JP2008264732A - Porous ion exchanger and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porous ion exchanger which is composed of inorganic carrier and ion exchange resin, has high ion exchange speed, has high exchange capacity and also is excellent in mechanical strength, and to provide a manufacturing method thereof. <P>SOLUTION: The porous ion exchanger is composed of the inorganic carrier and the ion exchange resin deposited on the inorganic carrier, wherein the average volume is 5×10<SP>-4</SP>mm<SP>3</SP>/piece or more, the total micropore volume measured by a mercury porosimetry is 0.5 to 1.5 cm<SP>3</SP>/g and through-holes exist in the porous ion exchanger. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a porous ion exchanger and a method for producing the same. Specifically, the present invention relates to a porous ion exchanger made of an inorganic porous simple substance and an ion exchange resin and having through holes, and a method for producing the same.

  Conventionally, ion-exchange resins have been used as adsorbents, separation agents, high-performance liquid chromatography (HPLC) column fillers, and the like. However, the ion exchange resin alone may be inferior in shape retention and strength, and its application is limited.

  On the other hand, inorganic oxide particles such as silica are excellent in mechanical strength, have high chemical stability, and are easily available in various shapes and sizes at a low cost. It is used in various applications such as spacers for semiconductors, fillers such as semiconductor sealing resins, dental resins or various rubbers, HPLC column fillers, film antiblocking agents, and toner external additives.

  When using inorganic oxide particles, the surface of the inorganic oxide silica particles is generally coated with various substances according to the application and purpose, and the dispersibility and miscibility are improved, or the function is improved. It is done to give sex. As a typical technique for such surface modification, there is a surface treatment with a silane coupling agent. As the silane coupling agent, those having various functional groups such as an alkyl group, a mercapto group, an amino group, a quaternary ammonium group, a sulfonic acid group, an epoxy group, a methacryloxy group, and a vinyl group have been proposed. (See, for example, Patent Documents 1 and 2), many have already been put to practical use.

  Various methods for introducing functional groups into particles by a treatment other than a coupling agent such as a silane coupling agent have also been proposed. For example, a compound having a vinyl group is obtained by coating inorganic oxide particles with a cyclic siloxane having a Si—H group, and then reacting the Si—H group with a compound having a vinyl group using a platinum catalyst. Has been proposed (see, for example, Patent Documents 3 and 4).

  Furthermore, in order to impart various functionalities to the inorganic oxide particles, a method for imparting functionality by coating the inorganic oxide particles with a vinyl polymer has been proposed. As a method of coating inorganic oxide particles with a vinyl-based polymer, after coating with a vinyl-based polymerizable monomer, the monomer is polymerized, and a method of directly coating with a vinyl-based polymer. Broadly divided.

  For example, as a method of polymerizing the monomer after adsorbing a vinyl polymerizable monomer and coating the particle, colloidal silica particles can be used as a method for producing particles for white pigment used in paints and the like. A hollow particle is proposed that is dispersed in a polymer, coated and polymerized with a carboxylic acid-based vinyl monomer such as acrylic acid, and further coated and polymerized with a vinyl-based monomer such as methyl methacrylate or styrene. (For example, see Patent Document 5). In addition, as a method for producing filler particles for ion exchange liquid chromatography, an unsaturated carboxylic acid such as maleic acid and a polyvinyl compound copolymerizable with the unsaturated carboxylic acid (pentaerythritol tetraacrylate, divinyl) are used in a solution. Benzene etc.) and silica particles are added to adjust the suspension, concentrated and dried to form a film comprising an unsaturated carboxylic acid and a polyvinyl compound on the silica surface, and further polymerized by heating to form a crosslinked ion exchange composition As a method for forming coated particles for spacers of liquid crystal display devices (for example, see Patent Document 6), silica-based particles are treated with a vinyl-based silane coupling agent, and then this is dissolved in a polar solvent. Disperse, add monofunctional vinyl monomer to this, polymerize it and coat with non-crosslinked vinyl polymer How to obtain the particles (e.g., Patent Document 7 references) it has been proposed.

  In addition, as a method of directly coating with a polymer, for example, as a method for producing coated particles for spacers of a liquid crystal display device, a vinyl polymer is dispersed in a solvent, and this is mixed with silica particles. A method of coating (for example, see Patent Document 8), a method in which silica-based particle powder and polymer powder are mixed by a wet or dry method using a ball mill or the like, and a resin layer is formed on the particle surface by mechanical stress (for example, Patent Document 9) has been proposed.

  However, the silane coupling agent has an M-OH group (M is an M-OH group) in which Si-OH produced by hydrolysis of Si-X (X is a halogen atom, an alkoxy group, etc.) is present on the surface of the inorganic oxide particles. By reacting with the metal element constituting the inorganic oxide particles, the particles are bonded onto the particles. Therefore, the processing amount of the silane coupling agent greatly depends on the surface area of the particles to be processed and the amount of M-OH groups. For this reason, even if it is going to introduce | transduce various functional groups to an inorganic oxide particle, there exists a problem that the quantity does not increase so much. Further, since the silane coupling agent does not completely react with the M-OH group on the surface of the inorganic oxide particles, it may cause hydrolysis or the like under severe conditions. In addition, there is a limit to the number of functional groups that can be introduced even after a method of reacting with a compound having a vinyl group after coating with a cyclic siloxane having a Si-H group. There is a problem that it is difficult to remove.

