JP5290604B2 - 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 monolithic organic porous body which is chemically stable and hydrophobic, has pores having high continuity and nearly uniform size, and exhibits low pressure drop during permeation of a fluid, and to provide a monolithic organic porous ion exchanger which has a large ion exchange capacity per volume in addition to the properties, and methods for manufacturing them and a chemical filter. <P>SOLUTION: The monolithic organic porous ion exchanger is a co-continuous structure which is composed of: three-dimensionally continuous skeletons which are formed of an aromatic vinyl polymer containing a cross-linking structure unit in an amount of 0.3-5.0 mol% based on all constitutive units each having an ion exchange group and have thickness of 1-60 &mu;m; and three dimensionally continuous pores formed among the skeletons and having diameters of 10-100 &mu;m, and the monolithic organic porous ion exchanger has a total pore volume of 0.5-5 mL/g and ion exchange capacity of &ge;0.3 mg-equivalent/mL per volume in a moist condition, and includes ion exchange groups uniformly distributed therein. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a monolithic organic porous body, a monolithic organic porous ion exchanger having a co-continuous structure useful as an ion exchanger used in an adsorbent, a chromatography filler, a deionized water production apparatus, and the like, And a chemical filter.

  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, in the organic porous ion exchanger, when the total pore volume is reduced to increase the ion exchange capacity per volume in a water-wet state, the mesopores that become common openings are remarkably reduced, and the total pore volume is further reduced. Due to the structural limitation that the common opening disappears as it is reduced, the ion exchange capacity per volume decreases when trying to achieve the practically required low pressure loss, and the exchange capacity per volume increases. As a result, the pressure loss increased.

  Japanese Patent Application Laid-Open No. 2004-321930 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.

On the other hand, as a structure of an organic porous body, a co-continuous structure in which a three-dimensional continuous skeleton phase and a three-dimensional continuous pore phase between the skeleton phases are intertwined is known. . Japanese Patent Application Laid-Open No. 2007-154083 discloses a non-particle-aggregated organic polymer having a micrometer-sized average diameter and having a co-continuous structure consisting of a three-dimensional network-like pore 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. Also, 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 2007-154083 A (Claim 1) JP 2004-321930 A (Claim 1)

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

  For this reason, it is chemically stable hydrophobic, has high continuity of pores, and its size is not biased, and the pressure when a continuous pore is large and allows fluid such as water or gas to pass through. Development of a monolithic organic porous body with low loss has been desired. In addition to the above characteristics, it has been desired to develop a monolithic organic porous ion exchanger having a large ion exchange capacity per volume. In addition, it has been desired to develop a chemical filter having a higher ability to adsorb and remove gaseous pollutants than ever before.

  Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art, is chemically stable hydrophobic, has high continuity of pores, and has no bias in its size. Another object of the present invention is to provide a monolithic organic porous body having a low pressure loss during fluid permeation, a monolithic organic porous ion exchanger having a large ion exchange capacity per volume in addition to the above characteristics, and a method for producing the same. . Another object of the present invention is 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. is there.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, in the presence of a monolithic organic porous material (intermediate) having a large pore volume obtained by the method described in JP-A-2002-306976. When the aromatic vinyl monomer and the crosslinking agent are allowed to stand in a specific organic solvent, the aromatic vinyl polymer skeleton is composed of a three-dimensionally continuous aromatic vinyl polymer skeleton and three-dimensionally continuous pores between the skeleton phases. It is possible to obtain a hydrophobic monolith with a co-continuous structure in which both phases are intertwined. This monolith with a co-continuous structure has high continuity of pores, no bias in its size, and low pressure loss during fluid permeation. Further, since the skeleton of this co-continuous structure is thick, if an ion exchange group is introduced, a monolithic organic porous ion exchanger having a large ion exchange capacity per volume can be obtained, and the monolithic organic porous ion exchanger , Ion exchange is quick and uniform, ion exchange zone length is overwhelmingly short, adsorption capacity per unit volume and ion exchange capacity are large, continuous pores are large, pressure loss is extremely small, mechanical strength is High monolithic organic porosity that is excellent in handling properties, can maintain adsorption / removal capability of gaseous pollutants even when the gas permeation rate is high, and can be removed even with extremely small amounts of gaseous pollutants. The present invention has been completed by finding out that the quality ion exchanger could not be achieved and having excellent characteristics.

  That is, the present invention provides a three-dimensionally continuous skeleton having a thickness of 0.8 to 40 μm made of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units, A monolithic organic porous body having a total pore volume of 0.5 to 5 ml / g, which is a co-continuous structure composed of three-dimensionally continuous pores having a diameter of 8 to 80 μm between the skeletons. It is to provide.

  The present invention also includes a three-dimensionally continuous skeleton having a thickness of 0.8 to 40 μm and comprising an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units, A co-continuous structure composed of three-dimensionally continuous pores having a diameter of 8 to 80 μm between the skeletons, the total pore volume being 0.5 to 5 ml / g, and the following steps: ion exchange Preparing a water-in-oil emulsion by stirring a mixture of oil-free monomers, surfactants and water free of groups, and then polymerizing the water-in-oil emulsion to a total pore volume of greater than 16 ml / g; Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure of 30 ml / g or less, an aromatic vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, an aromatic vinyl monomer or a crosslinking agent Dissolves but aroma A polymer formed by polymerization of an aromatic vinyl monomer is prepared by preparing a mixture comprising an organic solvent that does not dissolve and a polymerization initiator, Step II, the mixture obtained in Step II is left standing, and a monolithic form obtained in Step I The present invention provides a monolithic organic porous material obtained by performing the step III in which polymerization is carried out in the presence of the organic porous intermediate.

  The present invention also provides a three-dimensional thickness of 1 to 60 μm in thickness composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units into which ion exchange groups have been introduced. A co-continuous structure composed of a continuous skeleton and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, and has a total pore volume of 0.5 to 5 ml / g, Monolithic organic porous ion characterized in that the ion exchange capacity per volume in a wet state is 0.3 mg equivalent / ml or more, and the ion exchange groups are uniformly distributed in the porous ion exchanger An exchange is provided.

