JP5131911B2 - Monolithic organic porous body, production method thereof, and monolithic organic porous ion exchanger - Google Patents

Description

  The present invention relates to a double porous structure in which the skeleton of a continuous macrovoid structure useful as an adsorbent or ion exchanger used in an adsorption device, deionized water production device or gaseous pollutant removal device is a co-continuous structure. The present invention relates to a monolithic organic porous material having a solid structure, a method for producing the same, and a monolithic organic porous ion exchanger.

  A monolithic organic porous body having a continuous macropore structure having a common opening in a macropore and a macropore wall connected to each other, and a monolithic organic porous ion exchanger having an ion exchange group introduced into the porous body, It is disclosed in JP-A-2002-306976. The organic porous material and organic porous ion exchanger are useful as ion exchangers used in adsorbents, chromatographic fillers, deionized water production apparatuses, and the like.

  However, when the organic porous ion exchanger increases the total pore volume due to restrictions on its production method and attempts to achieve a low pressure loss that is practically required, the skeletal structure becomes thin, resulting in water wetting. If the ion exchange capacity per volume in the state is significantly reduced, conversely, if the total pore volume is reduced and the skeletal structure is thickened, the mesopores that become common openings will be significantly reduced, and the pressure loss will be significantly increased. It had the disadvantage that it would end up.

  Further, as a structure of the organic porous body, a co-continuous structure in which a three-dimensionally continuous skeleton phase and a three-dimensionally continuous pore phase between the skeleton phases are intertwined and both phases are entangled is known. Japanese Patent Application Laid-Open No. 2007-154083 discloses a non-particle-aggregated organic polymer having a micrometer-sized average diameter and having a co-continuous structure composed of pores continuous in a three-dimensional network and a skeleton phase rich in organic substances. A gel-like affinity carrier, wherein the affinity carrier comprises at least one of at least one of bifunctional or higher vinyl monomer compounds, methacrylate compounds and acrylate compounds as a crosslinking agent, and a monofunctional hydrophilic monomer. An affinity carrier that is a copolymer and has a volume ratio of 100 to 10: 0 to 90 of the cross-linking agent and the monofunctional hydrophilic monomer in the affinity carrier is disclosed. This affinity carrier has a high crosslinking density of the skeleton in order to maintain the monolith structure. Further, this affinity carrier has a hydrophilic property that sufficiently suppresses non-specific adsorption. In addition, N. Tsujioka et al., Macromolecules 2005, 38, 9901 discloses a monolithic organic porous body having a co-continuous structure and made of an epoxy resin.

  However, in Japanese Patent Application Laid-Open No. 2007-154083, since the affinity carrier actually obtained is nanometer-sized pores, the pressure loss when allowing the fluid to permeate is high, and a large flow rate of water under low pressure loss. It was difficult to fill a deionized water production apparatus that needs to be treated into an ion exchanger. In addition, since the affinity carrier is hydrophilic, there is a problem that a complicated operation such as a hydrophobic treatment on the surface is necessary to use it as an adsorbent for a hydrophobic substance. There is also a problem that it is not easy to introduce functional groups such as ion exchange groups into the epoxy resin.

For this reason, it is chemically stable and hydrophobic, has high continuity of pores, is not biased in size, has large continuous pores, and pressure when water or gas or other fluid is permeated Development of a monolithic organic porous body with low loss has been desired. In addition to the above characteristics, it has been desired to develop a monolithic organic porous ion exchanger having a large ion exchange capacity per volume.
JP 2002-306976 A JP2007-154083A

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and has a large continuous macrovoid structure with a uniform structure and pressure loss when a fluid such as water or gas is permeated. It is an object of the present invention to provide a monolithic organic porous material having a novel structure useful as an adsorbent or ion exchanger, a production method thereof, and a monolithic organic porous ion exchanger.

  Under such circumstances, the present inventors have conducted intensive studies. As a result, a large number of particulate templates were added to the water-in-oil emulsion with a relatively small amount of the crosslinking agent obtained by the method described in JP-A-2002-306976. Is allowed to stand for polymerization, and then the particulate template is removed, so that the skeleton of the continuous macrovoid structure becomes a continuous macropore structure (intermediate) having a low-crosslinking skeleton. If a vinyl monomer and a small amount of a crosslinking agent are allowed to stand in a specific organic solvent in the presence of a solid, a monolith with a unique structure in which a continuous macrovoid structure and a co-continuous structure coexist can be obtained. Since the monolith of this type has a thick skeleton, if ion exchange groups are introduced, the flow rate of water, gas, etc. can be reduced without significantly reducing the ion exchange capacity per volume in a water-wet state. It found such that it is possible to greatly reduce the pressure loss at the time of not transmit, and have completed the present invention.

That is, the present invention relates to an organic porous body having a continuous macrovoid structure in which macrovoids overlap each other, and the overlapping portion is an opening having an average radius of 0.1 to 25 mm, and the apparent skeleton of the continuous macrovoid structure A three-dimensionally continuous skeleton having a thickness of 0.8 to 40 μm composed of an aromatic vinyl polymer containing 0.3 to 2.5 mol% of a crosslinked structural unit among all the structural units, and between the skeletons A monolithic organic material having a three-dimensionally continuous hole having a radius of 4 to 100 μm, and the radius of the macrovoid is not less than five times the radius of the hole A porous body is provided.

  In addition, the present invention includes the following steps: aromatic vinyl monomer, surfactant, water, crosslinking agent and, if necessary, polymerization initiator, weight ratio (M) of aromatic vinyl monomer (M) to water (W). : (W) 1: 49-1: 3, the cross-linking agent is mixed so that the total amount of vinyl monomer and cross-linking agent is 0.3-2.5 mol%, and the mixture is stirred to drop water in oil Step I for preparing a type emulsion, Step II for polymerizing under standing in the presence of a large number of particulate templates in the water-in-oil emulsion, and removing the particulate template from the polymer to form a continuous macrovoid structure Step III to obtain a monolithic organic porous intermediate that coexists with a continuous macropore structure, aromatic vinyl monomer, cross-linking agent, aromatic vinyl monomer and cross-linking agent dissolve, but polymer produced by polymerization of aromatic vinyl monomer is Melting The organic solvent and the polymerization initiator that are not mixed with the vinyl monomer in an amount that is 5 to 50 times the amount of the monolithic organic porous intermediate, are mixed, and the mixture obtained in the IV step and the IV step is left standing, And performing the polymerization in the presence of the monolithic organic porous intermediate obtained in step III, and performing step V to obtain an organic porous material in which a continuous macrovoid structure and a co-continuous structure coexist. A method for producing a monolithic organic porous material is provided.

  In the present invention, an ion exchange group is introduced on the skeleton surface and inside the skeleton of the monolithic organic porous material, and the ion exchange capacity per volume in a water-wet state is 0.075 mg equivalent / ml. The present invention provides a monolithic organic porous ion exchanger characterized by the above.

  The monolithic organic porous body of the present invention is a double structure having a continuous macrovoid structure and a thick joint structure, so that the porous structure is compared with a monolithic organic porous body having a conventional continuous macropore structure. In addition to being able to replace low-pressure, large-flow processing, the conventional synthetic adsorbents can be replaced. Application to new fields of application such as adsorption removal of gaseous substances and removal of gaseous pollutants becomes possible. Moreover, according to the method for producing a monolithic organic porous body of the present invention, the monolithic organic porous body can be produced easily and reliably. Moreover, since the monolithic organic porous ion exchanger of the present invention has substantially the same structure as the monolithic organic porous body, water treatment at a low pressure and a large flow rate is possible, and conventionally used ion exchange resins can be used. Not only can it be replaced, but it can also be suitably used by removing gas contaminants such as ion removal and chemical filters in high-viscosity components that could not be handled by ion-exchange resin by taking advantage of its excellent fluid permeability. Can be used.

  In the present specification, when describing both “monolithic organic porous material” and “monolithic organic porous ion exchanger”, they are also simply referred to as “monolithic porous material etc.”. In addition, “monolithic organic porous intermediate” is simply “monolith intermediate”, “monolithic organic porous body” is simply “monolith”, and “monolithic organic porous ion exchanger” is simply “monolithic ion”. Also called “exchanger”.