  In addition, a method in which an inorganic oxide such as silica-based particles is dispersed in a solvent and a vinyl monomer is adsorbed and polymerized in the dispersion can form a relatively uniform coating layer. Since control of the thickness is relatively easy, there is an advantage that a large amount of functional groups can be introduced. However, in this method, there are not a few vinyl monomers that are polymerized outside the particle surface. Therefore, the loss of the vinyl monomer is large, and further, polymer particles of the vinyl monomer polymerized on the surface other than the particle surface may be generated and mixed. Further, since the polymerization is performed in a solvent, the vinyl monomer is easily polymerized in a state in which the solvent is taken in, and the resulting coating layer of the polymer is likely to be rough. Furthermore, when it coat | covers with the vinyl polymer which has an ionic group, it is difficult to raise the functional group density by ionic repulsion. Furthermore, in order to obtain a cross-linked polymer coating, when a plurality of types of polymerizable monomers are used, such as a cross-linking agent, the distribution coefficient of these monomers on the particle surface and the solvent may be different. In many cases, the composition ratio of the obtained polymer is different from the charged value, and control is also required for the control. In particular, in order to obtain a crosslinked polymer having a highly hydrophilic functional group such as a quaternary ammonium base or a sulfonic acid group, a polymerizable monomer having these functional groups is used in combination with a crosslinking agent. However, since the monomer used as a crosslinking agent is usually a hydrophobic compound, the distribution tendency is completely different, and in fact, particles coated with a crosslinked polymer having such a functional group cannot be obtained. There wasn't.

  Furthermore, in the method of coating a polymer that has been polymerized in advance, it is difficult to generate polymer particles or charge value, but in order to dissolve in a solvent, it is necessary to use a non-crosslinked polymer. In order to obtain it, complicated operations are often required separately, and it is also difficult to adjust the degree of crosslinking. On the other hand, the method of directly coating with a cross-linked polymer requires a strong mechanical stress, which is not only energetically disadvantageous, but also particles may be crushed when this stress is applied. In addition, in the method using such a solvent, as post-processes, steps such as filtration, washing, and drying are required, which is industrially complicated, and particles are difficult to disintegrate in these processes. In many cases, it strongly aggregates.

Accordingly, there has been a demand for providing a method that can easily provide a coating layer having a high thickness and a high density, has few by-products, and is simple in operation and easy to manufacture industrially.
In such a situation, the present applicant, while stirring the core particle powder, causes the polymerizable monomer to adsorb onto the core particle by contacting the polymerizable monomer by spraying or the like, and then polymerizable. By polymerizing the monomer, a polymer can be suitably formed on the particles, and a compound having a highly hydrophilic functional group such as a sulfonic acid group or an ammonium group is used as the polymerizable monomer In the case of using particles that have not been subjected to surface treatment or, on the contrary, if highly hydrophobic polymerizable monomers such as styrene are used, particles that have been hydrophobized by cyclic siloxane treatment or the like can be used for efficient adsorption. In addition, when the polymerizable monomer used as a raw material does not have the target functional group, we have found that it is only necessary to introduce a functional group according to the production method of the ion exchange resin, Already proposed (patent text) Reference 10). In this method, polymer-coated inorganic oxide particles having a coating layer with a large thickness and a high density on the entire particle surface are obtained.

However, inorganic oxide particles coated with a resin having ion exchange properties have been desired to have a higher ion exchange rate and a higher exchange capacity.
As a result of intensive research in this situation, the inventor of the present invention has a through-hole and retains porosity even after the inorganic carrier and the ion exchange resin form a complex, and the ion exchange rate is high. The inventors have found that the exchange capacity is excellent and have completed the present invention.
JP-A-6-199621 JP 9-48610 A Japanese Patent Laid-Open No. 10-267908 JP-A-8-105874 JP-A-3-281579 JP-A-5-96184 Japanese Patent Laid-Open No. 10-226512 JP-A-5-181144 Japanese Patent Laid-Open No. 9-80445 Japanese Patent Laid-Open No. 2005-60668

  The present invention provides a porous ion exchanger comprising an inorganic carrier and an ion exchange resin, having a high ion exchange rate, a high exchange capacity, and excellent mechanical strength, and a method for producing the same. It is an issue.

The porous ion exchanger of the present invention comprises an inorganic porous carrier and an ion exchange resin supported thereon, and has an average volume of 5 × 10 ⁻⁴ mm ³ / piece or more, and is measured by a mercury intrusion method. The total pore volume is 0.5 to 1.5 cm ³ / g and has through holes.

In the porous ion exchanger of the present invention, the volume occupied by pores having pore diameters in the range of 0.5 to 15 μm (through holes derived from macropores) is 0.4 to 1.5 cm ³ / g. It is preferable that

In the porous ion exchanger of the present invention, the ion exchange resin is preferably a cation exchange resin.
The method for producing a porous ion exchanger of the present invention has macropores having a pore diameter of 0.1 to 30 μm, mesopores having a pore diameter of 1 to 50 nm, and an average volume of 5 × 10. ^-4 mm ³ / piece or more of the porous inorganic carrier (A) and the monomer (B) that forms an ion-exchange resin or its precursor by polymerization, and the monomer (B) is polymerized A total pore volume measured by a mercury intrusion method is 0.5 to 1.5 cm ³ / g, including a polymerization step, and
It is characterized by obtaining a porous ion exchanger having through holes.

In the ion exchanger production method of the present invention, after the polymerization step, the volume occupied by pores in the pore diameter range of 0.5 to 15 μm measured by mercury porosimetry is 0.4 to 1.5 cm ^3.
It is preferable to adjust the contact amount of the monomer (B) so as to be / g.

In the method for producing a porous ion exchanger of the present invention, it is preferable that the inorganic porous carrier (A) is a binary pore silica particle, and the binary pore silica particle has a macropore volume of 0. in the range of .6~2.0cm ³ / g, the volume of mesopores and more preferably within a range of 0.4~1.5cm ³ / g. In the method for producing a porous ion exchanger according to the present invention, the binary pore silica particles are obtained by gelling a sol solution containing a silicon raw material, a water-soluble polymer and an acid catalyst in a phase separation transient structure. The particles are preferably produced and obtained by hydrothermal treatment of the gel body.

  According to the present invention, by having a through-hole, the initial ion exchange rate is particularly fast, the ion exchange capacity is large, the mechanical strength is excellent, the heat resistance is also excellent, and various catalysts, separation agents, adsorbents, etc. The porous ion exchanger which can be used conveniently, and its manufacturing method can be provided.

Hereinafter, the present invention will be specifically described.
Porous ion exchanger The porous ion exchanger of the present invention comprises an inorganic porous carrier and an ion exchange resin supported on the inorganic porous carrier.

