TWI447150B - Monolithic organic porous material, monolithic organic porous ion exchanger, and method of producing same - Google Patents

Description

Monolith organic porous body, monolithic organic porous ion exchanger, and methods for producing the same

The present invention relates to a monolith-like organic porous body which is effective as an ion exchange body for a sorbent or a deionized water producing apparatus and the like, and has a coarse skeleton structure, and has a continuous skeleton. Monolithic organic porous ion exchanger of macroporous structure and methods for producing the same.

A method for producing an oil-soluble monomer containing no ion exchange group, a surfactant, water, and a polymerization initiator as needed to obtain a water-drop type emulsification in oil is disclosed in Japanese Laid-Open Patent Publication No. 2002-306976. The liquid was polymerized to obtain a monolithic organic porous body having a continuous macroporous structure. The organic porous material obtained by the above method or the organic porous ion exchanger to which the ion exchange group is introduced can be effectively used as an ion exchange agent for a sorbent, a color layer analysis filler, a deionized water production apparatus, or the like. body.

However, in the organic porous ion exchanger, when the total pore volume is decreased and the ion exchange capacity per unit volume in the water-wet state is increased, the mesopores which become common openings are remarkably small. Further, the total pore volume is lowered to make the common opening disappear, and due to the structural limitation, the ion exchange capacity per unit volume is lowered when the practically required lower pressure loss is desired, and the increase is increased. The disadvantage of increased pressure loss per unit volume of exchange capacity.

Similarly, in the monolithic organic porous body or the organic porous ion exchanger obtained by the above method, the area of the skeleton portion of the theoretically cross-section is unlikely to be 25% or more. The reason for this is that the monolithic organic porous system of the continuous macroporous structure belonging to the intermediate of the organic porous ion exchanger is produced by a water-drop type emulsion. In order to form a continuous macropore structure, it is necessary to make the water droplets in the water-drop type emulsion in the oil contact each other, and therefore, the volume fraction of the water droplets is limited to 75% or more. Since the monolithic organic porous system obtained by the static polymerization of the water-drop type emulsion in the oil is a form in which the emulsion structure is immobilized, the void ratio is 75% or more, and the organic porous body is cut. The aperture ratio of the profile is also 75% or more. Therefore, the area of the skeleton portion of the cut section is less than 25%, and the skeleton portion area of the cut section cannot be raised by the present manufacturing method.

On the other hand, a monolithic organic porous body or a monolithic organic porous ion exchanger having a structure other than the above-described continuous macroporous structure is disclosed in Japanese Patent Laid-Open No. Hei 7-501140, etc. A porous body of agglomerated structure. However, the continuous pores in the porous body obtained by this method are only a small value of about 2 μm at the maximum, and cannot be used in an industrial-scale deionized water producing apparatus or the like which requires a large flow rate treatment at a low pressure. Further, the porous system having the particle agglomerated structure has a low mechanical strength, and when it is cut into a desired size and filled in a column or an analysis cell, the operational property such as breakage is likely to be deteriorated.

Therefore, it is expected to develop a monolithic organic compound which is chemically stable and has high mechanical strength, and has a large ion exchange capacity per unit volume, a large continuous pore, and a low pressure loss when a fluid such as water or gas penetrates. Porous ion exchanger.

On the other hand, as the structure of the organic porous body, a co-continuous structure in which a three-dimensional continuous skeleton phase and a three-dimensional continuous pore phase between the skeleton phases are formed, and two phases are entangled with each other is known. In Japanese Patent Laid-Open Publication No. 2007-154083, an affinity carrier having an average diameter of a micron size having a co-continuous shape formed by a continuous three-dimensional network of pores and an organic-rich skeleton phase is disclosed. An organic polymer gel-like affinity carrier, which is not a particle agglutination type, and an affinity carrier as a crosslinking agent, at least a difunctional or higher vinyl monomer compound, a methacrylate compound, and an acrylate compound At least one of the copolymers with the monofunctional hydrophilic monomer, and the volume ratio of the crosslinking agent to the monofunctional hydrophilic monomer in the affinity carrier is from 100 to 10:0 to 90. This affinity carrier increases the crosslink density of the backbone in order to maintain a monolithic structure. Further, this affinity carrier has a hydrophilic property which sufficiently suppresses non-specific sorption. Further, in N. Tsujioka et al., Macromolecules 2005, 38, 9901, there is disclosed a monolithic organic porous body having a co-continuous structure formed of an epoxy resin.

However, in the Japanese Patent Laid-Open Publication No. 2007-154083, the actually obtained affinity carrier is a pore having a nanometer size, so that the pressure loss when the fluid penetrates is high, and it is difficult to be filled as a low pressure loss. An ion exchanger in a deionized water production apparatus required to treat large amounts of water. Further, since the affinity carrier is hydrophilic, in order to use a sorbent as a hydrophobic substance, there is a problem that a hydrophobic treatment such as a surface is required, and a high-cost operation is required. Further, there is also a problem that the introduction of an epoxy resin by a functional group such as an ion exchange group is difficult.

Therefore, it is desired to develop a monolithic material which is chemically stable and has a high degree of continuity, a high degree of continuity, and an unbiased size, a continuous large pore, and a low pressure loss when a fluid such as water or gas penetrates. Organic porous ion exchanger. Further, in addition to the above characteristics, it has been desired to develop a monolithic organic porous ion exchanger having a large ion exchange capacity per unit volume.

On the other hand, MR type ion exchange resins are known to be in a copolymer having a large mesh structure, exhibiting a particle composite having micropores formed between macropores and agglomerates of smaller spherical gel particles. structure. However, the diameter of the particles forming the micropores in the MR type ion exchange resin is also at most 1 μm, and it has not been known that there are particles of more than 1 μm or a composite type organic monolith having protrusions on the surface.

(Patent Document 1) Japanese Patent Laid-Open No. 2002-306976 (Application No. 1 of the patent scope, paragraph number 0017)

(Patent Document 2) Japanese Patent Special Table No. 7-501140

(Patent Document 3) Japanese Patent Laid-Open Publication No. 2004-321930 (Patent Application No. 1)

(Patent Document 4) Japanese Patent Laid-Open No. 2007-154083 (Application No. 1)

Accordingly, a first object of the present invention is to solve the above problems of the prior art and to provide a sorbent which is chemically stable and has high mechanical strength, low pressure loss at the time of fluid penetration, and large sorption capacity, or It is possible to use a monolithic organic porous body having a continuous macroporous structure as a chemically stable and high mechanical strength, a low pressure loss at the time of fluid penetration, and a large ion exchange capacity per unit volume, and having continuous Monolithic organic porous ion exchanger of macroporous structure and methods for producing the same.

Further, a second object of the present invention is to provide a monolithic organic porous body which is chemically stable and which is hydrophobic, has high continuity of pores, is not biased in size, and has low pressure loss at the time of fluid penetration; In addition to the above characteristics, a monolithic organic porous ion exchanger having a large ion exchange capacity per unit volume and a method for producing the same are provided.

Further, a third object of the present invention is to solve the above problems of the prior art and to provide a high mechanical strength, a high contact efficiency with a fluid when a fluid penetrates, a low pressure loss when a fluid penetrates, and a large sorption capacity. The monolithic organic porous body of the sorbent further provides a monolithic organic porous ion exchanger having high mechanical strength, high contact efficiency with fluid when fluid is penetrated, and low pressure loss when fluid penetrates. And its manufacturing methods.

Under the circumstances, the inventors of the present invention have conducted intensive studies and found that the following superior characteristics which cannot be achieved by a conventional monolithic organic porous body or monolithic organic porous ion exchanger are completed. In the presence of a monolithic organic porous body (intermediate) having a large pore volume obtained by the method described in JP-A-2002-306976, the vinyl monomer is blended with When the crosslinking agent is subjected to static polymerization in a specific organic solvent, a coarse skeleton monolith having a large opening diameter and a skeleton having a coarser skeleton than the organic porous body of the intermediate can be obtained; if ion exchange is introduced into a monolithic block of the coarse skeleton Since the base is larger in swelling due to the coarse skeleton, the opening can be further enlarged; the monolithic block of the coarse skeleton or the monolithic ion exchanger to which the ion exchange group is introduced, not only makes the adsorption or ion exchange rapid and uniform, The absorption capacity per unit volume or the ion exchange capacity is large, and the average diameter of the opening is large, so the pressure loss is exceptionally small, and the continuous macroporous structure is maintained, so that the mechanical strength is high and the operability is superior. , Even if the gas penetration speed can be maintained sorption ability to remove the gaseous pollutants, the gaseous pollutants, even if the amount of ultrafine still be removed and the like.

In other words, the present invention (first invention) provides a monolithic organic porous body characterized in that the bubble-like macropores are superposed on each other, and the overlapping portion is a continuous macroporous opening having an average diameter of 20 to 200 μm. The structure has a thickness of 1 mm or more and a total pore volume of 0.5 to 5 ml/g, and in the SEM image of the cut section of the continuous macroporous structure (dry body), the area of the skeleton portion indicated by the section is in the image area. ~50%.

Further, the present invention (first invention) provides a monolithic organic porous body in which bubble-like macropores are superposed on each other, and the overlapping portion is a continuous macroporous structure having an opening having an average diameter of 20 to 200 μm, and the thickness is 1mm or more, the total pore volume is 0.5~5ml/g, which is obtained by performing the following steps:

In the first step, the oil-soluble monomer, the surfactant, and the water mixture containing no ion exchange group are prepared by stirring to prepare a water-drop type emulsion, and then the water-drop type emulsion in the oil is polymerized to obtain a total pore. a monolithic organic porous intermediate having a continuous macroporous structure with a volume of 5 to 16 ml/g;

In the second step, a polymerization agent containing a vinyl monomer, having at least two vinyl groups in one molecule, and dissolving a vinyl monomer or a crosslinking agent but not dissolving the polymerization of the vinyl monomer is prepared. a mixture of an organic solvent and a polymerization initiator;

In the third step, the mixture obtained in the step II is subjected to polymerization under the condition of standing, and in the presence of the monolithic organic porous intermediate obtained in the first step, to obtain a skeleton having a larger skeleton than the organic porous intermediate. The skeleton of the skeleton is an organic porous body.

Further, the present invention (first invention) provides a monolithic organic porous ion exchanger characterized in that the bubble-like macropores overlap each other, and the overlapping portion becomes a continuous giant of an opening having an average diameter of 30 to 300 μm. The pore structure has a thickness of 1 mm or more, a total pore volume of 0.5 to 5 ml/g, and an ion exchange capacity per unit volume in a wet state of water of 0.4 mg equivalent/ml or more, and an ion exchange group is uniformly distributed in the porous ion. In the SEM image of the cross section of the continuous macroporous structure (dry body) in the exchange body, the area of the skeleton portion indicated by the cross section is 25 to 50% in the image area.

Further, the present invention (first invention) provides a method for producing a monolithic organic porous body, which is characterized in that the following steps are carried out:

In the first step, the oil-soluble monomer, the surfactant, and the water mixture containing no ion exchange group are prepared by stirring to prepare a water-drop type emulsion, and then the water-drop type emulsion in the oil is polymerized to obtain a total pore. a monolithic organic porous intermediate having a continuous macroporous structure with a volume of 5 to 16 ml/g;

In the second step, a polymerization agent containing a vinyl monomer, having at least two vinyl groups in one molecule, and dissolving a vinyl monomer or a crosslinking agent but not dissolving the polymerization of the vinyl monomer is prepared. a mixture of an organic solvent and a polymerization initiator;

In the third step, the mixture obtained in the step II is subjected to polymerization under the condition of standing, and in the presence of the monolithic organic porous intermediate obtained in the first step, to obtain a skeleton having a larger skeleton than the organic porous intermediate. The skeleton of the skeleton is an organic porous body.

Further, the present invention (first invention) provides a method for producing a monolithic organic porous ion exchanger, which is characterized in that, in addition to steps I to III in the method for producing the monolithic organic porous body, further In the IV step, the crude skeleton organic porous body obtained in the step III is introduced into the ion exchange group.

In addition, the inventors of the present invention have conducted intensive studies and found that the following superior characteristics are not achieved by a conventional monolithic organic porous ion exchanger, and the second invention is completed: if it is prescribed by Japanese Patent Laid-Open 2002 In the presence of a monolithic organic porous body (intermediate) having a large pore volume obtained by the method described in the publication No. 306976, the aromatic vinyl monomer and the crosslinking agent are allowed to stand in a specific organic solvent. By polymerization, a hydrophobic monolith formed of a three-dimensional continuous aromatic vinyl polymer skeleton and three-dimensional continuous pores between the skeleton phases and two phases entangled with each other can be obtained; The continuity of the block hole is high and its size is not biased, and the pressure loss when the fluid penetrates is low. Moreover, since the skeleton of the co-continuous structure is coarse, if the ion exchange group is introduced, the unit volume can be obtained. Monolithic organic porous ion exchanger with large ion exchange capacity; the monolithic organic porous ion exchange system has rapid and uniform ion exchange, and the length of the ion exchange band is overwhelmingly short, and further Since the sorption capacity or ion exchange capacity per unit volume is large and the continuous pores are large, the pressure loss is exceptionally small, the mechanical strength is high, and the operability is superior. Moreover, even if the gas penetrates fast, the gaseous pollutants can be maintained. The sorption and removal ability can be removed even if the gaseous pollutants are ultra-micro.

That is, the present invention (second invention) provides a monolithic organic porous body having a co-continuous structure of a skeleton and pores: the total structural unit contains a crosslinked structural unit of 0.3 to 5.0 moles. a three-dimensional continuous skeleton formed of an aromatic vinyl polymer of a molar amount of 0.8 to 40 μm; and a three-dimensional continuous pore having a diameter of 8 to 80 μm between the skeletons; a total pore volume of 0.5~ 5ml/g.

Further, the present invention (second invention) provides a monolithic organic porous body having a co-continuous structure having a skeleton and pores: 0.3 to 5.0 moles of a crosslinked structural unit in a total constituent unit. a three-dimensional continuous skeleton formed of a certain aromatic vinyl polymer and having a thickness of 0.8 to 40 μm; and a three-dimensional continuous pore having a diameter of 8 to 80 μm between the skeletons; a total pore volume of 0.5 to 5 ml /g, and by the following steps: Step I, the mixture of the oil-soluble monomer, the surfactant, and the water without the ion exchange group is prepared by stirring to prepare a water-drop type emulsion in the oil, and then The water-in-water emulsion is polymerized to obtain a monolithic organic porous intermediate having a continuous pore structure having a total pore volume of more than 16 ml/g and 30 ml/g or less; in the second step, the preparation contains an aromatic vinyl type single An organic solvent having at least two or more vinyl cross-linking agents in one molecule, and an aromatic vinyl-type monomer or a cross-linking agent, but not dissolving a polymer formed by polymerization of an aromatic vinyl-type monomer, And a mixture of polymerization initiators; The mixture obtained in the second step was allowed to stand under standing, and polymerization was carried out in the presence of the monolithic organic porous intermediate obtained in the first step.

Further, the present invention (second invention) provides a monolithic organic porous ion exchanger having a co-continuous structure having a skeleton and pores which are contained in a total constituent unit of the introduced ion exchange group. a three-dimensional continuous skeleton formed by a combination of 0.3 to 5.0 mol% of an aromatic vinyl polymer and having a thickness of 1 to 60 μm; and a three-dimensional continuous pore having a diameter of 10 to 100 μm between the skeletons; It is characterized in that the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the water wet state is 0.3 mg equivalent/ml or more, and the ion exchange group is uniformly distributed in the porous ion exchanger.

Further, the present invention (second invention) provides a method for producing a monolithic organic porous body, which comprises the steps of: step I, an oil-soluble monomer having no ion exchange group, a surfactant, and The water mixture is prepared into a water-drop type emulsion by stirring, and then the water-drop type emulsion is polymerized in the oil to obtain a monolithic structure having a continuous pore structure having a total pore volume of more than 16 ml/g and 30 ml/g or less. An organic porous intermediate; a step of preparing a crosslinking agent containing an aromatic vinyl monomer and having 0.3 to 5 mol% of a total oil-soluble monomer having at least two vinyl groups in one molecule, and dissolving An aromatic vinyl monomer or a crosslinking agent, but does not dissolve a mixture of an organic solvent of a polymer formed by polymerization of an aromatic vinyl monomer, and a polymerization initiator; and a step III, the mixture obtained in the second step is The polymerization was carried out while standing still in the presence of the monolithic organic porous intermediate obtained in the first step to obtain a co-continuous structure.

Further, the present invention (second invention) provides a method for producing a monolithic organic porous ion exchanger, which comprises the steps of: step I, an oil-soluble monomer having no ion exchange group, and interfacial activity The mixture of the agent and the water is prepared into a water-drop type emulsion by stirring, and then the water-drop type emulsion in the oil is polymerized to obtain a monolithic structure having a total pore volume of more than 16 ml/g and 30 ml/g or less. An organic porous intermediate; a step of preparing a crosslinking agent containing an aromatic vinyl monomer and having 0.3 to 5 mol% of a total oil-soluble monomer having at least two vinyl groups in one molecule, a mixture of an organic solvent that polymerizes a polymer formed by polymerization of an aromatic vinyl monomer and a polymerization initiator, in which an aromatic vinyl monomer or a crosslinking agent is dissolved; and a step III, which is obtained in the second step. The mixture is allowed to stand under the conditions of standing, and is polymerized in the presence of the monolithic organic porous intermediate obtained in the first step to obtain a co-continuous structure; and the IV step is the co-continuous structure obtained in the step III. Introduction of ion exchange groups

In addition, the inventors of the present invention have conducted intensive studies and found that the following advantageous properties are not achieved by a conventional monolithic organic porous body or a monolithic organic porous ion exchanger; In the monolith obtained by the method described in JP-A-2002-306976, ethylene is produced under specific conditions in the presence of a monolithic organic porous body (intermediate) having a large pore volume. When the monomer and the crosslinking agent are subjected to static polymerization in a specific organic solvent, a single structure having a composite structure in which a plurality of particles having a diameter of 2 to 20 μm or a protrusion is formed on the surface of the skeleton constituting the organic porous body can be produced. Further, the composite structural monolith or the composite monolithic ion exchanger into which the ion exchange group is introduced is fast and extremely uniform in adsorption or ion exchange, has small pressure loss, and maintains a continuous pore structure inside the skeleton. High mechanical strength and excellent operability. Moreover, even if the gas penetration speed is fast, the absorbing and removing ability of the gaseous pollutants can be maintained, and even if the gaseous pollutants are ultra-trace, they can be removed. .

That is, the present invention (third invention) provides a monolithic organic porous body, which is a composite structure of an organic porous body and a particle body or a protrusion: a continuous skeleton phase and a continuous pore phase. The organic porous body; a plurality of particles having a diameter of 2 to 20 μm adhered to the surface of the skeleton of the organic porous body, or a plurality of protrusions having a maximum diameter of 2 to 20 μm formed on the surface of the skeleton of the organic porous body; The thickness is 1 mm or more, the average diameter of the pores is 8 to 100 μm, and the total pore volume is 0.5 to 5 ml/g.

Further, the present invention (third invention) provides a monolithic organic porous ion exchanger which is a composite structure of an organic porous body and a particle body or a protrusion: a continuous skeleton phase and a continuous pore phase The organic porous body; a plurality of particle bodies having a diameter of 4 to 40 μm adhered to the surface of the skeleton of the organic porous body; and a plurality of protrusions having a maximum diameter of 4 to 40 μm formed on the surface of the skeleton of the organic porous body; The thickness thereof is 1 mm or more, the average diameter of the pores is 10 to 150 μm, the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the wet state of water is 0.2 mg equivalent/ml or more, and the ion exchange groups are uniformly distributed. In the composite structure.

Further, the present invention (third invention) provides a method for producing a monolithic organic porous body, which comprises the steps of: step I, wherein an oil-soluble monomer containing no ion-exchange group is contained in one molecule The first crosslinking agent having at least two vinyl groups, the surfactant, and the water mixture are prepared by stirring to prepare a water-drop type emulsion, and then the water-in-water emulsion is polymerized to obtain a total pore volume. a monolithic organic porous intermediate having a continuous macroporous structure of 5 to 30 ml/g; and a second crosslinking agent having a vinyl monomer and having at least two or more vinyl groups in one molecule, a mixture of an organic solvent that polymerizes a polymer formed by polymerization of a vinyl monomer and a polymerization initiator, although dissolving a vinyl monomer or a second crosslinking agent; and a mixture of the steps II, The polymerization is carried out in the presence of the monolithic organic porous intermediate obtained in the first step, and the monolayer organic porous body is produced in the following conditions (1) to (5). Perform step II or step III under conditions of at least one of :

(1) The polymerization temperature in the step III is a temperature lower than the 10-hour half-life of the polymerization initiator at least 5 ° C;

(2) The molar % of the second crosslinking agent used in the second step is twice or more the molar % of the first crosslinking agent used in the step I;

(3) The vinyl monomer used in the step II is a vinyl monomer having a different structure from the oil-soluble monomer used in the first step;

(4) The organic solvent used in the step II is a polyether having a molecular weight of 200 or more;

(5) The concentration of the vinyl monomer used in the step II is 30% by weight or less in the mixture of the step II.

