JP5021540B2 - Monolithic organic porous body, monolithic organic porous ion exchanger, production method thereof and chemical filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monolith-like organic porous material having high mechanical strength, high contact efficiency with liquid in permeating the liquid and low pressure loss in permeating the liquid, and suitable as an absorber having high absorption capacity, and to provide a monolith-like organic porous ion exchanger and a method for producing thereof. <P>SOLUTION: The monolith-like organic porous material is a composite structural body comprising the organic porous material consisting of a continuous skeleton phase and a continuous pore phase, and a large number of particle bodies having 2-20 &mu;m diameter and adhered to the skeleton surface of the organic porous material or a large number of protrusion bodies formed on the skeleton surface of the organic porous material and having 2-20 &mu;m max. size, and has &ge;1 mm thickness, 8-100 &mu;m average pore diameter and 0.5-5 ml/g whole micropore volume. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a monolithic organic porous body useful as an ion exchanger used in an adsorbent, a deionized water production apparatus, etc., a monolithic organic porous ion exchanger using the same, a production method thereof, and a chemical filter Is.

  In JP-A-2002-306976, an oil-soluble monomer not containing an ion exchange group, a surfactant, water and a polymerization initiator as necessary are mixed to obtain a water-in-oil emulsion, which is polymerized. A production method for obtaining a monolithic organic porous body having a continuous macropore structure is disclosed. The organic porous material obtained by the above method and the organic porous ion exchanger into which an ion exchange group is introduced are useful as an ion exchanger used in an adsorbent, a chromatography filler, a deionized water production apparatus, and the like. .

  However, since the organic porous ion exchanger has a slightly low contact efficiency with the fluid at the time of fluid permeation, the adsorption capacity in a low concentration region tends to decrease when used as an adsorbent. When used as an adsorbent for trace amounts of ions, it has drawbacks such as a decrease in dynamic ion exchange capacity as the ion exchange zone length increases.

  On the other hand, as monolithic organic porous bodies and monolithic organic porous ion exchangers having a structure other than the above-described continuous macropore structure, porous bodies having a particle aggregation type structure are disclosed in JP 7-501140 A and the like. ing. However, the porous body obtained by this method has a large specific surface area and a high contact efficiency with the fluid during fluid permeation, but the continuous pores are as small as about 2 μm at the maximum, and a high flow rate treatment is performed at a low pressure. Therefore, it could not be used for an industrial scale deionized water production apparatus or the like. Furthermore, the porous body having a particle aggregation type structure has low mechanical strength, and is inferior in handling properties, such as being easily damaged when cut into a desired size and packed in a column or cell.

  As a structure of an 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 an average diameter of a micrometer size 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.

JP 2004-321930 A discloses a chemical filter using a monolithic organic porous ion exchanger having an open cell structure as an adsorption layer. According to this chemical filter, the ability to adsorb and remove gaseous pollutants can be maintained even if the gas permeation rate is high, and even if the amount of gaseous pollutants is extremely small, it can be removed.
JP 2002-306976 A JP 2007-154083 A (Claim 1) JP 2004-321930 A

  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 a monolithic organic porous body that has high mechanical strength, high contact efficiency with fluid during fluid permeation, and large continuous pores and low pressure loss when fluid such as water or gas is permeated. Development of monolithic organic porous ion exchangers has been desired. In addition, it has been desired to develop a chemical filter having a higher ability to adsorb and remove gaseous pollutants than ever before.

  On the other hand, MR type ion exchange resins are known to exhibit a particle composite structure having a micropore formed between agglomerates of macropores and small spherical gel particles in a copolymer having a huge network structure. However, the diameter of the particles forming the micropores of the MR type ion exchange resin is 1 μm at the maximum, and a composite organic monolith in which particles or protrusions exceeding 1 μm are fixed on the surface is not yet known.

  Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art, and has high mechanical strength, high contact efficiency with fluid during fluid permeation, and low pressure loss during fluid permeation, Monolithic organic porous material suitable as an adsorbent with a large adsorption capacity, monolithic organic porous ion exchange with high mechanical strength, high contact efficiency with fluid during fluid permeation, and low pressure loss during fluid permeation It is to provide a body and a method for producing them. It is another object of the present invention to provide a chemical filter that can retain the adsorption and removal ability of gaseous pollutants even when the gas permeation rate is high, and can be removed even if the amount of gaseous pollutants is extremely small.

  Under such circumstances, as a result of intensive studies, the present inventors have determined that a monolithic organic porous material (intermediate) having a relatively large pore volume among monoliths obtained by the method described in JP-A-2002-306976. ) In the presence of), the vinyl monomer and the crosslinking agent are allowed to stand in a specific organic solvent, and a large number of particles having a diameter of 2 to 20 μm are fixed on the surface of the skeleton constituting the organic porous material. In addition, a monolith having a composite structure with protrusions formed can be produced, and the composite monolith ion exchanger having an ion exchange group introduced therein can be adsorbed and ion-exchanged quickly and extremely uniformly. , Pressure loss is small, the inside of the skeleton maintains a continuous pore structure, high mechanical strength, excellent handling, and gaseous pollutants even at high gas permeation rates Excellent properties that could not be achieved by conventional monolithic organic porous materials or monolithic organic porous ion exchangers, such as the ability to retain adsorption and removal, and even removal of gaseous pollutants, even in extremely small amounts. As a result, the present invention has been completed.

  That is, the present invention relates to an organic porous body composed of a continuous skeleton phase and a continuous pore phase, a large number of particles having a diameter of 2 to 20 μm fixed to the skeleton surface of the organic porous body, or the skeleton of the organic porous body. A composite structure with a large number of protrusions having a maximum diameter of 2 to 20 μm formed on the surface, having a thickness of 1 mm or more, an average pore diameter of 8 to 100 μm, and a total pore volume of 0.5 to 5 ml / g A monolithic organic porous material is provided.

  The present invention also relates to an organic porous body composed of a continuous skeleton phase and a continuous pore phase, a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body, or a skeleton surface of the organic porous body. It is a composite structure with a large number of protrusions having a maximum diameter of 4 to 40 μm formed on the top, and has a thickness of 1 mm or more, an average diameter of pores of 10 to 150 μm, and a total pore volume of 0.5 to 5 ml / g. Monolithic organic porous ion exchange characterized by having an ion exchange capacity per volume in a water-wet state of 0.2 mg equivalent / ml or more and having ion exchange groups uniformly distributed in the composite structure Provide the body.

The present invention also provides a water-in-oil type by stirring a mixture of an oil-soluble monomer containing no ion exchange group, a first crosslinking agent having at least two vinyl groups in one molecule, a surfactant and water. Preparation of the emulsion, followed by polymerization of the water-in-oil emulsion to obtain a monolithic organic porous intermediate of continuous macropore structure with a total pore volume of 5 to 30 ml / g, step I, vinyl monomer, in one molecule Preparation of a mixture comprising an organic solvent and a polymerization initiator that dissolves a second crosslinking agent having at least two or more vinyl groups, a vinyl monomer or a second crosslinking agent but not a polymer formed by polymerization of the vinyl monomer II Process,
Step III, in which the mixture obtained in Step II is allowed to stand still and in the presence of the monolithic organic porous intermediate obtained in Step I, Step III
When producing a monolithic organic porous body, the following (1) to (5):
(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 second cross-linking agent used in step II is at least twice the mol% of the first cross-linking agent used in step I;
(3) The vinyl monomer used in Step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in Step I;
(4) The organic solvent used in step II is a polyether having a molecular weight of 200 or more;
(5) The concentration of the vinyl monomer used in the step II is 30% by weight or less in the mixture of the step II; the step II or the step III is performed under a condition satisfying at least one of the conditions A method for producing a monolithic organic porous body is provided.

  The present invention also provides a method for producing a monolithic organic porous ion exchanger characterized by performing an IV step of introducing an ion exchange group into the monolithic organic porous material obtained by the production method. is there.

  The present invention also provides a chemical filter using the monolithic organic porous material as an adsorption layer.

  The present invention also provides a chemical filter characterized in that the monolithic organic porous ion exchanger is used as an adsorption layer.

  The composite monolithic porous body of the present invention has a composite structure in which the skeleton surface of the skeleton phase constituting the organic porous body is coated with a large number of particles having a specific size or a large number of protrusions are formed. High contact efficiency between fluid and monolith during fluid permeation, fast and extremely uniform adsorption, low pressure loss, and skeletal structure maintains a continuous pore structure, so mechanical strength High and easy to handle. Therefore, not only can the synthetic adsorbents used in the past be replaced, but it can also be applied to new application fields such as adsorption removal of trace components that could not be handled by synthetic adsorbents by taking advantage of its excellent adsorption characteristics. It becomes.

  In addition, the composite monolithic porous ion exchanger of the present invention has a composite structure similar to that of the composite monolithic porous body, so that the ion exchange is quick and extremely uniform, and the mechanical strength is high. It has the feature that it is possible to pass the water to be treated for a long time at a low pressure and a large flow rate, and it has a two-bed three-column pure water production device, an ultrapure water production device, an electric deionized water production device. It can be suitably used as a chemical filter adsorbent.