  In the present invention, the inorganic porous carrier is an inorganic porous material having through holes, and may be artificially synthesized or a natural mineral. Examples thereof include those formed from silica, alumina, silica alumina, titania and the like.

The shape of the inorganic porous carrier used in the present invention is not particularly limited as long as it has a porous structure having through-holes. Spherical shape, cubic shape, cylindrical shape, prismatic shape, elliptical shape, plate shape, irregular shape Any shape may be sufficient, and it may be mixed. Of these, a spherical shape or a similar shape is preferable. The average volume of the inorganic porous carrier is 5 × 10 ⁻⁴ mm ³ / piece or more, preferably the average volume is 1 × 10 ⁻³ mm ³ / piece or more. For example, when the inorganic porous support is in the form of particles, the average volume is preferably about 5 × 10 ^{−4 to} 1000 mm ³ / piece, more preferably about 1 × 10 ^{−3 to} 150 mm ³ / piece. . Although not particularly limited, the average diameter of the inorganic porous carrier (the average value of the longest diameter of the inorganic porous carrier) is desirably 100 μm or more. For example, the inorganic porous carrier is particulate. In this case, it is desirable that the average particle diameter (average value of the longest diameter of the particles) is about 100 μm to 5 mm.

  The inorganic porous carrier according to the present invention may be porous as long as it has pores including through-holes. Preferably, the microporous pore size macropores and the angstrom region pore size mesopores are used. It is preferably a binary pore particle having two types of pores, a macropore having a pore diameter of 0.1 to 30 μm, a mesopore having a pore diameter of 1 to 50 nm, More preferably, it is a binary pore particle having. Among these, the inorganic porous carrier according to the present invention is particularly preferably a biporous silica particle.

When the inorganic porous carrier according to the present invention is a binary pore particle, preferably a binary pore silica particle, the volume of macropores having a pore diameter of 0.1 to 30 μm, Preferably 0
. The volume of mesopores having a pore diameter of 1 to 50 nm, preferably 0.4 to 1, is in the range of 6 to 2.0 cm ³ / g, more preferably 0.7 to 1.5 cm ³ / g. It is desirable that the thickness be in the range of 0.5 cm ³ / g, more preferably 0.5 to 1.2 cm ³ / g.

  The ion exchange resin constituting the porous ion exchanger of the present invention is not particularly limited as long as it is a resin having an ion exchange group. Even if it is a cation (cation) exchange resin, an anion (anion) It may be an ion) exchangeable resin. Among these, in the present invention, the ion exchange resin is preferably a cation exchange resin.

The porous ion exchanger according to the present invention is obtained by supporting an ion exchange resin on the inorganic porous carrier.
The ion-exchange resin may be supported on the inorganic porous carrier by any method, such as a method of directly supporting the ion-exchange resin on the inorganic porous carrier, or a resin having no ion exchange property. A method for introducing a functional group having ion exchange capacity after being supported on a porous carrier, a method for polymerizing a polymerizable monomer supported on an inorganic porous carrier, and introducing a functional group having ion exchange capacity if necessary Any of these methods can be employed, but it can be preferably carried out by the method for producing a porous ion exchanger of the present invention described later.

The porous ion exchanger of the present invention comprises the above-described inorganic porous carrier and an ion exchange resin carried thereon, and the average volume is 5 × 10 ⁻⁴ mm ³ / piece or more, preferably 5 ×. 10 ^-4
It is desirable that the thickness is about 1000 mm ³ / piece, more preferably about 1 × 10 ^{−3 to} 150 mm ³ / piece. The average diameter (average value of the longest diameter) is usually 100 μm or more, preferably about 100 μm to 5 mm. The size and shape of the porous ion exchanger of the present invention usually depends largely on the shape of the inorganic porous carrier, but a plurality of the ion-exchange resins supported on the inorganic porous carrier are combined. It may be a structure and is not particularly limited.

The porous ion exchanger of the present invention desirably has a total pore volume measured by the mercury intrusion method of 0.5 to 1.5 cm ³ / g, preferably 0.7 to 1.4 cm ³ / g. .
The porous ion exchanger of the present invention has a through-hole having a pore diameter of 0.5 to 15 μm, preferably 1 to 10 μm, and all the pores of the inorganic porous carrier are ion-exchangeable. It is not filled with resin. Such a through-hole is used when, for example, the porous ion exchanger of the present invention is used as a column filler for high performance liquid chromatography (HPLC), such as when it is used for an ion exchange in contact with a liquid or gas. Acts as a flow path for the liquid or gas in contact therewith, and this is expected to improve the ion exchange rate.

  It can be confirmed by an electron micrograph that the porous ion exchanger of the present invention has a through-hole. The surface of the through hole may or may not be coated with an ion exchange resin. Moreover, the pore diameter of the through hole can be obtained from the measurement result of the pore distribution by the mercury intrusion method.

  In the porous ion exchanger of the present invention, when the inorganic porous carrier is a binary porous inorganic carrier, at least a part of the mesopores, preferably 50% or more of the pore volume of the mesopores is ion-exchangeable. It is preferable that the macropores that are filled with the resin and that are the through holes of the inorganic porous carrier are held as the through holes. In this case, the inner surface of the through hole may be coated with an ion exchange resin, and the inner wall of the inorganic carrier may be exposed.

The porous ion exchanger of the present invention is not particularly limited, but is BE by N ₂ adsorption.
The specific surface area measured by the T method is preferably 5 m ² / g or more, more preferably 50 to 3
It is preferably 00 m ² / g.

  Furthermore, the porous ion exchanger of the present invention preferably has an ion exchange capacity determined by a titration method of 0.1 to 2.0 meq / g, more preferably 0.5 to 1.8 meq / g. .

Such a porous ion exchanger of the present invention has excellent ion exchange performance and also exhibits a high ion exchange rate.
Method for Producing Porous Ion Exchanger The method for producing a porous ion exchanger of the present invention comprises a specific inorganic porous carrier (A) and a monomer (B) that forms an ion exchange resin or its precursor by polymerization. And a polymerization step of polymerizing the monomer (B).

