JP2003166982A - Organic porous material, manufacturing method therefor, and organic porous ion exchanger - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic porous material that can be used as an adsorbent, having a superior adsorption capacity and a high adsorption rate, an ion exchanger having high durability with respect to swelling and shrinkage, and filler for chromatography having superior dividability for a high-molecular weight compound and has a markedly large specific surface area. <P>SOLUTION: This organic porous material has a continuous cell structure, containing macro-pores connected to each other and meso-pores having a mean pore diameter of 1-1,000 μm in the walls of the macro-pores. This material also has noncontinuous micro-pores, having a means pore diameter of 5-800 μm in the internal wall of the cell structure constituted of the macro-pores and meso-pores. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic porous material useful as an adsorbent, a packing material for chromatography, and an ion exchanger, a method for producing the same, and an organic porous ion exchanger.

[0002]

2. Description of the Related Art An open-cell structure having macropores and mesopores in the walls of macropores that are connected to each other,
Further, as a porous body having micropores on the inner wall of the cell structure, an inorganic porous body made of silica or the like is known (US Pat. No. 5,624,875). The inorganic porous material has been actively developed as a packing material for chromatography. However, since this inorganic porous material is hydrophilic, it has been necessary to perform a complicated and costly operation such as hydrophobic treatment on the surface in order to use it as an adsorbent. Further, when this inorganic porous material is kept in water for a long time, silicate ions generated by hydrolysis of silica are eluted in water, and therefore it is not suitable to use as an ion exchanger for producing pure water or ultrapure water. It was possible.
On the other hand, it has been reported that when the above inorganic porous material is used as a packing material for chromatography, a marked improvement in performance can be achieved compared to the case where a conventional granular packing material is used. Has a maximum of 50 μm, and thus has been restricted when processing a large flow rate at a low pressure. In addition, since the pore size of the micropores is about 100 nm at the maximum, there is a problem that the fractionation of high molecular weight components becomes insufficient in the separation of high molecular weight compounds such as proteins and enzymes.

On the other hand, as an organic porous material having continuous pores, a porous material having a particle aggregation type structure is F.Sve.
c, Science, 273, 205 to 211 (1996) and the like.
However, since the porous body obtained by this method has a particle agglomeration type structure, the pore volume is small and the mesopores cannot be large, so that it has been restricted when performing a large flow rate at low pressure. In addition, since the presence of micropores is unclear and the specific surface area is small, the adsorption capacity is low when used as an adsorbent, and it is difficult to fractionate high molecular compounds by molecular weight when used as a packing material for chromatography. there were.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art.
Adsorbents with excellent adsorption capacity and adsorption rate, ion exchangers with excellent durability against swelling and shrinkage, and chromatographic packing materials with excellent fractionation properties for high molecular weight compounds have a remarkably large specific surface area. An object is to provide an organic porous material, a method for producing the same, and an organic porous ion exchanger.

[0005]

Under the circumstances, as a result of intensive investigations by the present inventors, in the oil containing an oil-soluble monomer containing no ion exchange group, a specific precipitating agent, a surfactant and water. An organic porous material obtained by polymerizing a water droplet type emulsion has an adsorbent excellent in adsorption capacity and adsorption rate, a low pressure, and a large flow rate while maintaining strength and having a remarkably large pore volume and specific surface area. It is possible to complete the present invention by discovering that it is suitable as an ion exchanger having excellent durability against swelling and shrinkage, and as a packing material for chromatography having excellent fractionation characteristics of high molecular weight compounds. I arrived. That is, in the present invention (1), the average pore size is 1 to 100 in the macropores and the walls of the macropores that are connected to each other.
An organic porous body having an open cell structure having 0 μm mesopores and further having micropores which are non-continuous pores having an average pore diameter of 5 to 800 nm on the inner wall of the cell structure formed of the macropores and the mesopores. Is provided. This organic porous body has a specific open cell structure, and has a novel structure which is completely different from the conventional particle aggregation type porous body. Further, since the organic porous body can have a relatively large mesopore and a micropore having discontinuous pores while maintaining strength, the pore volume and the specific surface area can be remarkably increased. Therefore, it is possible to process adsorbents with excellent adsorption capacity and adsorption rate, low pressure, and large flow rates.
It is suitable as an ion exchanger having excellent durability against swelling and contraction, and as a packing material for chromatography having excellent fractionation characteristics of high molecular weight compounds.

