JP2009035668A - Monolithic organic porous ion exchanger, method of use thereof, production method of the same, and casting mold used in production of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monolithic organic porous ion exchanger which is chemically stable, provides low pressure drop when a fluid permeates through it, and has a large ion exchange capacity, and to provide a production method of the same and a casting mold used in the production method. <P>SOLUTION: The monolithic organic porous ion exchanger is characterized in that in an organic porous body of a continuous pore structure, which has three-dimensionally continuous pores among the skeletons of a three-dimensionally continuous organic polymer and a thickness of ≥5 mm, a plurality of linear or spiral through-holes each extending in the thickness direction and having a radius of 0.05-0.30 mm are formed in a direction orthogonal to the thickness direction, and ion exchange groups are uniformly introduced. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a monolithic organic porous ion exchanger that is chemically stable, has a low pressure loss during fluid permeation, and can have a large ion exchange capacity, a method for using the same, a manufacturing method, and a mold used in the manufacturing method. .

  Japanese Patent Laid-Open No. 2003-246809 has a continuous macropore structure having macropores connected to each other and mesopores having a radius of 0.01 to 10 μm in the wall of the macropore, and the total pore volume is 1 to 50 ml / g. There is further disclosed an organic porous ion exchanger having a value obtained by dividing the half width at the main peak of the pore distribution curve by the radius of the main peak being 0.5 or less and containing an ion exchange group Yes. The organic porous ion exchanger is particularly excellent in the adsorption rate, and particularly excellent in the ability to trap trace ions in water.

  On the other hand, 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.

Such an organic porous ion exchanger is promising as a filler for analytical equipment as well as water treatment equipment. A low water resistance is desired for the adsorbent or ion exchange material incorporated in these devices. This is because by reducing the water flow resistance, the pressure resistance performance of the filling container can be set low, and a large amount of water to be treated can be treated in a short time.
JP 2003-246809 A (Claim 5) Special table hei 7-501140 (page 4, lower left column, lines 3 to 8)

  However, the organic porous ion exchanger described in Japanese Patent Application Laid-Open No. 2003-246809 has a common macropore structure in a continuous macropore structure that forms a water passage when polymerized by increasing the ratio of oil-soluble monomers in order to increase the ion exchange capacity. Since the opening is small, there is a problem that the water flow differential pressure increases. In addition, as described above, 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.

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and is monolithic organic porous ions that are chemically stable, have low pressure loss during fluid permeation, and can increase ion exchange capacity. An object of the present invention is to provide an exchanger, a manufacturing method thereof, and a mold used for the manufacturing method.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, organic porous having a continuous pore structure having a thickness of 5 mm or more having three-dimensionally continuous pores between the skeletons of three-dimensionally continuous organic polymers. A large number of linear or spiral through-holes having a radius of 0.05 to 0.25 mm extending in the thickness direction are formed in the material in a direction perpendicular to the thickness direction, and ion exchange groups are uniformly introduced. Thus, the present inventors have found that it is chemically stable, has a low pressure loss during fluid permeation, and can increase the ion exchange capacity.

  That is, the present invention provides an organic porous body having a continuous pore structure having a three-dimensionally continuous pore between three-dimensionally continuous organic polymer skeletons having a thickness of 5 mm or more and a radius 0 extending in the thickness direction. A monolithic organic porous ion exchanger in which a large number of linear or spiral through-holes of 0.05 to 0.25 mm are formed in a direction perpendicular to the thickness direction and ion-exchange groups are uniformly introduced Is to provide.

  Further, the monolithic organic porous ion exchanger is a cylindrical object, and the end surfaces are brought into contact with each other with two or more cylindrical objects, and the adjacent cylindrical objects are rotated by a predetermined angle around the axis. And a method for using a monolithic organic porous ion exchanger that is used by being stacked and filled in a container.

  The present invention also includes a step of mixing a vinyl monomer, a surfactant, water and, if necessary, a polymerization initiator and a crosslinking agent, stirring the mixture to prepare a water-in-oil emulsion, Arranging many needles in the water-in-oil emulsion so that the longitudinal direction of the needles is in the thickness direction, polymerizing under standing, removing the many needles from the polymer, and organic porous obtained The present invention provides a method for producing a monolithic organic porous body having a step of introducing an ion exchange group into a mass.

  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 comprising an agent, a step of arranging a number of needles in the liquid mixture in a container so that the longitudinal direction of the needles is in the thickness direction, and polymerizing under standing, and from the polymer The present invention provides a method for producing a monolithic organic porous ion exchanger having a step of removing a large number of needles and a step of introducing ion exchange groups into the obtained organic porous body.

  Further, the present invention is a mold used in the manufacturing method, wherein a plurality of through holes through which a needle having a radius of 0.05 to 0.25 mm passes are formed in a predetermined region of a pedestal held at a predetermined height by a leg portion. And providing a mold in which the needle formed with a stopper portion having a size that does not pass through the through hole is supported in a suspended manner through the through hole from the tip of the needle. .

  The monolithic organic porous ion exchanger of the present invention is excellent in the ability to effectively trap trace ions in water, and can increase the ion exchange capacity while reducing the water differential pressure. In addition, when the continuous pore structure is a continuous macropore structure, a large number of through holes having a specific shape are formed even if the common opening is reduced by increasing the monomer concentration ratio. Water treatment becomes possible. Further, when the continuous pore structure is a particle aggregation type pore structure, a very unique structure which has never been obtained is adopted, and the same effect as described above is obtained.

