JP2009019188A - Monolith-shaped organic porous body, its manufacturing method, monolith-shaped organic porous ion exchanger and chemical filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monolith-shaped organic porous body of a new structure having a continuous macro-void structure of a uniform and large structure, low in a pressure loss when permeating fluid such as water and gas, and useful as an adsorbent and an ion exchanger; its manufacturing method; a monolith-shaped organic porous ion exchanger; and a chemical filter. <P>SOLUTION: In an organic porous body of a continuous macro-void structure, a connected part of mutually connected macro-void and macro-void becomes an opening of a radius of 0.1-25 mm. In the monolith-shaped organic porous body, a skeleton part of the organic porous body is a particle-coagulated pore structure having a three-dimensionally continuous pore by coagulating an organic polymer particle. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a monolithic organic porous material having a continuous macrovoid structure useful as an adsorbent or an ion exchanger used in an adsorption device, a deionized water production device, a gaseous pollutant removal device, or the like, a production method thereof, and a monolith The present invention relates to an organic porous ion exchanger and a chemical filter.

  An inorganic porous body made of silica or the like is known as a monolithic porous body having a particle aggregation type pore structure having a common opening in a macropore and a macropore wall connected to each other (US Patent) No. 5624875). The inorganic porous material has been actively developed as a chromatographic filler.

  However, since this inorganic porous body is hydrophilic, in order to use it as an adsorbent, a complicated operation such as a hydrophobic treatment on the surface, etc., is necessary. In addition, since this inorganic porous material is vulnerable to alkali, not only the regeneration operation using alkali usually performed in an ion exchange resin cannot be carried out, but also when it is simply kept in neutral water for a long time, Since silicate ions generated by decomposition are eluted in water, it was impossible to use as an ion exchanger for producing pure water or ultrapure water. Furthermore, the above-mentioned inorganic porous body has a common opening, which is a continuous pore, having a maximum opening of 20 μm or less because of its manufacturing method. It was difficult to fill a deionized water production apparatus that needs to be treated and use it as an ion exchanger.

  JP-A-2002-306976 discloses a monolithic organic porous body having a similar structure and a monolithic organic porous ion exchanger having an ion exchange group introduced into the porous body. The organic porous material or organic porous ion exchanger overcomes the disadvantages of the inorganic porous material, and is useful as an ion exchanger used in adsorbents, chromatographic fillers, deionized water production apparatuses, and the like. . However, the organic porous ion exchanger, due to its structural limitations, when trying to achieve a low pressure loss that is practically required, the structure becomes uneven due to the formation of large voids partially. The reproducibility in production was extremely inferior, the mixture became unstable, and eventually the structure collapsed.

  On the other hand, as a monolithic organic porous body having a structure other than the above-mentioned particle aggregation type pore structure, a porous body having a particle aggregation type structure is disclosed in JP 7-501140 A. This particle-aggregated monolithic organic porous material has small pores of less than about 200 nm and large pores having a diameter ranging from about 600 nm to about 3000 nm, and is a plug suitable for a chromatography column.

JP 2004-321930 A discloses a chemical filter using a monolithic organic porous ion exchanger having an open cell structure as an adsorption layer. According to this chemical filter, the ability to adsorb and remove gaseous pollutants can be maintained even if the gas permeation rate is high, and even if the amount of gaseous pollutants is extremely small, it can be removed. However, the chemical filter using the above monolith as the adsorption layer has a very high pressure loss during ventilation, and a blower for ventilation requires a very large capacity. It has been desired to develop a chemical filter that can be ventilated by a blower and has a high ability to adsorb and remove gaseous pollutants.
US Pat. No. 5,624,875 (Claim 1) JP 2002-306976 (Claim 1) Special table hei 7-501140 (page 4, lower left column, lines 3 to 8) JP 2004-321930 A (Claim 1)

  However, the porous body obtained by the method described in JP-A-7-501140 has a continuous pore diameter as small as about 3 μm at the maximum, and is required to perform a large flow rate treatment at a low pressure. There is a problem that it cannot be used for an industrial scale deionized water production apparatus.

  Therefore, the development of a monolithic organic porous ion exchanger having a remarkably low pressure loss when a fluid such as water or gas is permeated, a uniform structure and large pores, and the monolithic organic porous Development of a production method capable of producing a porous ion exchanger has been desired. In addition, it has been desired to develop a chemical filter having a higher ability to adsorb and remove gaseous pollutants than ever before.

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

  In such a situation, the present inventors have conducted an intensive study, and as a result, the macrovoids that are connected to each other are organic porous bodies having a continuous macrovoid structure in which the connected portions of the macrovoids have an opening with a radius of 0.1 to 25 mm. If the skeleton of the organic porous body is a monolithic organic porous body having a particle aggregation type pore structure in which organic polymer particles are aggregated and have three-dimensionally continuous pores, water or gas As a result, the present inventors have found that the pressure loss when a fluid such as a liquid is permeated is low and that it is useful as an adsorbent, an ion exchanger, or a chemical filter.

  That is, the present invention relates to an organic porous body having a continuous macrovoid structure in which the connected portions of macrovoids connected to each other are openings having a radius of 0.1 to 25 mm, and the skeleton of the organic porous body The present invention provides a monolithic organic porous body characterized in that the part has a particle aggregation type pore structure in which organic polymer particles are aggregated to have three-dimensionally continuous pores.

  The present invention also includes a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, and polymerization initiation. A step of preparing a liquid mixture made of an agent, a step of polymerizing under standing in the presence of a number of particulate templates in the liquid mixture in a container, and a step of removing the particulate template from the polymer The present invention provides a method for producing a monolithic organic porous material.