The present invention (2) also provides an oil-soluble monomer containing no ion-exchange group, a precipitant which is a poor solvent for the polymer formed by polymerization of the oil-soluble monomer and which dissolves the oil-soluble monomer, a surfactant, and It is intended to provide a method for producing the above organic porous material by polymerizing a water-in-oil type emulsion containing water, removing unreacted materials, and then drying. By adopting such a configuration, the organic porous body can be easily and reliably manufactured.

Further, in the present invention (3), the average pore diameter is 1 to 1 in the macropores and the walls of the macropores which are connected to each other.
It has an open cell structure having 000 μm mesopores, and further has micropores, which are discontinuous pores having an average pore diameter of 5 to 800 nm, on the inner wall of the cell structure formed by the macropores and the mesopores, and has an ion exchange capacity of 0. .1 μg equivalent /
g An organic porous ion exchanger having a dry porous body or more is provided. This organic porous ion exchanger is excellent in durability against swelling and shrinkage and can be treated by filling the space between the ion exchange membranes of an electric deionized water producing apparatus to form a desalting chamber. It is possible to pass water at a low pressure and a large flow rate.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The basic structure of the organic porous material and the organic porous ion exchanger of the present invention is such that the average pore diameter is 1 to 10 in the macropores and the walls of the macropores which are connected to each other.
It has an open cell structure having mesopores of 00 μm, preferably 5 to 100 μm, and an average pore diameter of 5 to 8 is further formed on the inner wall of the cell structure formed of the macropores and the mesopores.
It has micropores that are discontinuous pores of 00 nm, preferably 5 to 500 nm. That is, the open-cell structure usually has macropores having an average pore diameter of 2 to 5000 μm and macropores that overlap with each other, and the overlapping portions have mesopores that serve as common openings, and that portion has an open pore structure. In the open pore structure, when a liquid or gas is made to flow, the inside of the bubble structure formed by the macropores and the mesopores becomes a flow path. The number of macropores that overlap is 1 to 12 per macropore, and 3 to 3 for most macropores.
It is ten. If the average pore diameter of the mesopores is less than 1 μm, the pressure loss during liquid permeation or gas permeation increases, which is not preferable. On the other hand, if the average pore diameter of the mesopores is larger than 1000 μm, the contact between the liquid or gas and the porous ion exchanger becomes insufficient, and as a result, the adsorption characteristics and the ion exchange characteristics deteriorate, which is not preferable. When the structure of the organic porous material and the organic porous ion exchanger has the above-described open cell structure, macropore groups and mesopore groups can be uniformly formed, and FS
The pore volume can be remarkably increased as compared with the particle aggregation type porous ion exchanger as described in vec, Science, 273, 205 to 211 (1996).

Furthermore, by introducing the micropores having an average pore diameter of 5 to 800 nm into the inner wall of the cell structure, the specific surface area can be remarkably increased. The micropores are formed by minute irregularities of indefinite shape, and the average pore diameter thereof is determined by the known mercury intrusion method. When the average pore size of the micropores is less than 5 nm, not only the specific surface area does not become so large, but also when used as a packing material for chromatography, it is difficult to obtain excellent performance, which is not preferable. On the other hand, the average pore size of the micropores is 800
When it exceeds nm, the strength of the organic porous material or the organic porous ion exchanger decreases, which is not preferable. The specific surface area of the organic porous material and the organic porous ion exchanger of the present invention largely varies depending on the setting of the total pore volume of the porous material, but it can be arbitrarily set within the range of 10 to 500 m ² / g. it can. The specific surface area of the organic porous material or the organic ionic porous material of the present invention is at most 10 m ² / g in the conventional porous synthetic adsorbent or ion exchange resin, and therefore exceeds the conventional high ratio. A surface area can be used. In particular, when the organic porous material of the present invention is used as an adsorbent, one having a specific surface area of 50 to 500 m ² / g is suitable because the adsorption efficiency is remarkably improved. Specific surface area is B
It can be determined by the ET method.