  The basic structure of the monolithic organic porous ion exchanger of the present invention (hereinafter also simply referred to as “monolith”) has a thickness having three-dimensionally continuous pores between three-dimensionally continuous organic polymer skeletons. A through-hole having a predetermined shape extending in the thickness direction is formed in a direction perpendicular to the thickness direction in a porous body having a continuous pore structure of 5 mm or more. That is, in the monolith according to the present invention, the through hole and the hole having the continuous hole structure are connected to each other, and in the through hole, a large flow path through which liquid or gas flows with a low pressure loss is formed. A flow path smaller than the through hole through which liquid or gas permeates is formed.

  The monolith of the present invention has a thickness of 5 mm or more, and is distinguished from a membrane-like porous body. If the thickness is less than 5 mm, the ion exchange capacity is extremely lowered, which is not preferable. The thickness of the organic porous ion exchanger is preferably 5 mm to 1000 mm.

  As the continuous pore structure constituting the monolith of the present invention, the continuous macropores having a radius of 0.01 to 10 μm and a total pore volume of 2 to 20 ml / g are connected to each other. Organic polymer particles having a structure (hereinafter also referred to simply as “continuous macropore structure”) or cross-linked structural units and having a radius of 0.5 to 25 μm aggregate to form a three-dimensional continuous skeleton portion, and between the skeletons Examples thereof include a particle aggregation type pore structure having three-dimensionally continuous pores having a pore radius of 10 to 50 μm (hereinafter also simply referred to as “particle aggregation type pore structure”).

  The continuous macropore structure is a structure in which the macropores connected to each other have openings having a radius of 0.01 to 10 μm, preferably 0.1 to 10 μm. That is, the continuous macropore structure usually has a structure in which a macropore having a radius of 0.2 to 250 μm and a macropore overlap each other, and this overlapping portion is an opening, and the portion has an open pore structure. In the open pore structure, when a liquid or gas is flowed, the pore structure formed by the macropore and the opening becomes a flow path. The macropores having the same radius are uniformly distributed in the continuous macropore structure, but larger pores exceeding the above numerical range may be scattered in some places.

  The number of overlapping macropores is 1-2 for one macropore, and 3-10 for many. If the radius of the opening is less than 0.01 μm, the pressure loss during liquid or gas permeation increases, which is not preferable. On the other hand, if the radius of the opening exceeds 10 μm, the density of the skeletal structure decreases, so that the ion exchange capacity per volume decreases. As a result, the adsorption characteristics and the ion exchange characteristics decrease, which is not preferable. .

  The continuous macropore structure has a total pore volume of 2 to 20 ml / g, preferably 3 to 20 ml / g. If the total pore volume is too small, the amount of water flow per unit cross-sectional area becomes small, which makes it difficult for the fluid to flow. On the other hand, if the total pore volume is too large, the proportion of the polymer in the skeleton portion decreases, which is not preferable in that the strength of the porous body is remarkably reduced and a large number of ion exchange groups cannot be introduced. The total pore volume in the continuous macropore structure can be measured by mercury porosimetry. The polymer of the skeleton part that forms the continuous macropore structure uses an organic polymer material having a crosslinked structure, and the polymer material contains 10 to 90 mol% of the crosslinked structural unit with respect to all the structural units constituting the polymer material. Is preferred. If the cross-linking structural unit is less than 10 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 90 mol%, it is difficult to introduce an ion exchange group, and the ion exchange capacity is decreased. Absent. The total pore volume in the continuous macropore structure can be generally known by obtaining the average macropore diameter by SEM.

  There are no particular limitations on the type of material constituting the continuous macropore structure. For example, styrene polymers such as polystyrene, poly (α-methylstyrene), and polyvinylbenzyl chloride; polyolefins such as polyethylene and polypropylene; polyvinyl chloride, polytetrafluoro Poly (halogenated polyolefins) such as ethylene; Nitrile polymers such as polyacrylonitrile; (Meth) acrylic polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate; Styrene-divinylbenzene copolymer, vinyl Examples thereof include benzyl chloride-divinylbenzene copolymer. The polymer may be a single monomer and a polymer obtained by polymerizing a crosslinking agent as necessary, or may be a polymer obtained by polymerizing a plurality of monomers and, if necessary, a crosslinking agent, Two or more kinds of polymers may be blended. Among these organic polymer materials, styrene-divinylbenzene copolymer and vinylbenzyl chloride-divinylbenzene copolymer are used because of their ease of ion-exchange group introduction, high mechanical strength, and high stability against acids and alkalis. A polymer is mentioned as a preferable material.

  In the particle aggregation type pore structure, 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, etc. The contact becomes insufficient, and as a result, the ion exchange characteristics deteriorate, which is not preferable. 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 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-dimensional continuous pore diameter existing between the skeletons was obtained by the mercury intrusion method for the aggregated pore structure, and the maximum pore distribution curve obtained by the mercury intrusion method was obtained. Points to the value.

  The particle aggregation type pore structure has the same total pore volume as the continuous macropore structure. Moreover, the organic polymer material of the skeleton part constituting the structure has a constitutional unit composed of a vinyl monomer and a crosslinking agent structural unit having two or more vinyl groups in the molecule, and the polymer material is a polymer. It preferably contains 1 to 5 mol%, particularly preferably 1 to 4 mol% of cross-linked structural units with respect to all the structural units constituting the material. When the number of cross-linking structural units is too small, it is not preferable because the mechanical strength is insufficient. On the other hand, when the number is too large, the diameter of pores existing three-dimensionally continuously between the skeletons becomes small, resulting in a large pressure loss. This is not preferable.

