JP4587376B2 - Metal ion-supported inorganic particle powder - Google Patents

Description

  The present invention relates to a powder of inorganic particles carrying a polyvalent metal ion, useful as a gas adsorbent, a filler, a rust preventive, a synthesis reaction catalyst, and the like.

  Inorganic oxide particles such as silica are excellent in mechanical strength, have high chemical stability, and are easily available with various shapes, specific surface areas, and pores at low cost. It is used in various applications such as adsorbents and fillers such as various rubbers.

  Conventionally, carbon-based materials such as charcoal and activated carbon, and mineral-based materials have been used as gas adsorbing materials because they are inexpensive and have a large specific surface area. In the case of using a carbon-based material, a material in which an amine or an inorganic salt is supported or attached to a base material is used for the purpose of enhancing the adsorption effect (see, for example, Patent Document 1).

  In addition, when inorganic oxide particles are used, the surface of the inorganic oxide silica-based particles is generally coated with various substances according to the type of gas and the purpose thereof to provide an adsorption function. Modifications are also being carried out. Typical examples of the surface-modified inorganic oxide particles include particles subjected to silane coupling treatment. 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. (For example, see Patent Documents 2 and 3), and many applications have already been put into practical use for the purpose of gas adsorption.

  On the other hand, as a functional group introduced into the particles by a treatment other than a coupling agent such as a silane coupling agent, various proposals were made by coating inorganic oxide particles with a vinyl polymer to add functionality. Has been.

  For example, after adsorbing a vinyl polymerizable monomer and coating the particles, the monomer is polymerized, and colloidal silica particles are dispersed in a solvent, and a carboxylic acid vinyl such as acrylic acid is used. There has been proposed a hollow particle which is coated and polymerized with a monomer, and further coated and polymerized with a vinyl monomer such as methyl methacrylate and styrene (for example, see Patent Document 4). In addition, an unsaturated carboxylic acid such as maleic acid, a polyvinyl compound copolymerizable with the unsaturated carboxylic acid (pentaerythritol tetraacrylate, divinylbenzene, etc.) and silica particles are added to the solution to prepare a suspension. Concentrated and dried to form a film composed of an unsaturated carboxylic acid and a polyvinyl compound on the silica surface, and further polymerized by heating to form a crosslinked ion exchange composition (for example, see Patent Document 5), silica The particles are treated with a vinyl silane coupling agent, then dispersed in a polar solvent, a monofunctional vinyl monomer is added thereto, and this is polymerized to form a non-crosslinked vinyl polymer. Have been proposed (see, for example, Patent Document 6).

JP 2000-217897 A JP-A-6-199621 JP 9-48610 A JP-A-3-281579 JP-A-5-96184 Japanese Patent Laid-Open No. 10-226512

  When activated carbon is used as the adsorbing material, the activated carbon itself is black, so that there is a problem that the use of this is limited. Further, when activated carbon is impregnated with an inorganic salt or the like, when used under humid conditions, there is a problem that the adsorption performance deteriorates due to the elution of salts and amines as adsorbing components.

  In addition, in inorganic particles whose surface has been modified with a silane coupling agent, Si—OH produced by hydrolysis of Si—X (X is a halogen atom, an alkoxy group, etc.) of the silane coupling agent is inorganic. Since it is a production method in which M-OH groups (M is a metal element constituting the inorganic oxide particles) existing on the surface of the oxide particles are bonded to the particles, the treatment amount of the silane coupling agent is There is a problem in that the amount of functional groups is not so much depending on the surface area of the particles to be treated and the amount of M-OH groups. In addition, since the silane coupling agent does not completely react with the M-OH group on the surface of the inorganic oxide particles, hydrolysis or the like may occur under severe conditions, and the performance may be deteriorated.

  Accordingly, there is a need to provide a material that can be used as a gas adsorbent that is excellent in gas adsorbing ability and has a color tone that is not limited as in activated carbon and that is less likely to deteriorate in performance under various conditions. It was.

  The present inventors have intensively studied to solve the above problems. In addition, inorganic oxides such as silica are chemically stable, usually not colored, and moreover, those having different particle sizes and particle size distributions can be obtained easily and inexpensively. Various studies have been conducted on methods using inorganic oxides, and as a result, the present invention has been completed.

  That is, the present invention provides a metal ion, characterized in that it is coated with a crosslinked polymer having a cation exchange group, and at least a part of the counter ion in the cation exchange group is a polyvalent metal cation. It is a supported inorganic particle powder.

  In the metal ion-carrying inorganic particle powder of the present invention, since the coating layer having a functional group for carrying metal ions is formed of a cross-linked polymer, the cation exchange group does not desorb in high humidity or in a solution. Further, the particles having functional groups at a much higher concentration than those obtained by directly introducing functional groups with a silane coupling agent, and can carry various polyvalent metal ions. Since the inorganic particles are the core, the chemical stability and mechanical strength are excellent. Therefore, the metal ion-carrying inorganic particle powder of the present invention is suitable for use as a gas adsorbent having excellent stability under various conditions and high gas adsorbing ability. Furthermore, according to the polyvalent metal ion to carry, it can be used conveniently also as a catalyst support | carrier and rust preventive of a synthetic reaction.

  In the metal ion-carrying inorganic particle powder of the present invention, the core inorganic particles (hereinafter also referred to as “nuclear particles”) are coated with a crosslinked polymer having a cation exchange group, and the crosslinked polymer has At least a part of the counter ion in the cation exchange group is a polyvalent metal cation.

  The core particles are not particularly limited as long as they are inorganic particles, and may be appropriately selected according to the use of the metal ion-carrying inorganic particle powder of the present invention. A variety of different particle diameters, specific surface areas, pore volumes, shapes, etc. are readily available, and are excellent in chemical stability. Silicon, titanium, aluminum, zirconium, tin, lead, iron, A single oxide or composite oxide of a metal such as zinc or a semimetal is preferable. As the composite oxide, those containing an alkali metal or alkaline earth metal such as sodium, potassium, magnesium and calcium are also suitable. Among these, a silicon single oxide or a composite oxide containing silicon as a constituent element (hereinafter referred to as silicon-based oxide) is particularly excellent in chemical stability and easily available in various properties. ) Is preferred.