Further, the present invention (third invention) provides a method for producing a monolithic organic porous ion exchanger, which is characterized in that the step of introducing an ion exchange group into the monolithic organic porous body obtained by the above production method is carried out. .

(effect of the invention)

In the monolith of the present invention (the first invention), since the opening diameter of the overlapping portion between the macropore and the macropore is large, the treatment of the low pressure and the large flow rate can be performed, and further, the skeleton of the continuous macroporous structure is large and Since the thickness of the wall portion constituting the skeleton is also large, the sorption capacity is also excellent. Therefore, it can be used not only in place of the synthetic sorbent used in the prior art, but also in the use of its superior sorption characteristics, and in the field of new applications such as sorption and removal of trace components which cannot be corresponding to synthetic sorbents. Moreover, the monolithic ion exchange system of the present invention has high mechanical strength, and has a large ion exchange capacity per unit volume in a wet state of water, and the common opening diameter is also extra large, so that the treated water can be subjected to low pressure and large flow rate. It is used for a long time and is suitable for being filled in a 2-bed 3-tower pure water producing device or an electric deionized water producing device.

Further, the monolithic organic porous body of the co-continuous structure of the present invention (second invention) is capable of being processed because the continuity of the three-dimensional continuous pores is high and the size thereof is not biased, and the pores are large. The water passes through the water at a low pressure and a large flow rate for a long time. Moreover, since the three-dimensional continuous skeleton is large, the sorption capacity is also superior. Therefore, it can be used not only in place of the synthetic sorbent used in the prior art, but also in the use of its superior sorption characteristics, and in the field of new applications such as sorption and removal of trace components which cannot be corresponding to synthetic sorbents.

Further, the monolithic organic porous ion exchanger of the present invention (second invention) is capable of being treated because the ion exchange capacity per unit volume in a water-wet state is large and the three-dimensional continuous pores are large. The water is water-passed for a long period of time at a low pressure and a large flow rate, and is suitably used in a 2-bed 3-tower pure water producing apparatus or an electric deionized water producing apparatus. Moreover, since the porosity is high in continuity and its size is not biased, the sorption behavior of ions is extremely uniform, the length of the ion exchange band is extremely short, and the number of theoretical segments is also high. Moreover, since the adsorption property of ultra-fine ions in ultrapure water is also excellent, it can be suitably used as a filler for color layer analysis or an ion exchanger filled in an ultrapure water production apparatus.

Moreover, according to the production method of the second aspect of the invention, the monolithic organic porous ion exchanger or the monolithic organic porous ion exchanger can be produced easily and reproducibly.

The composite monolithic porous body of the present invention (third invention) has a composite structure in which a surface of a skeleton constituting a skeleton phase of the organic porous body is covered with a plurality of particles of a specific size or a plurality of protrusions are formed, so that the fluid The fluid at the time of penetration has high contact efficiency with the monolith, the adsorption is rapid and extremely uniform, the pressure loss is small, and the continuous pore structure is maintained due to the skeleton structure, so the mechanical strength is high and the operability is superior. Therefore, it can be used not only in place of the synthetic sorbent used in the prior art, but also in the use of its superior sorption characteristics, and in the field of new applications such as sorption and removal of trace components which cannot be corresponding to synthetic sorbents.

Further, the composite monolithic porous ion exchanger of the present invention (the third invention) has the same composite structure as the above-mentioned composite monolithic porous body, and therefore has rapid ion exchange and extremely uniform, and has high mechanical strength. The treated water can be used for long-term water passage at a low pressure and a large flow rate, and can be suitably used in a 2-bed 3-tower pure water production device, an ultra-pure water production device, or an electric deionized water production device. Or it can be suitably used as a sorbent for chemical filters.

<Description of First Invention>

Hereinafter, the "invention of the object", the "invention of the manufacturing method", and the "invention of the chemical filter" of the first invention will be described in order.

In the present specification, the "monolithic organic porous body" may be simply referred to as "single block", and the "monolithic organic porous ion exchanger" may be simply referred to as "monolithic ion exchanger", and "single block" The organic porous intermediate is simply referred to as "monolithic intermediate".

(Description of a single block)

The basic structure of the monolith of the present invention is such that the bubble-like macropores overlap each other, and the overlapping portion becomes a continuous macroporous structure of a common opening (gap hole), and the average diameter of the opening is 20 to 200 μm, preferably 20 to 150 μm. It is particularly preferably 20 to 100 μm, and the pores formed by the macropores and the openings become flow paths. The more suitable structure of the continuous macropore structure is the uniform structure of the size of the macropore or the diameter of the opening, but it is not limited thereto, and in the uniform structure, the point size is relatively uniform and the pore size is large. Uniform giant hole. If the average diameter of the opening is less than 20 μm, the pressure loss due to fluid penetration becomes large, which is not preferable. If the average diameter of the opening is too large, the contact between the fluid and the monolith is insufficient, and as a result, the sorption characteristics are lowered, so good. The average diameter of the above-mentioned clearance holes means the maximum value of the pore distribution curve obtained by the mercury intrusion method. In the Japanese Patent Publication No. 2002-306976, the common opening of the monolith is 1 to 1000 μm. However, the monolith having a small pore volume of 5 ml/g or less in total pore volume has to be reduced in oil. Since the amount of water droplets in the water-drop type emulsion is small, the common opening is small, and it is impossible to manufacture a substantial average opening diameter of 20 μm or more.

The monolithic structure of the present invention has a novel structure with a large opening diameter and a large skeleton. The structure of the coarse skeleton can be confirmed by an SEM (two-dimensional electronic image of a scanning electron microscope) image in which the continuous macroporous structure (dry body) is cut. In the SEM image of the cut section of the monolith, the area of the skeleton shown by the cross section is 25 to 50%, preferably 25 to 45%, in the image area. If the area of the skeleton shown in the cross section is less than 25% in the image area, the sorption capacity per unit volume is lowered due to the fine skeleton, which is not preferable. If it exceeds 50%, the skeleton becomes too thick and the suction is lost. The uniformity of the characteristics is not good. In the monolith described in Japanese Laid-Open Patent Publication No. 2002-306976, the skeleton portion is thickened even if the mixing ratio of the oil phase portion with respect to water is increased. However, in order to secure the common opening, there is a limit to the blending ratio. The maximum area of the skeleton shown in the section cannot exceed 25% in the image area.

The condition for obtaining the SEM image may be a condition for vividly presenting the skeleton portion indicated by the cross section of the cross section, for example, a magnification of 100 to 600, and a photograph area of about 150 mm × 100 mm. The SEM observation can be performed by excluding a slice taken at an arbitrary position of an arbitrary cut section of the subjective block or an image of three or more, preferably five or more, which are different at the shooting position. The cut piece is in a dry state for supply to an electron microscope. The skeleton portion of the cut section of the SEM image will be described with reference to Figs. 1 and 7 . Further, Fig. 7 is a transfer of the skeleton portion shown by the cross section of the SEM photograph of Fig. 1. 1 and 7, the skeleton portion (component symbol 12) shown in the cross section of the present invention is shown in a cross-sectional shape, and the circular hole shown in Fig. 1 is an opening (gap hole). Also, the larger curvature or curved surface is a giant hole (component symbol 13 in Fig. 7). The area of the skeleton shown in the cross section of Fig. 7 is 28% in the rectangular photo area 11. In this way, the skeleton portion can be clearly determined.

In the SEM photograph, the method of measuring the area of the skeleton portion as shown in the cross section of the cross section is not particularly limited, and for example, the skeleton portion is subjected to a known computer processing or the like, and then automatically calculated by a computer or the like. The calculation method by manual calculation. As a manual calculation, for example, a method in which an indefinite shape is replaced with a collection of a quadrangle, a triangle, a circle, or a trapezoid, and the like is obtained by integrating the same.

Further, in the monolith of the present invention, the thickness of the wall portion constituting the skeleton of the continuous macroporous structure is about 20 to 200 μm. Wall thickness of the wall portions of the system adjacent to the difference of the two megapores, refers to the thickness of the line (line XX of 7) connecting the two centers of megapores of the cutting portion (FIG. 7 of the D _1, d ₂ ). Therefore, for example, the column portion surrounded by three or more adjacent macropores is not the wall portion of the present invention. When the thickness of the formed wall portion is less than 20 μm, the sorption capacity per unit volume is lowered, which is not preferable. When the thickness exceeds 200 μm, the uniformity of the absorbing characteristics is lost, which is not preferable. The thickness of the wall portion of the organic porous body is also the same as that of the skeleton portion of the cross-section, and is preferably at least three times of SEM observation, and is obtained by taking five or more points of the obtained image. Further, as described above, the monolith described in Japanese Laid-Open Patent Publication No. 2002-306976 is limited to the formation of the W/O type emulsion, and the maximum pore volume is 5 μm or less, and the maximum amount is 10 μm.

Further, the monolithic system of the present invention has a total pore volume of 0.5 to 5 ml/g, preferably 0.8 to 4 ml/g. If the total pore volume is too small, the pressure loss at the time of fluid penetration becomes large, which is not preferable. Further, the amount of the penetrating fluid per unit sectional area becomes small, and the treatment ability is lowered, which is not preferable. On the other hand, if the total pore volume is too large, the sorption capacity per unit volume is lowered, which is not preferable. Since the monolith of the present invention has an average diameter and a total pore volume of the opening within the above range and is a coarse skeleton, when it is used as a sorbent, the contact area with the fluid is large, and the fluid can be smoothly smoothed. It is circulated, so it can exert superior performance.

In addition, the pressure loss when water passes through a single block is the pressure loss when the water is passed through the water column at a line speed (LV) of 1 m/h for a column filled with a porous body of 1 m (hereinafter referred to as "pressure difference". The coefficient ") is preferably in the range of 0.005 to 0.1 MPa/m ‧ LV, and particularly preferably 0.005 to 0.05 MPa/m ‧ LV.

In the monolith of the present invention, the material constituting the skeleton of the continuous macroporous structure is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, and is 0.3 to 50 mol%, preferably 0.3 to 5 mol%, based on the total constituent unit of the polymer material. When the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, and if it exceeds 50 mol%, the porous body is embrittled, and the flexibility is lost, which is especially poor. In the case of an ion exchanger, it is not preferable because the amount of introduction of the ion exchange group is reduced. The kind of the polymer material is not particularly limited, and examples thereof include polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinyl chloride benzyl, polyvinylbiphenyl, and polyvinyl. An aromatic vinyl polymer such as naphthalene; a polyolefin such as polyethylene or polypropylene; a poly(halogenated polyolefin) such as polyvinyl chloride or polytetrafluoroethylene; a nitrile polymer such as polyacrylonitrile; A crosslinked polymer of a (meth)acrylic polymer such as methyl acrylate, polyglycidyl methacrylate or polyethyl acrylate. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or may be Two or more polymers are blended. Among these organic polymer materials, the ease of formation of the continuous macropore structure, the ease of introduction of the ion exchange group and the mechanical strength, and the stability of the acid/base are preferably aromatic vinyl polymerization. The cross-linking polymer of the material may, for example, be a styrene-divinylbenzene copolymer or a chlorovinylbenzyl-divinylbenzene copolymer.

The monolith of the present invention has a thickness of 1 mm or more and is different from a film-like porous body. If the thickness is less than 1 mm, the sorption capacity of each porous body is extremely lowered, which is not preferable. The thickness of the monolith is preferably from 3 mm to 1000 mm. Further, since the monolith of the present invention has a large skeleton, the mechanical strength is high.

When the monolith of the present invention is used as a sorbent, the monomer is cut into a shape that can be inserted into the column and filled as a sorbent, for example, in a cylindrical column or a square column. Further, the treated water containing a hydrophobic substance such as benzene, toluene, phenol or paraffin is passed through water, and the hydrophobic substance is efficiently adsorbed onto the sorbent.

(Description of a single ion exchanger)

Next, the monolithic ion exchanger of the present invention will be described. In the monolithic ion exchanger, the same components as those of the monolith are omitted, and the differences will be mainly described. In the monolithic ion exchange system, the bubble-like macropores overlap each other, and the overlapping portion is a continuous macropore structure having an opening (macroporous) having an average diameter of 30 to 300 μm, preferably 30 to 200 μm, and particularly preferably 35 to 150 μm. The average diameter of the openings of the monolithic ion exchangers is such that when the ion exchange groups are introduced into the monoliths, the average diameter of the openings of the monoliths is larger because the monoliths are swollen as a whole. If the average diameter of the opening is less than 30 μm, the pressure loss due to fluid penetration becomes large, and if the average diameter of the opening is too large, the contact between the fluid and the monolithic ion exchanger becomes insufficient, and as a result, ion exchange characteristics are obtained. It is not good to lower. The average diameter of the openings refers to a value calculated by multiplying the average diameter of the porous body before introduction of the ion exchange group by the swelling ratio of the porous body before and after introduction of the ion exchange group.

In the SEM image of the cross section of the continuous macroporous structure in the monolithic ion exchanger, the area of the skeleton shown by the cross section is 25 to 50%, preferably 25 to 45%, in the image area. If the area of the skeleton portion shown in the cross section is less than 25% in the image region, the ion exchange capacity per unit volume is lowered because it is a fine skeleton. If it exceeds 50%, the skeleton becomes too large and loses. The uniformity of the ion exchange characteristics is not good. The specific method and measurement method of the skeleton portion are the same as the single block.

In the monolithic ion exchanger, the thickness of the wall portion constituting the skeleton of the continuous macroporous structure is about 30 to 300 μm. When the thickness of the wall portion is less than 30 μm, the ion exchange capacity per unit volume is lowered, which is not preferable. If it exceeds 300 μm, the uniformity of the ion exchange characteristics is lost, which is not preferable. The definition and measurement method of the wall portion of the monolithic ion exchanger are the same as those of the monolith.

In addition, the total pore volume of the monolithic ion exchanger is the same as the total pore volume of the monolith. That is, even if the ion exchange group is introduced into the monolith to swell and the opening diameter is increased, the total pore volume hardly changes due to the coarse skeleton portion. If the total pore volume is less than 0.5 ml/g, the pressure loss at the time of fluid penetration becomes large, which is not preferable. Further, the amount of the penetrating fluid per unit sectional area becomes small, and the treatment ability is lowered, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml/g, the ion exchange capacity per unit volume is lowered, which is not preferable.

Moreover, the pressure loss when water passes through a single ion exchanger is the same as the pressure loss when water penetrates a monolith.

In the monolithic ion exchanger of the present invention, the ion exchange capacity per unit volume in a water-wet state has an ion exchange capacity of 0.4 mg equivalent/ml or more, preferably 0.4 to 1.8 mg equivalent/ml. In order to achieve a practically required lower pressure loss, a conventional monolithic organic porous ion exchanger having a continuous macroporous structure different from the present invention, as described in JP-A-2002-306976, When the opening diameter is increased, since the total pore volume is also increased, the ion exchange capacity per unit volume is lowered, and if the total pore volume is decreased in order to increase the exchange capacity per unit volume, The disadvantage of increased pressure loss due to the smaller opening diameter. On the other hand, the monolithic ion exchanger of the present invention can increase the opening diameter and thicken the skeleton of the continuous macroporous structure (thickening the wall portion of the skeleton), thereby suppressing the pressure loss. The ion exchange capacity per unit volume is dramatically increased. When the ion exchange capacity per unit volume is less than 0.4 mg equivalent/ml, the amount of water containing ions which can be treated to breakage, that is, the production ability of deionized water is lowered, which is not preferable. Further, the ion exchange capacity per unit volume of the monolithic ion exchanger of the present invention is not particularly limited, and is 3 to 5 mg equivalent/g in order to uniformly introduce the ion exchange group into the surface of the porous body and the inside of the skeleton. Further, the ion exchange capacity of the porous body in which the ion exchange group is introduced only to the surface cannot be determined depending on the type of the porous body or the ion exchange group, but is at most 500 μg equivalent/g.

Examples of the ion exchange group to be introduced into the monolith of the present invention include a cation exchange group such as a sulfonic acid group, a carboxylic acid group, an iminodiacetate group, a phosphoric acid group, or a phosphate group; a quaternary ammonium group and a tertiary amine; Anion exchange group of a base, a secondary amine group, a primary amine group, a polyethyleneimine group, a third fluorenyl group, a fluorenyl group, etc.; an amino phosphate group, a sulfonic acid beet group And the zwitterionic exchange group.

In the monolithic ion exchanger of the present invention, the introduced ion exchange group is not only distributed on the surface of the porous body but also uniformly distributed inside the skeleton of the porous body. The "uniform distribution of ion exchange groups" herein means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton at a level of at least μm. The distribution of the ion exchange groups can be confirmed relatively simply by using EPMA or the like. Further, if the ion exchange group is distributed not only on the surface of the monolith but also uniformly distributed inside the skeleton of the porous body, the physical properties and chemical properties of the surface and the interior can be made uniform, thereby improving the durability against swelling and shrinkage.

The monolith of the present invention is obtained by performing the above steps I to III. In the method for producing a monolith of the present invention, in the first step, a water-drop type emulsion in an oil is prepared by stirring a mixture of an oil-soluble monomer, a surfactant, and water which do not contain an ion exchange group, and then water droplets are made in the oil. The emulsion is polymerized to obtain a monolithic intermediate having a continuous pore structure of a total pore volume of 5 to 16 ml/g. The first step of obtaining a monolithic intermediate can be carried out according to the method described in JP-A-2002-306976.

(Manufacturing method of monolithic intermediate)

The oil-soluble monomer which does not contain an ion-exchange group is, for example, a monomer which does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, and has low solubility in water and lipophilicity. Preferred examples of such monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isobutylene, butadiene, and B. Glycol dimethacrylate and the like. These monomers may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining a desired mechanical strength when a large amount of ion exchange groups are introduced in the subsequent step, crosslinking property such as divinylbenzene or ethylene glycol dimethacrylate is preferably selected. The monomer is at least an oil-soluble monomer component, and the content thereof is 0.3 to 50 mol%, preferably 0.3 to 5 mol%, based on the total oil-soluble monomer.

When the surfactant is a mixture of an oil-soluble monomer having no ion-exchange group and water, a water-drop type (W/O) emulsion can be formed in the oil, and sorbitan monooleate can be used. Ester, sorbitan monolaurate, sorbitan monostearate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearate a nonionic surfactant such as a base ether or a polyoxyethylene sorbitan monooleate; an anionic surfactant such as potassium oleate, sodium dodecylbenzenesulfonate or dioctylsulfonate succinate; a cationic surfactant such as distearyl dimethyl ammonium chloride; lauryl dimethyl sweet benzene Etc. Sexual surfactants. These surfactants may be used alone or in combination of two or more. Further, the term "water droplet type emulsion" refers to an emulsion in which an oil phase is a continuous phase in which water droplets are dispersed. The amount of the surfactant to be added varies greatly depending on the type of the oil-soluble monomer and the size of the target emulsion particles (macropores), so it cannot be said in general terms, but with respect to the oil-soluble monomer and the surfactant. The total amount can be selected within a range of about 2 to 70%.

Further, in the first step, when forming a water-drop type emulsion in oil, a polymerization initiator may be used as needed. The polymerization initiator is preferably a compound which generates a radical by heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include azobisisobutyronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, and ammonium persulfate. , hydrogen peroxide - ferrous chloride, sodium persulfate - acidic sodium sulfite, thiolan and the like.

The method of mixing the oil-soluble monomer, the surfactant, the water, and the polymerization initiator which do not contain an ion-exchange group to form a water-drop type emulsion is not particularly limited, and the components may be mixed at once. a method of uniformly dissolving an oil-soluble component of an oil-soluble monomer, a surfactant, and an oil-soluble polymerization initiator, and a water-soluble component of water or a water-soluble polymerization initiator, and then mixing the components. . The mixing device for forming the emulsion is not particularly limited, and a general mixer or homogenizer, a high-pressure homogenizer, or the like can be used, and an appropriate device for obtaining the particle size of the target emulsion can be selected. Further, the mixing conditions are not particularly limited, and the number of stirring rotations or the stirring time at which the particle diameter of the target emulsion can be obtained can be arbitrarily set.

