WO2015016103A1 - Adsorbant et son procédé de fabrication - Google Patents

Adsorbant et son procédé de fabrication Download PDF

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Publication number
WO2015016103A1
WO2015016103A1 PCT/JP2014/069362 JP2014069362W WO2015016103A1 WO 2015016103 A1 WO2015016103 A1 WO 2015016103A1 JP 2014069362 W JP2014069362 W JP 2014069362W WO 2015016103 A1 WO2015016103 A1 WO 2015016103A1
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adsorbent
group
component
polymer component
particles
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PCT/JP2014/069362
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English (en)
Japanese (ja)
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天野雄介
森川圭介
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株式会社クラレ
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    • 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
    • B01J20/22—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
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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
    • B01J20/22—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
    • B01J20/267—Cross-linked polymers

Definitions

  • the present invention relates to an adsorbent capable of efficiently adsorbing an object to be adsorbed such as metal ions and a method for producing the same.
  • affinity with water can be improved and a metal can be adsorbed effectively by using a polymer having a highly polar structure as a base material.
  • Patent Document 1 discloses a noble metal ion scavenger that introduces a chelating functional group in a polymer having a crosslink between chitosan molecules.
  • this scavenger since the molecular skeleton has a cross-linked structure, it is not dissolved in an acidic solution suitable for adsorption of noble metal ions, and a functional group having a chelating ability is bonded.
  • Patent Document 2 discloses a chelate ion-adsorbing membrane produced by introducing a chelate-forming group into a graft copolymer membrane obtained by graft copolymerizing glycidyl methacrylate and a crosslinking agent on a porous membrane. ing.
  • Such chelate-type ion-adsorbing films are used for removing metal ions and are described as having excellent performance in elution resistance, chemical durability, and throughput.
  • Patent Document 3 discloses a cation adsorbent in which ion exchange groups are introduced by graft polymerization of styrene sulfonate in one step on a sheet-like, film-like, or fiber-like organic polymer substrate. Has been. This document also describes that a graft-crosslinked structure can be obtained by coexisting a polyfunctional monomer during graft polymerization.
  • Patent Document 4 discloses a crosslinked copolymer particle which is based on a copolymer of glycidyl methacrylate and a crosslinking agent and swells significantly in water. This document describes that the crosslinked copolymer particles are useful for separating high molecular substances such as proteins.
  • Patent Documents 1, 2, and 4 have remarkable resin swelling when it contains water because of its high hydrophilicity.
  • Patent Document 3 since the styrene skeleton is present in the graft chain, the matrix is hydrophobic, and once dried, the original adsorption performance is not exhibited.
  • a particle shape having a high bulk density is preferable.
  • the change in the bulk density due to swelling is remarkable, and the adsorption capacity per unit volume is increased.
  • a high degree of swelling control is required to keep it high.
  • a highly hydrophilic adsorbent has a large volume fluctuation due to an external factor such as an exposed temperature, there is a concern that the resin swells in a use environment and a problem such as column breakage occurs.
  • the present invention has been made to solve the above problems, and provides an adsorbent having a hydrophilic skeleton and having a controlled swelling property derived from a crosslinked structure, and such an adsorbent. It aims at providing the manufacturing method of.
  • the inventors of the present invention have intensively studied to achieve the above object, and as a result, (i) in the prior art, when efficiently recovering an object to be adsorbed such as metal ions, attention is paid to the recovery efficiency as a single adsorbent.
  • research is focused on improving hydrophilicity to increase the adsorption efficiency and increasing the amount of adsorbed functional groups introduced.
  • the adsorbent when actually using the adsorbent, the adsorbent itself swells. It has been noticed that, in conjunction with the increase in the property, the packing efficiency of the adsorbent itself when packed in a closed space such as a column is lowered.