  The basic structure of the monolithic porous body or the like of the present invention is an organic porous body having a continuous macrovoid structure in which the macrovoids connected to each other and the connected portions of the macrovoids have a predetermined opening size, The skeleton portion of the void structure is a co-continuous structure in which a three-dimensional continuous skeleton and a three-dimensional continuous flow path smaller than the continuous macrovoid structure are formed. That is, in a monolithic porous body or the like, in a continuous macrovoid structure, a large flow path through which liquid or gas flows with low pressure loss is formed, and in a co-continuous structure, it is smaller than the continuous macrovoid through which liquid or gas permeates. A flow path is formed. In the present specification, an apparent skeleton part that forms a continuous macrovoid structure is referred to as a “skeleton part”, and a substantial skeleton part that forms a co-continuous structure is referred to as a “skeleton”.

  As shown in the schematic diagram of FIG. 1, the continuous macrovoid structure in the monolithic porous body or the like of the present invention has a radius of 0.1 to 25 mm, preferably a connected portion of the macrovoid 11 and the macrovoid 11 connected to each other. Is a structure in which the opening 12 is 0.5 to 15 mm, particularly preferably 0.5 to 10 mm. That is, the continuous macrovoid structure X usually has a structure in which the macrovoids 11 and the macrovoids 11 having a radius of 0.5 to 50 mm overlap each other, and the overlapping portion becomes the opening 12, and this portion has an open pore structure. It is. In the open pore structure, when a liquid or gas is flowed, the inside of a large pore structure formed by the macro void 11 and the opening 12 becomes a main flow path. That is, in a monolithic porous body or the like, three-dimensionally continuous pores 2 having a continuous structure and an open pore structure having a continuous macrovoid structure X are mixed and connected to each other to form a flow path.

  The overlap of the macro void 11 and the macro void 11 is 1 to 2 for one macro void 1 and 3 to 10 for many. If the radius of the opening 12 is less than 0.1 mm, the pressure loss during liquid or gas permeation is large, and it is difficult to obtain a sufficient effect of reducing the pressure loss. On the other hand, if the radius of the opening exceeds 25 mm, the contact between the liquid or gas and the organic porous body or organic porous ion exchanger becomes insufficient, and as a result, the adsorption characteristics and ion exchange characteristics deteriorate. It is not preferable. The macro voids 11 are distributed substantially uniformly in the continuous macro void structure X. Those having an opening radius in the vicinity of 25 mm are applied when producing an adsorbent or ion exchanger having a large volume. Moreover, in this invention, the suitable porosity of a continuous macrovoid structure part is about 75% in a monolithic porous body etc.

  The shape of the macro void is not particularly limited, and examples thereof include a cube, a rectangular parallelepiped, an elliptic sphere, a true sphere, or an indefinite shape. Among these, the macro void is removed from the particulate template after standing polymerization. From the viewpoint of the uniformity of uniform filling and the uniformity of the common opening structure such as the monolithic porous body after removing the template, the spherical shape is preferable.

  The co-continuous structure in the monolithic porous body or the like of the present invention has a three-dimensional continuous skeleton having a thickness of 0.8 to 40 μm and a three-dimensional continuous space having a radius of 4 to 100 μm between the skeletons. This is a structure in which holes are arranged. That is, as shown in the schematic diagrams of FIGS. 1 and 2, the co-continuous structure is a structure Y in which the continuous skeleton phase 1 and the continuous pore phase 2 are intertwined and each of them is continuously three-dimensionally. The continuous pores 2 have higher continuity of the pores than the conventional open-cell monolith and particle aggregation type monolith, and the size thereof is not biased. Therefore, it is possible to achieve extremely uniform ion adsorption behavior. Moreover, since the skeleton is thick, the mechanical strength is high.

  If the radius of the three-dimensionally continuous pores is less than 4 μm, the pressure loss at the time of fluid permeation increases, which is not preferable. If the radius exceeds 100 μm, the density of the skeletal structure decreases, resulting in a decrease in volume per volume. The ion exchange capacity decreases, and as a result, the adsorption characteristics and ion exchange characteristics deteriorate, which is not preferable. The size of the three-dimensionally continuous pores can be obtained as a maximum value of the pore distribution curve by measuring the pore distribution curve by an SEM image or a mercury intrusion method.

  The thickness of the skeleton of the co-continuous structure is 0.8 to 40 μm, preferably 1 to 30 μm. If the thickness of the skeleton is less than 0.8 μm, it is not preferable because the adsorption capacity per volume decreases and mechanical strength decreases. On the other hand, if the thickness exceeds 40 μm, the uniformity of the adsorption characteristics is lost. Absent. The thickness of the skeleton of the monolith may be calculated by performing SEM observation at least three times and measuring the thickness of the skeleton in the obtained image.

  The monolith co-continuous structure of the present invention preferably has a total pore volume of 0.5 to 5 ml / g. If the total pore volume is less than 0.5 ml / g, the amount of water flow per unit cross-sectional area becomes small, which makes it difficult for the fluid to flow. On the other hand, when the total pore volume exceeds 5 ml / g, the proportion of the polymer in the skeleton part decreases, and the ion exchange capacity per volume decreases, resulting in a decrease in adsorption characteristics and ion exchange characteristics. Therefore, it is not preferable.

  In the monolithic porous body or the like of the present invention, the average radius of the macrovoids 11 is at least twice the radius of the three-dimensionally continuous pores 2 of the co-continuous structure, preferably 2 to 250,000 times, particularly 5 to 10,000. Times, and further 10 to 1000 times. If the average radius of the macrovoids is less than twice the average radius of the three-dimensionally continuous pores of the co-continuous structure, the pressure loss during liquid or gas permeation is large, and the sufficient effect of reducing the pressure loss can be obtained. It is not preferable because it is difficult to obtain. In addition, if the radius of the macrovoid is too large, the contact between the liquid or gas and the organic porous body or organic porous ion exchanger becomes insufficient, resulting in a decrease in adsorption characteristics and ion exchange characteristics. It is not preferable. The radius of a three-dimensionally continuous hole having a macrovoid and a co-continuous structure can be clearly recognized in an SEM photograph or the like. For this reason, the average radii of these may be obtained by extracting the radii of at least 10 arbitrary points, preferably 20 arbitrary points in an SEM photograph or the like. In addition, when the shape of the macro void is a shape other than a true sphere, the shape is compared in terms of a true sphere.

  In the monolithic porous body and the like of the present invention, the continuous macrovoid structure X and the co-continuous structure Y are uniformly present in the porous body and the like. It is a structure in which a continuous macrovoid structure X is formed in a matrix, and a double structure in which the continuous macrovoid structure X is used as a matrix and the co-continuous structure Y is formed in the matrix.

  In the present invention, the polymer constituting the skeleton is an aromatic vinyl polymer having a crosslinked structure, and the aromatic vinyl polymer material is 0.3 to 2.5 mol% with respect to all the structural units constituting the polymer material. It is preferable that a crosslinked structural unit is included. If the cross-linking structural unit is less than 0.3 mol%, the crosslink density is lowered, and the mechanical strength of the monolith intermediate is significantly reduced. On the other hand, if it exceeds 2.5 mol%, Polymerization by impregnating a monolith intermediate with a mixture of an organic solvent and a polymerization initiator that dissolves the aromatic vinyl monomer, crosslinking agent, aromatic vinyl monomer and crosslinking agent, but does not dissolve the polymer produced by polymerization of the aromatic vinyl monomer. In the step of carrying out the step, the monolith intermediate porous body has a crosslinking density that is too high so that sufficient swelling is not performed and the polymerization reaction proceeds while maintaining a continuous macropore structure. However, it is not preferable because it does not have a co-continuous structure but a continuous macropore structure.

  There is no restriction | limiting in particular in the kind of aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, a styrene-divinylbenzene copolymer is used because of its ease of forming a co-continuous structure, ease of introduction of ion exchange groups, high mechanical strength, and high stability against acids and alkalis. And vinylbenzyl chloride-divinylbenzene copolymer is preferred.

  When using the monolithic organic porous material of the present invention as an adsorbent, for example, a cylindrical column or a square column is filled with an organic porous material cut into a shape that can be inserted into the column as an adsorbent, If the water to be treated containing a hydrophobic substance such as benzene, toluene, phenol, paraffin or the like is allowed to flow through this, the hydrophobic substance is efficiently adsorbed on the adsorbent.