  More specific examples of silicon-based oxides include silicas such as quartz, precipitated silica, fumed silica, sol-gel silica; silica-titania, silica-zirconia, silica-barium oxide, silica-alumina, silica-calcia, silica -Strontium oxide, silica-magnesia, silica-titania-sodium oxide, silica-titania-potassium oxide, silica-zirconia-sodium oxide, silica-zirconia-potassium oxide, silica-alumina-sodium oxide, or silica-alumina-potassium oxide And complex oxides such as calcium silicate, talc, zeolite, and montmorillonite.

  The crosslinked polymer having a cation exchange group is not particularly limited, and may be a known crosslinked polymer composed of a cation exchange group and a base resin, which is generally known as a cation exchange resin. By using a crosslinked polymer, the solubility in a solvent or the like is lost, and the stability and durability under a high humidity environment and a wet condition are excellent. In addition, since the polymer has a cation exchange group, the polyvalent metal ions are easily retained, and are less likely to be easily detached by washing with water or the like. In the present invention, not only an acid type (proton type) state but also a state (salt) substituted with a cation other than a proton such as a metal ion is called a cation exchange group. Unless otherwise specified, the acid state or the salt state is simply referred to as “... acid group” (for example, when referred to as a sulfonic acid group, an acid type sulfonic acid group and Both salt type sulfonic acid groups are shown).

  Specific examples of cation exchange groups include sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, thiol groups, perfluoro tertiary alcoholic hydroxyl groups, arsenic acid groups, selenic acid groups, and the like. Is mentioned. Among these, it is excellent in chemical stability and not only easy to produce a polyvalent metal ion as a counter ion, but also easy to produce a crosslinked polymer itself having the cation exchange group, A sulfonic acid group and a carboxylic acid group are preferable, and a sulfonic acid group is particularly preferable. Moreover, you may have several different cation exchange groups as needed.

  The polymer skeleton portion (matrix resin) to which the cation exchange group is bonded is not particularly limited as long as it is a crosslinked type and has a structure capable of bonding a cation exchange group. However, the cross-linking of the cross-linked polymer in the present invention indicates covalent cross-linking and does not include ionic cross-linking.

  The base resin may be any known cross-linked resin such as polystyrene, (meth) acrylic, epoxy, polyester, polyamide, polyimide, polyurethane, polysulfone, polyether, and polyethersulfone. Among these, in terms of easy production of the metal ion-carrying inorganic particle powder of the present invention, polystyrene and (meth) acrylic are preferable, particularly for chemical stability such as hydrolysis resistance. It is preferable that it is a polystyrene-type crosslinked resin at the point which is also excellent.

  The crosslinked polymer having the cation exchange group coats the core particles. In the present invention, this coating means not only the state in which the crosslinked polymer covers the outermost surface of the core particles, but also the core particles. When it has a pore, the state which covered the wall surface of this pore, the state which exists so that this pore may be filled, or the state which combined them is also included.

  The polyvalent metal ion carried by the metal ion-carrying inorganic particle powder of the present invention is not particularly limited as long as it is a metal ion having a valence of 2 or more. Examples of such polyvalent metal ions include Mg, Ca, Sr, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, and W. In addition, what can take a different valence among the said metals should just be 2 valence or more in the carried state, and is not limited to a specific valence. Moreover, the metal ion carrying | support inorganic particle powder of this invention may carry | support two or more types of metal ions from which an element seed | species and a valence differ.

In the metal ion-carrying inorganic particles constituting the metal ion-carrying inorganic particle powder of the present invention, the polyvalent metal ion is present as a counter ion in the cation exchange group. That is, at least a part of the cation exchange group exists in the state of a salt (or complex) of polyvalent metal ions. Since cation exchange groups such as sulfonic acid groups and carboxylic acid groups are monovalent, when they form a salt with a polyvalent metal ion, usually one of the polyvalent metal ions and a number corresponding to the valence. Cation exchange group residues (R—SO ₃ ⁻ , R—CO ₂ ^—, etc., R is a base resin) are involved in the formation of a set of salts, but some of the polyvalent metal ions are It may exist in the state of a half salt. For example, a cation exchange group sulfonic acid group, when the valence of the polyvalent metal ion is a _divalent, a state of the _{R-SO 3 -M-OSO 2} -R (M represents a metal atom) but, in _part, (the L ligand) -SO 3 -M-L may exist in the form of. Conversely, not all of the cation exchange groups need to exist in the form of a salt with a polyvalent metal ion, but a part of the cation exchange group is in an acid form, or a monovalent such as an alkali metal ion or ammonium ion. It may exist in the form of a salt with ions.

  The amount of polyvalent metal ions supported in the metal ion-supported inorganic particle powder of the present invention is not particularly limited, and may be appropriately selected according to the purpose of use. Usually, the larger the carrying amount, the easier it is to obtain the effects required in various applications, but on the other hand, it is too expensive or carried for the effect obtained by carrying it to some extent. The process for making it complicated becomes complicated. For example, when used for a gas adsorbent or a rust preventive, it is preferably 0.01 to 2 mmol / g, and particularly preferably 0.05 to 1.5 mmol / g.

  As described above, in the metal ion-carrying inorganic particle powder of the present invention, the polyvalent metal ion is present as a counter ion in the cation exchange group. Therefore, the polyvalent metal ions supported as counter ions can be supported in large amounts as the cation exchange capacity in the metal ion-supported inorganic particle powder increases, but those with extremely large ion exchange capacity are produced. In some applications, cation exchange groups that do not participate in counter ion formation with polyvalent metal ions may have an adverse effect. The cation exchange capacity (= number of cation exchange groups) in the metal ion-carrying inorganic particle powder of the present invention is preferably 0.005 to 4 mmol / g (weight of dry powder; the same applies hereinafter), and 0.1 to 3 mmol. / G is more preferable. In addition, when the crosslinked polymer having a cation exchange group of the present invention is produced by a production method as described later, generally, inorganic particle powder having a cation exchange capacity of Xmmmol / g is highly N-valent. The amount of valence metal ions supported is about 1.2 to 0.3 times (mmol / g) of X / N.

  The particle size, particle size distribution, shape, and the like of the metal ion-carrying inorganic particles constituting the metal ion-carrying inorganic particle powder of the present invention are not particularly limited, and may be appropriately selected according to the application. These particle sizes, particle size distributions, shapes, and the like can be controlled by selection of core particles, the amount of polymerizable monomer used for coating, and the like by a manufacturing method as described later.