  In the present invention, the through hole is a linear or spiral hole having a radius of 0.05 to 0.30 mm, preferably 0.08 to 0.20 mm, extending in the thickness direction of the organic porous body having a continuous pore structure. Thus, a large number are formed at a predetermined pitch in a direction orthogonal to the thickness direction. If the radius of the through hole is too small, the effect of reducing the water differential pressure is hardly seen, which is not preferable. It is not preferable in that it becomes extremely long. A straight through hole is preferable in that the mold structure may be simple, the hole diameter can be easily controlled, and the needle can be easily pulled out.

  Examples of the straight through-hole include a through-hole that extends straight in the thickness direction, a through-hole that extends slightly in an inclined shape, and a slightly tapered through-hole. Note that slightly tapering is a slightly larger diameter if the liquid passing direction is the opposite direction. In the present invention, slightly tapered and slightly larger diameter are synonymous. Examples of the inclined through holes include those in which all the through holes are in the same direction, and those in which each extends in an arbitrary direction.

  The shape of the spiral through-hole is not particularly limited, but a shape close to a straight line as much as possible is preferable because it can be easily formed in the organic polymer. The spiral shape preferably has a radial length (corresponding to a radius in plan view) within 0.5 mm from the central axis of the spiral shape, and a length (P) of one pitch in the thickness direction of the spiral shape is P / Thickness (same unit) is 1 or less. The spiral shape includes a twisted shape having no regularity.

  A large number of through holes are formed in a direction orthogonal to the thickness direction, but the pitch between adjacent through holes may or may not be constant, and is determined as appropriate. The volume ratio at the time of swelling of the through holes with respect to the apparent volume of the monolithic organic porous body is usually 0.5 to 16%, preferably 1 to 8%. If the volume ratio is less than 0.5%, the effect of reducing the water differential pressure is hardly seen, which is not preferable. If the volume ratio exceeds 12%, the contact efficiency between the inner wall of the through hole and the liquid flowing through the through hole is poor. It is not preferable in that it is lowered or the number of through holes formed is increased and it is difficult to manufacture.

  The monolith of the present invention is a monolith-like organic porous material 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, but is a volume in a water-wet state. The ion exchange capacity per unit is 0.2 mg equivalent / ml or more, preferably 0.3 mg equivalent / ml or more. If the ion exchange capacity per volume in a water-wet state is less than 0.2 mg equivalent / ml, the amount of water containing ions that can be processed before breakthrough, that is, the ability to produce deionized water is reduced. It is not preferable.

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

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

  Next, the manufacturing method of the monolithic organic porous body of this invention is demonstrated. That is, the production method comprises a step IA in which a vinyl monomer, a surfactant, water and, if necessary, a polymerization initiator and a crosslinking agent are mixed, and the mixture is stirred to prepare a water-in-oil emulsion. A plurality of needles are placed in the water-in-oil emulsion in the container so that the longitudinal direction of the needles is in the thickness direction, and polymerized under standing, and the many needles are removed from the polymer III A first production method and vinyl monomer having a -A step and an IV-A step of introducing an ion exchange group into the obtained organic porous material, a crosslinking agent having at least two vinyl groups in one molecule, A step IB for preparing a liquid mixture comprising an organic solvent and a polymerization initiator that dissolves the vinyl monomer and the cross-linking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, and the needle in the liquid mixture in the container. Longitudinal direction is thickness A plurality of needles arranged so as to be oriented, a step II-B in which the polymer is allowed to stand, a step III-B in which a number of needles are removed from the polymer, and an ion exchange group on the resulting organic porous material. The 2nd manufacturing method which has IV-B process to introduce | transduce is mentioned.

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

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

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

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

  In the step IA, there is no particular limitation as a mixing method when forming a water-in-oil emulsion by mixing a vinyl monomer, a surfactant, water and, if necessary, a polymerization initiator and a crosslinking agent to form a water-in-oil emulsion, Method of mixing each component at once, oil-soluble monomer, surfactant, and oil-soluble component that is oil-soluble polymerization initiator and water-soluble component that is water and water-soluble polymerization initiator separately and uniformly dissolved Then, a method of mixing the respective components can be used. The mixing apparatus for forming the emulsion is not particularly limited, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain a 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 mixing ratio of the oil-soluble component and the water-soluble component is (oil-soluble component) / (water-soluble component) = 5/95 to 30/70, preferably 10/90 to 25/75 in weight ratio. It can be set arbitrarily. As a result, a product having a total pore volume of 2 to 20 ml / g, preferably 3 to 10 ml / g can be produced.

  The opening radius of 0.01 to 10 μm is determined by appropriately determining the amount of vinyl monomer added, the amount of surfactant added, the number of stirring revolutions and the stirring time in stirring and mixing in the step of obtaining a water-in-oil emulsion. Can be achieved. Moreover, it can also adjust by making alcohol, carboxylic acid, or a hydrocarbon coexist in the case of stirring and mixing. In the vicinity of the opening radius of 0.01 μm, by increasing the addition amount of vinyl monomer and surfactant, increasing the rotation speed of stirring, and increasing the stirring time, conversely, in the vicinity of radius of 100 μm, the surface activity is increased. This can be achieved by reducing the addition amount of the agent, lowering the rotation speed of stirring, or shortening the stirring time.

