TW201024342A - Monolithic organic porous material, monolithic organic porous ion exchanger, and method of producing same - Google Patents

Abstract

A monolithic organic porous material has a continuous macropore structure formed of overlapping macropore foams. The overlapping portions of the macropores form openings with an average diameter of 20 to 200 μ m. In a section of the continuous macropore structure (dry material) with a thickness of 1 mm or more and the total pore volume of 0.5 to 5 ml/g, the percentage of the areas which form the skeleton exposed on the surface is 25 to 50% when observed in an SEM photograph. The monolithic organic porous material and a monolithic ion exchanger produced by introducing ion-exchange groups into the monolithic organic porous material are chemically stable, have high mechanical strength, and exhibit a low pressure loss when a liquid permeates through. The porous material and the ion exchanger are useful as an adsorber having a large adsorption capacity or an ion exchanger having a large ion-exchange capacity.

Description

201024342 r VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a monolithic structure having a continuous macroporous structure which can be effectively used as an ion exchanger for a sorbent or a deionized water production apparatus or the like and having a coarse skeleton. (monolith) organic porous body, monolithic organic porous ion exchanger having a continuous macroporous structure of a coarse skeleton, and a method for producing the same. [Previous Art] The following production method is disclosed in Japanese Patent Laid-Open Publication No. 2002-306976: mixing an oil-soluble monomer containing no ion exchange group, a surfactant, water, and optionally polymerization to obtain a water droplet type in oil. The emulsion is 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 the ion exchange capacity per unit volume is lowered when the desired low pressure is lost due to the structural control. The disadvantage of increased pressure loss per unit volume of exchange capacity. Similarly, 'in the monolithic organic porous body obtained by the above method 戋 organic 097149356 4 201024342 k > ^1 ion ^ body in the 'the theoretical (four) face of the skeleton area _ a ° 〃 reason is that belongs to the organic A monolithic organic porous system (4) of a continuous macroporous structure of a corpus callosum in a porous body. In order to form a continuous pupil structure, the water_emulsion_emulsion+water droplets are in contact with each other" is determined to be 75% to 4%. The volume fraction of this water droplet is 1/5.乂上. Since the water-based emulsion is obtained as a monolithic organic porous system, the structure of the emulsion is fixed to a ratio of 75% or more. The opening ratio of the organic porous body is also (10). Therefore, the bone of the cut section (4) is full. 'As long as the manufacturing method is used, it is impossible to raise the cut (4) of the lean rack and the other side, as the grass having the structure other than the above-mentioned continuous macroporous structure = organic porous A plastid or monolithic organic porous f ion exchanger is disclosed in Japanese porous j = thousand 2:5:: = and has a particle agglomerated structure. However, the porous wealth obtained by this method is also continuous. It is only a small value of about 2 _, and it is not possible to make industrial-scale deionized water for the processing of the maximum flow rate, etc. Further, the porous system of the particle agglomerated structure has low mechanical strength, Cut the size = fill and fill the column or sub-(4) (e,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Large, continuous holes So that ilk such as water or gas pressure at the time of penetrating the body 0,971,493,565,201,024,342 low loss monolithic porous organic ion exchanger.

On the other hand, as the structure of the organic porous body, a co-continuous structure in which a skeleton phase of a three-dimensional property is formed and a three-dimensional continuous pore phase between the phases ((iv)) is formed, and two phases are entangled with each other is known. It is disclosed in Japanese Patent Laid-Open No. 2〇〇7七娜3号, which has an average affinity of micron size, and has a continuous pore and a skeleton rich in organic matter in a three-dimensional network. a co-continuous structure formed by a phase, not an organic polymer gel-like affinity carrier of a particle agglutination type, and an affinity carrier as a crosslinking agent, at least a difunctional or higher vinyl monomer compound, a methyl group (tetra) a copolymer of at least one of a compound and a vinegar compound and a monofunctional hydrophilic monomer, and a volume ratio of the above crosslinking agent to the monofunctional hydrophilic monomer in the affinity carrier is trace 1Q : Oh,. This affinity carrier maintains the monolithic structure and increases the crosslink density of the backbone. Further, this affinity carrier system has a hydrophilic property which sufficiently suppresses non-specific adsorption. Also, in N

In Tsujioka et al., Macromolecules 2005, 38, 9901, a monolithic organic porous body having a co-continuous structure and formed of an epoxy resin is disclosed. However, in Japanese Patent Laid-Open Publication No. 2007-154-83, the actually obtained affinity carrier is a pore having a nanometer size, so that the loss of force at the time of fluid penetration 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, the problem of 097149356 201024342 is not easy to be complicated and requires a high cost. Further, there is also a problem that the functional group such as an ion exchange group or the epoxy resin is guided.

Therefore, it is expected to develop a monolithic material which is chemically stable and has a high hydrophobicity, a continuous high t-hole, an unbiased size, a large continuous 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, the MR type ion exchange resin is known to be attached to a copolymer having a large mesh structure, and exhibits micropores which are formed between the macropores and the smaller spherical gel particles. Particle composite construction. However, in the Mr-type ion parent-replacement resin, the diameter of the particles which are microporous is the largest, and it is not known that there are more than one particle or a composite type organic monolith having protrusions on the surface. (Patent Document 1) Japanese Patent Laid-Open No. 2002-306976 (Application No. 1, paragraph No. 1) (Patent Document 2) Japanese Patent Laid-Open No. Hei 7_5〇114 No. (Patent Document 3) Japanese Patent Laid-Open 2〇〇4_32193〇号号 (Application No. 1 of the patent application) (Patent Document 4) 曰本专利专区 2〇〇7_154〇83 (Application No. 1) [Summary of the Invention] 097149356 7 201024342 \ Therefore' A first object of the present invention is to solve the above problems of the prior art. It is possible to use a sorbent which is chemically stable and has high mechanical strength, low pressure loss at the time of fluid penetration, and a large capacity, or can be used. As a monolithic organic porous body with a continuous macroporous structure and a continuous giant, it is a chemically stable and high-intensity, low pressure loss at the time of fluid penetration, and a large ion exchange capacity per unit volume. Monolithic organic porous ion exchanger having a pore structure and methods for producing the same. In addition, the purpose of the present invention is to provide a monolithic organic porous body which is chemically hydrophobic and which is hydrophobic, has high continuity of pores, is not biased in size, and has low pressure loss during 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 problems of the above-mentioned conventional techniques and provide a high mechanical strength, a high fluid exchange rate with a fluid, a low pressure loss at the time of penetration, and a sorption capacity. The monolithic organic porous body of the large sorbent provides a monolithic organic porous ion exchange with high mechanical strength, high efficiency of fluid penetration and fluid production, and pressure loss of miscellaneous material. Body and its manufacturing method. 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 of 097149356 〇201024342 obtained by the method described in JP-A-2002-306976, the vinyl type is used. When the monomer and the crosslinking agent are subjected to static polymerization in a specific organic solvent, it is possible to obtain a coarse skeleton monolith having a large opening diameter, a skeleton having an organic porous body which is more intermediate than the intermediate body, and a skeleton; When the ion exchange group is introduced into the block, the opening is enlarged because of the large skeleton, so that the opening can be further enlarged; the monolithic block of the coarse skeleton or the monolithic ion exchanger in which the ion exchange group is introduced, because not only the adsorption or Ion exchange is fascinating and uniform, and the capacity per unit volume is large, and the sub-exchange capacity is large, and the average diameter A of π is opened. Therefore, the loss of Lili is extremely small, and the continuous giant pore structure is maintained. The mechanical strength is high and the operability is higher. Further, even if the gas penetrates quickly, 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. The present invention (first invention) provides a monolithic organic porous body characterized in that the bubble-like macropores overlap each other, and the overlapping portion has a flat diameter of 20 to 200" The continuous macroporous structure of the opening has a thickness of more than or equal to the total pore volume 〇 5 to 5 ml/g, and the SEM image of the cross section of the continuous macroporous structure (dry can) is shown in the cross section. The area of the skeleton is image. 25 to 50% in the area. Further, the present invention (first invention) provides a monolithic organic porous problem in which bubble-like macropores are superposed on each other, and the overlapping portion becomes a continuous macroporous structure having an opening of an average of 2 〇 to 200 Å. , thickness is! Above Li, the total pore volume 〇. 5~5ml/g, obtained by the following steps: 097149356 9 201024342 i step, the mixture contains ionic cross-linked oil (4), surfactant and water mixture _ The mixture is made into a water-repellent liquid in the oil, and then the water-emulsion in the oil is polymerized to obtain a monolithic organic porous intermediate having a continuous pore structure of 5 to i6 mi/g of the total pore volume. II step, To prepare a cross-linking agent containing a vinyl monomer and having at least two or more ethylene groups in one molecule, and dissolving the ethylene-type monomer or cross-linking agent but not dissolving by ethylene (4). And a mixture of polymerization initiators; and the hydrazine step is carried out by allowing the mixture obtained in the hydrazine step to stand under the conditions of a monolithic organic porous intermediate obtained by the step 21 A coarse lunar organic porous body having a skeleton thicker than the skeleton of the organic porous intermediate. The exchanger (first invention) provides a monolithic organic porous ion exchanger, which is characterized in that the average straightness is 30 3 〇Γ and the overlap is 1 or more, and the opening is _ _ Continuous macroporous structure, thickness ° · 5 ^ 5ml / g * basal sentence is distributed in the more than two = 〇. 4mg equivalent / ml or more, ion exchange (dry body) in the splitter exchanger, and the continuous In the 25 to 5 ()% sem image in the image area of the macropore structure, the area of the skeleton portion indicated by the scraping surface is another. The present invention (the method for producing the i-th invention, which is characterized by two monolithic organic porous bodies) The following steps are carried out: 624 & The process of 201024342 ι is to prepare an oil-soluble dry body, a surfactant and a water substance without an ion exchange group into a water-drop type emulsion by using a cake, and then A monolithic organic porous intermediate which is obtained by polymerizing a water-drop type emulsion in oil to obtain a total pore-contained macroporous structure: 6 ml/g of the 11-step process is prepared to contain a vinyl monomer, and has a More than one vinyl crosslinker, although dissolved by B (tetra) ~ liver that ι early body or crosslinker but Dissolving a mixture of a polymer starting agent formed by polymerization of an ethylene type precursor; and a mixture of the medium and the polymerization step, the mixture obtained in the step of the step is subjected to the step of the I step, and the mixture is obtained. Right: Polymetallic skeleton in the presence of a porous intermediate. This is a coarse skeleton of the skeleton of a porous body of a porous organic intermediate. The body Si:: hair:) provides a monolithic In the method for producing an organic porous excipient, it is indicated that 'in addition to the above-mentioned monolithic organic porous system, the step IV is carried out step by step, and the step is carried out. The coarse skeleton organic porous material into the ion exchange another (four) is the person _ single block organic multi (four) research, ° fruit hair _ has a customary nature, 遂 complete the 2 2 ^ 矣 can not be achieved by the body In the following U.S. Patent No. 2002-306976, a porous body (intermediate), a monolithic organic _356 having a large pore volume, and an aromatic vinyl monomer When the static polymerization is carried out in a specific organic solvent with the cross-linking agent 201024342, a three-dimensional continuous θ-mercaptoethylene-based polymer skeleton and three-dimensional continuous pores between the skeleton phases are formed, and the two phases are entangled with each other. Continuously constructed hydrophobic monolith; the continuous structure of the monolithic system has high continuity and its size is not biased, and the loss of force when the fluid penetrates is low, and further, due to the skeleton of the co-continuous structure Large, so if the introduction of the ion money base, the monolithic organic porous ion exchanger with a large exchange capacity per unit of the financial phase; the monolithic organic porous ion exchange system is fast and uniform, ion exchange Exchange belt length pressure Sexually short, in addition, because each unit _ "capacity or ion money capacity is large, = large hole, so the dynamic loss is exceptionally small, machine _ high, operability is superior, and then 'even if the gas penetration speed is still It can maintain the sorption and removal ability of gaseous pollutants, even if the smear is pure and can be removed, etc. =, the invention (4) invention provides a monolithic pain plastid, 7 = the skeleton and the total Continuous structure: a skeleton formed by a total of ❹ 1 = crosslinked structural unit G·3 to 5. G mol% of an aromatic vinyl group, and the thickness is a three-dimensional continuous skeleton; Between the heads, the diameter is 8~8〇# m, the three-dimensional 0.5-cut ge continuous working hole; the total pore volume is the system = the next invention (second invention) provides a kind of mono-block organic porous, skeleton and empty Co-continuous structure of a hole: a three-dimensional continuous skeleton which is aggregated into a 'and a thickness of 0·8~4〇μ' in the total composition unit 2(4) structural unit D.3'5.G^%; And a three-dimensional continuous hole with a diameter of 8~80# m between the 097149356 201024342 skeleton; the total pore volume is 0·5~5ml/g 'and The following steps are carried out: in the step I, the oil-soluble monomer, the surfactant, and the water mixture containing no ion parent base are prepared by mixing to form a water-drop type emulsion in the oil, and then the water droplets are made in the oil. The plastic emulsion is mixed into a monolithic organic porous intermediate having a continuous pore volume of more than 16 ml/g and 30 ml/g; the second step is to prepare an aromatic vinyl type single a ruthenium crosslinker having at least two or more ethylidene groups, although the aromatic vinyl monomer or crosslinker is cold-decomposed but does not dissolve the polymer formed by polymerization of the aromatic acetylene 3L monomer. The organic solvent, and the pharmacule of the polymerization initiator, and the step 111, the mixture obtained by the hydrazine step is supplied to the monolithic organic porous intermediate obtained by the step of the first step. Texture of organic porous separation and intrusion of ion exchange groups: a unitary two-hole co-continuous structure: formed by a skeleton of Nalole% aromatic ethylene with a crosslinked structural unit of 0.3 to 5 · three-dimensional continuous And the thickness is a 60-core-continuous hole; its special diameter is 1〇~ 1〇〇_三; -In the state of each unit borrowed 'total pore volume is 0.5~5ml/g, water wet; upper, ion exchange C exchange capacity is. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . In the first step, the mixture of the oil-soluble monomer, the surfactant, and the water which does not contain the exchange group of 201024342 is prepared by dispersing it into a water-drop type emulsion, and then the water-drop type emulsion in the oil is polymerized to obtain a total a continuous macroporous pore having a pore volume exceeding a wrist/g or 3 〇ml/g or less: a monolithic organic porous intermediate produced; a π step, which is prepared by modulating a aryl-containing vinyl monomer, in one molecule, At least 2 or more vinyl total oil-soluble monomers, G· 3 to 5 mol% of the total, although dissolved in the group of ethylenic monomers or cross-linking agents but not dissolved by the aromatic vinyl-type monomer a mixture of the organic solvent of the produced polymer and the polymerization initiator; and the ιπ step, the mixture obtained by the hydrazine step is allowed to stand, and in the monolithic organic porous material obtained by the hydrazine step The polymerization was carried out to obtain a co-continuous structure. Further, the present invention (second invention) provides a method for producing a monolithic organic porous ion exchanger, which is characterized in that: (4) riding the following steps: the step of removing the oil-free frequency and the boundary The water-containing compound is prepared by dissolving the water droplets in the oil, and then polymerizing the oil droplets in the oil to obtain a rapid pore with a pore volume exceeding 16 ml/g and 3{) mi/g or less. In the monolithic organic porous structure of the structure _ ; π step, the sun modulation contains an aromatic ethylenic monomer, and has at least (10) a total of the oil-soluble monomer in a molecule of 稀. 3~5 mo The ear of the ear, the dissolution of the #香乙乙 monomer or the intersection of (four) dissolved (four) a mixture of the organic solvent of the polymer formed by the aromatic vinyl type single vessel, and a mixture of polymerization initiator; The mixture obtained in the step is subjected to polymerization under the condition of standing, and in the presence of the monolithic organic porous intermediate of 097149356 201024342, and: continuous structure and '1' and 1v step are attached to the m The resulting co-continuous structure is introduced into the ion exchange group. ❹ ❹ 嫂 嫂 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; In the monolith obtained by the method described in Japanese Laid-Open Patent Publication No. Hei-3-76, in the presence of a monolithic organic porous body (intermediate) having a large pore volume, under specific conditions, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ And the 'combination structure deblocking or the introduction of the ion-crossing composite single secret sub-recorder, the material _ sub-exchange fast red extremely uniform sentence soil, the pressure loss is small 'the skeleton maintains the continuous pore structure, so High mechanical strength and superior operability 'Further, that is, silk (four) slaves can touch

The dyeing material absorbs the silk removal force, that is, the money body (4) (4) is removed for the super 2. In other words, the present invention (third invention) provides a monolithic organic porous body which is an organic porous filament body or a protrusion composite structure which is formed by a continuous skeleton phase and a continuous pore phase. The organic porous body; the majority of the particles having a diameter of 2, _ adhered to the surface of the skeleton of the organic porous body, or the maximum diameter formed on the surface of the skeleton of the organic porous body is 097149356 201024342 The body has a thickness of 1 mm or more, the average diameter of the pores is 8 to loo in m, and the total pore volume is 0·5 to 5 ml/g. Further, according to the third aspect of the invention, the monolithic organic porous ion exchanger is a composite structure of the following organic (tetra) heteroparticle thief protrusions, and the organic skeleton formed by the continuous skeleton 4 mesh and the continuous pore phase a porous body; a plurality of particles having a diameter of 4 to 4 Å which are fixed to the surface of the skeleton of the organic porphyrin; and a maximum diameter of 4 40 //m formed on the surface of the skeleton of the organic porous body a number of protrusions; the thickness of the protrusion is 1 coffee or more, the average diameter of the hole is 总·5~5ml/g of the total pore volume, and the ion exchange capacity per unit volume in the wet state of water is Q·(4)# quantity/mi Above, the ion exchange group is uniformly divided into a material (four) towel. Further, the present invention (third 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 ion-free body is contained, and at least one molecule has at least one molecule. The mixture of the first chelating agent, the interface living axis and the water of the two or more ethylene groups is prepared by the lining to form a pore-forming liquid, and then the water-drop type emulsion in the oil is polymerized to obtain at least two: : an organic solvent containing an ethylene monomer, a molecule or a second crosslinking crosslinking agent; and an ethylene solvent-dissolving monomer; a polymer obtained by polymerizing a vinyl monomer; And a mixture of polymerization initiators; the mixture obtained with the π II step is allowed to stand under the static setting, and the presence of the single 097149356 201024342 bulk organic porous intermediate obtained by the I step When the porous body is removed, it is polymerized in a mixture; the polymerization temperature in the dHn step is carried out under conditions of at least one of the conditions of the production of the monolith, and at least the conditions of the fish edges (1) to (5): , is a temperature lower than the fading temperature by at least π; Λ ° 1G small of the initiator The mole % of the second crosslinking agent used in the half (2) step is twice or more the mole % of the first crosslinking agent used in the step; 、 (3) The vinyl monomer used in the step 11 'Xing I step in the persimmon, the soluble monomer is a vinyl monomer of no structure; mu oil (4) The organic solvent used in the 11 steps, the system /C:, TT spear knife amount of 200 or more The polyether; (5) The concentrated production of the vinyl monomer used in the 11 step, / / 30% by weight or less in the mixture of the X 'system II steps. Further, the present invention provides a method for producing a monolithic organic porous ion exchanger, which comprises introducing an ion exchange group into the monolithic organic porous body obtained by the above production method. Step (Effect of the Invention) The monolith of the present invention (the first invention) is characterized in that the opening of the macropore and the macropore has a large opening π diameter, so that the low pressure and the large flow H can be performed. The skeleton of the macroporous structure is thick and the thickness of the wall portion constituting the skeleton is also large, so that the sorption capacity is also excellent. Therefore, it is possible to use not only the synthetic sorbent used in the prior art, but also the superior sorption characteristics, and the application to the field of sorption and removal of trace components which cannot be matched by the human sorbent. 097149356 17 201024342 Also, the hair of the hair 1_ shirt __ (four) == Γ ion exchange capacity is large, open to open =: people filled in 2 beds 3 Γ ^ low pressure, large flow for long-term water, and appropriate "= pure The water-making apparatus or the electric deionized water producing apparatus, and the monolithic organic multi-continuous structure of the present invention (second invention)

==τContinue the continuity of the hole is high and its size is not biased and the hole is large, so it can be used to carry out the water and the amount of water, and further, because of the three-dimensional continuous skeleton, _ It can not only replace the synthetic sorbent used in the past, but also: it is superior in absorbing and mixing, and it is used in new applications such as sorption and removal of the corresponding amount of granules.