The organic porous body and the organic porous ion exchanger have a total pore volume of 1 to 50 ml / g. If the total pore volume is less than 1 ml / g, the amount of permeated liquid or gas per unit cross-sectional area will be small, and the processing capacity will be reduced, such being undesirable. On the other hand, if the total pore volume exceeds 50 ml / g, the strength of the organic porous material and the organic porous ion exchanger will be significantly reduced, which is not preferable. The total pore volume of the conventional porous synthetic adsorbent and ion exchange resin is at most 0.
Since it is 1 to 0.9 ml / g, it is possible to use one having a high pore volume of 1 to 50 ml / g, preferably 5 to 50 ml / g, which has not been conventionally exceeded.

The liquid permeability and gas permeability of the organic porous body and the organic porous ion exchanger are determined by using water as a representative of liquid and air as a representative of gas. The permeation rate when the thickness of the ion exchanger is 10 mm is 100 to 100,000 L /
Min · m ² · MPa, 100 to 50,000 m ³ / min · m ² ·
It is preferably in the range of MPa. If the permeation rate, total pore volume and specific surface area are within the above ranges, when it is used as an adsorbent, an ion exchanger or a packing material for chromatography, the contact area with the liquid or gas is large and the liquid or gas is In addition to allowing smooth distribution, the excellent performance can be exhibited due to the sufficient mechanical strength.
The material of the skeleton portion forming the open cell structure is an organic polymer material having a crosslinked structure. The polymer material preferably contains 10 to 90 mol% of a crosslinked structural unit with respect to all the constituent units constituting the polymer material. If the cross-linking structural unit is less than 10 mol%, the mechanical strength will be insufficient, which is not preferable. On the other hand, if it exceeds 90 mol%, introduction of ion-exchange groups will be difficult and the ion-exchange capacity will decrease, which is preferable. Absent.

The type of the polymer material is not particularly limited,
For example, polystyrene, poly (α-methylstyrene),
Styrene polymers such as polyvinylbenzyl chloride; polyolefins such as polyethylene and polypropylene; poly (halogenated olefins) such as polyvinyl chloride and polytetrafluoroethylene; nitrile polymers such as polyacrylonitrile; polymethyl methacrylate, polyethyl acrylate (Meth) acrylic polymers such as;
Examples thereof include styrene-divinylbenzene copolymer and vinylbenzyl chloride-divinylbenzene copolymer. The polymer may be a homopolymer obtained by polymerizing a single monomer, a copolymer obtained by polymerizing a plurality of monomers, or a blend of two or more kinds of polymers. . Among these organic polymer materials, a styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are mentioned as preferable materials because of easy introduction of ion exchange groups and high mechanical strength. The open cell structure of the organic porous material or organic porous ion exchanger of the present invention can be observed by SEM. The pore size of macropores and the pore size of mesopores are also determined by SEM observation.

When the organic porous material of the present invention is used as an adsorbent, for example, a cylindrical column or a rectangular column, which is cut into a shape capable of inserting the organic porous material into the column, is packed as the adsorbent. , Benzene, toluene,
By passing water to be treated containing a hydrophobic substance such as phenol or paraffin, the hydrophobic substance is efficiently adsorbed to the adsorbent. The specific surface area and pore volume of conventional porous synthetic adsorbents are large at most 10 m ² / g
Since it is 0.9 ml / g, the adsorbent of the present invention can obtain adsorbent having several times or more adsorption ability as compared with the conventional adsorbent.