  In the present invention, an ion exchange group is introduced on the skeleton surface and inside the skeleton of the monolithic organic porous material, and the ion exchange capacity per volume in a water wet state is 0.01 mg equivalent / ml. The present invention provides a monolithic organic porous ion exchanger characterized by the above.

  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 of the present invention has a continuous macrovoid structure that is significantly larger than that of the conventional monolithic organic porous body having a particle-aggregated pore structure or an open-cell structure, and therefore has a low pressure and a large flow rate. In addition to being able to replace conventional synthetic adsorbents that can be processed, it is possible to take advantage of its excellent fluid permeability and adsorb and remove high-viscosity components that could not be handled by synthetic adsorbents. Application to new application fields such as substance removal becomes possible. Moreover, according to the method for producing a monolithic organic porous body of the present invention, the monolithic organic porous body can be produced easily and reliably. In addition, the monolithic organic porous ion exchanger of the present invention has a continuous macrovoid structure that is much larger than that of the conventional monolithic organic porous ion exchanger having a particle aggregation type pore structure or an open cell structure. High-viscosity components that cannot be used with ion-exchange resins due to their excellent fluid permeation characteristics as well as being able to replace conventional ion-exchange resins. It can be suitably used by filling in a gaseous pollutant removing device such as ion removal inside and chemical filter.

  The basic structure of the monolithic organic porous body and the monolithic organic porous ion exchanger of the present invention (hereinafter also referred to as “monolithic porous body etc.” when both are described) is shown in the schematic diagram of FIG. As shown in the figure, the skeleton part of the organic porous body exhibiting a continuous macrovoid structure with a specific structure in which macrovoids are connected to each other has a particle aggregation type in which organic polymer particles are aggregated to have three-dimensionally continuous pores It becomes a pore structure. In the monolithic porous body or the like of the present invention, in the continuous macrovoid structure Y, a large flow path through which liquid or gas flows with low pressure loss is formed, and in the particle aggregation type pore structure X, the liquid or gas penetrates. A channel smaller than a continuous macrovoid is formed.

  The skeleton portion of the monolithic porous body or the like has a particle aggregation type pore structure in which organic polymer particles are aggregated and have three-dimensionally continuous pores. As an example, as shown in the schematic diagram of FIG. In addition, organic polymer particles having a radius of 0.5 to 25 μm, preferably 0.5 to 15 μm, having a crosslinked structural unit aggregate to form a three-dimensionally continuous skeleton part 3, and a pore radius between the skeletons Is a particle aggregation type pore structure X having three-dimensionally continuous pores 4 of 10 to 50 μm, preferably 10 to 45 μm.

  In the particle aggregation type pore structure X, if the radius of the organic polymer particles is too small, the continuous pore radius between the skeletons becomes too small, which is not preferable. If too large, the liquid or gas and the monolithic porous body As a result, the contact with the resin becomes insufficient, and as a result, the adsorption characteristics and the ion exchange characteristics are deteriorated. Also, if the size of the three-dimensional continuous pore radius existing between the skeletons is too small, it is not preferable because the pressure loss when a fluid such as water or gas is permeated increases. If it is too high, contact between the liquid or gas and the organic porous body or organic porous ion exchanger becomes insufficient, and the adsorption characteristics and ion exchange characteristics deteriorate, which is not preferable. The size of the organic polymer particles can be easily measured by using SEM. In addition, the size of the three-dimensionally continuous pore diameter existing between the skeletons can be obtained from SEM photographs, and the maximum value of the pore distribution curve obtained by the mercury intrusion method for the aggregated pore structure portion. Can also be sought.

  The particle aggregation type pore structure preferably has a total pore volume of 1 to 5 ml / g. If the total pore volume is too small, the pressure loss at the time of fluid permeation increases, which is not preferable. Furthermore, the amount of permeate liquid or gas per unit cross-sectional area decreases, and the processing capacity decreases, which is not preferable. . On the other hand, if the total pore volume is too large, the amount of adsorption per volume and the ion exchange capacity per volume decrease, which is not preferable.

  The material of the skeleton part in which the organic polymer particles are aggregated to be three-dimensionally continuous is an organic polymer material having a crosslinked structural unit. That is, the organic polymer material has a constitutional unit composed of a vinyl monomer and a crosslinker structural unit having two or more vinyl groups in the molecule, and the polymer material comprises all constitutional units constituting the polymer material. On the other hand, it preferably contains 1 to 5 mol%, particularly preferably 1 to 4 mol% of crosslinked structural units. If the cross-linking structural unit is too small, it is not preferable because the mechanical strength is insufficient. On the other hand, if the cross-linking structural unit is too large, the pore diameter that exists three-dimensionally continuously between the skeletons becomes small, and the pressure loss increases. This is not preferable.

  The continuous macrovoid structure Y is formed in a monolithic porous body or the like. In the continuous macrovoid structure Y, the connecting portions of the macrovoid 1 and the macrovoid 1 connected to each other have an opening 2 having a radius of 0.1 to 25 mm, preferably 0.5 to 15 mm, particularly preferably 0.5 to 10 mm. It is the structure which becomes. That is, the continuous macrovoid structure Y usually has a structure in which a macrovoid 1 and a macrovoid 1 having a radius of 0.5 to 50 mm overlap each other, and this overlapping portion becomes an opening 2, and this portion has an open pore structure. It is. In the open pore structure, if a liquid or a gas is flowed, the pore structure formed by the macro void and the opening becomes a flow path. That is, in a monolithic porous body or the like, three-dimensionally continuous pores of a particle aggregation type pore structure and open pores of a continuous macrovoid structure are mixed and connected to each other to form a flow path.