  The smaller the average particle size, the larger the specific surface area, the larger the contact area with the surroundings, the better the effects when used in various applications, and the excellent dispersibility and coating properties when kneaded into resins, etc. The average primary particle diameter of the metal ion-carrying inorganic particle powder of the present invention is preferably 0.005 to 300 μm, more preferably 0.005 to 100 μm, and particularly preferably 0.005 to 10 μm. Is preferred.

  The shape is not particularly limited and may be any shape such as a spherical shape, a plate shape, a layer shape, a whisker shape, or an indefinite shape.

  In addition, the inorganic particles in the metal ion-carrying inorganic particle powder of the present invention are those in which the core particles are coated with a crosslinked polymer, and the ratio of both is not particularly limited. Usually, the greater the proportion of the crosslinked polymer, the more cation exchange groups can be present, and thus the greater the amount of polyvalent metal ions supported, but if the proportion is too large, Therefore, the average thickness of the crosslinked polymer coating layer is preferably 1/10 or less and 1000 nm or less of the diameter of the core particles.

  The method for producing the metal ion-carrying inorganic particle powder of the present invention is not particularly limited. Preferably, the inorganic particles coated with a crosslinked polymer having a cation exchange group are treated with polyvalent metal ions. What is necessary is just to process with the solution to contain, to carry out ion exchange, and to make it dry. According to this method, various metal ions can be selected as the polyvalent metal ion solution used for the treatment, and therefore, a powder carrying any polyvalent metal ion can be produced very easily.

  Also, the method for producing inorganic particles coated with a crosslinked polymer having a cation exchange group is not particularly limited, but preferably, the inorganic particle powder is brought into contact with the polymerizable monomer under stirring. Then, the polymerizable monomer is adsorbed on the particles, and then the adsorbed polymerizable monomer is polymerized, and a cation exchange group is introduced as necessary (this method is The present inventors have already filed the application as Japanese Patent Application No. 2004-131887). In this method, since it is performed in a powder state when the core particles are brought into contact with the polymerizable monomer, it is likely to occur when performed in a non-powder state such as a suspension or paste, for example, by dispersing in a solvent. Problems such as difficulty in controlling the thickness and chemical composition of the coating layer, and in some cases the desired polymer coating layer may not be obtained. Hereinafter, these methods will be described more specifically.

  First, a method for producing inorganic particles (powder) coated with a crosslinked polymer having a cation exchange group will be described. In this method, a powder composed of particles having a structure in which core particles are covered with a crosslinked polymer is produced. The core particles are core particles in the metal ion-carrying inorganic particle powder of the present invention. Therefore, as described above, the particle size, the particle size distribution, the shape, and the like of the finally obtained metal ion-carrying inorganic particle powder greatly depend on which particle (powder) is used as the core particle.

  In this method, a polymerizable monomer that generates a cross-linked polymer by polymerization is brought into contact with and adsorbed on the core particles. Since the core particles are not dispersed in the solvent, the phenomenon that the polymerizable monomer used remains dissolved in the solvent and hardly adsorbs hardly occurs, but in order to adsorb the polymerizable monomer efficiently, the polymerizable monomer It may be preferable to modify the surface of the core particle depending on the physical properties of the monomer.

  Specifically, the polymerizable monomer to be adsorbed (in the case of a mixture, the main component polymerizable monomer) is a carboxyl group, phosphonic acid group, phosphoric acid group, sulfonic acid group or the like. In the case of a compound having a cation exchange group and thereby having a solubility in water of 5% by mass or more, it is generally preferable to use particles having a water / n-hexane dispersibility tendency on the water side as the core particles. In particular, when the compound has a sulfonic acid group and has a solubility in water of 5% by mass or more and a solubility in n-hexane of 5% by mass or less, particles having a water / n-hexane dispersibility tendency on the water side are used. It is important to obtain coated particles having a uniform polymer layer.

  On the other hand, a polymerizable monomer having a solubility in water of less than 5% by mass is adsorbed because it has no cation exchange group or has a large influence of a hydrophobic group even if it has a cation exchange group. In this case, it is preferable to use particles having a water / n-hexane dispersibility tendency on the hexane side. In particular, when a polymerizable monomer having a solubility in water of less than 1% by mass such as styrene is to be adsorbed, not only the water / n-hexane dispersibility tends to be on the hexane side but also the modified hydrophobicity degree. It is preferable to use 40% by mass or more (particularly 50 to 90% by mass) of particles as core particles.

  In addition, the water / n-hexane dispersibility is said to be obtained by adding substantially equal amounts of water and n-hexane to a glass test tube, etc., adding a small amount of particle powder thereto, and shaking well so that the particles are mixed with water and hexane. It can be judged by which side it is distributed. The modified hydrophobization degree is a methanol concentration at which the amount of suspension obtained by a method of measuring the suspension ratio of the particle powder with respect to a solution with a changed water-methanol ratio is 50%.

  In general, inorganic particles such as inorganic oxide particles not subjected to any surface treatment have a water / n-hexane dispersibility tendency on the water side. The method for setting the dispersibility of such inorganic particles to the n-hexane side is not particularly limited, and a known surface treatment method may be employed. Specific examples include treatment with a silane coupling agent, a titanate coupling agent, silicone oil, cyclic siloxane, hexaalkyldisilazane, and the like. Among these, even when the amount of reactive groups such as silanol groups on the surface of the particle is small, it is uniformly processed, and since there are only one or two reaction ends, the treatment agent itself gels and fine particles are formed. An agglomerate generated by mixing or gelation does not adhere to the surface of the inorganic particles to form a non-uniform surface, and further, because it is highly reactive, it becomes an efficiently treated particle and is not immobilized. The treatment with cyclic siloxane or hexaalkyldisilazane is preferred in that the treatment agent is less likely to elute. Furthermore, in the case of particles treated with cyclic siloxane or hexaalkyldisilazane, the acid resistance and alkali resistance of the coated particles obtained by the production method of the present invention are higher than in the case of particles treated only with a silane coupling agent. Tend to be better.

  Among cyclic siloxanes, the following general formula is used because it is easy to obtain inorganic particles whose surface is uniformly coated due to large strain and easy cleavage.