  In this specification, “monolithic organic porous body” is simply “composite monolith”, “monolithic organic porous ion exchanger” is simply “composite monolithic ion exchanger”, and “monolithic organic porous intermediate”. "Body" is also simply called "monolith intermediate".

(Description of composite monolith)
The composite monolith of the present invention is formed on an organic porous body composed of a continuous skeleton phase and a continuous pore phase, a large number of particles fixed to the skeleton surface of the organic porous body, or a skeleton surface of the organic porous body. It is a composite structure with a large number of protrusions. In the present specification, “particle bodies” and “projections” may be collectively referred to as “particle bodies”.

  The continuous skeleton phase and the continuous pore phase of the organic porous body can be observed by SEM images. Examples of the basic structure of the organic porous material include a continuous macropore structure and a co-continuous structure. The skeletal phase of the organic porous material appears as a columnar continuum, a concave wall continuum, or a composite thereof, and has a shape that is clearly different from a particle shape or a protrusion shape.

  A preferred structure of the organic porous body is a continuous macropore structure (hereinafter referred to as “first organic porous body”) in which bubble-shaped macropores overlap each other, and the overlapping portion becomes an opening having an average diameter of 20 to 200 μm. ) And a three-dimensionally continuous skeleton having a thickness of 0.8 to 40 μm, and a three-dimensionally continuous pore having a diameter of 8 to 80 μm between the skeletons (hereinafter referred to as “first” 2 is also referred to as “organic porous body 2”).

  In the first organic porous body, a preferable value of the average diameter of the openings is 20 to 150 μm, particularly 20 to 100 μm, and the pores formed by the macropores having a diameter of 40 to 400 μm and the openings serve as flow paths. The continuous macropore structure is preferably a uniform structure having the same macropore size and aperture diameter, but is not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do. If the average diameter of the openings is less than 20 μm, the pressure loss at the time of fluid permeation increases, which is not preferable. If the average diameter of the openings is too large, the contact between the fluid and the composite monolith becomes insufficient. This is not preferable because the adsorption characteristics are deteriorated. The average diameter of the opening is the maximum value of the pore distribution curve obtained by the observation result of the SEM image or the mercury intrusion method.

  In the second organic porous material, if the size of the three-dimensionally continuous pores is less than 8 μm, it is not preferable because the pressure loss at the time of fluid permeation increases, and if it exceeds 80 μm, the fluid and the monolith As a result, the adsorption behavior becomes inhomogeneous and the adsorption behavior of the substance to be adsorbed at a low concentration decreases. The size of the three-dimensionally continuous pores is the maximum value of the pore distribution curve obtained by the observation result of the SEM image or the mercury intrusion method. Further, 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, the adsorption capacity per volume is lowered and the mechanical strength is disadvantageously reduced. On the other hand, if the thickness exceeds 40 μm, the uniformity of the adsorption characteristics is lost. Therefore, it is not preferable.

  The thickness of the skeleton of the organic porous body and the diameter of the opening may be calculated by performing SEM image observation of the organic porous body at least three times and measuring the diameter and opening of the skeleton in the obtained image.

  In the composite monolith of the present invention, a large number of particles having a diameter of 2 to 20 μm adhering to the skeleton surface of the organic porous material and a large number of protrusions having a maximum diameter of 2 to 20 μm formed on the skeleton surface are observed by SEM images. can do. Particles and the like are integrated with the surface of the skeletal phase, and those observed in the form of particles are referred to as particles, and those that are partly embedded in the surface and can no longer be called particles are referred to as protrusions. The surface of the skeletal phase is preferably coated with 40% or more, preferably 50% or more, with a particle or the like.

  A preferable value of the diameter of the particle body and the maximum diameter of the protrusion is 3 to 15 μm, particularly 3 to 10 μm, and the ratio of the 3 to 5 μm particle body in all the particle bodies is 70% or more, particularly 80% or more. It is. Further, the particle bodies may be aggregated to form an aggregate. In this case, the diameter of the particle body refers to that of an individual particle. Further, it may be a composite protrusion in which the particle body is fixed to the protrusion. In the case of a composite protrusion, the above-mentioned diameter and maximum diameter refer to the values of individual protrusions and the values of particle bodies.

  If the size of the particles covering the surface of the skeletal phase deviates from the above range, the effect of improving the contact efficiency between the fluid and the surface of the composite monolith skeleton and the inside of the skeleton tends to be small. Also, if the coverage of the skeleton surface with particles is less than 40%, the effect of improving the contact efficiency between the fluid and the surface of the composite monolith skeleton and the inside of the skeleton is reduced, and the uniformity of the adsorption behavior tends to be impaired. It is not preferable. The size and coverage of the above-mentioned particle bodies and the like can be obtained by image analysis of a monolith SEM image.

  The composite monolith of the present invention has a total pore volume of 0.5 to 5 ml / g, preferably 0.8 to 4 ml / g. If the total pore volume is too small, the pressure loss at the time of fluid permeation increases, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area decreases, and the processing capacity decreases. On the other hand, if the total pore volume is too large, the adsorption capacity per volume decreases, which is not preferable. The composite monolith of the present invention is a composite structure in which particles and the like are fixed to the wall and surface of the skeletal phase forming the monolith structure. Therefore, when this is used as an adsorbent, the contact efficiency with the fluid is high, and the fluid Therefore, it is possible to exhibit excellent performance.

  The pore diameter of the composite monolith is an average diameter of 8 to 100 μm, preferably 10 to 80 μm. When the organic porous body constituting the composite monolith is the first organic porous body, the preferred value of the pore size of the composite monolith is 10 to 80 μm, and the organic porous body constituting the composite monolith is the second organic porous body. In this case, a preferable value of the pore size of the composite monolith is 10 to 60 μm. When the pore size of the composite monolith is in the above range and the diameter of the particles is in the above range, the contact efficiency between the fluid and the surface of the composite monolith skeleton and the inside of the skeleton is improved. The pore size of the composite monolith is the maximum value of the pore distribution curve obtained by the mercury intrusion method.

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

  When the composite monolith of the present invention is used as an adsorbent, for example, a cylindrical column or a square column is filled with an adsorbent obtained by cutting the composite monolith into a shape that can be inserted into the column. When the water to be treated containing a hydrophobic substance such as phenol or paraffin is passed, the hydrophobic substance is efficiently adsorbed on the adsorbent.

  The pressure loss when water is allowed to permeate through the composite monolith is the pressure loss when water is passed through the column filled with 1 m of the composite monolith at a water passage speed (LV) of 1 m / h (hereinafter referred to as “differential pressure coefficient”). In other words, it is preferably in the range of 0.005 to 0.1 MPa / m · LV, particularly 0.005 to 0.05 MPa / m · LV.

  In the composite monolith of the present invention, the material constituting the skeleton phase of the continuous pore structure is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. It is preferable. If the cross-linking structural unit is less than 0.3 mol%, it is not preferable because the mechanical strength is insufficient. On the other hand, if it exceeds 10 mol%, the embrittlement of the porous body proceeds and flexibility is lost. In particular, in the case of an ion exchanger, the amount of ion exchange groups introduced is decreased, which is not preferable. The type of the polymer material is not particularly limited, and examples thereof include aromatic vinyl polymers such as polystyrene, poly (α-methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, and polyvinyl naphthalene; polyolefins such as polyethylene and polypropylene; Poly (halogenated polyolefin) such as vinyl chloride and polytetrafluoroethylene; Nitrile-based polymer such as polyacrylonitrile; Cross-linking weight of (meth) acrylic polymer such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate Coalesce is mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, the cross-linking of aromatic vinyl polymers is based on the ease of forming a continuous pore structure, the ease of introducing ion-exchange groups, the high mechanical strength, and the high stability to acids and alkalis. A polymer is preferable, and a styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.

  In the composite monolith of the present invention, the material constituting the skeletal phase of the organic porous body and the particles formed on the surface of the skeletal phase are of the same material in which the same structure is continuous, or a structure that is not the same. Examples of the materials are different from each other. For materials with different structures with different continuous structures, such as materials with different types of vinyl monomers, materials with different blending ratios even if the types of vinyl monomers and crosslinking agents are the same, etc. Is mentioned.

(Description of composite monolith ion exchanger)
Next, the composite monolith ion exchanger of the present invention will be described. In the composite monolith ion exchanger, the description of the same components as those of the composite monolith is omitted, and different points are mainly described. The composite monolith ion exchanger is composed of an organic porous body composed of a continuous skeleton phase and a continuous pore phase, a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body, or the organic porous body. A composite structure with a large number of protrusions having a maximum diameter of 4 to 40 μm formed on the skeleton surface, having a thickness of 1 mm or more, an average pore diameter of 10 to 150 μm, and a total pore volume of 0.5 to 5 ml / g The ion exchange capacity per volume in a wet state of water is 0.2 mg equivalent / ml or more, and the ion exchange groups are uniformly distributed in the composite structure.

