WO2014034442A1 - Procédé de production de particules noyau-coque - Google Patents

Procédé de production de particules noyau-coque Download PDF

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Publication number
WO2014034442A1
WO2014034442A1 PCT/JP2013/072016 JP2013072016W WO2014034442A1 WO 2014034442 A1 WO2014034442 A1 WO 2014034442A1 JP 2013072016 W JP2013072016 W JP 2013072016W WO 2014034442 A1 WO2014034442 A1 WO 2014034442A1
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core
particles
shell
polymer
base material
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PCT/JP2013/072016
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Japanese (ja)
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卓也 上田
秀幸 大槻
興祐 福澤
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信和化工株式会社
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B01D15/362—Cation-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
    • B01J20/288—Polar phases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3225—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating involving a post-treatment of the coated or impregnated product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3289—Coatings involving more than one layer of same or different nature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/05—Processes using organic exchangers in the strongly acidic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/26—Cation exchangers for chromatographic processes

Definitions

  • the present invention relates to a method for producing core-shell particles that can be used as a separating agent.
  • ion exchange resin among polymer separation agents used in liquid chromatography, ion exchange groups are imparted to crosslinked polymer substances such as styrene-divinylbenzene copolymer, acrylic resin, polyvinyl acetate, and polyacrylate.
  • crosslinked polymer substances such as styrene-divinylbenzene copolymer, acrylic resin, polyvinyl acetate, and polyacrylate.
  • the core-shell particle having a core-shell structure is composed of portions having two different compositions of a core portion and a shell portion. For this reason, the core-shell particle can express various functions that cannot be obtained with a single particle, depending on the characteristics of the core part and the shell part.
  • core-shell particles Many such core-shell particles have been reported, including toners, paint matting agents, light diffusion additives, filters, separation membranes, dispersants, powder coatings, resin modifiers, coating agents. It is widely used for various applications such as insulating fillers, crystal nucleating agents, chromatographic fillers, and immunodiagnostic reagent carriers.
  • the shell part is produced by radical polymerization such as suspension polymerization or emulsion polymerization (Patent Document 1).
  • the present invention is intended to provide a method for producing core-shell particles that can be used as a separating agent having excellent separating ability.
  • the method for producing core-shell particles according to the present invention includes base material core particles composed of inorganic particles mainly composed of a porous inorganic compound, a polymer layer formed on the surface of the base material core particles, A method for producing core-shell particles having an ion exchange group introduced into a molecular layer, wherein the polymer layer comprises a hydrophobic crosslinkable monomer (A) and / or a hydrophobic non-crosslinkable monomer (B )
  • the base material core particles are added to a reaction system in which the polymerization reaction of the polymer continues, and the polymerization reaction of the polymer
  • the coupling agent for bonding the base material core particles and the polymer layer is added to the reaction system of the polymerization reaction of the polymer at any time before or during the start of the process.
  • the separation ability increases as the shell portion becomes multilayered. It is considered that the deterioration is caused because the pores of the base core particles are filled with the monomer and the size exclusion mode does not function.
  • the base material core particles are added to the polymerization reaction system when the polymer constituting the polymer layer becomes a prepolymer having a certain molecular weight. It is possible to prevent the pores of the core particle from being filled with the monomer. Further, when a coupling agent is allowed to coexist in the polymerization reaction system of the polymer constituting the polymer layer, the coupling agent functions as a stopper for the polymerization reaction of the polymer. For this reason, it can prevent that the molecular weight of a polymer goes up too much and a polymer gelatinizes.
  • a method for adding the coupling agent to the reaction system of the polymerization reaction is not particularly limited.
  • a method in which the surface of the base material core particle is previously treated with the coupling agent, or the coupling agent is added is added.
  • Examples thereof include a method of previously mixing with the monomer before the start of the polymerization reaction.
  • the present invention is particularly effective when the polymer layer has a multilayer structure.