When the organic porous material of the present invention is used as a packing material for chromatography, for example, a packing material obtained by cutting an organic porous material into a shape capable of being inserted into the column or a rectangular column is used as the packing material. If the solution to be treated containing high-molecular compounds such as proteins and enzymes is passed through it, the contact area can be increased while maintaining strength. Is done well. In a conventional inorganic porous body having an open-cell structure, the pore size of the micropores is 100 nm at the maximum, so the packing material for chromatography of the present invention is superior to the conventional packing material in the fractionation ability of the polymer component. You can get what you want. Chromatography can include ion chromatography, reverse phase liquid chromatography and normal phase liquid chromatography.

The organic porous ion exchanger of the present invention comprises
1 μg equivalent / g or more of dried porous body, preferably 1.0 μ
It has an ion exchange capacity equal to or more than g equivalent / g dry porous body. Ion exchange capacity is 0.1 μg equivalent / g
If the amount is less than that of the dry porous body, the ion exchange capacity will be reduced, which is not preferable. As the ion exchange group to be introduced into the organic porous material, cation exchange groups such as sulfonic acid group, carboxylic acid group, iminodiacetic acid, phosphoric acid group, and phosphoric acid ester group; quaternary ammonium group, tertiary amino group, secondary ion group Anion exchange groups such as primary amino group, primary amino group, polyethyleneimine, tertiary sulfonium group and phosphonium group; amphoteric ion exchange groups such as betaine and sulfobetaine.

The organic porous material and the organic porous ion exchanger of the present invention have a continuous cell structure having macropores connected to each other and mesopores having an average pore diameter of 1 to 1000 μm in the walls of the macropores. The inner wall of the cell structure formed of the mesopores further has micropores having non-continuous pores having an average pore diameter of 5 to 800 nm, which is a novel structure completely different from the conventional particle aggregation type porous body, The pore volume and the specific surface area can be remarkably increased while maintaining the strength of the porous body.

An example of the method for producing the above organic porous material is shown below. That is, the organic porous material is an oil-soluble monomer containing no ion-exchange group, a precipitant that is a poor solvent for the polymer formed by polymerization of the oil-soluble monomer and that dissolves the oil-soluble monomer, a surfactant, water and necessary A water-in-oil type emulsion is prepared by mixing with a polymerization initiator according to the above and polymerized to produce.

The oil-soluble monomer containing no ion-exchange group refers to a lipophilic monomer which does not contain an ion-exchange group such as a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group and has low solubility in water. Is. Specific examples of these monomers include styrene, α-methylstyrene,
Vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isobutene, butadiene, isoprene, chloroprene, vinyl chloride, vinyl bromide, vinylidene chloride, tetrafluoroethylene, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, acrylic Ethyl acid, butyl acrylate,
2-ethylhexyl acrylate, trimethylolpropane triacrylate, butanediol diacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate , Ethylene glycol dimethacrylate and the like. These monomers may be used alone or in combination of two or more. However, in the present invention, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is 10 to 90 mol%, preferably 12 of all the oil-soluble monomers. It is preferably set to -80 mol% from the viewpoint of obtaining the mechanical strength necessary for introducing a large amount of ion exchange groups in the subsequent step.