  Step II-A is a step in which a large number of needles are arranged in the water-in-oil emulsion in the container so as to extend in the thickness direction and polymerize while standing. In the step II-A, the water-in-oil emulsion may be introduced into the container, and then a large number of needles may be installed (first method). A water-in-oil emulsion may be introduced (second method). A release agent may be applied to the needle in advance in order to improve the release property between the organic polymer after completion of polymerization and the needle. Examples of the mold release agent include silicone oil and surfactant.

  Many needles used in the II-A process are present in the emulsion or polymer while maintaining their shape during standing and polymerization, and are removed from the container after polymerization to form through holes of the shape in the polymer. Is. When a large number of needles are straight needles, for example, the sword-mount mold shown in FIGS. 1 and 2 may be used. 1A is a plan view of the mold, FIG. 1B is a front view of the mold, and FIG. 2 is a view for explaining a method of supporting the needle on the base. 1 has a through hole 5 through which a straight needle 4 having a radius of 0.05 to 0.25 mm passes through a predetermined region 3 of a pedestal 2 held by a leg 1 at a predetermined height from an installation surface. Are formed, and a straight needle 4 formed with a stopper 6 having a size that does not pass through the through hole 5 at the rear end (head) 7 is supported in a suspended manner through the through hole 5 from the tip of the straight needle 4. It is a thing. In FIG. 1, the predetermined area 3 is an area having a square shape in plan view located at the center of the square plate-like object. The shape of the region is not limited to this, and is appropriately determined depending on the shape of the monolith to be manufactured and the shape of the container. Usually, the plan view is circular.

  In addition, it is preferable that the length of the straight needle 4 is slightly shorter than the length of the leg portion 1 because the suspended straight needle 4 can be supported vertically and stably on the base 2. In addition, by shortening the length of the straight needle 4, the monolith in the lower part is manufactured without a through hole, but the part is cut in a direction perpendicular to the thickness to form a through hole in the thickness direction. can do. Further, the inner diameter of the through hole 5 of the pedestal 2 is preferably such that the main body 7 of the linear needle 4 passes through without any gap in that the perpendicularity of the needle to the surface of the pedestal 2 can be maintained.

  In the step II-A, a container that accommodates the needle portion of the sword-shaped mold 10 and can be installed inside the leg portion 1 is prepared. The container is set so that a large number of needles 4 of the sword mountain-shaped mold 10 can enter, and then the water-in-oil emulsion is gently poured into the container. Alternatively, the water-in-oil emulsion may first be poured into the container, and then the sword mountain-shaped mold 10 may be installed.

  According to the sword mountain-shaped mold 10, by making the straight needle 4 detachable, cleaning becomes easy and it can be used repeatedly. Moreover, by using the straight needle 4, the control of the through hole is facilitated. In addition, even if the straight needle 4 is bent, only the bent straight needle 4 can be replaced. Further, even when a polymer compound (release agent) such as polyethylene is applied to the linear needle 4, it is easy to apply a uniform release agent. Further, by providing the stopper portion 6 at the head of the straight needle 4, it is possible to prevent the straight needle 4 from falling off the pedestal 2, and it is easy to pick and remove it.

  The base 2 is preferably excellent in chemical resistance and workability. Thereby, the deformation | transformation and deterioration of the material by the organic solvent in a superposition | polymerization and a washing | cleaning process can be prevented, and a fine hole can be opened accurately. The shape of the tip of the straight needle 4 on the side immersed in the solution or emulsion is any shape as long as it does not significantly damage the gel structure having a continuous pore structure at the contact portion between the needle and the solution or emulsion during extraction. However, for example, a flat shape, a dome shape, a mountain shape, and the like can be given.

  The sword-mount mold 10 shown in FIG. 1 can also be applied when a spiral through-hole is formed. That is, in the sword mountain-shaped mold 10, a spiral needle may be used instead of the straight needle 4. At this time, it is preferable that the through hole 5 of the pedestal 2 has a shape commensurate with the spiral shape, and the length in the radial direction in plan view should be reduced so that adjacent spiral needles do not interfere during insertion and removal. Alternatively, it is preferable to increase the interval (pitch) between adjacent needles.

  In the step II-A, 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.

  Step III-A is a step of removing a large number of needles from the polymer. That is, after the polymerization is completed, a large number of needles 4 are extracted from the sword-shaped mold 10 while maintaining the shape of the through holes in the organic polymer. The extraction of the needles 4 is performed by selecting as appropriate, such as a method of extracting needles one by one, a method of extracting parts collectively, or a method of extracting all at once. In the case of a spiral needle, it is preferable that each needle is extracted while being rotated as the center of the shaft because the shape of the through-hole formed in the polymer is not damaged. Next, the contents are taken out from the container and extracted with a solvent such as 2-propanol for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a monolithic organic porous material.

  The IV-A step is a step of introducing an ion exchange group into the obtained organic porous material. The monolithic organic porous ion exchanger obtained in this step is a monolithic organic porous body in which ion-exchange groups are uniformly introduced on the skeleton surface and inside the skeleton, and the volume per volume in a wet state of water is The ion exchange capacity is 0.2 mg equivalent / ml or more, preferably 0.3 to 5.0 mg equivalent / ml. Thus, the method of manufacturing a monolithic organic porous body in advance and then introducing an ion exchange group is preferable in that the porous structure of the monolithic organic porous ion exchanger can be strictly controlled.