  • the inorganic particles include those containing at least one selected from the group consisting of silica gel, glass, carbon, and ceramic as a main component.
  • these inorganic particles those having silica gel as a main component and a particle size of 1.0 to 50 ⁇ m are preferably used.
  • the inorganic particles are mainly composed of silica gel
  • those having a functional group having reactivity with a silanol group and a vinyl group are preferably used as the coupling agent.
  • Examples of the ion exchange group include cation exchange groups having hydrogen ions, sodium ions, calcium ions, lead ions, silver ions, and the like as counter ions.
  • the core-shell particles obtained by the production method according to the present invention are also one aspect of the present invention.
  • the core-shell particles those in which the polymer contains an acidic monomer and / or a basic monomer in a monomer component can also be suitably used.
  • the use of the core-shell particles according to the present invention is not particularly limited, and examples thereof include separation agents such as a liquid chromatography separation agent and a pretreatment separation agent.
  • core-shell particles that can be suitably used as a separating agent having excellent separating ability can be obtained.
  • the core-shell particles can be easily adjusted in the particle diameter of the core-shell particles, and the particle size distribution is narrow and the mechanical strength is strong. It can be manufactured.
  • FIG. 2 is an SEM image of shell-forming particles obtained in Example 1.
  • FIG. 3 is an SEM image of shell-forming particles obtained in Example 2.
  • FIG. 4 is an SEM image of shell-forming particles obtained in Example 3.
  • FIG. 4 is an SEM image of shell-forming particles obtained in Example 4.
  • FIG. 4 is an SEM image of shell-forming particles obtained in Example 4.
  • 6 is an SEM image of shell-forming particles obtained in Example 5.
  • FIG. 5 is an SEM image of shell-forming particles obtained in Example 5.
  • 4 is an SEM image of shell-forming particles obtained in Example 6.
  • 3 is an SEM image of shell-forming particles obtained in Comparative Example 1.
  • 3 is an SEM image of shell-forming particles obtained in Comparative Example 2.
  • 14 is a chromatographic data of high performance liquid chromatography performed using the core-shell particles obtained in Comparative Example 2.
  • 4 is an SEM image of shell-forming particles obtained in Comparative Example 3.
  • 14 is a chromatographic data of high performance liquid chromatography performed using the core-shell particles obtained in Comparative Example 3. Chromatographic data of high performance liquid chromatography performed using non-porous silica gel.
  • the present invention relates to a base material core particle composed of inorganic particles mainly composed of a porous inorganic compound, a polymer layer formed on the surface of the base material core particle, and an ion exchange introduced into the polymer layer. And a method for producing core-shell particles having a group.
  • the base material core particle used as the core part in the present invention is composed of inorganic particles mainly composed of a porous inorganic compound.
  • the inorganic particles are not particularly limited as long as they have a porous inorganic compound as a main component.
  • a main component such as silica gel, glass, carbon, ceramics such as alumina, zirconia, and titania.
  • a main component such as silica gel, glass, carbon, ceramics such as alumina, zirconia, and titania.
  • silica gel is the main component. Those that do are preferred.
  • the average particle diameter and average pore diameter of the inorganic particles may be appropriately selected according to the separation target.
  • the average particle diameter is 1.0 to 50 ⁇ m, preferably 1.0 to 10 ⁇ m. Having a thickness of 5 to 30 nm, preferably 8 to 12 nm.
  • the average particle diameter is a value obtained by the Coulter counter method, and the average pore diameter is a value obtained by the BET method.
  • a polymer layer is further formed as a shell portion on the surface of the base material core particles.
  • the polymer layer is mainly composed of a polymer containing a hydrophobic crosslinkable monomer (A) and / or a hydrophobic non-crosslinkable monomer (B) as a monomer component. That is, the polymer includes a polymer of a hydrophobic crosslinkable monomer (A), a copolymer of a hydrophobic crosslinkable monomer (A) and a hydrophobic non-crosslinkable monomer (B), a hydrophobic And a non-crosslinkable monomer (B) polymer.