  The monolithic organic porous ion exchanger of the present invention is a monolithic organic porous body in which ion exchange groups are further uniformly introduced into the skeleton surface and inside the skeleton, and the ion exchange capacity is not particularly limited. However, the ion exchange capacity per volume in a water-wet state is 0.075 mg equivalent / ml or more, preferably 0.1 mg equivalent / ml. If the ion exchange capacity per volume in a water-wet state is less than 0.075 mg equivalent / ml, the amount of water containing ions that can be processed before breakthrough, that is, the ability to produce deionized water is reduced. It is not preferable.

  The introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA, SIMS, or the like. In addition, if the ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling And durability against shrinkage is improved.

  Examples of ion exchange groups to be introduced into the organic porous material include cation exchange groups such as sulfonic acid groups, carboxylic acid groups, iminodiacetic acid groups, phosphoric acid groups, and phosphoric acid ester groups; quaternary ammonium groups, tertiary amino groups, Examples include anion exchange groups such as secondary amino group, primary amino group, polyethyleneimine group, tertiary sulfonium group, and phosphonium group; amphoteric ion exchange groups such as aminophosphate group and sulfobetaine.

  Next, the manufacturing method of the monolithic organic porous body of this invention is demonstrated. That is, in the production method, an aromatic vinyl monomer, a surfactant, water, a crosslinking agent and, if necessary, a polymerization initiator, a weight ratio (M) of the aromatic vinyl monomer (M) to water (W): ( W) is 1:49 to 1: 3, and the cross-linking agent is mixed so that the total amount of vinyl monomer and cross-linking agent is 0.3 to 2.5 mol%, and the mixture is stirred to form a water-in-oil emulsion. Step I for preparing a polymer, Step II for polymerizing under standing in the presence of a large number of particulate templates in the water-in-oil emulsion, and removing the particulate template from the polymer to provide a continuous macrovoid structure. Step III to obtain a monolithic organic porous intermediate coexisting with macropore structure, aromatic vinyl monomer, cross-linking agent, aromatic vinyl monomer and cross-linking agent dissolve, but polymer produced by polymerization of aromatic vinyl monomer dissolves. The organic solvent and the polymerization initiator that are not mixed with the vinyl monomer in an amount that is 5 to 50 times the amount of the monolithic organic porous intermediate, are mixed, and the mixture obtained in the IV step and the IV step is left standing, In addition, there is a V step in which polymerization is carried out in the presence of the monolithic organic porous intermediate obtained in the step III to obtain an organic porous body in which a continuous macrovoid structure and a co-continuous structure coexist.

  The aromatic vinyl monomer used in Step I is not particularly limited as long as it contains a polymerizable vinyl group in the molecule, has low solubility in water, and is a lipophilic monomer. Specific examples of these vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyl toluene, and vinyl benzyl chloride; α-olefins such as ethylene, propylene, 1-butene, and isobutene; butadiene, isoprene, chloroprene, and the like. Diene monomers; Halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; Nitrile monomers such as acrylonitrile and methacrylonitrile; Vinyl esters such as vinyl acetate and vinyl propionate; Methyl acrylate and Acrylic Ethyl acetate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate Examples include (meth) acrylic monomers such as syl, benzyl methacrylate, and glycidyl methacrylate. These monomers can be used alone or in combination of two or more. Among these monomers, preferred are aromatic vinyl monomers, and vinyl monomers suitably used in the present invention are styrene monomers such as styrene and vinyl benzyl chloride.

  As the crosslinking agent used in the step I, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis.

  The surfactant used in Step I is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when an aromatic vinyl monomer and water are mixed. Sorbitan monooleate and sorbitan mono Nonionic surfactants such as laurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan monooleate; potassium oleate, dodecylbenzene Anionic surfactants such as sodium sulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyl dimethyl ammonium chloride; amphoteric surfactants such as lauryl dimethyl betaine can be used. These surfactants can be used alone or in combination of two or more. The water-in-oil emulsion refers to an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the surfactant added is not unclear because it varies greatly depending on the type of the oil-soluble monomer and the size of the target emulsion particles, but the total amount of the oil-soluble monomer and the surfactant A range of about 2 to 70% can be selected.

  As the polymerization initiator used in step I, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) 1,1′-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide and the like. The amount of the polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in a range of about 0.01 to 5% with respect to the total amount of vinyl monomer and crosslinking agent.

  In the step I, there is no particular limitation as a mixing method for forming a water-in-oil emulsion by mixing an aromatic vinyl monomer, a surfactant, water, and if necessary, a crosslinking agent or a polymerization initiator, Method of mixing each component at once, oil-soluble monomer, crosslinking agent, surfactant and oil-soluble polymerization initiator oil-soluble component and water-soluble water-soluble polymerization initiator water-soluble component separately For example, a method in which each component is mixed after being uniformly dissolved in the solution can be used. There is no particular limitation on the mixing apparatus for forming the emulsion, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain the desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily.

  In step I, the weight ratio (M) :( W) of the aromatic vinyl monomer (M) to water (W) is from 1:49 to 1: 3, preferably from 1:40 to 1: 3, more preferably 1: 35 to 1: 3. By setting the blending ratio of (M) and water (W) within the above range, the total pore volume in the continuous macropore structure of the monolith intermediate obtained in the step III can be 4 to 30 ml / g.

  Step II is a step in which a large number of particulate templates are present in a water-in-oil emulsion in a container and polymerized under standing. A water-in-oil emulsion may be introduced into the container, and then a number of particulate templates may be placed (first method), a number of particulate templates may be placed in the container, and then a water-in-oil emulsion may be added. It may be introduced (second method).

  In the first method, after a large number of particulate templates are put, it is preferable that the particulate templates are slightly pressed by a method such as a drop lid in that close-packing or close filling is possible. In addition, in the second method, when introducing the water-in-oil emulsion, degassing can be performed, so that the water-in-oil emulsion can be sufficiently distributed in the gaps between a large number of particulate templates. This is preferable in that the macropore structure and the continuous macrovoid structure can be formed uniformly. In either case of the first method or the second method, it is preferable to gently introduce the water-in-oil emulsion into the container without disrupting the emulsion structure.

  The particulate template used in step II is present in the emulsion or polymer while retaining its shape during standing and during polymerization, and is removed by the removing means after polymerization. As the particulate template, polysaccharide hydrogel is preferred from the viewpoints of stability to water-in-oil emulsion, ease of macrovoid formation, and ease of filling and removal. Specific examples of the polysaccharide hydrogel include hydrogels such as agar, calcium alginate, gelatin, carrageenan, pectin, and glucomannan. These may be used alone or in combination of two or more. Among these particulate templates, agar and calcium alginate hydrogel are preferred because of the availability of the particulate template and the ease of the template removal step after polymerization under standing.

  The polysaccharide hydrogel beads can be easily obtained by a known production method. As a method for producing agar hydrogel beads, for example, a method in which an agar solution is sprayed and solidified on a cooled gas phase portion (Japanese Patent Laid-Open No. 6-254382), a method in which an agar solution is dropped and solidified on a cooled liquid phase portion (Japanese Patent Laid-Open No. 6-254382). 2000-185229 and JP-A-5-49911). Examples of the method for producing calcium alginate hydrogel beads include gelling methods by dropping a sodium alginate aqueous solution into a calcium chloride aqueous solution (Japanese Patent Laid-Open Nos. 63-139108 and 11-137188).

  The shape of the particulate template is not particularly limited, and examples thereof include a cube, a rectangular parallelepiped, an elliptic sphere, and a true sphere. Among these, since the macrovoid is formed by removing the template after polymerization under standing, the monolithic porous after the removal of the template It is preferable from the viewpoint of uniformity of a common opening structure such as a body.

  The particle size of the particulate template is 0.5 to 50 mm, preferably 0.5 to 25 mm, and particularly preferably 0.5 to 10 mm in terms of a true sphere. That is, after removing the particulate template, a macro void with a radius of 0.5 to 50 mm and a macro void are overlapped, and the overlapping portion forms an opening structure, and the portion becomes an open pore structure. When flowing, the inside of the pore structure formed by the macro void and the opening becomes a flow path. If the template radius is less than 0.5 mm, the pressure loss during liquid or gas permeation is large, and it is difficult to obtain a sufficient effect of reducing the pressure loss, which is not preferable. On the other hand, when the template radius exceeds 50 mm, the contact between the liquid or gas and the monolithic porous body becomes insufficient, and as a result, the adsorption characteristics and the ion exchange characteristics deteriorate, which is not preferable. In addition, when the shape of the particulate template is a cube or a rectangular parallelepiped, when introduced into the water-in-oil emulsion, the templates contact each other in a random direction in a stationary state without any special operation. A suitable continuous macrovoid structure can be formed.