(Wherein R ¹ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom or a hydroxyl group, Me is a methyl group, and n is an integer of 3 to 6)
It is preferable to treat with a cyclic siloxane represented by

In the above formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms. The hydrocarbon group is not particularly limited as long as it has 1 to 18 carbon atoms, and may be any known group. Specific examples of the hydrocarbon group include straight chain or branched alkyl groups having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and an octadecyl group, a carbon such as a cyclopentyl group and a cyclohexyl group. A cyclic alkyl group having 4 to 6 carbon atoms; an alkenyl group having 2 to 18 carbon atoms such as vinyl group, allyl group, isopropenyl group, and octadecynyl group; phenyl group, naphthyl group, tolyl group, styryl group, xylyl group, mesityl group, etc. A substituted or unsubstituted aryl group having 6 to 18 carbon atoms; an aralkyl group having 7 to 9 carbon atoms such as a benzyl group and a phenethyl group;

  Among the hydrocarbon groups, a linear alkyl group having 1 to 3 carbon atoms, a phenyl group, a phenethyl group, or a vinyl group is particularly preferable. Moreover, in said formula, n is 3-6, Most preferably, it is 3-4.

  Specific examples of such cyclic siloxanes include octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, trimethyltrivinyl. Examples thereof include cyclotrisiloxane, tetramethylcyclotetrasiloxane, and trimethylcyclotrisiloxane.

  In the case of treatment with hexaalkyldisilazane, the following general formula

(In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 18 carbon atoms.)
A hexaalkyldisilazane represented by In the above formula, examples of the alkyl group represented by R ^{2 to} R ⁷ include the same groups as those exemplified as R ¹ in the cyclic siloxane. In order to obtain high processing efficiency, the R ^{2 to} R ⁷ are preferably a linear alkyl group having 1 to 3 carbon atoms. R ^{2 to} R ⁷ may be different from each other, but are preferably the same group from the standpoint of availability and surface treatment efficiency.

  Specific examples of particularly preferred hexaalkyldisilazane include hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane and the like.

  The cyclic siloxane and hexaalkyldisilazane may be used alone or in combination with two or more different compounds. Moreover, you may use together with another surface treating agent.

  The method of surface treating and hydrophobizing inorganic particles using the surface treating agent as described above is not particularly limited as long as it is in accordance with a known technique, but aggregation is unlikely to occur during the treatment. A method using a dry process that does not use a solvent is preferable because it does not require time and effort such as removal.

  For example, when the treatment with hexaalkyldisilazane is performed, it is preferable to employ the methods described in Japanese Patent No. 2886037 and Japanese Patent No. 2886105. In this method, powder of inorganic particles is introduced into a container, and the container is sealed so that the partial pressure of hexamethyldisilazane is about 25 to 150 kPa in an inert gas atmosphere at a temperature of about 200 to 300 ° C. And is maintained for a certain period of time, preferably about 0.5 to 2 hours. At this time, water vapor is present in the container at a partial pressure of about 30 to 100 kPa, and a basic gas such as ammonia is allowed to coexist at a partial pressure of about 10 to 100 kPa as necessary.

  In the case of treating with cyclic siloxane, a liquid or gaseous cyclic siloxane is added to the inorganic particle powder while stirring, and then heated in a sealed reaction system. To describe this method more specifically, first, while stirring particles with a high-speed stirring device such as a Henschel mixer in an inert gas atmosphere such as nitrogen or argon, a cyclic siloxane or the like is added in a gaseous or liquid state thereto, It can be produced by heating to a predetermined temperature in a sealed reaction system. The method of adding cyclic siloxane or the like to the particles may be either liquid or gaseous, and when added in liquid form, it may be added dropwise or by spraying. It is particularly preferable to add it in the form of a gas from the viewpoint that it can be uniformly processed. The heating temperature is not particularly limited as long as the particle surface can be hydrophobized by cyclic siloxane or the like, but in general, it is preferably not less than the boiling point of the cyclic siloxane to be used, and usually about 100 to 300 ° C. It is. Further, the stirring speed at the time of stirring is not particularly limited, and cannot be generally specified depending on the stirring device used, but is generally about 100 to 3000 rpm.

  By adopting such a dry treatment, it is possible to prevent agglomeration in the surface treatment step of inorganic particles, and if necessary, it is possible to coat with a polymer in the same reaction vessel, which is industrially advantageous. is there.

  Next, the polymerizable monomer is adsorbed on the hydrophobic or hydrophilic particles as described above. The polymerizable monomer may be any polymer as long as it generates a cross-linked polymer by polymerization and has a cation exchange group or can introduce a cation exchange group after polymerization. It may be a mixture. Preferably, a mixture of a monofunctional polymerizable monomer having a cation exchange group or having a functional group capable of introducing a cation exchange group and a polyfunctional polymerizable monomer serving as a crosslinking agent It is. Moreover, it is preferable that it is a polymerizable monomer which has radically polymerizable unsaturated double bonds, such as a (meth) acryl group and a styryl group, at the point which is excellent in polymerizability.

  Specific examples of these polymerizable monomers include the following.

1. Monofunctional monomers having a cation exchange group Aromatic vinyl monomers such as styrene sulfonic acid and its salts, vinyl naphthalene sulfonic acid and its salts. (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. Vinyl monomers having a phosphonic acid group such as vinylphosphonic acid and salts thereof.

2. Monomers having functional groups capable of introducing cation exchange groups Styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, p-tert-butylstyrene, chloromethylstyrene, p-chlorostyrene, vinylnaphthalene Aromatic vinyl monomers such as; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Trimethydecyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylic acid Monofunctional (meth) acrylic acid ester such as 2-methoxyethyl and 2-ethoxyethyl (meth) acrylate Lu monomer.

3. Polyfunctional polymerizable monomers that serve as crosslinking agents Aromatic vinyl monomers such as polyfunctional aromatic vinyl compounds such as divinylbenzene, divinylbiphenyl, trivinylbenzene, and divinylnaphthalene; 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, trimethylolmethane tri (meth) acrylate, tetra Polyfunctional non-fluorine (meth) acrylic monomers such as methylolmethane tetra (meth) acrylate, methylenebis (meth) acrylamide, hexamethylenedi (meth) acrylamide; divinylsulfone, diallyl phthalate, etc.