In addition, the monolithic porous ion exchanger of the present invention (the second invention) has a large exchange capacity per unit of material in the water leak state, and the two-dimensional continuous "large pores" can be The treated water is subjected to long-term (four) water at a low pressure and a large flow rate, and is used in a two-bed, three-tower pure water producing apparatus or an electric deionized water producing apparatus. Moreover, since the pores are highly continuous and their size is not biased, the sorption behavior of the ions is extremely uniform, the length of the ion exchange band is extremely short, and the number of theoretical stages is also high. Further, since the adsorption property of ultra-micro 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. Further, according to the production method of the present invention (second invention), the monolithic organic multi-block organic porous ion exchanger can be easily produced by easily reproducing the 097149356 18 201024342 porous ion exchanger or the above-described ones. The composite monolithic porous body of the present invention (third invention) has a conformal surface of the skeleton phase of the organic porous body of the summer

The composite structure with a plurality of protrusions or a plurality of protrusions formed by the sub-particles has a high contact efficiency with the monolith, and the absorption is fast: and the second is because the skeleton structure can maintain the continuous pore structure, so the mechanical strength is two. Loss is superior. Therefore, it is possible to synthesize not only the corresponding four (four) properties, but also the new application fields of the absorbing and removing materials of the minor components which are not compatible with the nucleating agent.

Further, the composite monolithic porous ion exchange system of the present invention (3rd (4th)) has the same composite structure as the above-mentioned composite monolithic porous body, so that the ion money is rapid and extremely uniform, and the mechanical strength is high, so that it can be The treated water is used for long-term water flow at low pressure and large flow rate, and can be filled in a 2-bed 3-tower pure water manufacturing device or an ultrapure water manufacturing device or an electric deionized water manufacturing device. It is suitable for use as a sorbent for chemical filters. [Embodiment] [Description of the first invention] The following describes the "invention of the object", the "invention of the manufacturing method", and the "invention of the chemical filter" of the first invention. In the present specification, the "monolithic organic porous body" may be simply referred to as "single 097149356 201024342 block intermediate". The organic porous intermediate is simply referred to as "single (indicated by a single block). The basic structure of the monolith of the present invention. The overlapping portion ''rolled cavities are superposed on each other, and the I-knife becomes a common opening (gap average) The diameter is 20, the heart, the preferred continuous macropore structure...the macro hole of the opening and the opening form ^,^5()_, especially good 2G~ then _' is more suitable for the size of the giant hole Gomen' The mouth becomes a flow path. The size of the continuous giant hole structure or the straightness of the opening (4) is not limited to this, and may be a large (h) / a large size h (four). If the opening of the material is uniform, the giant hole. If the average diameter is less than 20, the pressure loss at the time of penetration becomes large, and the shirt is good. If the average diameter of the opening is too large, the contact of the body scale is insufficient, and the result is poor due to the decrease in the sorption characteristics. The average diameter is the maximum value of the pore distribution curve obtained by the mercury intrusion method. In Japanese Patent Laid-Open Publication No. 2001-3G6976, the common opening of the monolith is described as Μ_ /zm' but with respect to the total pores. A monolith with a small volume of pores of 5mi/g or less, because it is necessary to reduce the amount of water droplets in the oil. Since the amount of water droplets in the chemical liquid is small, the common opening is small, and it is impossible to manufacture a substantial average opening diameter of 20 #m or more. The monolithic structure of the present invention has a new structure having a large opening diameter and a large skeleton. The SEM (two-dimensional electronic image of a scanning electron microscope) image of the surface of the continuous macroporous structure (dry body) can be confirmed by SEM149149356 20 201024342. In the SEM image of the cut section of the monolith, The area of the skeleton shown in the cross section is 25 to 50%, preferably 25 to 45% in the image area. If the area indicated by the section is less than 25% in the image area, since it becomes a thin skeleton, each sheet is included. Since the sorption capacity of the volume is lowered, it is not preferable, and if it exceeds the coffee, the skeleton becomes too thick, and the uniformity of the sorption characteristics is lost, which is not preferable. Further, Japanese Patent Laid-Open Publication No. Hei 2-2-3-76 discloses Monolithic, in fact, is expected to increase the phase of the oil phase relative to the water of the Nabi than the skeleton of the money, but for the heterogeneous common opening ratio, there is a limit, the maximum area of the skeleton shown in the section is in the image area and Can't exceed 25%. y = get Na image Conditions, if the condition of the skeleton paste shown in the section of the cut section is presented, for example, the magnification is about 150 mm x l 〇〇 mi ^ SEM observation..., the month & field is + " by excluding the subjective monolithic tone It is carried out in any of the sections of the cut section, preferably five or more images. The three different sections of the household are placed in an electron microscope and are in a dry state. The reference/single block is used to supply images. In addition, the item 7 shows the shape of the SEM photograph of the transfer portion shown in the skeleton section of the beach section, and the section shown in the cross section is 'indefinitely-symbol (2)' in the present invention, Fig. The skeleton part of the surface shown (the curvature of the component or the curved surface is a giant hole (the opening of the figure), and the area of the skeleton shown by the larger surface is the rectangle: symbol 13). As shown in Fig. 7, the skeleton portion can be clearly determined. In the photo area 11, it is 28%. 097149356 21 201024342 In the photograph, the method of calculating the electric field of the skeleton portion is not particularly limited, and the method of calculating the known portion of the skeleton portion is not particularly limited. As an automatic calculation of a computer or the like, or a manual calculation, it is a quadrangle, and (4) 1 calculation, for example, a collection of a circular shape or a ladder material in which an indefinite shape is replaced by an area, and the same is calculated in a single block. The wall 构成 constituting the skeleton of the continuous E-hole structure Λ The thickness of the wall portion is distinguished by the two adjacent giant pythons, the Χ-Χ line of the line (4) at the center of the two giant holes. The thickness of the part (Fig. kdl, d2). Therefore, for example, the column portion surrounded by the adjacent three upper holes is not the wall portion of the present invention. If the thickness of the formed wall portion is less than 20 mm, the sorption capacity per one plucking is lowered, which is not preferable. If it exceeds 200 Å, the uniformity of the absorbing characteristics is lost. 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 obtained by performing at least three SEM observations and taking five or more points out of the obtained image. In the case of the w/〇 type emulsion formed as described above, the monolithic structure of the Japanese Patent Publication No. 2〇〇2_3〇6976 is limited to the maximum pore volume of 5 ml/g or less. Mostly 1〇em. Further, the column of the present invention has a total pore volume of from 5 to 5 ml/g, preferably from 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 of 097149356 22 201024342 is lowered, which is not preferable. Since the monolith of the present invention has the average diameter of the opening and the total pore volume within the above range and is a large particle skeleton, when it is 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 water line speed (LV) lm/h (hereinafter referred to as "pressure difference coefficient". 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 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, and the crosslinking density of the polymer material is not particularly limited to the total of the constituent materials of the filament composite. The constituent unit contains: 0 soil 3. ~50 mol%, preferably 3 to 5 mol% of the crosslinked structural unit. If the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, and if it exceeds 50 mol%, the embrittlement of the porous body occurs, and the softness is lost, which is not preferable. In the case of an ion exchanger, it is not preferable because the introduction of the ion exchange group is reduced. The surface of the polymer material is not limited, and examples thereof include polyethene, poly(α-mercaptostyrene), polyvinyl albino, poly. gasification, and polyethylene. An aromatic B-alkenyl polymer such as polyvinyl naphthalene; a polyolefin of polyethylene or polypropylene; a poly(ethylene) such as polyethylene oxide or polytetrafluoroethylene; and a nitrile such as polyacrylonitrile. A crosslinked polymer such as a polymer; a poly(methyl methacrylate), a polymethyl methacrylate (4), a poly(acrylic acid), or the like (meth) propylene polymer. The above polymer may be 097149356 23 201024342 ==??_subsequent to the (10) compound, or may be polymerized by polymerizing the seed with the crosslinking agent to polymerize the polymer on the -_. In the case of the continuous macroporous structure, the materiality and mechanical strength of the polylayer are easy to collect, and the introduction of the ion exchange group is easy. For the stability of the acid and alkali, it is preferable for the woman. - Erna fit, touch shots such as stupid aggregates. The body or the chlorinated wire is a base of the invention. The thickness of the monolith of the present invention is more than or equal to the lorn, and the disk-like porous temporary enthalpy is distinguished. If it is thick, the amount of the porous body of the job is extremely reduced, because the absorption of each porous body is too good: not good. The thickness of the monolith is preferably 3 jobs ~__. Moreover, since the early block has a large skeleton, the mechanical strength is high. The monolith of the present invention is used as a sorption tube, and the monomer is cut into a shape that can be inserted into the column to be filled as a sorbent and to contain benzene. The sex phase of toluene, argon, and stone is water-passed by the treated water, and * the hydrophobic substance is adsorbed on the sorbent. (Description of Monolithic 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 bubble-like macropores overlap each other, and the overlapping portion has an average diameter of 30 to 30 〇 #m, preferably 30 to 200 #ιη, and particularly preferably 35 to 15 〇 097149356 201024342 ❿ ❹

A continuous macropore structure of the opening (macropores) of Mm. The average diameter of a single ion of six ports is based on the fact that the ion exchange group is guided to the open block of the reading body in a single block, so that the average straightness of the opening of the single block is larger than the average diameter of the single block. //m, due to the pressure of the fluid as it penetrates. If the average diameter of the opening is too large, the contact between the body and the monolith is too large, and the contact becomes insufficient. As a result, the ion exchange characteristics are reduced. The average diameter of the mouth of the exchanger refers to the introduction of the ion exchange group. The former porous material is said to be the above-mentioned opening = multiplied by the swelling ratio of the porous body before and after the introduction of the ion exchange group. In the early block ion exchanger, the skeleton portion image of the cut surface of the continuous macroporous structure is shown on the image side. (4) 25~5G%, preferably 25; 4: The area of the skeleton shown in the cross section is not full in the image area. Since it becomes a fine skeleton and the ion exchange capacity per unit volume is lowered, it is unsatisfactory. If it exceeds 5 (10), the skeleton becomes coarse and large, and ions are lost. The special uniformity is not good. The specific method and measurement method of the skeleton portion are the same as the single block. In the β ion exchanger, the thickness of the wall portion constituting the skeleton of the continuous macroporous structure is about 30 to 300 π μ. If the thickness of the wall portion is less than 3 〇 in m, the ion exchange capacity per single Z product is lowered. Therefore, if it is not good, if it exceeds 30〇vm, then the average sentence of < childhood _ sex is not good. The definition and measurement method of the wall of a monolithic ion exchanger are deblocked (4). The total pore volume of the monolithic ion exchanger is the same as the total pore volume of the monolithic 097149356 25 201024342. That is, even if the opening diameter is increased by introducing the ion exchange group into the monolith, the total pore volume is almost constant due to the coarse skeleton portion. If the total pore volume is less than ml5 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. Still, the pressure loss when water passes through a single ion exchanger is the same as the pressure loss when water is passed through a single block. In the monolithic ion exchanger of the present invention, the amount of ion exchange per unit volume in the water-wet state has an ion exchange capacity of Q. eq/ml or more, preferably 〇 4 to 1. 8 mg. In the conventional monolithic organic porous ion exchanger having the continuous macroporous structure similar to the present invention, as described in Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. No. Hei. No. 6,976, in order to achieve practical requirements. The low pressure loss 'called A opening (four), then the total pore volume increases accordingly, so the ion exchange capacity per unit volume decreases, and the total pore volume is reduced if the parental capacity per unit volume is increased. Small, there is a disadvantage that the pressure loss increases due to the smaller opening diameter. On the other hand, in the monolithic ion exchanger of the present invention, the skeleton of the continuous macropore structure can be thickened (the wall portion of the skeleton is thickened) while further increasing the opening diameter, so that the gambling loss can be reduced. The ion exchange capacity per unit volume is dramatically increased. If the ion exchange capacity per unit volume is less than 4 mg equivalent/mi, the amount of water containing ions that can be treated to breakdown is reduced, that is, the manufacturing capacity of 097149356 26 201024342 is reduced. good. 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 parent base 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/z g equivalent/g. The ion exchange group to be introduced into the monolith of the present invention may, for example, be a cation exchange group such as an acid group, a hydrazine carboxylic acid group, an iminodiacetate group, a phosphoric acid group or a phosphate group; a quaternary ammonium group and a third stage; An anion exchange group of an amine group, a secondary amine group, a primary amine group, a polyethyleneimine group, a third group, a scaly group or the like; an amphoteric ion exchange group such as an amine group acid group or a rhegidyl betaine. In the single (10) child money of the present invention, the ion base of the person to be introduced is not only distributed on the surface of the porous body but also uniformly distributed inside the skeleton of the porous body. Here, the "distribution of the material X" means that the ion exchange groups are distributed such that at least the layers are evenly distributed on the surface and inside the money. The distribution of the ion exchange groups can be confirmed relatively simply by using EPMA or the like. Moreover, if the ion exchange group is not only distributed on the surface of the monolith, but also uniformly distributed to the bone of the porous body, the internal and the physical properties and chemical properties of the surface and the interior are uniform, thereby enhancing the swelling and shrinkage. Long-term financial. The present invention: the single secret is obtained by performing the above steps 1 to ΠΙ. In the method for producing the early block of the present invention, the first step is to prepare the oil 097149356 27 201024342 by using a mixture of the oil-soluble monomer, the surfactant, and the water without ion exchange to prepare the water-drop type emulsion. The water droplet 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 16 m 1 /g. The I step of obtaining a monolithic intermediate can be carried out in accordance with the method described in JP-A-2002-306976. (Manufacturing method of monolithic intermediate) * As the oil-soluble monomer which does not contain an ion-exchange group, for example, an ion-exchange group which does not contain a carboxylic acid group, a carboxylic acid group, a quaternary group or the like, and solubility in water Low, lipophilic monomer. Preferred examples of such monomers include styrene, fluorene methyl styrene, vinyl methyl styrene, vinyl benzyl chloride, divinyl benzene, 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, it is preferable to select diethyl benzene, ethylene glycol dimethyl acrylate or the like. The cross-linking monomer is used as the at least oil-soluble monomer component, and the content thereof is set to be 总. 3~5〇mol%, preferably 〇. 3~5 moles, interface 'tongue' The agent is used in an oil-soluble monomer containing no ion exchange group and water. When the 'water/water droplet type (w/〇) emulsion can be formed, there is no particular limitation. It can be used to make sorbitan monooleic acid, sorbitol laurel lauric acid vinegar, sorbitan oleic acid vinegar, sorbitan Single stearic acid vinegar, sorbitan trioleate, ! 1 poly!: nonionic surfactant activity of vinyl nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sulphate, monooleic acid vinegar, etc. Anionic surfactants such as oleic acid slanting, twelfing base, sodium sulphate, acid sulphonate, dioctyl hydride, etc.; 097149356 28 201024342 cation surfactant such as distearyl dimercapto ammonium hydride An amphoteric surfactant such as lauryl dimethyl sweet. These surfactants may be used alone or in combination of two or more. Further, the term "water droplet type emulsion" means 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 from about 2 to 70%. 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 examples thereof include azobisisobutyronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile benzoyl peroxide, persulfate, and 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 in the oil 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 monovalent body, 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. Method etc. 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. In addition, the mixing conditions 097149356 29 201024342 The mixing speed of the target emulsion particle size is not particularly limited, and the number of revolutions or the scramble time can be arbitrarily set. Tian Xunzhi's monolithic intermediate system has a continuous macropore structure. If the basin and the polymerization are coexisting, the structure of the towel is used as a material to have a porous structure with a coarse skeleton. Further, the monolithic intermediate system has a crosslinked structure of an organic polymer material. The constituting unit of the polymer (4) is defined as a unit of the micro-crosslinked structural unit. (4) If the structural unit is not full ^ Mo %%, the mechanical strength is not good. In particular, in the case where the total pore volume is as large as 1 〇, _, in order to maintain the continuous pore structure, it is preferred to contain 2 mol% or more of the crosslinked structural unit. On the other hand, if it exceeds 50%, it is unfavorable because the porous body is embrittled and the recording property is lost. There is no limitation on the kind of the polymeric batter in the monolith, and it can be exemplified by the same as the above-mentioned monolithic polymer material. Thereby, the same polymer can be formed in the skeleton of the monolithic intermediate body, and the skeleton can be made thick to obtain a monolithic structure. The total pore volume of the monolithic intermediate is 5 to 16 ml/g, preferably (one) 6_. If the total pore volume is too small, the total pore volume of the monolith obtained by polymerizing the vinyl monomer becomes too small. 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 not good from the continuous macroporous structure. 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 097149356 30 201024342 about 1: 5 to 1 : 2 〇 . In addition, the average diameter of the macropores and the pores of the single intermediate system, the opening TM, makes the single-material composite material full, and the pressure loss when the ❹ 穿透 penetrates becomes large, which is not preferable. / = The opening diameter becomes smaller, and the fluid causes the B-things to be transferred to the surface, (4) over-, and the opening diameter of the connection with the monolithic or monolithic ion exchanger becomes too large, and the fluid sub-exchange characteristics are lowered. Not good. In a single block, the body is light enough to result in a uniform structure of the sorption characteristics or the diameter of the kiln, but the limit = giant: the ruler: or the size of the open structure is larger than the uniform macropore size ( The manufacturing method of the monolith is as follows: 11 steps are prepared by modulating a monomer containing ethylene, having a cross-linking of -2 or more in the molecule, and an insoluble bond from the B-early or cross-linking agent: :::=:; machine solvent, and _ after the I step, MUM / step has no order, can be used as ττ+ or step I can be followed by step I. The ethylene monomer used in the step is The oleophilic vinyl type 3 having a high solubility in an organic solvent is not particularly limited, and it is preferred to form a polymer material of the same kind or similar to that of the ifmr in the above polymerization system. Ethylene-type methylbenzene = socially-recognized, for example, styrene, ", vinyl toluene, vinyl chloride benzyl, vinyl biphenyl, 097149356 31 201024342 vinyl naphthalene, etc. Monomer; women's hydrocarbons such as ethylene, propylene, 1-butene, isobutylene, etc.; disaccharide, diterpene, dioxane Single iv desert m, vinylidene gas, tetrafluoroethylene dilute feed of U = alkenyl nitrile,? a vinyl ester such as a nitrile monomer such as a nitrile group; a vinyl ester such as vinyl acetate; a decyl acrylate, an ethyl acrylate, a butyl acrylate, a 2-ethylhexyl acrylate, a methyl methacrylate, a methyl propyl acrylate Acetyl propyl acrylate, methyl acetonate butyl vinegar, methacrylic acid 2 - ethyl hexanoic acid, methyl propylene hexanoic acid, methacrylic acid vinegar, epoxy propylene vinegar, etc. Base) acrylic acid monomer. These monomers may be used alone or in combination of two or more. The ethylene monomer suitable for use in the present invention is an aromatic ethylenic monomer such as ethylene or a vaporized ethylenic group. The amount of such a monomer to be added is 3, times, preferably 4, by weight relative to the monomer which coexists at the time of polymerization, and if the amount is less than 3 times with respect to the porous body, Second, the thickness of the wall of the monolithic skeleton cannot be thickened, and the ion per unit volume per unit volume = ion exchange group is excellent. On the other hand, if the amount of the ethylenic monomer added exceeds a small amount, the magic loss at the time of fluid penetration becomes large, which is not preferable. ...the opening of the I: the crosslinking agent used in the step is suitable for use in a molecule containing at least two polymerizable vinyl groups, and the solubility in the organic solvent is high. For example, diethyl benzene, two Ethylene-based Cai,: $crosslinking agent ethylene glycol dimethacrylate, three? ~Vinylbiphenyl, T-propane diacrylate, butanediol 097149356 ❹ 32 201024342 Dipropylene. Material delivery _ can be used separately. From the viewpoint of mechanical strength and stability to hydrolysis, it is preferred that the agent is -vinyl wire, diethyl naphthalene, and the aroma of the second county joint:: ethylene and _ 衩 preferably 0. 3, Moer%, Tejiao. 3~5mol%: 吏==0.3m ear due to insufficient strength of the monolithic maple: Loss of two 'if more than Μmol%' due to the occurrence of monolithic The problem of embrittlement and loss of flexibility is that the introduction amount of the ion exchange group is reduced. Further, the above-mentioned amount of the cross-linking is preferably used in such a manner that the cross-linking density of the mono-complex which coexists in the polymerization of the monomer-crosslinking agent is almost the same. If the amount of the two is too large to be separated, the generated distribution of distribution is biased, and the ion exchange group leads to the reverse crack. The Π step is used: there is a solvent, which is an organic solvent which dissolves the ethylene monomer or the crosslinking agent but does not dissolve the polymer formed by the polymerization of the ethylene monomer. In other words, the ethylene monomer is polymerized. The resulting polymer is a poor solvent. The organic solvent is different from the type of the vinyl monomer, and the duck is different. For example, in the ethylene type single solvent, methanol, ethanol, propanol, butanol, caproic acid, cyclohexanol, octanol, 2-ethylhexanol, fermentation, fermentation, ethylene glycol, Propylene glycol, butylene glycol,