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

  The ion exchange capacity can be adjusted as appropriate by selecting the porous material and the reaction reagent. For example, when producing a porous body having a cation exchange capacity of 0.2 mg equivalent / g, a porous body mainly composed of divinylbenzene having a low reactivity with a sulfonation reagent such as concentrated sulfuric acid or chlorosulfonic acid is used. This can be achieved by sulfonation. Further, when the cation exchange group is introduced by a graft reaction, the cation exchange capacity can be slightly lowered by suppressing the introduction amount of the radical initiating group or chain transfer group introduced into the porous body to be slightly low. 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.

  Next, the second manufacturing method will be described. Step IB consists of a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, an organic solvent that dissolves the vinyl monomer and crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, and polymerization initiation. It is a step of preparing a liquid mixture comprising an agent.

  The vinyl monomer used in step IB 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 step IB is a styrene monomer such as styrene or vinyl benzyl chloride.

  As the crosslinking agent used in the step IB, one having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the 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 the step IB 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. It is. Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, 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 the step IB, 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. Moreover, a release agent can be blended in the liquid mixture in order to improve the release property between the organic polymer after completion of polymerization and the needle. Examples of mold release agents include silicone oil and surfactants.

  Step II-B is a step in which a number of needles are placed in a liquid mixture containing a vinyl monomer, a cross-linking agent, an organic solvent and a polymerization initiator in a container and polymerized while standing. Since the II-B process may be read as a liquid mixture instead of the water-in-oil emulsion in the II-A process, detailed description is omitted. If the polymerization of the II-B process is performed under the condition that the polymerization of the vinyl monomer dissolved in the organic solvent proceeds quickly, the organic polymer particles having a radius of about 0.5 μm settle and aggregate to form a three-dimensional continuous skeleton. A portion can be formed. 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. Also, in order to make the total pore volume of the porous body 2 to 29 ml / g, although it varies depending on the vinyl monomer, the crosslinking agent, the polymerization initiator and the polymerization temperature and cannot be determined unconditionally, it is generally an organic solvent, a monomer, a crosslinking 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-B is a step of removing a large number of needles from the polymer. Step III-B is the same as step III-A, and the description thereof is omitted. The IV-B step is a step of introducing an ion exchange group into the obtained organic porous material. The IV-B process is the same as the IV-A process, and the description thereof is omitted.

  A method of using the monolith of the present invention will be described with reference to FIG. FIG. 3A is a diagram showing a state in which a cylindrical object is cut into three rings, FIG. 3B is a diagram showing a state in which a small cylindrical object that has been cut into a circle is rotated by a predetermined angle, respectively, and FIG. It is a top view of three small cylindrical objects of (B). In the method of use of the present invention, the monolithic organic porous ion exchanger 20 is a cylindrical object, and is cut into three small cylindrical objects 21, 22 by cutting so that the cutting direction of the cylindrical object is the radial direction. 23 is obtained. Although the through holes having a predetermined shape are omitted in the drawing, a large number of through holes are formed so as to be in the axial direction. Next, adjacent small columnar objects 21 and 22, and 22 and 23 are rotated by a predetermined angle α and (β−α), respectively, and are stacked and used in a cylindrical container. The reason why the small cylindrical objects are rotated by a predetermined angle is to avoid overlapping of the through holes through which the fluid flows. If there is an overlap between the through holes through which the fluid flows, the through holes serve as a main liquid passing path, the fluid is short-passed, and the ion exchange zone length becomes long, which is not preferable. Therefore, the predetermined angle for rotating the small cylindrical objects is preferably an angle at which there is substantially no overlap between the through holes through which the fluid flows. Since the area ratio of the through hole in the circular end surface 24 is 0.5 to 4% and the radius of the through hole is 0.05 to 0.25 mm, the rotation angle may be small. A few degrees is sufficient. By setting it as such a lamination | stacking method, ion exchange zone length can be shortened, suppressing water flow resistance low.

  In the above embodiment, the cylindrical object is cut in the radial direction to obtain three small cylindrical objects 21, 22, and 23. However, the present invention is not limited to this. For example, the cylindrical object Is cut in the radial direction to obtain two or four or more small cylindrical objects, and then the adjacent small cylindrical objects are rotated by a predetermined angle around the axis center to form a laminate A. In addition, a through hole having a thickness of 5 mm or more having a three-dimensionally continuous pore structure between the skeleton of the monolithic organic porous ion exchanger of the cylindrical shape of the present invention and a three-dimensionally continuous organic polymer. It may be a laminate B with no continuous pore structure. The continuous hole structure without through holes is manufactured without using a large number of needles in the manufacturing method of the present invention.

  In addition, two or more of the cylindrical objects are produced in separate batches without rounding, the end surfaces of the two or more obtained cylindrical objects are brought into contact with each other, and adjacent cylindrical objects are axially centered. It is good also as a laminated body D rotated by a predetermined angle. In this case, it is possible to obtain a laminate in which a short pass does not occur by using a mold having the same shape and minimizing batch differences.

  In the method of using the monolith according to the present invention, the number of stacked layers depends on the thickness of the ion exchanger and the water passage speed, but at least a stacking height of 6 cm or more is used by using two or more ion exchanges having a thickness of 5 mm or more. It is preferable to laminate. If it is 6 cm or less, the ion exchange band length inherent to the ion exchanger cannot be secured, which is not preferable. In the method of use of the present invention, by stacking one or more types of monoliths in multiple stages, effects such as enhancing the effect of removing impurity ions in water can be expected. For example, a porous cation exchanger and a porous anion exchanger can be applied to a module of a pure water production apparatus by laminating each other.