  The number of macrovoids overlapped with one macrovoid is 1-2, and many are 3-10. If the radius of the opening is less than 0.1 mm, the pressure loss during liquid or gas permeation is large, and it is difficult to obtain a sufficient effect of reducing the pressure loss. On the other hand, if the radius of the opening exceeds 25 mm, the contact between the liquid or gas and the monolithic porous body becomes insufficient, and as a result, the adsorption characteristics and the ion exchange characteristics are deteriorated. Macrovoids are generally uniformly distributed in the continuous macrovoid structure. Those having an opening radius in the vicinity of 25 mm are applied when producing an adsorbent or ion exchanger having a large volume.

  In the monolithic porous body or the like of the present invention, the pore radius of the macrovoid and the particle aggregation type pore structure can be clearly recognized in the SEM photograph or the like.

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

  In the present invention, the porosity of the continuous macrovoid structure portion is preferably about 75% in the monolithic porous body or the like, and the porosity of the monolithic porous body or the like of the present invention is preferably about 60%. is there. Note that the monolithic porous body of the present invention has a particle agglomerated pore structure and a continuous macrovoid structure uniformly, so that the particle agglomerated pore structure is used as a matrix and the continuous macrovoids are contained in the matrix. The structure is a structure in which a continuous macrovoid structure is used as a matrix, and a particle aggregation type pore structure is formed in the matrix.

  There is no restriction | limiting in particular in the kind of material which comprises the monolithic organic porous body of this invention, For example, Styrenic polymers, such as a polystyrene, poly ((alpha) -methylstyrene), polyvinyl benzyl chloride; Polyolefins, such as polyethylene and a polypropylene; Poly Poly (halogenated polyolefins) such as vinyl chloride and polytetrafluoroethylene; Nitrile polymers such as polyacrylonitrile; (Meth) acrylic polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate; Styrene-divinyl Examples thereof include a benzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer. The polymer may be a polymer obtained by copolymerizing a single monomer and a crosslinking agent, or may be a polymer obtained by polymerizing a plurality of monomers and a crosslinking agent, and two or more kinds of polymers are blended. It may be a thing. Among these organic polymer materials, styrene-divinylbenzene copolymer is used because it is easy to form a particle aggregate structure, easy to introduce ion exchange groups, high mechanical strength, and high stability against acids and alkalis. Preferred materials include a polymer and a vinylbenzyl chloride-divinylbenzene copolymer. The glycidyl methacrylate-ethylene glycol dimethacrylate copolymer described in the examples of JP-T-7-501140 is low in acid / alkali stability and is susceptible to hydrolysis. It is not very suitable as an ion exchanger filled in a deionized water production apparatus that is frequently repeated.

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

  The monolithic organic porous ion exchanger of the present invention is a monolithic organic porous body in which ion exchange groups are further uniformly introduced into the skeleton surface and inside the skeleton, and the ion exchange capacity is not particularly limited. However, the ion exchange capacity per volume in a wet state of water is preferably 0.01 mg equivalent / ml or more, particularly preferably 0.05 to 5.0 mg equivalent / ml. If the ion exchange capacity per volume in a water-wet state is less than 0.01 mg equivalent / ml, the amount of water containing ions that can be processed before breakthrough, that is, the ability to produce deionized water will decrease. It is not preferable.

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

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

  Next, the manufacturing method of the monolithic organic porous body of this invention is demonstrated. That is, the production method includes a vinyl monomer, a cross-linking agent having at least two vinyl groups in one molecule, an organic solvent in which a vinyl monomer or a cross-linking agent is dissolved but a polymer formed by polymerization of the vinyl monomer is not dissolved, and polymerization There are a step of preparing a mixture of initiators, a step of polymerizing under standing in the presence of a number of particulate templates in the mixture in a container, and a step of removing the particulate templates from the polymer.

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

  As the crosslinking agent used in the step I, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The crosslinking agent is used in a proportion of 1 to 5 mol%, preferably 1 to 4 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. The amount of the crosslinking agent used greatly affects the resulting particle aggregation type pore structure, and if the crosslinking agent is used in excess of 5 mol%, the size of the continuous pores formed between the skeletons becomes small. It is not preferable. On the other hand, when the amount of the crosslinking agent used is less than 1 mol%, the mechanical strength of the porous body is insufficient, and it is not preferable because it deforms greatly during water passage or causes the porous body to break.

  The organic solvent used in step I is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, in other words, a poor solvent for the polymer formed by polymerization of the vinyl monomer. . Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, alcohols such as ethylene glycol, tetramethylene glycol, and glycerine; chain ethers such as diethyl ether and ethylene glycol dimethyl ether; hexane, octane, decane, dodecane, etc. And the like. Among these, it is preferable to use alcohols as the organic solvent because a particle aggregation structure is easily formed by static polymerization and pores continuous in three dimensions are increased. Moreover, even if it is a good solvent of polystyrene like benzene 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.

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

  Step II is a step in which a large number of particulate templates are present in a liquid mixture containing a vinyl monomer, a crosslinking agent, an organic solvent, and a polymerization initiator in the container, and polymerization is performed under standing. As a method of introducing the raw material into the container, a liquid mixture may be introduced into the container, and then a large number of particulate templates may be placed (first method), and a large number of particulate templates are placed in the container, Thereafter, a liquid mixture may be introduced (second method). In the first method, after a large number of particulate templates are put, it is preferable that the particulate templates are slightly pressed by a method such as a drop lid in that close-packing or close filling is possible. In addition, in the second method, when introducing the liquid mixture, degassing can be performed so that the liquid mixture can be sufficiently distributed in the gaps between a large number of particulate templates. It is preferable at the point which can form a continuous macrovoid structure uniformly.