  The present invention also provides a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer that does not contain an ion exchange group, a surfactant, and water, and then polymerizes the water-in-oil emulsion to form all pores. Step I to obtain a monolithic organic porous intermediate having a continuous macropore structure having a volume of more than 16 ml / g and not more than 30 ml / g, aromatic vinyl monomer, whole oil having at least two or more vinyl groups in one molecule In a soluble monomer, a mixture of an organic solvent and a polymerization initiator that dissolves 0.3 to 5 mol% of a crosslinking agent, an aromatic vinyl monomer and a crosslinking agent but does not dissolve a polymer formed by polymerization of the aromatic vinyl monomer. Step II to be prepared, the mixture obtained in Step II is allowed to stand, and polymerization is carried out in the presence of the monolithic organic porous intermediate obtained in Step I to form a co-continuous structure. That step III, there is provided a method of manufacturing a monolithic organic porous material and performing.

  The present invention also provides a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer that does not contain an ion exchange group, a surfactant, and water, and then polymerizes the water-in-oil emulsion to form all pores. Step I to obtain a monolithic organic porous intermediate having a continuous macropore structure having a volume of more than 16 ml / g and not more than 30 ml / g, aromatic vinyl monomer, whole oil having at least two or more vinyl groups in one molecule In a soluble monomer, a mixture of an organic solvent and a polymerization initiator that dissolves 0.3 to 5 mol% of a crosslinking agent, an aromatic vinyl monomer and a crosslinking agent but does not dissolve a polymer formed by polymerization of the aromatic vinyl monomer. Step II to be prepared, the mixture obtained in Step II is allowed to stand, and polymerization is carried out in the presence of the monolithic organic porous intermediate obtained in Step I to obtain a co-continuous structure. Obtaining step III, there is provided a method of manufacturing a monolithic organic porous ion exchanger which is characterized in that the IV process, for introducing ion exchange groups into the resulting co-continuous structure in the step III.

  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 monolithic organic porous body having a co-continuous structure according to the present invention has high continuity of three-dimensionally continuous pores and is not biased in size, and the pores are large. It is possible to pass water at a large flow rate for a long period of time, and since the three-dimensional continuous skeleton is thick, it has an excellent adsorption capacity. 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 monolithic organic porous ion exchanger of the present invention has a large ion exchange capacity per volume in a water-wet state and large three-dimensional continuous pores, so that the water to be treated has a low pressure and a large flow rate. It can be used for a long period of time, and can be suitably used by filling it into a two-bed three-column pure water production apparatus or an electric deionized water production apparatus. Further, since the continuity of the vacancies is high and the size thereof is not biased, the ion adsorption behavior is extremely uniform, the ion exchange zone length is extremely short, and the number of theoretical plates is also high. Moreover, since it is excellent also in the adsorption | suction characteristic of the ultra-trace amount ion in ultrapure water, it can use suitably as an ion exchanger with which the filler for chromatography and an ultrapure water manufacturing apparatus are filled.

  Moreover, according to the manufacturing method of this invention, the said monolithic organic porous ion exchanger or the said monolithic organic porous ion exchanger can be manufactured simply and with sufficient reproducibility.

  In addition, the chemical filter of the present invention has a remarkably large pore volume and specific surface area used as an adsorption layer, and ion exchange groups are introduced at a high density on the surface and inside thereof. The ability to adsorb and remove gaseous pollutants can be maintained, and even gaseous trace contaminants can be removed.

  In the present specification, “monolithic organic porous body” is simply “monolith”, “monolithic organic porous ion exchanger” is simply “monolith ion exchanger”, and “monolithic organic porous intermediate”. Is also simply referred to as “monolith intermediate”.

(Description of monolith)
The basic structure of the monolith having a co-continuous structure of the present invention is a three-dimensional continuous skeleton having a thickness of 0.8 to 40 μm and three-dimensional continuous pores having a diameter of 8 to 80 μm between the skeletons. Is a structure in which is arranged. That is, as shown in the schematic diagram of FIG. 1, the co-continuous structure is a structure 10 in which a continuous skeleton phase 1 and a continuous vacancy phase 2 are intertwined and each of them is three-dimensionally continuous. The continuous pores 2 have higher continuity of the pores than the conventional open-cell monolith and particle aggregation type monolith, and the size thereof is not biased. Therefore, it is possible to achieve extremely uniform ion adsorption behavior. Moreover, since the skeleton is thick, the mechanical strength is high.

  If the diameter of the three-dimensional continuous holes is less than 8 μm, the pressure loss at the time of fluid permeation increases, which is not preferable. If it exceeds 80 μm, the contact between the fluid and the monolith becomes insufficient. This is not preferable because the adsorption characteristics are deteriorated. The size of the three-dimensionally continuous pores can be obtained as a maximum value of the pore distribution curve by measuring the pore distribution curve by mercury porosimetry.

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

  The monolith of the present invention has a total pore volume of 0.5 to 5 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of fluid permeation increases, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area becomes smaller, and the fluid throughput decreases. This is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the adsorption capacity per volume decreases, which is not preferable. The monolith of the present invention has a rod-like skeleton thickness, pore diameter, and total pore volume within the above ranges, and when used as an adsorbent, it has a large contact area with the fluid and allows smooth fluid flow. Therefore, excellent performance can be demonstrated.

  The pressure loss when water is allowed to permeate through the monolith is the pressure loss when water is passed through a column filled with 1 m of a porous body at a water flow velocity (LV) of 1 m / h (hereinafter referred to as “differential pressure coefficient”). In this case, it is in the range of 0.005 to 0.5 MPa / m · LV, particularly 0.01 to 0.1 MPa / m · LV.

  In the monolith of the present invention, the material constituting the skeleton of the co-continuous structure contains 0.3 to 5 mol%, preferably 0.5 to 3.0 mol% of cross-linked structural units in all the structural units. It is an aromatic vinyl polymer and is hydrophobic. If 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 5 mol%, the structure of the porous body tends to deviate from the bicontinuous structure. There is no restriction | limiting in particular in the kind of this aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, a styrene-divinylbenzene copolymer is used because of its ease of forming a co-continuous structure, ease of introduction of ion exchange groups, high mechanical strength, and high stability against acids and alkalis. And vinylbenzyl chloride-divinylbenzene copolymer is preferred.