  When the organic porous material is the first organic porous material, the organic porous material has bubble-like macropores that overlap each other, and the overlapping portion has an average diameter of 30 to 300 μm, preferably 30 to 200 μm, particularly 35 to 150 μm. It is a continuous macropore structure which becomes an opening (mesopore). The average diameter of the opening of the composite monolith ion exchanger is larger than the average diameter of the opening of the composite monolith because the entire composite monolith swells when an ion exchange group is introduced into the monolith. If the average diameter of the openings is less than 30 μm, the pressure loss at the time of fluid permeation increases, which is not preferable. If the average diameter of the openings is too large, the contact between the fluid and the monolith ion exchanger becomes insufficient. As a result, the ion exchange characteristics deteriorate, which is not preferable. The average diameter of the opening is the value calculated by multiplying the observation result of the SEM image by the swelling ratio when the dry state is changed to the wet state, or the average diameter of the composite monolith before the introduction of the ion exchange group before and after the introduction of the ion exchange group. It is a value calculated by multiplying the swelling ratio.

  When the organic porous body is the second organic porous body, the organic porous body has a three-dimensionally continuous skeleton having a diameter of 1 to 50 μm and a three-dimensionally continuous 10 to 100 μm between the skeletons. It is a co-continuous structure with pores. If the size of the three-dimensionally continuous pores is less than 10 μm, the pressure loss during fluid permeation increases, which is not preferable. If it exceeds 100 μm, contact between the fluid and the composite monolith ion exchanger is not preferable. As a result, the ion exchange behavior becomes non-uniform and the ion exchange zone length increases, and the trapping efficiency of low-concentration ions decreases. The size of the three-dimensional continuous pores is a value calculated by multiplying the observation result of the SEM image by the swelling rate when the dry state changes to the wet state, or the continuous fineness of the composite monolith before introducing the ion exchange group. This is a value calculated by multiplying the pore size by the swelling rate before and after the introduction of the ion exchange group.

  Moreover, if the diameter of the three-dimensionally continuous skeleton is less than 1 μm, it is not preferable because the ion exchange capacity per volume is lowered and the mechanical strength is lowered. On the other hand, if it exceeds 50 μm, This is not preferable because the uniformity of the exchange characteristics is lost. The diameter of the skeleton of the composite monolith ion exchanger is calculated by multiplying the observation result of the SEM image by the swelling ratio when the dry state is changed to the wet state, or the skeleton diameter of the monolith before the introduction of the ion exchange group. It is a value calculated by multiplying the swelling ratio before and after introduction of the exchange group.

  The average diameter of the pores of the composite monolith ion exchanger is 10 to 150 μm, preferably 10 to 120 μm. When the organic porous body constituting the composite monolith ion exchanger is the first organic porous body, the preferred value of the pore size of the composite monolith ion exchanger is 10 to 120 μm, and the organic porous body constituting the composite monolith ion exchanger In the case of the second organic porous body, a preferable value of the pore diameter of the composite monolith ion exchanger is 10 to 90 μm.

  In the composite monolith ion exchanger of the present invention, the diameter of the particle body and the maximum diameter of the protrusion are 4 to 40 μm, preferably 4 to 30 μm, particularly 4 to 20 μm. The proportion occupied by the particles is 70% or more, particularly 80% or more. Further, the surface of the skeletal phase is covered with particle bodies or the like for 40% or more, preferably 50% or more. If the size of the particle covering the wall surface or the skeleton deviates from the above range, the effect of improving the contact efficiency between the fluid and the skeleton surface of the composite monolith ion exchanger and the inside of the skeleton is not preferable. The diameter or maximum diameter of the particles attached to the skeleton surface of the composite monolith ion exchanger is a value calculated by multiplying the observation result of the SEM image by the swelling rate when the dry state changes to the wet state, or the ion exchange group It is a value calculated by multiplying the particle diameter of the composite monolith before introduction by the swelling ratio before and after introduction of the ion exchange group.

  When the coverage of the skeletal phase surface with particles and the like is less than 40%, the effect of improving the contact efficiency between the fluid and the inside of the skeleton of the composite monolith ion exchanger and the skeleton surface is reduced, and the uniformity of the ion exchange behavior is reduced. Since it will be damaged, it is not preferable. Examples of the method for measuring the coverage with the above-mentioned particle bodies include an image analysis method using a monolith SEM image.

  The total pore volume of the composite monolith ion exchanger is the same as the total pore volume of the composite monolith. That is, even when the ion exchange group is introduced into the composite monolith to swell and increase the opening diameter, the total pore volume hardly changes because the skeletal phase is thick. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of fluid permeation increases, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area decreases, and the processing capacity decreases. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable.

  Note that the pressure loss when water is permeated through the composite monolith ion exchanger is the same as the pressure loss when water is permeated through the composite monolith.

  The composite monolith ion exchanger of the present invention has an ion exchange capacity per volume in a water-wet state of 0.2 mg equivalent / ml or more, preferably 0.3 to 1.8 mg equivalent / ml. If the ion exchange capacity per volume is less than 0.2 mg equivalent / ml, the amount of water containing ions that can be processed before breakthrough, that is, the ability to produce deionized water is not preferred. In addition, the ion exchange capacity per weight in the dry state of the composite monolith ion exchanger of the present invention is not particularly limited, but since the ion exchange groups are uniformly introduced to the skeleton surface and the skeleton inside the composite monolith, 5 mg equivalent / g. The ion exchange capacity of the organic porous material in which the ion exchange group is introduced only on the surface of the skeleton cannot be determined depending on the kind of the organic porous material or the ion exchange group, but is 500 μg equivalent / g at most.

  Examples of the ion exchange group to be introduced into the composite monolith of the present invention include cation exchange groups such as a sulfonic acid group, a carboxylic acid group, an iminodiacetic acid group, a phosphoric acid group, and a phosphoric acid ester group; a quaternary ammonium group and a tertiary amino group. And 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.

  In the composite monolith ion exchanger of the present invention, the introduced ion exchange groups are uniformly distributed not only on the surface of the skeleton of the composite monolith but also inside the skeleton phase. Here, “the ion exchange groups are uniformly distributed” means that the distribution of the ion exchange groups is uniformly distributed at least on the order of μm on the surface of the skeleton phase and inside the skeleton phase. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA or the like. In addition, when the ion exchange groups are uniformly distributed not only on the surface of the composite monolith but also inside the skeleton phase, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and shrinkage can be prevented. Durability is improved.

  The composite monolith of the present invention can be obtained by performing the above steps I to III. In the method for producing a monolith according to the present invention, in the step I, an oil-soluble monomer not containing an ion exchange group, a first crosslinking agent having at least two or more vinyl groups in one molecule, a mixture of a surfactant and water are stirred. In this step, a water-in-oil emulsion is prepared, and then the water-in-oil emulsion is polymerized to obtain a monolith intermediate having a continuous macropore structure having a total pore volume of 5 to 30 ml / g. The step I for obtaining the monolith intermediate may be performed according to the method described in JP-A-2002-306976.

(Method for producing monolith intermediate)
Examples of the oil-soluble monomer that does not contain an ion exchange group include an oleophilic monomer that does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, has low solubility in water. Preferable examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, ethylene glycol dimethacrylate, and the like. These monomers can be used alone or in combination of two or more.

  Examples of the first crosslinking agent having at least two or more vinyl groups in one molecule include divinylbenzene, divinylnaphthalene, divinylbiphenyl, and ethylene glycol dimethacrylate. These crosslinking agents can be used singly or in combination of two or more. A preferred first cross-linking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl because of its high mechanical strength. The amount of the first crosslinking agent used is 0.3 to 10 mol%, particularly 0.3 to 5 mol%, and more preferably 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the first crosslinking agent. Is preferred. If the amount of the first crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, the monolith becomes more brittle and the flexibility is lost, and the amount of ion exchange groups introduced decreases, which is not preferable.

  The surfactant is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion exchange group and water are mixed, and sorbitan monooleate, Nonionic surfactants such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan monooleate; potassium oleate Anionic surfactants such as sodium dodecylbenzenesulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; amphoteric surfactants such as lauryldimethylbetaine 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 may vary depending on the type of oil-soluble monomer and the size of the target emulsion particles (macropores), but it cannot be generally stated, but the total amount of oil-soluble monomer and surfactant Can be selected within a range of about 2 to 70%.

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

  There is no particular limitation on the mixing method when mixing the oil-soluble monomer containing no ion exchange group, the first cross-linking agent, the surfactant, water and the polymerization initiator to form a water-in-oil emulsion, A method of mixing components all at once, an oil-soluble monomer, a first crosslinking agent, a surfactant, an oil-soluble component that is an oil-soluble polymerization initiator, and a water-soluble component that is water or a water-soluble polymerization initiator For example, a method in which each component is mixed after being uniformly dissolved separately can be used. There is no particular limitation on the mixing apparatus for forming the emulsion, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain the desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily.

  The monolith intermediate obtained in Step I has a continuous macropore structure. When this coexists in the polymerization system, particles or the like are formed on the surface of the skeleton phase of the continuous macropore structure using the structure of the monolith intermediate as a template, or particles or the like are formed on the surface of the skeleton phase of the co-continuous structure. Or The monolith intermediate is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, the porous body becomes brittle and the flexibility is lost, which is not preferable.

  The total pore volume of the monolith intermediate is 5-30 ml / g, preferably 6-28 ml / g. If the total pore volume is too small, the total pore volume of the monolith obtained after polymerizing the vinyl monomer becomes too small, and the pressure loss during fluid permeation increases, which is not preferable. On the other hand, if the total pore volume is too large, the structure of the monolith obtained after polymerizing the vinyl monomer tends to be non-uniform, and in some cases, the structure collapses, which is not preferable. In order to set the total pore volume of the monolith intermediate in the above numerical range, the ratio (weight) of the monomer to water may be set to approximately 1: 5 to 1:35.