  In step II, the filling of the numerous particulate templates into the water-in-oil emulsion of the container is such that the respective particulate templates are in contact with each other, in particular close-packed filling, in order to form appropriate openings. It is preferable to perform filling close to closest packing. Even if the particulate template is filled such that the contact with each other is a point contact, the polymer material portion contracts during the polymerization, so that an appropriate opening can be formed. In order to form an opening having a radius close to 0.1 mm, it is possible to obtain an opening having a small and uniform particle diameter, and to form an opening having a radius close to 25 mm. The particle diameter is large and can be obtained by close packing.

  In step II, various polymerization conditions can be selected depending on the type of aromatic vinyl monomer and the type of polymerization initiator. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate and the like were used as polymerization initiators. Sometimes, heat polymerization may be performed at 30 to 100 ° C. for 1 to 48 hours in a sealed container under an inert atmosphere.

  Step III is a step of removing the particulate template from the polymer. That is, after the polymerization is completed, the contents are taken out from the container, the particulate template is removed, and then extracted with a solvent such as 2-propanol for the purpose of removing unreacted vinyl monomer and organic solvent. A monolithic organic porous intermediate in which a continuous macropore structure coexists is obtained.

  The method for removing the particulate template is not particularly limited, and examples thereof include heat dissolution, hydrolysis, enzymatic decomposition, oxidative decomposition, ion exchange treatment with a chelating agent such as ethylenediaminetetraacetic acid and sodium hexametaphosphate. Among these particulate template removal methods, heat dissolution or ion exchange treatment with a chelating agent such as ethylenediaminetetraacetic acid or sodium hexametaphosphate is preferable in terms of simplicity in experimental operation and ease of template removal.

  The monolith intermediate obtained in the step III has a continuous macropore structure in which the skeleton part of the continuous macrovoid structure has a low-bridge skeleton. The continuous macropore structure is a continuous macropore structure in which the macropores overlap each other, and the overlapping portion becomes an opening having an average radius of 0.01 to 100 μm. The continuous macropore structure is a structure in which the macropores connected to each other and the connected portion of the macropores have an opening with a radius of 0.01 to 100 μm, preferably 0.1 to 100 μm, particularly preferably 5 to 60 μm. That is, the continuous macropore structure usually has a structure in which a macropore having a radius of 0.2 to 500 μm and a macropore overlap each other, and this overlapping portion becomes an opening, and this portion has an open pore structure.

  The continuous macropore structure of the monolith intermediate preferably has a total pore volume of 4 to 30 ml / g. If the total pore volume is less than 4 ml / g, the skeleton density is high, which adversely affects the structure formation of the monolithic organic porous material obtained later, and the structure of the organic porous material is derived from the monolith intermediate This is not preferable because of the continuous macropore structure. On the other hand, when the total pore volume exceeds 30 ml / g, the proportion of the polymer in the skeleton portion decreases, and the aromatic vinyl monomer, the crosslinking agent, the aromatic vinyl monomer and the crosslinking agent dissolve in the monolith intermediate, but the aromatic In the process of polymerizing by impregnating a mixture of an organic solvent and a polymerization initiator that does not dissolve the polymer produced by polymerization of the vinyl monomer, a sufficient amount of aromatic vinyl monomer cannot be adsorbed or distributed to the skeleton. It is not preferable.

  The radius of the opening 0.01-100 μm, which is the overlapping part of the macropores and macropores of the monolith intermediate, determines the amount of surfactant added, the stirring rotation speed and stirring time in the step of obtaining the water-in-oil emulsion. This can be achieved by appropriately determining. Moreover, it can also adjust by making alcohol, carboxylic acid, or a hydrocarbon coexist in the case of stirring and mixing. In the vicinity of the radius of 0.01 μm, the addition amount of the surfactant is increased, the number of rotations of stirring is increased, or the stirring time is lengthened. Conversely, in the vicinity of the radius of 100 μm, the addition amount of the surfactant is reduced. Can be achieved by reducing the number of rotations of stirring or shortening the stirring time.

  Step IV is a step of preparing a mixture of an organic solvent and a polymerization initiator that dissolves the aromatic vinyl monomer, the crosslinking agent, the aromatic vinyl monomer and the crosslinking agent, but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer. It is.

  The aromatic vinyl monomer used in step IV is not particularly limited as long as it contains a vinyl group that can be polymerized in the molecule as in step I, has low water solubility, and is oleophilic. Specific examples of these vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyl toluene, and vinyl benzyl chloride; α-olefins such as ethylene, propylene, 1-butene, and isobutene; butadiene, isoprene, chloroprene, and the like. Diene monomers; Halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; Nitrile monomers such as acrylonitrile and methacrylonitrile; Vinyl esters such as vinyl acetate and vinyl propionate; Methyl acrylate and Acrylic Ethyl acetate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate Examples include (meth) acrylic monomers such as syl, benzyl methacrylate, and glycidyl methacrylate. These monomers can be used alone or in combination of two or more. Among these monomers, preferred are aromatic vinyl monomers, and vinyl monomers suitably used in the present invention are styrene monomers such as styrene and vinyl benzyl chloride.

  The addition amount of these aromatic vinyl monomers is 5 to 50 times by weight with respect to the monolith intermediate obtained in the step III. If the amount of aromatic vinyl monomer added is less than 5 times that of the porous material, the resulting monolith skeleton cannot be thickened, and the adsorption capacity per volume and the ion exchange capacity per volume after introduction of ion exchange groups are small. This is not preferable. On the other hand, if the amount of the aromatic vinyl monomer added exceeds 50 times, the opening diameter becomes small and the pressure loss during fluid permeation increases, which is not preferable.

  As the cross-linking agent used in the step IV, those having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent are preferably used as in the step I. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis.

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

  As the polymerization initiator used in the IV step, a compound that generates radicals by heat and light irradiation as in the I step is preferably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) 1,1′-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide and the like. The amount of the polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in a range of about 0.01 to 5% with respect to the total amount of vinyl monomer and crosslinking agent.

  In step V, the mixture obtained in step IV is allowed to stand and polymerized in the presence of the monolithic organic porous intermediate obtained in step III, so that a continuous macrovoid structure and a co-continuous structure coexist. This is a step of obtaining an organic porous body. Further, the co-continuous structure as the skeleton part has a total pore volume of 0.5 to 5 ml / g, and contains 0.3 to 2.5 mol% of a crosslinked structural unit in all the structural units. It is a porous structure having a skeleton thicker than the skeleton.

  The monolith intermediate used in the V process plays an extremely important role in creating the monolith having the novel structure of the present invention. As disclosed in JP-A-7-501140 and the like, when an aromatic vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic material is obtained. A porous body is obtained. On the other hand, as in the present invention, the polymerization system has a monolith intermediate of a continuous macropore structure containing a total pore volume of 4 to 30 ml / g and 0.3 to 2.5 mol% of cross-linked structural units in all the structural units. When the body is present, the structure of the monolith after polymerization changes dramatically, the particle aggregation structure and the continuous macropore structure disappear, and the above-mentioned monolith having the above-described bicontinuous structure is obtained. The reason for this has not been elucidated in detail, but in the absence of a monolith intermediate, the cross-linked polymer produced by polymerization precipitates and precipitates in the form of particles, while a particle aggregate structure is formed. If a porous body (intermediate) having a relatively low cross-linkage is present in the system, the vinyl monomer and the cross-linking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization proceeds in the porous body. It is considered that the skeleton constituting the structure is changed from a two-dimensional wall portion to a one-dimensional rod-shaped skeleton to obtain a monolith with a co-continuous structure.

  In step V, various conditions can be selected depending on the type of aromatic vinyl monomer and the type of polymerization initiator, as in step II. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate and the like were used as polymerization initiators. Sometimes, heat polymerization may be performed at 30 to 100 ° C. for 1 to 48 hours in a sealed container under an inert atmosphere. After completion of the polymerization, the contents are taken out from the container and extracted with a solvent such as 2-propanol for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a monolithic organic porous material.