Alcohols such as glycerin, ethyl ether, ethylene glycol, dimethyl sulfonate, acesulfame, butyl acesulfame, polyethylene glycol, polyene, acesulfame, sulfhydryl π-alcohol, polybutane Alcohol, etc. 097149356 33 201024342

Chain-like (poly)ethers; chain-like saturation meanings such as traits, branches, branches, Wei, and 12th courtyard; vinegar H-acetate, _ _ _ _ _ _ _ _ _ _ _ s day . Further, even a good medium which is a mixture of benzene and benzene, which is used in the same manner as the above-mentioned poor solvent, can be used as an organic solvent. The amount of the organic solvent used is preferably such that the amount of the right organic solvent is out of the above range and the concentration of the ethylenic monomer is less than 3% by weight, so that the concentration of the ethyl monomer is 30 to 80% by weight. The polymerization rate is lowered, or the monolithic structure after polymerization is out of the range of the present month, which is not preferable. On the other hand, if the concentration of the ethylenic monomer exceeds the other weight %, the polymerization may be out of control, which is not preferable.

As the polymerization initiator, a radical compound which generates heat by heat and light irradiation is suitably used. The polymerization starts with (iv) rotation. Specific examples of the combination initiator used in the present invention include, for example, 2,2'-azobis(isobutyronitrile), -oxybis(2,4-dimethylvaleronitrile), 2, 2, nitrogen bis(2-methylnitrile), 2'2, azobis(4-methoxy-2,4, dimethyl pentane), 22, azobisisobutyric acid , 4, 4, Yishuang (4_cyanovaleric acid) ~, azobis(cyclohexane-1-carbonitrile), peroxide abrupt A, rolling Benzoyl, peroxide lauryl, sulfur peroxide Self-invitation, sulfur _, sulfur _. The amount of use in the polymerization (4) varies greatly depending on the type of the monomer, the polymerization temperature, etc., and can be used in the range of about 1 to 5% with respect to the total amount of the ethylene type single ''linking agent. The resulting mixture is obtained from a single piece of _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Important =, _ 明之_新构造- in. ^ 犯. As disclosed in Japanese Patent Special Table 7-501140, 4 single (four) _ there is no child in the specific organic extraction + 'main early body When the static polymerization is carried out in the parent medium, the particle 隼 = = organic porous body can be obtained. On the other hand, in the above-described poly-system, the monolithic structure of the continuous teaching hole structure exists in the above-mentioned poly-system, and the riding is performed. The structure of the single block after the occurrence of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The particle-aggregation structure is formed by the precipitation of the cross-linked polymer produced by the polymerization. Hide this phase, if the polymerization "^ presence of a porous material (Intermediate) '_ the B monomer and a crosslinking agent from the liquid sorbent or partitioned months of shelf Xizai plastid. (5) Polymerization in a porous body to obtain a monolithic monolithic block. Further, although the opening diameter is narrowed by the progress of polymerization, the total pore volume of the monolithic intermediate is large, so even if the skeleton becomes coarse The skeleton can also obtain an opening diameter of a moderate size. If the product in the reaction vessel is limited to the size of the monolithic intermediate in the reaction vessel, when the monolithic substrate is placed in the reaction vessel, It can be any one of the single-piece intermediates in a plan view, or a single-piece intermediate without any gaps in the reaction vessel. Among them, the aggregated monolithic monolith is not squeezed by the inner wall of the container. Pressure, without any gap placed in the reaction vessel, is a single block without strain, no waste of reaction materials and effective 097149356 35 201024342 rate. In addition, even if the internal volume of the reaction vessel is larger, the monolithic after polymerization In the case where there is a gap around it, since the vinyl monomer or the crosslinking agent is adsorbed and distributed to the monolith intermediate, no particle coagulation structure is formed in the gap portion in the reaction container. Life τ, early Intermediate system to dissolve a mixture of: a state of containing the mixture was placed leaching step with that obtained from a single block of the intermediate complex .II aforesaid example, with respect to the preferred system according monolith intermediate, single ethylene,

The amount of addition is carried out in a manner of 3 to 40 times, preferably 4 to 3 times, by weight. Thereby, a block having an appropriate opening diameter and having a large skeleton can be obtained. In the reaction vessel, it is difficult to carry out the polymerization in which the ethylenic monomer and the crosslinking agent in the mixture are occluded and distributed to the monolithic intermediate which is left to stand. Read on the skeleton of the early block intermediate f. Select various conditions 1

Methyl valeronitrile), peroxyformic acid dibasic 2,2-anionic double (", when used as a starter, in an inert environment, C is heated to polymerize for 48 hours 4 "Yi Nei" 3 (M〇{ is assigned to the single _ = by heating polymerization, so that sorption, polymerization, the skeleton is coarse. Poly-dioxane and cross-linking agent into the skeleton into the unreacted B-monomer After the organic second =, the content is taken out to remove the extraction to obtain the crude bone I, and the solvent axis of the propylene network or the like is 097149356 36 201024342 / time, and the monolithic ion exchanger of the present invention is illustrated. The method for producing the monolithic ion exchange system is not a special ship, and the monolithic ion exchange body can be closely controlled, and the monolithic method can be used to manufacture a monolith. The method of introducing the ion exchange group is preferably carried out. The method of introducing the ion exchange group into the monolith is not particularly limited, and a known method such as 13⁄4 molecular reaction or pure polymerization can be used. For example, as a method of introducing a reductive acid group 'For example, if the monolith is styrene-diethylene Benzene conjugated polymer, etc.' is a method for hardening sulphuric acid or concentrated sulphuric acid or fuming sulfuric acid; in a monolithic block, the radical starting group or chain is shifted to the surface of the frame and the inside of the skeleton A method of graft-polymerizing sodium or acrylamide 2 -methylpropanoic acid; similarly, a method of grafting a methyl group with an epoxy group and a method of converting a functional group to a human base by grafting polymerization. As a method of introducing a four-stage recording base, for example, if the monolith is a phenylethylene-diethylene benzene-based polymer, etc., by a chloromethylmethyl group, a chlorohydrazine group, and a tertiary amine ^ 反 反 ; method; in a single shot, the free radical starting group or bond moving group is introduced into the surface of the skeleton and the inside of the skeleton, so that Ν, Ν, Ν~ trimethyl sulfoacetate or Ν , Ν,Ν-trimethylammonium propyl acrylamide, a method of graft polymerization; similarly, methyl propylene acrylate is grafted and polymerized, and then introduced into the fourth stage by functional-based conversion. The method of introducing an ammonium group, etc. Further, as a method of injecting a beet, for example, a method of introducing a tertiary amine into a monolith by the above method allows a single shift A method of introducing acetic acid into a reaction, etc. In the viewpoint of introducing an ion exchange group uniformly and uniformly, in the method of introducing a rhyme group, 097149356 37 201024342 preferably uses chlorosulfate to phenyl bromide. The method for introducing an acid group into a dilute benzene benzene copolymer is used as a method for introducing a quaternary substrate, preferably by introducing a gas methyl group by a chlorophenyl decyl ether or the like. Thereafter, a method of reacting with a tertiary amine or a method of producing a monolith by co-polymerization of chloromethylstyrene and divinylbenzene, and reacting with a tertiary amine. Further, as an ion exchange introduced The base may, for example, be a cation exchange group such as a carboxylic acid group, an iminodiacetate group, a sulfonic acid group, an acid group or a carboxylic acid ester group; a quaternary ammonium group, a tertiary amino group, a secondary amine group, and a first order An anion exchange group of an amine group, a polyethyleneimine group, a third fluorenyl group, a squara group or the like; an amphoteric ion exchange group such as an amino phosphate group, a beet oxime or a sulfobetaine. The monolithic ion exchange system of the present invention greatly expands to, for example, 1.4 to 1.9 times the coarse skeleton by introducing an ion exchange group into a monolithic block of the coarse skeleton. That is, the degree of swelling is much larger than that of the ion exchange group in the conventional block described in Japanese Patent Laid-Open No. 2〇〇2_3〇6976. Therefore, even if the opening diameter of the coarse skeleton is small, the opening diameter of the monolithic ion exchanger is changed by about the above magnification, so that the opening diameter is increased due to swelling, and the total pore volume is not changed. Therefore, the monolithic ion exchanger of the present invention has a large opening diameter only, and has a high mechanical strength due to a thick moon frame. In addition, since the skeleton is coarse, the ion exchange capacity of each of the aging threats and the volume of the early volume can be increased in the wet state of the water, and the water to be treated can be produced for a long time, and can be filled with water. It is used in a 2-bed 3-tower system or an electrical deionized water production unit. <Description of the second invention> 097149356 38 201024342 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 a monolith having a co-continuous structure of the present invention is a three-dimensional continuous skeleton having a degree of 0.8 to 40 A, and a three-dimensional continuous space between the skeletons. The construction of the hole. That is, as shown in the schematic diagram of Fig. 18, the continuous skeleton structure is a structure in which a continuous skeleton phase is entangled with a continuous pore phase 2 and each has a three-dimensional continuous structure. Since the continuous pore 2 is more continuous than the conventional continuous bubble type monolith or particle agglutination type monolith, and its size is not biased, extremely uniform ion sorption behavior can be achieved. Also, the mechanical strength is high due to the large skeleton. If the diameter of the two-dimensional continuous pores is less than gem, the pressure of the mussels becomes large due to the fluid penetration, so it is not good, and if the right is over, the contact between the fluid and the monolith is insufficient, and as a result, the adsorption characteristics are lowered. Therefore, the size of the above-mentioned three-dimensional continuous hole refers to the measurement of the pore distribution curve by the mercury intrusion method, which 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 〇 8 to 4 〇 m, preferably 1 to 〆 10 . If the thickness of the skeleton is less than 88/zm, the sorption capacity of the bit volume is reduced or the mechanical strength is lowered, and the mechanical strength is lowered. On the other hand, if it exceeds 40#m, the sorption characteristics are lost. The uniformity is not good. 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. ~ 097149356 39 201024342 In addition, 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 5 inl/g ', the pressure loss during fluid penetration becomes large, which is not preferable. Further, the amount of penetrating fluid per unit sectional area becomes small, and the treatment capacity 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. The circulation of the ground can be used to give superior performance. In addition, the pressure loss when the water penetrates the monolith is the pressure loss when the water is passed through the column line filled with the porous body lm at a water velocity (LV) lm/h (hereinafter referred to as "pressure difference". 005〜0. 5MPa/m . LV range, especially good. 01~0. IMPa/m · LV. In the monolith of the present invention, the material constituting the skeleton of the co-continuous structure is a colloidal structural unit containing G. 3 to 5 mol%, preferably 〇 5 to 3 · 〇 mol % in the total constituent unit. The family of vinyl ketones is hydrophobic. If the cross-linked structure is less than G·3 mol%, it is not good due to mechanical shortage, and the other =::Super: 5 mol%, the structure of the porous body is easily separated from the co-continuous: There are no restrictions on the type of the compound, such as polythene, poly(methylstyrene), polyvinyl albino, polyaminated olefinic benzyl, polyvinylbiphenyl, polyvinylnaphthalene and the like. The above-mentioned polycondensation allows the copolymerization of the individual ethylidene monomer and the cross-linking agent to obtain the copolymer of the ethylenic monomer and the (iv) agent to obtain ^^ 097149356 201024342, or may be two More than one polymer blender. Among these organic polymer materials, the ease of formation of the co-continuous structure, the ease of introduction of the ion exchange group, the strength of the mechanical strength, and the stability to the acid/base are preferably styrene-two. Vinyl benzene copolymer or chlorovinylbenzyl-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. Further, the method of absorbing the monolithic material of the second invention is the same as the method of making the monolith of the first invention as a sorbent, and the description thereof is omitted (the description of the monolithic ion exchanger). A monolithic ion exchanger of the invention. In the monolithic ion exchanger, the same constituent elements as the monolith are omitted. Monolithic ion exchange (4) having the following skeleton and pores; continued: a two-dimensional continuous skeleton having a thickness of a conductor ion exchange group of 6 Mm, preferably 3 to 58 mm; and between the skeletons, The three-dimensional continuous pores of diameter 1 (Μ00_, preferably 15~9〇_, Tejiaguan_). The surface of the skeleton of the single ion exchanger is the surface of the (4) sub (four) base when it is introduced into the monolith. i Due to the swelling of the monolithic whole body, it is more straight and large than the skeleton of the monolithic block. The continuity of the pores of the continuous hollow hole is recorded as a continuous disordered monolithic organic porous f ion exchange filament. The sub-agglomerated monolithic organic porous ion has a higher cross-linking, and its size is not _, so the ion sorption behavior of the extremely uniform sentence can be achieved. If the diameter of the three-dimensional continuous pore is less than 10_, 097149356 201024342 is due to fluid wear. If the loss of the material becomes large, the contact with the organic porous ion exchanger becomes insufficient, and as a result, the ion read characteristic is not uniform or the capture ability of the ultra-micro ion is lowered, which is not preferable. If the thickness of the skeleton is less than 1 Am, the ions per unit volume will occur. The disadvantages such as a decrease in the amount of exchange volume and a decrease in mechanical strength are not preferable. On the other hand, if the thickness of the skeleton is too large, the uniformity of the ion exchange characteristics is lost, and the length of the ion exchange belt becomes long, which is not preferable. The diameter of the pores of the body can be described as the method of calculating the diameter of the hole in the filament subdomain, and the method of calculating the diameter of the monolithic block before and after the introduction of the _ sub-wire guide (4); A method for analyzing by a known method, and a method of calculating the thickness of the skeleton in at least three readings of the image obtained by at least three readings in the image obtained by multiplying the ion exchange group into the early block, And the method of analyzing the image in the form of a square: square = line. The skeleton is a rod-shaped and circular cross-sectional shape, but may also have an average of a different diameter and a long diameter such as a circular cross-sectional shape. The thickness is a short diameter single. In the block ion exchanger, 'three-dimensional connection, if the thickness of each single_product 7 is less than 097,149,356 ❹ super--there is a poor loss due to the loss of ions, 'if the monolithic ion is poured, and the material is Poor. In addition, the total pore volume of a single ion Two::::: [49356 42 201024342 The product is the same. That is, even if the _ in the monolith is guided by the ion exchange group to swell and the opening 仏 becomes large, the total pore volume hardly changes due to the coarse skeletal portion. If the total filament volume is less than na. 5na/g, the waste force and loss will become better due to the penetration. In addition, the frequency of each surface of the single (four) material becomes smaller, and the treatment is reduced. On the other hand, if the total pore volume exceeds 5 ml/g, the material exchange capacity per unit volume is not reduced. If the size of the three-dimensional continuous pores and the total pore volume are in the above range, then the fluid is called. The contact pole is uniform and the contact area is large, and the fluid can be penetrated under low pressure loss, so it can play the superior performance as an ion clock. Moreover, the pressure loss when water passes through a single ion exchanger is The pressure loss when water passes through a single block is the same. In the monolithic ion-equivalent of the present invention, the ion exchange capacity per unit volume in the water wet state has an ion exchange capacity of G. 3 mg equivalent/ffll or more, preferably G 4 to i 8 mg when set/ml. In order to achieve practical requirements, a conventional monolithic organic porous ion having a continuous macroporous structure different from the present invention, as described in the Japanese Patent Laid-Open Publication No. 2, No. Hei. When the pressure is reduced, and the opening diameter is increased, the total pore volume is also increased as the total pore volume increases, so that the ion exchange capacity per unit volume is lowered, and if the exchange capacity per unit volume is increased, the total volume is reduced. When the pore volume is reduced, there is a disadvantage that the pressure loss increases because the opening diameter becomes small. 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 is not increased even if the total pore volume is lowered. Therefore, the ion exchange capacity per unit volume can be dramatically increased under the pressure loss of 097149356 43 201024342. 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, i.e., 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 preferably 500/zg equivalent/g at most. 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 monolith of the first invention, and the description thereof is 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 mixing a mixture of an oil-soluble monomer, a surfactant, and water which does not contain an ion exchange group, and then in an oil. The water droplet type 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) 097149356 44 201024342 The base, the rhyme base, and the four-scale material are similar, such as a monomer which does not contain lipophilicity. As a low-transition L, aromatic ethylene, vinyl toluene, vaporized ethylene, benzene, ethylene-based Cai and other aromatic ethylenic monomers; B = base, ethyl women-based, "hydrocarbon; Women, different:::~, olefin: early body · 'chlorinated acetonitrile, austenated ethylene, partial ethylene, ethylene, etc.::: two of the two; smoke; two acrylonitrile, ^ 埽, etc.: C: thin, B Paper _ acid = B: :: ~ propionate 2-ethyl hexanoic acid, methyl ethyl: hydrazine, ethyl acrylate, methyl propyl acid k 曰 5 曰, methyl propyl 2-ethyl hexose, methyl _环二二二=methylpropyl _::cyclo-(, _ _ _;:::7 propyl hydrazine vinyl acetophenone, gasified vinyl benzyl group, dimethyl basic diol, one alone or in combination 2 kinds of soil. These monomers can be more ion exchanged and laughed. 'The second step is selected as the at least oil-soluble monomer component by the preferred step in the subsequent steps, (4), etc., the combination of single 〇. 3~5 Mol%, preferably 〇. 3~3 莫耳: The acknowledgment ~ by the soluble monomer in the surfactant system is the same as the i-th invention, and the description thereof is omitted. The surfactant phase used in the first step is 097149356 45 201024342

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, 丨'1'-azobis(cyclohexane-1-indene nitrile), benzoyl peroxide base, Peroxidized laurel base, persulfate unloading, persulfate, thiocyanate, hydrogen peroxide-ferrous chloride, sodium persulfate-acidic sulfite, etc. as an oil-soluble monomer, interface containing no ion exchange group The method of mixing the active agent, the water, and the polymerization initiator to form a water-drop type emulsion in the oil is the same as the method of the first step in the first step of the first invention, and the description thereof is omitted. Intermediate system with organic polymerization of crosslinked structure

The material is preferably an aromatic vinyl polymer. The intersection of the polymer material: the total constituent unit of the constituent polymer material. The % of the composition is preferably 〇·3. If the structural unit is less than 〇3 耳q 旲 ear% of the crosslinked structural unit. Handover: On the other hand, if Zhao Man R, it is not good due to insufficient mechanical strength. b Mo %%, the continuous structure of the head 1 is not good. In particular, since the structure of the monolith is easily detached, in the case of a small value in the middle, the volume of the pores and the pore volume of 16 to 20 ml/g is preferably less than 3 mol. ;, a continuous structure, so the cross-linked structure 097149356 46 201024342 The type of the polymer material of the monolithic body is the same as the type of the polymer material of the monolithic intermediate of the invention of the second invention, and the description thereof is omitted.