The inorganic porous carrier (A) includes macropores having a pore diameter of 0.1 to 30 μm, preferably 0.5 to 15 μm, and mesopores having a pore diameter of 1 to 50 nm, preferably 2 to 20 nm. And an average volume of 5 × 10 ⁻⁴ mm ³ / piece or more, preferably 1 × 10 ⁻³ mm ³ / piece or more can be used. Here, at least a part of the macropores of the inorganic porous carrier (A) is a through-hole. The average volume of the inorganic porous carrier (A) is preferably 5 × 10 ^{−4 to} 1000 mm ³ / piece, more preferably 1 × 10 ⁻³ when the inorganic porous carrier is in the form of particles, for example.
What is about -150 mm < ³ > / piece can be used suitably.

  Although not particularly limited, the average diameter of the inorganic porous carrier (the average value of the longest diameter of the inorganic porous carrier) is desirably 100 μm or more. For example, the inorganic porous carrier is particulate. In this case, it is desirable that the average particle diameter (average value of the longest diameter of the particles) is about 100 μm to 5 mm.

Examples of such inorganic porous carrier (A) include binary pore particles formed from silica, alumina, silica alumina, titania and the like, and among these, binary pore silica particles are particularly preferably used. The inorganic porous carrier (A) used in the present invention has a macropore volume of 0.5 to 2.5 cm ³ / g, preferably 0.6 to 2.0 cm ³ / g, more preferably 0.7 to The range of 1.5 cm ³ / g is desirable.

Particularly when the inorganic porous carrier (A) is a binary porous silica particle, the macropore volume is in the range of 0.6 to 2.0 cm ³ / g, preferably 0.7 to 1.5 cm ³ / g. In addition, it is desirable that the volume of the mesopores is in the range of 0.4 to 1.5 cm ³ / g, preferably 0.5 to 1.2 cm ³ / g.

  The binary pore particles used as the inorganic porous carrier (A) may be produced by any method. For example, in the case of binary pore silica particles, silicon raw material, water-soluble polymer and The sol solution containing the acid catalyst is preferably gelled in a phase separation transient structure to form a gel body, and the gel body is obtained by hydrothermal treatment. In the production of such binary pore silica particles, it is also preferable to dry and sinter the gel body after the gel body is formed and before the hydrothermal treatment, and the hydrothermal treatment of the gel body is performed at 100 to 150 ° C. It is also preferable to carry out within the range. Examples of the binary porous silica suitably used as the inorganic porous carrier (A) according to the present invention include, for example, JP-A-2006-213588, JP-A-2006-104016, International Publication WO2002 / 87585, etc. Can be mentioned.

The production method of the present invention includes a step of bringing the inorganic porous carrier (A) described above into contact with the monomer (B) that forms an ion-exchange resin or a precursor thereof by polymerization. The contact between the inorganic porous carrier (A) and the monomer (B) is not particularly limited and may be performed by any method, and the monomer (B) is contacted under either liquid phase or gas phase conditions. May be. Examples of the contact method in the liquid phase include spraying the liquid monomer (B) onto the inorganic porous carrier (A), immersing the inorganic porous carrier (A) in the liquid monomer (B), and the like. Is mentioned. Here, the liquid monomer (B) may be dissolved or dispersed in a solvent as necessary.

In the present invention, the contact between the inorganic porous carrier (A) and the monomer (B) is conducted after the polymerization step after the contact, and the total pore volume measured by mercury porosimetry is 0.5 to 1.5 cm ³ / It is preferable to adjust the contact amount of the monomer (B) so as to have a through-hole, and the fine pore diameter measured by mercury porosimetry is in the range of 0.5 to 15 μm. The contact amount of the monomer (B) may be adjusted so that the volume occupied by the pores is preferably 0.4 to 1.5 cm ³ / g, more preferably 0.4 to 1.2 cm ³ / g. desirable. Here, the pores having a pore diameter in the range of 0.5 to 15 μm are desirably through-holes derived from the macropores of the inorganic porous carrier (A).

  That is, in the present invention, the amount of the monomer (B) supported on the inorganic porous carrier (A) by the contact between the inorganic porous carrier (A) and the monomer (B) is set to the pore volume and the through hole. It is desirable to adjust so as to satisfy the average pore diameter. As such a method, the amount of the monomer (B) used for contact is controlled, the concentration of the monomer (B) used for contact is controlled, the contact time is controlled, and an appropriate method such as centrifugation after contact is used. Examples thereof include a method of removing the monomer (B). Since the method of bringing the monomer (B) into contact with the inorganic porous carrier (A) under a gas phase condition is relatively difficult to control, the contact between the inorganic porous carrier (A) and the monomer (B) is It is more preferable to select conditions under which the monomer (B) becomes a liquid phase. Moreover, it is preferable to select the conditions that the inorganic porous carrier (A) after contacting with the monomer (B) can be handled as a powder without aggregation of particles during polymerization. Although the usage-amount of a monomer (B) is not specifically limited, For example, it can be set as about 0.001-0.4g per 1g of inorganic porous support | carriers (A).

  In the present invention, the inorganic porous carrier (A) may be subjected to a surface treatment prior to the contact between the inorganic porous carrier (A) and the monomer (B). The surface treatment on the inorganic porous carrier (A) can be carried out according to the type of the monomer (B) used, and this also controls the amount of the monomer (B) carried on the inorganic porous carrier (A). can do. Examples of the surface treatment include a treatment for imparting known hydrophilicity and a treatment for imparting hydrophobicity. For example, when a compound having a highly functional group such as a sulfonic acid group or an ammonium group is used as the monomer (B), it is preferable to use an inorganic porous carrier (A) that has not been subjected to surface treatment or the like. Conversely, when using a highly hydrophobic monomer (B) such as styrene, it is desirable to use an inorganic porous carrier (A) whose surface has been hydrophobized by cyclic siloxane treatment or the like.