  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.

  43.1 g of styrene, 2.3 g of divinylbenzene, 1.9 g of sorbitan monooleate, 180 g of water, and 0.26 g of azobisisobutyronitrile are uniformly mixed in a 74 mm diameter polyethylene container to form a water-in-oil emulsion. Prepared (Step IA). A number of swords (needles) were immersed in the emulsion in the container using a sword mountain-shaped mold having the same structure as that shown in FIG. -A process). The sword used was silicon oil coated. The needle used had a radius of 0.1 mm and a length of 70 mm, and the tip of the needle and the bottom of the container were 2 mm apart. After the polymerization was completed, the needles were pulled out one by one from the pedestal, and finally the pedestal with legs was removed. FIG. 4 is an electron micrograph of the porous body after the needle is removed. It can be seen that the monolith shown in FIG. 4 has linear holes formed in the continuous pore structure, and the pores of the continuous pore structure and the linear holes are connected to each other to form a flow path. Subsequently, the porous body was extracted with acetone in a Soxhlet extractor and then dried under vacuum conditions for 24 hours. The bottom of 3 mm thickness was cut off to obtain an organic porous body having a through hole (III- Step A).

  Subsequently, in order to make this organic porous body into a cation exchange type, the obtained organic porous body is cut, 13.5 g is taken, 900 ml of dichloromethane is added, heated at 35 ° C. for 60 minutes, and then brought to room temperature. After cooling, 71.6 g of chlorosulfuric acid was gradually added and reacted at 35 ° C. for 24 hours (step IV-A). The obtained cation exchange type monolith had a diameter of 114 mm.

  The obtained ion exchanger has an ion exchange capacity per volume of 0.38 equivalent / ml in the water-wet state, and the common opening radius formed by the overlap of the macropore and the macropore is defined as the pore diameter of the organic porous body and the water. When estimated from the swelling ratio of the cation exchanger in a wet state, it was 8 μm. The radius of the straight through hole of the organic porous ion exchanger in the water wet state was estimated to be 0.15 mm based on the diameter of the container and the diameter of the cation exchanger in the water wet state. That is, when the needle is pulled out, a linear through hole with a radius of 0.1 mm is opened in a container with a diameter of 74 mm, and after the ion exchange group is imparted, it expands to 114 mm, so 0.1 mm × (114 mm / 74 mm) = 0. 15 mm. Moreover, the volume fraction of the linear through-hole was 6%.

  An organic porous ion exchanger was prepared in the same manner as in Example 1 except that a sword-shaped mold was not used and a straight through-hole was not formed, and the total pore volume was determined by mercury porosimetry. . That is, the total pore volume in the continuous macropore structure was 4.3 ml / g.

(Water flow test)
A PFA tube having an outer diameter of 12 mm and an inner diameter of 10 mm was filled with the organic porous cation exchanger having a length of 3 cm in the direction of water flow. The relationship between the flow rate of the exchanger during passage of pure water and the differential pressure of water was measured, and the pressure loss coefficient was determined from the slope of the straight line in FIG. The obtained pressure loss coefficient was 0.029 MPa / m · LV. In the measurement of the ion exchange zone length, the tube was filled with the organic porous cation exchanger having a length of 5 cm in the direction of water flow, and the water to be treated having a NaCl concentration of 4 mN was passed through. Further, the ion exchange zone length at a water line speed of 10 m / h and a time of 116 minutes from the start to the end of breakthrough was 23 cm.

  The ion exchange zone length is determined according to the following formula: h = C × LV × Δt / (q + 0.5 × C). In the formula, h is the ion exchange zone length, C is the ion concentration, LV is the water passage speed, Δt is the time from the start to the end of breakthrough, and q is the ion exchange capacity. In addition, it is preferable for measurement to be performed with an ion exchanger filling height that is at least twice the ion exchange zone length. However, in the present invention, since the needle length is 7 cm, the filling height is 20 cm or more. It was difficult to produce the layer, and it was necessary to estimate it with the above formula.

  The same procedure as in Example 1 was performed except that a needle having a radius of 0.15 mm was used instead of the needle having a radius of 0.1 mm, and that the volume fraction of the linear through hole was changed to 14% instead of 6%. A water flow test was conducted.

  As a result, the ion exchange capacity per volume of the obtained ion exchanger in the wet state was 0.34 mg equivalent / ml, and the radius of the common opening formed by the overlap of the macropore and the macropore was reduced. It was 8 μm when estimated from the pore diameter and the swelling ratio of the cation exchanger in a water-wet state. The radius of the straight through hole of the organic porous ion exchanger in the water wet state was estimated based on the diameter of the container and the cation exchanger in the water wet state, and was 0.23 mm. Moreover, the volume fraction of the linear through hole was 14%. Moreover, the pressure loss coefficient in the water flow test was 0.020. The ion exchange zone length at a water line speed of 10 m / h and a time of 150 minutes from the start to the end of breakthrough was 32 cm.

  The monolith obtained in Example 1 was cut (sliced) along the radial direction to obtain two small cylindrical objects having the same length. Next, the adjacent small cylinders were rotated several degrees around the axis and stacked in a container. Thereby, each through-hole became a thing which does not overlap substantially. Further, a water passage test was conducted in the same manner as in Example 1.