  • hydrophobic crosslinkable monomer (A) examples include diglycol such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate.
  • divinylbenzene is preferable because it has rigidity and easily maintains a network structure when it acts as a crosslinking agent, and is easily available.
  • the amount of the hydrophobic crosslinkable monomer (A) used is a charging ratio with respect to 1.00 parts by mass of the base material core particles, preferably 0.080 to 0.180 parts by mass, more preferably 0.00. 110 to 0.150 parts by mass.
  • the amount of the hydrophobic crosslinkable monomer (A) used is less than 0.080 parts by mass, the polymer film is not properly formed, and when it exceeds 0.180 parts by mass, gelation may occur. .
  • hydrophobic non-crosslinkable monomer (B) examples include styrene, methylstyrene, chloromethylstyrene, butoxystyrene, 2-vinylnaphthalene, 2-vinylanthracene, t-butylstyrene, 1,1-diphenylethylene. And styrenic monomers such as allylbenzene.
  • styrene is preferably used because sulfonation is easy and availability is also easy.
  • the amount of the hydrophobic non-crosslinkable monomer (B) used is a charging ratio with respect to 1.00 parts by mass of the base material core particles, preferably 0.40 to 0.80 parts by mass, more preferably 0. .50 to 0.60 parts by mass. If the amount of the hydrophobic non-crosslinkable monomer (B) used is less than 0.40 parts by mass, a polymer film is not sufficiently formed, and if it exceeds 0.80 parts by mass, gelation may occur. is there.
  • the degree of crosslinking of the polymer can be changed within a certain range. By changing the degree of crosslinking, the swellability and toughness of the core-shell particles can be changed.
  • the degree of crosslinking of the polymer is preferably 0 to 80%, more preferably 5 to 50%, and still more preferably 15 to 25%. If the degree of crosslinking of the polymer exceeds 80%, gelation may occur.
  • the degree of crosslinking of the polymer is determined according to the following formula.
  • hydrophobic crosslinkable monomer (A) and the hydrophobic non-crosslinkable monomer (B) one type of monomer may be used or two or more types of monomers may be used in combination. May be.
  • an acidic monomer such as an unsaturated fatty acid such as methacrylic acid or undecenoic acid, or a basic monomer such as vinylpyridine or vinylpyrrolidone is used. These may be block copolymerized.
  • the core-shell particles can be designed to take a separation behavior suitable for sugar analysis or organic acid analysis.
  • the polymer layer may have a multilayer structure composed of a plurality of layers.
  • the polymer layer has a multilayer structure, it is easy to adjust the film thickness of the polymer layer and the particle diameter of the core-shell particles.
  • the core-shell particles obtained in the present invention are imparted with alkali resistance or ion exchange.
  • the capacity can be adjusted.
  • the ion exchange capacity of the core-shell particles is increased, the ligand exchange mode works more strongly, so that the resolution is improved.
  • the polymer in order to form a polymer layer on the surface of the base material core particle, first, the polymer is polymerized. Polymerization of the polymer is performed, for example, by stirring the monomer constituting the polymer in a toluene solvent at a liquid temperature of 50 to 90 ° C. and a stirring rotation speed of 250 rpm for 1 hour or more in a nitrogen atmosphere. Polymerization is started by adding a polymerization initiator.
  • the polymerization initiator is not particularly limited as long as it is a known radical polymerization agent that generates radicals, and examples thereof include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, and perbenzoic acid.
  • Organic peroxide initiators such as tertiary butyl, methyl ethyl ketone peroxide and methylcyclohexanone peroxide; azo initiators such as 2,2-azobisisobutyronitrile and 2,2-azobis (2,4-dimethylvaleronitrile) Agents and the like.