  Next, the manufacturing method of the monolithic organic porous ion exchanger of this invention is demonstrated. In the monolithic organic porous ion exchanger, after the monolithic organic porous body obtained by the above method was produced, ion exchange groups were uniformly introduced into the skeleton surface and inside the skeleton of the monolithic organic porous body. The ion exchange capacity per volume in a wet state of water is 0.075 mg equivalent / ml or more, preferably 0.1 to 5.0 mg equivalent / ml. Thus, the method of manufacturing a monolithic organic porous body in advance and then introducing an ion exchange group is preferable in that the porous structure of the monolithic organic porous ion exchanger can be strictly controlled.

  The method for uniformly introducing ion exchange groups into the surface of the monolithic organic porous material and inside the skeleton is not particularly limited, and known methods such as polymer reaction and graft polymerization can be used. For example, as a method for introducing a sulfonic acid group, if the organic porous material is a styrene-divinylbenzene copolymer or the like, a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid; surface of the organic porous material And a method of grafting polymerization of sodium styrene sulfonate or acrylamide-2-methylpropane sulfonic acid by introducing a radical initiating group or chain transfer group into the skeleton; similarly, graft polymerization of glycidyl methacrylate followed by functional group conversion to sulfonic acid Examples thereof include a method for introducing a group. Moreover, as a method of introducing a quaternary ammonium group, if the organic porous material is a styrene-divinylbenzene copolymer or the like, a method of introducing a chloromethyl group with chloromethyl methyl ether or the like and then reacting with a tertiary amine A method in which an organic porous material is produced by copolymerization of chloromethylstyrene and divinylbenzene and reacted with a tertiary amine; a radical initiating group or a chain transfer group is introduced into the surface of the organic porous material and inside the skeleton; A method of graft polymerization of N, N-trimethylammonium ethyl acrylate or N, N, N-trimethylammoniumpropylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion, etc. It is done. Examples of the method for introducing betaine include a method in which a tertiary amine is introduced into an organic porous material and then introduced by reacting with monoiodoacetic acid. Among these methods, the method of introducing a sulfonic acid group includes a method of introducing a sulfonic acid group into a styrene-divinylbenzene copolymer using chlorosulfuric acid, and a method of introducing a quaternary ammonium group includes styrene. -An organic porous material is produced by introducing a chloromethyl group into a divinylbenzene copolymer with chloromethyl methyl ether and then reacting with a tertiary amine, or by copolymerizing chloromethylstyrene and divinylbenzene. Is preferable in that the ion exchange group can be uniformly and quantitatively introduced into the skeleton surface and inside the skeleton. The ion exchange groups to be introduced include cation exchange groups such as carboxylic acid groups, iminodiacetic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphoric ester groups; quaternary ammonium groups, tertiary amino groups, and secondary amino groups. Groups, primary amino groups, polyethyleneimine groups, tertiary sulfonium groups, phosphonium groups and the like; and amphoteric ion exchange groups such as aminophosphate groups, betaines and sulfobetaines.

  The ion exchange capacity can be adjusted as appropriate by selecting the porous material and the reaction reagent. For example, when producing a porous body having a relatively low cation exchange capacity of 0.075 mg equivalent / g, a porous material mainly composed of divinylbenzene having a low reactivity with a sulfonation reagent such as concentrated sulfuric acid or chlorosulfonic acid. This can be achieved by sulfonating the mass. In addition, when introducing a cation exchange group by a graft reaction, the cation exchange capacity can be lowered by suppressing the introduction amount of radical initiation groups and chain transfer groups introduced into the porous body. On the other hand, when it is desired to increase the cation exchange capacity, a porous material mainly composed of styrene having a high reactivity with the sulfonation reagent is sulfonated. Further, when a graft reaction is used, the amount of radical initiation group or chain transfer group introduced into the porous body may be increased. In addition, in the case of anion exchange capacity or amphoteric ion exchange capacity, the same method as in the case of the cation exchange capacity can be used.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

(Production of monolithic organic porous intermediate)
4.66 g of styrene, 0.10 g of divinylbenzene, 0.25 g of sorbitan monooleate, and 0.07 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / sorbitan monooleate / 2,2′-azobis (isobutyronitrile) mixture was added to 45.0 g of pure water, and a vacuum stirring defoaming mixer (EM The product was stirred for 2 minutes under a reduced pressure of 13.3 kPa at a revolution speed of 1000 revolutions / minute and a rotation speed of 330 revolutions / minute to obtain a water-in-oil emulsion (Step I).

  The water-in-oil emulsion obtained in Step I was gently poured into a cylindrical container. Next, the emulsion was closely packed with aspherical hydrogel having a spherical shape and a particle radius of 1.5 mm, the system was sufficiently substituted with nitrogen, sealed, and polymerized at 60 ° C. for 24 hours under standing (II). Process). As the agar hydrogel beads, those produced by dropping and solidifying the agar solution into the cooled solution were used.

  After completion of the polymerization, the contents were taken out and stirred in pure water heated to 90 ° C. or higher for 1 hour to remove the agar hydrogel. Thereafter, Soxhlet extraction is performed with 2-propanol for 6 hours to remove unreacted monomers, water and sorbitan monooleate, followed by drying under reduced pressure at 85 ° C. for one day to obtain a crosslinking component made of a styrene / divinylbenzene copolymer. A monolithic organic porous intermediate having a continuous macrovoid structure and containing 3 mol% was obtained (step III).

  The internal structure of the organic porous intermediate was such that a continuous macrovoid structure and a continuous macropore structure were uniformly mixed and connected to each other. In the continuous macrovoid structure, most of the macrovoids having an average radius of 1.5 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.6 mm. Further, in the continuous macropore structure of the skeleton portion, most of the macropores having an average radius of 32 μm overlapped, the average radius of the openings formed by the overlap of the macropores and the macropores was 14 μm, and the total pore volume was 8.8 ml / g. The obtained porous body was a cylindrical shape having a weight of 4.3 g, a diameter of 70.0 mm, and a height of 41.2 mm. The results are summarized in Table 1.

(Production of monolithic organic porous material)
39.2 g of styrene, 0.8 g of divinylbenzene, 60 g of 1-octanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (IV step).

  Next, the monolith intermediate obtained in the above step III was cut into a disk shape having a thickness of about 20 mm, and 2.0 g was collected. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 88 mm, immersed in the styrene / divinylbenzene / 1-octanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the contents are taken out, extracted with Soxhlet with acetone, and then dried under reduced pressure at 85 ° C. overnight to contain 1.3 mol% of a cross-linking component composed of a styrene / divinylbenzene copolymer. A monolith-like organic porous body having V was obtained (Step V).

  The internal structure of the monolithic organic porous material containing 1.3 mol% of the cross-linking component composed of the styrene / divinylbenzene copolymer thus obtained is a mixture of a continuous macrovoid structure and a co-continuous structure uniformly. They were connected to each other. In the continuous macrovoid structure, most of the macrovoids having an average radius of 1.3 mm overlap each other, and the average radius of the openings formed by the overlap of the macrovoids and the macrovoids is 0.5 mm. Moreover, the result of having observed the co-continuous structure of the frame | skeleton part by SEM is shown in FIG. When the internal structure of the monolithic organic porous body (dried body) was observed by SEM, it was a co-continuous structure in which the skeleton and pores were each three-dimensionally continuous and both phases were entangled. Moreover, the thickness of the skeleton measured from the SEM image was 11 μm. Moreover, about the co-continuous structure separately prepared by the same method except not using a particulate template, the void | hole size and the total pore volume were measured by the mercury intrusion method. The size of the three-dimensionally continuous pores of the monolith measured by the mercury intrusion method was 21 μm, and the total pore volume was 2.9 ml / g. Moreover, the obtained porous body was a disk shape having a weight of 34.0 g, a diameter of 88.0 mm, and a height of 25.1 mm. The results are summarized in Table 2.

(Production of monolithic organic porous cation exchanger)
To the organic porous material obtained in Example 1, 1800 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or lower, 186.4 g of chlorosulfuric acid was gradually added, and the temperature was raised to 35 ° C. For 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolithic organic porous cation exchanger having a continuous macrovoid structure.

  The swelling rate before and after the reaction of the obtained cation exchanger was 1.69 times, the diameter was 148.7 mm, and the ion exchange capacity per volume was 0.15 mg equivalent / ml in a wet state. In the water wet state, the average macrovoid radius of the continuous macrovoid structure was 2.2 mm, and the average radius of the openings formed by the overlap of the macrovoids and the macrovoids was 1.0 mm.

  Further, the co-continuous structure of the skeleton part was estimated from the diameter of the organic porous material and the swelling ratio of the cation exchanger in a water-wet state. As a result, the skeleton diameter was 19 μm, the continuous pore size was 35 μm, and the total pore volume. Was 2.9 ml / g. The results are summarized in Table 3.