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

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

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

  In step II, filling the mixture of containers into a large number of particulate templates can be done in such a way that the respective particulate templates are in contact with each other, in particular close-packing or close-packing, in order to form suitable openings. Close filling is preferred. Even if the particulate template is filled such that the contact with each other is a point contact, the polymer material portion contracts during the polymerization, so that an appropriate opening can be formed. In order to form an opening having a radius close to 0.1 mm, it is possible to obtain an opening having a small and uniform particle diameter, and to form an opening having a radius close to 25 mm. The particle diameter is large and can be obtained by close packing.

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

  If the polymerization conditions in step II are such that the polymerization of the vinyl monomer dissolved in the organic solvent proceeds faster, organic polymer particles with a radius of 0.5 μm settle and aggregate to form a three-dimensional continuous skeleton. be able to. The conditions under which the polymerization of the vinyl monomer proceeds rapidly vary depending on the vinyl monomer, the crosslinking agent, the polymerization initiator, the polymerization temperature, etc., but cannot be determined unconditionally, but increase the crosslinking agent, increase the monomer concentration, increase the temperature, etc. is there. In consideration of such polymerization conditions, the polymerization conditions for aggregating organic polymer particles having a radius of 0.5 to 25 μm may be appropriately determined. In order to form three-dimensionally continuous pores having a pore radius of 10 to 50 μm between the skeletons, the crosslinking agent is 1 to 5 mol% with respect to the total amount of the vinyl monomer and the crosslinking agent. Good. Moreover, in order to make the total pore volume of the porous body 1 to 5 ml / g, it varies depending on the vinyl monomer, the crosslinking agent, the polymerization initiator, the polymerization temperature, etc., but cannot be determined unconditionally. What is necessary is just to superpose | polymerize on the conditions that the usage-amount of the organic solvent with respect to the total usage-amount of an agent is 30-80%, Preferably it is 40-70%.

  Step III is a step of removing the particulate template from the polymer. That is, after the polymerization is completed, the contents are taken out from the container, and the particulate template is removed. Then, for the purpose of removing unreacted vinyl monomer and organic solvent, a monolithic organic porous body is obtained by extraction with a solvent such as acetone. .

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

  Next, the manufacturing method of the monolithic organic porous ion exchanger of this invention is demonstrated. In the monolithic organic porous ion exchanger, after the monolithic organic porous body obtained by the above method was produced, ion exchange groups were uniformly introduced into the skeleton surface and inside the skeleton of the monolithic organic porous body. The ion exchange capacity per volume in a water-wet state is 0.01 mg equivalent / ml or more, preferably 0.05 to 5.0 mg equivalent / ml. Thus, the method of manufacturing a monolithic organic porous body in advance and then introducing an ion exchange group is preferable in that the porous structure of the monolithic organic porous ion exchanger can be strictly controlled.

  There is no restriction | limiting in particular as a method to introduce | transduce an ion exchange group into said monolithic organic porous body, 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 monolithic organic porous material is a styrene-divinylbenzene copolymer or the like, a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid; Introducing radical initiator groups and chain transfer groups on the skeleton surface and inside the skeleton, and graft polymerizing sodium styrene sulfonate or acrylamide-2-methylpropane sulfonic acid; similarly graft polymerization of glycidyl methacrylate followed by functional group conversion And a method for introducing a sulfonic acid group. As a method for introducing a quaternary ammonium group, if the monolithic organic porous material is a styrene-divinylbenzene copolymer or the like, after introducing a chloromethyl group with chloromethyl methyl ether or the like, it reacts with a tertiary amine. A method of producing a monolithic organic porous material by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine; a radical initiating group or chain transfer on the skeleton surface and inside the skeleton of the monolithic organic porous material A method of grafting N, N, N-trimethylammonium ethyl acrylate or N, N, N-trimethylammonium propylacrylamide by introducing a group; similarly, glycidyl methacrylate is graft-polymerized, and then quaternary ammonium group is converted by functional group conversion. The method etc. which introduce | transduce are mentioned. Examples of the method for introducing betaine include a method in which a tertiary amine is introduced into a monolithic organic porous material by the above-described method and then reacted 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. -A monolithic organic porous material is produced by introducing a chloromethyl group into the divinylbenzene copolymer using chloromethyl methyl ether or the like and then reacting with a tertiary amine or copolymerizing chloromethylstyrene and divinylbenzene. A method of reacting with a secondary amine 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 ion exchange capacity can be adjusted as appropriate by selecting the porous material and the reaction reagent. For example, when producing a porous body having a relatively low cation exchange capacity of 0.01 mg equivalent / g, a porous material mainly composed of divinylbenzene having a low reactivity with a sulfonation reagent such as concentrated sulfuric acid or chlorosulfonic acid. This can be achieved by sulfonating the mass. In addition, when introducing a cation exchange group by a graft reaction, the cation exchange capacity can be lowered by suppressing the introduction amount of radical initiation groups and chain transfer groups introduced into the porous body. On the other hand, when it is desired to increase the cation exchange capacity, a porous material mainly composed of styrene having a high reactivity with the sulfonation reagent is sulfonated. Further, when a graft reaction is used, the amount of radical initiation group or chain transfer group introduced into the porous body may be increased. In addition, in the case of anion exchange capacity or amphoteric ion exchange capacity, the same method as in the case of the cation exchange capacity can be used.