  • the amount of the polymerization initiator used is a charge ratio with respect to a total of 1.00 parts by mass of the monomers, preferably 0.01 to 0.04 parts by mass, more preferably 0.01 to 0.03 parts by mass. Part.
  • the amount of the polymerization initiator used is less than 0.01 parts by mass, the polymerization is not appropriately performed.
  • the amount exceeds 0.04 parts by mass the molecular weight of the polymer to be coated becomes small, and the separation is adversely affected.
  • the base material core particles are added to a reaction system in which the polymerization reaction of the polymer is continued, and at any point before or during the start of the polymerization reaction of the polymer, A coupling agent that binds the base material core particles and the polymer layer is added to the reaction system of the polymerization reaction.
  • the polymer becomes a prepolymer having a certain molecular weight
  • the coupling agent serves as a stopper for the polymerization reaction of the polymer. For this reason, it can prevent that the molecular weight of a polymer goes up too much and a polymer gelatinizes.
  • a method for adding the coupling agent to the reaction system of the polymerization reaction is not particularly limited. For example, a method in which the surface of the base material core particle is previously treated with the coupling agent, or the coupling agent is added. A method of previously mixing with the monomer before the start of the polymerization reaction can be used.
  • the coupling agent is not particularly limited and may be appropriately selected according to a combination of the inorganic particles and the polymer.
  • the inorganic particles are mainly composed of silica gel, and the polymer
  • the layer contains a vinyl monomer as a constituent component, for example, a functional group having reactivity with a silanol group such as an alkoxysilane group, a halogenosilane group, an acetoxysilane group, and a vinyl group.
  • the silane coupling agent which has is used suitably.
  • the vinyl group is interpreted in the broadest sense, and includes an acryloyl group, a methacryloyl group, an allyl group and the like in addition to the vinyl group itself.
  • silane coupling agents examples include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxy). ) Silane, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane, vinyltriacetoxysilane, ⁇ -methacryloxypropylmethyldiethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ - And methacryloxypropylmethyldimethoxysilane.
  • the amount of the silane coupling agent used is a charge ratio with respect to 1.00 part by mass of silica gel, preferably 0.70 to 1.20 parts by mass, and more preferably 0.90 to 1.10 parts by mass.
  • the amount of the silane coupling agent used is less than 0.70 parts by mass, the polymer coating is not appropriately performed, and when it exceeds 1.20 parts by mass, the separation tends to be adversely affected.
  • the base material core particles and the coupling agent are heated in a toluene solvent under a nitrogen atmosphere at a liquid temperature of 105 to 115 ° C., What is necessary is just to stir at the stirring rotation speed of 200 rpm, and to react for 6 hours or more.
  • a catalyst may be added when the surface of the base material core particles composed of inorganic particles mainly composed of silica gel is treated with a silane coupling agent. When the catalyst is added, the reaction is accelerated and more silane coupling agent reacts with the silica gel.
  • the catalyst include p-toluenesulfonic acid monohydrate, imidazole and the like.
  • the amount of the catalyst used is a charge ratio with respect to 1.00 parts by mass of the silane coupling agent, preferably 0.005 to 0.015 parts by mass, and more preferably 0.0075 to 0.0125 parts by mass.
  • the amount of the catalyst used is less than 0.005 parts by mass, the catalytic effect is not sufficiently exhibited.
  • the amount exceeds 0.015 parts by mass the reaction proceeds excessively and a silane coupling agent is introduced more than necessary. End up.
  • the above polymerization process may be repeated a plurality of times.
  • the same core-shell particles as in the present invention can be obtained even if a polymer polymerized in advance is bonded to the surface of the base material core particle separately.
  • a polymerization step including a polymerization termination reaction and a polymer layer forming step on the surface of the base material core particle (coating step Therefore, the manufacturing process of the core-shell particles is complicated as compared with the present invention.
  • ion exchange groups are further introduced into the polymer layer.