(Production of monolithic organic porous intermediate)
A monolithic organic porous intermediate was produced in the same manner as in Example 1 except that an agar hydrogel having a particle radius of 2.5 mm was used instead of an agar hydrogel having a particle radius of 1.5 mm.

  The internal structure of the organic porous intermediate was such that a continuous macropore structure and a continuous macrovoid structure were uniformly mixed and connected to each other. In the continuous macrovoid structure, most of the macrovoids having an average radius of 2.5 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 1.0 mm. Further, in the continuous macropore structure of the skeleton part, most of the macropores having an average radius of 30 μm overlapped, the average radius of the openings formed by the overlap of the macropores and the macropores was 12 μm, and the total pore volume was 8.9 ml / g. The obtained porous body was a cylindrical shape having a weight of 4.1 g, a diameter of 70.5 mm, and a height of 41.5 mm. The results are summarized in Table 1.

(Production of monolithic organic porous material)
The monolithic organic porous intermediate obtained in Example 2 was converted into a styrene / divinylbenzene / 1-octanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture in the same manner as in Example 1. It was immersed and a polymerization reaction was performed to produce a monolithic organic porous body. The internal structure of the monolithic organic porous material containing 1.3 mol% of the cross-linking component made of the styrene / divinylbenzene copolymer was obtained by uniformly mixing the continuous macrovoid structure and the co-continuous structure. Met. In the continuous macrovoid structure, most of the macrovoids having an average radius of 2.4 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.9 mm. Moreover, the result of having observed the continuous macropore structure which is a frame | skeleton part by SEM is shown in FIG. The SEM image in FIG. 6 is an image at an arbitrary position on the cut surface of the skeleton obtained by cutting the monolith at an arbitrary position as in FIG. Regarding the co-continuous structure of the skeleton part, the skeleton diameter determined by the same method as in Example 1 was 12 μm. Moreover, the size of the continuous pores of the monolith obtained by the same method as in Example 1 was 20 μm, and the total pore volume was 2.8 ml / g. Moreover, the obtained porous body was a disk shape having a weight of 33.5 g, a diameter of 87.5 mm, and a height of 24.5 mm. The results are summarized in Table 2.

(Production of monolithic organic porous cation exchanger)
The monolithic organic porous material obtained in Example 2 was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic organic porous cation exchanger. The swelling rate before and after the reaction of the obtained cation exchanger was 1.73 times, the diameter was 151.3 mm, and the ion exchange capacity per volume was 0.14 mg equivalent / ml in a wet state. In the water wet state, the macrovoid average radius of the continuous macrovoid structure was 4.2 mm, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 1.7 mm. Further, the co-continuous structure of the skeleton part was estimated from the diameter of the organic porous body and the swelling ratio of the cation exchanger in a water-wet state. As a result, the skeleton diameter was 21 μm, the continuous pore size was 35 μm, and the total pore volume. Was 2.8 ml / g. The results are summarized in Table 3.

(Production of monolithic organic porous intermediate)
A monolithic organic porous intermediate was produced in the same manner as in Example 1 except that an agar hydrogel having a particle radius of 12.5 mm was used instead of an agar hydrogel having a particle radius of 1.5 mm.

  The internal structure of the organic porous intermediate was such that a continuous macropore structure and a continuous macrovoid structure were uniformly mixed and connected to each other. In the continuous macrovoid structure, most of the macrovoids having an average radius of 12.5 mm overlap each other, and the average radius of the opening formed by the overlap between the macrovoids and the macrovoids is 5.5 mm. Further, in the continuous macropore structure of the skeleton, most of the macropores having an average radius of 31 μm overlapped, the average radius of the openings formed by the overlap of the macropores and the macropores was 13 μm, and the total pore volume was 8.6 ml / g. The obtained porous body was a cylindrical shape having a weight of 4.2 g, a diameter of 70.0 mm, and a height of 40.6 mm. The results are summarized in Table 1.

(Production of monolithic organic porous material)
The monolithic organic porous intermediate obtained in Example 3 was converted into a styrene / divinylbenzene / 1-octanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture in the same manner as in Example 1. It was immersed and a polymerization reaction was performed to produce a monolithic organic porous body. The internal structure of the monolithic organic porous material containing 1.3 mol% of the cross-linking component made of the styrene / divinylbenzene copolymer was obtained by uniformly mixing the continuous macrovoid structure and the co-continuous structure. Met. In the continuous macrovoid structure, most of the macrovoids having an average radius of 11.5 mm overlap each other, and the average radius of the opening formed by the overlap of the macrovoids and the macrovoids is 4.6 mm. Moreover, the result of having observed the continuous macropore structure which is a frame | skeleton part by SEM is shown in FIG. The SEM image in FIG. 7 is an image at an arbitrary position on the cut surface of the skeleton obtained by cutting the monolith at an arbitrary position as in FIG. Regarding the co-continuous structure of the skeleton part, the skeleton diameter determined by the same method as in Example 1 was 11 μm. Moreover, the size of the continuous pores of the monolith measured by the mercury intrusion method was 21 μm, and the total pore volume was 2.7 ml / g. Moreover, the obtained porous body was a disk shape having a weight of 34.5 g, a diameter of 87.8 mm, and a height of 24.3 mm. The results are summarized in Table 2.

(Production of monolithic organic porous cation exchanger)
The monolithic organic porous material obtained in Example 3 was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic organic porous cation exchanger. The swelling rate before and after the reaction of the obtained cation exchanger was 1.74 times, the diameter was 152.8 mm, and the ion exchange capacity per volume was 0.14 mg equivalent / ml in a wet state. In the water wet state, the average macrovoid radius of the continuous macrovoid structure was 21.0 mm, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 9.6 mm. Further, the co-continuous structure of the skeleton part was estimated from the diameter of the organic porous body and the swelling ratio of the cation exchanger in a water-wet state. As a result, the skeleton diameter was 19 μm, the continuous pore size was 37 μm, and the total pore volume. Was 2.7 ml / g. The results are summarized in Table 3.

(Production of monolithic organic porous intermediate)
The calcium alginate hydrogel having a particle radius of 1.5 mm was used in place of the agar hydrogel having a particle radius of 1.5 mm, and the template removal conditions were stirred for 1 hour in pure water heated to 90 ° C. or higher. Instead, a monolithic organic porous intermediate was produced in the same manner as in Example 1 except that stirring was performed in a 10% sodium hexametaphosphate aqueous solution for 4 hours. As the calcium alginate hydrogel beads, those obtained by dropping a sodium alginate aqueous solution into a calcium chloride aqueous solution to form a gel were used.

  The internal structure of the organic porous intermediate was such that a continuous macropore structure and a continuous macrovoid structure were uniformly mixed and connected to each other. In the continuous macrovoid structure, most of the macrovoids having an average radius of 1.5 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.6 mm. Further, in the continuous macropore structure of the skeleton part, most of the macropores having an average radius of 30 μm overlapped, the average radius of the openings formed by the overlap of the macropores and the macropores was 14 μm, and the total pore volume was 8.7 ml / g. The obtained porous body was a cylindrical shape having a weight of 4.2 g, a diameter of 70.3 mm, and a height of 40.0 mm. The results are summarized in Table 1.

(Production of monolithic organic porous material)
The monolithic organic porous intermediate obtained in Example 4 was converted into a styrene / divinylbenzene / 1-octanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture in the same manner as in Example 1. It was immersed and a polymerization reaction was performed to produce a monolithic organic porous body. The internal structure of the monolithic organic porous material containing 1.3 mol% of the cross-linking component made of the styrene / divinylbenzene copolymer was obtained by uniformly mixing the continuous macrovoid structure and the co-continuous structure. Met. In the continuous macrovoid structure, most of the macrovoids having an average radius of 1.4 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.5 mm. Moreover, the result of having observed the continuous macropore structure which is a frame | skeleton part by SEM is shown in FIG. The SEM image in FIG. 8 is an image at an arbitrary position on the cut surface of the skeleton obtained by cutting the monolith at an arbitrary position as in FIG. Regarding the co-continuous structure of the skeleton part, the skeleton diameter determined by the same method as in Example 1 was 10 μm. Further, the size of continuous pores of the monolith measured by the mercury intrusion method was 21 μm, and the total pore volume was 2.8 ml / g. Moreover, the obtained porous body was a disk shape having a weight of 34.2 g, a diameter of 87.0 mm, and a height of 24.5 mm. The results are summarized in Table 2.