The total pore volume of the monolithic intermediate is more than 16 mi/g and 3 〇ml/g or less, preferably 6 to 25 ml/ge, that is, the monolithic intermediate system is basically a continuous macroporous structure due to macropores and The opening (gap hole) of the overlapping portion of the macropore is extraordinarily large, so that the bone constituting the monolithic structure has a structure in which the two-dimensional wall surface is infinitely approximate to the one-dimensional rod-shaped skeleton. When it is coexisted with the polymeric strand, the structure of the monolithic intermediate is used as a mold to form a porous (four) having a co-continuous structure. If the total pore volume is too small, since the structure of the monolith obtained by polymerizing the vinyl monomer changes from the continuous structure of the mound to the continuous macroporous structure, it is not preferable, and if the total pore volume is too large, the It is not preferable that the mechanical strength of the monolith obtained after the polymerization of the monomer is lowered or the ion volume per revolution volume is lowered. When the monolithic pore volume is set to a specific range of the present invention, the ratio of monomer to water can be set to about 1:20 to 1:40. The opening of the overlap between the macropore and the macropore in the intermediate system of the singularity (the gap is 5~1 is called m°, and if the average diameter of the opening is less than 5_'), the monolithic block obtained after the polymerization of the monomer is changed, h The fluid sound permeability makes the breasts unsatisfactory. On the other hand, if it exceeds 10_, the opening diameter of the monolith obtained after the polymerization of the monolithic Ge-I body becomes a society, and the flow and the soap block are early. The block ion exchange exchange property is reduced by h. The result is that the sorption characteristics or the diameter is uniform. The monolithic intermediate is preferably a macroporous size or an open structure, but is not limited thereto. In order to uniformly structure 097149356 201024342, there is a non-uniform giant k with a relatively uniform macropore size. (Manufacturing method of monolith) The second step is to prepare an aromatic ethylenic monomer, having at least 2 in one molecule. More than one vinyl ether-soluble monomer in the total amount of 交联剂. 3~5 mol% of the cross-linking agent, dissolving the aromatic vinyl-type monomer or cross-linking agent but not dissolving the polymerization formed by the ethylenic monomer The step of mixing the organic solvent of the substance with the polymerization initiator. The steps I and II are not smooth. In the order of I, the step II can be carried out after the step I. The step I can also be carried out after the step π. The aromatic vinyl monomer used in the second step is an organic solvent which is polymerizable in the molecule. The lipophilic aromatic vinyl type monomer having high solubility is not particularly limited, and it is preferred to select a monomer which is the same or similar polymer material as the monolith intermediate which coexists in the above polymerization system. Specific examples of such a vinyl monomer include, for example, styrene, 0:-methylstyrene, vinyltoluene, vaporized ethylenevinylbiphenyl, vinylcaine, etc. These monomers can be used alone, 2 The present invention is suitable for the aromatic use of ethylene, ethylene chloride, etc. The early body, such as the stupid B of such aromatic vinyl monomer addition amount of monolith intermediate - double the weight The amount of the rare monomer added in time is less than that of the porous body. 1 The fragrant rod-shaped skeleton cannot be thickened, and the amount of ionic ions per unit volume generated by the absorption capacity per unit volume Volume change = ion transfer base 097149356 on the other hand 4 8 201024342 If the amount of vinyl monomer added exceeds 50 times', the diameter of the continuous pores becomes smaller, and the pressure loss when the fluid penetrates becomes too large. The symmetry of the π step is suitable for the test molecule to contain at least Two polymerizable B counties, the high turnover of the financial media. As a specific example of the cross-linking agent, for example, divinylbenzene, divinylnaphthalene, diethylene-based, and ethyl dimethyl ether may be mentioned. Propylene, tris(tetra)-propylpropanol-triacetin vinegar, butanediol dipropylene roasting vinegar, etc. These cross-linking agents can be used alone or in combination with two kinds of h by mechanical strength and the hydrolysis of thieves Sexually, the cross-linking agent is an aromatic polyethylene compound such as diethyl benzene, diethyl phthalene, divinyl phenyl, etc.. _ use (iv) relative to (iv) the total amount of the coupling agent (total The oil-soluble monomer is preferably &amp; Ο" 〇. 3~3 mol%. If the cross-linking amount is less than Q3 mol%, the mechanical strength of ° is less than g. In addition, (4), if (4)/the early block is deuterated and loses its softness, the ion guide wire produces a single problem, which is not good. Further, the cross-linking amount of the above-mentioned cross-linking agent is preferably used in the same manner as the cross-linking of the monolithic intermediate which is coexisting in the polymerization of the cross-linking monomer/crosslinking agent. If the usage of the two is too large and separate, it will be biased in the monolithic distribution. In the reaction of the lead, the II step is organically secreted, although it is an aromatic solvent or a cross-linking agent but does not dissolve the organic solvent of the W-type 097149356 which is composed of the aryl (tetra) ethyl (tetra) monomer, in other words, the aromatic vinyl Type = poly == 49 201024342 The polymer is a poor medium. Since the organic solvent is largely different depending on the type of the aromatic vinyl monomer, it is difficult to cite the type of the monomer. The ethylene monomer, MeT, for example, when the aromatic is ethylene, the organic solvent is methanol or ethanol. Alcohols such as propanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decyl alcohol, twelfth alcohol, alcohol, butanol; diethyl butyl, butyl Key-like (poly) hydrazines such as celecoxime, polyethylene glycol polypropanol, polytetramethylene glycol, etc.; bond-like saturation of hexane, gamma, cinnabar, isomorphic, sputum, and twelve Tobacco; acetic acid ethyl acetate, isopropyl acetate, sodium acetate, and propionic acid. Further, even a good solvent such as m, or benzene-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 to be used is preferably such that the aromatic vinyl monomer concentration is from 4 to 30% 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 3% 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 aromatic vinyl monomer exceeds 8% by weight, the polymerization may be out of control, 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 polymerized in the presence of the monolithic intermediate obtained in the step i, and the continuous macroporous structure of the monolithic intermediate is changed into a co-continuous structure. The step of a single block of the skeleton. The monolithic intermediate used in the ΠΙ step is not only the one that creates the 097149356 50 201024342 of the present invention, but also plays an important role in the negative electrode. As disclosed in Japanese Patent No. B01HG, if a vinyl monomer and a cross-linking specific organic ray are allowed to stand still in a single block, a monolithic organic porous material obtained by particle coagulation (4) is obtained. body. On the other hand, if the monolithic intermediate of the continuous macroporous structure is stored in the above polymerization system as in the present month, the structure of the aggregate after the polymerization is drastically changed, and the particle agglomerate structure is lost: A monomer that is continuously constructed. The reason for this has not been explained in detail, and it can be said that in the absence of a monolithic intermediate, it is precipitated and precipitated into particles to form a sub- &lt; twin-aggregated polymer agglutination structure. The quality of the daring (intermediate thinking)', the ethylene type single Zhao and the cross-linking agent 2 are matched to the skeleton of the porous f-Zhao, and the poly-portion is formed in the porous structure. The skeleton constituting the monolithic structure is formed from the two skeletons and has a co-continuous structure. The content of the monolithic organic porous body in the shape of the rod-shaped anti-f container is the same as the internal product of the reaction capacity n of the first judgment, and the description thereof is omitted. In the step (1), the intermediate system of the reaction vessel is placed in an aged state. In the second step, the jin is as described above, and the preferred product: is compounded with a single intermediate. The amount of the aromatic compound added is (four) times, preferably, by weight. In this way, you can get a suitable way to enter the Α愧 Α愧, 隹 你 你 你 ▲ ▲ ▲ 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 ▲ 灭 灭 灭 ▲ 灭In the material family B _ monomer wealth coffee, J standing: 097149356 51 201024342 single-block intermediate on the skeleton, polymerization in the skeleton of a single 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 watered for a long time at a low pressure and a water flow rate, and can be suitably 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 the third invention> Hereinafter, the invention of the third invention, the invention of the production method, and the invention of the chemical filter 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". 097149356 52 201024342 (Description of composite monolith) The composite structure of the composite monolith of the present invention is an organic porous body having the following organic porous body and a particle or a Wei-like composite structure: an organic porous body formed by a material (four) and a relatively porous phase And (4) a plurality of particle bodies 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 (4). Further, in the description of the third invention, the "particle body" may be used. The combination of "protrusions" is called "particles, etc."

The continuous framework phase of the organic porous body and the continuous pore phase can be observed by image. The basic structure of the organic porous body may, for example, be a continuous macroporous structure and a co-continuous structure. The skeleton phase of the organic porous body exhibits a columnar continuous body, a continuum 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 body: the bubble-like macropores are superposed on each other, and the overlapping portion is an opening having a mean diameter of (4) 〇_ (4) a continuous macroporous structure (hereinafter sometimes referred to as "the first organic porous" The plastid ".); and the thickness is U~, 40 (10) three-dimensional continuous", and the diameter between the skeleton (four)

The bubble formed in I becomes a flow path. Continuous macroporous structure 097149356 The uniform structure of the size or the opening of the straight ♦, but not limited to this, may also be 53 201024342 in the uniform structure, the point has a more uniform macroporous size of the uneven macropores. If the average diameter of the opening is less than 2 〇 wm, 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. So it is not good. The average diameter of the above opening means 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 m, the pressure loss at the time of fluid penetration becomes large, which is not preferable, and if it exceeds 8 〇 in m ', the fluid and the monolith are The result of insufficient contact is not good because of the sorption behavior of the absorbing substance or the low concentration of the absorbed substance. 8〜40/z米之间。 The three-dimensional continuous pore size is the maximum value of the pore distribution curve obtained by the SEM image observation method or the mercury intrusion method, and the skeleton thickness of the continuous structure is 0. 8~40/zm, Good 1~30#m. If the thickness of the skeleton is less than 〇., the sorption capacity per unit volume is lowered and the mechanical strength is lowered, which is not preferable. On the other hand, if it exceeds 40/zm, the uniformity of the sorption characteristics is lost. So it is not good. The skeleton thickness and the opening diameter of the above-mentioned organic porous body can be calculated by performing SEM image observation of at least three times of the organic porous body, and measuring the skeleton diameter and opening in the obtained image. In the composite monolith of the present invention, a plurality of particles having a diameter of 2 to 20/m on the surface of the skeleton of the organic porous body and a plurality of protrusions having a maximum diameter of 2 to 20/m are formed on the surface of the skeleton. Body can be observed by SEM image. Particles 097149356 54 201024342 The body is integrated with the surface of the skeleton phase. The particles that are observed as particles are called particles, and the particles are partially buried in the surface, and those that cannot be called particles are called protrusions. The surface of the skeleton phase is preferably coated with a particle body or the like by 40% or more, preferably 5 or more. ° The diameter of the particle body and the maximum diameter of the protrusion are preferably 3 to 15/^m, and the ratio of the particle size of '3 to 5//m in the total particle size of 3~l〇em' total particle body, etc. It is 70% or more, and particularly preferably 80% or more. Further, the particle body may also be generated by the particle bodies. At this time, the diameter of the particle body refers to an individual particle straight melon. 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 above diameter and maximum diameter refer to the value of 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 coating ratio of the particles to 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 sorption behavior is impaired. The tendency is 'not good. The size or coverage of the above-mentioned particle body or the like can be obtained by performing image analysis on the SEM image of the single block. The total pore volume of the composite monolithic system of the present invention is 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 unsatisfactory, and the amount of 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 097149356 55 201024342 is too large, the per unit of bribes will be low. The composite monolith of the present invention has a high efficiency in contact with a fluid because the filament body or the like is attached to the composite structure on the wall surface or the surface of the skeleton phase forming the monolithic structure. The fluid circulates smoothly, so it can exert superior performance. The aperture diameter of the composite monolith is 8~1〇〇em, preferably 1〇~8〇em. When the organic porous body constituting the composite monolith is the first organic porous body, the preferred pore diameter of the composite monolith is 1 〇 8 8 〇 em, and the organic porous constituting the composite monolith is the second organic porous body. In the case of a plastid, the preferred value of the pore diameter of the composite monolith is 10 to 60/zro. 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 or more, which is different from the porous body in the form of a film. If the right 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 'passes water to be treated with a water-repellent substance containing a hydrophobic substance such as stupid, benzene, benzene, or stone, and the above-mentioned hydrophobic substance is efficiently absorbed on the sorbent. 097149356 56 201024342 Still, the pressure loss when water penetrates the composite monolith, if the pressure is lost when the water is passed through the water column speed (LV) lm/h of the pipe column filled with the composite monolithic lm (hereinafter referred to as For the "pressure difference coefficient", it is preferably 0·005~0. lMPa/m · LV range, special 〇. 00 〇. 〇 5MPa/m · Lv. The composite single piece of the present invention constitutes a skeleton phase of the teaching hole structure, and is an organic polymer material having a crosslinked structure. The cross-linking density of the polymer material is not determined by ❹m, and the cross-linking structural unit of 0.3% by mole, preferably 〇3 to 5 mol%, based on the total constituent unit of the filament-forming material. If the cross-linked structural unit is less than 〇3 mol%, the mechanical strength is insufficient, so if the 'other-side' exceeds 1%, the embrittlement of the porous body occurs, and the softness is lost. Especially in the case of ion exchangers, the amount of ion exchange groups is reduced due to the amount of ion exchange groups. The description (4) of the monolithic polymer material of the invention 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 materials are different from each other, for example, a material having a different blending ratio of the ethylene-based monomer J cross-linking agent (the description of the composite monolithic ion exchanger) is as follows. The composite monolithic ion exchanger of the present invention. In the composite exchanger, the description of the constituent elements of the composite monolith (4) is omitted, and the main difference is 971149356 57 201024342. 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 # m on the surface of the skeleton, or a plurality of protrusions having a maximum diameter of 4 to 40 formed on the surface of the skeleton of the organic porous body; the thickness of which is 1 mm or more and the average diameter of the pores is 1〇 〜15〇# 111, total pore volume 0. 5~5ml/g, ion exchange capacity per unit volume in water wet state 〇. 2mg equivalent / mi or more, ion exchange groups are evenly distributed in the composite structure ❹ . When the organic porous material is the second organic porous body, the bubble-like macropores of the organic porous system are overlapped with each other, and the heavy-duty portion has an average diameter of 30 to 300 //m, preferably 3〇~2〇 (^ m, a continuous giant pore structure of an opening (gap hole) of 35 to 150 mmm. The average diameter of the opening of the composite monolithic ion exchanger is when the ion exchange group is introduced into the monolith, due to the composite monolithic whole Swelling occurs, so the diameter of the opening of the composite single block is larger. The diameter of the opening is less than 3〇vm, and the pressure loss due to fluid penetration becomes poor. Then, the contact between the fluid and the composite monolithic ion exchanger becomes insufficient, and as a result, the (IV) ion mass is reduced, which is not preferable. The average diameter of the above-mentioned opening refers to the observation result of the SEM image, and multiplied by the self-drying state to become a wet state. The value calculated by the swelling ratio or the average 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. 097149356 58 201024342

When the organic porous material is the second organic porous body, the organic porous system has a three-dimensional continuous skeleton having a diameter of 1 to 5 〇wm, and is co-continuous with a three-dimensional continuous pore of 10 to 100/zm between the skeletons. structure. If the three-dimensional continuous = the pore size is less than 10 from m', the pressure loss due to fluid penetration becomes larger. If the 'more than 'the body and the composite monolithic ion exchanger are connected = become insufficient' the result is due to the ion The exchange behavior is uneven and the ion exchange band is increased by a large amount or the capture efficiency of the low concentration ion is lowered. Therefore, the above three-dimensional and continuous pore size refers to the observation result of the rich image, multiplied by the self-drying state. The value calculated by the swelling ratio in the wet state or the value of the continuous pores of the composite monolith before the introduction of the ion exchange group is multiplied by the swelling ratio after the ion exchange group guide. In addition, if the diameter of the three-dimensional continuous skeleton is less than 1/m, the disadvantage of reducing the ion exchange capacity per unit body and reducing the thief is caused, so that it is not good, and if it exceeds 5G/zni However, it is not preferable because the uniformity of ion exchange characteristics is lost. The skeleton diameter of the above-mentioned composite monolithic ion exchanger is a value calculated by observing the SEM image, multiplied by the swelling ratio from the dry state to the wet 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 average diameter of the pores of the composite monolithic ion exchanger is 1 〇 15 15 μm, preferably 10 to 120 / zm. When the organic porous body constituting the composite monolithic ion exchanger is the first organic porous body, the preferred pore diameter of the composite monolithic ion exchanger is 10 to 120αιπ' in the organic porous material constituting the composite monolithic ion exchanger. 097149356 59 201024342 is the second organic porous bribe 'composite single _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The diameter is 4 to 40, and the preferred value is particularly preferably 4 to 2 〇. In the total particle body or the like, the proportion of the particle body of 4 to 1 G_ is more than 80%. Further, the surface of the skeleton phase is coated with particles or the like in an amount of preferably 50% or more. If the size of the particles of the _ plane or the f frame is out of the above range, the effect of improving the contact efficiency between the fluid and the skeleton surface of the composite monolithic ion exchanger and the inside of the skeleton becomes small, which is not preferable. The diameter or the maximum diameter of the particle body or the like attached to the surface of the skeleton of the composite monolithic ion exchanger is calculated by multiplying the observation result of the SEM I image by the swelling ratio when the self-drying state is in a wet state. Or directly control the particles of the ion-domain-based composite block, multiply the value calculated by the ion exchange group before and after the lead. If the particle, which is equal to the coverage of the surface of the skeleton phase, is less than 40%, the contact efficiency between the fluid and the interior of the composite monolithic ion exchanger and the surface of the skeleton is improved, and the effect of the six-fruit transformation is detrimental to 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 due to the flow of the liquid 097149356 60 201024342 becomes large, and the amount of penetrating fluid per unit sectional area becomes small, and the treatment capacity is lowered. Not good. On the other hand, if the total pore volume exceeds 5 ral/g', the ion exchange capacity per unit volume is lowered. The pressure loss when the water does not penetrate the composite monolith exchanger is the same as the pressure loss when the water penetrates the composite monolith. In the composite monolith ion exchanger of the present invention, the ion exchange capacity per unit volume of the water-wet state has an ion exchange capacity of 〇. 2 mg equivalent / η α 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/mi, the amount of water containing ions, i.e., the production capacity of deionized water, is lowered, which is not preferable. Further, the ion exchange capacity per unit weight of the filament of the composite single-pump body of the present invention is not particularly limited, and is equivalent to the introduction of the ion exchange group into the skeleton surface of the composite monolith and the skeleton. /g. Further, the ion exchange capacity ' of the porous body in which the ion exchange group is only introduced to the surface cannot be determined depending on the type of the porous body or the ion exchange group, but is at most 500 yg 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 is omitted. In the composite single-subject (4) of the present invention, the ion exchange group of the donor is distributed not only on the surface of the porous body but also uniformly distributed inside the skeleton of the porous body. The (4) system of uniform distribution is the same as (4) of the W invention. 097149356 Λ1 201024342 The complex D block of this month is the manufacturing method of the monolithic piece of the present month by performing the above steps I to III, and the J step is performed by the h-single without the ion parent a mixture of a first cross-linking agent having at least two vinyl groups and a mixture of water and a mixture of water to prepare a water-drop type emulsion in the oil, and then polymerizing the water-drop type emulsion in the oil* A monolithic intermediate having a continuous pore structure of 5 to 3 Gml/g. The I step of obtaining a monolithic intermediate can be carried out in accordance with the method described in Japanese Patent Laid-Open Publication No. Hei. (Manufacturing method of monolithic intermediate) As an oil-cleaving monomer which does not contain an ion exchange group, (4) if it does not contain an ionic hetero group such as a tick acid group, a horizontal acid group or a quaternary ammonium group, the solubility in water is low. , lipophilic monomer. Preferred as such monomers are, for example, stupid ethylene, α-methylstyrene, ethylidene, chlorinated benzyl benzene, ethylene, propylene, isobutylene, butadiene. Vinyl chloride, ethylene glycol dimethacrylate, and the like. These monomers may be used alone or in combination of two or more. The polymer having at least two or more W groups in one molecule may, for example, be divinylbenzene, diethylpyrene, _$1 chelating agent, monovinylbiphenyl or ethylene glycol dimercapto acrylate. These crosslinking agents may be used alone or in combination of one or more. In terms of the strength of the mechanical strength, two kinds of dilute base, divinyl naphthalene, diethyl hydrazide, and agglomerate = chelating agent are used as the diethyl conjugate. The amount of the first crosslinking agent is 0. 3~10 mol% in the ethylene monomer and the first, the best 〇 3~5 Ear %, 097149356 62 201024342 0. 3~3 mole %. If the amount of the first crosslinking agent used is less than 3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, when it exceeds 1 mol%, the embrittlement of the monoblock is lost, the flexibility is lost, and the amount of introduction of the ion exchange group is reduced, which is not preferable. The surfactant is the same as the interface activity used in the 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 step, 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 drip-wetting liquid in the oil is not particularly limited, and can be used. By separately mixing the components, the oil-soluble component of the oil-soluble early body, the i-th crosslinking agent, the surfactant, and the oil-soluble polymerization initiator is separated from the water-soluble two of the water or the water-soluble polymerization initiator. After evenly rotating, the method P for mixing the components is used for the shape mixing device without special functions, and can be used as a general mixer or a pressure homogenizer, and can be selected for obtaining the target emulsion particle size. The condition is not particularly limited, and the number of rotations or _ time of the target emulsion particle size can be obtained by setting the tone. "Two: Γ monolithic _ has a continuous macroporous structure. If it is stored with H, _ fresh block continues macroporous structure (four) 097149356 63 201024342 skeleton phase of the surface of the filament body, etc. a composite material having a crosslinked structure. (10) The density of the material (4) is defined as the total constituent unit of the phase-contained silk compound, containing 〇, ,, mol%, preferably G.3~5 Do (4) structural unit. (4) If the structural unit is less than 〇·3 mol%, it is not good due to insufficient machine_degree. Another: 1Q (four) and more, the ship's position, loss of softness, can not live.