The precipitating agent which is a poor solvent for the polymer formed by polymerizing the oil-soluble monomer and which dissolves the oil-soluble monomer can be variously selected depending on the kind of the oil-soluble monomer. For example, when a mixture of styrene and divinylbenzene is used as the oil-soluble monomer, the precipitant is hexane, heptane, octane, isooctane,
Aliphatic hydrocarbons such as decane; alcohols such as 1-butanol, 2-butanol, 2-methyl-2-butanol, and methylisobutylcarbinol can be used. The addition amount of the precipitant varies depending on the content of divinylbenzene in the oil-soluble monomer, but is selected in the range of 10 to 70%, preferably 20 to 60% with respect to the total amount of the oil-soluble monomer and the precipitant. can do. By adding the above precipitant,
For example, the initial polymer of styrene and divinylbenzene becomes difficult to dissolve in oil components such as oil-soluble monomers, and as a result, it precipitates in the form of microparticles, and these microparticulates form aggregates, with minute irregularities on the surface. Express. When the amount of the precipitant added is large, many micropores are expressed, but the strength tends to decrease, and when the amount is small, the micropores are hard to be expressed. Further, the pore size of the micropores can be controlled by appropriately selecting the compounding amount of the precipitating agent or appropriately selecting the compounding ratio of the crosslinkable monomer and the precipitating agent.
As a method of forming the micropores, in addition to the addition of the precipitating agent, for example, a method of adding a linear polymer which is a polymer of an oil-soluble monomer, a good solvent for a polymer formed by polymerization of the oil-soluble monomer And a method in which the linear polymer and the swelling agent or precipitating agent are used in combination.

The surfactant is a water-in-oil type (W / W) when an oil-soluble monomer containing no ion exchange group is mixed with water.
O) There is no particular limitation as long as it can form an emulsion, and sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl. Nonionic surfactants such as ether and polyoxyethylene sorbitan monooleate; anionic surfactants such as potassium oleate, sodium dodecylbenzene sulfonate, dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride Agents: Amphoteric surfactants such as lauryl dimethyl betaine can be used. These surfactants can be used alone or in combination of two or more. The water-in-oil emulsion is an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the above-mentioned surfactant added varies greatly depending on the type of the oil-soluble monomer and the size of the intended emulsion particles (macropores), so it cannot be said unequivocally, but the total amount of the oil-soluble monomer and the surfactant is On the other hand, it can be selected in the range of about 2 to 70%.

As the polymerization initiator, compounds that generate radicals by heat and light irradiation are preferably used. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include azobisisobutyronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, and persulfate. Examples thereof include hydrogen oxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and tetramethylthiuram disulfide. However, in some cases, even if the polymerization initiator is not added, there is a system in which the polymerization proceeds only by heating or only by irradiation of light, so that the addition of the polymerization initiator is not necessary in such a system.

An oil-soluble monomer containing no ion exchange group,
Mix the precipitant, surfactant, water and polymerization initiator,
The mixing method for forming the water-in-oil emulsion is not particularly limited, and a method of mixing the components at once; an oil-soluble monomer, a precipitating agent, a surfactant and an oil-soluble polymerization initiator. A method in which an oil-soluble component and water or a water-soluble component which is a water-soluble polymerization initiator are separately and uniformly dissolved and then the respective components are mixed can be used. There is also no particular limitation on the mixing device for forming the emulsion, and an ordinary mixer, homogenizer, high-pressure homogenizer, rotation / revolution super mixer, vacuum stirring defoaming mixer, etc. can be used to obtain a desired emulsion particle size. An appropriate device can be selected for this. The mixing conditions are also not particularly limited, and the stirring rotation speed and stirring time with which the desired emulsion particle size can be obtained can be arbitrarily set. The mixing ratio of the oil-soluble component and the water-soluble component is (oil-soluble component) / (water-soluble component) = 2/98 to 50/50, preferably 5/95 to the weight ratio.
It can be arbitrarily set within the range of 30/70.

The polymerization conditions for polymerizing the water-in-oil emulsion thus obtained can be selected from various conditions depending on the type of monomer and the polymerization initiator system. For example, when azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, or the like is used as a polymerization initiator, it is 1 to 4 at 30 to 100 ° C. in a sealed container under an inert atmosphere.
It is sufficient to heat-polymerize for 8 hours, and when hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite or the like is used as a polymerization initiator, at 0 to 30 ° C. in a sealed container under an inert atmosphere. Polymerization may be performed for 1 to 48 hours. After the completion of the polymerization, the content is taken out, and if necessary, the organic porous material is obtained by extracting with a solvent such as isopropanol for the purpose of removing the unreacted monomer and the surfactant. That is, in the water-in-oil emulsion, the oil component is polymerized to form a skeleton structure, and the water droplet portion forms a bubble structure portion.