  In order to coat the core particles with a crosslinked polymer, the monofunctional monomer having a cation exchange group or a monomer having a functional group capable of introducing a cation exchange group and a polyfunctional monomer serving as a crosslinking agent are used. A mixture with a polymerizable monomer may be used. Typically, a polyfunctional polymerizable monomer serving as a cross-linking agent is preferably about 0.05 to 99% by mass in the total polymerizable monomer. For this, a polymerizable monomer blended in an amount of about 0.5 to 30% by mass may be used. The above polymerizable monomers may be used in combination with a plurality of different monomers as required.

  Further, in order to facilitate the adsorption of the polymerizable monomer as described above to the core particles, and to impart various other physical properties, it is also possible to use a mixture of polymerizable monomers other than those described above. . For example, in the case where the monofunctional monomer having a cation exchange group or the monomer having a functional group capable of introducing a cation exchange group is a solid at normal temperature and normal pressure, it can be co-polymerized with the polymerizable monomer. It is also preferable to dissolve in a liquid polymerizable monomer to be polymerized. Such polymerizable monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N-methylol (meth) ) (Meth) acrylic monomers having a hydroxyl group such as acrylamide; (meth) acrylonitrile, (meth) acrolein, vinyl acetate, N-vinylpyrrolidone, diacetone (meth) acrylamide, methyl vinyl ketone and the like.

  The polymerizable monomer (or a mixture thereof) may be brought into contact with the core particles alone, but is preferably added as a mixture with a polymerization initiator added in order to efficiently perform the polymerization step described later. .

  As a polymerization initiator to be used, a known polymerization initiator may be appropriately selected and used according to the polymerizable monomer to be used, and is not particularly limited. However, the polymerization initiator exhibits a polymerization initiation 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 polymerizable monomer.

  Moreover, you may use what mix | blended other additives, such as a polymerization inhibitor, a polymerization inhibitor, and an ultraviolet absorber, as needed. Further, when the polymerizable monomer is a solid, it can be made liquid by using a small amount of a solvent.

  When contacting the above-mentioned polymerizable monomer and a mixture of optional components blended as necessary (hereinafter, polymerizable monomer mixture) with the powder of the core particles, the core particle powder Is preferably carried out with stirring. Without stirring, the coating layer will be non-uniform. The stirring method is not particularly limited, and any known method may be used as long as particles can be floated by the stirring. For example, it may be directly mechanically stirred using a Henschel mixer or the like, or may be agitated by blowing a high-speed air stream, or a method of giving vibration or swinging from the outside. The stirring speed in the case of direct mechanical stirring cannot be generally specified depending on the material, shape, and particle diameter of the core particles, but generally it may be about 100 to 3000 rpm.

  The method for bringing the polymerizable monomer mixture into contact with the core particles is not particularly limited. Preferably, the polymerizable monomer mixture is gaseous or liquid in an inert gas atmosphere such as nitrogen or argon. More preferably, the liquid polymerizable monomer mixture is sprayed and added in an inert gas atmosphere. 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 core particles. The temperature conditions for adding these are not particularly limited, and may be under cooling or under heating. However, since the monomer is polymerized before coating at an excessively high temperature, generally about −10 to 40 ° C. is preferable. .

The amount of the polymerizable monomer to be added is not particularly limited and may be appropriately set depending on the desired coating thickness. However, when the amount of the polymerizable monomer mixture used is too large, the particles are aggregated. In order to obtain the metal ion-carrying inorganic particle powder of the present invention, a pulverization step is required thereafter. If the amount is too large, the core particles are present in the polymer, making it difficult to obtain the powder of the present invention. The amount of the polymerizable monomer used to form a coating layer having an appropriate thickness depends on the specific surface area and particle diameter of the core particles and cannot be generally stated, but in general, the specific surface area of the particles is 1 m. per ^2, the use of polymerizable monomer ^{2 × 10 -4 ~8 × 10 -4} g, since the coating layer having a thickness of about 1nm equivalent is formed, based on this value, the particle size Ya It can be appropriately determined according to the specific surface area. A typical use amount of the polymerizable monomer is 0.001 to 0.4 g per 1 g of core particles.

  Moreover, when adding the above-mentioned solvent or other optional components, if the amount of the solvent used is too large, the particles are likely to aggregate. Therefore, even when all the polymerizable monomers, solvents, and other components to be added are added, it is preferable that the amount of the polymerizable monomer, the solvent, and the other components be within the range that does not form a paste or dispersion and maintains the powder state. In order to avoid agglomeration between particles, generally the amount of polymerizable monomer, solvent and other components to be added is the amount of oil absorption of the powder composed of core particles (mixture of polymerizable monomer, solvent and other components). 3/4 or less, more preferably 1/2, further preferably 1/3 or less, particularly preferably 1/5 or less, and most preferably 1/10 or less.

  In this way, by adding the polymerizable monomer (and other optional components) to the stirred core particle, the polymerizable monomer (and other optional component) is adsorbed on the core particle. . In the production method of the present invention, the polymerizable monomer is then polymerized to form a polymer, and the powder is made of particles in a state where the core particles are covered with the polymer.

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

  Further, when the polymerizable monomer used is a vinyl monomer, these operations are preferably performed in an inert gas atmosphere such as nitrogen or argon in order to prevent polymerization inhibition by oxygen.

  The pressure in the reaction vessel is not particularly limited, and may be pressurized, normal pressure, or reduced pressure. Depending on the type of polymerizable monomer 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.

  The method for producing particles coated with the above-mentioned crosslinked polymer is an example, and it may be produced by a wet method or coated with a non-crosslinked polymer and then crosslinked by electron beam irradiation or the like. May be.

  When the particles coated with the crosslinked polymer obtained as described above are produced using a polymerizable monomer having a cation exchange group such as a sulfonic acid group or a carboxylic acid group, it will be described later. What is necessary is just to use for the process of carrying a polyvalent metal ion.

  On the other hand, when a monomer having a functional group capable of introducing a cation exchange group is used, it is necessary to introduce a cation exchange group before supporting the polyvalent metal ion. This can be carried out according to the method for introducing a cation exchange group in the method for producing an exchange resin.

  For example, when a polymerizable monomer such as styrene is used 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, etc. Sulfonation or the like may be performed by a method. In the case of a polymer having an ester structure such as a methyl methacrylate polymer, an acid group can be introduced by hydrolysis of the ester. Furthermore, when it has an epoxy group or a chloromethyl group, it can be sulfonated by using sulfanilic acid, sodium sulfite or the like to introduce a sulfonic acid group.