  In the present invention, the type of the monomer (B) may be selected according to the target ion exchange resin, and is not particularly limited. However, in terms of excellent polymerizability, a (meth) acryl group, A polymerizable monomer having a radically polymerizable unsaturated double bond such as a styryl group (hereinafter referred to as a vinyl monomer) is preferable.

Specific examples of the vinyl monomer used as the monomer (B) include the following.
1. Vinyl monomers having no ion-dissociable hydrophilic group; styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, p-tert-butylstyrene, chloromethylstyrene, p-chlorostyrene, Monofunctional aromatic vinyl monomers such as vinyl naphthalene; aromatic vinyl monomers such as polyfunctional aromatic vinyl compounds such as divinylbenzene, divinylbiphenyl, trivinylbenzene, and divinylnaphthalene . (Meta)
Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tritridecyl (meth) acrylate, benzyl (meth) acrylate, ( Phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, di Monofunctional non-fluorine (meth) acrylic monomers such as acetone methacrylamide, methacrylonitrile, methacrylolein and the like. Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol methanetri (meta ) Polyfunctional non-fluorinated (meth) acrylic monomers such as acrylate, tetramethylolmethanetetra (meth) acrylate, methylenebis (meth) acrylamide, hexamethylenedi (meth) acrylamide and the like. Perfluoroalkyl esters of (meth) acrylic acid such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, perfluorobutyl (meth) acrylate, and perfluoro-2-ethylhexyl (meth) acrylate. Vinyl acetate, methyl vinyl ketone, vinyl pyrrolidone, ethyl vinyl ether, divinyl sulfone, diallyl phthalate, etc.

  2. Vinyl monomers having hydrophilic groups capable of ion dissociation; styrene sulfonic acid and its salts, vinyl naphthalene sulfonic acid and its salts, vinyl benzyltrimethylamine, vinylbenzyltriethylamine, vinylpyridine, vinylimidazole, and other aromatic vinyl-based monomers Monomers. (Meth) acrylic having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, etc. Series of monomers. (Meth) acrylic acid, maleic acid, 2- (meth) acryloyloxyethyl succinate and its salts, 2- (meth) acryloyloxyethyl maleate and its salts, 2- (meth) acryloyloxyethyl phthalate, etc. (Meth) acrylic monomers having a carboxyl group and salts thereof. (Meth) acrylic monomers having a phosphate group such as (meth) acryloxyethyl acid phosphate and salts thereof. (Meth) acrylic monomers having a sulfonic acid group such as 2- (meth) acrylamido-2-methylpropanesulfonic acid and 3-methacryloyloxypropanesulfonic acid, and salts thereof. (Meth) acrylic monomers having an amino group such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (Meth) acrylic monomers having a quaternary ammonium base such as (meth) acrylic acid dimethylaminoethyl methyl chloride salt and (meth) acrylic acid dimethylaminoethylbenzyl chloride salt. Vinyl monomers having a phosphonic acid group such as vinylphosphonic acid and salts thereof.

  In the production method of the present invention, these polymerizable monomers constituting the monomer (B) may be used alone or in combination of two or more kinds depending on the intended polymer coating layer. For example, by using 0.05 to 100% by mass of the polyfunctional polymerizable monomer in the total amount of the monomer (B), a crosslinked polymer insoluble in the solvent can be obtained. In addition, when the polymerizable monomer as the main component of the monomer (B) is a solid at room temperature and normal pressure, it may be dissolved in a liquid polymerizable monomer copolymerized with the polymerizable monomer. preferable.

Examples of the method of using a plurality of polymerizable monomers in combination as the monomer (B) include the following methods (1), (2) and (3).
(1) A method in which only a monofunctional aromatic vinyl monomer or a monofunctional (meth) acrylic monomer is used as the monomer (B). As a result, a film made of a non-crosslinked polymer is produced. (2) Mainly monofunctional aromatic vinyl monomers having no hydrophilic group, and polyfunctional monomers (preferably polyfunctional aromatic vinyl monomers) as monomers (B ) A method of using, as the monomer (B), a mixture blended in the range of 0.05 to 40 parts by mass (preferably 0.1 to 10 parts by mass) with respect to 100 parts by mass in total. In this method, the polymer obtained is superior in chemical stability such as hydrolysis resistance than when a (meth) acrylic monomer is mainly used, and the resulting polymer is an inorganic porous carrier (A) even under harsher conditions. ) From peeling and decomposition. In addition, the polymer obtained by this method has excellent chemical stability because it is easy to introduce an ion-dissociable group into an aromatic group by the method described later, and ion exchange It is possible to obtain a porous ion exchanger excellent in functionality such as functionality.
(3) Monofunctional (meth) acrylic monomers having a hydrophilic group are mainly used, and polyfunctional monomers (preferably polyfunctional (meth) acrylic monomers) are used as monomers. (B) A method of using a polymerizable monomer mixture blended in a range of 0.05 to 40 (preferably 0.1 to 10 parts by mass) as a monomer (B) with respect to 100 parts by mass of the total amount. For (meth) acrylic monomers, compounds having various functional groups are provided industrially at low cost, and it is easier to produce coated particles having a polymer coating layer having such functional groups. It is. This also makes it easy to control the chemical structure of the polymer layer, for example, it is easy to adjust a polymer coating layer having different functional groups in a specific ratio. Furthermore, it can be purified in a monomer state, and even if an undesired side reaction occurs when a functional group is introduced and impurities are mixed in, it can be easily removed by the purification.

  In the production method of the present invention, the monomer (B) composed of one or more polymerizable monomers is brought into contact with the inorganic porous carrier (A) and adsorbed. The monomer (B) may be used alone for contact, but may be contacted with the inorganic porous carrier (A) with a mixture in which a polymerization initiator is added in order to efficiently carry out the polymerization step described later.

