , the reaction vessel was sealed and allowed to stand at 50° C. for 24 hours to polymerize. After completion of the polymerization, the contents were taken out, subjected to Soxhlet extraction with acetone, and dried under reduced pressure (Step III).

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

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

（４）
（式中、Ｐｏｌｙｍｅｒは、スチレン―ジビニルベンゼン共重合体を表す。） (Production of monolithic ion exchanger)
390 mL of THF and 30 mL of N,N-dimethylbenzylamine as a tertiary amine were added to 20 g of the chloromethylated monolith, and reacted at 60° C. for 6 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a monolithic ion exchanger composed of polymer chains represented by the following formula (4).

(4)
(In the formula, Polymer represents a styrene-divinylbenzene copolymer.)

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

The monolithic ion exchanger obtained in Example 1 is hereinafter referred to as "benzyl type monolithic anion exchanger".

（５）
（式中、Ｐｏｌｙｍｅｒは、スチレン―ジビニルベンゼン共重合体を表す。） <Comparative Example 1>
The procedure was carried out in the same manner as in Example 1 except that a 30% trimethylamine aqueous solution was used instead of N,N-dimethylbenzylamine as the tertiary amine, and composed of polymer chains represented by the following formula (5). A monolithic ion exchanger was obtained.

(5)
(In the formula, Polymer represents a styrene-divinylbenzene copolymer.)

Hereinafter, the monolithic ion exchanger obtained in Comparative Example 1 is referred to as "trimethyl type monolithic anion exchanger".

<Example 2>
The benzylic monolithic anion exchanger obtained in Example 1 was cut into a size of 600 mm×150 mm×100 mm. This was immersed in 300 mL of water at room temperature (25 ± 2 ° C.) for 30 minutes to make it water wet, and then methanol, 2-propanol, N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF) as organic solvents. After washing three times with 150 mL each to sufficiently replace the moisture, the size was measured and the swelling rate (%) (length ratio) from the water-wet state was estimated. The results are shown in FIG.

<Comparative Example 2>
The procedure of Example 2 was repeated except that the benzyl-type monolithic anion exchanger was changed to a trimethyl-type monolithic anion exchanger. The results are shown in FIG.

Thus, the ion exchangers of Examples showed less shrinkage when contacted with an organic solvent in a water-wet state compared to the ion exchangers of Comparative Examples.

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

Claims (8)

General formula (1)

(In the formula, R ¹ is an optionally substituted alkyl group having 4 to 22 carbon atoms; or an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, or an optionally substituted carbon number 1 to ⁶ alkoxy groups, optionally substituted amino groups, cyano groups ^, or benzyl groups optionally substituted with nitro groups; 4 represents an alkyl group, L represents a linker moiety, and Polymer represents a polymer chain.)
An ion exchanger characterized by comprising a polymer chain represented by: An ion exchanger according to claim 1,
An ion exchanger, wherein L in general formula (1) is a methylene group. The ion exchanger according to claim 1 or 2,
The ion exchanger according to claim 1, wherein the polymer chain of the ion exchanger is a styrene-divinylbenzene copolymer. An ion exchanger according to any one of claims 1 to 3,
The ion exchanger is a non-particulate organic porous ion exchanger, and consists of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, and the average diameter is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL/g, and the ion exchange capacity per weight in the dry state is in the range of 1 to 9 mg equivalent/g. , an ion exchanger characterized in that the ion exchange groups are distributed in the organic porous ion exchanger. general formula (2)

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

(In the formula, R ¹ is an optionally substituted alkyl group having 4 to 22 carbon atoms; or an optionally substituted alkyl group having 1 to 6 carbon atoms, a halogen atom, or an optionally substituted carbon number 1 to ⁶ alkoxy groups, optionally substituted amino groups, cyano groups ^, or benzyl groups optionally substituted with nitro groups; represents the alkyl group of 4.)
A tertiary amine represented by
A method for producing an ion exchanger, characterized by reacting A method for producing an ion exchanger according to claim 5,
A method for producing an ion exchanger, wherein L in general formula (1) is a methylene group. A method for producing an ion exchanger according to claim 5 or 6,
A method for producing an ion exchanger, wherein the polymer chain of the ion exchanger is a styrene-divinylbenzene copolymer. A method for producing an ion exchanger according to any one of claims 5 to 7,
The ion exchanger is a non-particulate organic porous ion exchanger, and consists of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, and the average diameter is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL/g, and the ion exchange capacity per weight in the dry state is in the range of 1 to 9 mg equivalent/g. A method for producing an ion exchanger, wherein ion exchange groups are distributed in the organic porous ion exchanger.

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