  The 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 monolith is preferably 3 mm to 1000 mm. In addition, the monolith of the present invention has high mechanical strength due to its high structural uniformity.

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

(Description of monolith ion exchanger)
Next, the monolith ion exchanger of the present invention will be described. In the monolith ion exchanger, the description of the same components as those of the monolith is omitted, and different points are mainly described. The monolith ion exchanger has a three-dimensional continuous skeleton having an ion exchange group introduced therein and having a thickness of 1 to 60 μm, preferably 3 to 58 μm, and a diameter of 10 to 100 μm, preferably 15 to 90 μm between the skeletons. In particular, it is a co-continuous structure composed of three-dimensionally continuous pores of 20 to 80 μm. The thickness of the skeleton of the monolith ion exchanger and the diameter of the pores are larger than the thickness of the skeleton of the monolith and the diameter of the pores because the entire monolith swells when an ion exchange group is introduced into the monolith. These continuous pores have higher continuity of pores and are not biased in size compared to conventional open-cell monolithic organic porous ion exchangers and particle-aggregated monolithic organic porous ion exchangers. Therefore, extremely uniform ion adsorption behavior can be achieved. If the diameter of the three-dimensionally continuous pores is less than 10 μm, the pressure loss at the time of fluid permeation increases, which is not preferable. If the diameter exceeds 100 μm, contact between the fluid and the organic porous ion exchanger is not preferable. As a result, the ion exchange characteristics become non-uniform and the trapping ability of long trace ions decreases, which is not preferable.

  In addition, if the thickness of the skeleton is less than 1 μm, it is not preferable because the ion exchange capacity per volume decreases and the mechanical strength decreases, which is not preferable. On the other hand, if the skeleton thickness is too large, Since the uniformity of the exchange characteristics is lost and the ion exchange zone length becomes long, it is not preferable. The diameter of the pores of the continuous structure is calculated by multiplying the diameter of the pores of the monolith before the introduction of the ion exchange groups by the swelling ratio of the monolith before and after the introduction of the ion exchange groups, and the SEM image is analyzed by a known method The method of doing is mentioned. Also, the thickness of the skeleton is determined by performing SEM observation of the monolith before introduction of the ion exchange group at least three times, measuring the thickness of the skeleton in the obtained image, and determining the swelling rate of the monolith before and after introduction of the ion exchange group. The method of multiplying and calculating and the method of analyzing an SEM image by a well-known method are mentioned. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

  Monolithic ion exchangers are not preferred when the thickness of a three-dimensionally continuous rod-like skeleton is less than 10 μm, because the ion exchange capacity per volume decreases, and when it exceeds 100 μm, the uniformity of ion exchange characteristics Is not preferable because it is lost. The definition and measurement method of the wall of the monolith ion exchanger are the same as those of the monolith.

  The total pore volume of the monolith ion exchanger is the same as the total pore volume of the monolith. That is, even when the ion exchange group is introduced into the monolith and swells to increase the opening diameter, the total pore volume hardly changes because the skeleton 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. If the three-dimensional continuous pore size and total pore volume are within the above ranges, contact with the fluid is extremely uniform, the contact area is large, and the fluid can be permeated under low pressure loss. It can exhibit excellent performance as an ion exchanger.

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

  The monolith ion exchanger of the present invention has an ion exchange capacity per volume in a water-wet state of 0.3 mg equivalent / ml or more, preferably 0.4 to 1.8 mg equivalent / ml. In the conventional monolithic organic porous ion exchanger having a continuous macropore structure different from the present invention as described in JP-A-2002-306976, in order to achieve a low pressure loss that is practically required, When the opening diameter is increased, the total pore volume is increased accordingly, so that the ion exchange capacity per volume is decreased, and the total pore volume is decreased to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases. On the other hand, since the monolith ion exchanger of the present invention has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, it is possible to dramatically increase the ion exchange capacity per volume while keeping the pressure loss low. If the ion exchange capacity per volume is less than 0.3 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, although the ion exchange capacity per weight in the dry state of the monolith ion exchanger of the present invention is not particularly limited, since the ion exchange groups are uniformly introduced to the skeleton surface and the skeleton inside the porous body, 5 mg equivalent / g. The ion exchange capacity of a porous body in which ion exchange groups are introduced only on the surface of the skeleton cannot be determined unconditionally depending on the kind of the porous body or ion exchange groups, but is at most 500 μg equivalent / g.

  Examples of the ion exchange group introduced into the 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 ester group; a quaternary ammonium group, a tertiary amino group, Examples include anion exchange groups such as secondary amino group, primary amino group, polyethyleneimine group, tertiary sulfonium group, and phosphonium group; amphoteric ion exchange groups such as aminophosphate group and sulfobetaine.

  In the monolith ion exchanger of the present invention, the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body. Here, “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 skeleton surface and inside the skeleton. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA or the like. Further, when the ion exchange groups are uniformly distributed not only on the skeleton surface of the monolith but also inside the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and Durability against shrinkage is improved.

  The 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, step I comprises preparing a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer not containing an ion exchange group, a surfactant and water, and then a water-in-oil emulsion. Is a step of obtaining a monolith intermediate having a continuous macropore structure having a total pore volume of more than 16 ml / g and not more than 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. Specific examples of these 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; butadiene Diene monomers such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethyl methacrylate Sill, cyclohexyl methacrylate, benzyl methacrylate, and (meth) acrylic monomer of glycidyl methacrylate. Among these monomers, preferred are aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene and the like. These monomers can be used alone or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and its content is 0.3 to 5 mol%, preferably 0.3 to the total oil-soluble monomer. 3 mol% is preferable in that a mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.

  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, tetramethylthiuram disulfide, hydrogen peroxide-ferrous chloride Sodium persulfate-sodium acid sodium sulfite and the like.