Next, a method for producing the organic porous ion exchanger of the present invention will be described. The method for producing the organic porous ion exchanger is not particularly limited, and a method of forming a component containing an ion exchange group into the organic porous ion exchanger in one step, or the organic porous material by the above method or the like is used. After manufacturing
Examples include a method of introducing an ion exchange group. Among these, the method of introducing an ion exchange group after producing the organic porous material is preferable in that the structure control of the obtained organic porous ion exchanger can be strictly controlled.

The method for introducing an ion-exchange group into the above organic porous material is not particularly limited, and known methods such as polymer reaction and graft polymerization can be used. For example, as a method of introducing a sulfonic acid group, if the organic porous material is a styrene-divinylbenzene copolymer or the like, a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid; Method of introducing sulfonic acid group by reacting porous body with sodium sulfite; introducing radical initiation group or chain transfer group into organic porous body and grafting sodium styrenesulfonate or acrylamido-2-methylpropanesulfonic acid Polymerization method; a method in which glycidyl methacrylate is similarly graft-polymerized and then a sulfonic acid group is introduced by functional group conversion in the same manner as described above. As a method of introducing a quaternary ammonium group, if the organic porous material is a styrene-divinylbenzene copolymer or the like, a method of introducing a chloromethyl group with chloromethyl methyl ether or the like and then reacting with a tertiary amine A method of producing an organic porous material by copolymerization of chloromethylstyrene and divinylbenzene and reacting it with a tertiary amine; introducing a radical initiation group or a chain transfer group into the organic porous material, N, N, N-trimethyl A method of graft-polymerizing ammonium ethyl acrylate or N, N, N-trimethylammonium propyl acrylamide;
Similarly, a method of introducing a quaternary ammonium group by converting a functional group after graft-polymerizing glycidyl methacrylate can be mentioned. Examples of the method of introducing betaine include a method of introducing a tertiary amine into the organic porous material by the above-mentioned method and then reacting it with monoiodoacetic acid, and the like. The ion exchange group to be introduced is a cation exchange group such as a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group or a phosphoric acid ester group; a quaternary ammonium group, a tertiary amino group or a secondary amino group. Anion exchange groups such as primary amino group, polyethyleneimine, tertiary sulfonium group and phosphonium group; amphoteric ion exchange groups such as betaine and sulfobetaine.

When the organic porous ion exchanger of the present invention is used as an adsorbent, similar to the organic porous material, for example, in a cylindrical column or a rectangular column, the organic porous ion exchanger is applied to the column. When the adsorbent is cut into a shape that can be inserted, and a sugar solution is passed through the adsorbent, the dye is efficiently adsorbed to the adsorbent.

When the organic porous ion-exchanger of the present invention is used as a packing material for chromatography, the organic porous ion-exchanger can be applied to, for example, a cylindrical column or a rectangular column as in the organic porous material. By packing as a packing material that is cut into a shape that can be inserted into the column, and passing an aqueous solution containing ions through it, the contact area can be increased while maintaining strength. Is done well. As the chromatography, similar to the organic porous material, ion chromatography,
Mention may be made of reverse phase liquid chromatography and normal phase liquid chromatography.