  When the ratio of this monomer to water is approximately 1: 5 to 1:20, a monolith intermediate having a total pore volume of 5 to 16 ml / g and a continuous macropore structure can be obtained and obtained through Step III. The obtained composite monolithic organic porous body is the first organic porous body. Further, if the blending ratio is approximately 1:20 to 1:35, a monolith intermediate having a total pore volume of more than 16 ml / g and a continuous macropore structure of 30 ml / g or less can be obtained. The organic porous body of the composite monolith obtained through the above is obtained as the second organic porous body.

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is 20-200 micrometers in a monolith intermediate. If the average diameter of the openings is less than 20 μm, the opening diameter of the composite monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of fluid permeation increases, which is not preferable. On the other hand, if it exceeds 200 μm, the opening diameter of the composite monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the fluid and the composite monolith or composite monolith ion exchanger becomes insufficient, resulting in adsorption characteristics. In addition, the ion exchange characteristics deteriorate, which is not preferable. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

(Production method of composite monolith)
Step II is an organic solvent in which a vinyl monomer, a second cross-linking agent having at least two vinyl groups in one molecule, a vinyl monomer or a second cross-linking agent dissolves, but a polymer formed by polymerization of the vinyl monomer does not dissolve. And a step of preparing a mixture comprising a polymerization initiator. In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

  The vinyl monomer used in step II is not particularly limited as long as it is a lipophilic vinyl monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. Specific examples of these vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; Diene monomers such as butadiene, isoprene and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl such as vinyl acetate and vinyl propionate Esters: methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-methacrylic acid 2- Hexyl, cyclohexyl methacrylate, benzyl methacrylate, and (meth) acrylic monomer of glycidyl methacrylate. These monomers can be used alone or in combination of two or more. The vinyl monomer suitably used in the present invention is an aromatic vinyl monomer such as styrene or vinyl benzyl chloride.

  The added amount of these vinyl monomers is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate coexisting during polymerization. If the amount of vinyl monomer added is less than 3 times that of the porous material, particles cannot be formed in the skeleton of the produced monolith, and the adsorption capacity per volume and the ion exchange capacity per volume after the introduction of ion exchange groups are reduced. Since it becomes small, it is not preferable. On the other hand, if the amount of vinyl monomer added exceeds 40 times, the opening diameter becomes small and the pressure loss during fluid permeation increases, which is not preferable.

  As the second crosslinking agent used in Step II, one having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the second crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These 2nd crosslinking agents can be used individually by 1 type or in combination of 2 or more types. A preferred second crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl because of its high mechanical strength and stability to hydrolysis. The amount of the second crosslinking agent used is preferably 0.3 to 20 mol%, particularly 0.3 to 10 mol%, based on the total amount of the vinyl monomer and the second crosslinking agent. When the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it exceeds 20 mol%, the monolith becomes more brittle and the flexibility is lost, and the amount of ion exchange groups introduced decreases, which is not preferable.

  The organic solvent used in step II is an organic solvent that dissolves the vinyl monomer and the second cross-linking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, in other words, a poor solvent for the polymer formed by polymerization of the vinyl monomer. It is. Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Alcohols such as hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol; chain (poly) ethers such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane, etc .; Ethyl acetate, isopropyl acetate, cellosolve acetate, ethyl propionate, etc. Ethers, and the like. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the vinyl monomer is 10 to 30% by weight. If the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 10% by weight, the polymerization rate decreases, which is not preferable. On the other hand, when the vinyl monomer concentration exceeds 30% by weight, the unevenness on the surface of the skeleton phase, which is a feature of the present invention, is not preferable.

  As the polymerization initiator, 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, tetramethylthiuram disulfide and the like. The amount of 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 second crosslinking agent. .

  In step III, the mixture obtained in step II is allowed to stand, and in the presence of the monolith intermediate obtained in step I, polymerization is performed to obtain a composite monolith. The monolith intermediate used in the step III plays a very 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 a vinyl monomer and a second cross-linking 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, when a monolith intermediate having a continuous macropore structure is present in the polymerization system as in the present invention, the structure of the monolith after polymerization changes dramatically, the particle aggregation structure disappears, and the specific skeleton described above is lost. A monolith having a structure is obtained.

  The internal volume of the reaction vessel is not particularly limited as long as it is large enough to allow the monolith intermediate to exist in the reaction vessel. When the monolith intermediate is placed in the reaction vessel, there is a gap around the monolith in plan view. Or a monolith intermediate in the reaction vessel with no gap. Of these, the monolith after polymerization does not receive any pressure from the inner wall of the vessel and enters the reaction vessel without any gap, so that the monolith is not distorted and the reaction raw materials are not wasted and efficient. Even when the internal volume of the reaction vessel is large and there are gaps around the monolith after polymerization, the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate, so the gaps in the reaction vessel A particle aggregate structure is not generated in the portion.

  In step III, the monolith intermediate is placed in a reaction vessel impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate is 3 to 40 times by weight, preferably 4 to 30 times by weight, relative to the monolith intermediate. It is suitable to mix. Thereby, it is possible to obtain a monolith having a specific skeleton while having an appropriate opening diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that has been allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.

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

  When the above-mentioned composite monolith is produced, the skeleton, which is the characteristic structure of the present invention, is obtained by performing the II step or the III step under the conditions satisfying at least one of the following conditions (1) to (5). A composite monolith having particles or the like formed on the surface can be produced.

(1) The polymerization temperature in step III is a temperature that is at least 5 ° C. lower than the 10-hour half-life temperature of the polymerization initiator.
(2) The mol% of the second cross-linking agent used in step II is at least twice the mol% of the first cross-linking agent used in step I.
(3) The vinyl monomer used in step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in step I.
(4) The organic solvent used in step II is a polyether having a molecular weight of 200 or more.
(5) The concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture of Step II.

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

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

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

  The upper limit of the second crosslinker mol% used in step II is not particularly limited, but if the second crosslinker mol% is extremely large, cracks occur in the monolith after polymerization, and the brittleness of the monolith proceeds and flexibility is increased. This is not preferable because it causes a problem that the amount of ion exchange groups to be lost is reduced. A preferred multiple of the second crosslinking agent mol% is 2 to 10 times. On the other hand, even when the mol% of the first cross-linking agent used in step I is set to be twice or more the mol% of the second cross-linking agent used in step II, the formation of particles on the surface of the skeleton phase does not occur. The composite monolith of the present invention was not obtained.

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

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

  The upper limit of the molecular weight of the polyether is not particularly limited as long as it is 200 or more. However, when the molecular weight is too high, the viscosity of the mixture prepared in the step II becomes high, and it is difficult to impregnate the monolith intermediate. Therefore, it is not preferable. The molecular weight of the preferred polyether is 200 to 100,000, particularly preferably 200 to 10,000. The terminal structure of the polyether may be an unmodified hydroxyl group, etherified with an alkyl group such as a methyl group or an ethyl group, or esterified with acetic acid, oleic acid, lauric acid, stearic acid, or the like. It may be made.

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

(Production method of composite monolith ion exchanger)
Next, the manufacturing method of the composite monolith ion exchanger of this invention is demonstrated. The production method of the composite monolith ion exchanger is not particularly limited, but the method of introducing the ion exchange group after producing the composite monolith by the above method strictly restricts the porous structure of the obtained composite monolith ion exchanger. It is preferable in that it can be controlled.

  The method for introducing an ion exchange group into the composite monolith is not particularly limited, and a known method such as polymer reaction or graft polymerization can be used. For example, as a method of introducing a sulfonic acid group, if the composite monolith is a styrene-divinylbenzene copolymer, etc., a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid, or fuming sulfuric acid; radical initiating groups uniformly on the composite monolith And a method of grafting sodium styrene sulfonate or acrylamido-2-methylpropane sulfonic acid by introducing a chain transfer group into the skeleton surface or inside the skeleton; Similarly, after graft polymerization of glycidyl methacrylate, the sulfonic acid group is converted by functional group conversion. The method etc. which introduce | transduce are mentioned. In addition, as a method of introducing a quaternary ammonium group, if the composite monolith 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 of producing monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine; uniformly introducing a radical initiating group or chain transfer group into the monolith on the skeleton surface and inside the skeleton, and N, N, N- Examples include a method of graft polymerization of trimethylammonium ethyl acrylate or N, N, N-trimethylammonium propylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. Examples of the method for introducing betaine include a method in which a tertiary amine is introduced into a monolith by the above method 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. -Introducing a chloromethyl group into the divinylbenzene copolymer with chloromethyl methyl ether, etc., then reacting with a tertiary amine, or producing a monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine The method is preferable in that the ion exchange group can be introduced uniformly and quantitatively. 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 chemical filter of the present invention includes the composite monolith, a composite monolith provided with a through hole, a composite monolith ion exchanger or a composite monolith ion exchanger provided with a through hole, and a known ion exchange The structure of the filter is not particularly limited as long as it includes a combination of an adsorption layer using a resin or ion exchange fiber and the above monolith as an adsorption layer, but usually the adsorption layer and a support frame that supports the adsorption layer It is composed of a body (casing). The support frame supports the adsorbing layer and has a function of managing joining with existing equipment (installation location). The gas distribution portion of the support member is made of a material such as stainless steel, aluminum, or plastic that is not degassed. The shape of the adsorbing layer is not particularly limited, and examples thereof include a block shape having a predetermined thickness, a laminated shape in which a plurality of thin plates are stacked, and a packed structure in which a large number of regular or irregular shaped particles are filled. In addition, when there is a possibility that trace amounts of gaseous organic pollutants may be generated from the adsorption layer, or when the concentration of organic gaseous pollutants in the gas to be treated is high, a physical adsorption layer is provided downstream of the adsorption layer. It is preferable that the remaining gaseous organic pollutant that could not be removed by the upstream adsorption layer in the downstream physical adsorption layer can be reliably removed.