The monolithic intermediate system obtained from the I step has a continuous macropore structure. When it coexists with a polymerization system, the structure of a monolithic intermediate is used as a mold to form the porous structure which has a coarse skeleton. Further, the monolithic intermediate system has an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, and is 0.3 to 50 mol%, preferably 0.3 to 5 mol%, based on the total constituent unit of the polymer material. If the crosslinked structural unit is less than 0.3 mol%, it is not good because of insufficient mechanical strength. In particular, when the total pore volume is as large as 10 to 16 ml/g, in order to maintain the continuous macroporous structure, it is preferred to contain 2 mol% or more of a crosslinked structural unit. On the other hand, when it exceeds 50 mol%, it is unfavorable because the porous body is embrittled and loses flexibility.

The type of the polymer material as the monolithic intermediate is not particularly limited, and may be, for example, the same as the above-mentioned monolithic polymer material. Thereby, the same polymer can be formed on the skeleton of the monolithic intermediate body, and the skeleton can be made coarse to obtain a monolithic structure having a uniform skeleton structure.

The total pore volume of the monolithic intermediate is 5 to 16 ml/g, preferably 6 to 16 ml/g. When the total pore volume is too small, the total pore volume of the monolith obtained by polymerizing the vinyl monomer becomes too small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable. On the other hand, if the total pore volume is too large, the monolithic structure obtained by polymerizing the vinyl monomer is desorbed from the continuous macropore structure, which is not preferable. When the total pore volume of the monolith intermediate body is set to the above numerical range, the ratio of monomer to water can be set to about 1:5 to 1:20.

Further, the opening (gap hole) of the overlapping portion of the macropores and the macropores of the monolithic intermediate system has an average diameter of 20 to 200 μm. When the average diameter of the openings is less than 20 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable. On the other hand, when it exceeds 200 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes too large, and the contact between the fluid and the monolith or monolithic ion exchanger is insufficient, and as a result, the adsorption property or the ion exchange property is obtained. It is not good to lower. The monolithic intermediate is preferably a uniform structure in which the macropore size or the diameter of the opening is uniform, but is not limited thereto, and may be a heterogeneous macropore having a larger uniform pore size in a point structure in a uniform structure.

(manufacturing method of single block)

The second step is a method of preparing a polymer containing a vinyl monomer, having at least two vinyl groups in one molecule, dissolving the vinyl monomer or a crosslinking agent, but not dissolving a polymer formed by polymerizing the vinyl monomer. a step of a mixture of an organic solvent and a polymerization initiator. Further, the steps I and II are not in the order, and the step II can be performed after the step I, or the step I can be performed after the step II.

The vinyl type monomer used in the second step is not particularly limited as long as it contains a vinyl group which can be polymerized in the molecule, and has high solubility in an organic solvent, and is preferably selected and produced. A vinyl monomer of the same type or a similar polymer material in which the monolithic intermediates coexist in the above polymerization system. Specific examples of such a vinyl monomer include aromatic vinyl types such as styrene, α-methylstyrene, vinyltoluene, vinyl chloride benzyl, vinylbiphenyl, and vinylnaphthalene. Alpha-olefin such as ethylene, propylene, 1-butene or isobutylene; diene monomer such as butadiene, isoprene or chloropentadiene; vinyl chloride, vinyl bromide and vinylidene chloride; Halogenated olefin such as tetrafluoroethylene; nitrile monomer such as acrylonitrile or methacrylonitrile; vinyl ester such as vinyl acetate or vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 2- Ethylhexyl ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate A (meth)acrylic monomer such as an ester or a glycidyl methacrylate. These monomers may be used alone or in combination of two or more. The vinyl type monomer which is suitably used in the present invention is an aromatic vinyl type monomer such as styrene or vinylbenzyl chloride.

The amount of the vinyl monomer added is 3 to 40 times, preferably 4 to 30 times by weight, based on the monolithic intermediate which is present during the polymerization. When the amount of the vinyl monomer added is less than 3 times with respect to the porous body, the skeleton of the monolith (the thickness of the wall portion of the monolith skeleton) cannot be made thick, and the sorption capacity per unit volume or the ion exchange group. The ion exchange capacity per unit volume after introduction becomes small, which is not preferable. On the other hand, when the amount of the vinyl monomer added exceeds 40 times, the opening diameter becomes small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable.

The crosslinking agent used in the second step is suitably used in a molecule having at least two polymerizable vinyl groups and having high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylic acid. Ester and the like. These crosslinking agents may be used alone or in combination of two or more. The crosslinking agent is preferably an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl from the strength of mechanical strength and the stability to hydrolysis. The amount of the crosslinking agent used is preferably from 0.3 to 50 mol%, particularly preferably from 0.3 to 5 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. If the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, when it exceeds 50 mol%, the occurrence of embrittlement of the monolith is lost, the flexibility is lost, and the introduction amount of the ion exchange group is reduced, which is not preferable. Further, the amount of the crosslinking agent used is preferably such that it is almost the same as the crosslinking density of the monolithic intermediate which coexists in the polymerization of the vinyl monomer/crosslinking agent. If the amount of both is too large to be separated, the resulting monolith has a bias in the crosslink density distribution, and cracks are likely to occur when the ion exchange group is introduced into the reaction.

The organic solvent used in the second step is an organic solvent which dissolves a vinyl monomer or a crosslinking agent but does not dissolve a polymer formed by polymerization of a vinyl monomer, in other words, a polymer obtained by polymerizing a vinyl monomer. It is a poor solvent. Since the organic solvent differs greatly depending on the type of the vinyl monomer, it is difficult to enumerate a general specific example. For example, when the vinyl monomer is styrene, the organic solvent is methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decyl alcohol, and twelve. Alcohols such as alkanol, ethylene glycol, propylene glycol, butanediol, glycerin, etc.; diethyl ether, ethylene glycol dimethyl ether, celecoxib, methyl acesulfame, butyl cycad, poly Chain (poly)ethers such as diol, polypropylene glycol, polybutylene glycol, etc.; chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane, etc.; ethyl acetate , esters of isopropyl acetate, ceramide acetate, ethyl propionate, and the like. Again, even two A good solvent for alkane, THF or toluene-like polystyrene may be used as an organic solvent when it is used together with the above-mentioned poor solvent and used in a small amount. The amount of the organic solvent used is preferably such that the concentration of the vinyl monomer is 30 to 80% by weight. When the amount of the organic solvent used is out of the above range and the concentration of the vinyl monomer is less than 30% by weight, the polymerization rate is lowered, or the monolithic structure after polymerization is out of the range of the present invention, which is not preferable. On the other hand, if the concentration of the vinyl monomer exceeds 80% by weight, the polymerization may be uncontrolled, which is not preferable.

As the polymerization initiator, a compound which generates a radical by heat and light irradiation is suitably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). , 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-even Dimethyl bis-isobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzammonium peroxide Base, peroxidic lauryl sulfhydryl, potassium persulfate, ammonium persulfate, sulphur blue, and the like. The amount of the polymerization initiator to be used varies greatly depending on the type of the monomer, the polymerization temperature, and the like, and can be used in the range of about 0.01 to 5% based on the total amount of the vinyl monomer and the crosslinking agent.

Step III is a step of polymerizing the mixture obtained in the second step under standing and in the presence of the monolithic intermediate obtained in the first step to obtain a coarse skeleton monoblock having a skeleton larger than the skeleton of the monolith intermediate. . The monolithic intermediate used in the third step is an important function of the negative electrode in addition to the monolithic structure having the novel structure of the present invention. As disclosed in Japanese Patent Laid-Open No. Hei 7-501140, if a vinyl monomer and a crosslinking agent are allowed to stand still in a specific organic solvent in the absence of a monolithic intermediate, a particle agglomerated type can be obtained. Monolithic organic porous body. On the other hand, when a monolith intermediate having a continuous macroporous structure is present in the above polymerization system as in the present invention, the structure of the monolith after polymerization is drastically changed, and the particle aggregating structure disappears, and the above-mentioned coarse skeleton is obtained. body. The reason for this has not been explained in detail, and it is considered that in the absence of a monolithic intermediate, the crosslinked polymer produced by the polymerization is precipitated and precipitated into a particulate form to form a particle agglomerated structure, whereas in the case of a porous system in the polymerization system, In the body (intermediate), the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton portion of the porous body, and are polymerized in the porous body to obtain a monolithic monolithic block. Further, although the opening diameter is narrowed by the progress of the polymerization, since the total pore volume of the single intermediate body is large, the opening diameter of an appropriate size can be obtained even if the skeleton becomes a coarse skeleton.

The internal volume of the reaction vessel is not particularly limited as long as the monolithic intermediate is present in the reaction vessel. When the monolithic intermediate is placed in the reaction vessel, it may have a gap around the monolith in a plan view. Or any one of the individual intermediates placed in the reaction vessel without a gap. Among them, the bulk skeleton after the polymerization is not squeezed by the inner wall of the container, and is placed in the reaction container without a gap, so that the single block does not undergo strain, and the reaction raw material is not wasted and is efficient. Further, even if the internal volume of the reaction container is large, there is a gap around the monolith after polymerization, and since the vinyl monomer or the crosslinking agent is adsorbed and distributed to the monolith intermediate, the gap in the reaction container is present. Part of the particle agglutination structure is not generated.

In the third step, in the reaction vessel, the monolithic intermediate system is placed in a state of being impregnated with the mixture solution. The mixture of the mixture obtained in the step II and the monolith intermediate is preferably, as described above, the amount of the vinyl monomer added is 3 to 40 times, preferably 4 to 30 times by weight relative to the monolithic intermediate. Ways to deploy. Thereby, a monolith having a suitable opening diameter and having a large skeleton can be obtained. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the standing monolithic intermediate, and polymerization is carried out in the skeleton of the monolithic intermediate.

The polymerization conditions can be selected depending on the type of the monomer and the type of the initiator. For example, using 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzammonium peroxide, laurel peroxide When potassium persulfate or the like is used as a starter, it may be heated and polymerized at 30 to 100 ° C for 1 to 48 hours in a sealed container under an inert atmosphere. By heating polymerization, the vinyl monomer adsorbed and distributed on the monolith intermediate is polymerized in the skeleton to make the skeleton coarse. After the completion of the polymerization, the contents are taken out to remove the unreacted vinyl monomer and the organic solvent, and the mixture is extracted with a solvent such as acetone to obtain a monolithic monolith.

(Manufacturing method of monolithic ion exchanger)

Next, a method of producing the monolithic ion exchanger of the present invention will be described. The method for producing the monolithic ion exchanger is not particularly limited, and a method of introducing an ion exchange group by producing a monolith by the above method from the viewpoint of strictly controlling the porous structure of the monolithic ion exchanger obtained can be controlled. It is preferred.

The method of introducing the ion exchange group into the monolith is not particularly limited, and a known method such as polymer reaction or graft polymerization can be used. For example, as a method of introducing a sulfonic acid group, for example, when a monolith is a styrene-divinylbenzene copolymer or the like, a method of deuteration using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid is used; a method in which a radical starting group or a chain moving group is introduced into the surface of the skeleton and the inside of the skeleton, and sodium styrene sulfonate or acrylamide-2-methylpropane sulfonic acid is graft-polymerized; A method in which a propyl ester is subjected to graft polymerization, and a sulfonic acid group is converted by a functional group. In addition, as a method of introducing a quaternary ammonium group, for example, when a monolith is a styrene-divinylbenzene copolymer or the like, a chloromethyl group is introduced by chloromethyl methyl ether or the like, and then a tertiary amine is used. a method of reacting; in a monolith, uniformly introducing a radical starting group or a chain moving group into the surface of the skeleton and the inside of the skeleton to make N, N, N-trimethylammonium acrylate or N, N, N- A method of graft polymerization of trimethylammonium propyl acrylamide; a method of graft-polymerizing glycidyl methacrylate in the same manner, followed by conversion of a functional group into a quaternary ammonium group. Also, as a beet The method may be, for example, a method in which a tertiary amine is introduced into a monolith by the above method, and a monoiodoacetic acid is reacted and introduced. In these methods, from the viewpoint of introducing the ion exchange group uniformly and quantitatively, it is preferred to introduce a sulfonic acid group into the styrene-divinylbenzene copolymer using chlorosulfuric acid. The method for introducing a quaternary ammonium group is preferably a method in which a styrene-divinylbenzene copolymer is introduced into a chloromethyl group by a chloromethyl methyl ether or the like, and then reacted with a tertiary amine, or Copolymerization of chloromethylstyrene with divinylbenzene to produce a monolithic process for reaction with a tertiary amine. Further, examples of the ion-exchange group to be introduced include a cation exchange group such as a carboxylic acid group, an iminodiacetate group, a sulfonic acid group, a phosphoric acid group, or a phosphate group; a quaternary ammonium group and a tertiary amine group; Anion exchange group of a secondary amine group, a primary amine group, a polyethyleneimine group, a third fluorenyl group, a fluorenyl group or the like; an amine phosphate group, a sugar beet Sulfonic acid beet And the zwitterionic exchange group.

The monolithic ion exchange system of the present invention is greatly swollen to, for example, 1.4 to 1.9 times the coarse skeleton by introducing an ion exchange group into a monolithic block. That is, the degree of swelling is much larger than that of the introduction of the ion exchange group in the conventional monolith described in Japanese Patent Laid-Open Publication No. 2002-306976. Therefore, even if the opening diameter of the coarse skeleton is small, the opening diameter of the monolithic ion exchanger becomes larger at about the above magnification. Further, even if the opening diameter is increased due to swelling, the total pore volume does not change. Therefore, the monolithic ion exchanger of the present invention has a large opening diameter only, and has a high mechanical strength due to a large skeleton. In addition, since the skeleton is coarse, the ion exchange capacity per unit volume in the wet state of the water can be increased, and the treated water can be passed through the water at a low pressure and a water flow for a long time, and can be filled in a 2 bed 3 tower type pure. It is used in a water production device or an electric deionized water production device.

<Description of Second Invention>

Hereinafter, the "invention of the object", the "invention of the manufacturing method", and the "invention of the chemical filter" of the second invention will be described in order.

(Description of a single block)

The basic structure of the monolith having the co-continuous structure of the present invention is a three-dimensional continuous skeleton having a thickness of 0.8 to 40 μm and a three-dimensional continuous pore having a diameter of 8 to 80 μm between the skeletons. That is, the co-continuous structure is a structure 10 in which the continuous skeleton phase 1 is entangled with the continuous pore phase 2 and each of which is three-dimensionally continuous, as shown in the schematic view of FIG. This continuous pore 2 can achieve extremely uniform ion sorption behavior because the pore continuity is higher than that of the conventional continuous bubble type monolith or particle agglutination type monolith, and its size is not biased. Moreover, since the skeleton is coarse, the mechanical strength is high.

If the diameter of the three-dimensional continuous pores is less than 8 μm, the pressure loss at the time of fluid penetration becomes large, which is not preferable. If it exceeds 80 μm, the contact between the fluid and the monolith is insufficient, and as a result, the adsorption characteristics are lowered, so good. The size of the above three-dimensional continuous pores means that the pore distribution curve is determined by mercury intrusion method, and can be obtained according to the maximum value of the pore distribution curve.

In the monolith of the present invention, the skeleton of the co-continuous structure has a thickness of 0.8 to 40 μm, preferably 1 to 30 μm. When the thickness of the skeleton is less than 0.8 μm, the adsorption capacity per unit volume is lowered or the mechanical strength is lowered, which is not preferable. On the other hand, when the thickness exceeds 40 μm, the uniformity of the sorption characteristics is lost, which is not preferable. The skeleton thickness of the monolith can be calculated by performing at least three SEM observations and measuring the skeleton thickness in the obtained image.

Further, the monolithic system of the present invention has a total pore volume of 0.5 to 5 ml/g. If the total pore volume is less than 0.5 ml/g, the pressure loss at the time of fluid penetration becomes large, which is not preferable. Further, the amount of the penetrating fluid per unit sectional area becomes small, and the treatment ability is lowered, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml/g, the sorption capacity per unit volume is lowered, which is not preferable. In the monolith of the present invention, since the thickness of the rod-shaped skeleton, the diameter of the pores, and the total pore volume are within the above range, when used as a sorbent, the contact area with the fluid is large, and the fluid can be smoothed. It is circulated, so it can exert superior performance.

In addition, the pressure loss when water passes through a single block is the pressure loss when the water is passed through the water column at a line speed (LV) of 1 m/h for a column filled with a porous body of 1 m (hereinafter referred to as "pressure difference". The coefficient ") is preferably in the range of 0.005 to 0.5 MPa/m LV, particularly preferably 0.01 to 0.1 MPa/m LV.

In the monolith of the present invention, the material constituting the skeleton of the co-continuous structure is an aromatic vinyl polymerization containing 0.3 to 5 mol%, preferably 0.5 to 3.0 mol% of the crosslinked structural unit in the total constituent unit. Matter, and is hydrophobic. When the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, and if it exceeds 5 mol%, the structure of the porous body is likely to be separated from the co-continuous structure. The type of the aromatic vinyl polymer is not particularly limited, and examples thereof include polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinyl chloride benzyl, and polyvinylbiphenyl. Polyvinyl naphthalene and the like. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or may be Two or more polymers are blended. Among these organic polymer materials, the ease of formation of the co-continuous structure, the ease of introduction of the ion-exchange group and the strength of the mechanical strength, and the stability to the acid and alkali are preferably styrene-divinyl. a benzene conjugate or a chlorovinyl benzyl-divinyl benzene copolymer.

The thickness of the monolith of the present invention is the same as the thickness of the monolith of the first invention, and the description thereof is omitted. Moreover, the method of using the monolith of the second invention as a sorbent is the same as the method of using the monolith of the first invention as a sorbent, and the description thereof will be omitted.

(Description of a single ion exchanger)

Next, the monolithic ion exchanger of the present invention will be described. In the monolithic ion exchanger, the same components as those of the monolith are omitted, and the differences will be mainly described. The monolithic ion exchange system has a co-continuous structure of a skeleton and a pore: a three-dimensional continuous skeleton having a thickness of 1 to 60 μm, preferably 3 to 58 μm, introduced into the ion exchange group; and a diameter between the skeleton Three-dimensional continuous pores of 10 to 100 μm, preferably 15 to 90 μm, and particularly preferably 20 to 80 μm. The skeleton thickness and the diameter of the pores of the monolithic ion exchanger are such that when the ion exchange group is introduced into the monolith, the bulk of the monolith is swollen, and the skeleton thickness of the monolith and the diameter of the pores are larger. The continuity of the pores of the continuous pores is higher than that of the conventional continuous-bubble monolithic organic porous ion exchanger or the particle agglomerated monolithic organic porous ion exchanger, and the size thereof is not biased. A very uniform ion sorption behavior can be achieved. If the diameter of the three-dimensional continuous pores is less than 10 μm, the pressure loss at the time of fluid penetration becomes large, which is not preferable. If it exceeds 100 μm, the contact between the fluid and the organic porous ion exchanger becomes insufficient, and as a result, ion exchange characteristics are obtained. The ability to capture uneven or ultra-micro ions is poor, which is not good.

Further, when the thickness of the skeleton is less than 1 μm, the ion exchange capacity per unit volume is lowered, and the mechanical strength is lowered, which is disadvantageous. On the other hand, if the thickness of the skeleton is too large, the ion exchange property is high. The loss of uniformity and the length of the ion exchange belt become long, which is not preferable. The pore diameter of the continuous structure may be, for example, a method in which the pore diameter of the monolith before the introduction of the ion exchange group is multiplied by the swelling ratio of the monolith before and after the introduction of the ion exchange group; The SEM image is analyzed by a known method. Further, the thickness of the skeleton was observed by SEM observation of a monolith before introduction of at least three ion exchange groups, and the skeleton thickness in the obtained image was measured and multiplied by the swelling ratio of the monolith before and after the introduction of the ion exchange group. The method and the method of analyzing the SEM image by a known method. Further, the skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-sectional shape such as a circular cross-sectional shape. The thickness at this time is the average of the short diameter and the long diameter.

In the monolithic ion exchanger, if the thickness of the three-dimensional continuous rod-shaped skeleton is less than 10 μm, the ion exchange capacity per unit volume is lowered, which is not preferable, and if it exceeds 100 μm, the uniformity of ion exchange characteristics is lost. good. The definition and measurement method of the wall portion of the monolithic ion exchanger are the same as those of the monolith.