  The mixing method for mixing the oil-soluble monomer not containing an ion exchange group, a surfactant, water, and a polymerization initiator to form a water-in-oil emulsion is not particularly limited. Method of mixing at once, oil-soluble monomer, surfactant and oil-soluble polymerization initiator oil-soluble component and water or water-soluble polymerization initiator water-soluble component separately and uniformly dissolved, A method of mixing the components 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 is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 5 mol%, preferably 0.3 to 3 mol% of crosslinked structural units with respect to all 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 5 mol%, the structure of the monolith tends to deviate from the co-continuous structure, which is not preferable. In particular, when the total pore volume is as small as 16 to 20 ml / g in the present invention, the cross-linking structural unit is preferably less than 3 mol in order to form a co-continuous structure.

  The type of the polymer material of the monolith intermediate is not particularly limited, and examples thereof include the same materials as the monolith polymer material described above. Thereby, the same polymer can be formed in the skeleton of the monolith intermediate, and the rod-like skeleton can be thickened to obtain a monolith having a uniform continuous skeleton structure.

  The total pore volume of the monolith intermediate is more than 16 ml / g and not more than 30 ml / g, preferably 6-25 ml / g. In other words, this monolith intermediate basically has a continuous macropore structure, but the opening (mesopore) that is the overlapping part of the macropore and the macropore is remarkably large, so that the skeleton constituting the monolith structure is primary from the two-dimensional wall surface. It has a structure as close as possible to the original rod-like skeleton. When this coexists in the polymerization system, a porous body having a co-continuous structure is formed using the structure of the monolith intermediate as a template. If the total pore volume is too small, the structure of the monolith obtained after polymerizing the vinyl monomer is not preferable because it changes from a co-continuous structure to a continuous macropore structure. On the other hand, if the total pore volume is too large, This is not preferable because the mechanical strength of the monolith obtained after polymerizing the vinyl monomer is lowered and the ion exchange capacity per volume is lowered. In order to make the total pore volume of the monolith intermediate within the specific range of the present invention, the ratio of monomer to water may be about 1:20 to 1:40.

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is a monolith intermediate body is 5-100 micrometers. If the average diameter of the openings is less than 5 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss during fluid permeation increases, which is not preferable. On the other hand, if it exceeds 100 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, resulting in insufficient contact between the fluid and the monolith or monolith ion exchanger, resulting in adsorption characteristics or ion exchange. This is not preferable because the characteristics deteriorate. 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.

(Monolith manufacturing method)
In Step II, the aromatic vinyl monomer and the total oil-soluble monomer having at least two vinyl groups in one molecule dissolve 0.3 to 5 mol% of the crosslinking agent, the aromatic vinyl monomer and the crosslinking agent. This is a process for preparing a mixture comprising an organic solvent and a polymerization initiator that do not dissolve the polymer produced by polymerization of the aromatic vinyl monomer. 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 aromatic vinyl monomer used in Step II is not particularly limited as long as it is a lipophilic aromatic vinyl monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. It is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate coexisting in the system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl, vinyl naphthalene and the like. These monomers can be used alone or in combination of two or more. Aromatic vinyl monomers preferably used in the present invention are styrene, vinyl benzyl chloride and the like.

  The amount of these aromatic vinyl monomers added is 5 to 50 times, preferably 5 to 40 times, by weight with respect to the monolith intermediate coexisting during polymerization. If the amount of aromatic vinyl monomer added is less than 5 times that of the porous material, the rod-like skeleton cannot be made thick, and the adsorption capacity per volume and the ion exchange capacity per volume after introduction of ion exchange groups are reduced. It is not preferable. On the other hand, if the amount of the aromatic vinyl monomer added exceeds 50 times, the diameter of the continuous pores becomes small, and the pressure loss at the time of fluid permeation increases, which is not preferable.

  As the crosslinking agent used in step II, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of the crosslinking agent used is 0.3 to 5 mol%, particularly 0.3 to 3 mol%, based on the total amount of vinyl monomer and crosslinking agent (total oil-soluble monomer). 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. This is not preferable because a problem arises in that the amount of introduction of is reduced. In addition, it is preferable to use the said crosslinking agent usage-amount so that it may become substantially equal to the crosslinking density of the monolith intermediate body coexisted at the time of vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion exchange group introduction reaction.

  The organic solvent used in step II is an organic solvent that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer, in other words, is formed by polymerization of the aromatic vinyl monomer. It is a poor solvent for polymers. Since the organic solvent varies greatly depending on the type of the aromatic vinyl monomer, it is difficult to list general specific examples. For example, when the aromatic vinyl monomer is styrene, the organic solvent includes methanol, ethanol, Alcohols such as propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol; chain structures such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (Poly) ethers; chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane; ethyl acetate, isopropyl acetate, cellosolve acetate, propionic acid Esters such as chill 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 aromatic vinyl monomer is 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the aromatic vinyl monomer concentration becomes less than 30% by weight, the polymerization rate is lowered, or the monolith structure after polymerization deviates from the scope of the present invention, which is not preferable. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may run away, which is not preferable.

  As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) 1,1′-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide and the like. The amount of polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but it can be used in a range of about 0.01 to 5% with respect to the total amount of aromatic vinyl monomer and 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, and the continuous macropore structure of the monolith intermediate is changed to a co-continuous structure. This is a step of obtaining a monolith having a thick bone skeleton. 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 crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic porous material is obtained. The body is obtained. On the other hand, when a monolith intermediate having a specific 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 above-mentioned co-polymerization structure is lost. A monolith with a continuous structure is obtained. The reason for this has not been elucidated in detail, but in the absence of a monolith intermediate, the cross-linked polymer produced by polymerization precipitates and precipitates in the form of particles, while a particle aggregate structure is formed. When a porous body (intermediate) having a large total pore volume is present in the system, the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization proceeds in the porous body. It is considered that the skeleton constituting the monolith structure is changed from a two-dimensional wall surface to a one-dimensional rod-like skeleton to form a monolithic organic porous body having a co-continuous structure.