The specific surface area of the chemical filter of the present invention is 1 to ²⁰ m ² / g, preferably ² to 18 m ² / g. If the specific surface area is too small, it is not preferable because the processing ability is lowered, and if it is too large, the strength of the composite monolith or the composite monolith ion exchanger is remarkably reduced, which is not preferable. In order to make the specific surface area within the above range, polymerization may be carried out under the conditions (1) to (5) in the production method. The specific surface area can be measured by a mercury intrusion method.

As the physical adsorption layer, an adsorbent that can be used for deodorization can be used. Specific examples include activated carbon, activated carbon fiber, and zeolite. The adsorbent is preferably a porous body having a specific surface area of 200 m ² / g or more, and more preferably a porous body having a specific surface area of 500 m ² / g or more. In addition, when there is a possibility that a physical adsorbent or the like is scattered from the physical adsorption layer, it is preferable to arrange a cover material having air permeability on the downstream side of the physical adsorption layer. Examples of the cover material include a nonwoven fabric and a porous film made of an organic polymer material, and a mesh made of aluminum and stainless steel. Among these, non-woven fabrics and porous membranes made of organic polymer materials are particularly suitable because they can permeate gas with low pressure loss and have a high particulate collection ability.

  In the block-shaped composite monolith or composite monolith ion exchanger having a predetermined thickness, a plurality of through holes are preferably formed so as to extend in the ventilation direction. By providing the through hole, the air pressure difference can be further reduced. When a composite monolith or a composite monolith ion exchanger provided with through holes is used as the adsorption layer, the porosity of the through holes in the apparent composite monolith is 20 to 50%, preferably 25 to 40%. If the porosity of the through hole is too low, the tendency of the air pressure difference to decrease is reduced, and if the porosity of the through hole is too high, the removal efficiency of the gaseous pollutant decreases.

  The chemical filter of the present invention is an organic or inorganic gaseous pollutant contained in the air or atmosphere in a clean room in order to form a highly clean space such as a clean room or clean bench used in the semiconductor industry or medical applications. And other contaminants are removed by ion exchange or adsorption. Gaseous pollutants and other pollutants include acid gases such as sulfur dioxide, hydrochloric acid, hydrofluoric acid, and nitric acid, basic gases such as ammonia, salts such as ammonium chloride, and various plasticizers represented by phthalate esters And phenolic and phosphorus antioxidants, ultraviolet absorbers such as benzotriazole, phosphorus and halogen flame retardants, and the like. Acid gas, basic gas and salts can be removed by ion exchange, and various plasticizers, antioxidants, ultraviolet absorbers and flame retardants have strong polarity and can be removed by adsorption.

The use conditions of the chemical filter of the present invention can be performed under known conditions. The humidity of the use atmosphere is about 30 to 80% in relative humidity. Although it does not restrict | limit especially as a gas permeation | transmission speed | rate, For example, it is the range of 0.1-10 m / s. When a conventional granular ion exchange resin is used as the adsorption layer, the gas permeation rate is about 0.3 to 0.5 m / s, but according to the chemical filter of the present invention, the gas permeation rate is 5 to 10 m / s. Even at such a high speed, the skeletal part has a continuous macropore structure or a co-continuous structure, and the ion exchange capacity is large and ion exchange is performed efficiently, so that gaseous pollutants can be adsorbed and removed. Further, the concentration of contaminants in the air to be processed, according to the conventional chemical filter, the applicable range in the case of ammonia, usually 0.1-10 / ^{m 3,} the case of hydrogen chloride, typically 5-50 ng ^{/ m} 3, In the case of sulfur dioxide, it is usually 0.1 to 10 μg / m ³ , and in the case of phthalate ester, it is usually 0.1 to 5 μg / m ³ , but according to the chemical filter of the present invention, in addition to the above range, ammonia Even a trace concentration of 100 ng / m ³ or less, hydrogen chloride 5 ng / m ³ or less, sulfur dioxide 100 ng / m ³ or less, and phthalate ester 100 ng / m ³ or less can be sufficiently removed. In addition, the composite monolith ion exchanger used as an adsorption layer is used by processing the obtained composite monolith ion exchanger by a known regeneration method as in the case of conventional ion exchange resins. That is, the composite monolith cation exchanger is used as an acid form by acid treatment, and the composite monolith anion exchanger is used as an OH form by alkali treatment. In addition, it is preferable that the chemical filter is previously set to a moisture content that provides an equilibrium moisture content in the use space so that the chemical filter treatment gas has a humidity of the use atmosphere in terms of omitting the break-in operation. When the chemical filter of the present invention is used in a block shape and the gas permeation rate is 5 to 10 m / s, the length of the block-shaped adsorption layer in the ventilation direction is approximately 50 to 200 mm.

  In the chemical filter of the present invention, the pore volume and specific surface area of the composite monolith or composite monolith ion exchanger used as the adsorption layer are remarkably large, and ion exchange groups are introduced at a high density on the surface or inside thereof. Even if the permeation speed is high, the adsorption removal ability of gaseous pollutants can be maintained, and even if the amount of gaseous pollutants is extremely small, it can be removed. That is, the conventional granular ion exchange resin has a slow ion exchange inside the particles, and the entire ion exchange capacity is not used effectively. For example, in the case of a granular ion exchange resin having a particle diameter of 500 μm, assuming that the range in which the efficient adsorption is performed is 100 μm from the surface, the volume fraction of the surface layer is about 50%, and the ion exchange in the range in which the efficient adsorption is performed. The capacity is about half. On the other hand, since the composite monolith ion exchanger according to the present invention has a wall thickness of 2 to 10 μm, all ion exchange groups are efficiently used.

  The monolithic porous ion exchanger used for the adsorption layer of the chemical filter of the present invention is also about 1/4 of the ion exchanger length as compared with the conventional granular ion exchange resin, and uses the same volume of the adsorption layer. Even the life is extended.

  The chemical filter of the present invention can be used in combination with a blower unit or incorporated in a blower unit. Although there is no restriction | limiting in particular as an air blower unit, Usually, it is connected to the air blower which uses an axial fan or a blower as an air supply source, the controller which adjusts the output, the air blower, the 1st casing which accommodates the controller, and the casing The HEPA or ULPA filter for removing fine particles and a second casing that houses the HEPA or ULPA filter. The to-be-processed gas distribution parts of the first casing and the second casing are made of a material such as stainless steel, aluminum, or plastic that is not degassed. The filter medium for the particulate removal filter is not particularly limited, and general glass fiber or PTFE can be used. When used in a clean room or the like, glass fiber or PTFE that does not release boron or organic matter is still more preferable.

  The chemical filter of the present invention is attached upstream of the HEPA or ULPA filter for removing fine particles. As a form which combines the chemical filter and blower unit of this invention, the method of connecting and mutually using casings is mentioned. As a form which incorporates the chemical filter of this invention in a fan unit, it is a form which incorporates an adsorption layer in a fan unit. In the form in which the chemical filter is incorporated in the blower unit, either the blower or the chemical filter may be located upstream. Use of the chemical filter of the present invention in combination with a blower unit is preferable in that both gaseous pollutants and fine particles can be removed.

  In the present invention, since the composite monolith or the composite monolith ion exchanger is used as the adsorption layer of the chemical filter, the large flow path and the uniformly introduced ion exchange group enable efficient treatment even in a small fan with a small static pressure. Impurities in the gas can be removed. Further, since the ion exchange capacity per volume and the specific surface area are very large and the ion exchange groups are uniformly introduced, the removal rate can be improved and the life can be extended.

EXAMPLES Next, the present invention will be specifically described with reference to examples. However, this is merely an example and does not limit the present invention.

(Step I; production of monolith intermediate)
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was used under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The average diameter of the opening (mesopore) where the macropores and macropores of the monolith intermediate overlap was 40 μm, and the total pore volume was 15.8 ml / g.