  As a result, the pressure loss coefficient in the water flow test was 0.030 MPa / m · LV, the water flow speed was 10 m / h, and the ion exchange zone length in the time 41 minutes from the breakthrough start to the end was 8 cm.

  A monolith obtained in Example 1 and a monolith without a through-hole were obtained in the same volume, and a two-layer laminate was obtained in the container. A monolith without a through-hole is an organic porous ion exchanger obtained by the same method as in Example 1 except that no sword-mount mold was used. The average ion exchange capacity per volume of the two ion exchangers in a wet state with water was 0.39 mg equivalent / ml, and the volume fraction of the linear through holes was 3%. Further, a water passage test was conducted in the same manner as in Example 1.

  As a result, the pressure loss coefficient in the water flow test was 0.043, the water flow rate was 10 m / h, and the ion exchange zone length in the time 35 minutes from the breakthrough start to the end was 7 cm.

Comparative Example 1
The same method as in Example 1 was performed except that the sword-mount mold was not used. Further, a water passage test was conducted in the same manner as in Example 1. The average ion exchange capacity per volume of the ion exchanger in a water wet state was 0.40 mg equivalent / ml. As a result, the pressure loss coefficient was 0.058 MPa / m · LV. The ion exchange zone length at a water passage speed of 10 m / h and a time of 22 minutes from the start to the end of breakthrough was 4 cm.

  38.8 g of styrene, 1.2 g of divinylbenzene, 60 g of 1-butanol and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II-A). Divinylbenzene was 1.9 mol% with respect to the total amount of styrene and divinylbenzene. Next, the styrene / divinylbenzene / 1-butanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture is placed in a 74 mm diameter polyethylene cylindrical container, and a large number of swords (needles) are immersed therein. After purging with nitrogen three times, the mixture was sealed and polymerized at 60 ° C. for 24 hours while standing (step II-B). The sword's needle had a radius of 0.1 mm and a length of 70 mm, and the tip of the needle and the bottom of the container were 2 mm apart. After the polymerization was completed, the needles were pulled out one by one from the pedestal, and finally the pedestal with legs was removed. When the obtained monolith was observed with an electron microscope, organic polymer particles having a substantially uniform particle size with a radius of 5 μm were aggregated to form a three-dimensionally continuous skeleton portion, and the pore radius between the skeleton was three-dimensionally with a pore radius of 40 μm. In the particle aggregation type pore structure having continuous pores, linear holes are formed, and the pores of the particle aggregation type pore structure and the linear holes are connected to each other to form a flow path. all right. Subsequently, the monolithic contents were taken out, extracted with Soxhlet for 10 hours with acetone to remove unreacted monomer and 1-butanol, and then dried under reduced pressure at 85 ° C. overnight (step III-B).

  The organic porous body produced by the above method was cut into a disk shape having a thickness of about 15 mm so that a linear through hole was obtained. To this was added 900 ml of dichloromethane, heated at 35 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 113.5 g of chlorosulfuric acid, heated up and reacted at 35 ° C. for 24 hours (step IV-B). ). 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 radius of the straight through hole was 0.14 mm, and the volume fraction of the straight through hole was 5%. The ion exchange capacity per volume of the obtained cation exchanger was 1.11 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 25 μm.

  An organic porous ion exchanger was prepared in the same manner as in Example 5 except that a sword-shaped mold was not used and a linear through hole was not formed, and the total pore volume was determined by mercury porosimetry. . That is, the total pore volume in the particle aggregation type pore structure was 2.5 ml / g.

(Water flow test)
A PFA tube having an outer diameter of 12 mm and an inner diameter of 10 mm was filled with the organic porous cation exchanger having a length of 5 cm in the direction of water flow. Water to be treated having a NaCl concentration of 4 mN was passed through this. The relationship between the flow rate of pure water passing through the exchanger and the differential pressure was measured, and the resulting pressure loss coefficient was 0.031 MPa / m · LV. In addition, the ion exchange zone length in a water passage speed of 50 m / h and a time of 85 minutes from the start to the end of breakthrough was 22 cm.

  The same procedure as in Example 5 was performed, except that a needle having a radius of 0.15 mm was used instead of the needle having a radius of 0.1 mm, and that the volume fraction of the linear through hole was changed to 12% instead of 6%. A water flow test was conducted.

  As a result, the ion exchange capacity per volume of the obtained ion exchanger in a wet state of water was 1.01 mg equivalent / ml, the total pore volume determined by the mercury intrusion method was 2.5 ml / g, and the macropore and macropore The radius of the common opening formed by the overlap was estimated from the pore diameter of the organic porous material and the swelling ratio of the cation exchanger in a wet state of water, and found to be 9 μm. Moreover, the pressure loss coefficient in the water flow test was 0.025 MPa / m · LV. The ion exchange zone length was 30 cm at a water passage speed of 50 m / h and a time of 120 minutes from the start to the end of breakthrough.

  The monolith obtained in Example 5 was cut (sliced) along the radial direction to obtain two small cylindrical objects having the same length. Next, the adjacent small cylinders were rotated several degrees around the axis and stacked in a container. Thereby, each through-hole became a thing which does not overlap substantially. Further, a water passage test was conducted in the same manner as in Example 1.

  As a result, the pressure loss coefficient in the water flow test was 0.034 MPa / m · LV, the water flow speed was 50 m / h, and the ion exchange zone length in the time 15 minutes from the breakthrough start to the end was 4 cm.