  The chemical filter of the present invention is provided with the above monolithic porous body or the like as an adsorption layer, and further, an adsorption layer using a combination of an adsorption layer using an already known ion exchange resin or ion exchange fiber and the above monolith as an adsorption layer. As long as the filter is provided, the configuration of the filter is not particularly limited, but is usually configured by an adsorption layer and a support frame (casing) that supports the adsorption layer. The support frame supports the adsorbing layer and has a function of managing joining with existing equipment (installation location). The gas distribution portion of the support member is made of a material such as stainless steel, aluminum, or plastic that is not degassed. The shape of the adsorbing layer is not particularly limited, and examples thereof include a block shape having a predetermined thickness, a laminated shape in which a plurality of thin plates are stacked, and a packed structure in which a large number of regular or irregular shaped particles are filled. In addition, when there is a possibility that trace amounts of gaseous organic pollutants may be generated from the adsorption layer, or when the concentration of organic gaseous pollutants in the gas to be treated is high, a physical adsorption layer is provided downstream of the adsorption layer. It is preferable that the remaining gaseous organic pollutant that could not be removed by the upstream adsorption layer in the downstream physical adsorption layer can be reliably removed.

The specific surface area of the chemical filter of the present invention is 1 to ²⁰ m ² / g, preferably ² to 18 m ² / g. If the specific surface area is too small, it is not preferable because the processing ability decreases, and if it is too large, the strength of the monolithic porous body or the like is significantly decreased. In order to make the specific surface area within the above range, depending on the vinyl monomer, the crosslinking agent, the polymerization initiator, the polymerization temperature and the like, it cannot be determined unconditionally. Polymerization may be performed under conditions of 30 to 80%, preferably 40 to 70%. 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.

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

The use conditions of the chemical filter of the present invention can be performed under known conditions. The humidity of the use atmosphere is about 30 to 80% in relative humidity. Although it does not restrict | limit especially as a gas permeation | transmission speed | rate, For example, it is the range of 0.1-10 m / s. When a conventional granular ion exchange resin is used as the adsorption layer, the gas permeation rate is about 0.3 to 0.5 m / s, but according to the chemical filter of the present invention, the gas permeation rate is 5 to 10 m / s. Even at such a high speed, the skeleton part has a particle aggregation type structure, a large ion exchange capacity and efficient ion exchange, so that gaseous pollutants can be adsorbed and removed. Further, the concentration of contaminants in the air to be processed, according to the conventional chemical filter, the applicable range in the case of ammonia, usually 0.1-10 / ^{m 3,} the case of hydrogen chloride, typically 5-50 ng ^{/ m} 3, In the case of sulfur dioxide, it is usually 0.1 to 10 μg / m ³ , and in the case of phthalate ester, it is usually 0.1 to 5 μg / m ³ , but according to the chemical filter of the present invention, in addition to the above range, ammonia Even a trace concentration of 100 ng / m ³ or less, hydrogen chloride 5 ng / m ³ or less, sulfur dioxide 100 ng / m ³ or less, and phthalate ester 100 ng / m ³ or less can be sufficiently removed. In addition, when using the monolithic organic porous ion exchanger used as the adsorption layer, the obtained organic porous ion exchanger is used by a known regeneration method as in the case of conventional ion exchange resins. That is, the porous cation exchanger is used as an acid type by acid treatment, and the porous anion exchanger is used as an OH type 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 monolithic 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 the speed is high, the adsorption removal ability of gaseous pollutants can be maintained, and even if the amount of gaseous pollutants is extremely small, it can be removed. That is, the conventional granular ion exchange resin has a slow ion exchange inside the particles, and the entire ion exchange capacity is not used effectively. For example, in the case of a granular ion exchange resin having a particle diameter of 500 μm, assuming that the range in which the efficient adsorption is performed is 100 μm from the surface, the volume fraction of the surface layer is about 50%, and the ion exchange in the range in which the efficient adsorption is performed. The capacity is about half. On the other hand, since the organic porous ion exchanger according to the present invention has a wall thickness of 2 to 10 μm, all ion exchange groups are efficiently used.

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

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

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

  In the present invention, since a monolithic porous body or the like is used as an adsorption layer of a chemical filter, a large flow path by macrovoids and ion exchange groups introduced uniformly can efficiently cover even a small fan with a small static pressure. Impurities in the processing gas can be removed. Further, since the ion exchange capacity per volume and the specific surface area are very large and the ion exchange groups are uniformly introduced, the removal rate can be improved and the life can be extended.

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

(Production of monolithic organic porous material)
9.9 g of styrene, 0.3 g of divinylbenzene, 15.3 g of 1-decanol and 0.1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly. Divinylbenzene was 1.9 mol% based on the total amount of styrene and divinylbenzene (Step I).

  Next, the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture was put into a polyethylene cylindrical container, and a spherical calcium alginate hydrogel having a particle radius of about 1.5 mm. Was tightly packed, the inside of the system was sufficiently substituted with nitrogen, sealed, and polymerized at 60 ° C. for 24 hours under standing (step II).

  After completion of the polymerization, the monolithic contents were taken out and stirred in a 10% aqueous sodium hexanemetaphosphate solution for 4 hours to remove the calcium alginate hydrogel. Thereafter, Soxhlet extraction with 2-propanol was performed for 10 hours to remove unreacted monomers and 1-decanol, followed by drying under reduced pressure at 85 ° C. overnight to obtain 1.9 mol% of a crosslinking component composed of a styrene / divinibenzene copolymer. The contained monolithic organic porous material was obtained. The result of observing the internal structure of this monolithic organic porous material with SEM is shown in FIG.