(Manufacture of composite monolith)
Next, 36.0 g of styrene, 4.0 g of divinylbenzene, 60 g of 1-decanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). The 10-hour half-life temperature of 2,2′-azobis (2,4-dimethylvaleronitrile) used as the polymerization initiator was 51 ° C. The amount of divinylbenzene used is 6.6 mol% with respect to the total amount of styrene and divinylbenzene used in Step II, while the crosslink density of the monolith intermediate is 1.3 mol%, and the crosslink density ratio is 5.1 times. Met. Next, the monolith intermediate was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 3.2 g was collected. The separated monolith intermediate is placed in a reaction vessel having an inner diameter of 73 mm, immersed in the styrene / divinylbenzene / 1-decanol / 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 monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

  The results of observing the internal structure of the composite monolith (dried body) composed of the styrene / divinylbenzene copolymer thus obtained by SEM are shown in FIGS. The SEM images in FIG. 1 to FIG. 3 have different magnifications, and are images at arbitrary positions on a cut surface obtained by cutting a monolith at an arbitrary position. As apparent from FIGS. 1 to 3, the composite monolith has a continuous macropore structure, and the surface of the skeletal phase constituting the continuous macropore structure is coated with particles having an average particle diameter of 4 μm. The rate was 80%. Moreover, the ratio for which the particle size of 2-5 micrometers accounted for the whole particle size was 90%.

  Moreover, the average diameter of the opening of the composite monolith measured by mercury porosimetry was 16 μm, and the total pore volume was 2.3 ml / g. The results are summarized in Tables 1 and 2. In Table 1, the preparation column shows the vinyl monomer, the crosslinking agent, the organic solvent used in Step II, and the monolith intermediate obtained in Step I in order from the left. Further, the particle bodies and the like are shown as particles.

(Production of complex monolith cation exchanger)
The composite monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the monolith was 19.6 g. To this, 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or less, 98.9 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a composite monolith cation exchanger.

  The swelling rate before and after the reaction of the obtained cation exchanger was 1.3 times, and the ion exchange capacity per volume was 1.11 mg equivalent / ml in a water wet state. The average diameter of the opening of the organic porous ion exchanger in the water-wet state is 21 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water-wet state, and is obtained by the same method as for the monolith. The particle coverage on the skeleton surface was 80%, the average particle size of the coated particles was 5 μm, and the total pore volume was 2.3 ml / g. Moreover, the ratio for which the particle body with a particle size of 3-7 micrometers occupied to the whole particle body was 90%. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.057 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. Further, the length of the ion exchange zone was 9 mm, showing a remarkably short value. The results are summarized in Table 2.

  Next, in order to confirm the distribution state of the sulfonic acid group in the composite monolith cation exchanger, the distribution state of sulfur atoms was observed by EPMA. The results are shown in FIGS. 4 and 5, the left and right photographs correspond to each other. FIG. 4 shows the distribution of sulfur atoms on the surface of the cation exchanger, and FIG. 5 shows the distribution of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. 4 and 5, it can be seen that the sulfonic acid groups are uniformly introduced on the skeleton surface of the cation exchanger and inside the skeleton (cross-sectional direction).

Examples 2-5
(Manufacture of composite monolith)
The amount of vinyl monomer used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate that coexists during polymerization in step III, the crosslinking density and the amount used, and the polymerization temperature are shown in Table 1. A monolith was produced in the same manner as in Example 1 except for the change. The results are shown in Tables 1 and 2. Moreover, the result of having observed the internal structure of composite monolith (dry body) by SEM is shown in FIGS. 6 to 8 are of the second embodiment, FIGS. 9 and 10 are of the third embodiment, FIG. 11 is of the fourth embodiment, and FIGS. 12 and 13 are of the fifth embodiment. In Example 2, the crosslinking density ratio (2.5 times), in Example 3, the type of organic solvent (PEG; molecular weight 400), in Example 4, vinyl monomer concentration (28.0%), Example For No. 5, the polymerization temperature (40 ° C .; 11 ° C. lower than the 10-hour half-life temperature of the polymerization initiator) was produced under conditions satisfying the production conditions of the present invention. From FIG. 6 to FIG. 13, what adhered to the skeleton surface of the composite monoliths of Examples 3 to 5 were protrusions rather than particles. The “particle average diameter” of the protrusion is the average diameter of the maximum diameter of the protrusion. From FIG. 6 to FIG. 13 and Table 2, the average diameter of the particles adhering to the monolith skeleton surface of Examples 2 to 6 was 3 to 8 μm, and the particle coverage was 50 to 95%. Further, in Example 2, the proportion of particles having a particle diameter of 3 to 6 μm occupying the entire particles is 80%, and in Example 3, the proportion of protrusions having a particle diameter of 3 to 10 μm is occupying the entire particles. In Example 4, the proportion of particles having a particle diameter of 2 to 5 μm in the total particles was 90%, and in Example 5, the proportion of particles having a particle diameter of 3 to 7 μm in the total particles was 90%. .

(Production of complex monolith cation exchanger)
The composite monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a composite monolith cation exchanger. The results are shown in Table 2. The average diameter of the continuous pores of the composite monolith cation exchanger in Examples 2 to 5 is 21 to 52 μm, the average diameter of the particles attached to the skeleton surface is 5 to 17 μm, and the particle coverage is also 50 to 95. %, The differential pressure coefficient was as small as 0.010 to 0.057 MPa / m · LV, and the ion exchange zone length was as extremely small as 8 to 12 mm. Moreover, the ratio for which the particle body with a particle size of 5-10 micrometers occupied to the whole particle body was 90%.

Example 6
(Manufacture of composite monolith)
Table 1 shows the type and amount of vinyl monomer used, amount of crosslinking agent used, type and amount of organic solvent, monolith intermediate porous structure coexisting during polymerization in step III, crosslinking density and amount used. A monolith was produced in the same manner as in Example 1 except for the change. The results are shown in Tables 1 and 2. Moreover, the result of having observed the internal structure of composite monolith (dry body) by SEM is shown in FIGS. What adhered to the skeleton surface of the composite monolith of Example 6 was a protrusion. In the monolith of Example 6, the average diameter of the maximum diameter of the protrusions formed on the surface was 10 μm, and the particle coverage was 100%. Moreover, the ratio for which the particle body with a particle size of 6-12 micrometers occupied to the whole particle body was 80%.

(Production of complex monolith anion exchanger)
The composite monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the composite monolith was 17.9 g. To this was added 1500 ml of tetrahydrofuran, heated at 40 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 114.5 g of a 30% trimethylamine aqueous solution, heated to react at 40 ° C. for 24 hours. After completion of the reaction, the resultant was washed with methanol to remove tetrahydrofuran, and further washed with pure water to obtain a monolith anion exchanger.

  The obtained composite anion exchanger had a swelling ratio of 2.0 times before and after the reaction, and the ion exchange capacity per volume was 0.32 mg equivalent / ml in a water-wet state. The average diameter of the continuous pores of the organic porous ion exchanger in the water wet state was 58 μm as estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water wet state. The average body diameter was 20 μm, the particle coverage was 100%, and the total pore volume was 2.1 ml / g. The ion exchange zone length was as short as 16 mm. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.041 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. Moreover, the ratio for which the particle body with a particle size of 12-24 micrometers occupied to the whole particle body was 80%. The results are summarized in Table 2.

  Next, in order to confirm the distribution state of the quaternary ammonium groups in the porous anion exchanger, the anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chlorine atoms was observed by EPMA. As a result, it was confirmed that the chlorine atoms were uniformly distributed not only on the skeleton surface of the anion exchanger but also inside the skeleton, and the quaternary ammonium groups were uniformly introduced into the anion exchanger.

Comparative Example 1
(Manufacture of monoliths)
Except for changing the usage amount of the vinyl monomer, the usage amount of the crosslinking agent, the type and usage amount of the organic solvent, and the usage amount of the monolith intermediate coexisting during the polymerization in Step III to the blending amounts shown in Table 1, Example 1 and A monolith was produced in a similar manner. The results are shown in Tables 1 and 2. From the SEM photograph (not shown), the formation of particles and protrusions was not observed at all on the skeleton surface. From Table 1 and Table 2, when a monolith is produced under conditions deviating from the specific production conditions of the present invention, that is, conditions deviating from the requirements (1) to (5) above, particle formation on the surface of the monolith skeleton is caused. It turns out that it is not recognized.

(Production of monolith cation exchanger)
The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolith cation exchanger. The results are shown in Table 2. The obtained monolith cation exchanger had an ion exchange zone length of 26 mm, which was a large value compared to the examples.

Comparative Examples 2-4
(Manufacture of monoliths)
The amount of vinyl monomer used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate that coexists during polymerization in step III, the crosslinking density, and the amount used were changed to the amounts shown in Table 1. Produced a monolith in the same manner as in Example 1. The results are shown in Tables 1 and 2. For Comparative Example 2, the crosslinking density ratio (0.2 times), for Comparative Example 3, the type of organic solvent (2- (2-methoxyethoxy) ethanol; molecular weight 120), and for Comparative Example 4, the polymerization temperature (50 And 1 ° C. lower than the 10-hour half-life temperature of the polymerization initiator). The results are shown in Table 2. For the monoliths of Comparative Examples 2, 4, and 5, no particles were formed on the skeleton surface. In Comparative Example 3, the isolated product was transparent, and the porous structure was collapsed and disappeared.

(Production of monolith cation exchanger)
Except for Comparative Example 3, the organic porous material produced by the above method was reacted with chlorosulfuric acid in the same manner as in Comparative Example 1 to produce a monolith cation exchanger. The results are shown in Table 2. The obtained monolith cation exchanger had an ion exchange zone length of 23 to 26 mm, which was a large value compared to the examples.