  A monolith obtained in Example 5 and a monolith without a through-hole were obtained in the same volume, and a two-layer laminate was obtained in the container. The monolith without a through-hole is an organic porous ion exchanger obtained by the same method as in Example 5 except that no sword-mount mold was used. The average ion exchange capacity per volume of the two ion exchangers in a wet state with water was 1.18 mg equivalent / ml, and the volume fraction of the linear through-holes was 1.5%. Further, a water passage test was conducted in the same manner as in Example 1.

  As a result, the pressure loss coefficient in the water flow test was 0.051 MPa / m · LV, the water flow rate was 50 m / h, and the length of the ion exchange zone in the time 12 minutes from the breakthrough start to the end was 3 cm.

Comparative Example 2
The same method as in Example 5 was performed except that the sword-mount mold was not used. Further, a water flow test was conducted in the same manner as in Example 5. The average ion exchange capacity per volume of the ion exchanger in a water wet state was 1.15 mg equivalent / ml. As a result, the pressure loss coefficient was 0.060 MPa / m · LV. The length of the ion exchange zone at a water passage speed of 50 m / h and a time of 6 minutes from the start to the end of breakthrough was 1.5 cm.

  The monolith of the present invention is a unique structure in which a large number of through holes are uniformly mixed in a continuous pore structure. In addition, the continuous pore structure increases the ratio of the organic polymer portion, so that the ion exchange capacity can be increased and the pressure loss can be lowered when a fluid such as water or gas is allowed to flow. It is useful as an ion exchanger or a solid acid / base catalyst used by being filled in a pure water production apparatus or an electric deionized water production apparatus, and can be applied to a wide range of application fields.

(A) is a plan view of the sword mountain mold, (B) is a front view of the sword mountain mold. These are the figures explaining the support method of the needle | hook to a base. It is a figure explaining the usage method of the monolith of this invention, (A) is a figure which shows the state which cut the circular object into three, (B) is a predetermined angle each about the small cylindrical object made into the circular cut about an axis center, respectively The figure which shows the state which rotated, (C) is a top view of three small cylindrical objects of (B). It is an electron micrograph of the cut surface of the monolith of this invention. It is a figure which shows the relationship between the linear flow velocity of Example 1 and Comparative Example 1, and water flow differential pressure | voltage.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Leg part 2 Base 3 Predetermined area | region in which a needle is installed 4 Needle 5 The through-hole through which a needle passes 6 Stopper part 7 Needle main-body part 10 Sword mountain mold 20 Cylindrical thing (monolith)
21, 22, 23 Small cylindrical object

Claims (9)

  An organic porous body having a continuous pore structure having a thickness of 5 mm or more having a three-dimensionally continuous pore between three-dimensionally continuous organic polymer skeletons, and a radius of 0.05 to 0.30 mm extending in the thickness direction A monolithic organic porous ion exchanger characterized in that a large number of linear or spiral through-holes are formed in a direction perpendicular to the thickness direction, and ion-exchange groups are uniformly introduced.   2. The monolithic organic porous ion exchanger according to claim 1, wherein a volume ratio of the through holes to an apparent volume of the monolithic organic porous body is 0.5 to 16%.   The continuous pore structure is a continuous macropore structure in which the macropores connected to each other have an opening having a radius of 0.01 to 10 μm and a total pore volume of 2 to 20 ml / g. The monolithic organic porous ion exchanger according to claim 1 or 2.   In the continuous pore structure, organic polymer particles having a radius of 0.5 to 25 μm having a crosslinked structural unit aggregate to form a three-dimensionally continuous skeleton portion, and the pore radius is 10 to 50 μm between the skeletons. 3. The monolithic organic porous ion exchanger according to claim 1, wherein the monolithic organic porous ion exchanger has a particle aggregation type pore structure having three-dimensionally continuous pores.   5. The monolithic organic porous material according to claim 4, wherein the skeleton portion of the particle aggregation type pore structure is 1 to 5 mol% in the total structural units constituting the organic polymer particles. Quality ion exchanger.   The monolithic organic porous ion exchanger according to any one of claims 1 to 5 is a cylindrical object, and the end surfaces are brought into contact with each other with two or more cylindrical objects, and adjacent cylindrical objects. A method of using a monolithic organic porous ion exchanger, characterized in that they are rotated by a predetermined angle around each other, stacked, filled into a container, and used. Mixing a vinyl monomer, a surfactant, water and, if necessary, a polymerization initiator and a crosslinking agent, stirring the mixture to prepare a water-in-oil emulsion,
Placing a large number of needles in the water-in-oil emulsion in the container so that the longitudinal direction of the needles is the thickness direction, and polymerizing under standing;
Removing the multiple needles from the polymer;
And a step of introducing an ion exchange group into the obtained organic porous body. A method for producing a monolithic organic porous ion exchanger. 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;
Placing a large number of needles in the liquid mixture in the container so that the longitudinal direction of the needles is in the thickness direction, and polymerizing under standing;
Removing the plurality of needles from the polymer;
And a step of introducing an ion exchange group into the obtained organic porous body. A method for producing a monolithic organic porous ion exchanger.   A mold used in the manufacturing method according to claim 7 and claim 8, wherein a plurality of through holes through which a needle having a radius of 0.05 to 0.25 mm passes are provided in a predetermined region of the base held at a predetermined height by the legs. A mold formed by supporting the needle formed at the rear end with a stopper portion having a size that does not pass through the through hole from the tip of the needle through the through hole. .

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