The total pore volume of the monolithic intermediate is 5 to 3 〇ml/g, preferably, if the total pore volume is too small, since the monolithic product obtained by polymerizing the ethylene monomer becomes too small, when the fluid penetrates If the pressure loss becomes large, the total pore volume is too large, so that the monolithic structure obtained after the polymerization of the vinyl monomer is not uniform, and the structure of the I-form is collapsed as appropriate. The total pore volume is set to the above value. The ratio of monomer to water is set to _1:5^35. ❹ If the ratio of the monomer to water is about 1:5-7, a continuous macroporous structure with a total pore volume of 5 to 16 ml/g for a single intermediate can be obtained and obtained via III. The organic porous body of the composite monolith obtained in the step is the second organic porous body. Further, when the blending ratio is set to about 1:20 to 1:35, a continuous pore structure of a monolithic intermediate having a total pore volume of more than 16 ml/g and a concentration of 3 〇ml/g or less is obtained. The organic porous body of the composite monolith obtained in the third step is the second organic porous body. In addition, the average straightness of the opening (the gap 097149356 64 201024342 hole) of the overlap between the macro hole and the macro hole of the monolithic intermediate system is 20~2〇〇_. If the average diameter of the openings is less than 2 Å/zm, the opening diameter of the composite monolith obtained by polymerizing the vinyl monomer becomes small. The pressure loss at the time of fluid penetration becomes large, which is not preferable. On the other hand, if the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ money. The monolith is preferably a macropore size or opening. The diameter is uniform—the uniform structure is defined, but it is limited to the uneven pores in which the uniform construction towel is present (4)#. (Manufacturing method of composite monolith) The Π step contains ethylene monomer, more than one molecule = the second cross of the base, and the dissolved (four) type of single compound is not allowed to be polymerized. = a step of a mixture of a vehicle and a polymerization initiator. In addition, there is no order, and the step I can be performed after the I step. There is no particular limitation on the type of the ethylenic monomer used in the step of the step, and the ethylene group to be polymerized, and the monomer of the organic solvent contains a monomer. #间的脂油型乙妇型, such as phenelzine, &quot; base = thin monomer specific examples, may be based on, vinyl, stupid, vinyl styrene benzene, chlorinated women's banquet , butadiene, isobutyl aromatic ethyl women monomer, · 乙妇, 097149356, Ding Kunquan a, smoke; τ diene 'isohalide dilute, 65 201024342 gas pentadiene and other diene monomers; a halogenated olefin such as vinyl chloride, vinyl bromide, vinylidene chloride or tetrafluoroethylene; a nitrile monomer such as acrylonitrile or methacrylonitrile; a vinyl ester such as vinyl acetate or vinyl propionate; Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, A (mercapto)acrylic monomer such as cyclohexyl methacrylate, benzyl methacrylate or glycidyl methacrylate. These monomers may be used alone or in combination of two or more. The ethylene type monomer which is suitable for use in the present invention is an aromatic vinyl type monomer such as styrene or a vaporized vinylbenzyl group. The amount of the vinyl monomer to be added is 3 to 40 times, preferably 4 to 30 times by weight, based on the monolithic intermediate which coexists at the time of 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 dimercapto acrylate, trihydroxydecylpropane triacrylate, and butylene glycol. Diacrylate and the like. These second cross-linking agents can be used alone or in groups 097149356 66 201024342 &amp; use more than 2 kinds by mechanical strength • 2nd cross-linking agent-based benzene, 2::== for Echi Na Na, special佳〇·_莫耳β. If the amount of cross-linking is not used, the softness is lost due to the occurrence of deuteration in the single-segment, and the ion exchange: the introduction of the soil is reduced, so it is not good. ,

The specific example of the organic solvent used in the bovine step is the same as the II =:::::: of the first invention, and _. These organic-series make the upper (4) lysate concentration (4). If the amount of organic solvent used. Mei Mancai f Mei low; =:::=- method forms the hair, the second =::r π - = =: =: 合:,, step structure monolithic intermediate, in addition to creating the invention : There is a single block of Le Xin, which also plays an important role in the negative pole. It

As disclosed in 7,114° et al., if a single intermediate is not present in J 097149356 ^ 67 201024342, the vinyl monomer and the second crosslinking agent are allowed to stand still in a specific organic solvent to obtain a particle agglomerated type. Monolithic organic porous body. On the other hand, when the monolith intermediate having a continuous macroporous structure is present in the above-mentioned polymerization system # as in the present invention, the structure of the monolith after polymerization changes drastically, and the particle aggregation structure disappears, and the specific skeleton structure described above can be obtained. Monolithic. The internal volume of the reaction vessel is the same as that of the internal volume of the reaction vessel of the first invention, and the description thereof is omitted.

In the step of 'reaction volume H, the monolithic + interstitial system is impregnated with the mixture liquid (), the mixture obtained by the mixture is mixed with the monolith (4), as described above, preferably based on the monolith intermediate , the weight of the body (4) body is 3~4G times, preferably 4 times, the weight is added to the handle. Thereby, a block having an appropriate opening diameter and having a specific skeleton can be obtained. The anti-age H towel's mixture in the mixture of _ single difficult (four) agent

On the (4) of the monolithic block, the bone is corrected in the monolithic phase. The temperature is set to 2〇~1〇〇.其余 The rest of the invention and the polymerization conditions according to the following steps are the same except that the conditions of the polymerizations G) to (5) are carried out. At least one St: can satisfy the characteristic 槿, 止 仃 step or 1 Η step in the following (1) vouchers, and can manufacture the invention (1) 111 steps: + on the surface of the skeleton, or the particle body, etc. Composite monolithic: (Gusaki's material temperature, _ surface _ material half 097149356 68 201024342 fading temperature is at least 5 ° C temperature. (2) 第 step used in the second cross-linker mol%, system &amp; The amount of the first crosslinking agent is twice or more the molar amount of the first crosslinking agent. The oxime monomer used in the step (3) is a berry monomer having a different structure from the viscous monomer used in the step I. (4) The organic solvent used in the step is a molecular weight of 2 〇〇 or more, and (5) the concentration of the vinyl monomer used in the step, 30% by weight or less of the compound. The mixing of the steps (described in (1) above ), the characteristic value of the spicy 'degree of the starter, if you decide to use the poly &amp; start, you can know the temperature of the first half, the half-life of the time. In addition, Η) the half-life temperature of the hour can be selected with its Polymerization initiator

In the middle of the sputum, the borrowing of the temperature (10) and the combination of the financial and the silk are formed on the surface of the skeleton phase. The reason is that since the concentration of the monolith in the interior of the hidden skeleton phase in the monolith becomes gentle, the velocity of the monomer from the liquid phase to the monolithic intermediate is lowered, so the remaining monomer is in a single towel. The vicinity of the surface of the skeleton layer of the interlayer is concentrated and polymerized there. The polymerization temperature of the preferred polymerization temperature is 1 () hour half-life / the dish is as low as 彡1〇 c. 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 a half-life temperature of 1 hour. Low range of 5~2〇t. 097149356 69 201024342 (Description of (2)) If the molar % of the second crosslinking agent used in the second step is set to be twice or more the mole % of the first crosslinking used in the first step, polymerization is carried out. The composite monolith of the present invention is obtained. The reason is that the compatibility between the mono-sheet body and the polymer formed by the polymerization is reduced, and phase separation occurs. Therefore, the polymer formed by the immersion polymerization is excluded from the skeleton of the monolith. In the vicinity of the surface of the phase, irregularities such as particles are formed on the surface of the skeleton phase. Further, the amount of the crosslinking agent (%) is the amount of the crosslinking agent (% by mole) of the total amount of the vinyl monomer and the crosslinking agent. The upper limit of the molar amount of the second crosslinking agent in the second step is not particularly limited. If the second crosslinking agent is __ large, cracks occur in the monolith after polymerization, and embrittlement 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 a multiple of . On the other hand, 'Even if the first crosslinking agent mol used in the first step is 2 times the molar amount of the second crosslinking agent used in the second step, the particle size does not occur on the surface of the skeleton phase. If it is formed, it is impossible to obtain (the description of (3)). The material of the step (4), if it is a vinyl monomer of the same structure as the soluble monomer used in the crucible (4), the present invention can be obtained. Complex ^ single block. For example, if styrene is the same as chlorinated ethane, the structure of ethylene: the structure is only slightly different, and a composite monolith can be formed on the surface of the skeleton phase to form a granule 3 097149356 70 201024342. In general, the two homopolymers known from the construction of only slightly different monomers are incompatible with each other. Therefore, if a single block having a different structure than the monomer used in the formation of the monolith intermediate in the step I is used in the step η, the polymerization is carried out in the step III, and the monomer used in the π step is uniformly Dispensing or immersing in a monolithic intermediate, but if the polymerization proceeds to form a t-complex, since the formed polymer is incompatible with the monolithic intermediate, phase separation occurs, and the resulting polymer is excluded to In the vicinity of the surface of the zero skeleton phase of the monolithic intermediate, irregularities such as particle bodies are formed on the surface of the skeleton phase. (Description of (4)) If the organic solvent used in the step II 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 monolith intermediate, especially a low molecular weight cyclic polyether is a good solvent for polystyrene, and the low molecular weight chain polyether is not a good solvent but has an affinity. However, when the molecular weight of the ruthenium compound 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 affinity is used in an organic solvent, the matrix of the monomer toward the monolithic intermediate is hindered. Internal diffusion 'Results Since the monomer is polymerized only in the vicinity of the skeleton surface of the monolithic intermediate*, A particle body or the like is formed on the surface of the skeleton phase, and irregularities are formed on the surface of the skeleton. If the molecular weight of ruthenium is 200 or more, the upper limit is not particularly limited, but if the molecular weight is too high, the viscosity of the mixture prepared in the second step becomes high, and it is difficult to immerse the 996149356 71 201024342 into a single fiscal body _, so Not good. The preferred molecular weight is 1_GG, particularly preferably 20G~1G_. Further, the end structure of (4) may be esterified with acetic acid, oleic acid, lauric acid, stearic acid or the like even if it is unmodified (4). (Description of (5)) The concentration of the ethylene monomer used in the π step is 30% by weight or less of the mixture in the π 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. As the monomer concentration decreases, the polymerization rate decreases, and the polymerization time is prolonged to a practically unacceptable level. Therefore, the monomer concentration is preferably set to 1 〇 to 3 (). % 0 (Manufacturing method of composite monolithic ion exchanger) The method for producing the composite monolithic ion exchanger of the present invention is the same as that of the method for producing the monolithic ion exchanger of the second invention, and the description thereof is omitted. (Examples) The present invention is illustrated by the following examples, but is not intended to limit the invention. <Example of the first invention> (Example 1) (I step; manufacture of a monolithic intermediate) 097149356 72 201024342 styrene 19· 2 §, a vinyl stupid 1. Og, sorbitan monooleate (hereinafter referred to as SM〇) l·Og and 2, 2'-azobis(isobutyronitrile) 〇. 26g is mixed and uniformly dissolved. Next, the stupid ethylene/divinylbenzene/SM0/2, 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 Seiko Co., Ltd.) was stirred under reduced pressure in a temperature range of 5 to 2 (TC) to obtain a water-drop type emulsion. The emulsion was quickly transferred to a reaction vessel, sealed and allowed to stand at 60° under standing. C. Polymerization for 24 hours. After the 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 macropores and giants in the monolithic The average diameter of the opening (gate gap) of the part of the hole is #5 ml/g. (Manufacture of a single piece) The styrene is 49.0g, and the styrene is stupid. !- 癸 〇 5〇g,

II, Qianshuang (2, 4-didecyl valeronitrile) Q 5g is mixed to dissolve it uniformly (Π step). Next, the monolith intermediate body was cut into a disk shape having an outer diameter of 70 Å and a thickness, and was taken out. The separated monolithic intermediate is placed in a reaction vessel of 9 〇 〇 ,, immersed in the styrene/divinyl cumene/2'2, _ azobis (2 4 dimethyl hydrazine) In the nitrile mixture, after decompressing until: defoaming, the reaction vessel was sealed and allowed to stand under (10). c Perform a gathering for 24 hours. After the end of the polymerization, 'take out the monolithic content of about 30mm thick ^ ^ ah ah _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Formed