  As the polymerization initiator, a known polymerization initiator may be appropriately selected and used according to the type of the monomer (B) to be used, and is not particularly limited. However, the polymerization initiator exhibits a polymerization initiating ability by heating. This is preferable because the operation is simpler. For example, when a vinyl monomer is used as the polymerizable monomer, octanoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxide Organic peroxides such as oxyisobutyrate, t-butylperoxylaurate, t-hexylperoxybenzoate, di-t-butylperoxide, 2,2, -azobisisobutyronitrile and 2,2 An azobis-based polymerization initiator such as, -azobis- (2,4, -dimethylvaleronitrile) can be cited as a suitable polymerization initiator. These polymerization initiators are generally used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the monomer (B).

  Moreover, you may use what mix | blended other additives, such as a polymerization inhibitor, a polymerization inhibitor, and an ultraviolet absorber, as needed. Furthermore, when the monomer (B) is a solid, it may be used in a liquid state with a small amount of solvent.

  As described above, the contact of the inorganic porous carrier (A) with the monomer (B) and the mixture of optional components blended as necessary is not particularly limited, but preferably nitrogen, argon, etc. In the inert gas atmosphere, the monomer (B) or a mixture thereof is added in a gaseous or liquid state, and more preferably, the liquid monomer (B) or a mixture thereof is added by spraying in an inert atmosphere. is there. A known spray nozzle or the like can be suitably used for spraying. The addition rate is not particularly limited and may be determined according to various other conditions, but is generally 1 to 20 ml / min per 100 g of the inorganic porous carrier (A). The temperature conditions for adding these are not particularly limited, and may be under cooling or under heating. However, since the monomer (B) is polymerized before loading at an excessively high temperature, it is generally about −10 to 40 ° C. preferable.

  The contact between the inorganic porous carrier (A) and the monomer (B) is preferably carried out with stirring. Further, after the contact operation between the inorganic porous carrier (A) and the monomer (B), the inorganic porous carrier ( In order to disperse the monomer (B) in A), it is more preferable to continue stirring for an appropriate time such as about 30 minutes to 3 hours.

In such a contact step according to the present invention, it is considered that the monomer (B) is preferentially adsorbed on the mesopores of the inorganic porous carrier (A).
In the present invention, as described above, the inorganic porous carrier (A) and the monomer (B) are brought into contact with each other, and after the monomer (B) is adsorbed to the inorganic porous carrier (A), the monomer ( A polymerization step for polymerizing B) is performed.

  As a method of polymerizing the monomer (B) adsorbed on the inorganic porous carrier (A), a known method may be adopted as a polymerization method of the monomer (B) used, and it is not particularly limited. A preferable method includes a method of initiating polymerization by heating. When the monomer (B) is a vinyl monomer, it can be polymerized more efficiently by using a thermal polymerization initiator as described above. Moreover, the said heating temperature should just set suitably well-known conditions with the kind of monomer (B) and polymerization initiator which were used, etc., and generally is 40-230 degreeC, Preferably it is about 50-180 degreeC.

  When the monomer (B) used is a vinyl monomer, it is preferable to perform the polymerization step in an inert gas atmosphere such as nitrogen or argon in order to prevent polymerization inhibition due to oxygen.

  The pressure in the polymerization reaction vessel is not particularly limited, and may be pressurized, normal pressure, or reduced pressure. Depending on the type of monomer (B) used, pressurization is preferred among them. The pressure for pressurization is generally about 0.01 to 0.6 MPa. The polymerization time may be appropriately set according to the other conditions as described above, and is generally about 30 to 180 minutes.

  In the present invention, when the contact between the inorganic porous carrier (A) and the monomer (B) is carried out without using a solvent, the step of drying the polymerized particles is unnecessary, and the solvent is used. When it is carried out, it can be appropriately dried before or after the polymerization as required.

After such a polymerization step, the obtained particles have a pore volume measured by mercury porosimetry of 0.5 to 1.5 cm ³ / g, preferably 0.7 to 1.4 cm ³ / g. And it has a through hole. These through holes have an average pore diameter of usually 0.5 to 15 μm, preferably 1 to 10 μm. This through hole is usually derived from the macropores of the inorganic porous carrier.

  In the present invention, when a polymerizable monomer having a carboxyl group, a sulfonic acid group, an amino group, an ammonium group or the like is used as the monomer (B), a porous ion having ion exchange properties derived from these functional groups. It can be an exchanger.

  When a monomer having no functional group exhibiting ion exchange properties is used as the monomer (B), the precursor of the ion exchange resin is added to the inorganic porous carrier (A) after the polymerization step. Supported particles are generated. In this invention, it can be set as a porous ion exchanger by introduce | transducing the functional group which shows ion exchange property into this particle | grains according to the manufacturing method of well-known ion exchange resin.

The functional group exhibiting ion exchange properties to be introduced may be appropriately selected according to the purpose and is not particularly limited. For example, as a group capable of dissociating a cation, a sulfonic acid group, a carboxylic acid group, a phosphonic acid Groups, phosphoric acid groups, phenolic hydroxyl groups, thiol groups, perfluoro tertiary alcoholic hydroxyl groups, arsenic acid groups, selenic acid groups, and salts thereof. Examples of groups capable of dissociating anions are quaternary. Alternatively, a tertiary ammonium base, a tertiary amine group, a pyridinium base, an imidazolium base, and the like can be given. Among these, sulfonic acid groups or salts thereof, quaternary or quaternary are preferred because they are highly useful and easy to manufacture such as introduction of an aromatic vinyl monomer into a polymer. A tertiary ammonium base is particularly preferred.