In addition, the total pore volume of the monolithic ion exchanger is the same as the total pore volume of the monolith. That is, even if the ion exchange group is introduced into the monolith to swell and the opening diameter is increased, the total pore volume hardly changes due to the coarse skeleton portion. If the total pore volume is less than 0.5 ml/g, the pressure loss at the time of fluid penetration becomes large, which is not preferable. Further, the amount of the penetrating fluid per unit sectional area becomes small, and the treatment ability is lowered, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml/g, the ion exchange capacity per unit volume is lowered, which is not preferable. If the size of the three-dimensional continuous pores and the total pore volume are in the above range, the contact with the fluid is extremely uniform and the contact area is large, and the fluid can be penetrated under a low pressure loss, so that it can function as an ion exchanger. Superior performance.

Moreover, the pressure loss when water passes through a single ion exchanger is the same as the pressure loss when water penetrates a monolith.

In the monolithic ion exchanger of the present invention, the ion exchange capacity per unit volume in a water-wet state has an ion exchange capacity of 0.3 mg equivalent/ml or more, preferably 0.4 to 1.8 mg equivalent/ml. In order to achieve a practically required lower pressure loss, a conventional monolithic organic porous ion exchanger having a continuous macroporous structure different from the present invention, as described in JP-A-2002-306976, When the opening diameter is increased, since the total pore volume is also increased, the ion exchange capacity per unit volume is lowered, and if the total pore volume is decreased in order to increase the exchange capacity per unit volume, The disadvantage of increased pressure loss due to the smaller opening diameter. On the other hand, in the monolithic ion exchanger of the present invention, since the continuity or uniformity of the three-dimensional continuous pores is high, the pressure loss does not increase even if the total pore volume is lowered. Therefore, the ion exchange capacity per unit volume can be dramatically increased under the suppression of the pressure loss. If the ion exchange capacity per unit volume is less than 0.3 mg equivalent/ml, the amount of water containing ions which can be treated to failure, that is, the production ability of deionized water is lowered, which is not preferable. Further, the ion exchange capacity per unit weight in the dry state of the monolithic ion exchanger of the present invention is not particularly limited, and is 3 to 5 mg equivalent in order to uniformly introduce the ion exchange group into the skeleton surface and the skeleton inside the porous body. /g. Further, the ion exchange capacity of the porous body in which the ion exchange group is introduced only to the surface of the skeleton cannot be determined depending on the type of the porous body or the ion exchange group, but is at most 500 μg equivalent/g.

The ion exchange group to be introduced into the monolith of the present invention is the same as the ion exchange group introduced into the first invention monolith, and the description thereof will be omitted.

In the monolithic ion exchanger of the present invention, the introduced ion exchange group is not only distributed on the surface of the porous body but also uniformly distributed inside the skeleton of the porous body. The definition of the uniform distribution is the same as the definition of the uniform distribution of the first invention.

The monolith of the present invention is obtained by performing the above steps I to III. In the method for producing a monolith of the present invention, in the first step, a water-drop type emulsion in an oil is prepared by stirring a mixture of an oil-soluble monomer, a surfactant, and water which do not contain an ion exchange group, and then water droplets are made in the oil. The emulsion was polymerized to obtain a monolithic intermediate having a continuous pore structure having a total pore volume of more than 16 ml/g and 30 ml/g or less. The first step of obtaining a monolithic intermediate can be carried out according to the method described in JP-A-2002-306976.

(Manufacturing method of monolithic intermediate)

The oil-soluble monomer which does not contain an ion-exchange group is, for example, a monomer which does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, and has low solubility in water and lipophilicity. Specific examples of such monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylvinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene; Alpha-olefin such as ethylene, propylene, 1-butene or isobutylene; diene monomer such as butadiene, isoprene or chloropentadiene; ethylene chloride, ethylene bromide and vinylidene chloride; Halogenated olefin such as tetrafluoroethylene; nitrile monomer such as acrylonitrile or methacrylonitrile; vinyl ester such as vinyl acetate or vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 2- Ethylhexyl ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate a (meth)acrylic monomer such as an ester or a glycidyl methacrylate; and among these monomers, an aromatic vinyl monomer is preferred, and examples thereof include styrene and α-methylstyrene. Vinyl toluene, vinyl benzyl chloride, divinyl benzyl, and the like. These monomers may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining a desired mechanical strength when a large amount of ion exchange groups are introduced in the subsequent step, crosslinking property such as divinylbenzene or ethylene glycol dimethacrylate is preferably selected. The monomer is at least an oil-soluble monomer component, and the content thereof is 0.3 to 5 mol%, preferably 0.3 to 3 mol%, based on the total oil-soluble monomer.

The surfactant is the same as the surfactant used in the first step of the first invention, and the description thereof is omitted.

Further, in the step I, when forming a water-drop type emulsion in oil, a polymerization initiator may be used as needed. The polymerization initiator is preferably a compound which generates a radical by heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and may, for example, be 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2 , 2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azo double Dimethyl isobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, Peroxidic lauryl sulfhydryl, potassium persulfate, ammonium persulfate, thiocyanate, hydrogen peroxide-ferrous chloride, sodium persulfate-acid sodium sulfite, and the like.

The method of mixing the oil-soluble monomer, the surfactant, the water, and the polymerization initiator which do not contain an ion exchange group to form a water-drop type emulsion is the same as the mixing method in the first step of the first invention. And the description thereof is omitted.

The monolithic intermediate system obtained in the first step has an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. The crosslinking density of the polymer material is not particularly limited, and is 0.3 to 5 mol%, preferably 0.3 to 3 mol%, based on the total constituent unit of the polymer material. If the crosslinked structural unit is less than 0.3 mol%, it is not good because of insufficient mechanical strength. On the other hand, if it exceeds 5 mol%, the structure of a monolith is easily deviated from the co-continuous structure, which is not preferable. In particular, in the case where the total pore volume is 16 to 20 ml/g, which is a small value in the present invention, since the co-continuous structure is formed, the crosslinking structural unit is preferably less than 3 moles.

The type of the polymer material of the monolithic intermediate is the same as that of the polymer material of the monolithic intermediate of the first invention, and the description thereof is omitted.

The total pore volume of the monolith intermediate is more than 16 ml/g and 30 ml/g or less, preferably 6 to 25 ml/g. That is, the monolithic intermediate system is basically a continuous macropore structure, and since the opening (gap hole) of the overlapping portion of the giant hole and the macro hole is extraordinarily large, the skeleton system constituting the monolithic structure has an infinite approximation from the two-dimensional wall surface. The structure of the rod-shaped skeleton. When it coexists with a polymerization system, the structure of a monolithic intermediate is used as a mold, and the porous body of the cocontinuous structure is formed. If the total pore volume is too small, the structure of the monolith obtained by polymerizing the vinyl monomer changes from a co-continuous structure to a continuous macroporous structure, which is not preferable. On the other hand, if the total pore volume is too large, The mechanical strength of the monolith obtained after the polymerization of the vinyl monomer is lowered, or the ion exchange capacity per unit volume is lowered, which is not preferable. When the total pore volume of the monolith intermediate is set to a specific range of the present invention, the ratio of monomer to water can be set to be about 1:20 to 1:40.

Further, the opening (gap hole) of the overlapping portion of the macropores and the macropores of the monolithic intermediate system has an average diameter of 5 to 100 μm. When the average diameter of the openings is less than 5 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable. On the other hand, when it exceeds 100 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes too large, and the contact between the fluid and the monolith or monolithic ion exchanger is insufficient, and as a result, the adsorption property or the ion exchange property is obtained. It is not good to lower. The monolithic intermediate is preferably a uniform structure in which the macropore size or the diameter of the opening is uniform, but is not limited thereto, and may be a heterogeneous macropore having a larger uniform pore size in a point structure in a uniform structure.

(manufacturing method of single block)

The second step is to prepare a crosslinking agent containing an aromatic vinyl monomer and having 0.3 to 5 mol% of the total oil-soluble monomer having at least two vinyl groups in one molecule, and dissolving the aromatic vinyl monomer or The step of crosslinking the crosslinking agent but not dissolving the mixture of the organic solvent of the polymer formed by the polymerization of the vinyl monomer and the polymerization initiator. Further, the steps I and II are not in the order, and the step II can be performed after the step I, or the step I can be performed after the step II.

The aromatic vinyl monomer used in the second step is not particularly limited as long as it contains a vinyl group which can be polymerized in the molecule and has high solubility in an organic solvent. A vinyl type monomer which produces a polymer material of the same kind or similar to the monolithic intermediate which coexists in the above polymerization system is selected. Specific examples of such a vinyl monomer include styrene, α-methylstyrene, vinyltoluene, vinyl chloride benzyl, vinylbiphenyl, and vinylnaphthalene. These monomers may be used alone or in combination of two or more. The aromatic vinyl type monomer suitable for use in the present invention is, for example, styrene, vinyl benzyl chloride or the like.

The amount of the aromatic vinyl monomer to be added is 5 to 50 times, preferably 5 to 40 times by weight based on the monolithic intermediate which is present during the polymerization. When the amount of the aromatic vinyl monomer added is less than 5 times with respect to the porous body, the formed rod-shaped skeleton cannot be made thick, and the sorption capacity per unit volume or the ion per unit volume after introduction of the ion exchange group The exchange capacity is getting smaller and it is not good. On the other hand, when the amount of the vinyl monomer added exceeds 50 times, the diameter of the continuous pores becomes small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable.

The crosslinking agent used in the second step is suitably used in those having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylic acid. Ester and the like. These crosslinking agents may be used alone or in combination of two or more. The crosslinking agent is preferably an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl from the strength of mechanical strength and the stability to hydrolysis. The amount of the crosslinking agent used is preferably 0.3 to 5 mol%, particularly preferably 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the crosslinking agent (total oil-soluble monomer). If the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it is too much, since the occurrence of embrittlement of a single block and loss of flexibility and the introduction amount of the ion exchange group are reduced, it is not preferable. Further, the amount of the crosslinking agent used is preferably such that it is almost the same as the crosslinking density of the monolithic intermediate which coexists in the polymerization of the vinyl monomer/crosslinking agent. If the amount of both is too large to be separated, the resulting monolith has a bias in the crosslink density distribution, and cracks are likely to occur when the ion exchange group is introduced into the reaction.

The organic solvent used in the second step is an organic solvent which dissolves the aromatic vinyl monomer or the crosslinking agent but does not dissolve the polymer formed by the polymerization of the aromatic vinyl monomer, in other words, the aromatic vinyl type The polymer formed by bulk polymerization is a poor solvent. Since the organic solvent is largely different depending on the type of the aromatic vinyl monomer, it is difficult to enumerate a general specific example. For example, when the aromatic vinyl monomer is styrene, the organic solvent is methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol or decyl alcohol. Alcohols such as dodecyl alcohol, propylene glycol, butylene glycol; chain (poly) ethers such as diethyl ether, butyl siatone, polyethylene glycol, polypropylene glycol, polybutylene glycol; Chain-saturated hydrocarbons such as heptane, octane, isooctane, decane, and dodecane; esters of ethyl acetate, isopropyl acetate, ceramide acetate, ethyl propionate, and the like. Again, even two A good solvent for alkane, THF or toluene-like polystyrene may be used as an organic solvent when it is used together with the above-mentioned poor solvent and used in a small amount. The amount of the organic solvent used is preferably such that the aromatic vinyl monomer concentration is 30 to 80% by weight. When the amount of the organic solvent used is out of the above range and the concentration of the aromatic vinyl monomer is less than 30% by weight, the polymerization rate is lowered, or the monolithic structure after polymerization is out of the range of the present invention, which is not preferable. On the other hand, when the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization is uncontrolled, which is not preferable.

The polymerization initiator is the same as the polymerization initiator used in the step II of the first invention, and the description thereof is omitted.

In the third step, the mixture obtained in the step II is subjected to polymerization under the condition of standing and the monolith intermediate obtained in the step I, thereby obtaining a continuous macroporous structure of the monolithic intermediate into a co-continuous structure and a coarse skeleton. The monolithic steps. The monolithic intermediate used in the third step is an important function of the negative electrode in addition to the monolithic structure having the novel structure of the present invention. As disclosed in Japanese Patent Laid-Open No. Hei 7-501140, if a vinyl monomer and a crosslinking agent are allowed to stand still in a specific organic solvent in the absence of a monolithic intermediate, a particle agglomerated type can be obtained. Monolithic organic porous body. On the other hand, when a monolith intermediate having a continuous macroporous structure is present in the polymerization system as described in the present invention, the structure of the monolith after polymerization is drastically changed, and the particle aggregation structure disappears, and the above-described co-continuous structure is obtained. monomer. The reason for this has not been explained in detail, and it is considered that in the absence of a monolithic intermediate, the crosslinked polymer produced by the polymerization is precipitated and precipitated into a particulate form to form a particle agglomerated structure, whereas in the case of a porous system in the polymerization system, In the body (intermediate), the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton portion of the porous body, and are polymerized in the porous body to form a skeleton of the monolithic structure to be formed from the two-dimensional wall surface. A monolithic organic porous body having a co-continuous structure which is a one-dimensional rod-shaped skeleton.

The internal volume of the reaction container is the same as that of the internal volume of the reaction container of the first invention, and the description thereof is omitted.

In the third step, in the reaction vessel, the monolithic intermediate system is placed in a state of being impregnated with the mixture. The mixture of the mixture obtained in the step II and the monolith intermediate is preferably, as described above, the amount of the aromatic vinyl monomer added in an amount of 5 to 50 times, preferably 5 to 40, based on the weight of the monolithic intermediate. Multiply the way. Thereby, a monolith having a co-continuous structure in which the pores of an appropriate size are three-dimensionally continuous and the coarse bones are three-dimensionally continuous can be obtained. In the reaction vessel, the aromatic vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the standing monolith intermediate, and polymerization is carried out in the skeleton of the monolith intermediate.

The polymerization conditions are the same as those of the polymerization conditions of the third step of the first invention, and the description thereof is omitted.

(Manufacturing method of monolithic ion exchanger)

The method for producing the monolithic ion exchanger of the present invention is the same as the method for producing the monolithic ion exchanger of the first invention, and the description thereof will be omitted.

The monolithic ion exchange system of the present invention is greatly swollen to, for example, 1.4 to 1.9 times the monolith, since the ion exchange group is introduced into a monolithic structure. Further, even if the pore diameter is increased due to swelling, the total pore volume does not change. Therefore, the monolithic ion exchanger of the present invention has only a large three-dimensional continuous pore size, and has a high mechanical strength due to a large skeleton. In addition, since the skeleton is coarse, the ion exchange capacity per unit volume in the wet state of the water can be increased, and the treated water can be passed through the water at a low pressure and a water flow for a long time, and can be filled in a 2 bed 3 tower type pure. It is used in a water production device or an electric deionized water production device.

<Description of Third Invention>

Hereinafter, the "invention of the object", the "invention of the manufacturing method", and the "invention of the chemical filter" of the third invention will be described in order.

In the description of the third invention, the "monolithic organic porous body" may be simply referred to as "composite monolithic body", and the "monolithic organic porous ion exchanger" may be simply referred to as "composite monolithic ion exchanger". The "monolithic organic porous intermediate" is simply referred to as "monolithic intermediate".

(Description of composite block)

The composite structure of the composite monolith of the present invention is a composite structure of an organic porous body and a particle body or a protrusion: an organic porous body formed by a continuous skeleton phase and a continuous pore phase; A plurality of particles on the surface of the skeleton of the organic porous body, or a plurality of protrusions formed on the surface of the skeleton of the organic porous body. Further, in the description of the third invention, the "particle body" and the "protrusion body" may be collectively referred to as "particle body or the like".

The continuous framework phase of the organic porous body and the continuous pore phase can be observed by SEM image. The basic structure of the organic porous body is, for example, a continuous macroporous structure and a co-continuous structure. The skeleton phase of the organic porous body exhibits a columnar continuous body, a continuous body of concave wall surfaces, or a composite of these, which is distinctly different from the particle shape or the protrusion shape.

A preferred structure of the organic porous material: a bubble-like macropores which are superposed on each other, and the overlapping portion is a continuous macroporous structure having an opening having an average diameter of 20 to 200 μm (hereinafter sometimes referred to as "first organic porous" a continuum structure formed by a three-dimensional continuous skeleton having a thickness of 0.8 to 40 μm and a three-dimensional continuous pore having a diameter of 8 to 80 μm between the skeletons (hereinafter sometimes referred to as "second Organic porous body".).

In the first organic porous body, the average diameter of the opening is preferably 20 to 150 μm, particularly preferably 20 to 100 μm, and the pores having a diameter of 40 to 400 μm and the inside of the bubble formed by the opening serve as a flow path. The more suitable structure of the continuous macropore structure is the uniform structure of the size of the macropore or the diameter of the opening, but it is not limited thereto, and in the uniform structure, the point size is relatively uniform and the pore size is large. Uniform giant hole. If the average diameter of the opening is less than 20 μm, the pressure loss due to fluid penetration becomes large, which is not preferable. If the average diameter of the opening is too large, the contact between the fluid and the composite monolith is insufficient, and as a result, the sorption characteristics are lowered. Not good. The average diameter of the above openings refers to the maximum value of the pore distribution curve obtained by SEM image observation or mercury intrusion.

In the second organic porous body, if the size of the three-dimensional continuous pores is less than 8 μm, the pressure loss at the time of fluid penetration becomes large, which is not preferable. If the thickness exceeds 80 μm, the contact between the fluid and the monolith is insufficient. The sorption performance of the sorbed substance with uneven sorption behavior or low concentration is lowered, so it is not good. The above three-dimensional continuous pore size refers to the maximum value of the pore distribution curve obtained by the SEM image observation result or the mercury intrusion method. Further, the skeleton of the continuous continuous structure has a skeleton thickness of 0.8 to 40 μm, preferably 1 to 30 μm. When the thickness of the skeleton is less than 0.8 μm, the sorption capacity per unit volume is lowered and the mechanical strength is lowered, which is not preferable. On the other hand, if the thickness exceeds 40 μm, the uniformity of the sorption characteristics is lost. Not good.

The skeleton thickness and the opening diameter of the organic porous body can be observed by SEM image observation of the organic porous body at least three times, and the skeleton diameter and the opening in the obtained image are measured.

In the composite monolith of the present invention, a plurality of particles having a diameter of 2 to 20 μm fixed on the surface of the skeleton of the organic porous body and a plurality of protrusions having a maximum diameter of 2 to 20 μm formed on the surface of the skeleton can be imaged by SEM Observe. A particle body or the like is integrated with the surface of the skeleton phase, and a particle shape is referred to as a particle body, and a part of the particle is buried in the surface, and a particle cannot be called a protrusion. The surface of the skeleton phase is preferably coated with a particle body or the like by 40% or more, preferably 50% or more.

The diameter of the particle body and the maximum diameter of the protrusion are preferably 3 to 15 μm, particularly preferably 3 to 10 μm, and in the total particle body, the proportion of the particle body of 3 to 5 μm is 70% or more, and particularly preferably 80%. the above. Further, the particle body may also form agglomerates by forming agglomerates of the particle bodies. At this time, the diameter of the particle body means the individual particle diameter. Further, it may be a composite protrusion in which a particle body is fixed to the protrusion. In the case of a composite protrusion, the diameter and the maximum diameter refer to the value of the individual protrusions and the value of the particle body.

When the size of the particle body or the like covering the surface of the skeleton phase is out of the above range, the effect of improving the contact efficiency between the fluid and the surface of the composite monolith skeleton and the inside of the skeleton tends to be small, which is not preferable. Further, if the coverage of the particles on the surface of the skeleton is less than 40%, the effect of improving the contact efficiency between the fluid and the surface of the composite monolith skeleton and the inside of the skeleton is reduced, or the uniformity of the adsorption behavior tends to be impaired. It is not good. The size or coverage of the above-mentioned particle body or the like can be obtained by performing image analysis on a single SEM image.

Further, the composite monolith of the present invention has a total pore volume of 0.5 to 5 m1/g, preferably 0.8 to 4 ml/g. If the total pore volume is too small, the pressure loss at the time of fluid penetration becomes large, which is not preferable. Further, the amount of the penetrating fluid per unit sectional area becomes small, and the treatment ability is lowered, which is not preferable. On the other hand, if the total pore volume is too large, the sorption capacity per unit volume is lowered, which is not preferable. Since the composite monolith of the present invention has a composite structure in which the particles or the like are fixed to the wall surface or the surface of the skeleton phase forming the monolithic structure, when it is used as a sorbent, the contact with the fluid is high, and The fluid is smoothly circulated, so that superior performance can be achieved.