Observe, and divide the internal structure of the monolith (dry body), and cut the monolithic 咐L j by SEM. The tank image of Figure 1 ° is attached to any position, χ el el el el el el The image of the location. It can be seen from Fig. 1 that the skeleton of the structure of the perforation is much thicker. 5 or Fig. 6 is thicker and the thickness of the wall portion constituting the skeleton is also smaller than that at the position where the position is different from the above position, and the obtained SM image is measured at 2 points and 3 points at random. The thick part of the wall and the area of the skeleton shown in the section. The wall thickness is the average of 8 points in the photo of the μ leg, and the frame area is obtained by image analysis. The wall portion is as defined above. Further, the area of the skeleton is represented by the average of the three images. As a result, the average thickness of the wall portion was · m, 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; um, and the total pore volume was 2. 2 mi/g. The results are shown in Tables and Table 2. In the form, the filling sheds sequentially indicate the vinyl type monomer used in the step, the crosslinking agent, the monolith intermediate obtained in the step, and the organic solvent used in the step II. (Manufacture of early block 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 coffee. The weight of the monolith is 27 g. After adding dioxane 15 〇〇mi, it was heated at 35 ° C for 1 hour, and then cooled to 1 (rc or less, and slowly added to thiosulfan 097149356 74 201024342 145g, and the temperature was raised and reacted at 35 ° C for 24 hours. Thereafter, methanol was added, and the remaining gas was quenched and quenched, and then washed with decyl alcohol to remove the gas, and then washed with pure water to obtain a monolithic cation exchanger having a continuous macroporous structure. The cation exchange rate before and after the reaction of the cation exchanger is 1.7 times, and the ion exchange capacity per unit volume is 〇.67 mg equivalent/ml in the wet state of water. The cation from the value of the organic porous body and the wet state of the water The swelling ratio of the exchange body is estimated as the average diameter of the opening of the organic porous ion exchanger in the wet state of water, and the result is 54 # m, and the average thickness of the wall portion constituting the skeleton obtained by the same method as the single block is 5〇Am, the area of the skeleton is 28% in the photo area of the SEM photograph, and the total pore volume is 2.2 ml/g. Further, the pressure difference coefficient of the pressure loss index when the water penetrates is 〇. 〇16MPa/ m · LV, compared to the pressure required for practical use The force loss is a lower pressure loss. 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 is observed. The results are shown in Fig. 2 and Fig. 3. Fig. 2 shows the distribution state of sulfur atoms on the surface of the cation exchanger, and Fig. 3 shows the state of distribution in the cross section (thickness) direction of the cation exchanger of the sulfur atom. 3 It is understood that the sulfonic acid group is uniformly introduced on the skeleton surface of the cation exchanger and the inside of the skeleton (scraping direction). (Examples 2 to 11) (Manufacture of a single block) 097149356 201024342 In addition to the use of stupid ethylene The amount and amount of the crosslinking agent, the type and amount of the organic solvent, the porous structure of the monolithic intermediate coexisting in the styrene and divinylbenzene impregnation polymerization, the crosslinking density, and the amount of use are changed to A monolith was produced in the same manner as in Example 1 except for 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 As can be seen from Table 2 The average diameter of the openings of the single blocks of Examples 2 to 11 is as large as 22 to 7 〇 Am, and the average thickness of the wall portion constituting the skeleton is also as thick as 25 to 50/zm, and the area of the skeleton is 26 to 44 in the SEM image area. %, and belongs to a coarse skeleton monolith. (Manufacture of monolithic cation exchanger) The monoliths produced by the above method were reacted with chlorosulfuric acid in the same manner as in Example 1 to produce a single continuous pore structure. The block cation exchangers 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, and the average thickness of the wall portion constituting the skeleton is 45 to 110 thick. The area of the skeleton is 26 to 44% in the image area of the SEM image, and the differential pressure coefficient is also as small as 〇· 〇〇6~〇. 〇31 MPa/m · LV, and the exchange capacity per unit volume also shows a larger value. . Further, the mechanical properties of the monolithic cation exchangers of Example 8 were also evaluated. (Evaluation of Mechanical Properties of Monolithic Cation Exchanger) The monolithic cation exchanger obtained in Example 8 was cut into a short strip of 4ππηχ5ιηιηχ10ιηιη in a wet state of water to obtain a test piece for tensile strength test. The test piece was mounted on a tensile strength tester, and the speed of the slider was set to 097149356 76 201024342 0. 5 mm/min, and 25 in water. 〇 Experiment. As a result, the tensile strength and the tensile modulus of elasticity were 45 kPa and 50 kPa, respectively, which showed a value larger than that of the conventional monolithic cation exchanger. Further, the tensile fracture is extended to 25%, which is a larger value than the conventional monolithic cation exchanger. (Example 12) (Manufacturing of a single block) Except that the amount of use of the present invention, the amount of the crosslinking agent used, and the amount of the organic solvent used were changed to the amounts shown in Table 1, In the same manner, a monolith having the same composition and construction as in Example 4 was produced. The results are shown in Tables 1 and 2. Further, in the monolithic structure of the embodiment 丨2, the average opening diameter of the overlapping portion of the macropores and the macropores is as large as 38 /zm, and the organic porous body having a thicker wall portion having an average thickness of the wall portion of the skeleton of 25 μm is also thick. . (Manufacturing of Monolithic Anion Exchanger) The monolith " manufactured 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 2 ml of tetra-stannized tin were added thereto, and 560 m of chlorosulfuric acid was added dropwise under ice cooling, and then the temperature was raised and reacted at 35 C for 5 hours to introduce a gas thiol group. After completion of the reaction, the mother liquor was extracted by siphoning - washed with a mixed solvent of THF / water = 2 / 1, and then washed with THF. - 600 ml of a 30% aqueous solution of THFlmi and trimethylamine was added to the chloroformylated monolithic organic porous body, and 6 (TC reaction was carried out for 6 hours. After the reaction was completed, the product was treated with methanol/ The water mixed solvent is washed, then washed with pure water and separated. 097149356 77 201024342 The obtained anion exchanger has a swelling ratio of 16 times before and after the reaction, and the ion exchange capacity per unit volume is in the wet state of water. 〇·% equivalent/ml. The value of the organic porous material from the cation of the water-wet state = the swelling ratio of the opening of the organic porous ion exchanger in the water-wet state, the result is 'with The average thickness of the wall portion constituting the skeleton obtained by the same method is 4 〇 _, the framing portion is 26% of the image area of the leg image, and the total pore volume is 2.9 ml/g. The pressure difference coefficient of the pressure loss index at the time of penetration is 〇〇2〇MPa/m.Lv, which is lower than the pressure loss required in practical use, and the low waste loss is obtained. The results are shown in Table 2. Secondly, 'in order to confirm the monolithic anion exchanger When the anion exchanger is treated with an aqueous solution of hydrochloric acid to form a vaporized form, the distribution state of the chlorine atoms is observed. As a result, the chlorine atoms are not uniformly distributed on the skeleton surface of the anion exchanger, and are uniform. It was confirmed that the quaternary ammonium group was uniformly introduced into the anion exchanger ❹. (Comparative Example 1) (Manufacture of monolithic organic porous body having a continuous macroporous structure) According to Japanese Patent The method of the invention described in JP-A-2002-306976, which produces a monolithic organic porous body having a continuous macroporous structure, that is, styrene 19.2 g, divinylbenzene 1. 〇g, SMOl. 〇g and 2, 2,-azobis(isobutyronitrile)〇.26g mixed' to dissolve it uniformly. Next, the styrene/divinyl 097149356 78 201024342 benzene/_/mouth,-azobis(isobutyronitrile) The mixture "pure water to _, using a vacuum agitation defoaming device (10) made by a planetary mixing device) at 5~2 〇. (: in the temperature range, stirring under reduced pressure, obtained by Commercial emulsion. This milk The liquid was quickly transferred to the reaction vessel, and === was polymerized for 24 hours at 6 (TC). After the end of the polymerization, the contents were taken out, and the extraction was carried out with a suspension of C-class to reduce the drying, thereby producing a monolithic structure having a continuous macroporous structure. Organic porous body. The internal structure of the organic porous body containing 3.3 mol% of the cross-linking component formed by the styrene/diethyl stupid copolymer obtained in this way is observed and leaked. As can be seen from Fig. 4 (4) 5, although the organic porous body has a continuous macropore structure, the thickness of the wall portion constituting the skeleton of the (four) pore structure is thinner than that of the embodiment, and the average thickness of the wall portion measured by the SEM image is 5_. 'The area of the skeleton is (10) in the image. The average pore volume of the core was 8.6 nU/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. (Single-slit, porous cation exchange body having a continuous macroporous structure) & The organic porous body produced by the above method was cut into a disc shape having an outer diameter of about 15 mm. The weight of the organic porous body was two, and the lGGGml was calcined, and after heating at 35 ° C for a few hours, it was cooled to the order below, and 1* and It was added to the gas sulfuric acid 3 〇 g ' to raise the temperature. C reaction is small. After 097149356 79 201024342, methanol is added, and the remaining gas is quenched by sulfuric acid, then washed with methanol to remove methylene chloride and then washed with pure water to obtain a monolithic organic porous cation exchanger having a continuous macroporous structure. . The swell rate 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 eq / π α 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 cm, and the average thickness of the wall portion constituting the skeleton is 8毫升/克。 The total area of the pore volume is 8.6ml / g. Further, the pressure difference coefficient of the pressure loss index when the water is penetrated is 0. 013 MPa/m · LV. The results are shown in Table 3, and the differential pressure coefficient is shown to be smaller than the value of (4), but the ion exchange capacity per unit volume is relatively low compared to the examples. Further, the mechanical properties of the monolithic cation exchanger obtained in Comparative Example 1 were also evaluated. (Evaluation of Mechanical Properties of 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, (4), the tensile modulus coefficient was 4 28 kPa, 12 kPa, which was a lower value than the monolithic cation exchanger of Example 8. Further, the tensile fracture is extended to m, which is a smaller value than the monolithic cation exchanger of the present invention. (Comparative Examples 2 to 4) (Manufacture of monolithic organic porous body having a continuous macropore structure) 097149356 80 201024342 In addition to changing the amount of styrene used, the amount of divinylbenzene used, and the amount of SM0 to In the same manner as in Comparative Example 1, except for the blending amount shown in Table 3, a monolithic organic porous body having a continuous macroporous structure was produced by a conventional technique. 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 below the oil phase portion. In the single block of Comparative Examples 2 to 4, the opening diameter was as small as 9 to 18/zm, 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 area. % less value. (Production 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 continuous macroporous structure. Monolithic organic porous cation exchanger. The results are shown in Table 3. When the diameter of the opening is to be increased, the thickness of the 卩 σ 变 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 pressure drop coefficient ', the ion exchange capacity per unit volume decreases, and if the ion exchange capacity is increased, the pressure difference coefficient increases. 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 . From Fig. 4, the α α , , relative to the example, the differential pressure coefficient of the comparative example and the ion exchange capacity are poor. On the other hand, it is understood that the ion exchange capacity per unit volume of 097149356 81 201024342 is larger, and the differential pressure coefficient is also lower. (Comparative Example 5) An attempt was made to produce a monolith in the same manner as in Example 1 except that the type of the organic solvent used in the second step was changed to a hexane or the like of a good solvent of polystyrene. However, the single-off product was transparent, showing collapse and disappearance of the porous structure. Although SEM observation for confirmation was performed, only a dense structure was observed, and the continuous macropore structure disappeared. 097149356 82 201024342 3 3/ss «bo%5 3bo#阳的Mm«铋ns-馎馎一:3⁄4 反逆ss_ 锲藓e«wce^~~®wls鄕鄕§ ~mmMflss^ 裔5 ss^ (5 泰^^ί4os Min you 'Ln Bu coLn00 a «5 Bu ε · ί 0·ΙΪ 4^ Dare ou 0. Write - ite.Ψ装ΊΜ-装^灭&lt;- S &lt;- &lt;- g § § S § &lt;&lt;- 4 - &lt; - &lt;-- &lt;- &lt;- &lt; n-glycan 1-butanol 1-nonanol &lt;- &lt;&lt;-&lt;- to b · r- H 卜 · iO 卜 · OO L 〇 F - H &lt; - &lt; - in 卜 · &lt; - &lt; - &lt; - &lt; - CO CO ID CO &lt; - &lt; CD LD &lt; - &lt;&lt;-&lt;- CO 〇· o CO CO CO &lt;- &lt;- CO &lt;- oa 00 CO Bu · Bu Bu · inch 00 Bu · ¢ 33⁄4 Bu · inch CO ΙΟ CO ca 00 Bu · &lt;- &lt;&lt;-&lt;-&lt;&lt;-&lt;-&lt;-&lt;-&lt;&lt;-&lt;-&lt;-&lt;-&lt;- CO &lt;〇c=&gt; CO T* &lt;1 ~ ★···· &lt;- &lt;- 03 ,丨&lt; OO o C3 CO &lt;=5 CM c=? T—^ oo ¢=5 &lt;=&gt; 1 &lt; CO OJ oo c=&gt ; &lt;- &lt;- &lt;- &lt;- &lt;- &lt;- &lt;- &lt;- Diethylene Benzene diphenyl benzene oo oo in CO oo CO &lt;NI ai CO CO 03· CO 寸 05 CO OO oo in &lt;=? 05 . inch oa 05 CO o 05 卜 OJ 05 CO &lt;- &lt;- &lt;-&lt;-&lt;«-&lt;-&lt;-&lt;-&lt;- Embodiment 2 Embodiment 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 s 9-6 inch U60 201024342 V «Ν _ and β # «ή- H' sp 0.67 r-Η &lt;ζ&gt; 0.80 g C? so 0.77 0.57 0.70 0.52 0.59 0.62 0.56 key 蕺 $ 5 W 13⁄4 &lt;- &lt; 1 &lt;- &lt;- &lt;- &lt;- &lt;- &lt;- &lt;- &lt;- Four-level recording base single ion exchange pressure difference coefficient MPa / m · LV 0.016 0.026 0.031 0.014 0.006 0.006 0.006 0.006 0.020 total fine pores ml/g oi ιη F· 1 Ο Τ-Η 05 oi inch OO CNi CO od σϊ 05 od 05 r—H 00 01 05 (Μ* skeleton area % 〇〇(NI CO CO co CQ LO CO 05 &lt;M co CD &lt;N1 00 oa oo OJ CO (Nl wall thickness // m § ο ο rH LO § § § LO inch § s LO through gap? L diameter μ\Ά inch LO CO S CO CO oo CO rH CO s OO CO CO o 5 total pore volume ml/g C&lt;l c&lt;i LO Ο 05 οά inch 03 00 01 CO CN1 05 σϊ oi 05 oo 03 CD oi skeleton area % 00 Cv3 CO CO CO oa LO CO 05 03 Another CO CD 03 OO CNI 00 &lt;NI CO CvJ Wall thickness μιη Another guide s LO oa Guide LO 呀 in OJ Another LO (NJ ΙΛ (Nl clearance hole diameter / / m co CO OQ OJ CM oo CO CO CO 00 CO CO CO CO CO 00 CO Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Inch 099S Inch U60 (co&lt; ) V »w 饀漤Μ 饀漤Μ ^ s®l-屮mg equivalent/ml oa Csl CD CO CD C=&gt; OO IT&gt; ci Organic porous ion exchanger differential pressure coefficient MPa/m · LV 0.013 0.027 0.105 0.418 Total pores ml/g CD CO LO iri CO c&gt;d skeleton area o CO Bu CNI CNI wall thickness B 〇〇 03 03 LTD &lt;NI CO oa clearance hole diameter ε 4 CD inch 05 CM LO organic porous body total Fine hole ml/g CD od LO LO c〇od Two wall thickness m L〇LO LO LO Clearance hole diameter m Oi CNI oo ΟΪ Pure water bO g &lt;- &lt;- &lt;- 1 bfl o rH LO r-&lt; i CO c&lt;i Filling divinylbenzene g mol% CO CO C5 1—· &lt;—— LO &lt;- CNI οά &lt;- oa CO Styrene bo 19.2 28.7 41.5 60.1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 9^6ΗΑ60 201024342 <Example of the second invention> (Example 13) (I step; manufacture of a monolith intermediate) == Rare 5.4g, Eryi County u.17g, sorbitol acid = ^_.42 and 2,2', nitrogen double (nitrile) 0 is mixed and = vinyl stupid with _ iso nitrile) age added magic The feet are pure water, so that the riding star-type turbulence Ϊ Ϊ 胜 胜 胜 胜 ( ( ( ( ( ( ( ( 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 After the milk was sealed, the mixture was sealed for 6 generations and 24 hours, and dried under reduced pressure. After the completion, the contents were taken out, extracted with methanol, and the resulting core was formed into a monolithic structure having a continuous macroporous structure. Intermediate. In this way, the internal structure of the towel body (dry body) is shaped by the SEM image (Fig. 19). However, the wall of the two giant holes adjacent to each other is a very thin hole. The continuous pore structure 'the average diameter of the opening (gap hole) of the macropore and the macropore core measured by the mercury pressing method is 70_, and the total pore volume is 2l.〇ml/g. (Manufacturing of a continuous continuous monolith) 2 2 followed by Γglycol 76· 〇g, diethyl phenyl benzene 4, 1 - sterol 1 coffee, (II step, double (2'4~ dimethyl 戍 guess) ) 〇 8g mixed to make it evenly dissolved). Next, the above-mentioned monolith was cut into a disc shape having a diameter m and a thickness of about 4 〇, and 4 分 was taken out. The separated monolithic intermediate 097149356 86 201024342 was placed in a reaction vessel having an inner diameter of 75 liters, and impregnated in the styrene/divinylbenzene/1-nonanol/2,2,-azobis (2) After defoaming in a decompression chamber in a mixture of 4 to dimethylvaleronitrile, the reaction vessel was sealed and allowed to stand under static conditions for 24 hours. After the completion of the polymerization, a monolithic content having a thickness of about 6 ounces was taken out, and Soxhlet extraction was carried out with acetone, followed by drying under reduced pressure at 85 ° C for one night (step). The internal structure of a monolith (dry body) containing 3.2 mol% of a cross-linking component formed of the styrene/divinylbenzene copolymer thus obtained was observed by sem, and the monolithic skeleton and empty were observed. The holes are respectively subjected to a three-dimensional continuous and two-phase entangled co-continuous structure. Further, the skeleton thickness measured from the SEM image was l 〇 Vm. And a total pore volume of 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) 单 The monolith produced by the above method was cut into a disk shape having a diameter of 75 legs and a thickness of about 15 coffee. The weight of the monolith is 18g. Dichlorosilane i5 〇〇 ml was added thereto, and after heating at 35 ° C for 1 hour, it was cooled to 10 ° C or lower, and 99 g of sulfuric acid gas was gradually added thereto, and the temperature was raised and reacted at 35 ° C for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, and the methane was removed by washing with decyl alcohol, followed by washing with pure water to obtain a monolithic cation exchanger having a co-continuous structure. A part of the obtained cation exchanger was cut out, and after drying, the internal structure was observed by s ’, and it was confirmed that the monolithic cation system maintained the co-linkage 097149356 87 201024342. This SEM image is shown in Fig. 2A. 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 〇. 74 mg equivalent/m 1 in the wet state. The swelling rate of the cation exchanger from the value of the monolith and the water-wet state is estimated to be the monolith of the water-wet state - the size of the continuous pores is 24βιη, the diameter of the skeleton is I4々m, and the total pore volume is 2 . 9ml / 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 length of the ion exchange band was measured for the sodium ion of the monolithic cation exchanger, and as a result, the length of the ion father of the LV = 20 m/h was i6 mm, compared to the AMBERLITE IR120B of the commercially available strong acid cation exchange resin. The value (320 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 cation exchanger having a continuous cell structure. The results are shown in Table 5. Next, in order to confirm the distribution state of the acid group in the monolithic cation exchanger, the distribution state of the sulfur atom was observed by the enthalpy. 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 the distribution state of the sulfur atom on the surface of the cation exchanger, and Fig. 22 shows the distribution state in the cross section (thickness) direction of the cation exchanger of the sulfur atom. In the photograph on the left side of Fig. 21, the left and right oblique extensions are the skeleton portions, and Fig. 22 - the left circular photographs have two skeleton shapes as skeleton skeletons. 21 and 22, the sulfonic acid group was uniformly introduced on the skeleton surface of the cation exchanger and the inside of the skeleton (cross-sectional direction) 097149356 88 201024342, respectively. (Examples 14 and 15) (Production of monolith having a co-continuous structure) In addition to the amount of styrene used, the amount of the crosslinking agent used, the kind and amount of the organic solvent, and the styrene and divinylbenzene impregnation The porous structure, crosslink density, and amount of use of the monolithic intermediates coexisting during polymerization were changed to those shown in Table 4.

A monolith having a co-continuous structure was produced in the same manner as in Example 13 except for the dosing. The results are shown in Tables 4 and 5. (Production of a monolithic cation exchanger having a co-continuous structure) The monoliths produced by the above methods are reacted with chlorosulfuric acid in the same manner as in the examples to produce a monolithic cation having a co-continuous structure. = body. The results are shown in Table 5. Further, the structure of the (4) structure of the monolithic cation domain having the structure of the second structure obtained by the beach image observation is not shown in Figs. 23 and 24, respectively. It can be seen from Table 5 that the cation exchange system of Shiyou 彳丨u block shows the single large, ion exchange band obtained by the difference of the number 14 and 15; the small number, the exchange capacity per unit volume = ion exchanger, also carried out Maple ^ (mechanical property of the early block % ion exchanger) The monolith obtained in Example 14 was cut into 4, x5, xl, and the short-selling scorpion, which was placed in a water-wet state. Test the wire for the light (four) test of the pull material. 0. 5 coffee / minute, in the water ♦ 4 test machine ‘ set the pull speed to perform the test. As a result, the tensile strength, 097149356 89 201024342 tensile elastic modulus were 23 kPa and 15 kPa, respectively, which showed an extremely large value compared to the conventional monolithic cation exchanger. Again, the tensile rupture extends to a greater value than the conventional monolithic cation exchanger. (Example 16) - (Manufacture of monolith having a co-continuous structure) In addition to the amount of styrene used, the amount of the crosslinking agent used, the amount of the organic solvent used, and the styrene and divinylbenzene impregnation polymerization The monolithic structure having a co-continuous structure was produced in the same manner as in Example 13 except that the porous structure, the crosslink density, and the amount of use of the coexisting monolithic intermediate were changed to those shown in Table 4. The results are shown in Tables 4 and 5. (Manufacturing 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 7 Qmm and a thickness of about 15 faces. Here, dioxomethoxypyrene 14 〇〇m b tetragastronized tin 2〇mi was added, and the weiwei 560 m was dropped under ice cooling, and the temperature was raised and the human methyl group was introduced in the π C reaction 5]. After the completion of the reaction, the mother liquid was extracted by siphoning, and the mixture was washed with a mixed solvent of THF/water = 2/1, and then washed with Cao. To the chloromethylated monolithic organic porous body, 600 ml of TH_〇mi and a trimethylamine 30% aqueous solution were added, and 6 (rc reaction was carried out for 6 hours. After the reaction was completed, the product was dissolved in methanol/nuclear acid. Miscellaneous, then read the water to wash and separate. - The obtained anion exchanger has a swelling rate of 16 times before and after the reaction, and the ion exchange capacity per unit volume is Q 44 in water wet state. Equivalent 097149356 90 201024342 /ml from the value of the monolith and the swell rate of the cation exchanger in the water-wet state, the diameter of the continuous pores of the monolithic ion exchanger in the wet state of the water, the result is 29em, the skeleton thickness is 13em, the total pores The volume is 2 〇ml/g. Moreover, the pressure difference coefficient of the pressure loss index when the water is penetrated is 0. 020 MPa/m · LV, which is a practical low pressure loss. Further, the needle is Dong 10 The ion exchange band length of the anion exchanger was measured, and the length of the ion exchange zone of LV-20m/h was 22 mm, compared to the commercially available strong beta basic anion exchange resin AMBERLITE IRA402BL (R〇hm and Haas a The value of the system (165mm) 'not only overwhelming The shorter value is shorter than the value of the monolithic neon yoke clock which has a continuous bubble structure. The results are shown in Table 5. Further, the SEM image is observed to have a continuous continuation. The results of the internal structure of the monolithic anion exchanger are shown in Fig. 25 °. Next, in order to confirm the distribution of the quaternary ammonium group in the monolithic anion exchanger, the anion exchanger is treated with an aqueous solution of hydrochloric acid to form a gas. The chemical Wei'# ΕΡΜΑ observed the distribution state of the chlorine atoms. As a result, the chlorine atoms were not evenly distributed on the surface of the anion exchanger, but also uniformly distributed inside, and it was confirmed that the quaternary money system was uniformly introduced into the anion exchanger. (Comparative Example 6) (Production of monolithic organic porous (IV) having a continuous macroporous structure) A monolithic organic porous body was produced in the same manner as in Comparative Example 1. The styrene/divinylbenzene thus obtained was obtained. The internal structure of the organic porous body containing the 3·3 097149356 201024342 mole % cross-linking component formed by the copolymer was observed by SEM, and the results are shown in Fig. 26. 'The organic porous body has a continuous macroporous structure. Further, the thickness of the wall portion measured by the SEM image is 5/zm, and the macropores and macropores of the organic porous body are determined by mercury intrusion method. The average diameter of the overlapping portion (opening) is 29//m', and the total pore volume is 8.6 ml/g. The results are shown in Tables 4 and 5. In Tables 4 and 5, the clearance pore diameter refers to the opening. Average diameter (manufacture of monolithic cation exchanger having a continuous macroporous structure) A monolithic cation exchanger was produced in the same manner as in Comparative Example 1, except that the organic porous body produced in Comparative Example 6 was used. 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) (Production of monolithic organic porous material having a continuous cell structure) The amount of ethylene used, the amount of divinylbenzene used, and the amount of S ribs were changed to those shown in Table 4. Except for the amount, a monolithic organic porous body having a continuous macroporous structure was produced by the same method as in Comparative Example 6. The results are shown in Tables 4 and 5. (Production of a monolithic anion exchanger having a continuous cell structure) The organic porous body produced by the above method was introduced into a chloromethyl group in the same manner as in Example 6 to react with tridecylamine by a known technique. A monolithic anion exchanger having a 972149356 92 201024342 continuous cell construction was fabricated. The results are shown in Table 5, and the pressure difference coefficient shows the same small value as the example, but the ion exchange capacity per unit volume is lower than that of the embodiment, and the length of the ion exchange belt is as long as about 4 times that of the embodiment. (Comparative Example 8) A monolith having a co-continuous structure was produced in the same manner as in Example 13 except that the type of the organic solvent used in the step II was changed to dioxane as a good solvent for polystyrene. . However, the single-off product is transparent, showing collapse and disappearance of the porous structure. Although the SEM observation for confirmation was performed, only the dense structure was observed, and the continuous bubble structure disappeared.