  The structure of the organic porous body of Example 1 was such that the skeleton part of the continuous macrovoid structure was a particle aggregation type pore structure, and the flow paths of both structures were connected to each other. That is, in the continuous macrovoid structure, most of the macrovoids having an average radius of 1.5 mm overlap each other, and the average radius of the openings formed by the overlap of the macrovoids and the macrovoids is 0.8 mm. Further, in the particle aggregation type pore structure, crosslinked polystyrene particles having an average radius of 5 μm aggregate to form a three-dimensional continuous skeleton portion. Moreover, the average radius of the hole portion was 25 μm. The obtained porous body was a columnar shape having a weight of 8.3 g, a diameter of 73.5 mm, and a height of 30.0 mm.

  In addition, the measurement of the pore radius of the particle aggregation type pore structure of the monolithic organic porous material was performed on a particle aggregation type organic porous material prepared separately and having no continuous macrovoid structure. That is, a monolithic organic porous material was prepared in the same manner as in Example 1 except that calcium alginate hydrogel was not used. When the internal structure of the obtained organic porous material was observed by SEM, the organic porous material was aggregated with crosslinked polystyrene particles having a radius of about 5 μm to form a three-dimensionally continuous skeleton portion. Further, the pore distribution curve of the organic porous material measured by the mercury intrusion method was sharp, and the radius of the maximum value of the pore distribution curve was 25 μm. Further, the total pore volume of the particle-aggregated organic porous material was 2.4 ml / g.

(Production of monolithic organic porous cation exchanger)
To the organic porous material obtained in Example 1, 1800 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or lower, 22.3 g of chlorosulfuric acid was gradually added, and the temperature was raised to 35 ° C. For 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolithic organic porous cation exchanger. The obtained cation exchanger had a diameter of 122.0 mm and an ion exchange capacity per volume of 0.212 mg equivalent / ml in a wet state.

  In the organic porous cation exchanger in a water-wet state, the average macrovoid radius in the continuous macrovoid structure was 2.5 mm, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 1.3 mm ( (See FIG. 3). Further, the average pore radius of the particle-aggregated pore structure portion in the water wet state was estimated from the average pore radius of the organic porous body and the swelling ratio of the cation exchanger in the water wet state, and was 41 μm.

(Production of monolithic organic porous material)
A monolithic organic porous material was produced in the same manner as in Example 1 except that a calcium alginate hydrogel having a particle radius of about 2.5 mm was used instead of the calcium alginate hydrogel having a particle radius of about 1.5 mm. The result of observing the internal structure of the monolithic organic porous body with SEM is shown in FIG.

  The structure of the organic porous body of Example 2 was such that the skeleton part of the continuous macrovoid structure was a particle aggregation type pore structure, and the flow paths of both structures were connected to each other. That is, in the continuous macrovoid structure, most of the macrovoids having an average radius of 2.5 mm overlap each other, and the average radius of the openings formed by the overlap of the macrovoids and the macrovoids is 1.2 mm. Further, in the particle aggregation type pore structure, crosslinked polystyrene particles having an average radius of 5 μm aggregate to form a three-dimensional continuous skeleton portion. Moreover, the average radius of the pores was 26 μm. The obtained porous body was a columnar shape having a weight of 8.4 g, a diameter of 72.9 mm, and a height of 31.0 mm.

(Production of monolithic organic porous cation exchanger)
The monolithic organic porous material obtained in Example 2 was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic organic porous material. The obtained cation exchanger had a diameter of 122.4 mm and an ion exchange capacity per volume of 0.221 mg equivalent / ml in a wet state.

  In the organic porous cation exchanger in the water-wet state, the average macrovoid radius of the continuous macrovoid structure was 4.2 mm, and the average radius of the openings formed by the overlap of the macrovoid and the macrovoid was 2.0 mm. The average pore radius of the water-wet state particle aggregation type pore structure portion was estimated to be 44 μm from the average pore radius of the organic porous material and the swelling rate of the water-wet cation exchanger.

(Production of monolithic organic porous material)
In place of calcium alginate hydrogel having a particle radius of about 1.5 mm, agar having a particle radius of about 12.5 mm was used, and heating was performed at 80 ° C. for 4 hours in an aqueous sulfuric acid solution having a template removal condition adjusted to pH≈1. A monolithic organic porous material was produced in the same manner as in Example 1 except that stirring was used. The result of observing the internal structure of this monolithic organic porous material with SEM is shown in FIG.

  The structure of this organic porous body was such that the skeleton part of the continuous macrovoid structure was a particle aggregation type pore structure, and the flow paths of both structures were connected to each other. That is, in the continuous macrovoid structure, most of the macrovoids having an average radius of 12.5 mm overlap each other, and the average radius of the openings formed by the overlap of the macrovoids and the macrovoids is 6.3 mm. In the particle aggregation type pore structure, crosslinked polystyrene particles having a radius of about 5 μm aggregate to form a three-dimensional continuous skeleton portion. Moreover, the average radius of the hole portion was 25 μm. The obtained porous body was a cylindrical shape having a weight of 8.5 g, a diameter of 73.4 mm, and a height of 31.7 mm.

(Production of monolithic organic porous cation exchanger)
The monolithic organic porous material obtained in Example 3 was reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic organic porous material having a continuous macrovoid structure. The obtained cation exchanger had a diameter of 123.2 mm and an ion exchange capacity per volume of 0.227 mg equivalent / ml in a wet state.

  In the organic porous cation exchanger in the water-wet state, the average macrovoid radius of the continuous macrovoid structure was 19.2 mm, and the average radius of the openings formed by the overlap of the macrovoid and the macrovoid was 9.8 mm. The average pore radius of the water-wet state particle aggregated pore structure portion was estimated to be 42 μm from the average pore radius of the organic porous material and the swelling rate of the water-wet cation exchanger.