The introduction of such functional groups exhibiting ion exchange properties can be carried out according to the method for introducing ion exchange groups in known methods for producing ion exchange resins.
For example, when styrene or the like is used as the monomer (B) and the polymer has an aromatic hydrocarbon ring such as a benzene ring in its structure, it is known to react with fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide or the like. Sulfonation or the like may be performed by a method. When the polymer has an acid ester structure such as a methyl methacrylate polymer, an acid group can be introduced by hydrolysis of the ester. Further, when the polymer has an amino group, it can be reacted with an alkyl halide, or when it has a halogenated alkyl group, it can be reacted with an amine compound to introduce an ammonium group. Furthermore, when it has an epoxy group, it can be sulfonated by using sulfanilic acid, sodium sulfite, etc. to introduce a sulfonic acid group, or an ammonium base can be introduced by reacting with an amine compound. . In addition, various ion exchange groups can be introduced by applying other known chemical reactions. When these functional groups are introduced, it is necessary to appropriately select the introduction form and reaction conditions so that the polymer supported on the inorganic porous carrier (A) is not lost due to peeling or the like. In general, a polymer of an aromatic vinyl monomer is chemically more stable than a (meth) acrylate monomer having an ester structure, and various functional groups can be easily introduced. The introduction of such functional groups is not particularly limited, but in order to prevent aggregation of the resulting porous ion exchanger, reaction conditions such as temperature and pressure are appropriately set without using a solvent, and the reaction is performed. It is preferable to employ a method in which the agent is in gaseous form and brought into contact with the particles. For example, in the introduction of the ion-exchange group, when a sulfonic acid group is introduced, a method of contacting with a sulfur trioxide gas can be suitably employed. Similarly, when introducing an ammonium base, it is preferable to select conditions such as reaction temperature and pressure so that the amine compound or alkyl halide to be used is in gaseous form and in contact with the particles.

  Depending on the application, polymers that are mainly composed of aromatic vinyl monomers have higher chemical stability than polymers that are mainly composed of (meth) acrylate monomers. This is preferable. Moreover, when the ion exchange resin formed has bridge | crosslinking, since generally high water resistance is obtained, it is preferable.

The thus obtained porous ion exchanger, a total pore volume measured by mercury mercury porosimetry is 0.5 to 1.5 cm ³ / g, preferably 0.7~1.4cm ³ / g Yes and has a through hole. The average pore diameter of the through-holes is desirably in the range of 0.5 to 15 μm, preferably 1 to 10 μm.

  The porous ion exchanger according to the present invention has through-holes, so that when used as an ion exchanger, the contact with the fluid becomes smoother, the ion exchange speed is faster, and the ion exchange resin and the inorganic material are inorganic. Since it has the advantages of a porous carrier, it has excellent heat resistance and mechanical strength. Such a porous ion exchanger according to the present invention includes a packing material for ion exchange chromatography, a solid phase catalyst for various acid or base catalytic reactions, a solid acid catalyst used for oxidation or dehydration reaction, and a packing for various resin products. It is useful for materials, water treatment agents, separation agents, metal adsorption / recovery agents, food or pharmaceutical purification applications, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

(Pore volume, average pore diameter)
The pore volume and average pore diameter of the sample were measured by a mercury intrusion method using a pore distribution measuring device (PoreMaster-60, manufactured by QUANTACHROME). The measurement is performed in the range of 3.7 nm to 100 μm in terms of pore diameter, and the total pore volume represents the volume of all pores in the range.

(Specific surface area)
The specific surface area of the sample is N ₂ using a specific surface area measuring device (SA-1000, manufactured by Shibata Kagaku).
The gas was determined by the BET method using an adsorption gas.

(Average particle size)
The sample is dispersed in water by ultrasonic waves, the particle size distribution is measured using a light scattering diffraction particle size distribution analyzer (Coulter LS230, manufactured by Beckman Coulter, Inc.), and the value of the volume-based arithmetic average diameter D ₅₀ is determined as the average particle diameter. did.

(Cation exchange capacity measurement)
After the sample was previously dried at 60 ° C. for 24 hours and the dry sample weight (W _C / g) was measured, 1 m
The mixture was stirred for 8 hours or more in an aqueous ol / dm ³ NaCl solution to replace the sodium ion type. Subsequently, the solution obtained by filtration was neutralized with a 0.2 mol / dm ³ NaOH aqueous solution using phenolphthalein as an indicator, and the amount of free hydrogen ions contained in the filtrate (A / mmol). Asked.

Based on the measured value, the cation exchange capacity is expressed by the following formula: cation exchange capacity (meq / g) = A / W _C (Equation 1)
Determined by

(Measurement of ion exchange rate)
In order to measure the ion exchange rate of the cation exchange ion exchanger, measurement was performed using iron (II) ions as cations. The measurement method is as follows.

Water is added to 0.35 g of ammonium iron (II) sulfate hexahydrate and 1 cm ³ of 6 mol / dm ³ hydrochloric acid to 500 cm ³ (solution (1)), and further diluted 10 times with water (solution (2)).
. Add 0.24 g of 1,10-phenanthroline hydrochloride to 200 cm ³ by adding water (solution (
3)). Water 50 cm ³ in addition to sodium acetate 0.42 g, further acetic acid aqueous solution of 0.1mol / dm ³ 50cm ³ added (solution (4)). 1 of 10g of hydroxyammonium chloride
Dissolve in 00 cm ³ of water (solution (5)).

Place 5 cm ³ of solution (2) in a beaker, add 15 cm ^{3 of} water, add 1.00 g of ion exchanger, and stir with a stirrer (20 mm stirrer chip, 500 rpm) for a predetermined time, and immediately perform vacuum filtration. Get the filtrate. To the filtrate, solution (3) 8 cm ³ ,
The solution (4) 8 cm ^3, solution (5) 5 cm ³ was added, further to 50 cm ³ by addition of water. The absorbance of the solution at a wavelength of 517 nm was measured with an absorptiometer (UV-240, manufactured by Shimadzu Corporation).

Separately, solution (1) 5 cm ³ , solution (3) 8 cm ³ , solution (4) 8 cm ³ , solution (5)
Mix 5cm ³ and add water to make 50cm ³ (Solution A), Solution (2) 5cm
³ , solution (3) 8 cm ³ , solution (4) 8 cm ³ , solution (5) 5 cm ³ , mixed with water to make 50 cm ³ (solution B), solution (2) 0.5 cm ³ , solution (3) 8 cm ^3, solution (4) 8 cm ^3, a mixed solution (5) 5 cm ^3, a calibration curve was obtained by using further mixed solution was 50 cm ³ by addition of water (solution C).

  Calculate the concentration of iron (II) ions in the solution from the absorbance obtained by the measurement and the calibration curve, and compare the ion exchange rate with the difference between the value and the initial concentration as the amount of ion exchange per unit time. It was.