097149356 93 201024342 Organic solvent usage bo § &lt;- &lt;- 1 1 species 1-sterol &lt;—— &lt;—— 1 1 Total pores heterogeneous 'ξ 21.0 17.8 17.8 1 1 Clearance pore diameter Β &lt;C&lt;l eg 〇1 1 Organic Porous Body Crosslinking Density Mole % CD CO 03 CO &lt;- 1 1 Use Amount · CO od Bu oi cJ 1 1 姊Copolymer type styrene-divinylbenzene Copolymer &lt;-&lt;-&lt;- 1 1 type usage Mohr% C&lt;J CO CO oa CO CO 1—H CO oo &lt;- crosslinker bfl diphenyl benzene 4.0 οο d &lt;- c=) (ΝΪ &lt;- oo o &lt;- o rH &lt;- &lt;- &lt;- vinyl monomer usage bO 76.0 39.2 &lt;=&gt; od CO 39.2 19.2 &lt;- type styrene &lt; - &lt; - &lt; - &lt; - &lt; - Example 13 Example 14 Example 15 Example 16 Comparative Example 6 Comparative Example 7 Inch 6 9-6Η-0 201024342 Nickel Nickel 5i f窭埤 Drama赞赞?F^c 饀铋Ίί你颦#:Tough?F璁赞?F^( ΦΙ钬缂枳屮几黩#w si Alkali Umbrella W 婼钕ltvBr Ίέ 纠 ??Fitll:雒ΦΤ乐蝻_JfJ.·衮-JIV 纠赞?F^il:祓Φ (LO&lt;) i ε/φί&lt;»ΒSm Λ1 · 1 S/B 1113⁄4 1113⁄4 bo/e 1113⁄4 1113⁄4 οο 5 inch 1—Η s* (NJ % inch 0. 74 0.46 0.80 &lt;=&gt; Csl &lt;&gt;α ς=ί sulfonate&lt;- &lt;- quaternary sulfonate C&lt;1 LO &lt;=&gt;&lt;=5 0.016 05 ΟΟ 〇 CD Ο Ο CO t—Η ο c=&gt; cn od &lt;=5 oi οα oi CD θά CO od &lt;NI CO σ&gt; 03 to CO CO oo 05 03 〇c&gt;J CNi &lt;ΝΪ ο (Νϊ CD Od 卜卜〇〇5* 05 OJ Ο 〇〇&lt;=&gt; οο CO ΐη Example 13 Example 14 Example 15 Example 16 Comparative Example 6: 3⁄4 f竣 i i 20.0 900 εοο 900 tsLn 61.0 ίο inch* 63

5S ^时«制5? ί^$^ϊ^£ί5$ ^ δκέ—13^$^$^ί£$ 9S£:6H/.60 201024342 <Embodiment of the third invention> (Example 17) ( I step; manufacturing of a monolithic intermediate) 9.28 g of styrene, 0.19 g of divinylbenzene, sorbitan monooleate (hereinafter abbreviated as SMO) 0.50 g and 2, 2'-azo double ( Isobutyronitrile) 〇·26g was mixed and allowed to dissolve evenly. Next, the styrene/divinylbenzene/SM0/2,2-azobis(isobutyronitrile) mixture is added to i8〇g pure water to make

The mixture was stirred under reduced pressure in a temperature range of 5 to 20 ° C by a vacuum stirring defoaming mixer (manufactured by Seiko Co., Ltd.) of a planetary stirring device to obtain a water-drop type emulsion. The emulsion was quickly transferred to a reaction vessel, and after sealing, polymerization was carried out at 0 C for 24 hours. 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 of the monolithic body overlap with the macropores has an average diameter of 4Q_, and the total pore volume is i5. (Production of composite monolith) Next, 36.0 g of styrene, 4 parts of divinylbenzene, and 4 g of diazobis(2,4-dimethylvaleronitrile) 癸 are mixed. Make it all sentenced (Step II). The hour and half temperature of 2,2,-azobis(2,4-di-benfenonitrile) as a polymerization initiator was used. The crosslink density relative to the monolithic intermediate is 1.3 mol%' relative to the total amount of benzene and diphenylbenzene used in the η step, and the amount of the diphenyl benzene used is 6.6 mol%. It is also 5. 1 times. Next, the above monolithic intermediate was cut into a disk shape of 097149356 96 201024342 70 mm and a thickness of about 20 mm, and 3.2 g was taken out. The monolithic intermediates taken out were 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-di) After defoaming in a decompression chamber in the methylvaleronitrile mixture, the reaction vessel was sealed, and polymerization was carried out at 60 ° C for 24 hours while standing. After the completion of the polymerization, the content of the monolith having a thickness of about 30 mm was taken out. Soxhlet extraction was carried out with acetone, and then dried at 85 t 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 Fig. 27 to Fig. 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 a single block at arbitrary positions are cut. As is apparent from Fig. 27 to Fig. 29, the composite monolith has a continuous macropore structure, and the surface of the skeleton phase constituting the continuous macropore structure is covered by the particle body having an average particle diameter of 4 mm, and the particle coverage is 80%. Further, the ratio of the particle body having a particle diameter of 2 to 5 mm to the total particle body was 90%. Further, the average diameter of the opening of the composite monolith as measured by the mercury intrusion method was a total pore volume of 2.3 ml/g. The results are shown in Tables 6 and 7. In Table 7, the filling column sequentially indicates the vinyl monomer, the crosslinking agent, and the organic solvent used in the n step from the left! The monolithic intermediate obtained in the step. Further, the particle body or the like is represented by particles. (Manufacturing of composite monolithic cation exchanger) The composite monolith manufactured by the above method was cut into a disk shape having a diameter of 7 mm and a thickness of about 097149356 97 201024342 15 mm. The weight of the single piece is 19 6g. The mixture was heated at 35 ° C for 1 hour, and then cooled to a temperature of i 〇 ° C or less, and then slowly added with 98.9 g of chlorosulfuric acid, and the mixture was heated at 35 ° C for 24 hours. Thereafter, methanol was added, and the remaining gas sulfuric acid was quenched, and then the dioxane was removed by washing with methanol, and then washed with pure water to obtain a composite monolithic cation exchanger. The cation exchange rate of the obtained cation exchanger before and after the reaction was 13 times, and the ion exchange capacity per unit volume was 丨. Umg equivalent / ml in the wet state of water. The average diameter of the opening of the organic porous ion exchanger in the water-wet state is estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water-wet state, and as a result, it is 21 m in the same manner as the monolith. The particle coverage of the obtained skeleton surface was 80%, the average particle diameter of the coated particles was 5 m, and the total pore volume was 2.3 ml/g. Further, the proportion of the particles having a particle diameter of 3 to 7/Zm in the entire particle body was 90%. Further, the pressure difference coefficient of the pressure loss index when the water is penetrated is 〇. MPa57 MPa/m · LV, which is lower than the pressure loss, which is a lower pressure loss than the practical requirement. Further, the ion exchange belt was 9 mm in length, showing a significantly shorter value, and the results are shown in Table 7. Next, the distribution state of the sulfur atom was observed by observing the distribution state of the sulfonic acid group in the composite monolithic cation exchanger. The results are shown in J3〇 and Fig. 3, Fig. 30 and Fig. 31, and the left and right photographs correspond to each other. Fig. 3A shows the distribution state of the sulfur atom on the surface of the cation exchanger. Fig. 8 shows the green state in the cross section (thickness) direction of the cation exchanger of the sulfur atom. ' As can be seen from ^ 30 and Fig. 31, the acid group is introduced on the skeleton surface of the cation exchanger and the skeleton 097149356 98 201024342 (IV) U'i ® . (Examples 18 to 21) (Manufacturing of composite monolith) In addition to the use of the vinyl monomer, the amount of the crosslinking agent, the type of the organic solvent, the amount of the organic solvent, and the amount of the ΙΠ_polymerization_ coexistence The porous structure of the body, (4) money and (4) 4, and the temperature of the material are smaller than those shown in the wire 6 . The results are similar to those of the solid surface. 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 Fig. 32 to Fig. 39. Fig. 18, Fig. 35 and Fig. 36 are the same as those of the embodiment of the present invention. Further, the following examples were carried out to satisfy the conditions of the article of the present invention: _18 = (2.5 times) 'The type of organic solvent of Example 19 (10): molecular weight; the vinyl monomer of Example 20. Concentration UU;, ,, compared with the polymerization initiator 32-Fig. 39 'The skeleton of the composite monolith of the embodiment 19~2丨 is represented by the figure, and it is called the particle body; ^ φ 〇 attached to the protrusion The coating ratio of the 7' embodiment of the particles adhered to the surface of the monomer skeleton of the bulk "material average diameter" is 50 to 95%. / = work...3~8 in m' grain. In Example 18, the ratio of the body to the whole particle body is

...the protrusion is in the whole particle body: %, the particle size of the body in Example 19 is the ratio of the body of the body, and the particle size of the particle size of 2 to 5/zm in the whole particle body is 097149356 99 201024342 The ratio of the particles in the particle size of 3 to 7 in Example 21 to the entire particle body was 90%. (Production 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 #m, and the average diameter of the particles or the like attached to the surface of the skeleton is 5 to 17/zm'. The particle coverage is also as high as 5 〇~95%, the differential pressure coefficient is also small to 〇·〇1〇~〇.057MPa/m· LV, and the ion exchange band long sound is also significantly smaller than 8~12miu. Further, the proportion of the particles having a particle diameter of 5 to 1 Å/m in the entire particle body was 9 % by weight. (Example 22) (Production of composite monolith) In addition to the type and amount of the ethylenic monomer, the type and amount of the organic solvent to be used in the crosslinking agent, and the polymerization in the hydrazine step, the intermediate was In addition to the single-quantity of the porous structure, the cross-linking density, and the amount of use, the basin knee is I. i ^ The adjustment of the indicator shows that the C is manufactured in a single block. (iv) in Tables 6 and 7. Further, the results of observing the composite internal structure by SEM are shown in Fig. 42. Attached to the surface of the skeleton of the embodiment is a protrusion. Example 22 =: The flat touch on the single surface of the body is the middle of the table = 097149356 ‘The particle is 100% by 201024342. Further, the proportion of the particle body having a particle diameter of 6 to 12/zm in the entire particle body was 80%. (Manufacture of composite monolith anion exchanger) The composite monolith produced by the above method was cut into a disk shape having an outer diameter of 7 mm and a thickness of about 15 mm. The weight of the composite monolith is 17 9g. 1500 ml of tetrahydrofuran was added thereto, and after heating for 4 hours, TC was cooled to 1 Torr or less, and 114.5 g of a trimethylamine 30% aqueous solution was gradually added thereto, and the temperature was raised and (10) reaction ❹ 24 hours i should be finished. The alcohol is washed to remove the tetrahydrogen, and then washed with pure water to obtain a monolithic anion exchanger. The obtained composite anion exchanger has a swelling ratio of 2 〇 before and after the reaction, and the ion exchange capacity per unit body is In the state of water (4), it is 〇. 32mg equivalent/m from the value of the monolith and the swelling ratio of the anion exchanger in the water wet state. The average fineness of the organic porous ion exchanger in the wet state is estimated. The average diameter of the protrusions obtained by the same method is 2Mm, the particles are (4) _, and the total pore volume is 1 々. In addition, the length of the ion exchange band shows a very short cell. The pressure difference coefficient of the pressure loss index is 〇.〇4 is old, and the pressure loss is lower than the pressure loss required by practical use. Moreover, the particle body of the grain twist 12~24(4) is in the whole The proportion of the particle body is 80%. It is shown in Table 7. Secondly, in order to confirm the distribution state of the tetra(tetra) group in the porous anion exchanger, the brix ion exchange is performed by listening and reading, and the gasification is performed by 097149356 201024342. The eighth &d &lt; knife cloth state. As a result, the gas atoms are not only uniformly distributed on the surface of the anion exchanger, but also uniformly distributed inside the skeleton, and it is confirmed that the quaternary ammonium system 祧I is uniformly introduced. (Comparative Example 9) (manufacture of a monolith) Except for the amount of the ethylene monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, and the polymerization in the m step The amount of the monolithic intermediate used was changed to the amount shown in Table 6, and the monolith was produced in the same manner as in Example 1 and the results are shown in Table 6 and Table 2. The SEM photographs are not lightly formed to the formation of the particles or the protrusions. It can be seen from Tables 6 and 7 that the conditions of the conditions of the above-mentioned (1) to (5) are made under the conditions of the manufacturing conditions of the linings, that is, the conditions of the above-mentioned (1) to (5). Monolithic, on a single skeleton surface The formation of particles was confirmed. (Production of Monolithic Cation Exchanger) A monolithic cation exchanger was produced by reacting a monolith produced by the above method with chlorosulfuric acid in the same manner as in Example 17. The results are shown in Table 7. The length of the ion exchange zone of the obtained monolithic cation exchanger was 26 coffee, which was larger than that of the examples. (Comparative Examples 10 to 12) (Manufacturing of a monolith) 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 097149356 102 201024342, the polyvalent porous structure in the 111 step, the cross-linking density, and the amount of the monomer used in the amount of use were the same as in Example 17. * The amount of 6 households is not included in Table 6 and Table 7. Also, a single piece is produced. The results are shown in the comparison: Comparative Example 1 交 Crosslinking 密 比 制造 之 之 之 之 之 之 比较 比较 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- The polymerization temperature of Example 12 (5 (TC; 乂 ethanol; molecular weight 120)' ❹ temperature was low. The results are shown in Table 7. The surface of the half-life frame was not formed for 10 hours of the polymerization initiator. Further, Comparative Example 1 】The monoliths of 1〇 and 12 are in the bone, and the porous structure collapses and disappears. · The product that is separated from the U is transparent (manufacture of a monolithic cation exchanger). In addition to the comparative example 11, the above method is compared with Example 9 The same method used to bribe the porphyrin plastids to produce a monolithic cation ❿ 乂 。 。 。 。 。 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造The length is 23 to 26 mm, which is a larger value than the examples. (Comparative Example 13) (Manufacturing of a single block) The amount of the vinyl monomer used, the amount of the crosslinking agent used, and the amount of the organic solvent used. The porous structure and use 4 of the monolithic intermediates coexisting during the polymerization in the step are changed to the ones shown in Table 1. The monoliths were produced in the same manner as in Comparative Example 9. The results are shown in Tables 6 and 7. It is understood that the monolithic skeleton surface 097149356 can be produced if the sedan is removed from the original date. 103 201024342 Particle formation was not recognized. (Manufacture of monolithic anion exchanger) The monolith produced by the above method was cut into a disk shape of 70 mm in diameter and 15 mm in thickness. Dimethoxymethane 14_ was added here. 4 〇ml of four gasified tin, 56 〇mi of sulfuric acid was added dropwise under ice cooling. After the completion of the dropwise addition, the temperature was raised and reacted at 35 C for 5 hours to introduce a sulfhydryl group. After the reaction, the mother liquor was extracted by siphoning to THF/ The mixed solvent of water = 2/1 was washed, and then washed with THF. THF 100 ml of this gas methylation monolith and 600 ml of trimethylamine 30% aqueous solution were reacted at 60 ° C for 6 hours. After that, 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 obtained anion exchange body had an anion exchange band length of 47 mm, which was larger than that of the examples. Value. 097149356 104 201024342 ❿ (94) Aggregate Finance υ B &lt;— &lt;- &lt;&gt;- s &lt;&lt;-&lt;- s § Total pores m ml/g 15.8 &lt;- &lt;- LO 15.8 17.2 15.8 15.9 15.8 15.8 LO Clearance hole diameter ε =1 &lt;- &lt;- CO ΙΛ oo OJ CO LO Monolithic Intermediate Crosslinking Density Moth 9^ CO &lt;- &lt;- &lt;- &lt;- 〇&gt; CO I 1Ί CO cd CO CO CO — _H usage bo 03 CO CO cd T—( cd 嶒od CO co CT> oi o cd inch · CO cd 〇> CO 05 copolymerized type styrene-divinylbenzene copolymer &lt;- &lt; — &lt;— &lt;— &lt;&lt;- &lt;- &lt;- &lt;- &lt;- &lt;- organic solvent usage ϋ〇s &lt;- &lt;- gsssss species 1-sterol&lt;- Sterol&lt;1- 1-butanol 1-octanol&lt;-Song 1 1-decyl alcohol&lt;- crosslink density ratio η/η τ-&lt; LO LO oi o &lt;- &lt;- inch o .. ...... oa c=so C3 C5 Moer %** CO cd CO cd CO &lt;- &lt;- inch CO &lt;- &lt;- &lt;- &lt;- crosslinker usage bfl o inch · C3 03 〇〇C5 OJ 1 蝎ot—H CO c=&gt; o oo C=3 o &lt;=» r-4 OO &lt;z&Gt; Species Diethylbenzene &lt;- &lt;- &lt;- &lt;- ^- &lt;- &lt;- &lt;- &lt;- &lt;- Weight % 36.0 o 00 CO 39.2 o od 03 49.0 39.4 49.0 CM ai CO 49.0 49.0 39.2 Vinyl monomer usage bo 36.0 o od CO oa C73 CO 〇〇od LO 49.0 inch 49.0 CM a&gt; CO 49.0 &lt;z&gt; CD inch 39.2 type styrene &lt;&lt;- &lt;- &lt;-styrene&lt;-&lt;-&lt;-&lt;-&gt; - Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 fcb^i Example 9 Comparative Example 10 \mm n Cap column 12 cases 13