  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. Among these, the monolith with a co-continuous structure after polymerization is not pressed from the inner wall of the container and enters the reaction vessel without any gap, and the monolith is not distorted, and the reaction raw materials are not wasted and efficient. is there. 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 5 to 50 times, preferably 5 to 40 times the weight of the aromatic vinyl monomer added to the monolith intermediate. It is preferable to blend them as described above. Thereby, it is possible to obtain a monolith having a co-continuous structure in which pores of an appropriate size are three-dimensionally continuous and a thick skeleton is three-dimensionally continuous. In the reaction vessel, the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that is 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, potassium persulfate, etc. are used as initiators In a sealed container under an inert atmosphere, heat polymerization may be performed at 30 to 100 ° C. for 1 to 48 hours. 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 co-continuous structure.

(Method for producing monolithic ion exchanger)
Next, the manufacturing method of the monolith ion exchanger of this invention is demonstrated. The production method of the monolith ion exchanger is not particularly limited, but the method of introducing the ion exchange group after producing the monolith by the above method can strictly control the porous structure of the obtained monolith ion exchanger. This is preferable.

  There is no restriction | limiting in particular as a method to introduce | transduce an ion exchange group into the said monolith, Well-known methods, such as a polymer reaction and graft polymerization, can be used. For example, as a method of introducing a sulfonic acid group, if the monolith is a styrene-divinylbenzene copolymer, etc., a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid; A method of grafting a sodium styrenesulfonate or acrylamido-2-methylpropanesulfonic acid by introducing a mobile group into the skeleton surface or inside the skeleton; Similarly, after graft polymerization of glycidyl methacrylate, a sulfonic acid group is introduced by functional group conversion. And the like. As a method for introducing a quaternary ammonium group, if the 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 in which chloromethylstyrene and divinylbenzene are produced by copolymerization and reacted with a tertiary amine; N, N, N-trimethylammonium is introduced into the monolith by introducing radical initiation groups and chain transfer groups uniformly into the skeleton surface and inside the skeleton. Examples include a method of graft polymerization of ethyl acrylate and N, N, N-trimethylammoniumpropylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. 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 monolith ion exchanger of the present invention swells to be 1.4 to 1.9 times larger than that of the monolith, for example, because the ion exchange group is introduced into the bilithic monolith. Further, the total pore volume does not change even if the pore diameter becomes larger due to swelling. Accordingly, the monolith ion exchanger of the present invention has a high mechanical strength because it has a thick bone skeleton even though the size of three-dimensionally continuous pores is remarkably large. In addition, since the skeleton is thick, it is possible to increase the ion exchange capacity per volume in a wet state of water, and it is possible to pass water to be treated for a long period of time at a low pressure and a large flow rate. It can be suitably used by filling an apparatus or an electric deionized water production apparatus.

  The chemical filter of the present invention includes the monolith, a monolith provided with a through hole, a monolith ion exchanger or a monolith ion exchanger provided with a through hole, and a known ion exchange resin or ion exchange. The structure of the filter is not particularly limited as long as it includes a combination of an adsorption layer using fibers and the above monolith as an adsorption layer, but usually the adsorption layer and a support frame (casing) that supports the adsorption layer It consists of. 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 capacity is lowered, and if it is too large, the strength of the monolith or monolith ion exchanger is remarkably reduced. In order to make the specific surface area within the above range, it depends on the aromatic vinyl monomer, the cross-linking agent, the polymerization initiator, the polymerization temperature, etc., but cannot be determined unconditionally. The polymerization may be performed by diluting with an organic solvent so that the aromatic vinyl monomer concentration is 30 to 80% by weight. 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 monolith or 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 monolith or a monolith ion exchanger provided with through holes is used as the adsorption layer, the porosity of the through holes in the apparent 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 if it is as fast as this, since it is a co-continuous structure, the ion exchange capacity is large and ion exchange is performed efficiently, gaseous contaminants 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 monolith ion exchanger used as an adsorption layer is used by processing the obtained monolith ion exchanger by a known regeneration method as in the case of conventional ion exchange resins. That is, the monolith cation exchanger is used as an acid form by acid treatment, and the 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 monolith or monolith ion exchanger used as the adsorption layer has a remarkably large pore volume and specific surface area, and ion exchange groups are introduced at a high density on the surface and inside thereof. Even if it is fast, it can retain the adsorption removal capability of gaseous pollutants, and it can be removed even if the amount of gaseous pollutants is extremely small. 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 monolith ion exchanger according to the present invention has a wall thickness of 2 to 10 μm, all ion exchange groups are used efficiently.

  The monolithic 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 compared with the conventional granular ion exchange resin. Becomes longer.

  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 a monolith or a monolith ion exchanger is used as an adsorption layer of a chemical filter, the gas to be treated can be efficiently processed even in a small blower with a small static pressure by using large pores and ion exchange groups introduced uniformly. Impurities 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)
5.4 g of styrene, 0.17 g of divinylbenzene, 1.4 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 was added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co.) as 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. This emulsion was quickly transferred to a reaction vessel and allowed to polymerize at 60 ° C. for 24 hours in a static state after sealing. After completion of the polymerization, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. When the internal structure of the monolith intermediate (dry body) obtained in this way was observed with an SEM image (FIG. 2), the wall section separating two adjacent macropores was very thin and rod-shaped, but the open cell structure The average diameter of the openings (mesopores) where the macropores overlap with each other as measured by the mercury intrusion method was 70 μm, and the total pore volume was 21.0 ml / g.

(Manufacture of monocontinuous monolith)
Subsequently, 76.0 g of styrene, 4.0 g of divinylbenzene, 120 g of 1-decanol, and 0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). Next, the monolith intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 40 mm to fractionate 4.1 g. The separated monolith intermediate is placed in a reaction vessel having an inner diameter of 75 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 monolithic contents having a thickness of about 60 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

  When the internal structure of the monolith (dry body) containing 3.2 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained in this way was observed by SEM, the monolith had a skeleton and pores, respectively. It was a three-dimensional continuous structure with both phases intertwined. Moreover, the thickness of the skeleton measured from the SEM image was 10 μm. Further, the size of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 17 μm, and the total pore volume was 2.9 ml / g. The results are summarized in Tables 1 and 2. In Table 2, the thickness of the skeleton is represented by the diameter of the skeleton.