The pore size of the composite monolith is 8 to 100 μm, preferably 10 to 80 μm. When the organic porous material constituting the composite monolith is the first organic porous material, the pore diameter of the composite monolith is preferably from 10 to 80 μm, and when the organic porous material constituting the composite monolith is the second organic porous body. The preferred value of the aperture of the composite monolith is 10 to 60 μm. When the pore diameter of the composite monolith is within the above range and the diameter of the particle body or the like is within the above range, the contact efficiency between the fluid and the surface of the composite monolith skeleton and the inside of the skeleton is improved. Further, the pore size of the composite monolith is the maximum value of the pore distribution curve obtained by the mercury intrusion method.

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

When the composite monolith of the present invention is used as a sorbent, for example, in a cylindrical column or a square column, the composite monomer is cut into a shape that can be inserted into the column and filled as a sorption. The agent is supplied with water to be treated containing a hydrophobic substance such as benzene, toluene, phenol or paraffin, and the hydrophobic substance is efficiently adsorbed onto the sorbent. In addition, the pressure loss when the water penetrates the composite monolith is the pressure loss when the water is passed through the water line speed (LV) of 1 m/h for the pipe column filled with the composite monolith 1 m (hereinafter referred to as "pressure". The difference coefficient ") is preferably in the range of 0.005 to 0.1 MPa/m ‧ LV, and particularly preferably 0.005 to 0.05 MPa/m ‧ LV.

In the composite monolith of the present invention, the material constituting the skeleton phase of the continuous pore structure is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, and is 0.3 to 10 mol%, preferably 0.3 to 5 mol%, based on the total constituent unit of the polymer material. When the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, and if it exceeds 10 mol%, the porous body is embrittled, and the flexibility is lost, which is especially poor. In the case of an ion exchanger, it is not preferable because the amount of introduction of the ion exchange group is reduced. The type of the polymer material is the same as that of the monolithic polymer material of the first invention, and the description thereof is omitted.

In the composite monolith of the present invention, the material constituting the skeleton phase of the organic porous body and the particle body formed on the surface of the skeleton phase may be the same material in which the same structure is continuous, or may be different materials which are different from each other in different tissues. . In the case where the materials of the different tissues are different from each other, for example, a material having a different blending ratio of the vinyl monomer or the cross-linking agent may be used.

(Description of composite monolithic ion exchanger)

Next, the composite monolithic ion exchanger of the present invention will be described. In the composite monolithic ion exchanger, the same components as those of the composite monolith are omitted, and the differences will be mainly described. Composite monolithic ion exchange system The following composite structure of an organic porous body and a particle body or a protrusion: an organic porous body formed by a continuous skeleton phase and a continuous pore phase; and a solid adhesion to the organic porous body a plurality of particle bodies having a diameter of 4 to 40 μm on the surface of the skeleton, or a plurality of protrusions having a maximum diameter of 4 to 40 μm formed on the surface of the skeleton of the organic porous body; the thickness of the skeleton is 1 mm or more, and the average diameter of the pores is 10 to 150 μm. The total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the wet state is 0.2 mg equivalent/ml or more, and the ion exchange group is uniformly distributed in the composite structure.

When the organic porous material is the first organic porous body, the porous pores of the organic porous system are superposed on each other, and the overlapping portion is an opening having an average diameter of 30 to 300 μm, preferably 30 to 200 μm, and particularly preferably 35 to 150 μm. A continuous macropore structure (gap hole). The average diameter of the openings of the composite monolithic ion exchanger is such that when the ion exchange group is introduced into the monolith, since the composite monolith is swollen as a whole, the average diameter of the openings of the composite monolith is larger. If the average diameter of the opening is less than 30 μm, the pressure loss at the time of fluid penetration becomes large, which is not preferable. If the average diameter of the opening is too large, the contact between the fluid and the composite monolithic ion exchanger becomes insufficient, and as a result, ion exchange occurs. The performance is degraded and it is not good. The average diameter of the opening refers to a value obtained by observing the SEM image, multiplied by the swelling ratio when the state is wet from the dry state, or the average diameter of the composite monolith before the introduction of the ion exchange group, multiplied by ion exchange. The value calculated by the swelling ratio before and after the introduction of the base.

When the organic porous material is the second organic porous material, the organic porous system has a three-dimensional continuous skeleton having a diameter of 1 to 50 μm and a co-continuous structure having three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons. If the three-dimensional continuous pore size is less than 10 μm, the pressure loss due to fluid penetration becomes large, which is not good. If it exceeds 100 μm, the contact between the fluid and the composite monolithic ion exchanger becomes insufficient, and as a result, ion exchange behavior The unevenness of the ion exchange band is increased, or the capture efficiency of low concentration ions is lowered, which is not preferable. The three-dimensional continuous pore size refers to a value obtained by observing the SEM image, multiplied by the swelling ratio when the self-drying state is wet, or a continuous pore of the composite monolith before the introduction of the ion exchange group. The size is calculated by multiplying the swelling ratio before and after the introduction of the ion exchange group.

Further, when the diameter of the three-dimensional continuous skeleton is less than 1 μm, the ion exchange capacity per unit volume is lowered and the mechanical strength is lowered, which is not preferable. On the other hand, if it exceeds 50 μm, the ion exchange characteristics are uniform. Sexual loss is not good. The skeleton diameter of the composite monolithic ion exchanger is a value calculated by observing the SEM image, multiplied by the swelling ratio when the state is wet from the dry state, or the skeleton diameter of the monolith before the introduction of the ion exchange group. The value calculated by multiplying the swelling ratio before and after the introduction of the ion exchange group.

The pores of the composite monolithic ion exchanger have an average diameter of 10 to 150 μm, preferably 10 to 120 μm. When the organic porous material constituting the composite monolithic ion exchanger is the first organic porous material, the pore diameter of the composite monolithic ion exchanger is preferably from 10 to 120 μm, and the organic porous material constituting the composite monolithic ion exchanger When the plastid is the second organic porous material, the pore diameter of the composite monolithic ion exchanger is preferably from 10 to 90 μm.

In the composite monolithic ion exchanger of the present invention, the diameter of the particle body and the maximum diameter of the protrusion are 4 to 40 μm, preferably 4 to 30 μm, particularly preferably 4 to 20 μm, and 4 to 10 μm in the total particle body or the like. The proportion of the particles or the like is 70% or more, and particularly preferably 80% or more. Further, the surface of the skeleton phase is coated with particles or the like by 40% or more, preferably 50% or more. When the size of the particle covering the wall surface or the skeleton is out of the above range, the effect of improving the contact efficiency between the fluid and the skeleton surface of the composite monolith ion exchanger and the inside of the skeleton becomes small, which is not preferable. The diameter or the largest diameter of the particle body or the like attached to the surface of the skeleton of the composite monolithic ion exchanger is a value calculated by observing the SEM image and multiplying the swelling ratio when the state is in a wet state from a dry state, or The particle diameter of the composite monolith before the introduction of the ion exchange group is multiplied by the swelling ratio before and after the introduction of the ion exchange group.

If the particle body is equal to the coverage of the surface of the skeleton phase, if the coating ratio is less than 40%, the effect of improving the contact efficiency between the fluid and the inside of the skeleton and the skeleton surface of the composite monolithic ion exchanger becomes small, which impairs the uniformity of the ion exchange behavior. good. As a method of measuring the coverage of the above-mentioned particle body or the like, for example, a method of analyzing an image of a single SEM image can be mentioned.

In addition, the total pore volume of the composite monolithic ion exchanger is the same as the total pore volume of the composite monolith. That is, even if the ion exchange group is introduced into the composite monolith to swell and the opening diameter is increased, the total pore volume hardly changes due to the coarse skeleton portion. If the total pore volume is less than 0.5 ml/g, the pressure loss at the time of fluid penetration becomes large, which is not preferable. Further, the amount of the penetrating fluid per unit sectional area becomes small, and the treatment ability is lowered, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml/g, the ion exchange capacity per unit volume is lowered, which is not preferable.

Moreover, the pressure loss when water penetrates the composite monolithic ion exchanger is the same as the pressure loss when water penetrates the composite monolith.

In the composite monolith ion exchanger of the present invention, the ion exchange capacity per unit volume in a water-wet state has an ion exchange capacity of 0.2 mg equivalent/ml or more, preferably 0.3 to 1.8 mg equivalent/ml. If the ion exchange capacity per unit volume is less than 0.2 mg equivalent/ml, the amount of water containing ions that can be treated to failure, that is, the production ability of deionized water is lowered, which is not preferable. Further, the ion exchange capacity per unit weight in the dry state of the composite monolithic ion exchanger of the present invention is not particularly limited, and is 3 to 5 mg in order to uniformly introduce the ion exchange group into the skeleton surface and the skeleton inside the composite monolith. Equivalent / g. Further, the ion exchange capacity of the porous body in which the ion exchange group is introduced only to the surface cannot be determined depending on the type of the porous body or the ion exchange group, but is at most 500 μg equivalent/g.

The ion exchange group to be introduced into the composite monolith of the present invention is the same as the ion exchange group introduced into the monolith of the first invention, and the description thereof will be omitted.

In the composite monolithic ion exchanger of the present invention, the introduced ion exchange group is not only distributed on the surface of the porous body but also uniformly distributed inside the skeleton of the porous body. The definition of the uniform distribution is the same as the definition of the uniform distribution of the first invention.

The composite monolith of the present invention is obtained by performing the above steps I to III. In the method for producing a monolith of the present invention, the first step is an oil-soluble monomer containing no ion-exchange group, a first crosslinking agent having at least two or more vinyl groups in one molecule, a surfactant, and water. The mixture was stirred to prepare a water-drop type emulsion in the oil, and then the water-drop type emulsion in the oil was polymerized to obtain a monolithic intermediate having a continuous pore structure of a total pore volume of 5 to 30 ml/g. The first step of obtaining a monolithic intermediate can be carried out according to the method described in JP-A-2002-306976.

(Manufacturing method of monolithic intermediate)

The oil-soluble monomer which does not contain an ion-exchange group is, for example, a monomer which does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, and has low solubility in water and lipophilicity. Preferred examples of such monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isobutylene, butadiene, and B. Glycol dimethacrylate and the like. These monomers may be used alone or in combination of two or more.

The first crosslinking agent having at least two or more vinyl groups in one molecule may, for example, be divinylbenzene, divinylnaphthalene, divinylbiphenyl or ethylene glycol dimethacrylate. These crosslinking agents may be used alone or in combination of two or more. The first crosslinking agent is preferably an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl, depending on the strength of mechanical strength. The amount of the first crosslinking agent used is 0.3 to 10 mol%, particularly preferably 0.3 to 5 mol%, more preferably 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the first crosslinking agent. . When the amount of the first crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, when it exceeds 10 mol%, since the embrittlement of the monoblock occurs, the flexibility is lost, and the introduction amount of the ion exchange group is reduced, which is not preferable.

The surfactant is the same as the surfactant used in the first step of the first invention, and the description thereof is omitted.

Further, in the step I, when forming a water-drop type emulsion in oil, a polymerization initiator may be used as needed. The specific compound of the polymerization initiator is the same as the polymerization initiator used in the first step of the second invention, and the description thereof is omitted.

The method of mixing the oil-soluble monomer, the first crosslinking agent, the surfactant, the water, and the polymerization initiator which do not contain an ion exchange group to form a water-drop type emulsion is not particularly limited, and can be used. a method of mixing the components once; and separating the oil-soluble component of the oil-soluble monomer, the first crosslinking agent, the surfactant, and the oil-soluble polymerization initiator with the water-soluble component of water or a water-soluble polymerization initiator A method in which each component is mixed after being uniformly dissolved. The mixing device for forming the emulsion is not particularly limited, and a general mixer or homogenizer, a high-pressure homogenizer, or the like can be used, and an appropriate device for obtaining the particle size of the target emulsion can be selected. Further, the mixing conditions are not particularly limited, and the number of stirring rotations or the stirring time at which the particle diameter of the target emulsion can be obtained can be arbitrarily set.

The monolithic intermediate system obtained from the I step has a continuous macropore structure. When it is coexisted with the polymerization system, a particle body or the like is formed on the surface of the skeleton phase of the continuous macroporous structure by using the structure of the monolithic intermediate as a mold, or a particle body or the like is formed on the surface of the skeleton phase of the co-continuous structure. Further, the monolithic intermediate system has an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, and is 0.3 to 10 mol%, preferably 0.3 to 5 mol%, based on the total constituent unit of the polymer material. If the crosslinked structural unit is less than 0.3 mol%, it is not good because of insufficient mechanical strength. On the other hand, when it exceeds 10 mol%, it is unfavorable because the porous body is embrittled and loses flexibility.

The total pore volume of the monolithic intermediate is 5 to 30 ml/g, preferably 6 to 28 ml/g. When the total pore volume is too small, the total pore volume of the monolith obtained by polymerizing the vinyl monomer becomes too small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable. On the other hand, if the total pore volume is too large, the monolith structure obtained by polymerizing the vinyl monomer tends to be uneven, and the structure collapses as the case may be, which is not preferable. When the total pore volume of the monolith intermediate body is set to the above numerical range, the ratio (weight) of the monomer to water can be set to about 1:5 to 1:35.

When the ratio of the monomer to water is about 1:5 to 1:20, a continuous macroporous structure having a total pore volume of 5 to 16 ml/g of a single intermediate can be obtained, and is obtained through the III step. The obtained organic porous body of the composite monolith is the first organic porous body. Further, when the blending ratio is set to about 1:20 to 1:35, a continuous macroporous structure in which the total pore volume of the monolithic intermediate exceeds 16 ml/g and 30 ml/g or less is obtained, and the step III is obtained. The obtained organic porous body of the composite monolith is a second organic porous body.

Further, the opening (gap hole) of the overlapping portion of the macropores and the macropores of the monolithic intermediate system has an average diameter of 20 to 200 μm. When the average diameter of the openings is less than 20 μm, the opening diameter of the composite monolith obtained by polymerizing the vinyl monomer becomes small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable. On the other hand, when it exceeds 200 μm, the opening diameter of the composite monolith obtained by polymerizing the vinyl monomer becomes too large, and the contact between the fluid and the composite monolith or the composite monolithic ion exchanger is insufficient, and as a result, the sorption characteristics or The reduction in ion exchange characteristics is not good. The monolithic intermediate is preferably a uniform structure in which the macropore size or the diameter of the opening is uniform, but is not limited thereto, and may be an uneven macroporous having a relatively uniform macropore size in a uniform structure. .

(Manufacturing method of composite monolith)

In the second step, a second crosslinking agent containing a vinyl monomer and having at least two or more vinyl groups in one molecule is prepared, and the vinyl monomer or the second crosslinking agent is dissolved but not dissolved by the vinyl monomer. A step of forming a mixture of an organic solvent of the polymer and a polymerization initiator. Further, the steps I and II are not in the order, and the step II can be performed after the step I, or the step I can be performed after the step II.

The vinyl type monomer used in the second step is not particularly limited as long as it contains a vinyl group which can be polymerized in the molecule and has high solubility in an organic solvent. Specific examples of such vinyl monomers include aromatic vinyl types such as styrene, α-methylstyrene, vinyltoluene, vinyl chloride benzyl, vinylbiphenyl, and vinylnaphthalene. Alpha-olefin such as ethylene, propylene, 1-butene or isobutylene; diene monomer such as butadiene, isoprene or chloropentadiene; vinyl chloride, vinyl bromide and vinylidene chloride; Halogenated olefin such as tetrafluoroethylene; nitrile monomer such as acrylonitrile or methacrylonitrile; vinyl ester such as vinyl acetate or vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 2- Ethylhexyl ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate A (meth)acrylic monomer such as an ester or a glycidyl methacrylate. These monomers may be used alone or in combination of two or more. The vinyl type monomer which is suitably used in the present invention is an aromatic vinyl type monomer such as styrene or vinylbenzyl chloride.

The amount of the vinyl monomer added is 3 to 40 times, preferably 4 to 30 times by weight, based on the monolithic intermediate which is present during the polymerization. When the amount of the vinyl monomer added is less than 3 times with respect to the porous body, the skeleton of the monolith formed cannot be formed into a particle body, and the adsorption capacity per unit volume or the unit volume after introduction of the ion exchange group The ion exchange capacity becomes small and is not good. On the other hand, when the amount of the vinyl monomer added exceeds 40 times, the opening diameter becomes small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable.

The second crosslinking agent used in the second step is preferably one which contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Specific examples of the second crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butylene glycol. Diacrylate and the like. These second crosslinking agents may be used alone or in combination of two or more. The second crosslinking agent is preferably an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl from the strength of mechanical strength and the stability to hydrolysis. The amount of the second crosslinking agent used is preferably from 0.3 to 20 mol%, particularly preferably from 0.3 to 10 mol%, based on the total amount of the vinyl monomer and the second crosslinking agent. If the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, when it exceeds 20 mol%, the occurrence of embrittlement of the monolith is lost, the flexibility is lost, and the introduction amount of the ion exchange group is reduced, which is not preferable.

Specific examples of the organic solvent used in the second step are the same as those of the organic solvent used in the second step of the first invention, and the description thereof is omitted. The amount of the organic solvent used is preferably such that the concentration of the vinyl monomer is 10 to 30% by weight. When the amount of the organic solvent used is out of the above range and the concentration of the vinyl monomer is less than 10% by weight, the polymerization rate is lowered, which is not preferable. On the other hand, when the concentration of the vinyl monomer exceeds 30% by weight, the unevenness of the surface of the skeleton phase which is characterized by the present invention cannot be formed, which is not preferable.

The polymerization initiator is the same as the polymerization initiator used in the second step of the first invention, and the description thereof is omitted.

The third step is a step of polymerizing the mixture obtained in the second step under standing and in the presence of the monolithic intermediate obtained in the first step to obtain a composite monolith. The monolithic intermediate used in the third step is an important function of the negative electrode in addition to the monolithic structure having the novel structure of the present invention. Aggregation of particles can be obtained by allowing the vinyl monomer and the second crosslinking agent to be statically polymerized in a specific organic solvent in the absence of a monolithic intermediate, as disclosed in Japanese Patent Laid-Open No. Hei 7-501140. A monolithic organic porous body of the type. On the other hand, when a monolithic intermediate having a continuous macroporous structure is present in the polymerization system as described in the present invention, the structure of the monolith after polymerization changes drastically, and the particle agglomerate structure disappears, and the specific skeleton structure described above can be obtained. Monolithic.

The internal volume of the reaction container is the same as that of the internal volume of the reaction container of the first invention, and the description thereof is omitted.

In the third step, in the reaction vessel, the monolithic intermediate system is placed in a state of being impregnated with the mixture (solution). The mixture of the mixture obtained in the step II and the monolith intermediate is preferably, as described above, the amount of the vinyl monomer added is 3 to 40 times, preferably 4 to 30 times by weight relative to the monolithic intermediate. Ways to deploy. Thereby, a monolith having a suitable opening diameter and having a specific skeleton can be obtained. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the standing monolithic intermediate, and polymerization is carried out in the skeleton of the monolithic intermediate.

The polymerization conditions are the same as those of the first step of the first invention except that the polymerization temperature is 20 to 100 ° C and the conditions of the following (1) to (5) are carried out.

When the composite monolith is produced, the step II or the third step is carried out under the condition that at least one of the following conditions (1) to (5) is satisfied, and the characteristic structure of the present invention can be produced and formed on the surface of the skeleton. Composite monoliths such as particle bodies:

(1) The polymerization temperature in the step III is a temperature at least 5 ° C lower than the 10-hour half-life temperature of the polymerization initiator.

(2) The mole % of the second crosslinking agent used in the second step is twice or more the molar % of the first crosslinking agent used in the step I.

(3) The vinyl monomer used in the second step is a vinyl monomer having a different structure from the oil-soluble monomer used in the first step.

(4) The organic solvent used in the second step is a polyether having a molecular weight of 200 or more.

(5) The concentration of the vinyl monomer used in the step II is 30% by weight or less in the mixture of the step II.

(Description of (1) above)

The 10-hour half-life temperature is the characteristic value of the polymerization initiator, and if the polymerization initiator used is determined, the 10-hour half-life temperature can be known. Further, if there is a required half-time half-life temperature, a polymerization initiator equivalent thereto can be selected. In the third step, by lowering the polymerization temperature, the polymerization rate can be lowered, and a particle body or the like can be formed on the surface of the skeleton phase. The reason is that since the concentration of the monolith in the interior of the skeleton phase of the monolithic intermediate becomes gentle, the distribution speed of the monomer from the liquid phase to the monolithic intermediate is lowered, so that the remaining monomer is in the middle of the monolith. The vicinity of the surface of the skeleton layer of the body is concentrated and polymerized there.