SI 砩#W 众 loqKt^ 00 inch «w^4?igMto^co*ff ^ %其&gt;机械裘|0-^ i4冬说硪su$to 当Ϊ* 9S£6 inch U60 201024342 (5 ions Crossing belt length mn %〇Is V »H _ per ^&lt;« S^- t+&gt; ω life few € ι-Η ι Η 0.78 0.56 0.48 0.68 0.32 0.64 0.73 0.65 0.56 Introduction of functional sulfonic acid groups &lt;- — &lt;— &lt; — Four-story Sulfosit S· &lt; — , — Four-stage Syrup Particles Composite Monolithic Ion Exchanger Differential Pressure Coefficient MPa/m · LV 0.057 0.015 0.041 0.010 0.032 0.041 0.016 0.028 0.014 0.020 Skeleton Constructing continuous macropores&lt;- &lt;- &lt;- co-continuous construction&lt;~ continuous macroporous m. &lt;- ·«- &lt;- particle coverage rate § om LO cn&gt; osg CD 〇oc particle average diameter βΧΑ LD 卜 CO lO oo S 1 1 1 1 total pores ml/g CO oi 00 cd 05 cd inch CM· 03 co c&gt;i oi oo CNI 05 oi continuous pores //m 03 L〇03 CO oo inch OQ OO LO m co LTD CO CO skeleton structure continuous macroporous m. &lt;*- &lt;- &lt;-co-continuous structure&lt;- continuous giant pore m. &lt;- &lt;- &lt;- particle composite monolith Particle coverage % § mm 03 S g τ*Ή c=&gt;&lt;=&gt; 〇o Average particle diameter m OO CO LO o 1 1 1 1 Total pores m ml/g CO oi oo co 03⁄4 r— ^ CO oi 寸 CO oi oi 00 01 oi continuous fine pores jum CO rH LO CO 2 〇3 03⁄4 C&lt;1 CD CO CO oo CO oo CO Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Comparative Example 9 Comparative Example 10 Comparative Example 12 Comparative Example 13 ❿ 901 ο * 9sis 201024342 (Industrial Applicability) Φ The first invention material and the subject ion interaction, the chemical stability and the mechanical strength are the same as 'there' The ion exchange capacity per unit volume is large, and the continuous pores are large, so that the pressure loss when the flow of water 4 gas or the like is low is low. Further, the monolithic and monolithic ion exchanger of the second invention has a hydrophobic and stable structure, and has a large skeleton and high mechanical strength, in particular, an ion exchange capacity A per unit volume, in a co-continuous structure. #, Three-dimensional continuous hollow holes are large, so that the water loss of the water or gas is less than the loss of the force, and the length of the ion illusion band is exceptionally long. Further, the monolithic and monolithic parental replacement of the third invention is chemically stable and has high mechanical strength. Further, the contact efficiency with the gripper is high when the fluid penetrates, and the pressure loss when the fluid penetrates is higher than that of the county. It can be effectively used as a chemical or sorbent because of the invention from the first invention to the third invention; it is filled with ions that are used in the 2-bed 3-tower pure water manufacturing device or the electric deionization manufacturing device. Exchange body; various color layer analysis fillers; solid _ / _ media; and should be secret (4) field. BRIEF DESCRIPTION OF THE DRAWINGS The H 4 ® of the first invention, the circular form is FIG. 17, and the second invention is shown in FIG. 18 to FIG. 26 'the third invention of the eve, the &amp; η moxibustion pattern Figure 27 to Figure 42. That is, Fig. 1 is an SEM image of a single block of J. Fig. 2 is a sputum image showing the distribution of sulfur atoms on the surface of the monolithic cation obtained in Example 1. Fig. 3 is a ΕΡΜΑ image showing the distribution of the melon atoms in the cross section (thickness) of the monolithic cation exchanger obtained by the length of &gt;6:1 Ί length 1. Fig. 4 is a view showing the comparative example of the embodiment and the ion exchange capacity per unit_ of the comparative example of 097149356 107 201024342. Figure 5 # # _ + &amp;&amp; j π Correlation The SEM image of a single block obtained by age. Figure 6. The SEM image of the monolith obtained in column 4. Fig. 7 is a manual transfer of the skeleton portion indicated by the cross section of the SEM image of the cabinet. 1 The component symbol U indicates a photo area, and the component symbol 12 indicates a cross-section of the frame portion, and the component symbol n is not the same as the SEMR of the second embodiment.圏9 is a monolithic SEM image of the monolith obtained in Example 3. Figure U is an SEM image of an early block of the known embodiment. Figure 12 is a single image obtained in Example 6. Figure 13 is a block diagram of the SM image obtained in Example 7. Figure 14 is an image of a monolith obtained from Example M. Figure 15 is the image obtained in Example 9. Figure 16 is a (four) image of the monolith obtained in Example 1. Π1: The monolithic (10) image. Fig. 18 is a view showing a co-continuous structure of a monolith of the invention. In the figure, the component symbol: indicates the skeleton phase, the component symbol 2 indicates the void phase, and the component symbol ι〇 is a monolithic block. Fig. 19 is a clear image of the monolithic intermediate obtained in Example 2. Figure 2G is a SEM read of a monolithic cation exchange with a co-continuous construction obtained in Example 2Q. Fig. 21 is a view showing an EPM II image of a sulfur atom distribution state on the surface of a monolithic cation exchanger having a co-continuous structure obtained in Example 2Q. Fig. 22 is a ΕΡΜΑ image showing the state of distribution of sulfur atoms in the cross section (thickness) direction of the single-cation positive parent having a co-continuous structure obtained in Example 2 (). Figure 23 is a SEM image of the 097149356 Ο 108 201024342 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 photograph of a monolith obtained by the comparative example η obtained in Example 23, which has a co-continuous structure, and Figure 26 is a sEm photograph of a monolith obtained in Example 31. SEM image. Fig. 28 is a magnification of 300 SEM image of the monolith obtained in Example 31. Fig. 29 is a leg image of a magnification of 3 单 obtained in Example 31. Fig. 3 shows the implementation of Φ Example 31 A ruthenium image of the distribution of sulfur atoms on the surface of the monolithic cation exchanger is shown in Fig. 31. Fig. 31 is a ΕΡΜΑ image showing the distribution of sulfur atoms in the cross-sectional (thickness) direction of the monolithic cation exchanger obtained in Example 31. The SEM image of the monolithic magnification of 1 所得 obtained in Example 32 was used to obtain a magnification of 6 〇〇❾ SEM image of the monolith obtained in Example 32. Fig. 34 is an image of the magnification surface of the monolith obtained in Example 32. ® 35 Series Example 33 SEM image of a magnification of 600 obtained from ❹. Fig. 36 is an SEM image of a magnification of 3000 obtained in Example 33. Fig. 37 is a SEM of a magnification of 3000 obtained in Example 34. Fig. 38 is a magnification of 100 of the monolith obtained in Example 35. SEM image. Figure 39 is an SEM image of a monolithic-magnification 3000 obtained in Example 35. Figure 40 is an SEM image of a single piece of the sample obtained in Example 36 at a rate of 1 〇 0. Figure 41 is obtained in Example 36. SEM image of a single block with a magnification of 6 。. Figure 42 is an SEM image of a single block with a magnification of 3 所得 obtained in Example 36. 097149356 109

Claims (1)

201024342 VII. Patent application scope: 1. A monolithic organic porous material is superposed on each other, and the overlapping portion is characterized as a continuous macroporous structure of a bubble-like giant pore whose thickness/average diameter is 2_" In the open image, the cross section of the skeleton (=) shown in the cross section is 2. The monolithic organic poly" is 25 ❿ ❿ 、 and the overlapping portions are stacked and the remaining macro holes are stacked on each other. The pore structure, the continuous giant of the opening having a thickness of 1 mm or more is obtained by the following steps: - pore volume 〇 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 = modulating the water droplet type emulsion: then the oil is a monolithic step II, which is prepared to contain more than one of the B cations; m has at least 2 solution polymerized by the vinyl type monomer: a mixture of a cross-linking agent but not a starter; an organic solvent of the agglomerate, and a polymerization enthalpy step, which is a monolith of the π step I:: the object is placed under standing, and Combine and obtain a poly-framework organic porous body in the presence of more than one (five) body The skeleton of the intermediate skeleton is thick 097149356 110 201024342 3. A monolithic organic porous ion exchanger characterized in that the bubble-like macropores overlap each other, and the heavy 4 parts become in the water A continuous macroporous structure having an opening of an average diameter of 30 to 3 GG/zm in a state, a thickness of _ above 'total pore volume 〇·5 to 5 ml/g, and an ion exchange capacity per unit volume in a wet state of water is 〇 .4mg#4/ml or more, the ion exchange group is distributed in the porous ion exchange, and the _ macroporous structure (dry In the SEM image of the cut section of the body, the area of the skeleton shown by the face is 25 to 50% in the image area. 4. A monolithic organic porous ion exchanger, which is a monolithic organic porous financial derivative ion exchange group according to item 2 of the patent application, the ion exchange capacity per unit volume in a water wet state is Above the equivalent enthalpy, the ion exchange group is uniformly distributed in the porous # ion exchanger. 5. The manufacture of a monolithic organic porous body according to the following method: The method is characterized in that the step I is carried out, and the mixture of the oil-containing body, the surfactant and the water of the material-containing exchange group is stirred. The water droplets in the silk are prepared, and then the water droplet type emulsion is polymerized to obtain a monolithic organic porous intermediate having a continuous pore structure of 5 to wrist. The second step is a modulation. An organic solvent containing ethylene monomer, having at least two or more of the B-cells in the molecule, and being polymerized by ethylene to form an organic solvent, and polymerization. a mixture of initiators; and a step of 097149356 111 201024342 III, which is obtained by multiplying the monolithic form obtained in the step I, and in the presence of the organic porous intermediate Organic porous body. The coarse frame of the lunar frame 6. As in the fifth method of the patent application, the bubble-like macropores of the monolithic porous body obtained in the first step of the town are superimposed on each other 'with: porous intermediate' The continuous macroporous structure of the opening of the system is divided into an average diameter of 5~16ml/g 〇 structure, and the total pore volume is 7. A monolithic surface porous f ion intersection is performed, and the following steps are performed: The characteristics and the mixture of water are polymerized by the oil-soluble green body of the sub-oil, the water-type emulsion in the surfactant oil, and the money-type emulsion, and then the sputum: the monolithic organic poly-two; = 5 ^ Π steps, the system of 盥 盥 女 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Or a mixture of a cross-linking agent but not a starter; an organic solvent for the polymer formed and a step of polymerizing the enthalpy of the step of the step of the step I obtained by standing in the first step, and From the combination, obtained and in the presence of a mobile &amp; organic porous intermediate for polymerization:: Skeleton with large skeleton: 112 201024342 Large skeleton organic porous body; and IV step, introducing the ion exchange group into the coarse skeleton organic porous body obtained in the third step. 8. Single monolithic organic porous body, 5〜5. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 a three-dimensional continuous bone truss formed by a molar amount of an aromatic vinyl polymer having a thickness of 0.8 to 40; and a three-dimensional continuous pore having a diameter of 8 to 80 between the skeletons. The monolithic organic porous body is a co-continuous structure having the following skeleton and pores, and has 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 by the aromatic vinyl polymer of the ear and having a thickness of 0.8 to 40 Am; and a three-dimensional continuous pore having a diameter of 8 to 80 #ιη between the skeletons; The following steps are carried out: © I step, the oil is dissolved in the ion-free group. The mixture of the monomer, the surfactant and the water is prepared by stirring to form a water-drop type emulsion, and then the water-drop type emulsion in the oil is polymerized to obtain a continuous total pore volume of more than 16 ml/g and less than 30 ml/g. a monolithic organic porous intermediate having a macroporous structure; a second step of preparing a crosslinker containing an aromatic vinyl monomer and having at least two vinyl groups in one molecule, and dissolving an aromatic vinyl type a monomer or a crosslinking agent but does not dissolve a mixture of an organic solvent of a polymerization of 097149356 113 201024342 and a polymerization initiator formed by polymerization of an aromatic vinyl monomer; and a mixture obtained by the step of step π π in the step I The monolithic organic porous intermediate obtained in the step =: and is combined. In the following, a poly-continuous structure of a monolithic organic porous ion exchanger and a pore is obtained, and the total pore volume is in the form of each skeleton in the skeleton state (four) · ml/g, On the water wet, the ion exchange is beautiful in the h~ is 〇.3 equivalent/ml is uniformly distributed on the m and the base is evenly distributed in the total constituent unit of the porous ion-exchanged ion exchange group, and contains cross-linking. & is formed by an aromatic B-counter polymer of 0.3 to 5. Q mole%, and a three-dimensional continuous skeleton of the unit unit; and a straight three-dimensional continuous pore between the skeletons. 〇1U0 11. A single porphyrin ion exchanger, which is a unit of ion exchange group in the monolithic organic porous body of the ninth paragraph of the application, and the ion per unit volume in the wet state of the water The exchange capacity is 〇.埘 equivalent/ml or more, and the ion exchange group is uniformly distributed in the porous ion exchanger. 12. A method for producing a monolithic bulk porous body, the dragon is performing the following steps: Step I is to mix a mixture of an oil-soluble monomer surfactant and water without an ion exchange group by stirring The water droplet type emulsion is prepared into an oil, and then the water droplet type emulsion is polymerized to obtain a monolithic organic eclipse having a total pore volume of more than 16 ml/g and a continuous macroporous structure of 097149356 114 201024342 3〇ml/g or less. In the middle of the 11-step process, a cross-linking agent containing 5 parts by mole of oleamole in the total oil-soluble monomer having an aromatic vinyl type monomer and having 2 or more vinyl groups is prepared. The organic solvent of the polymer formed by the polymerization of the vinyl monomer or the cross-linking agent J~5 Mo" is not dissolved in the mixture of the aromatic agent; and the polymerization initiation step ' The mixture obtained in the 11th step is passed from the mouth to the co-continuous structure by J2 of the monolithic organic porous intermediate. The monolithic organic porous body obtained in the step 12 of the patent application process, wherein the monolithic organic porous intermediate obtained in the step, the macropores of the shape are superposed on each other, and the overlapping portion becomes A continuous macroporous structure having an opening of an average diameter b to io〇em. A method for producing a monolithic organic porous ion exchanger, characterized in that the following steps are carried out: In the converter body and the surfactant, the ttr substance borrows (4) the water droplets in the oil, and then the oil 3〇t emulsion is polymerized to obtain the total pore volume exceeding _/g and the single continuous pore structure The block-shaped organic porous intermediate II step is prepared to contain an aromatic vinyl monomer, and the molecule has 097149356 201024342. The total oil-soluble monomer having at least two vinyl groups accounts for 0.3 to 5 mol%. a mixture of an organic solvent and a polymerization initiator which dissolves an aromatic vinyl monomer or a crosslinking agent but does not dissolve a polymer formed by polymerization of an aromatic vinyl monomer; III step, step II The resulting mixture is allowed to stand And, in this step by the presence of the resulting organic porous monolithic I of the polymerization intermediate, to give a co-continuous structure; and a step IV, the system obtained from step III co-continuous structure introduced ion exchange group. 15. A monolithic organic porous body, which is a composite structure of the following organic porous body and a particle body or a protrusion, and has a thickness of 1 liter or more, and an average diameter of the hole is 8 to 100 // m, total The pore volume is 0. 5~5ml/g: an organic porous body formed by a continuous skeleton phase and a continuous pore phase; a majority of the particles having a diameter of 2 to 20 #m adhered to the surface of the skeleton of the organic porous body; A plurality of protrusions having a maximum diameter of 2 to 20/m on the surface of the skeleton of the organic porous body. 16. The monolithic organic porous body according to claim 15, wherein the porous pores of the organic porous system are superposed on each other, and the overlapping portion becomes an opening having an average diameter of 20 to 200 &quot; Continuous giant pore structure. 17. The monolithic organic porous body according to claim 15, wherein the organic porous system has a three-dimensional continuous skeleton having a thickness of 0.8 to 40/zm and a diameter of 8 to 80/m between the skeletons. A co-continuous structure formed by three-dimensional continuous holes. 097149356 116 201024342 18. A monolithic organic porous material: a body characterized by performing the following steps, and the first step is to remove an oil-soluble monomer from the first group 1 having at least two or more ethyl amide groups, In a molecule, the mixture is polymerized by the preparation of a surfactant, a surfactant, and a water-drop type emulsion to obtain a monolithic organic porous material having a total fineness of two = emulsions followed by (four) water pore structure. The continuous giant II step: preparing a second swallowing knife containing a vinyl monomer and having more than one vinyl, and having a second cross-linking agent, and not dissolving the second cross-linking medium, The present invention of the polymerization initiator; the step of organic solvent 111 formed by the polymerization of the polymer formed by the formation of the monolithic substance obtained in the first step is carried out under static conditions, and When the half-life temperature is low, at least 5 = in the presence of 'polymerization. 19. The early secrets have rich holes (4) The composite structure system of the sub-axis and the particle body or the protrusions is 21 organic porous, τ + b, and the thickness is 1mm or more, and the average diameter of the holes is 1〇~15〇# m, the total pore volume is U. 5~5ml/g, and the ion money capacity in the wet state of the water is distributed in the composite structure Zhao Zhong: from the continuous skeleton phase and the continuous pore phase The organic porous body formed; a plurality of particle bodies having a diameter of 4 to 4 Mm on the surface of the skeleton of the organic matrix; and a plurality of protrusions having a maximum diameter of 4, _ formed on the surface of the skeleton of the organic porous body. 097149356 117 201024342 20. The monolithic organic porous ion exchanger of claim 19, wherein the porous pores of the organic porous system are superposed on each other' and the overlapping portion is in a wet state of water A continuous macropore structure having an average diameter of 30 to 300 openings. - 21. The monolithic organic porous ion exchanger according to claim 19, wherein the above organic porous system has a three-dimensional continuous skeleton having a thickness of 1 to 60/zm and a diameter of 1 〇 between the skeletons. A co-continuous structure formed by three-dimensional continuous holes of 100# m. ❿ 22. A method for producing a monolithic organic porous body, characterized in that the following steps are carried out: In the step I, an oil-soluble monomer containing no ion-exchange group has two or more ethylene groups in one molecule. The mixture of the second crosslinking agent, the surfactant and the water is prepared by mixing the water droplet type emulsion in the oil, and then the water droplet milk (10) is polymerized in the oil to obtain a total pore volume of 5, mi/g. a monolithic organic porous intermediate having a continuous macroporous structure; a second step of preparing a second crosslinking agent containing at least two vinyl groups in the molecule, and a dissolved ethylene type a monomer or a second cross-linking medium, and a mixture of an organic solvent and a poly-collection initiator which are polymerized by the polymerization of the B-type precursor; and the mixture obtained by the step n is placed under static conditions And in the presence of the monolithic compound obtained in the first step; in the presence of the organic chelating intermediate, poly 097149356 118 201024342 in the production of monolithic organic porous bodies, the following (1) to (5) are satisfied. Performing step II or III under conditions of at least one of the conditions Step: (1) The polymerization temperature in step 111 is a temperature lower than the 10-hour half-life temperature of the polymerization initiator at least 5 ° C; (2) the mole % of the second crosslinking agent used in step 11, It is twice or more the mole % of the first crosslinking agent used in the first step; (3) The vinyl monomer used in the 11 step is ethylene having a different structure from the oil 溶 soluble monomer used in the first step. (4) The organic solvent used in the step 11 is a polyether having a molecular weight of 200 or more; (5) the concentration of the vinyl monomer used in the step 11 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. 097149356 119