Comparative Example 5
(Manufacture of monoliths)
Comparative Example 1 except that the amount of vinyl monomer used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of monolith intermediate coexisting during polymerization in step III and the amount used were changed to the amounts shown in Table 1. A monolith was produced in the same manner as described above. The results are shown in Tables 1 and 2, and it can be seen that when a monolith is produced outside the specific production conditions of the present invention, no particle formation is observed on the surface of the monolith skeleton.

(Production of monolith anion exchanger)
The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropping, the temperature was raised and the reaction was carried out at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated. The results are shown in Table 2. The obtained monolith anion exchanger had an ion exchange zone length of 47 mm, which was a large value compared to the examples.

Example 7
(Production of complex monolith cation exchanger)
In the production of a composite monolith, instead of a 20 mm thick disk, the amount of reagent in the I step was doubled to produce a monolith intermediate to a thickness of 50 mm, and the amount of reagent in the II step was tripled Example 1 except that the composite monolith thickness 15 mm during production of the composite monolith cation exchanger was 50 mm, the amount of dichloromethane used was 1500 ml to 5000 ml, and the amount of chlorosulfuric acid was 98.9 g to 329 g. A composite monolith cation exchanger was produced by a compliant method.

(Adsorption of basic gas using composite monolith cation exchanger)
The composite monolith cation exchanger obtained by the above method was immersed in 3N hydrochloric acid for 24 hours, and then sufficiently washed with pure water and dried. The obtained composite monolith cation exchanger was allowed to stand at 25 ° C. and a relative humidity of 40% for 48 hours, then cut into a disk shape having a diameter of 50 mm and a thickness of 50 mm, and filled into a cylindrical column to prepare a chemical filter. When this filter was supplied with air with an ammonia concentration of 5,000 ng / m ^{3 at} a surface wind speed of 0.5 m / s under a temperature and humidity condition of 25 ° C. and 40%, the permeating gas was measured as ultrapure water. Sampling was performed by the impinger method, and ammonium ions were quantified by ion chromatography. As a result, the ammonia concentration in the air was less than 50 ng / m ³ , and ammonia could be completely removed.

Comparative Example 6
Production Example 1 (Production of organic porous cation exchanger)
38 g of styrene, 2.0 g of divinylbenzene, 2.1 g of sorbitan monooleate and 0.1 g of azobisisobutyronitrile were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / sorbitan monooleate / azobisisobutyronitrile mixture is added to 360 g of pure water, and 13 using a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Under reduced pressure of 3 kPa, the mixture was stirred for 2 minutes at a ratio of the bottom surface diameter to the height of the packing of 1: 1, a revolution speed of 1000 revolutions / minute, and a rotation speed of 330 revolutions / minute to obtain a water-in-oil emulsion. After completion of emulsification, the system was sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol to remove unreacted monomers, water and sorbitan monooleate, and then dried under reduced pressure at 85 ° C. overnight. As a result of observing the internal structure of the organic porous material containing 3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained by SEM, the organic porous material has an open-cell structure. It was.

  Next, the organic porous material was cut to obtain 18 g, and after adding 2400 ml of dichloroethane and heating at 60 ° C. for 30 minutes, the mixture was cooled to room temperature, 90 g of chlorosulfuric acid was gradually added, and the mixture was reacted at room temperature for 24 hours. Thereafter, acetic acid was added, and the reaction product was poured into a large amount of water and washed with water to obtain an organic porous cation exchanger. The ion exchange capacity of this organic porous cation exchanger is 4.8 mg equivalent / g in terms of dry porous material, and the organic porous material has sulfonic acid groups on the order of μm by mapping sulfur atoms using EPMA. It was confirmed that it was introduced uniformly. Moreover, it was confirmed by SEM observation that the open-cell structure of the organic porous material was retained even after the introduction of ion exchange groups. The organic porous cation exchanger had an average mesopore diameter of 30 μm and a total pore volume of 10.2 ml / g.

(Adsorption of basic gas using organic porous cation exchanger)
The organic porous cation exchanger produced in Production Example 1 was immersed in 3N hydrochloric acid for 24 hours, then sufficiently washed with pure water and dried. The obtained monolith cation exchanger was allowed to stand at 25 ° C. and a relative humidity of 40% for 48 hours, then cut into a disk shape having a diameter of 50 mm and a thickness of 50 mm, and filled into a cylindrical column to prepare a chemical filter. As a result of performing an ammonia removal test on this filter in the same manner as in Example 7, the ammonia concentration in the permeated air was 120 ng / m ³ , and ammonia could not be completely removed.

Example 8
Before immersing the composite monolith cation exchanger in 3N hydrochloric acid, the SUS316 pipe with an inner diameter of 2 mm is used to make the porosity of the hole with a diameter of 2 mm relative to the apparent circle of the cylindrical monolith 30%. A composite monolith cation exchanger having through-holes was obtained in the same manner as in Example 7, except that a through-hole extending in the same manner as in Example 7 was used. Further, basic gas was adsorbed in the same manner as in Example 7. As a result, the airflow differential pressure at a surface wind speed of 0.5 m / s was a very low pressure loss of 80 Pa, and the ammonia concentration in the air was 450 ng / m ³ .

Comparative Example 7
In place of the monolithic organic porous cation exchanger, an open-cell monolithic organic porous cation exchanger of Comparative Example 6 was used, except that a through-hole was formed in the same manner as in Example 8, and a base was used. Adsorption of sex gas was performed. As a result, the aeration differential pressure was 85 Pa, and the ammonia concentration in the air was 850 ng / m ³ .

Example 9
(Production of complex monolith anion exchanger)
In the production of a composite monolith, instead of a 20 mm thick disc, the amount of reagent in step I was doubled to produce a monolith intermediate to have a thickness of 50 mm, and the amount of reagent in step II was tripled , Except that the thickness of the composite monolith at the time of production of the composite monolith anion exchanger was set to 50 mm, the amount of tetrahydrofuran used was changed from 1500 ml to 5000 ml, and the amount of trimethylamine 30% aqueous solution was changed from 114.5 g to 381 g. A composite monolith anion exchanger was prepared according to Example 6.

(Adsorption of acid gas using composite monolith anion exchanger)
The composite monolith anion exchanger obtained by the above method was immersed in a 1N aqueous sodium hydroxide solution for 24 hours, then sufficiently washed with pure water and dried. The obtained composite monolith anion exchanger was allowed to stand at 25 ° C. and a relative humidity of 40% for 48 hours, then cut into a disk shape having a diameter of 50 mm and a thickness of 50 mm, and filled into a cylindrical column to prepare a chemical filter. The permeated gas was sampled by the ultrapure water impinger method when air with a sulfur dioxide concentration of 5,000 ng / m ³ was supplied at a surface wind speed of 0.5 m / s under the temperature and humidity conditions of 25 ° C. and 40%. Then, sulfate ion was quantified by ion chromatography. As a result, the sulfur dioxide concentration in the air was less than 50 ng / m ³ , and sulfur dioxide was completely removed.

Comparative Example 8
A monolithic organic porous material was produced in the same manner as in Comparative Example 6 except that chloromethylstyrene was used instead of styrene and the amount of sorbitan monooleate was changed to 4.5 g. The organic porous material was cut to take 15.0 g, 1500 g of tetrahydrofuran was added and the mixture was heated at 60 ° C. for 30 minutes, then cooled to room temperature, and 195 g of a trimethylamine (30%) aqueous solution was gradually added. After reacting for 3 hours, the mixture was allowed to stand overnight at room temperature. After completion of the reaction, the organic porous material was taken out, washed with acetone, washed with water, and dried to obtain an organic porous anion exchanger. The ion exchange capacity of this organic porous anion exchanger is 3.7 mg equivalent / g in terms of dry porous body, and trimethylammonium groups are uniformly introduced into the organic porous body in the order of μm by SIMS. It was confirmed. Moreover, it was confirmed by SEM observation that the open-cell structure of the organic porous material was retained even after the introduction of ion exchange groups. The organic porous anion exchanger had an average mesopore diameter of 25 μm and a total pore volume of 9.8 ml / g. The obtained anion exchanger was subjected to a sulfur dioxide removal test in the same manner as in Example 9. As a result, the concentration of sulfur dioxide in the air was 200 ng / m ³ and could not be completely removed.

Example 10
(Adsorption of organic gas using composite monolith)
The monolithic organic porous material produced according to Example 7 was sufficiently washed with pure water and dried. The obtained monolithic organic porous material was allowed to stand at 25 ° C. and a relative humidity of 40% for 48 hours, then cut into a disk shape having a diameter of 50 mm and a thickness of 50 mm, and filled into a cylindrical column to prepare a chemical filter. Using this solid adsorbent (TENAX-GR) as the permeating gas when air with a toluene concentration of 1,000 ng / m ³ was supplied at a surface wind speed of 0.5 m / s under a temperature condition of 25 ° C. and 40%. It was collected, and toluene was quantified by gas chromatography mass spectrometry. As a result, the toluene concentration in the air was 110 ng / m ^{3 and} the removal rate was about 89%.

Comparative Example 9
An open-cell monolithic organic porous material was produced according to Comparative Example 6, and a disc-shaped chemical filter having a diameter of 50 mm and a thickness of 50 mm was produced in the same manner as in Example 10.
This filter was subjected to a toluene removal test under the same conditions as in Example 10. As a result, the ammonia concentration in the permeated air was 200 ng / m 3 and the removal rate was about 80%, which was a lower removal rate than in Example 10. It was.