[0028]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but these are merely examples and do not limit the present invention. Example 1 (Production of Organic Porous Body) Styrene 32.91 g, divinylbenzene 17.72
g, n-heptane 21.70 g, sorbitan monooleate 8.04 g and azobisisobutyronitrile (A
BIBN) (0.29 g) was mixed and uniformly dissolved. Next, the styrene / divinylbenzene / n-heptane / sorbitan monooleate / azobisisobutyronitrile mixture was added to 450 ml of pure water, and the mixture was stirred at 20000 rpm for 2 minutes using a homogenizer, and then in oil. A water drop type emulsion was obtained. After completion of the emulsification, the water-in-oil emulsion was transferred to an autoclave, sufficiently replaced with nitrogen and then sealed, and allowed to stand and polymerize at 60 ° C. for 24 hours. After completion of polymerization
The contents were taken out and subjected to Soxhlet extraction with isopropanol for 18 hours to remove unreacted monomers, n-heptane, water and sorbitan monooleate, and then dried under reduced pressure at 85 ° C. overnight. 26 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained
The result of observing the internal structure of the contained organic porous body by SEM is shown in FIG. In FIG. 1, the central part that looks like a V-shape is the inner wall of the skeletal cell structure, and the dark parts on the upper right and left are the mesopores. In addition, the inner wall of the skeletal bubble structure is visible behind mesopore. Thus, the organic porous body has an open cell structure,
Most of the macropores with an average pore size of 40 μm overlap and
The pore size of mesopores formed by overlapping macropores and macropores is in the range of 1.6 to 40.2 μm, the average pore size is 8.6 μm, and the inner wall of the bubble structure formed of macropores and mesopores has an irregular shape. The microscopic unevenness was observed (unevenness on the surface of the skeleton structure portion in FIG. 1). The minute irregularities on the inner wall surface of this bubble structure have a pore diameter of 1 determined by the mercury injection method.
It is in the range of 2 to 1,200 nm, and the average pore size is 480 n.
It can be defined as a micropore which is a discontinuous pore of m. The total pore volume is 5.0 ml / g and the BET specific surface area is 64 m ^2.
It was / g.

Examples 2 to 4 (Production of organic porous material) The amounts of styrene, divinylbenzene, n-heptane, sorbitan monooleate and azobisisobutyronitrile charged were changed to the values shown in Table 1. Except for this, an organic porous material was produced in the same manner as in Example 1. The results are summarized in Table 2. In all cases, the organic porous material had a cell structure as shown in FIG. 1, introduction of micropores was confirmed, and a large value for BET specific surface area was obtained. .

Example 5 Instead of 40.50 g of styrene, 35.44 of styrene was used.
g and 5.06 g of glycidyl methacrylate were used to produce an organic porous material in the same manner as in Example 2. The results are summarized in Table 2. When the obtained organic porous body was observed by SEM, it was confirmed that it had a cell structure similar to that shown in FIG. 1, that is, the introduction of micropores.

Reference Example 1 An organic porous material was prepared in the same manner as in Example 4 except that n-heptane was not added and the amount of sorbitan monooleate added was changed to the value shown in Table 1. Manufactured. The results are shown in Table 2. The BET specific surface area was as small as about 1/6 of that of Example 4, and the presence of micropores was not recognized.

[0032]

[Table 1]

[0033]

[Table 2]

From Tables 1 and 2, it can be seen that the organic porous materials of the examples have BET specific surface areas 6 to 10 times as large as those of the organic porous materials of the reference example to which the precipitating agent is not added.

Example 6 (Production of Organic Porous Ion Exchanger) The organic porous body produced in Example 4 was cut to give 11.5 g.
Was collected, 800 ml of dichloroethane was added, and the mixture was mixed at 60 ° C for 3
After heating for 0 minutes, the mixture was cooled to room temperature and chlorosulfuric acid was 59.1.
g was gradually added and reacted at room temperature for 12 hours. afterwards,
Acetic acid was added, the reaction product was poured into a large amount of water, washed with water, and dried to obtain a porous cation exchanger. The ion exchange capacity of this porous body is 4.4 mg equivalent / g in terms of dry porous body.
Therefore, it was confirmed by the mapping of the sulfur atom using EPMA that the sulfonic acid group was uniformly introduced into the porous body. The internal structure of this organic porous ion exchanger has an open cell structure, most of macropores having an average pore diameter of 80 μm overlap each other, and the average value of the pore diameter of mesopores formed by the overlap of macropores and macropores is 1
0.0 μm, total pore volume of 8.2 ml / g, BET specific surface area of 36 m ² / g, average pore size of micropores is 80
was nm.