  • the ion exchange group include a cation exchange group such as a sulfo group.
  • a sulfonating agent may be added and reacted with the base material core particle having the polymer layer formed on the surface.
  • the sulfonating agent include sulfuric acid, fuming sulfuric acid, chlorosulfonic acid and the like.
  • the ion exchange group introduced into the polymer layer preferably has hydrogen ions, sodium ions, calcium ions, lead ions, silver ions and the like as counter ions.
  • the core-shell particles obtained in the present invention do not need to be classified like a polymer separating agent, and can be produced at low cost and in a short time. Although it does not specifically limit as a use of such a core-shell particle, For example, it uses suitably as separating agents, such as a separating agent for liquid chromatography, and a separating agent for pre-processing. Furthermore, the core-shell particles obtained in the present invention can be used as a functional material useful in various fields in addition to the separating agent. Examples of such a functional material include a water filter agent and a purification agent. And purification agents for various substances.
  • Example 1 (1) Surface treatment of base material core particles In a 200 mL four-necked flask, 10 g of silica gel (manufactured by AGC S-Itech Co., Ltd.) having an average particle size of 5 ⁇ m and an average pore size of 12 nm as base material core particles in a nitrogen atmosphere, 60 mL of toluene And 10 g of ⁇ -methacryloxypropylpyrtrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the reaction was performed for 6 hours or more. After completion of the reaction, the substrate was washed successively with chloroform (200 mL), methanol (300 mL), and acetone (100 mL) and then dried to obtain substrate core particles coated with a silane coupling agent.
  • silica gel manufactured by AGC S-Itech Co., Ltd.
  • the surface-treated base material core particles 10.0 g of the surface-treated base material core particles and 0.08 g of benzoyl peroxide (manufactured by Nacalai Tesque) were added, and the mixture was stirred at about 80 ° C. and reacted for 20 hours or more.
  • the substrate core particles (hereinafter referred to as shell formation) coated with a hydrophobic polymer layer are washed with chloroform 200 mL, methanol 200 mL, deionized water 200 mL, methanol 100 mL, and acetone 100 mL sequentially, and then dried. Called particles).
  • Example 2 (1) Surface treatment of base material core particles The surface treatment of base material core particles was carried out in the same manner as in Example 1.
  • Shell-forming particles (hereinafter referred to as secondary particles) were formed in the same manner as in Example 1, and after washing, the process was directly transferred to the next step.
  • Multi-layer coating step In a 200 mL four-necked flask, under a nitrogen atmosphere, 60 mL of toluene, 5.3 g of styrene (manufactured by Wako Pure Chemical Industries, Ltd.), 1.6 g of 80% purity divinylbenzene (manufactured by Sigma Aldrich), and Then, 0.08 g of benzoyl peroxide (manufactured by Nacalai Tesque) was added and stirred at 80 ° C. or higher for several hours.
  • Example 3 In the same manner as in Example 2, after obtaining two-layer coated shell-forming particles, the multilayer coating step was repeated to obtain four-layer coated shell-forming particles.
  • FIG. 5 shows an SEM image of the obtained four-layer coated shell-forming particles.
  • Example 4 (1) Surface treatment of base material core particles The surface treatment of base material core particles was carried out in the same manner as in Example 1.
  • the surface-treated base material core particles and 0.08 g of benzoyl peroxide manufactured by Nacalai Tesque
  • the substrate core particles (hereinafter referred to as shell-forming particles) coated with a polymer layer are washed successively with 200 mL of chloroform, 200 mL of methanol, 200 mL of deionized water, 100 mL of methanol, and 100 mL of acetone, and then dried. .)
  • Example 5 (1) Surface treatment of base material core particles The surface treatment of base material core particles was carried out in the same manner as in Example 1.
  • Multilayer coating step A multilayer coating step was performed in the same manner as in Example 2 to obtain two-layer coated shell-forming particles coated with two different polymer layers.