(Production of monolithic organic porous material)
A monolithic organic porous material was produced in the same manner as in Example 1 except that vinylbenzyl chloride was used instead of styrene, and 1-butanol was used instead of 1-decanol. The result of observing the internal structure of this monolithic organic porous body with SEM is shown in FIG.

  The structure of the organic porous body of Example 4 was such that the skeleton part of the continuous macrovoid structure was a particle aggregation type pore structure, and the flow paths of both structures were connected to each other. That is, in the continuous macrovoid structure, most of the macrovoids having an average radius of 1.5 mm overlap each other, and the average radius of the openings formed by the overlap of the macrovoids and the macrovoids is 0.8 mm. In the particle aggregation structure, crosslinked polyvinylbenzyl chloride particles having an average radius of 5 μm aggregated to form a three-dimensionally continuous skeleton portion. Moreover, the average radius of the pores was 30 μm. The obtained porous body was a columnar shape having a weight of 8.6 g, a diameter of 72.5 mm, and a height of 32.1 mm.

(Production of monolithic organic porous anion exchanger)
The organic porous material obtained in Example 4 was cut into a disk shape having a thickness of about 15 mm. To this was added 1500 ml of tetrahydrofuran, heated at 40 ° C. for 1 hour, then cooled to 10 ° C. or less, 140 g of a 30% trimethylamine aqueous solution was gradually added, and the temperature was raised and reacted at 40 ° C. for 24 hours. After completion of the reaction, the product was taken out and washed with methanol and pure water in this order to obtain a monolithic organic porous anion exchanger. The obtained anion exchanger had a diameter of 111.0 mm and an ion exchange capacity per volume of 0.163 mg equivalent / ml in a wet state.

  In the organic porous anion exchanger in a water-wet state, the average macrovoid radius in the continuous macrovoid structure was 2.3 mm, and the average radius of the opening formed by the overlap of the macrovoid and the macrovoid was 1.2 mm. . The average pore radius of the particle-aggregated pore structure portion in the water wet state was 46 μm as estimated from the average pore radius of the organic porous body and the swelling ratio of the anion exchanger in the water wet state.

Comparative Example 1
(Production of particle agglomerated monolithic organic porous material)
Comparative Example 1 was carried out in substantially the same manner as Example 1 except that calcium alginate hydrogel was not used. That is, 38.8 g of styrene, 1.2 g of divinylbenzene, 60 g of 1-decanol and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly. Divinylbenzene was 1.9 mol% with respect to the total amount of styrene and divinylbenzene. Next, the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture was placed in a polyethylene cylindrical container, purged three times with nitrogen, sealed, and left to stand for 60 minutes. Polymerization was carried out at 24 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone for 10 hours to remove unreacted monomers and 1-decanol, and then dried under reduced pressure at 85 ° C. overnight.

  When the internal structure of the organic porous material containing 1.9 mol% of the crosslinking component comprising the styrene / divinylbenzene copolymer thus obtained was observed by SEM, the organic porous material was a continuous macrovoid. It was found that cross-linked polystyrene particles having no structure and having a diameter of about 10 μm aggregated to form a three-dimensional continuous skeleton portion. Further, the pore distribution curve of the organic porous material measured by the mercury intrusion method was sharp, and the radius of the maximum value of the pore distribution curve was 25 μm. The total pore volume of the organic porous material was 2.4 ml / g.

(Production of particle aggregation type monolithic organic porous cation exchanger)
The organic porous material produced in Comparative Example 1 was cut into a disk shape having a thickness of about 15 mm. To this was added 1500 ml of dichloromethane, heated at 35 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 64.0 g of chlorosulfuric acid, heated to react 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 particle-aggregated monolithic porous cation exchanger. The obtained cation exchanger had a diameter of 122 mm and an ion exchange capacity per volume of 0.83 mg equivalent / ml in a wet state. When the pore diameter of the organic porous ion exchanger in the water-wet state was estimated from the pore diameter of the organic porous body and the swelling ratio of the cation exchanger in the water-wet state, it was 80 μm. The total pore volume determined by the mercury intrusion method was 2.4 ml / g.

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

Comparative Example 2
(Ion removal performance test)
Ion removal performance similar to that of Example 4 except that the particle aggregation type organic porous cation exchanger produced in Comparative Example 1 was used instead of the monolithic organic porous cation exchanger obtained in Example 1. A test was conducted. As a result, the Na ⁺ ion removal rate was 99% or more, but the pressure loss was 0.020 MPa.

(Adsorption of basic gas using monolithic organic porous cation exchanger)
The monolithic organic porous cation exchanger obtained in Example 1 was immersed in 3N hydrochloric acid for 24 hours, then sufficiently washed with pure water and dried. The obtained monolithic organic porous cation exchanger 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 filled into a cylindrical column to produce a chemical filter. did. 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 airflow differential pressure at a surface wind speed of 0.5 m / s was a very low pressure loss of 40 Pa, and the removal rate was about 96%.

Comparative Example 3
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 and defoaming mixer (EM Co., Ltd.) 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 an open-cell organic porous cation exchanger)
The open-cell organic porous cation exchanger obtained by the above method was immersed in 3N hydrochloric acid for 24 hours, washed thoroughly 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 the filter in the same manner as in Example 6, the air flow differential pressure when the surface wind speed was 0.5 m / s was a very high pressure loss of 2500 Pa, and the removal rate was about 98%. Compared with Example 6, it was comparable.

(Adsorption of acid gas using monolithic organic porous anion exchanger)
The monolithic organic porous anion exchanger produced in Example 4 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 airflow differential pressure at a surface wind speed of 0.5 m / s was a very low pressure loss of 40 Pa, and the removal rate was about 95%.