Example 7 (Production of Organic Porous Ion Exchanger) The organic porous body produced in Example 5 was cut and 6.1 g was taken and immersed in isopropanol, and the inside of the pores was filled with isopropanol. Replaced. Then, the above porous body was treated with sodium sulfite / isopropanol / water (weight ratio 10/1).
5/75) Immersed in 900 ml of mixed solution and allowed to stand at room temperature for 24 hours.
Reacted for hours. After the reaction is completed, the organic porous body is washed with water,
The ion exchange capacity was measured. The ion exchange capacity was 220 μg equivalent / g in terms of dry porous body and 210 μg equivalent / g in terms of wet porous body.

Example 8 (Use of Organic Porous Body as Adsorbent) The organic porous body produced in Example 1 had a bottom surface of 10 mm ×
Cut out into a prismatic shape with a height of 10 mm and a height of 30 mm, and the bottom surface is 1
It was packed in a square column having a size of 0 mm × 10 mm and a height of 30 mm. To this column, 1 liter of an aqueous solution of 2 ethyl 1-hexanol having a concentration of 100 μg / l was supplied at a rate of 50 ml / min, the aqueous solution after the column was recovered, and the concentration of 2 ethyl 1-hexanol was measured. As a result, the concentration of 2 ethyl 1-hexanol in the aqueous solution after passing through the column was 1 μg / l or less, and it was confirmed that the organic porous material of this example could be quantitatively adsorbed and removed.

[0038]

As is apparent from the above description, the organic porous material and the organic porous ion exchanger of the present invention have a large pore volume and a large specific surface area, and further have a high gas and liquid permeability. Due to its excellent properties, it is useful as a filter, an adsorbent, a substitute for existing ion-exchange resins, a substitute for a desalting module of an electric deionized water production device, a filler for various chromatography, and a solid acid or base catalyst. It can be applied to a wide range of applications.

[Brief description of drawings]

1 is a SEM photograph of an organic porous body obtained in Example 1. FIG.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01J 20/28 B01J 20/28 A 20/30 20/30 C08F 2/32 C08F 2/32 // G01N 30 / 00 G01N 30/00 C J 30/60 30/60 A 30/88 30/88 C F term (reference) 4D017 BA04 CA13 CA17 DA03 4G066 AC14B AC17B AE10B BA23 EA01 FA08 FA21 4J011 LA02 LA03 LA04 LA09 LB09

Claims (7)

[Claims] 1. A continuous pore structure having macropores and mesopores having an average pore size of 1 to 1000 μm in the walls of the macropores and the macropores which are connected to each other, and the inner wall of the bubble structure formed by the macropores and the mesopores is further averaged. An organic porous material having micropores which are discontinuous pores having a pore diameter of 5 to 800 nm. 2. The organic porous material according to claim 1, which is used as an adsorbent. 3. The organic porous material according to claim 1, which is used as a packing material for chromatography. 4. A water-in-oil droplet containing an oil-soluble monomer containing no ion exchange group, a precipitant which is a poor solvent for a polymer formed by polymerization of the oil-soluble monomer and which dissolves the oil-soluble monomer, a surfactant and water. The method for producing an organic porous material according to claim 1, wherein the type emulsion is polymerized, unreacted materials are removed, and then dried. 5. The continuous pore structure having macropores and mesopores having an average pore diameter of 1 to 1000 μm in the walls of the macropores and the macropores which are connected to each other is further provided on the inner wall of the bubble structure formed by the macropores and the mesopores. An organic porous ion exchanger having micropores which are non-continuous pores having a pore diameter of 5 to 800 nm and an ion exchange capacity of 0.1 μg equivalent / g dry porous body or more. 6. The organic porous ion exchanger according to claim 5, which is used as an adsorbent. 7. The organic porous ion exchanger according to claim 5, which is used as a packing material for chromatography.