  • Example 6 (1) Preparation of shell-forming particles In a 200 mL four-necked flask, under a nitrogen atmosphere, 60 mL of toluene, 5.3 g of styrene (manufactured by Wako Pure Chemical Industries, Ltd.), 1.6 g of 80% purity divinylbenzene (manufactured by Sigma-Aldrich) 1.6 g Then, 2.5 g of ⁇ -methacryloxypropylpyrtrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.08 g of benzoyl peroxide (manufactured by Nacalai Tesque) were added and stirred at 80 ° C.
  • silica gel manufactured by AGC S-Tech Co., Ltd.
  • 10 g of silica gel manufactured by AGC S-Tech Co., Ltd.
  • the substrate core particles (hereinafter referred to as shell formation) coated with a hydrophobic polymer layer are washed with chloroform 200 mL, methanol 200 mL, deionized water 200 mL, methanol 100 mL, and acetone 100 mL sequentially, and then dried. Called particles).
  • ⁇ Comparative Example 1> Surface treatment of base material core particle In a 500 mL four-necked flask, under a nitrogen atmosphere, 25 g of silica gel (manufactured by AGC S-Tech Co., Ltd.) having an average particle size of 10 ⁇ m and an average pore size of 12 nm as a base material core particle, 150 mL of toluene Then, 25 g of ⁇ -methacryloxypropylpyrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the reaction was performed for 6 hours or more. After completion of the reaction, the mixture was sequentially washed with 500 mL of chloroform, 750 mL of methanol, and 250 mL of acetone, and then dried to obtain base material core particles coated with a silane coupling agent.
  • silica gel manufactured by AGC S-Tech Co., Ltd.
  • the substrate core particles (hereinafter referred to as shell formation) covered with a hydrophobic polymer layer are washed with chloroform 500 mL, methanol 500 mL, deionized water 500 mL, methanol 250 mL, and acetone 250 mL, and then dried. Called particles).
  • ⁇ Comparative Example 2> Surface treatment of substrate core particles In a 500 mL four-necked flask, under a nitrogen atmosphere, 25 g of silica gel (manufactured by AGC S-Itech) with an average particle size of 10 ⁇ m and an average pore size of 12 nm, toluene 150 mL, ⁇ -methacryloxy The reaction was carried out for 6 hours or more by adding 25 g of purpyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.29 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.9 g of water. After completion of the reaction, the mixture was washed sequentially with 500 mL of chloroform, 750 mL of methanol, and 250 mL of acetone, and then dried to obtain base material core particles coated with a silane coupling agent.
  • the reaction mixture was washed successively with 500 mL of chloroform, 500 mL of methanol, 500 mL of deionized water, 250 mL of methanol, and 250 mL of acetone, and directly moved to the next step.
  • the obtained particles are referred to as secondary particles.
  • FIG. 15 shows an SEM image of the obtained two-layer coated shell-forming particles.
  • FIG. 17 shows an SEM image of the obtained four-layer coated shell-forming particles.
  • FIG. 19 shows chromatographic data of non-porous silica gel (silica gel having no pores). Comparing FIG. 19 with FIGS. It can be seen that the peak shape of the porous silica gel is approaching. Therefore, it is estimated that the pores are clogged each time the coating of the polymer layer is repeated.
  • FIG. 2 ⁇ FIG. 4 ⁇
  • FIG. 6 is arranged side by side, it can be seen that, unlike Comparative Examples 1 to 3, the peak shape is maintained even when the coating of the polymer layer is overlapped. Therefore, in Examples 1 to 3, it is presumed that the pores are not clogged even if the polymer layer is coated a plurality of times. Therefore, it can be seen that in Examples 1 to 3, it was possible to perform the multilayer coating of the polymer layer without impairing the separation ability.