The preferred polymerization temperature is a temperature at least 10 ° C lower than the 10-hour half-life of the polymerization initiator used. The lower limit of the polymerization temperature is not particularly limited. However, as the temperature is lowered, the polymerization rate is lowered, and the polymerization time is extended to a practically unacceptable level. Therefore, it is preferred to set the polymerization temperature to be lower than the 10-hour half-life temperature. 5~20°C range.

(Description of (2))

When the molar % of the second crosslinking agent used in the second step is set to be twice or more the molar % of the first crosslinking agent used in the first step, polymerization is carried out, whereby the composite monolith of the present invention can be obtained. . The reason for this is that since the compatibility between the monolithic intermediate and the polymer formed by the immersion polymerization is lowered, phase separation occurs, and the polymer formed by the immersion polymerization is excluded from the skeleton phase of the monolithic intermediate. In the vicinity of the surface, irregularities such as particle bodies are formed on the surface of the skeleton phase. Further, the molar % of the cross-linking agent is the cross-linking density % by mol, and means the amount of the cross-linking agent (% by mol) based on the total amount of the vinyl-type monomer and the crosslinking agent.

The upper limit of the second crosslinking agent mole % used in the second step is not particularly limited. If the second crosslinking agent molar % is significantly increased, cracks occur in the monolith after polymerization, and brittleness of the monolith occurs. The loss of flexibility and the reduction in the amount of introduction of the ion exchange group are not preferable. Preferably, the second crosslinking agent mole % is 2 to 10 times. On the other hand, even if the first crosslinking agent mol% used in the step I is set to be twice or more the molar ratio of the second crosslinking agent used in the second step, no particle body is formed on the surface of the skeleton phase. When formed, the composite monolith of the present invention could not be obtained.

(Description of (3))

The vinyl monomer used in the second step is a vinyl monomer having a structure different from that of the oil-soluble monomer used in the first step, whereby the composite monolith of the present invention can be obtained. For example, if the structure of the vinyl monomer is slightly different, such as styrene and vinyl chloride benzyl, a composite monolith which forms a particle body or the like on the surface of the skeleton phase can be formed. In general, the two homopolymers obtained from the construction of only slightly different monomers are incompatible with each other. Therefore, if the monomer used in the step I is formed in the step of forming the monolith intermediate is a monolith having a different structure, and the polymerization is carried out in the third step, the monomer used in the second step is uniformly Dispensing or immersing in a monolithic intermediate, but if the polymerization proceeds to form a polymer, the phase separation occurs due to the incompatibility of the resulting polymer with the monolithic intermediate, and the resulting polymer is excluded to the single The surface of the skeleton intermediate is in the vicinity of the surface of the skeleton, and irregularities such as particles are formed on the surface of the skeleton phase.

(Description of (4))

When the organic solvent used in the second step is a polyether having a molecular weight of 200 or more, the composite monolith of the present invention can be obtained. The polyether has a high affinity with a monolithic intermediate, especially a good solvent of a low molecular weight cyclic polyether polystyrene, and the low molecular weight chain polyether is not a good solvent but has an affinity. However, when the molecular weight of the polyether is increased, the affinity with the monolith intermediate is drastically lowered, and the affinity with the monolith intermediate is hardly exhibited. If such a solvent lacking in affinity is used in an organic solvent, the diffusion of the monomer into the interior of the skeleton of the monolithic intermediate is inhibited. As a result, since the monomer is polymerized only in the vicinity of the skeleton surface of the monolithic intermediate, the skeleton is A particle body or the like is formed on the surface of the phase, and irregularities are formed on the surface of the skeleton.

When the molecular weight of the polyether is 200 or more, the upper limit is not particularly limited. However, if the molecular weight is too high, the viscosity of the mixture prepared in the second step becomes high, and it is difficult to be impregnated into the interior of the monolithic intermediate, which is not preferable. The preferred polyether has a molecular weight of 200 to 100,000 and a particularly good 200 to 10,000. Further, even if the terminal structure of the polyether is an unmodified hydroxyl group, it may be etherified with an alkyl group such as a methyl group or an ethyl group, or may be esterified with acetic acid, oleic acid, lauric acid or stearic acid.

(Description of (5))

The concentration of the vinyl type monomer used in the second step is 30% by weight or less in the mixture in the second step, whereby the composite monolith of the present invention can be obtained. By lowering the monomer concentration in the second step and lowering the polymerization rate, particles or the like can be formed on the surface of the skeleton phase for the same reason as in the above (1), and irregularities are formed on the surface of the skeleton phase. The lower limit of the monomer concentration is not particularly limited, and as the monomer concentration decreases, the polymerization rate decreases, and the polymerization time is extended to a practically unacceptable level. Therefore, the monomer concentration is preferably set to 10 to 30% by weight.

(Manufacturing method of composite monolithic ion exchanger)

The method for producing the composite monolithic ion exchanger of the present invention is the same as the method for producing the monolithic ion exchanger of the first invention, and the description thereof will be omitted.

(Example)

The present invention is specifically described by the examples, but is merely illustrative and not restrictive.

<Embodiment of First Invention> (Example 1) (I step; manufacture of monolithic intermediates)

19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of sorbitan monooleate (hereinafter abbreviated as SMO), and 0.26 g of 2,2'-azobis(isobutyronitrile) were mixed and uniformly dissolved. . Next, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water containing THF 1.8 ml, and defoamed by vacuum stirring using a planetary stirring device. The mixer (manufactured by EME Co., Ltd.) was stirred under reduced pressure in a temperature range of 5 to 20 ° C to obtain a water-drop type emulsion. The emulsion was quickly transferred to a reaction vessel, and after sealing, polymerization was carried out at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with isopropyl alcohol, and dried under reduced pressure to produce a monolithic intermediate having a continuous macroporous structure. The opening (gap hole) of the portion where the macropore and the macropore overlapped in the monolithic intermediate had an average diameter of 56 μm and a total pore volume of 7.5 ml/g.

(Manufacture of single block)

Next, 49.0 g of styrene, 1.0 g of divinylbenzene, 50 g of 1-nonanol, and 0.5 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed to uniformly dissolve (II). step). Next, the monolith intermediate body was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 7.6 g of the mixture was taken out. The monolithic intermediate taken out is placed in a reaction vessel having an inner diameter of 90 mm and immersed in the styrene/divinylbenzene/1-nonanol/2,2'-azobis (2,4-dimethyl In the mixture of valeronitrile and defoaming in a decompression chamber, the reaction vessel was sealed, and polymerization was carried out at 60 ° C for 24 hours while standing. After completion of the polymerization, a monolithic content having a thickness of about 30 mm was taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C for one night (Step III).

The internal structure of a monolith (dry body) containing 1.3 mol% of a cross-linking component formed of the styrene/divinylbenzene copolymer thus obtained was observed by SEM, and the results are shown in Fig. 1 . The SEM image of Fig. 1 is an image of an arbitrary position of a cut section obtained by cutting a single block at an arbitrary position. As can be seen from Fig. 1, the monolith has a continuous macropore structure, and the skeleton constituting the continuous macroporous structure is much thicker than that of Fig. 5 or Fig. 6 of the comparative example, and the thickness of the wall portion constituting the skeleton is also thick.

Next, the obtained monolithic piece was cut at a position different from the above position, and the thickness of the wall portion and the area of the skeleton portion indicated by the cross-section were measured at two points from the obtained SEM image. The thickness of the wall portion is an average value of 8 points obtained from one SEM photograph, and the area of the skeleton portion is obtained by image analysis. Further, the wall portion is as defined above. Further, the skeleton portion area is represented by the average of three SEM images. As a result, the average thickness of the wall portion was 30 μm, and the area of the skeleton portion shown by the cross section was 28% in the SEM image. Further, the average diameter of the opening of the monolith measured by the mercury intrusion method was 31 μm, and the total pore volume was 2.2 ml/g. The results are shown in Tables 1 and 2. In Table 1, the filling column sequentially indicates the vinyl monomer used in the step II, the crosslinking agent, the monolith intermediate obtained in the first step, and the organic solvent used in the second step from the left.

(Manufacture of monolithic cation exchanger)

The monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the monolith is 27 g. 1500 ml of dichloromethane was added thereto, and the mixture was heated at 35 ° C for 1 hour, and then cooled to 10 ° C or lower. 145 g of chlorosulfuric acid was gradually added thereto, and the mixture was heated and reacted at 35 ° C for 24 hours. Thereafter, methanol was added, and the remaining chlorosulfuric acid was quenched, and then washed with methanol to remove methylene chloride, followed by washing with pure water to obtain a monolithic cation exchanger having a continuous macroporous structure.

The swelling ratio of the obtained cation exchanger before and after the reaction was 1.7 times, and the ion exchange capacity per unit volume was 0.67 mg equivalent/ml in a water-wet state. The average diameter of the opening of the organic porous ion exchanger in the water-wet state was estimated from the value of the organic porous material and the swelling ratio of the cation exchanger in the water-wet state, and was found to be 54 μm in the same manner as in the monolith. The wall portion constituting the skeleton had an average thickness of 50 μm, the skeleton portion area was 28% in the photograph area of the SEM photograph, and the total pore volume was 2.2 ml/g. Further, the pressure difference coefficient of the pressure loss index when the water is penetrated is 0.016 MPa/m ‧ LV, which is a lower pressure loss than the pressure loss required in practical use. The results are shown in Table 2.

Next, in order to confirm the distribution state of the sulfonic acid group in the monolithic cation exchanger, the distribution state of the sulfur atom was observed by EPMA. The results are shown in Fig. 2 and Fig. 3. Fig. 2 shows a distribution state of a sulfur atom on the surface of a cation exchanger, and Fig. 3 shows a distribution state in a cross section (thickness) direction of a cation exchanger of a sulfur atom. 2 and 3, the sulfonic acid group was uniformly introduced into the skeleton surface of the cation exchanger and the inside of the skeleton (cross-sectional direction).

(Examples 2 to 11) (Manufacture of single block)

In addition to the amount of styrene used, the type and amount of cross-linking agent, the type and amount of organic solvent, and the porous structure and crosslinking density of a monolithic intermediate coexisting in the polymerization of styrene and divinylbenzene. The monolith was produced in the same manner as in Example 1 except that the amount of use was changed to the amount shown in Table 1. The results are shown in Tables 1 and 2. Further, the SEM images of Examples 2 to 11 are shown in Figs. 8 to 17 . It can be seen from Table 2 that the average opening diameter of the monoliths of Examples 2 to 11 is as large as 22 to 70 μm, and the average thickness of the wall portion constituting the skeleton is also as thick as 25 to 50 μm, and the skeleton portion is 26 to 44 in the SEM image region. %, which belongs to the coarse skeleton monolith.

(Manufacture of monolithic cation exchanger)

The monoliths produced by the above methods were reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a monolithic cation exchanger having a continuous macroporous structure. The results are shown in Table 2. The average diameter of the openings of the monolithic cation exchangers of Examples 2 to 11 is 46 to 138 μm, the average thickness of the wall portion constituting the skeleton is 45 to 110 μm, and the area of the skeleton is 26 to 44 in the image region of the SEM image. %, the differential pressure coefficient is also as small as 0.006~0.031 MPa/m‧LV, and the exchange capacity per unit volume also shows a large value. Further, the mechanical properties of the monolithic cation exchanger of Example 8 were also evaluated.

(Evaluation of mechanical properties of monolithic cation exchangers)

The monolithic cation exchanger obtained in Example 8 was cut into a short strip of 4 mm × 5 mm × 10 mm in a wet state of water to obtain a test piece for a tensile strength test. The test piece was attached to a tensile strength tester, the speed of the slider was set to 0.5 mm/min, and the test was carried out at 25 ° C in water. As a result, the tensile strength and the tensile modulus of elasticity were 45 kPa and 50 kPa, respectively, which showed an extra large value compared to the conventional monolithic cation exchanger. Further, the tensile fracture is extended to 25%, which is a larger value than the conventional monolithic cation exchanger.

(Embodiment 12) (Manufacture of single block)

The same composition as in Example 4 was produced in the same manner as in Example 1 except that the amount of styrene used, the amount of the crosslinking agent used, and the amount of the organic solvent used were changed to those shown in Table 1. Single block. The results are shown in Tables 1 and 2. Further, in the monolithic system of Example 12, the average opening diameter of the overlapping portion of the macropores and the macropores was as large as 38 μm, and the organic porous body having a thick wall portion having an average thickness of the wall portion of the skeleton of 25 μm was also thick.

(Manufacture of monolithic anion exchanger)

The monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropwise addition, the temperature was raised and the reaction was carried out at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted by siphoning, washed with a mixed solvent of THF/water = 2/1, and then washed with THF. To the chloromethylated monolithic organic porous body, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, followed by washing with pure water and separation.

The swelling ratio of the obtained anion exchanger before and after the reaction was 1.6 times, and the ion exchange capacity per unit volume was 0.56 mg equivalent/ml in a water-wet state. The average diameter of the opening of the organic porous ion exchanger in the water-wet state was estimated from the value of the organic porous material and the swelling ratio of the cation exchanger in the water-wet state, and was found to be 61 μm in the same manner as in the monolith. The wall portion constituting the skeleton had an average thickness of 40 μm, the skeleton portion area was 26% in the image area of the SEM image, and the total pore volume was 2.9 ml/g. Further, the pressure difference coefficient of the pressure loss index when the water is penetrated is 0.020 MPa/m ‧ LV, which is a lower pressure loss than the pressure loss required in practical use. The results are shown in Table 2.

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

(Comparative Example 1) (Manufacture of monolithic organic porous bodies having a continuous macroporous structure)

According to the production method described in Japanese Laid-Open Patent Publication No. 2002-306976, a monolithic organic porous body having a continuous macroporous structure is produced. Namely, 19.2 g of styrene, 1.0 g of divinylbenzene, 1.00 g of SM, and 0.26 g of 2,2'-azobis(isobutyronitrile) were mixed and uniformly dissolved. Next, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (EME Company) using a planetary stirring device was used. The system was stirred under reduced pressure in a temperature range of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, and after sealing, polymerization was carried out at 60 ° C for 24 hours while standing. After the completion of the polymerization, the content was taken out, extracted with acetone, and dried under reduced pressure to produce a monolithic organic porous body having a continuous macroporous structure.

The internal structure of the organic porous body containing 3.3 mol% of the cross-linking component formed of the styrene/divinylbenzene copolymer obtained in this manner was observed by SEM, and the results are shown in Fig. 5 . As can be seen from Fig. 5, although the organic porous body has a continuous macroporous structure, the thickness of the wall portion constituting the skeleton of the continuous macroporous structure is thinner than that of the embodiment, and the average thickness of the wall portion measured by the SEM image is 5 μm. The area of the skeleton is 10% of the SEM image. Further, the average diameter of the opening of the organic porous body measured by the mercury intrusion method was 29 μm, and the total pore volume was 8.6 ml/g. The results are shown in Table 3. In Tables 1 to 3, the clearance hole diameter refers to the average diameter of the opening.

(Manufacture of monolithic organic porous cation exchanger having a continuous macroporous structure)

The organic porous body produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The organic porous body weighed 6 g. 1000 ml of dichloromethane was added thereto, and the mixture was heated at 35 ° C for 1 hour, and then cooled to 10 ° C or lower. 30 g of chlorosulfuric acid was gradually added thereto, and the mixture was heated and reacted at 35 ° C for 24 hours. Thereafter, methanol was added thereto, and the remaining chlorosulfuric acid was quenched, and then methylene chloride was removed by washing with methanol, followed by washing with pure water to obtain a monolithic organic porous cation exchanger having a continuous macroporous structure. The swelling ratio of the obtained cation exchanger before and after the reaction was 1.6 times, and the ion exchange capacity per unit volume was 0.22 mg equivalent/ml in the wet state of water, which was smaller than that of the examples. The average diameter of the interstitial pores of the organic porous ion exchanger in the water-wet state is estimated from the value of the organic porous material and the swelling ratio of the cation exchanger in the water-wet state. The result is 46 μm, and the average thickness of the wall portion constituting the skeleton is 8 μm, the area of the skeleton was 10% in the image area of the SEM image, and the total pore volume was 8.6 ml/g. Further, the pressure difference coefficient of the pressure loss index when the water was permeated was 0.013 MPa/m‧LV. The results are shown in Table 3, and the differential pressure coefficient shows the same small value as the example, but the ion exchange capacity per unit volume is a relatively low value compared to the examples. Further, the monolithic cation exchanger obtained in Comparative Example 1 was also evaluated for mechanical properties.

(Evaluation of mechanical properties of a conventional monolithic cation exchanger)

The monolithic cation exchanger obtained in Comparative Example 1 was subjected to a tensile test in the same manner as in the evaluation method of Example 8. As a result, the tensile strength and the tensile elastic modulus were 28 kPa and 12 kPa, respectively, which were lower than those of the monolithic cation exchanger of Example 8. Further, the tensile elongation at break was 17%, which was a smaller value than the monolithic cation exchanger of the present invention.

(Comparative examples 2 to 4) (Manufacture of monolithic organic porous bodies having a continuous macroporous structure)

In the same manner as in Comparative Example 1, except that the amount of styrene used, the amount of use of divinylbenzene, and the amount of SMO used were changed to those shown in Table 3, a continuous macroporous was produced by a conventional technique. A monolithic organic porous body constructed. The results are shown in Table 3. Further, the internal structure of the monolith of Comparative Example 4 was observed by SEM, and the results are shown in Fig. 6. Further, in Comparative Example 4, the total pore volume was minimized, and the opening was not formed with respect to the amount of water in the oil phase portion below. In the single block of Comparative Examples 2 to 4, the opening diameter was as small as 9 to 18 μm, and the average thickness of the wall portion constituting the skeleton was also as thin as 15 μm. Further, the area of the skeleton portion was only 22% in the SEM image region. Less value.

(Manufacture of monolithic organic porous cation exchanger having a continuous macroporous structure)

The organic porous body produced by the above method was reacted with chlorosulfuric acid in the same manner as in Comparative Example 1, to produce a monolithic organic porous cation exchanger having a continuous macroporous structure. The results are shown in Table 3. When the diameter of the opening is to be increased, the thickness of the wall portion becomes small, or the skeleton becomes thin. On the other hand, if the wall portion is to be thickened and the skeleton is thickened, the opening diameter tends to decrease. As a result, if the low pressure difference coefficient is used, the ion exchange capacity per unit volume is decreased, and if the ion exchange capacity is increased, the differential pressure coefficient is increased.

Further, the relationship between the pressure difference coefficient and the ion exchange capacity per unit volume of the monolithic ion exchanger produced in the examples and the comparative examples is shown in Fig. 4 . As is clear from Fig. 4, the balance between the differential pressure coefficient and the ion exchange capacity of the comparative example was poor with respect to the examples. On the other hand, it is understood that the ion exchange capacity per unit volume of the example strain is large, and the pressure difference coefficient is also low.

(Comparative Example 5)

In addition to changing the type of organic solvent used in step II to a good solvent for polystyrene Except for the alkane, the same procedure as in Example 1 was attempted to produce a monolith. However, the single-off product was transparent, indicating that the collapse of the porous structure disappeared. Although the SEM observation for confirmation was performed, only the dense structure was observed, and the continuous macropore structure disappeared.

<Embodiment of Second Invention> (Example 13) (I step; manufacture of monolithic intermediates)

5.4 g of styrene, 0.17 g of divinylbenzene, 1.4 g of sorbitan monooleate (hereinafter abbreviated as SMO), and 0.26 g of 2,2'-azobis(isobutyronitrile) were mixed and uniformly dissolved. . Next, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (EME Company) using a planetary stirring device was used. The system was stirred under reduced pressure in a temperature range of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, and after sealing, polymerization was carried out at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with methanol, and dried under reduced pressure to produce a monolithic intermediate having a continuous macroporous structure. The internal structure of the monolithic intermediate (dried body) thus obtained was observed by an SEM image (Fig. 19). As a result, although the wall portions of the two adjacent macropores were distinguished as extremely thin rods, they had a continuous pore structure. The opening (gap hole) of the portion where the macropore and the macropore overlapped by the mercury intrusion method had an average diameter of 70 μm and a total pore volume of 21.0 ml/g.