  In addition, various ion exchange groups can be introduced by applying other known chemical reactions. When introducing these functional groups, it is necessary to select the introduction form and reaction conditions as appropriate so that the covering polymer is not lost due to peeling or the like. In general, a polymer of an aromatic vinyl monomer is chemically stable as compared with a (meth) acrylic monomer having an ester structure, and various functional groups can be easily introduced.

  In introducing such a functional group, a method of appropriately setting reaction conditions such as temperature and pressure without using a solvent and contacting the reactive agent in gaseous form with the coated particles in order to prevent aggregation of the resulting particles. Is preferably adopted. For example, when introducing a sulfonic acid group in the introduction of the cation exchange group, a method of contacting with a sulfur trioxide gas can be suitably employed.

  Inorganic particles (powder) coated with a crosslinked polymer having a cation exchange group obtained by such a production method, the counter ion in the cation exchange group is exchanged with a polyvalent metal ion. Metal ion-carrying inorganic particle powder is made. As a method of exchanging the counter ion in the cation exchange group with the polyvalent metal ion, various conventionally known methods can be adopted and are not particularly limited. Preferably, mixing with the solution containing the target polyvalent metal ion, followed by filtration and further washing with ion-exchanged water, etc., or mixing with the solution containing the same polyvalent metal ion and then drying as it is Is mentioned.

  The polyvalent metal ion source in the solution containing polyvalent metal ions is not particularly limited as long as the solution can be adjusted. Specific examples include salts of inorganic acids such as nitrates, sulfates and hydrochlorides (chlorides), organic acid salts such as acetates, ammonium salts, hydroxides, and the like.

  The solvent in the case of the solution is not particularly limited, either water or an organic solvent may be used, but it is easy to prepare a solution containing polyvalent metal ions, and it is particularly preferable to use water from the economical, environmental, and safety aspects. . In addition, when it is necessary to adjust the solubility when preparing a solution containing polyvalent metal ions, an acid (sulfuric acid, nitric acid, hydrochloric acid, etc.) or alkali (ammonia, etc.) is additionally added to the solution. May be.

  The concentration of the polyvalent metal ion solution is not particularly limited, but a metal ion concentration of about 0.001 to 5 mol / L may be used in terms of easy preparation and excellent operability. Preferably it is about 0.01-1 mol / L.

  When mixing the inorganic particle powder coated with the cross-linked polymer having a cation exchange group and the polyvalent metal ion solution, the mixing ratio depends on the ion exchange capacity of the inorganic particle powder and the polyvalent metal ion solution. Although it cannot be said unconditionally depending on the concentration and the amount of polyvalent metal ions to be carried, etc., when performing filtration and washing, it is 1 or more times, preferably 1. It is preferable to use an excessive amount of polyvalent metal ions so as to be 5 times or more, more preferably 2 times or more, particularly preferably 3 times or more. On the other hand, there is a problem that even if the amount is too large, a large amount of waste liquid containing polyvalent metal ions is generated. On the other hand, when directly drying after mixing, the concentration and amount of the solution may be adjusted so as to be in the range of about 1.2 to 0.3 times the X / N.

  Further, it is preferable to mix the inorganic particle powder coated with the crosslinked polymer having a cation exchange group and the polyvalent metal ion solution with stirring. The mixing and stirring time is usually about 1 minute to 24 hours. The temperature at the time of mixing may be in the range from the freezing point to the boiling point of the solution, and usually at room temperature.

  When filtration and washing are performed, the filtration is not particularly limited as long as the target inorganic particles are retained, and a known filtration means may be selected as necessary. Further, centrifugal sedimentation or the like may be used instead of filtration.

  Washing is preferably performed with water that does not contain contaminating ions such as ion-exchanged water or distilled water. Washing may be performed until unnecessary components such as excess polyvalent metal ions and anion components eluted by ion exchange are washed away to a necessary level. The end point of washing can be confirmed by the polyvalent metal ion concentration, pH, color tone, etc. in the filtrate.

  The drying may be performed under the condition that the crosslinked polymer covering the core particles is not decomposed or the like, and any known drying method such as heat drying, air drying, or reduced pressure drying may be applied. When an aqueous solution is used, in order to save drying time, it may be dried after being replaced with a volatile organic solvent such as alcohol or acetone. When heating, the temperature is preferably 150 ° C. or lower, and more preferably 120 ° C. or lower. Note that in the case of metal ions whose valence changes when heated in the presence of oxygen, such as in the air, heating may be performed in an inert gas atmosphere such as nitrogen or argon. On the contrary, in the production of the metal ion-carrying inorganic particle powder of the present invention, after the metal ion is carried by the above method, the target value is obtained by positively oxidizing or reducing. It can also be a number of metal ions.

  The dried product obtained as described above is usually a powder having the same particle size and particle size distribution as the inorganic particles coated with the above-mentioned crosslinked polymer having a cation exchange group. May be agglomerated. Such agglomeration is usually pulverized under use conditions (for example, mixed with a resin component), but may be pulverized and pulverized as necessary. Conversely, granulation can also be performed by a known method for the purpose of improving the handleability.

  The metal ion-carrying inorganic particle powder of the present invention that can be produced as in the above example is derived from the mechanical strength of the core inorganic particles and the polyvalent metal ions present in the coating layer of the crosslinked polymer. It is an excellent powder that has various physical properties as well as the physical properties of the crosslinked polymer itself. For example, gas adsorption fillers, solid phase catalysts for various metal catalysis reactions, antibacterial fillers for various resin products, rust prevention It is highly useful as an agent. In use, a known method corresponding to each application may be applied. For example, the powder may be used as it is, dispersed in various solvents or binders, coated, dried, prepared with a curable resin, after molding It may be cured.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.

1. Measuring methods of physical properties Various physical properties of raw materials, intermediate products, and final products used in Examples and Comparative Examples were measured by the following methods.

Average particle size A (average primary particle size)
For particles photographed with a scanning electron microscope (SEM) or transmission electron microscope (TEM), each image is analyzed with high-definition image analysis software IP-1000PC (Asahi Engineering Co., Ltd.) using 1000 or more and less than 2000 images. Then, assuming that the shape of the particles is spherical, the average particle diameter of the primary particles was obtained.

Average particle size B
While dispersing the particle powder in ethanol and applying ultrasonic waves, the particle size distribution is measured by a light scattering diffraction type particle size distribution analyzer (Beckman Coulter, Inc .: Coulter LS230), and the value of the number-based arithmetic average diameter D ₅₀ is averaged. The particle diameter was set to B.