(Production of co-continuous monolithic cation exchanger)
The monolith produced by the above method was cut into a disk shape having a diameter of 75 mm and a thickness of about 15 mm. The weight of the monolith was 18 g. To this was added 1500 ml of dichloromethane, heated at 35 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 99 g of chlorosulfuric acid, heated up 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 monolith cation exchanger having a co-continuous structure.

  A part of the obtained cation exchanger was cut out and dried, and then its internal structure was observed by SEM. As a result, it was confirmed that the monolith cation body maintained a co-continuous structure. The SEM image is shown in FIG. Moreover, the swelling ratio before and after the reaction of the cation exchanger was 1.4 times, and the ion exchange capacity per volume was 0.74 mg equivalent / ml in a water-wet state. The size of the continuous pores of the monolith in the water wet state was estimated from the value of the monolith and the swelling ratio of the cation exchanger in the water wet state to be 24 μm, the skeleton diameter was 14 μm, and the total pore volume was 2. It was 9 ml / g.

  In addition, the differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.052 MPa / m · LV, which is a low pressure loss with no practical problem. Furthermore, when the ion exchange zone length for sodium ions of the monolith cation exchanger was measured, the ion exchange zone length at LV = 20 m / h was 16 mm. Amberlite IR120B (a commercially available strong acid cation exchange resin) It was not only overwhelmingly shorter than the value (320 mm) manufactured by Rohm and Haas, but also shorter than the value of the monolithic porous cation exchanger having a conventional open cell structure. The results are summarized in Table 2.

  Next, in order to confirm the distribution state of the sulfonic acid group in the 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. In the photograph on the left side of FIG. 4, a part extending in a horizontal direction is a skeleton part, and in the photograph on the left side of FIG. 5, two circular shapes are cross sections of the skeleton. 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 and 3
(Manufacture of monolith with co-continuous structure)
The amount of styrene used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used were changed to the amounts shown in Table 1. Except for the above, a monolith having a co-continuous structure was produced in the same manner as in Example 1. The results are shown in Tables 1 and 2.

(Production of monolith cation exchanger having a co-continuous structure)
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 having a co-continuous structure. The results are shown in Table 2. Moreover, the result of having observed the internal structure of the obtained monolith cation exchanger which has a co-continuous structure by the SEM image is shown in FIG.6 and FIG.7, respectively. From Table 2, the monolith cation exchangers obtained in Examples 2 and 3 exhibited excellent characteristics such as a small differential pressure coefficient, a large exchange capacity per volume, and a short ion exchange zone length. The monolith cation exchanger of Example 2 was also evaluated for mechanical properties.

(Mechanical property evaluation of monolith cation exchanger)
The monolith cation exchanger obtained in Example 2 was cut into a strip of 4 mm × 5 mm × 10 mm in a wet state and used as a test piece for the tensile strength test. The test piece was attached to a tensile tester, the head speed was set to 0.5 mm / min, and the test was performed at 25 ° C. in water. As a result, the tensile strength and the tensile modulus were 23 kPa and 15 kPa, respectively, which were significantly larger than the conventional monolith cation exchanger. Further, the tensile elongation at break was 50%, which was a value larger than that of the conventional monolith cation exchanger.

Example 4
(Manufacture of monolith with co-continuous structure)
Except for changing the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used as shown in Table 1. A monolith having a co-continuous structure was produced in the same manner as in Example 1. The results are shown in Tables 1 and 2.

(Production of monolith anion exchanger having a co-open cell structure)
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 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 monolithic organic porous material, 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 swelling ratio before and after the reaction of the obtained anion exchanger was 1.6 times, and the ion exchange capacity per volume was 0.44 mg equivalent / ml in a water-wet state. The diameter of the continuous pores of the monolith ion exchanger in the water wet state was estimated from the value of the monolith and the swelling ratio of the cation exchanger in the water wet state to be 29 μm, the thickness of the skeleton was 13 μm, and the total pore volume. Was 2.0 ml / g.

  Further, the differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.020 MPa / m · LV, which is a low pressure loss that does not impede practical use. Furthermore, when the ion exchange zone length regarding the fluoride ion of the monolith anion exchanger was measured, the ion exchange zone length at LV = 20 m / h was 22 mm, and amberlite which is a commercially available strong basic anion exchange resin. In addition to being overwhelmingly shorter than the value of IRA402BL (Rohm and Haas) (165 mm), it was also shorter than the value of a monolithic porous anion exchanger having a conventional open cell structure. The results are summarized in Table 2. Moreover, the result of having observed the internal structure of the obtained monolith anion exchanger which has a co-continuous structure by the SEM image is shown in FIG.

  Next, in order to confirm the distribution state of the quaternary ammonium groups in the monolith 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 surface of the anion exchanger but also inside, and the quaternary ammonium groups were uniformly introduced into the anion exchanger.

Comparative Example 1
(Manufacture of monolithic organic porous body having continuous macropore structure)
A monolithic organic porous body having a continuous macropore structure was produced according to the production method described in JP-A-2002-306976. That is, 19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of 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 monolithic organic porous body having a continuous macropore structure.

  FIG. 9 shows the result of observing the internal structure of the organic porous material containing 3.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained by SEM. As is apparent from FIG. 9, the organic porous body has a continuous macropore structure. Moreover, the average thickness of the wall part measured from the SEM image is 5 μm, the average diameter of the overlapping part (opening) of the macropore and the macropore of the organic porous body measured by the mercury intrusion method is 29 μm, and the total pore volume is 8.6 ml. / g. The results are summarized in Tables 1 and 2. In Tables 1 and 2, the mesopore diameter means the average diameter of the openings.