  • core-shell particles useful as a separating agent having excellent separating ability can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention a pour objet de réaliser un procédé de production de particules noyau-coque susceptibles d'être utilisées en tant qu'agent de décollement doté d'une excellente aptitude au décollement. Un procédé selon l'invention vise à produire des particules noyau-coque comprenant des particules-noyau de substrat comportant une particule inorganique principalement composée d'un composé inorganique poreux, une couche de macromolécules formée sur la surface des particules-noyau de substrat, et un groupe d'échange d'ions introduit dans la couche de macromolécules ; la couche de macromolécules étant principalement composée d'un polymère dans lequel un composant de monomère comprend un monomère hydrophobe réticulable (A) et / ou un monomère hydrophobe non réticulable (B), les particules-noyau de substrat étant ajoutées à un système de réaction dans lequel la réaction de polymérisation du polymère se poursuit, et la couche de macromolécules étant formée sur la surface des particules-noyau de substrat en ajoutant un agent de couplage pour lier ensemble les particules-noyau de substrat et la couche de macromolécules au système de réaction de la réaction de polymérisation du polymère soit à un instant précédant le début de la réaction de polymérisation du polymère, soit pendant que la réaction se poursuit.
PCT/JP2013/072016 2012-08-28 2013-08-16 Procédé de production de particules noyau-coque WO2014034442A1 (fr)

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Cited By (1)

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WO2017022695A1 (fr) * 2015-07-31 2017-02-09 株式会社ダイセル Phase stationnaire pour chromatographie à fluide supercritique

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JPS56115727A (en) * 1980-02-19 1981-09-11 Kuraray Co Ltd Carrier for immobilizing physiologically active substance
JP2007531891A (ja) * 2004-04-05 2007-11-08 ジーイー・ヘルスケア・バイオサイエンス・アクチボラグ 分離マトリックスの製造方法
JP2010236909A (ja) * 2009-03-30 2010-10-21 Sekisui Medical Co Ltd ヘモグロビン類分離用カラム充填剤、ヘモグロビンＡ１ｃ及び異常ヘモグロビン類の測定方法、並びに、ヘモグロビン類分離用カラム充填剤の製造方法
WO2011046494A1 (fr) * 2009-10-12 2011-04-21 Ge Healthcare Bio-Sciences Ab Matrices de séparation

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Publication number Priority date Publication date Assignee Title
JPS56115727A (en) * 1980-02-19 1981-09-11 Kuraray Co Ltd Carrier for immobilizing physiologically active substance
JP2007531891A (ja) * 2004-04-05 2007-11-08 ジーイー・ヘルスケア・バイオサイエンス・アクチボラグ 分離マトリックスの製造方法
JP2010236909A (ja) * 2009-03-30 2010-10-21 Sekisui Medical Co Ltd ヘモグロビン類分離用カラム充填剤、ヘモグロビンＡ１ｃ及び異常ヘモグロビン類の測定方法、並びに、ヘモグロビン類分離用カラム充填剤の製造方法
WO2011046494A1 (fr) * 2009-10-12 2011-04-21 Ge Healthcare Bio-Sciences Ab Matrices de séparation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017022695A1 (fr) * 2015-07-31 2017-02-09 株式会社ダイセル Phase stationnaire pour chromatographie à fluide supercritique
CN107923882A (zh) * 2015-07-31 2018-04-17 株式会社大赛璐 超临界流体色谱法用的固定相
JPWO2017022695A1 (ja) * 2015-07-31 2018-05-24 株式会社ダイセル 超臨界流体クロマトグラフィー用の固定相
EP3330704A4 (fr) * 2015-07-31 2018-08-08 Daicel Corporation Phase stationnaire pour chromatographie à fluide supercritique
US11014019B2 (en) 2015-07-31 2021-05-25 Daicel Corporation Stationary phase for supercritical fluid chromatography
CN107923882B (zh) * 2015-07-31 2021-10-15 株式会社大赛璐 超临界流体色谱法用的固定相

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