Examples 11-14
(Adsorption of basic gas using composite monolith cation exchanger)
A chemical filter was prepared in the same manner as in Example 7 except that the composite monolith cation exchanger of Examples 2 to 5 was used instead of the composite monolith cation exchanger of Example 1, and the treatment of ammonia-containing air was performed. Was done. That is, what used the composite monolith cation exchanger of Example 2 used Example 11 and what used the composite monolith cation exchanger of Example 3 used Example 12 and the composite monolith cation exchanger of Example 4. In Example 13, the composite monolith cation exchanger of Example 13 and Example 5 was used. There result, the ammonia concentration in air Example 11 is less than 50 ng / ^{m 3,} below Example 12 50 ng / ^{m 3,} under Example 13 is 50 ng / ^{m 3,} Example 14 is less than 50 ng / ^{m 3} It was.

Example 15
(Adsorption of basic gas under high wind speed using monolithic organic porous cation exchanger)
Instead of air ammonia concentration 5,000 ng / ^{m 3,} it has an air ammonia concentration 2,000 ng / ^{m 3,} in place of the face velocity 0.5 m / s, except that a 5.0 m / s, An ammonia removal test was conducted in the same manner as in Example 7. As a result, despite the high air permeation rate, the ammonia concentration in the permeated air was less than 50 ng / m ³ , and ammonia could be removed.

Example 16
(Adsorption of trace amount of basic gas using monolithic organic porous cation exchanger)
Instead of air ammonia concentration 2,000 ng / ^{m 3,} except that the air concentration of ammonia 100 ng / ^{m 3} were subjected to performance evaluation of ammonia removal in the same manner as in Example 15. As a result, the ammonia concentration in the permeated gas was less than 50 ng / m ³ , and even when the air permeation rate was as high as 5.0 m / s, a trace amount of ammonia could be completely removed.

Example 17
(Adsorption of high concentration basic gas using monolithic organic porous cation exchanger)
A life test for removing ammonia was conducted in the same manner as in Example 7 except that air having an ammonia concentration of 5,000 ng / m ³ was used instead of air having an ammonia concentration of 100 μg / m ³ . As a result, the period during which purification efficiency of 90% or more can be maintained was 27 days.

Comparative Example 10
Using the same chemical filter as in Comparative Example 6, the same life test for removing ammonia as in Example 17 was performed. As a result, the period during which the removal rate of 90% or more can be maintained was 10 days.

  The monoliths and monolith ion exchangers of the present invention have features such as chemically stable and high mechanical strength, high contact efficiency with fluid during fluid permeation, and low pressure loss during fluid permeation. Therefore, filters and adsorbents such as chemical filters; ion exchangers used by filling 2-bed 3-tower pure water production equipment and electrical deionized water production equipment; various chromatographic packing materials; solid acid / base It is useful as a catalyst and can be applied to a wide range of applications. In addition, the chemical filter of the present invention has a large pore volume and specific surface area, and has a high ion exchange group density. Therefore, the chemical filter has a high ability to remove gaseous contaminants. The ability to adsorb and remove gaseous contaminants can be maintained, and ultra-trace gaseous contaminants can also be removed. Therefore, not only can it be applied as a chemical filter for the existing semiconductor industry and medical clean rooms, but it is particularly useful as a chemical filter for clean rooms in the semiconductor industry, where the required cleanliness is expected to become ten times more severe in the future. .

2 is a SEM image of the monolith obtained in Example 1 at a magnification of 100. FIG. 2 is an SEM image of the monolith obtained in Example 1 at a magnification of 300. FIG. 2 is an SEM image of the monolith obtained in Example 1 at a magnification of 3000. 2 is an EPMA image showing the distribution state of sulfur atoms on the surface of the monolith cation exchanger obtained in Example 1. FIG. 2 is an EPMA image showing the distribution state of sulfur atoms in the cross-section (thickness) direction of the monolith cation exchanger obtained in Example 1. FIG. 4 is a SEM image of a monolith obtained in Example 2 at a magnification of 100. FIG. 4 is a SEM image of a monolith obtained in Example 2 at a magnification of 600. FIG. 3 is a SEM image of the monolith obtained in Example 2 at a magnification of 3000. 4 is a SEM image of a monolith obtained in Example 3 at a magnification of 600. FIG. 4 is an SEM image of the monolith obtained in Example 3 at a magnification of 3000. 4 is an SEM image of the monolith obtained in Example 4 at a magnification of 3000. 6 is a SEM image of a monolith obtained in Example 5 at a magnification of 100. FIG. 6 is an SEM image of the monolith obtained in Example 5 at a magnification of 3000. 6 is an SEM image of a monolith obtained in Example 6 at a magnification of 100. FIG. 6 is a SEM image of a monolith obtained in Example 6 at a magnification of 600. FIG. 6 is an SEM image of the monolith obtained in Example 6 at a magnification of 3000.

Claims (13)

An organic porous body composed of a continuous skeleton phase and a continuous pore phase;
A composite structure comprising a large number of particles having a diameter of 2 to 20 μm fixed to the skeleton surface of the organic porous body or a large number of protrusions having a maximum diameter of 2 to 20 μm formed on the skeleton surface of the organic porous body A monolithic organic porous material having a thickness of 1 mm or more, an average pore diameter of 8 to 100 μm, and a total pore volume of 0.5 to 5 ml / g.   2. The monolithic organic porous body according to claim 1, wherein the organic porous body is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion is an opening having an average diameter of 20 to 200 μm. .   The organic porous body is a co-continuous structure comprising a three-dimensionally continuous skeleton having a thickness of 0.8 to 40 μm and three-dimensionally continuous pores having a diameter of 8 to 80 μm between the skeletons. The monolithic organic porous body according to claim 1, wherein Preparing a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer free of ion exchange groups, a first crosslinking agent having at least two or more vinyl groups in one molecule, a surfactant and water; I step of polymerizing a water-in-oil emulsion to obtain a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume of 5 to 30 ml / g,
Vinyl monomer, second cross-linking agent having at least two or more vinyl groups in one molecule, organic solvent and polymerization initiator that dissolves vinyl monomer and second cross-linking agent but does not dissolve polymer formed by polymerization of vinyl monomer Step II to prepare a mixture consisting of
In the presence of the mixture obtained in Step II, and in the presence of the monolithic organic porous intermediate obtained in Step I, the polymerization is carried out at a temperature at least 5 ° C. lower than the 10-hour half-life temperature of the polymerization initiator. A monolithic organic porous material obtained by performing the III step. An organic porous body composed of a continuous skeleton phase and a continuous pore phase;
A composite structure with a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body or a large number of protrusions having a maximum diameter of 4 to 40 μm formed on the skeleton surface of the organic porous body The thickness is 1 mm or more, the average diameter of the pores is 10 to 150 μm, the total pore volume is 0.5 to 5 ml / g, and the ion exchange capacity per volume in a water wet state is 0.2 mg equivalent / ml or more. A monolithic organic porous ion exchanger characterized in that ion exchange groups are uniformly distributed in the composite structure.   6. The monolith-like structure according to claim 5, wherein the organic porous body is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion forms an opening having an average diameter of 30 to 300 μm in a wet state. Organic porous ion exchanger.   The organic porous body is a co-continuous structure composed of a three-dimensionally continuous skeleton having a thickness of 1 to 60 μm and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons. 6. The monolithic organic porous ion exchanger according to claim 5, wherein Preparing a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer free of ion exchange groups, a first crosslinking agent having at least two or more vinyl groups in one molecule, a surfactant and water; I step of polymerizing a water-in-oil emulsion to obtain a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume of 5 to 30 ml / g,
Vinyl monomer, second cross-linking agent having at least two or more vinyl groups in one molecule, organic solvent and polymerization initiator that dissolves vinyl monomer and second cross-linking agent but does not dissolve polymer formed by polymerization of vinyl monomer Step II to prepare a mixture consisting of
Step III, in which the mixture obtained in Step II is allowed to stand still and in the presence of the monolithic organic porous intermediate obtained in Step I, Step III
When producing a monolithic organic porous body, the following (1) to (5):
(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 second cross-linking agent used in step II is at least twice the mol% of the first cross-linking agent used in step I;
(3) The vinyl monomer used in Step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in Step I;
(4) The organic solvent used in step II is a polyether having a molecular weight of 200 or more;
(5) The concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture of Step II;
A method for producing a monolithic organic porous body, wherein the step II or the step III is performed under a condition satisfying at least one of the above conditions.   A method for producing a monolithic organic porous ion exchanger, comprising performing an IV step of introducing an ion exchange group into the monolithic organic porous material obtained by the production method according to claim 8.   A chemical filter using the monolithic organic porous material according to claim 1 as an adsorption layer.   A chemical filter using the monolithic organic porous ion exchanger according to claim 5 as an adsorption layer.   A chemical filter comprising a monolithic organic porous body according to claim 1, wherein a through-hole is provided as an adsorption layer.   8. A chemical filter comprising a monolithic organic porous ion exchanger according to claim 5 provided with a through hole as an adsorption layer.

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