(Production of monolithic organic porous cation exchanger)
The monolithic organic porous material obtained in Example 4 was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic organic porous cation exchanger. The swelling ratio before and after the reaction of the obtained cation exchanger was 1.70 times, the diameter was 147.9 mm, and the ion exchange capacity per volume was 0.15 mg equivalent / ml in a wet state. In the water wet state, the average macrovoid radius of the continuous macrovoid structure was 2.4 mm, and the average radius of the openings formed by the overlap of the macrovoids and the macrovoids was 1.0 mm.

  Further, the co-continuous structure of the skeleton part was estimated from the diameter of the organic porous body and the swelling ratio of the cation exchanger in a water-wet state. As a result, the skeleton diameter was 17 μm, the continuous pore size was 36 μm, and the total pore volume. Was 2.8 ml / g. The results are summarized in Table 3.

(Production of monolithic organic porous intermediate)
Example except that styrene 4.66 g, divinylbenzene 0.10 g, sorbitan monooleate 0.25 g were replaced with styrene 1.30 g, divinylbenzene 0.03 g, sorbitan monooleate 0.07 g. A monolithic organic porous intermediate was produced in the same manner as in Example 1.

  The internal structure of the organic porous intermediate was such that a continuous macropore structure and a continuous macrovoid structure were uniformly mixed and connected to each other. In the continuous macrovoid structure, most of the macrovoids having an average radius of 1.5 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.5 mm. Further, in the continuous macropore structure of the skeleton part, most of the macropores having an average radius of 57 μm overlapped, the average radius of the openings formed by the overlap of the macropores and the macropores was 21 μm, and the total pore volume was 15.5 ml / g. The obtained porous body was a cylindrical shape having a weight of 1.5 g, a diameter of 69.5 mm, and a height of 39.5 mm. The results are summarized in Table 1.

(Production of monolithic organic porous material)
Example 1 except that the monolith intermediate was cut into a disk shape having a thickness of about 20 mm and cut into a disk shape having a thickness of about 20 mm instead of being cut into 2.0 g. The monolithic organic porous intermediate obtained in Example 5 was immersed in a styrene / divinylbenzene / 1-octanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture in the same manner as in Example 1. And a polymerization reaction was carried out to produce a monolithic organic porous material. The internal structure of the monolithic organic porous material containing 1.3 mol% of the cross-linking component made of the styrene / divinylbenzene copolymer was obtained by uniformly mixing the continuous macrovoid structure and the co-continuous structure. Met. In the continuous macrovoid structure, most of the macrovoids having an average radius of 1.5 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.5 mm. Moreover, the result of having observed the continuous macropore structure which is a frame | skeleton part by SEM is shown in FIG. The SEM image in FIG. 9 is an image at an arbitrary position on the cut surface of the skeleton obtained by cutting the monolith at an arbitrary position as in FIG. Regarding the co-continuous structure of the skeleton part, the skeleton diameter determined by the same method as in Example 1 was 9 μm. Further, the size of the continuous pores of the monolith measured by mercury porosimetry was 23 μm, and the total pore volume was 3.2 ml / g. Moreover, the obtained porous body was a disk shape having a weight of 32.5 g, a diameter of 88.0 mm, and a height of 23.5 mm. The results are summarized in Table 2.

(Production of monolithic organic porous cation exchanger)
The monolithic organic porous material obtained in Example 5 was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic organic porous cation exchanger. The swelling rate before and after the reaction of the obtained cation exchanger was 1.79 times, the diameter was 157.5 mm, and the ion exchange capacity per volume was 0.14 mg equivalent / ml in a wet state. In the water wet state, the macrovoid average radius of the continuous macrovoid structure was 2.7 mm, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.9 mm. Further, the co-continuous structure of the skeleton portion was estimated from the diameter of the organic porous body and the swelling ratio of the cation exchanger in a water-wet state. As a result, the skeleton diameter was 16 μm, the continuous pore size was 41 μm, and the total pore volume. Was 3.2 ml / g. The results are summarized in Table 3.

(Production of monolithic organic porous intermediate)
Example except that styrene 4.66 g, divinylbenzene 0.10 g and sorbitan monooleate 0.25 g were replaced with styrene 10.5 g, divinylbenzene 0.22 g and sorbitan monooleate 0.56 g. A monolithic organic porous intermediate was produced in the same manner as in Example 1.

  The internal structure of the organic porous intermediate was such that a continuous macropore structure and a continuous macrovoid structure were uniformly mixed and connected to each other. In the continuous macrovoid structure, most of the macrovoids having an average radius of 1.5 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.5 mm. Further, in the continuous macropore structure of the skeleton portion, most of the macropores having an average radius of 16 μm overlapped, the average radius of the openings formed by the overlap of the macropores and the macropores was 6 μm, and the total pore volume was 4.5 ml / g. The obtained porous body was a cylindrical shape having a weight of 9.6 g, a diameter of 70.8 mm, and a height of 41.2 mm. The results are summarized in Table 1.

(Production of monolithic organic porous material)
Instead of the raw material of 39.2 g of styrene, 0.8 g of divinylbenzene and 60 g of 1-octanol, it was changed to the raw material of 34.3 g of styrene, 0.7 g of divinylbenzene and 45 g of 1-octanol, and the monolith intermediate had a thickness of about In the same manner as in Example 1 except that it was cut into a 20 mm disk shape and separated into 2.0 g, and cut into a disk shape with a thickness of about 20 mm, and 4.5 g was collected. The monolithic organic porous intermediate obtained in Example 6 was immersed in a styrene / divinylbenzene / 1-octanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture to conduct a polymerization reaction, A monolithic organic porous body was produced. The internal structure of the monolithic organic porous material containing 1.3 mol% of the cross-linking component made of the styrene / divinylbenzene copolymer was obtained by uniformly mixing the continuous macrovoid structure and the co-continuous structure. Met. In the continuous macrovoid structure, most of the macrovoids having an average radius of 1.5 mm overlap, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 0.6 mm. Moreover, the result of having observed the continuous macropore structure which is a frame | skeleton part by SEM is shown in FIG. The SEM image in FIG. 10 is an image at an arbitrary position on the cut surface of the skeleton obtained by cutting the monolith at an arbitrary position as in FIG. Regarding the co-continuous structure of the skeleton part, the skeleton diameter determined by the same method as in Example 1 was 15 μm. Further, the size of the continuous pores of the monolith measured by mercury porosimetry was 17 μm, and the total pore volume was 2.5 ml / g. Moreover, the obtained porous body was a disk shape having a weight of 33.5 g, a diameter of 89.0 mm, and a height of 24.5 mm. The results are summarized in Table 2.

(Production of monolithic organic porous cation exchanger)
The monolithic organic porous material obtained in Example 6 was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic organic porous cation exchanger. The swelling rate before and after the reaction of the obtained cation exchanger was 1.81 times, the diameter was 161.1 mm, and the ion exchange capacity per volume was 0.16 mg equivalent / ml in a wet state with water. In the water wet state, the macrovoid average radius of the continuous macrovoid structure was 2.7 mm, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 1.1 mm. Further, the co-continuous structure of the skeleton part was estimated from the diameter of the organic porous body and the swelling ratio of the cation exchanger in a water-wet state. As a result, the skeleton diameter was 27 μm, the continuous pore size was 31 μm, and the total pore volume. Was 2.5 ml / g. The results are summarized in Table 3.

(Production of monolithic organic porous anion exchanger)
A monolithic organic porous material was produced in the same manner as in Example 1. To the obtained organic porous material, 1405 ml of dimethoxymethane and 44.6 g of tin tetrachloride were added, and after cooling to 10 ° C. or lower, 978.7 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 5 hours. I let you. Thereafter, the reaction solution was cooled again to 10 ° C. or lower, and the reaction solution was taken out from the container, and washed with 1800 ml of a tetrahydrofuran / water = 1/1 mixed solution to obtain a chloromethylated organic porous material. 1800 ml of tetrahydrofuran was added to the chloromethylated organic porous material, and 879.1 g of a 30% aqueous solution of trimethylamine was added thereto, and the temperature was raised and reacted at 50 ° C. for 6 hours. Thereafter, the reaction solution was withdrawn from the vessel, washed with 1800 ml of a methanol / water = 1/1 mixed solution, and further washed with pure water to obtain a monolithic organic porous anion exchanger. The obtained anion exchanger had an ion exchange capacity per volume in a water-wet state of 0.12 mg equivalent / ml.