(Manufacture of a continuous continuous monolith)

Next, 76.0 g of styrene, 4.0 g of divinylbenzene, 120 g of 1-nonanol, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed to uniformly dissolve (11). step). Next, the above-mentioned monolithic intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 40 mm, and 4.1 g was taken out. The monolithic intermediate taken out was placed in a reaction vessel having an inner diameter of 75 mm and immersed in the styrene/divinylbenzene/1-nonanol/2,2'-azobis (2,4-dimethyl In the mixture of valeronitrile and defoaming in a decompression chamber, the reaction vessel was sealed, and polymerization was carried out at 60 ° C for 24 hours while standing. After completion of the polymerization, a monolithic content having a thickness of about 60 mm was taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C for one night (Step III).

The internal structure of a monolith (dry body) containing 3.2 mol% of a cross-linking component formed by the thus obtained styrene/divinylbenzene copolymer was observed by SEM, and as a result, the monolithic skeleton and the void were respectively A three-dimensional continuous, two-phase entangled co-continuous construction. Further, the skeleton thickness measured from the SEM image was 10 μm. Further, the three-dimensional continuous pore size of the monolith measured by the mercury intrusion method was 17 μm, and the total pore volume was 2.9 ml/g. The results are shown in Tables 4 and 5. In Table 5, the skeleton thickness is represented by the skeleton diameter.

(Manufacture of a continuous continuous monolithic cation exchanger)

The monolith produced by the above method was cut into a disk shape having a diameter of 75 mm and a thickness of about 15 mm. The weight of the monolith is 18g. 1500 ml of dichloromethane was added thereto, and the mixture was heated at 35 ° C for 1 hour, and then cooled to 10 ° C or lower. 99 g of chlorosulfuric acid was gradually added thereto, and the mixture was heated and reacted at 35 ° C for 24 hours. Thereafter, methanol was added thereto, and the remaining chlorosulfuric acid was quenched, and then washed with methanol to remove methylene chloride, followed by washing with pure water to obtain a monolithic cation exchanger having a co-continuous structure.

One of the obtained cation exchangers was cut out, dried, and the internal structure was observed by SEM. As a result, it was confirmed that the monolithic cation system maintained a co-continuous structure. This SEM image is shown in FIG. Further, the cation exchange rate before and after the reaction of the cation exchanger was 1.4 times, and the ion exchange capacity per unit volume was 0.74 mg equivalent/ml in a water-wet state. The swell rate of the cation exchanger from the value of the monolith and the water-wet state is estimated as the size of the continuous pores of the monolith in the wet state of water, and the result is 24 μm, the diameter of the skeleton is 14 μm, and the total pore volume is 2.9 ml/g. .

Further, the pressure difference coefficient of the pressure loss index when the water is penetrated is 0.052 MPa/m‧LV, which is a practically low pressure loss. Further, the ion exchange band length was measured for the sodium ion of the monolithic cation exchanger, and as a result, the ion exchange band length of LV = 20 m/h was 16 mm, compared to AMBERLITE IR120B (Rohm, which is a commercially available strong acid cation exchange resin). The value (320 mm) manufactured by Haas Co., Ltd. is not only a shorter value of overwhelming property, but also a shorter value than a conventional monolithic porous cation exchanger having a continuous cell structure. The results are shown in Table 5.

Next, in order to confirm the distribution state of the sulfonic acid group in the monolithic cation exchanger, the distribution state of the sulfur atom was observed by EPMA. The results are shown in Fig. 21 and Fig. 22. In Figs. 21 and 22, the left and right photos correspond to each other. Fig. 21 shows a distribution state of a sulfur atom on the surface of a cation exchanger, and Fig. 22 shows a distribution state in a cross-sectional (thickness) direction of a cation exchanger of a sulfur atom. In the photograph on the left side of Fig. 21, the left and right oblique extensions are the skeleton portions, and in the photograph on the left side of Fig. 22, the two circular shapes are the skeleton cross sections. 21 and 22, the sulfonic acid group was uniformly introduced into the skeleton surface of the cation exchanger and the inside of the skeleton (cross-sectional direction).

(Examples 14 and 15) (Manufacture of monoliths with a co-continuous structure)

In addition to the amount of styrene used, the amount of crosslinking agent used, the type and amount of organic solvent, the porous structure of the monolithic intermediates coexisting in the immersion polymerization of styrene and divinylbenzene, the crosslinking density and use A monolith having a co-continuous structure was produced in the same manner as in Example 13 except that the amount was changed to the amount shown in Table 4. The results are shown in Tables 4 and 5.

(Manufacture of a monolithic cation exchanger having a co-continuous structure)

The monoliths produced by the above methods were reacted with chlorosulfuric acid in the same manner as in Example 13 to produce a monolithic cation exchanger having a co-continuous structure. The results are shown in Table 5. Further, the internal structure of the monolithic cation exchanger having a co-continuous structure was observed by SEM image, and the results are shown in Fig. 23 and Fig. 24, respectively. As is clear from Table 5, the monolithic cation exchange systems obtained in Examples 14 and 15 exhibited a superior characteristic of a small differential pressure coefficient, a large exchange capacity per unit volume, and a short ion exchange band length. Further, the mechanical properties of the monolithic cation exchanger of Example 14 were also evaluated.

(Evaluation of mechanical properties of monolithic cation exchangers)

The monolithic cation exchanger obtained in Example 14 was cut into a short strip of 4 mm × 5 mm × 10 mm in a wet state of water to obtain a test piece for a tensile strength test. The test piece was mounted on a tensile strength tester, the slider speed was set to 0.5 mm/min, and the test was performed at 25 ° C in water. As a result, the tensile strength and the tensile modulus of elasticity were 23 kPa and 15 kPa, respectively, which showed an extra large value compared to the conventional monolithic cation exchanger. Further, the tensile breakage is extended to 50%, which is a larger value than the conventional monolithic cation exchanger.

(Embodiment 16) (Manufacture of monoliths with a co-continuous structure)

In addition to the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, and the porous structure, crosslink density, and amount of use of a single intermediate coexisting during styrene and divinylbenzene impregnation polymerization A monolith having a co-continuous structure was produced in the same manner as in Example 13 except for the amount shown in Table 4. The results are shown in Tables 4 and 5.

(Manufacture of a monolithic anion exchanger having a co-continuous structure)

The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropwise addition, the temperature was raised and the reaction was carried out at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted by siphoning, washed with a mixed solvent of THF/water = 2/1, and then washed with THF. To the chloromethylated monolithic organic porous body, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, followed by washing with pure water and separation.

The swelling ratio of the obtained anion exchanger before and after the reaction was 1.6 times, and the ion exchange capacity per unit volume was 0.44 mg equivalent/ml in a water-wet state. The swell rate of the cation exchanger from the value of the monolith and the water-wet state is estimated as the diameter of the continuous pore of the monolithic ion exchanger in the wet state of water, and the result is 29 μm, the skeleton has a thickness of 13 μm, and the total pore volume is 2.0. Ml/g.

Further, the pressure difference coefficient of the pressure loss index when the water is penetrated is 0.020 MPa/m ‧ LV, which is a practically low pressure loss. Further, the ion exchange band length was measured for the fluoride ion of the monolithic anion exchanger, and as a result, the ion exchange band length of LV = 20 m/h was 22 mm, compared to the AMBERLITE IRA402BL of a commercially available strong basic anion exchange resin. The value (165 mm) of the product (manufactured by Rohm and Haas Co., Ltd.) is not only a shorter value of the overwhelming property, but also a shorter value than the conventional monolithic porous anion exchanger having a continuous cell structure. The results are shown in Table 5. Further, the results of the internal structure of the monolithic anion exchanger having a co-continuous structure observed by SEM image are shown in Fig. 25.

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

(Comparative Example 6) (Manufacture of monolithic organic porous body having a continuous macroporous structure)

A monolithic organic porous body was produced in the same manner as in Comparative Example 1. The internal structure of the organic porous body containing 3.3 mol% of the cross-linking component formed of the styrene/divinylbenzene copolymer obtained in this manner was observed by SEM, and the results are shown in Fig. 26 . As can be seen from Fig. 26, the organic porous body has a continuous macroporous structure. Further, the average thickness of the wall portion measured by the SEM image was 5 μm, and the average diameter of the overlapping portion (opening) of the macropores and the macropores of the organic porous body measured by the mercury intrusion method was 29 μm, and the total pores were The volume is 8.6 ml/g. The results are shown in Tables 4 and 5. In Tables 4 and 5, the clearance hole diameter refers to the average diameter of the opening.

(Manufacture of a monolithic cation exchanger having a continuous macroporous structure)

A monolithic cation exchanger was produced in the same manner as in Comparative Example 1, except for the organic porous body produced in Comparative Example 6. The results are shown in Table 6, and the differential pressure coefficient shows the same small value as the example, but the ion exchange capacity per unit volume is relatively low compared to the example, and the ion exchange band length is as long as the example. About 3 times.

(Comparative Example 7) (Manufacture of monolithic organic porous body having a continuous cell structure)

Except that the amount of styrene used, the amount of divinylbenzene used, and the amount of SMO used were changed to the amounts shown in Table 4, the same method as in Comparative Example 6 was used to produce continuous macropores by the conventional technique. A monolithic organic porous body constructed. The results are shown in Tables 4 and 5.

(Manufacture of monolithic anion exchanger with continuous bubble structure)

The organic porous material produced by the above method was introduced into a chloromethyl group in the same manner as in Example 16 and reacted with trimethylamine to produce a monolithic anion exchanger having a continuous cell structure by a conventional technique. The results are shown in Table 5, and the differential pressure coefficient shows the same small value as in the examples, but the ion exchange capacity per unit volume is lower than that of the examples, and the length of the ion exchange belt is as long as about 4 times that of the examples.

(Comparative Example 8)

In addition to changing the type of organic solvent used in step II to a good solvent for polystyrene Except for the alkane, the same procedure as in Example 13 was attempted to produce a monolith having a co-continuous structure. However, the single-off product was transparent, indicating that the collapse of the porous structure disappeared. Although the SEM observation for confirmation was performed, only the dense structure was observed, and the continuous bubble structure disappeared.

<Embodiment of Third Invention> (Example 17) (I step; manufacture of monolithic intermediates)

9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2'-azobis(isobutyronitrile) were mixed and uniformly dissolved. . Next, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (EME Company) using a planetary stirring device was used. The system was stirred under reduced pressure in a temperature range of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, and after sealing, polymerization was carried out at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with isopropyl alcohol, and dried under reduced pressure to produce a monolithic intermediate having a continuous macroporous structure. The opening (gap hole) of the portion where the macropores and the macropores overlapped in the monolithic intermediate body had an average diameter of 40 μm and a total pore volume of 15.8 ml/g.

(manufacturing of composite monoliths)

Next, 36.0 g of styrene, 4.0 g of divinylbenzene, 60 g of 1-nonanol, and 0.4 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed to uniformly dissolve (II). step). The 10 hour half-life temperature of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator was 51 °C. The crosslink density is 1.3 mol% relative to the monolithic intermediate, and the amount of divinylbenzene used is 6.6 mol%, and the crosslink density ratio is 168 mol% relative to the total amount of styrene and divinylbenzene used in the second step. It is 5.1 times. Next, the above-mentioned single intermediate body was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 3.2 g was taken out. The separated monolith intermediate was placed in a reaction vessel having an inner diameter of 73 mm and immersed in the styrene/divinylbenzene/1-nonanol/2,2'-azobis (2,4-dimethyl In the mixture of valeronitrile and defoaming in a decompression chamber, the reaction vessel was sealed, and polymerization was carried out at 60 ° C for 24 hours while standing. After completion of the polymerization, a monolithic content having a thickness of about 30 mm was taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C for one night (Step III).

The internal structure of the composite monolith (dry body) formed of the styrene/divinylbenzene copolymer thus obtained was observed by SEM, and the results are shown in Figs. 27 to 29 . The SEM images of FIGS. 27 to 29 are different in magnification, and the images of arbitrary positions of the cut sections obtained by cutting the single block are cut at arbitrary positions. 27 to 29, the composite monolith has a continuous macroporous structure and constitutes a surface of a skeleton phase of a continuous macroporous structure, and is coated with a particle having an average particle diameter of 4 μm, and the particle coverage is 80%. Further, the proportion of the particle body having a particle diameter of 2 to 5 μm in the entire particle body was 90%.

Further, the opening of the composite monolith as measured by the mercury intrusion method had an average diameter of 16 μm and a total pore volume of 2.3 ml/g. The results are shown in Tables 6 and 7. In Table 7, the packing column sequentially indicates the vinyl monomer, the crosslinking agent, the organic solvent, and the monolith intermediate obtained in the step I, which are used in the second step, from the left. Further, the particle body or the like is represented by particles.

(Manufacture of composite monolithic cation exchanger)

The composite monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the monolith was 19.6 g. 1500 ml of dichloromethane was added thereto, and the mixture was heated at 35 ° C for 1 hour, and then cooled to 10 ° C or lower. Then, 98.9 g of chlorosulfuric acid was gradually added thereto, and the mixture was heated and reacted at 35 ° C for 24 hours. Thereafter, methanol was added, and the remaining chlorosulfuric acid was quenched, and then dichloromethane was washed away with methanol, and then washed with pure water to obtain a composite monolithic cation exchanger.

The swelling ratio of the obtained cation exchanger before and after the reaction was 1.3 times, and the ion exchange capacity per unit volume was 1.11 mg equivalent/ml in a water-wet state. The average diameter of the opening of the organic porous ion exchanger in the water-wet state was estimated from the value of the organic porous material and the swelling ratio of the cation exchanger in the water-wet state, and was found to be 21 μm in the same manner as in the monolith. The particle coverage of the skeleton surface was 80%, the average particle diameter of the coated particles was 5 μm, and the total pore volume was 2.3 m1/g. Further, the proportion of the particle body having a particle diameter of 3 to 7 μm in the entire particle body was 90%. Further, the pressure difference coefficient of the pressure loss index when the water is penetrated is 0.057 MPa/m‧LV, which is a lower pressure loss than the pressure loss required in practical use. Furthermore, the ion exchange tape has a length of 9 mm and shows a significantly shorter value. The results are shown in Table 7.

Next, in order to confirm the distribution state of the sulfonic acid group in the composite monolithic cation exchanger, the distribution state of the sulfur atom was observed by EPMA. The results are shown in Fig. 30 and Fig. 31. In Figs. 30 and 31, the left and right photographs correspond to each other. Fig. 30 shows the distribution state of the sulfur atom on the surface of the cation exchanger, and Fig. 31 shows the distribution state in the cross section (thickness) direction of the cation exchanger of the sulfur atom. 30 and 31, the sulfonic acid group was uniformly introduced into the skeleton surface of the cation exchanger and the inside of the skeleton (cross-sectional direction).

(Examples 18 to 21) (manufacturing of composite monoliths)

In addition to the amount of the vinyl monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, the porous structure of the monolithic intermediate which coexists in the polymerization in the III step, the crosslinking density and the amount used, and the polymerization temperature A monolith was produced in the same manner as in Example 17 except that the amount shown in Table 6 was changed. The results are shown in Tables 6 and 7. Further, the internal structure of the composite monomer (dry body) was observed by SEM, and the results are shown in Figs. 32 to 39. 32 to 34 are the embodiment 18, FIG. 35 and FIG. 36 are the embodiment 19, FIG. 37 is the embodiment 20, and FIG. 38 and FIG. 39 are the embodiment 21. Further, the following examples were carried out to satisfy the conditions of the production conditions of the present invention: the crosslinking density ratio (2.5 times) of Example 18, and the type of organic solvent of Example 19 (PEG; molecular weight: 400), Examples The vinyl monomer concentration of 20 (28.0%), the polymerization temperature of Example 21 (40 ° C; 11 ° C lower than the 10-hour half-life temperature of the polymerization initiator). From Fig. 32 to Fig. 39, the subjects attached to the surface of the skeleton of the composite monoliths of Examples 19 to 21, which are referred to as particle bodies, should be protrusions. The "average particle diameter" of the protrusion is the average diameter of the largest diameter of the protrusion. From Fig. 32 to Fig. 39 and Table 7, the average diameter of the particles attached to the surface of the monomer skeleton of Examples 18 to 21 was 3 to 8 μm, and the particle coverage was 50 to 95%. Further, in Example 18, the ratio of the particle body having a particle diameter of 3 to 6 μm to the entire particle body was 80%, and the ratio of the protrusion having a particle diameter of 3 to 10 μm in Example 19 to the entire particle body was 80%. In Example 20, the ratio of the particle body having a particle diameter of 2 to 5 μm to the entire particle body was 90%, and the ratio of the particle body having a particle diameter of 3 to 7 μm in Example 21 to the entire particle body was 90%.

(Manufacture of composite monolithic cation exchanger)

The composite monoliths produced by the above methods were reacted with chlorosulfuric acid in the same manner as in Example 17 to produce a composite monolithic cation exchanger. The results are shown in Table 7. The average pore diameter of the continuous pores of the composite monolithic cation exchangers of Examples 18 to 21 is 21 to 52 μm, and the average diameter of the particles attached to the surface of the skeleton is 5 to 17 μm, and the particle coverage is as high as 50 to 95%. The differential pressure coefficient is also as small as 0.010~0.057MPa/m‧LV, and the ion exchange zone length is also significantly smaller than 8~12mm. Further, the proportion of the particle body having a particle diameter of 5 to 10 μm in the entire particle body was 90%.

(Example 22) (manufacturing of composite monoliths)

In addition to the type and amount of the vinyl monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, and the porous structure of the monolithic intermediate which is present during the polymerization in the third step, the crosslinking density and the amount of use are changed. A monolith was produced in the same manner as in Example 17 except that the amount shown in Table 1 was used. The results are shown in Tables 6 and 7. Further, the internal structure of the composite monolith (dry body) was observed by SEM, and the results are shown in Figs. 40 to 42. The surface of the skeleton of the composite monolith of Example 22 was attached to the protrusion. In the monolith of Example 22, the average diameter of the largest diameter of the protrusion formed on the surface was 10 μm, and the particle coverage was 100%. Further, the proportion of the particle body having a particle diameter of 6 to 12 μm in the entire particle body was 80%.

(Manufacture of composite monolithic anion exchanger)

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

The swelling ratio of the obtained composite anion exchanger before and after the reaction was 2.0 times, and the ion exchange capacity per unit volume was 0.32 mg equivalent/ml in a water-wet state. The swelling ratio of the anion exchanger from the value of the monolith and the water-wet state is estimated as the average diameter of the continuous pores of the organic porous ion exchanger in the water-wet state, and as a result, it is 58 μm, and the protrusions obtained by the same method are obtained. The average diameter was 20 μm, the particle coverage was 100%, and the total pore volume was 2.1 ml/g. Also, the ion exchange tape length shows a very short 16 mm. Further, the pressure difference coefficient of the pressure loss index when the water is penetrated is 0.041 MPa/m ‧ LV, which is a lower pressure loss than the pressure loss required in practical use. Further, the proportion of the particle body having a particle diameter of 12 to 24 μm in the entire particle body was 80%. The results are shown in Table 7.

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

(Comparative Example 9) (Manufacture of single block)

The amount of the vinyl monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, and the amount of the monolith intermediate used in the polymerization in the third step were changed to the amounts shown in Table 6. The remainder was produced in the same manner as in Example 17. The results are shown in Tables 6 and 7. Further, the formation of the particles or the protrusions was not confirmed at all by the SEM photograph (not shown). As can be seen from Tables 6 and 7, it is not confirmed that the monolithic skeleton surface is produced under the conditions of the specific manufacturing conditions of the present invention, that is, under the conditions of the above-mentioned (1) to (5). Particle generation.

(Manufacture of monolithic cation exchanger)

The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Example 17 to produce a monolithic cation exchanger. The results are shown in Table 7. The length of the ion exchange zone of the resulting monolithic cation exchanger was 26 mm, which was a larger value than the examples.

(Comparative examples 10 to 12) (Manufacture of single block)

In addition to the amount of the vinyl monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, and the porous structure of the monolithic intermediate which is present during the polymerization in the third step, the crosslinking density and the amount of use are changed to the table. A monolith was produced in the same manner as in Example 17 except for the blending amount shown in FIG. The results are shown in Tables 6 and 7. Further, the production was carried out under the conditions that did not satisfy the production conditions of the present invention: the crosslinking density ratio of Comparative Example 10 (0.2 times), and the type of the organic solvent of Comparative Example 11 (2-(2-methoxyethoxy)). Ethanol; molecular weight 120), polymerization temperature of Comparative Example 12 (50 ° C; 1 ° C lower than the 10-hour half-life temperature of the polymerization initiator). The results are shown in Table 7. The monoliths of Comparative Examples 10 and 12 were not formed on the surface of the skeleton. Further, the product isolated from the comparative example 11 was transparent, and the porous structure collapsed and disappeared.