Specific surface area Using a specific surface area measuring apparatus (manufactured by Shimadzu Corporation: Flowsorb 2-2300 type), nitrogen gas was used as an adsorbed gas, and the BET method was used.

Carbon Amount The amount of carbon coating the particles was measured by heating the particle powder to 1350 ° C. in an oxygen atmosphere using a trace carbon analyzer (EMIA-511 type manufactured by Horiba Seisakusho). The amount of carbon obtained by this measurement was converted to 1 g of coated particles. In addition, as a pretreatment for the coating amount measurement, the particles powder is heated at 80 ° C., and the system is depressurized to remove monomers not involved in the surface coating and moisture adsorbed in the air. After that, the carbon content of the particle powder was determined.

Cation exchange capacity The particle powder is dispersed in 1 mol / l HCl aqueous solution and stirred for 10 hours or more to form a hydrogen ion type, followed by filtration and washing with water, and the residue in 1 mol / l NaCl aqueous solution for 10 hours. The mixture was stirred and replaced with the sodium ion type. Subsequently, the liberated hydrogen ions contained in the solution obtained by filtration were quantified with a potentiometric titrator (COMTITE-900, manufactured by Hiranuma Sangyo Co., Ltd.) (A: mol).

Subsequently, the particles are dispersed in a 1 mol / l HCl aqueous solution, stirred for 4 hours or more, and the residue obtained by filtration is thoroughly washed with ion-exchanged water, dried at 60 ° C. for 5 hours, and its weight is measured. (W _C : g). Based on the above measurements, the following equation cation exchange capacity * cation exchange capacity _{= A × 1000 / W C [} mmol / g- dry weight]
Determined by

Measurement of metal ion content The content of metal atoms was measured with a fluorescent X-ray analyzer (manufactured by Rigaku Corporation: X-ray spectrometer 3270) to determine the supported amount (mmol / g).

2. Production of raw material inorganic particle powder Among the inorganic particle powders used as production raw materials in each Example and Comparative Example, those not commercially available were produced from commercial products by the following method. The physical properties of the produced inorganic particle powder are shown in Table 1 together with the physical properties of the raw materials.

Production of QS102-D4 Specific surface area of 200 m ² / g produced by a thermal decomposition method, average particle diameter A (average primary particle diameter) of 0.016 μm, average particle diameter B (average secondary particle diameter) of 0.07 μm 50 g of silica powder (trade name: QS102; manufactured by Tokuyama Co., Ltd .; hereinafter referred to as QS102) not subjected to surface treatment was charged into a stainless steel autoclave having an internal volume of 1000 ml. After the inside of the autoclave was replaced with nitrogen gas, 20 g of octamethylcyclotetrasiloxane was atomized with a two-fluid nozzle while the stirring blade attached to the autoclave was rotated at 400 rpm and sprayed uniformly onto the silica powder. After stirring for 30 minutes with nitrogen gas flowing, the autoclave was sealed and heated at 275 ° C. for 1 hour. Subsequently, the system was depressurized while being heated to remove unreacted D4. Table 1 shows the physical properties of the obtained particle powder (hereinafter, QS102-D4). Moreover, the particle size distribution patterns before and after the treatment (according to the measuring method of the average particle diameter B) are shown in FIG.

X37B-D4 specific surface area 290 m ² / g manufactured by the precipitation method, the average particle diameter A is 3.7 .mu.m, silica powder having an average particle size B is not subjected to a surface treatment with 5.4 [mu] m (manufactured by Tokuyama Corp., trade A powder of cyclic siloxane-treated silica particles was obtained in the same manner as in Production Example 1 except that the name X37B; hereinafter, X37B) was used. Table 1 shows the physical properties of the obtained particle powder (hereinafter, X37B-D4).

Example 1
50 g of QS102-D4 was charged into a stainless steel autoclave having an internal volume of 1000 ml. After the inside of the autoclave was replaced with nitrogen gas, the stirring blade attached to the autoclave was rotated at 800 rpm to polymerize 5 g of styrene, 0.5 g of divinylbenzene, and 0.3 g of t-butylperoxy-2-ethylhexanoate. The monomer mixed solution was atomized with a two-fluid nozzle for about 15 seconds and sprayed onto silica powder to wet the surface. After stirring for 30 minutes, the autoclave cock was closed and sealed, the temperature was raised from 20 ° C. to 80 ° C. over 1 hour, and the monomer was polymerized by being held at the same temperature for 1 hour and coated with crosslinked polystyrene. A powder of particles was obtained. This powder had an average particle size A of 0.019 μm, an average particle size B of 0.082 μm, and a carbon content of 0.08 g / g.

50 g of the coated particles are transferred to a pressure-resistant polytetrafluoroethylene container, solid sulfur trioxide is put into a flask directly connected to the container, and the vaporized sulfur trioxide is filled with crosslinkable resin-coated silica with nitrogen gas. For 15 minutes, the sulfur trioxide gas concentration in the system is set to 30 vol% or more, nitrogen gas is further introduced into the system, the pressure is increased to about 0.3 MPa, and the mixture is stirred at 80 ° C. with stirring in a sealed state. Sulfonated by heating for hours. Subsequently, the system was evacuated to completely remove the unreacted sulfur trioxide gas and recover the powder. The specific surface area of the obtained powder was 130 m ² / g, and the ion exchange capacity was 1.01 mmol / g.

35 g of powder consisting of particles coated with crosslinked polystyrene introduced with cation exchange groups (sulfonic acid groups) is transferred to a glass container and dispersed by adding 700 ml of an aqueous solution of cupric chloride having a copper ion concentration of 0.1 mol / L. Then, ion exchange treatment was performed for 2 hours at room temperature with stirring. Subsequently, filtration was performed, and washing was further performed 4 times with 300 ml of ion exchange water. The filtrate in the last washing was a nearly neutral, colorless and transparent liquid. After washing, the powder was dried at 100 ° C. to obtain a slightly bluish powder having a specific surface area of 125 m ² / g, a copper ion carrying amount of 0.56 mmol / g.

  Furthermore, 10 g of the dry powder was washed again with 200 ml of ion exchange water and dried, and then the amount of copper ions carried was measured. However, there was no change before and after washing. From this, it is clear that copper chloride crystals are not simply attached to the particle surface.