Comparative Example 1
(Manufacture of monolithic organic porous body with open cell structure)
A raw material of 4.66 g of styrene, 0.10 g of divinylbenzene, 0.25 g of sorbitan monooleate, 0.07 g of 2,2′-azobis (isobutyronitrile) and 45.0 g of pure water, 19.24 g of styrene, divinyl Except for changing to 1.01 g of benzene, 1.07 g of sorbitan monooleate, 0.26 g of 2,2′-azobis (isobutyronitrile) and 180 g of pure water, and omitting the use of agar hydrogel beads, A monolithic organic porous material was produced in the same manner as the production method of the monolithic organic porous intermediate of Example 1.

  Since the obtained organic porous body does not use a particulate template, it does not form a continuous macrovoid structure and contains a continuous macropore containing 1.3 mol% of a cross-linking component made of a styrene / divinylbenzene copolymer. Only the structure was formed. The internal structure of this organic porous material is that most macropores with an average radius of 31 μm overlap, the size of continuous pores formed by the overlap of macropores and macropores is 24 μm, and the total pore volume is 8.6 ml / g. there were. Further, when the skeleton structure was observed by SEM, the wall thickness was 5 μm. The obtained porous body was a cylindrical shape having a weight of 16.7 g, a diameter of 70.8 mm, and a height of 42.0 mm. The results are summarized in Tables 1 and 2.

(Manufacture of monolithic organic porous cation exchanger with open cell structure)
The monolithic organic porous material having a continuous macropore structure obtained in Comparative Example 1 was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic organic porous cation exchanger. The obtained cation exchanger did not form a continuous macrovoid structure, the swelling ratio before and after the reaction was 1.92 times, the diameter was 135.9 mm, and the ion exchange capacity per volume was in a wet state of water. It was 0.19 mg equivalent / ml. The internal structure of the organic porous cation exchanger has a continuous macropore structure, and the average pore radius of the water wet state is determined by the size of the continuous pores of the organic porous body and the cation exchanger of the water wet state. As estimated from the swelling rate, the size of the continuous pores was 46 μm, and the skeleton diameter was 10 μm. The results are summarized in Table 3.

Reference example 1
(Production of monolithic organic porous cation exchanger)
The step of immersing the monolithic organic porous intermediate produced in Example 1 in a styrene / divinylbenzene / 1-octanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture and performing a polymerization reaction The monolithic organic porous cation exchanger was manufactured by omitting and performing the sulfonation reaction as it was.

  That is, the monolithic porous intermediate obtained in Step III of Example 1 was cut into a disk shape having a thickness of about 20 mm, and 2.0 g was collected. By reacting, a monolithic organic porous cation exchanger was produced. The swelling ratio before and after the reaction of the obtained cation exchanger was 1.87 times, the diameter was 132.8 mm, the total pore volume was 8.9 ml, and the ion exchange capacity per volume was 0.04 mg in a water-wet state. Equivalent / ml.

  In the water wet state, the macrovoid average radius of the continuous macrovoid structure was 2.6 mm, and the average radius of the openings formed by the overlap of the macrovoid and the macrovoid was 1.0 mm. Further, when the continuous macropore structure of the skeleton portion was estimated from the diameter of the organic porous body and the swelling ratio of the cation exchanger in a water-wet state, the size of the continuous pores was 49 μm and the wall thickness was 9 μm. The results are summarized in Table 1, Table 2, and Table 3.

(Ion removal performance test 1)
The monolithic organic porous cation exchanger obtained in Example 1 was packed in a column having an inner diameter of 10 mm and a height of 100 mm, and 0.004 mol / l sodium chloride aqueous solution (Na ⁺ ion concentration: 92.0 ppm) was The solution was passed at a speed of 10 m / h, and the removal performance of Na ⁺ ions was measured. As a result, the Na ⁺ ion removal rate was 99% or more, and the pressure loss was 0.002 MPa. Moreover, the monolithic organic porous cation exchanger had a strength that can withstand the ion removal performance test.

(Ion removal performance test 2)
In place of the monolithic organic porous cation exchanger obtained in Example 1, the ion-removing performance test 1 except that the open-cell structure type monolithic organic porous cation exchanger produced in Comparative Example 1 was used. A similar ion removal performance test was conducted. As a result, the Na ⁺ ion removal rate was 99% or more, but the pressure loss was 0.010 MPa.

  The monolithic porous body of the present invention has a unique structure in which a continuous macrovoid structure and a co-continuous structure are uniformly mixed, and the skeleton of the co-continuous structure is thick. From this, it can be expected that the pressure loss will be extremely low when a fluid such as water or gas is flowed, and it will be packed in filters and adsorbents; two-bed, three-column pure water production equipment and electric deionized water production equipment. It is useful as a solid acid / base catalyst, and can be applied to a wide range of application fields.

It is a schematic diagram which shows basic structures, such as a monolithic porous body of this invention. It is the figure which showed typically the co-continuous structure which is frame | skeleton parts, such as a monolithic porous body of this invention. 2 is a SEM photograph of the monolithic organic porous material obtained in Example 1. 2 is an appearance photograph of the monolithic organic porous cation exchanger obtained in Example 1. FIG. 4 is a SEM photograph of the monolithic organic porous material obtained in Comparative Example 1. 3 is a SEM photograph of the monolithic organic porous material obtained in Example 2. 4 is a SEM photograph of the monolithic organic porous material obtained in Example 3. 4 is a SEM photograph of the monolithic organic porous material obtained in Example 4. 4 is a SEM photograph of the monolithic organic porous material obtained in Example 5. 6 is a SEM photograph of the monolithic organic porous material obtained in Example 6.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Skeletal phase 2 Pore phase 10 Co-continuous structure 11 Macro void 12 Common opening X Continuous macro void structure

Claims (5)

The macrovoids overlap each other, and the overlapping portion is an organic porous body having a continuous macrovoid structure in which an opening having an average radius of 0.1 to 25 mm, and the apparent skeleton portion of the continuous macrovoid structure is the entire structural unit. Among them, a three-dimensional continuous skeleton composed of an aromatic vinyl polymer containing 0.3 to 2.5 mol% of a crosslinked structural unit and having a thickness of 0.8 to 40 μm, and a radius of 4 to 100 μm between the skeletons A monolithic organic porous body having a co-continuous structure composed of three-dimensionally continuous pores, wherein the radius of the macrovoid is at least five times the radius of the pores. 2. The monolithic organic porous material according to claim 1, wherein an average radius of the macrovoid is 5 to 250,000 times an average radius of the pores. Following steps;
The weight ratio (M) :( W) of the aromatic vinyl monomer (M) to water (W) is from 1:49 to the aromatic vinyl monomer, surfactant, water, crosslinking agent and, if necessary, the polymerization initiator. 1: 3, Mixing so that a crosslinking agent may be 0.3-2.5 mol% in the sum total of a vinyl monomer and a crosslinking agent, Stirring this mixture, and preparing the water-in-oil type emulsion, I process,
A step II in which a large number of particulate templates are present in the water-in-oil emulsion and polymerized by standing;
Step III for obtaining a monolithic organic porous intermediate in which a continuous macrovoid structure and a continuous macropore structure coexist by removing the particulate template from the polymer;
Aromatic vinyl monomer, crosslinker, aromatic vinyl monomer and crosslinker dissolve, but polymer formed by polymerization of aromatic vinyl monomer does not dissolve organic solvent and polymerization initiator, vinyl monomer is monolithic organic porous intermediate IV process which mix | blends with the quantity used as 5-50 times with respect to a body, and mixes,
An organic porous material in which the mixture obtained in the step IV is allowed to stand still and in the presence of the monolithic organic porous intermediate obtained in the step III, and a continuous macrovoid structure and a co-continuous structure coexist. V process to obtain
A method for producing a monolithic organic porous material characterized by comprising:   The method for producing a monolithic organic porous material according to claim 3, wherein the particulate template is a polysaccharide hydrogel.   An ion exchange group is introduced into the skeleton surface and inside the skeleton of the monolithic organic porous material according to claim 1 or 2, and the ion exchange capacity per volume in a water-wet state is 0.075 mg equivalent / ml. A monolithic organic porous ion exchanger characterized by the above.

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