(Manufacture of monolithic cation exchanger)

In the same manner as in Comparative Example 11, the organic porous body produced by the above method was reacted with chlorosulfuric acid in the same manner as in Comparative Example 9, to produce a monolithic cation exchanger. The results are shown in Table 7. The length of the ion exchange zone of the resulting monolithic cation exchanger was 23 to 26 mm, which was a larger value than the examples.

(Comparative Example 13) (Manufacture of single block)

The amount of the vinyl monomer used, the amount of the crosslinking agent used, the amount of the organic solvent used, and the porous structure and the amount of the monolithic intermediate which are coexisted during the polymerization in the third step are changed to the amounts shown in Table 1. A monolith was produced in the same manner as in Comparative Example 9 except for the rest. The results are shown in Tables 6 and 7. It is understood that when a monolith is produced without departing from the specific production conditions of the present invention, no particle formation is observed on the surface of the monolith skeleton.

(Manufacture of monolithic anion exchanger)

The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropwise addition, the temperature was raised and the reaction was carried out at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted by siphoning, washed with a mixed solvent of THF/water = 2/1, and then washed with THF. To the chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, and then washed with pure water to separate. The results are shown in Table 7. The length of the anion exchange zone of the obtained monolithic anion exchanger was 47 mm, which was a larger value than the examples.

(industrial availability)

The monolithic and monolithic ion exchanger according to the first aspect of the invention is chemically stable and has high mechanical strength. Further, the ion exchange capacity per unit volume is large, and the continuous pores are large to allow a fluid such as water or gas to penetrate. The strength of the lower pressure loss. Further, the monolithic and monolithic ion exchanger of the second invention is hydrophobic and chemically stable, has a large three-dimensional skeleton and high mechanical strength, and particularly has a large ion exchange capacity per unit volume, and is in a co-continuous structure. The three-dimensional continuous pores are large, so that the pressure loss when the fluid such as water or gas penetrates is low, and further, the length of the ion exchange belt is particularly short. Further, the monolithic and monolithic ion exchanger of the third invention is chemically stable and has high mechanical strength, and further has a high contact efficiency with fluid when the fluid penetrates and a low pressure loss when the fluid penetrates. Therefore, the first to third inventions can be effectively used as a chemical filter or a sorbent; and an ion exchanger which is used in a two-bed three-tower pure water producing apparatus or an electric deionized water producing apparatus; A filler for color layer analysis; a solid acid/base catalyst; and is used in a wide range of applications.

The drawings of the first invention are shown in Figs. 1 to 17, the drawings of the second invention are shown in Figs. 18 to 26, and the drawings of the third invention are shown in Figs. 27 to 42. That is, Fig. 1 is an SEM image of the monolith obtained in Example 1. Fig. 2 is an EPMA image showing the state of distribution of sulfur atoms on the surface of the monolithic cation exchanger obtained in Example 1. Fig. 3 is an EPMA image showing the state of distribution of sulfur atoms in the cross section (thickness) direction of the monolithic cation exchanger obtained in Example 1. Fig. 4 is a graph showing the correlation between the differential pressure coefficient of the example product and the comparative example and the ion exchange capacity per unit volume. Fig. 5 is a view showing the SEM image of the monolith obtained in Comparative Example 1. Fig. 6 is a view showing an SEM image of a monolith obtained in Comparative Example 4. Fig. 7 is a manual transfer of the skeleton portion shown by the cross section of the SEM image of Fig. 1. In Fig. 7, reference numeral 11 denotes a photograph area, reference numeral 12 denotes a skeleton portion indicated by a cross section, and reference numeral 13 denotes a macropore. Figure 8 is a SEM image of the monolith obtained in Example 2. Figure 9 is a SEM image of the monolith obtained in Example 3. Figure 10 is a SEM image of the monolith obtained in Example 4. Figure 11 is a SEM image of the monolith obtained in Example 5. Figure 12 is a SEM image of the monolith obtained in Example 6. Figure 13 is a SEM image of the monolith obtained in Example 7. Figure 14 is a SEM image of the monolith obtained in Example 8. Figure 15 is a SEM image of the monolith obtained in Example 9. Figure 16 is a SEM image of the monolith obtained in Example 10. Figure 17 is a SEM image of the monolith obtained in Example 11. Fig. 18 is a view schematically showing a co-continuous structure of a monolith of the second invention. In Fig. 18, the symbol 1 indicates the skeleton phase, the symbol 2 indicates the void phase, and the symbol 10 indicates the monolith. Figure 19 is a SEM image of the monolithic intermediate obtained in Example 20. Figure 20 is a SEM image of a monolithic cation exchanger having a co-continuous structure obtained in Example 20. Fig. 21 is a view showing an EPMA image of the distribution of sulfur atoms on the surface of a monolithic cation exchanger having a co-continuous structure obtained in Example 20. Fig. 22 is a view showing an EPMA image of a sulfur atom distribution state in a cross-sectional (thickness) direction of a monolithic cation exchanger having a co-continuous structure obtained in Example 20. Figure 23 is a SEM image of a monolithic cation exchanger having a co-continuous structure obtained in Example 21. Figure 24 is a SEM image of a monolithic cation exchanger having a co-continuous structure obtained in Example 22. Figure 25 is a SEM image of a monolithic cation exchanger having a co-continuous structure obtained in Example 23. Figure 26 is a SEM photograph of the monolith obtained in Comparative Example 11. Figure 27 is an SEM image of a magnification of 100 for the monolith obtained in Example 31. Figure 28 is an SEM image of a magnification of 300 of the monolith obtained in Example 31. Figure 29 is an SEM image of a magnification of 3000 obtained for the monolith obtained in Example 31. Fig. 30 is a view showing an EPMA image of the distribution of sulfur atoms on the surface of the monolithic cation exchanger obtained in Example 31. Fig. 31 is an EPMA image showing the state of distribution of sulfur atoms in the cross section (thickness) direction of the monolithic cation exchanger obtained in Example 31. Figure 32 is an SEM image of a magnification of 100 for the monolith obtained in Example 32. Figure 33 is an SEM image of a magnification of 600 for the monolith obtained in Example 32. Figure 34 is an SEM image of a magnification of 3000 of the monolith obtained in Example 32. Figure 35 is an SEM image of a magnification of 600 for the monolith obtained in Example 33. Figure 36 is an SEM image of a magnification of 3000 obtained for the monolith obtained in Example 33. Figure 37 is an SEM image of a magnification of 3000 of the monolith obtained in Example 34. 38 is an SEM image of a magnification of 100 for the monolith obtained in Example 35. Figure 39 is an SEM image of a magnification of 3000 of the monolith obtained in Example 35. Figure 40 is an SEM image of a magnification of 100 for the monolith obtained in Example 36. Figure 41 is an SEM image of a magnification of 600 for the monolith obtained in Example 36. Figure 42 is an SEM image of a magnification of 3000 of the monolith obtained in Example 36.

Claims (23)

A monolithic organic porous body characterized in that a bubble-like macropores are superposed on each other, and the overlapping portion is a continuous macroporous structure having an opening of an average diameter of 20 to 200 μm, and the thickness thereof is 1 mm or more. The pore volume is 0.5 to 5 ml/g, and in the SEM image of the cross section of the continuous macroporous structure (dry body), the area of the skeleton shown by the cross section is 25 to 50% in the image area. A monolithic organic porous body in which bubble-like macropores are superposed on each other, and the overlapping portion is a continuous macroporous structure having an opening of an average diameter of 20 to 200 μm, a thickness of 1 mm or more, and a total pore volume of 0.5. ~5ml / g, obtained by the following steps: Step I, the mixture of the oil-soluble monomer, the surfactant and the water without the ion exchange group is prepared by stirring to prepare the water droplet type emulsion in the oil, and then The water-repellent emulsion in the oil is polymerized to obtain a monolithic organic porous intermediate having a continuous pore structure of 5 to 16 ml/g; and the second step is to prepare a vinyl monomer in one molecule. a mixture of an organic solvent having a crosslinking agent of at least two or more vinyl groups, a polymer which is formed by dissolving a vinyl monomer or a crosslinking agent but not dissolving a polymer obtained by polymerizing a vinyl monomer; and a polymerization initiator; In the third step, the mixture obtained in the step II is subjected to polymerization under the condition of standing, and in the presence of the monolithic organic porous intermediate obtained in the first step, to obtain a skeleton having a larger skeleton than the organic porous intermediate. Skeleton of skeleton Machine porous body. A monolithic organic porous ion exchanger characterized in that a bubble-like macropores are superposed on each other, and the overlapping portion is a continuous macroporous structure having an opening having an average diameter of 30 to 300 μm in a wet state of water, The thickness is 1 mm or more, the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the wet state of water is 0.4 mg equivalent/ml or more, and the ion exchange group is uniformly distributed in the porous ion exchanger. In the SEM image of the cross section of the continuous macroporous structure (dry body), the area of the skeleton portion indicated by the cross section is 25 to 50% in the image region. A monolithic organic porous ion exchanger, which is introduced into an ion exchange group in a monolithic organic porous body of the second aspect of the patent application, has an ion exchange capacity per unit volume of 0.4 mg equivalent in a water wet state. Above /ml, the ion exchange group is uniformly distributed in the porous ion exchanger. A method for producing a monolithic organic porous body, comprising the step of: preparing a mixture of an oil-soluble monomer, a surfactant, and water without an ion exchange group by stirring; The water droplet type emulsion in the oil is then polymerized in a water droplet type emulsion to obtain a monolithic organic porous intermediate having a continuous pore structure of a total pore volume of 5 to 16 ml/g; a vinyl monomer, an organic solvent having at least two or more vinyl crosslinkers in one molecule, and a polymer which is formed by dissolving a vinyl monomer or a crosslinking agent but not dissolving a polymer formed by a vinyl monomer, and a mixture of a polymerization initiator; and a step of the step III, wherein the mixture obtained in the step II is allowed to stand under the reaction, and the polymerization is carried out in the presence of the monolithic organic porous intermediate obtained in the step I, to obtain a organic A coarse skeleton organic porous body having a skeleton of a porous intermediate body. The method for producing a monolithic organic porous body according to the fifth aspect of the invention, wherein the monolithic organic porous intermediate obtained in the first step is a bubble-like macropores which are superposed on each other, and the overlapping portion A continuous macroporous structure having an opening of an average diameter of 20 to 200 μm, and a total pore volume of 5 to 16 ml/g. A method for producing a monolithic organic porous ion exchanger, comprising the steps of: step I, stirring a mixture of an oil-soluble monomer, a surfactant, and water without an ion exchange group; Preparing a water-drop type emulsion in oil, and then polymerizing the water-drop type emulsion in oil to obtain a monolithic organic porous intermediate having a continuous pore structure of 5 to 16 ml/g; II step, An organic solvent containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, and a polymer obtained by dissolving a vinyl monomer or a crosslinking agent but not dissolving the polymer formed by the vinyl monomer is prepared. And the mixture of the polymerization initiator; the step of the step III is carried out by dissolving the mixture obtained in the step II, and in the presence of the monolithic organic porous intermediate obtained in the step I, to obtain The coarse-framed organic porous body having a skeleton having a large skeleton of the organic porous intermediate; and the IV step, introducing the ion-exchange group into the coarse-frame organic porous body obtained in the third step. A monolithic organic porous body characterized by having a co-continuous structure of the following skeleton and pores, and having a total pore volume of 0.5 to 5 ml/g: comprising a crosslinked structure in a total constituent unit A three-dimensional continuous skeleton formed of an aromatic vinyl polymer of 0.3 to 5.0 mol% and having a thickness of 0.8 to 40 μm; and a three-dimensional continuous pore having a diameter of 8 to 80 μm between the skeletons. A monolithic organic porous body having a co-continuous structure of the following skeleton and pores, and having a total pore volume of 0.5 to 5 ml/g: consisting of a crosslinked structural unit of 0.3 to 5.0 in the total constituent unit a three-dimensional continuous skeleton formed of a mole of an aromatic vinyl polymer and having a thickness of 0.8 to 40 μm; and a three-dimensional continuous pore having a diameter of 8 to 80 μm between the skeletons; In the step I, a mixture of an oil-soluble monomer, a surfactant, and a water which does not contain an ion exchange group is prepared by stirring to prepare a water-drop type emulsion, and then a water-drop type emulsion in the oil is polymerized. a monolithic organic porous intermediate having a continuous pore volume of more than 16 ml/g and 30 ml/g or less; and a step of preparing an aromatic vinyl type monomer having at least 2 in one molecule a vinyl cross-linking agent, an organic solvent which dissolves an aromatic vinyl monomer or a cross-linking agent but does not dissolve a polymer obtained by polymerizing an aromatic vinyl-type monomer, and a mixture of a polymerization initiator; Step, the mixture obtained in the step II is static Under, and in the presence of the polymerization step of the resulting organic porous monolithic I the intermediates. The monolithic organic porous ion exchanger is a co-continuous structure having the following skeleton and pores, and the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the water wet state is 0.3 mg eq/ml or more, the ion-exchange group is uniformly distributed in the porous ion exchanger: from the total constituent unit of the introduced ion-exchange group, the aromatic vinyl having a cross-linked structural unit of 0.3 to 5.0 mol% A three-dimensional continuous skeleton formed of a base polymer and having a thickness of 1 to 60 μm; and a three-dimensional continuous pore having a diameter of 10 to 100 μm between the skeletons. A monolithic organic porous ion exchanger, which is introduced into an ion exchange group in a monolithic organic porous body according to claim 9 of the patent application, characterized in that ion exchange capacity per unit volume in a water wet state The ion exchange group is uniformly distributed in the porous ion exchanger in an amount of 0.3 mg equivalent/ml or more. A method for producing a monolithic organic porous body, which comprises the steps of: step I, preparing a mixture of an oil-soluble monomer, a surfactant, and water without an ion exchange group by stirring to form an oil The medium-drop type emulsion is then polymerized in a water-drop type emulsion to obtain a monolithic organic porous intermediate having a continuous pore structure having a total pore volume of more than 16 ml/g and 30 ml/g or less; A crosslinking agent containing an aromatic vinyl monomer and having 0.3 to 5 mol% of a total oil-soluble monomer having at least two or more vinyl groups in one molecule, and dissolving an aromatic vinyl monomer or crosslinking And the mixture of the organic solvent of the polymer formed by the polymerization of the aromatic vinyl monomer and the polymerization initiator; and the step III, the mixture obtained in the step II is allowed to stand, and the I The polymerization is carried out in the presence of the monolithic organic porous intermediate obtained in the step to obtain a co-continuous structure. The method for producing a monolithic organic porous body according to claim 12, wherein the monolithic organic porous intermediate obtained in the first step is a bubble-like macropores which are superposed on each other, and the overlapping portion A continuous macroporous structure that is an opening having an average diameter of 5 to 100 μm. A method for producing a monolithic organic porous ion exchanger, characterized in that the following step is carried out: a step of preparing a mixture of an oil-soluble monomer, a surfactant, and water without an ion exchange group by stirring The water droplet type emulsion in the oil is then polymerized in a water droplet type emulsion to obtain a monolithic organic porous intermediate having a continuous pore structure having a total pore volume of more than 16 ml/g and 30 ml/g or less; A crosslinking agent containing 0.3 to 5 mol% of an aromatic ethylenic monomer having at least two vinyl groups in one molecule, and dissolving an aromatic vinyl monomer or a crosslinking agent a mixture of an organic solvent of a polymer formed by polymerization of an aromatic vinyl type monomer and a polymerization initiator; a step of the step III, wherein the mixture obtained in the step II is allowed to stand still under the The polymerization is carried out in the presence of the monolithic organic porous intermediate obtained in the step to obtain a co-continuous structure; and in the IV step, the ion-exchange group is introduced into the co-continuous structure obtained in the third step. The monolithic organic porous body is a composite structure of the following organic porous body, a particle body or a protrusion, and has a thickness of 1 mm or more, an average diameter of the pores of 8 to 100 μm, and a total pore volume of 0.5 to 5 ml/ g: an organic porous body formed by a continuous skeleton phase and a continuous pore phase; a plurality of particle bodies having a diameter of 2 to 20 μm adhered to a surface of the skeleton of the organic porous body; formed on a skeleton surface of the organic porous body The maximum diameter of the upper one is 2~20μm. The monolithic organic porous body according to the fifteenth aspect of the invention, wherein the porous pores of the organic porous system are superposed on each other, and the overlapping portion is a continuous macroporous structure having an opening having an average diameter of 20 to 200 μm. body. The monolithic organic porous body according to the fifteenth aspect of the patent application, wherein the organic porous system is formed by a three-dimensional continuous skeleton having a thickness of 0.8 to 40 μm and a three-dimensional continuous pore having a diameter of 8 to 80 μm between the skeletons. A co-continuous construct. A monolithic organic porous body obtained by the following steps: Step I, wherein the oil-soluble monomer having no ion-exchange group has at least two vinyl groups in one molecule The mixture of the crosslinking agent, the surfactant, and the water is prepared by stirring to form a water droplet type emulsion, and then the water droplet type emulsion is polymerized to obtain a continuous pore structure having a total pore volume of more than 5 to 30 ml/g. Monolithic organic porous intermediate; step II, preparing a second crosslinking agent containing a vinyl monomer, having at least two or more vinyl groups in one molecule, dissolving a vinyl monomer or a second crosslinking But not dissolving the organic solvent of the polymer formed by the polymerization of the vinyl monomer, and the mixture of the polymerization initiator; and the step III, the mixture obtained in the step II is allowed to stand, and obtained by the step I In the presence of the monolithic organic porous intermediate, the polymerization is carried out at a temperature at least 5 ° C lower than the 10-hour half-life of the polymerization initiator. The monolithic organic porous ion exchanger is a composite structure of the following organic porous body and a particle body or a protrusion, and has a thickness of 1 mm or more, an average diameter of the pores of 10 to 150 μm, and a total pore volume of 0.5 to 0.5%. 5 ml/g, the ion exchange capacity per unit volume in the wet state of water is 0.2 mg equivalent/ml or more, and the ion exchange group is uniformly distributed in the composite structure: organic porous formed by the continuous skeleton phase and the continuous pore phase a plurality of particles having a diameter of 4 to 40 μm adhered to the surface of the skeleton of the organic porous body; and a plurality of protrusions having a maximum diameter of 4 to 40 μm formed on the surface of the skeleton of the organic porous body. The monolithic organic porous ion exchanger according to claim 19, wherein the porous pores of the organic porous system are superposed on each other, and the overlapping portion has an average diameter of 30 to 300 μm in a wet state of water. A continuous giant pore structure of the opening. The monolithic organic porous ion exchanger according to claim 19, wherein the organic porous system has a three-dimensional continuous skeleton having a thickness of 1 to 60 μm and a three-dimensional continuous pore having a diameter of 10 to 100 μm between the skeletons. The co-continuous structure formed. A method for producing a monolithic organic porous body, which comprises the steps of: step I, wherein the oil-soluble monomer having no ion-exchange group has at least two or more vinyl groups in one molecule; The mixture of the crosslinking agent, the surfactant, and the water is prepared by stirring to prepare a water-drop type emulsion in the oil, and then the water-drop type emulsion in the oil is polymerized to obtain a continuous macroporous structure having a total pore volume of 5 to 30 ml/g. Monolithic organic porous intermediate; step II, preparing a second crosslinking agent containing a vinyl monomer, having at least two or more vinyl groups in one molecule, dissolving a vinyl monomer or a second crosslinking But not dissolving the organic solvent of the polymer formed by the polymerization of the vinyl monomer, and the mixture of the polymerization initiator; and the step III, the mixture obtained in the step II is allowed to stand, and obtained by the step I Polymerization is carried out in the presence of a monolithic organic porous intermediate; in the production of a monolithic organic porous body, the step II is carried out under conditions satisfying at least one of the following conditions (1) to (5) or Step III: (1) The polymerization temperature in the step III, a temperature lower than a 10-hour half-life of the polymerization initiator at least 5 ° C; (2) a mole % of the second crosslinking agent used in the step II, which is the first crosslinking agent used in the step I. (2) The vinyl monomer used in the step II is a vinyl monomer having a different structure from the oil-soluble monomer used in the first step; (4) the organic solvent used in the step II, The polyether having a molecular weight of 200 or more; and the concentration of the vinyl monomer used in the step (5) II is 30% by weight or less in the mixture of the second step. A method for producing a monolithic organic porous ion exchanger, which comprises the step of introducing an ion exchange group into a monolithic organic porous body obtained by the production method of claim 22 of the patent application.