(Production of monolith cation exchanger having a continuous macropore structure)
The organic porous material produced in Comparative Example 1 was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. The weight of the organic porous material was 6 g. To this was added 1000 ml of dichloromethane, and the mixture was heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or less, 30 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 washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolithic porous cation exchanger having a continuous macropore structure. The swelling rate before and after the reaction of the obtained cation exchanger was 1.6 times, and the ion exchange capacity per volume was 0.22 mg equivalent / ml in a water-wet state, which was a small value compared to the examples. The average diameter of the mesopores of the organic porous ion exchanger in the water-wet state is 46 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water-wet state. The thickness was 8 μm and the total pore volume was 8.6 ml / g. The differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.013 MPa / m · LV. The results are summarized in Table 3. The differential pressure coefficient showed a small value as in the example, but the ion exchange capacity per volume was considerably lower than in the example, and the ion exchange zone length was about 3 times that in the example. It was twice as long. The monolith cation exchanger obtained in Comparative Example 1 was also evaluated for mechanical properties.

(Mechanical property evaluation of conventional monolith cation exchanger)
The monolith cation exchanger obtained in Comparative Example 1 was subjected to a tensile test by the same method as the evaluation method of Example 2. As a result, the tensile strength and the tensile modulus were 28 kPa and 12 kPa, respectively, which were lower values than the monolith cation exchanger of Example 2. The tensile elongation at break was 17%, which was smaller than that of the monolith cation exchanger of the present invention.

Comparative Example 2
(Production of monolithic organic porous body having an open cell structure)
A monolithic organic porous material having a continuous macropore structure in the same manner as in Comparative Example 1 except that the amount of styrene used, the amount of divinylbenzene, and the amount of SMO used were changed to the amounts shown in Table 1. The body was manufactured. The results are shown in Tables 1 and 2.

(Production of monolith anion exchanger having an open cell structure)
A monolith anion exchanger having an open cell structure was produced by a conventional technique by introducing a chloromethyl group into the organic porous material produced by the above method and reacting with trimethylamine in the same manner as in Example 4. The results are shown in Table 2. The differential pressure coefficient showed a small value as in the example, but the ion exchange capacity per volume was lower than in the example, and the ion exchange zone length was about four times that in the example. It was long.

Comparative Example 3
An attempt was made to produce a monolith having a co-continuous structure in the same manner as in Example 1 except that the type of organic solvent used in Step II was changed to dioxane, which is a good solvent for polystyrene. However, the isolated product was transparent, suggesting collapse / disappearance of the porous structure. SEM observation was performed for confirmation, but only a dense structure was observed, and the open cell structure disappeared.

Example 5
(Manufacture of monocontinuous monolith)
A co-continuous structure monolith was produced in the same manner as in Example 1.

(Production of co-continuous monolith cation exchanger)
Instead of a disk having an outer diameter of 75 mm and a thickness of about 15 mm, a disk having an outer diameter of 75 mm and a thickness of 50 mm was used, 5,000 ml was substituted for 1,500 ml of dichloromethane, and 330 g was substituted for 99 g of chlorosulfuric acid. Except for this, a co-continuous monolith cation exchanger was produced in the same manner as in Example 1. The obtained monolith cation exchanger had the same swelling ratio before and after the reaction, the ion exchange capacity per volume, and the size of the continuous pores of the monolith in a water-wet state as in Example 1.

(Adsorption of basic gas using bicontinuous monolith cation exchanger)
The co-continuous structure monolith cation exchanger obtained in Example 5 was immersed in 3N hydrochloric acid for 24 hours, and 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. 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 4
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 5, the ammonia concentration in the permeated air was 120 ng / m ³ , and ammonia could not be completely removed.

Example 6
Before immersing the 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 to 30% with respect to the apparent circle of the cylindrical monolith in the axial direction. A monolith cation exchanger having through-holes was obtained in the same manner as in Example 5 except that the extending through-holes were opened, and further basic gas was adsorbed in the same manner as in Example 5. 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 5
In place of the monolithic organic porous cation exchanger, an open-cell monolithic organic porous cation exchanger of Comparative Example 4 was used, except that a through-hole was formed in the same manner as in Example 5, 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 7
(Production of co-continuous monolithic anion exchanger)
The production of the monolith anion exchanger was changed to 50 mm instead of the 15 mm thick disk, the amount of dimethoxymethane was changed from 1400 ml to 4700 ml, the amount of tin tetrachloride was changed from 20 ml to 67 ml, the use of chlorosulfuric acid A monolithic anion exchanger was produced according to Example 4 except that the amount was changed from 560 ml to 1870 ml, and the amounts of THF and trimethylamine 30% aqueous solution were changed from 1000 ml to 3400 ml and from 600 ml to 2000 ml, respectively.

(Adsorption of acid gas using bicontinuous monolithic anion exchanger)
The monolithic anion exchanger obtained by the above method was immersed in a 1N aqueous sodium hydroxide solution for 24 hours, and then sufficiently washed with pure water and dried. The resulting monolithic organic porous anion exchanger was allowed to stand for 48 hours at 25 ° C. and a relative humidity of 40%, then cut into a disk with a diameter of 50 mm and a thickness of 50 mm, and filled into a cylindrical column to produce a chemical filter. did. The air permeation pressure was measured 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 conditions of 25 ° C. and 40% temperature and humidity, and the permeated gas was ultrapure. Sampling was performed by a water impinger method, and sulfate ions were quantified by an ion chromatography method. 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 6
An open-celled monolithic organic porous body was produced in the same manner as in Comparative Example 4 except that chloromethylstyrene was used in place 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 7. As a result, the concentration of sulfur dioxide in the air was 200 ng / m ³ and could not be completely removed.

Example 8
(Adsorption of organic gas using bicontinuous monolith)
The co-continuous structure monolithic organic porous material produced according to Example 5 was sufficiently washed with pure water and dried. The obtained co-continuous structure monolithic organic porous material was allowed to stand for 48 hours at 25 ° C. and a relative humidity of 40%, then cut into a disk shape having a diameter of 50 mm and a thickness of 50 mm, and packed into a cylindrical column to obtain a chemical filter. Produced. A solid adsorbent (TENAX-GR) was used as the permeated 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 conditions of 25 ° C. and 40% temperature and humidity. The 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 7
An open-cell monolithic organic porous material was produced according to Comparative Example 4, 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 8.

This filter was subjected to a toluene removal test under the same conditions as in Example 8. 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 8. became.