Comparative Example 4
A monolithic organic porous material was produced in the same manner as in Comparative Example 3 except that chloromethylstyrene was used instead of styrene and the amount of sorbitan monooleate was changed to 4.5 g. The organic porous material was cut to take 15.0 g, 1500 g of tetrahydrofuran was added and the mixture was heated at 60 ° C. for 30 minutes, then cooled to room temperature, and 195 g of a trimethylamine (30%) aqueous solution was gradually added. After reacting for 3 hours, the mixture was allowed to stand overnight at room temperature. After completion of the reaction, the organic porous material was taken out, washed with acetone, washed with water, and dried to obtain an organic porous anion exchanger. The ion exchange capacity of this organic porous anion exchanger is 3.7 mg equivalent / g in terms of dry porous body, and trimethylammonium groups are uniformly introduced into the organic porous body in the order of μm by SIMS. It was confirmed. Moreover, it was confirmed by SEM observation that the open-cell structure of the organic porous material was retained even after the introduction of ion exchange groups. The organic porous anion exchanger had an average mesopore diameter of 25 μm and a total pore volume of 9.8 ml / g.

  The obtained anion exchanger was subjected to a sulfur dioxide removal test in the same manner as in Example 7. As a result, the airflow differential pressure at the surface wind speed of 0.5 m / s was a very high pressure loss of 2500 Pa, and the removal rate was about 96%, which was comparable to that in Example 7.

(Production of monolithic organic porous material)
A monolithic organic porous material was produced according to Example 1 except that the amount of reagent in Step I was doubled to produce a monolithic organic porous material.

(Adsorption of organic gas using monolithic organic porous material)
The monolithic organic porous material obtained by the above method was sufficiently washed with pure water and dried. The obtained monolithic organic porous material was allowed to stand at 25 ° C. and a relative humidity of 40% for 48 hours, then cut into a disk shape having a diameter of 50 mm and a thickness of 50 mm, and filled into a cylindrical column to prepare a chemical filter. 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 airflow differential pressure at a surface wind speed of 0.5 m / s was a very low pressure loss of 40 Pa, and the removal rate was about 78%.

Comparative Example 5
An open-cell monolithic organic porous body was produced according to Comparative Example 3, 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.

  As a result of performing a toluene removal test on this filter under the same conditions as in Example 8, the aeration differential pressure at a surface wind speed of 0.5 m / s is a very high pressure loss of 2500 Pa, and the removal rate is about 80%. Compared with Example 8, it was comparable.

  The monolithic porous body or the like of the present invention has a unique structure in which the skeleton part of the continuous macrovoid structure has a particle aggregation type pore structure. From this, it can be expected that the pressure loss will be extremely low when a fluid such as water or gas is flowed, and it will be packed in filters and adsorbents; two-bed, three-column pure water production equipment and electric deionized water production equipment. It is useful as a solid acid / base catalyst, and can be applied to a wide range of application fields. In addition, the chemical filter of the present invention has a large pore volume and specific surface area, and has a high ion exchange group density. Therefore, the chemical filter has a high ability to remove gaseous contaminants. The ability to adsorb and remove gaseous contaminants can be maintained, and ultra-trace gaseous contaminants can also be removed. Therefore, not only can it be applied as a chemical filter for the existing semiconductor industry and medical clean rooms, but it is particularly useful as a chemical filter for clean rooms in the semiconductor industry, where the required cleanliness is expected to become ten times more severe in the future. .

It is a schematic diagram which shows basic skeleton structures, such as a monolithic porous body of this invention. 2 is a SEM image of the monolithic organic porous cation exchanger of Example 1. FIG. 2 is an appearance photograph of the monolithic organic porous cation exchanger of Example 1. FIG. 2 is a SEM image of the monolithic organic porous material obtained in Example 2. 3 is a SEM image of the monolithic organic porous material obtained in Example 3. 4 is a SEM image of the monolithic organic porous material obtained in Example 4.

Claims (8)

  The macrovoids that are connected to each other are organic porous bodies having a continuous macrovoid structure in which the connecting portions of the macrovoids have an opening with a radius of 0.1 to 25 mm, and the skeleton of the organic porous body is an organic polymer particle. A monolithic organic porous material having a particle-aggregated pore structure in which particles are aggregated and have three-dimensionally continuous pores.   In the particle aggregation type pore structure, organic polymer particles having a radius of 0.5 to 25 μm having a crosslinked structural unit are aggregated to form a three-dimensional continuous skeleton part, and the pore radius is 10 to 10 between the skeletons. 2. The monolithic organic porous material according to claim 1, which has a structure having three-dimensionally continuous pores of 50 μm. A liquid mixture comprising a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, and a polymerization initiator. A step of preparing;
Presenting a number of particulate templates in the liquid mixture in a container and polymerizing under standing;
And a step of removing the particulate template from the polymer. A method for producing a monolithic organic porous material, comprising:   The method for producing a monolithic organic porous material according to claim 3, wherein the particulate template is a polysaccharide hydrogel.   5. The method for producing a monolithic organic porous material according to claim 3, wherein the crosslinking agent is used in an amount of 1 to 5 mol% based on the total amount of the vinyl monomer and the crosslinking agent.   An ion exchange group is introduced into the skeleton surface and inside the skeleton of the monolithic organic porous material according to claim 1 or 2, and the ion exchange capacity per volume in a water-wet state is 0.01 mg equivalent / ml. A monolithic organic porous ion exchanger characterized by the above.   A chemical filter using the monolithic organic porous material according to claim 1 or 2 as an adsorption layer.   A chemical filter using the monolithic organic porous ion exchanger according to claim 6 as an adsorption layer.

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