[Example 1]
In the presence of polyacrylic acid having an average molecular weight of 25,000 (hereinafter referred to as HPAA), biporous silica was produced from water glass (No. 3 silica). The charged composition was water: concentrated nitric acid: HPAA: water glass = 97: 37: 6.5: 55 by weight ratio, and stirred at room temperature to obtain a uniform sol solution.

After stirring, the sol solution was transferred to a plastic container and allowed to stand at 35 ° C. for 1 day to gel. Thereafter, the wet gel was washed with water to remove sodium, then immersed in 0.1 N ammonia and aged at 50 ° C. for 1 day. Then, it dried at 50 degreeC and baked at 600 degreeC for 2 hours. The calcined sample was pulverized with a mortar and sieved to obtain a dual pore silica powder. The physical properties of the obtained binary porous silica are shown in Table 1. 50 g of the obtained binary porous silica was charged into a Teflon (registered trademark) flask, and 13.3.019 g of styrene, 1.627 g of divinylbenzene, t-butyl perfluoroethylene. A polymerizable monomer mixed solution preliminarily mixed with 2.7 g of oxy-2-ethylhexanoate was sprayed with stirring, and the inside of the container was then replaced with N ₂ gas and sealed, and further at room temperature for 2 hours. Stir with. 1 container after stirring
The mixture was heated at 00 ° C. for 2 hours to obtain a styrene / divinylbenzene copolymer-coated binary porous silica.

  20 g of the obtained styrene / divinylbenzene copolymer-coated binary pore silica was charged into a Teflon (registered trademark) pressure vessel, and an open glass vessel containing 30 g of fuming sulfuric acid was placed in the vessel. The container was sealed. Thereafter, it was heated at 80 ° C. for 8 hours, washed with water and dried to obtain a porous ion exchanger.

  The ion exchange capacity of the obtained ion exchanger was 1.5 meq / g. In addition, other physical properties are shown in Table 1. Moreover, the pore distribution measured by the mercury intrusion method is shown in FIG. 1 (A), and the electron micrograph is shown in FIG. 2 (A). The results measured by the above “measurement of ion exchange rate” are shown in Table 2 and FIG.

[Example 2]
In Example 1, except that the composition of the polymerizable monomer mixed solution used was 5.208 g of styrene, 0.651 g of divinylbenzene, and 1.08 g of t-butylperoxy-2-ethylhexanoate. The same operation as in Example 1 was performed to obtain a porous ion exchanger.

The ion exchange capacity of the obtained ion exchanger was 0.44 meq / g. In addition, other physical properties are shown in Table 1. Moreover, the pore distribution measured by the mercury intrusion method is shown in FIG. 1 (B), and the electron micrograph is shown in FIG. 2 (B). The results measured by the above “measurement of ion exchange rate” are shown in Table 2 and FIG.
[Comparative Example 1]
As a measurement sample, a commercially available ion exchange resin (Amberlyst 15DRY, manufactured by Rohm and Haas) was used.

The ion exchange capacity of the ion exchange resin was 4.0 meq / g. The physical properties are shown in Table 1 together with other physical properties. The results measured by the above “measurement of ion exchange rate” are shown in Table 2 and FIG.

  The porous ion exchanger according to the present invention includes a packing material for ion exchange chromatography, a solid phase catalyst for various acid or base catalytic reactions, a solid acid catalyst used for oxidation or dehydration reaction, a packing material for various resin products, water It can be suitably used for treating agents, separation agents, metal adsorption / recovery agents, food or pharmaceutical purification applications, and the like.

FIG. 1 shows the pore distribution measured by the mercury intrusion method for the porous ion exchangers obtained in Examples 1 and 2. FIG. 2 shows electron micrographs of the porous ion exchangers obtained in Examples 1 and 2. FIG. 3 shows a graph of results obtained by measuring the ion exchange rate in Examples and Comparative Examples.

Claims (8)

It consists of an inorganic porous carrier and an ion exchange resin carried on the carrier, has an average volume of 5 × 10 ⁻⁴ mm ³ / piece or more, and has a total pore volume of 0.5 to 0.5 as measured by mercury porosimetry. A porous ion exchanger having a through-hole of 1.5 cm ³ / g. The volume occupied by pores having a pore diameter in the range of 0.5 to 15 μm is 0.4 to 1.5 cm ^3.
The porous ion exchanger according to claim 1, which is / g.   The porous ion exchanger according to claim 1 or 2, wherein the ion exchange resin is a cation exchange resin. An inorganic porous carrier having macropores having a pore diameter of 0.1 to 30 μm and mesopores having a pore diameter of 1 to 50 nm and having an average volume of 5 × 10 ⁻⁴ mm ³ / piece or more (A), a step of contacting the monomer (B) that forms an ion-exchange resin or a precursor thereof by polymerization, and a polymerization step of polymerizing the monomer (B), and the total amount measured by mercury porosimetry A method for producing a porous ion exchanger, wherein a porous ion exchanger having a pore volume of 0.5 to 1.5 cm ³ / g and having a through-hole is obtained. After the polymerization step, the monomer (B) is adjusted so that the volume occupied by pores in the pore diameter range of 0.5 to 15 μm measured by mercury porosimetry is 0.4 to 1.5 cm ³ / g. )
The method for producing a porous ion exchanger according to claim 4, wherein the amount of contact is adjusted.   The method for producing a porous ion exchanger according to claim 4 or 5, wherein the inorganic porous carrier (A) is a binary porous silica particle. The binary pore silica particles have a macropore volume in the range of 0.6 to 2.0 cm ³ / g and a mesopore volume in the range of 0.4 to 1.5 cm ³ / g. The method for producing a porous ion exchanger according to claim 6, wherein:   The binary porous silica particles are obtained by gelling a sol solution containing a silicon raw material, a water-soluble polymer and an acid catalyst in a phase separation transient structure, and hydrogelating the gel body. The method for producing a porous ion exchanger according to claim 6 or 7, wherein the porous ion exchanger is a fine particle.