Example 9
(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 performed in the same manner as in Example 5. 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 10
(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 9. 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 11
(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 5 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 8
Using the same chemical filter as in Comparative Example 4, the same life test for removing ammonia as in Example 11 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 are hydrophobic and chemically stable. In addition, the three-dimensionally continuous skeleton is thick and the mechanical strength is high, and the ion exchange capacity per volume is particularly large. In addition, in the co-continuous structure, the three-dimensionally continuous pores are large, and the pressure loss when a fluid such as water or gas is permeated is low, and the length of the ion exchange zone is remarkably short. Therefore, chemical filters and adsorbents; ion exchangers used in two-bed, three-column pure water production equipment and electric deionized water production equipment; various chromatographic fillers; solid acid / base catalysts And can be applied to a wide range of application fields.

It is the figure which showed typically the co-continuous structure of the monolith of this invention. 2 is a SEM image of the monolith intermediate obtained in Example 1. 2 is an SEM image of a monolith cation exchanger having a co-continuous structure obtained in Example 1. FIG. 2 is an EPMA image showing a distribution state of sulfur atoms on the surface of a monolith cation exchanger having a co-continuous structure obtained in Example 1. FIG. 2 is an EPMA image showing a distribution state of sulfur atoms in the cross-section (thickness) direction of the monolith cation exchanger having a co-continuous structure obtained in Example 1. FIG. 3 is a SEM image of a monolith cation exchanger having a co-continuous structure obtained in Example 2. 4 is a SEM image of a monolith cation exchanger having a co-continuous structure obtained in Example 3. 4 is a SEM image of a monolith anion exchanger having a co-continuous structure obtained in Example 4. 2 is an SEM photograph of the monolith obtained in Comparative Example 1.

Explanation of symbols

1 Skeletal phase 2 Pore phase 10 Monolith

Claims (11)

  Among all the structural units, a three-dimensionally continuous skeleton composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit and having a thickness of 0.8 to 40 μm, and a diameter between the skeletons A monolithic organic porous body, which is a co-continuous structure composed of three-dimensionally continuous pores of 8 to 80 µm, and has a total pore volume of 0.5 to 5 ml / g. Among all the structural units, a three-dimensionally continuous skeleton composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit and having a thickness of 0.8 to 40 μm, and a diameter between the skeletons A co-continuous structure consisting of three to three-dimensionally continuous pores of 8 to 80 μm, the total pore volume being 0.5 to 5 ml / g, and the following steps:
A water-in-oil emulsion is prepared by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion exchange groups, and then the water-in-oil emulsion is polymerized to a total pore volume of 16 ml / g. Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure exceeding 30 ml / g,
Aromatic vinyl monomers, crosslinkers having at least two vinyl groups in one molecule, organic solvents and polymers that dissolve aromatic vinyl monomers and crosslinkers but do not dissolve polymers formed by polymerization of aromatic vinyl monomers Step II for preparing a mixture of initiators,
A monolith obtained by performing the step III of performing polymerization in the presence of the mixture obtained in the step II while standing and in the presence of the monolithic organic porous intermediate obtained in the step I Organic porous body.   A three-dimensionally continuous skeleton having a thickness of 1 to 60 μm composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units having an ion exchange group introduced therein; A co-continuous structure comprising three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, the total pore volume being 0.5 to 5 ml / g, The monolithic organic porous ion exchanger is characterized in that the ion exchange capacity is 0.3 mg equivalent / ml or more and the ion exchange groups are uniformly distributed in the porous ion exchanger.   An ion exchange group introduced into the monolithic organic porous material according to claim 2, wherein the ion exchange capacity per volume in a water-wet state is 0.3 mg equivalent / ml or more, and the ion exchange group is in the porous state. Monolithic organic porous ion exchanger characterized by being uniformly distributed in the porous ion exchanger. A water-in-oil emulsion is prepared by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion exchange groups, and then the water-in-oil emulsion is polymerized to a total pore volume of 16 ml / g. Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure exceeding 30 ml / g,
Aromatic vinyl monomer, 0.3-5 mol% of cross-linking agent, aromatic vinyl monomer and cross-linking agent are dissolved in all oil-soluble monomer having at least two vinyl groups in one molecule, but aromatic vinyl monomer Step II for preparing a mixture comprising an organic solvent and a polymerization initiator in which the polymer produced by polymerization of the polymer does not dissolve,
It is characterized in that the step III obtained by carrying out the polymerization in the presence of the monolithic organic porous intermediate obtained in the step I while standing the mixture obtained in the step II to obtain a co-continuous structure is performed. A method for producing a monolithic organic porous body.   6. The monolithic organic porous intermediate obtained in the step I is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion becomes an opening having an average diameter of 5 to 100 μm. The manufacturing method of the monolithic organic porous body of description. A water-in-oil emulsion is prepared by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion exchange groups, and then the water-in-oil emulsion is polymerized to a total pore volume of 16 ml / g. Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure exceeding 30 ml / g,
Aromatic vinyl monomer, 0.3-5 mol% of cross-linking agent, aromatic vinyl monomer and cross-linking agent are dissolved in all oil-soluble monomer having at least two vinyl groups in one molecule, but aromatic vinyl monomer Step II for preparing a mixture comprising an organic solvent and a polymerization initiator in which the polymer produced by polymerization of the polymer does not dissolve,
Step III where the mixture obtained in Step II is allowed to stand and in the presence of the monolithic organic porous intermediate obtained in Step I to obtain a co-continuous structure,
An IV step for introducing an ion exchange group into the co-continuous structure obtained in the step III;
A process for producing a monolithic organic porous ion exchanger characterized in that   A chemical filter using the monolithic organic porous material according to claim 1 or 2 as an adsorption layer.   5. A chemical filter using the monolithic organic porous ion exchanger according to claim 3 as an adsorption layer.   A chemical filter using a monolithic organic porous material according to claim 1 or 2 provided with through holes as an adsorption layer.   A chemical filter using a monolithic organic porous ion exchanger according to claim 3 or 4 provided with through holes as an adsorbing layer.

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