  Separately, 10 g of the dry powder carrying copper was immersed in 200 ml of hot water for 24 hours, then allowed to cool, filtered and dried, and the amount of copper carried was measured to be 0.55 mmol / g. There was little change.

Comparative Example 1
In the same manner as in Example 1, particle powder coated with crosslinked polystyrene was obtained. An attempt was made to disperse this powder in an aqueous solution of cupric chloride without sulfonation, but it did not disperse at all. Then, it disperse | distributed to 700 ml of water-methanol solutions (20 mass% of water) of cupric chloride with a copper ion concentration of 0.1 mol / L, stirred for 2 hours at room temperature, and filtered. After washing 4 times with 300 ml of water-methanol solution and drying at 70 ° C., the amount of supported copper ions was measured, but copper was not detected.

From the comparison between Example 1 and Comparative Example 1, when no cation exchange group (sulfonic acid group) is present, copper ions are not supported, and therefore, the copper ions are used as counter ions in the ion exchange groups. It can be seen that it exists and is retained. Moreover, in Example 1, since a little larger amount of copper ions is supported with respect to the ion exchange capacity, a part of the copper ions is a half salt (R—SO ₃ —Cu (II) -L). Presumed to be retained on the particles.

Comparative Example 2
50 g of QS102 is put in a juicer mixer, and while stirring so as to be in a floating state, a solution in which 20 g of phenethyltrimethoxysilane (manufactured by Amax) is dissolved in 5 g of hexane is atomized with a two-fluid nozzle and sprayed onto silica powder. Wet the surface. Then, it moved to the 1 liter separable flask, and heated at 100 degreeC under nitrogen stream for 2 hours, and obtained the silica powder by which the surface was processed with the said alkoxysilane compound. Then, this was contacted with sulfur trioxide by the same treatment operation as in Example 1 for sulfonation. The obtained particle powder had a carbon content of 0.051 g / g-coated particles and a cation exchange capacity of 0.11 mmol / g.

  This powder was treated with an aqueous cupric chloride solution and ion exchanged in the same manner as in Example 1 to obtain a powder having a copper loading of 0.03 mmol / g. The amount of copper ions carried after treatment with hot water at 100 ° C. for 24 hours in the same manner as in Example 1 was 0.02 mmol / g, which was reduced to about 70%.

Examples 2-9
Instead of cupric chloride, the same operation as in Example 1 was performed except that an aqueous solution of metal salts shown in Table 2 (both had a metal ion concentration of 0.1 mol / L) was used to carry the metal ions. A powder of held particles was obtained. The specific surface area and metal ion carrying amount of the obtained powder are shown together in Table 2.

Example 10
A powder of particles carrying metal ions was obtained in the same manner as in Example 1 except that an aqueous zirconium acetate solution having a zirconium ion concentration of 15 wt% was used instead of cupric chloride. The specific surface area and metal ion carrying amount of the obtained powder are shown together in Table 2.

Example 11
Instead of QS102-D4, the same processing operation as in Example 1 was performed except that X37B-D4 was used to obtain inorganic particle powder coated with crosslinked polystyrene. This powder had an average particle diameter B of 4.8 μm and a carbon content of 0.08 g / g. This crosslinked polystyrene-coated powder was sulfonated in the same manner as in Example 1 to obtain a powder having a specific surface area of 140 m ² / g and an ion exchange capacity of 0.97 mmol / g. Furthermore, the dry powder obtained by treating with an aqueous cupric chloride solution in the same manner as in Example 1 had a specific surface area of 135 m ² / g and a copper ion carrying amount of 0.44 mmol / g.

Example 12
50 g of X37B was charged into a glass separable flask having an internal volume of 2000 ml. After replacing the interior with nitrogen gas, 15 g of acrylamido 2-methylpropanesulfonic acid sodium salt, 1 g of ethylene glycol dimethacrylate, 15 g of water, 16 g of 2-hydroxyethyl methacrylate and 0 g while rotating the stirring blade at 800 rpm A polymerizable monomer mixed solution composed of 0.5 g of t-butylperoxy-2-ethylhexanoate was sprayed in a mist form with a two-fluid nozzle for about 15 seconds. After stirring for 30 minutes, the temperature was raised from 20 ° C. to 90 ° C. over 1 hour, and kept at the same temperature for 1 hour to polymerize the monomer. The specific surface area of the obtained powder was 125 m ² / g, and the ion exchange capacity was 0.81 mmol / g.

This inorganic particle powder coated with a crosslinked acrylic resin having a cation exchange group (sulfonic acid Na salt) was treated with an aqueous cupric chloride solution in the same manner as in Example 1 to exchange ions, and obtained after drying. When the physical properties of the powder were measured, the specific surface area was 120 m ² / g, and the supported amount of copper ions was 0.32 mmol / g.

Example 14
3 g of dry powder of copper ion-supported silica obtained in Example 1 is placed in a 20 L acrylic container with a stirring device on the side, and methyl mercaptan gas is injected so that the initial gas concentration is 8 ppm. did. While stirring the gas phase, the residual gas concentration inside the container was measured at a predetermined time shown in Table 3 using a gas detector tube. The results are shown in Table 3 and FIG. 2 together with the case where no copper ion-supporting silica powder was added (blank value).

Comparative Example 3
Gas adsorption capacity was measured in the same manner as in Example 14 except that a commercially available functional activated carbon was used instead of the copper ion-supporting silica powder. The results are shown in Table 3 and FIG.

The figure which shows the particle size distribution pattern of the silica particle (QS102-D4) processed with the octamethylcyclotetrasiloxane used as a raw material, and the silica particle (QS102) before this process. The figure which shows the methyl mercaptan adsorption rate of the copper (II) ion carrying | support silica powder manufactured in Example 1, and a commercially available functional activated carbon.

Claims (3)

  A metal ion-supported inorganic particle powder, which is coated with a crosslinked polymer having a cation exchange group, and at least a part of the counter ion in the cation exchange group is a polyvalent metal cation.   A gas adsorbent comprising the metal ion-carrying inorganic particle powder according to claim 1. Inorganic particles coated with a crosslinked polymer having a cation exchange group are brought into contact with a solution containing a polyvalent metal ion to exchange at least a part of the counter ion in the cation exchange group with the polyvalent metal ion. And then drying the metal ion-supporting inorganic particle powder.

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