  • the base material is an ethylene-vinyl alcohol copolymer that is a hydrophilic polymer, and a hydrophilic (meth) acrylic acid ester skeleton is formed on the base material.
  • introducing a polymer component having an adsorptive functional group as a structural unit as a graft chain, and further crosslinking the polymer component makes it possible to suppress the swelling while maintaining the adsorptivity, and (iv) increase the packing efficiency
  • the final form of the polymer is crosslinked so that the adsorbent can be used even when a heating solvent is applied.
  • the first embodiment of the present invention is a polymer having an ethylene-vinyl alcohol copolymer as a base material, a polymer having an adsorption functional group having a (meth) acrylate skeleton as a structural unit as a graft chain on the base material.
  • the cross-linking component may have, for example, any one or more functional groups selected from the group consisting of amino groups, isocyanate groups, epoxy groups, carbodiimide groups, and azetidinium groups.
  • the adsorbing functional group is a glucamine group, a diol group, a polyol group, a group composed of a polyol and a nitrogen atom, an iminodiacetic acid group, an amino group, an ammonium group, an amidoxime group, a dithiocarbamic acid group, a thiourea group, It may be any one or more functional groups selected from the group consisting of an isothiourea group, a phosphoric acid group, and a phosphonic acid group.
  • the adsorbent may be a porous body.
  • the average value of the long diameters of the pores formed on the surface of the porous body may be in the range of 0.01 ⁇ m to 20 ⁇ m.
  • the adsorbent may be in the form of particles, for example, in which case the particle diameter range of the adsorbent may be about 10 to 2000 ⁇ m.
  • a second embodiment of the present invention is a method for producing the adsorbent, Preparing an ethylene-vinyl alcohol copolymer as a base component;
  • a polymer component introduction step of introducing a polymer component P 0 having a reactive (meth) acrylate skeleton as a structural unit into the base material component as a graft chain;
  • An adsorption functional group introduction step of introducing an adsorption functional group to the polymer component P 0 , having a (meth) acrylate skeleton as a structural unit, and obtaining a polymer component P 1 having an adsorption functional group;
  • a crosslinking step of crosslinking the polymer component P 0 or P 1 ; Is a method for producing an adsorbent comprising at least
  • the polymeric component P 0 may be provided with a graft chain introduction step is introduced as a graft chain to the substrate component.
  • ionizing radiation may act on the substrate component to introduce a graft chain.
  • the graft ratio of the graft chain introduced may be, for example, 30 to 900% by mass from the viewpoint of improving the adsorptivity to the adsorbed material.
  • adsorptive functional group introduction step adsorptive functional group concentration in the complex of the polymeric component P 1 and the substrate component is preferably in the range from 1.5 mmol / g or more.
  • the swelling property of the resin is controlled by the crosslinking treatment while using a highly hydrophilic skeleton as a base material, the swelling property is low while maintaining high adsorption performance, and the metal ions and the like are efficiently covered.
  • the adsorbate can be recovered.
  • the manufacturing method of the adsorbent of this invention the adsorbent which has the above outstanding performances can be manufactured efficiently.
  • a polymer component P having an ethylene-vinyl alcohol copolymer as a base material, a (meth) acrylate skeleton as a structural unit as a graft unit on the base material, and an adsorptive functional group. 1 is an adsorbent in which 1 is introduced and the polymer component P 1 is crosslinked.
  • a second embodiment of the present invention is a method for producing the adsorbent, Preparing an ethylene-vinyl alcohol copolymer as a base component; A polymer component introduction step of introducing a polymer component P 0 having a reactive (meth) acrylate skeleton as a structural unit into the base material component as a graft chain; The introducing adsorptive functional group on the polymer component P 0, and (meth) which has an acrylic acid ester skeleton as a structural unit, the functional group introduced to obtain a polymer component P 1 having an adsorbing functional group, A crosslinking step of crosslinking the polymer component P 0 or P 1 ; At least.
  • the adsorbent of the present invention contains an ethylene-vinyl alcohol copolymer as a base component.
  • An ethylene-vinyl alcohol copolymer is suitable as a base material for an adsorbent because it has high hydrophilicity, excellent moldability, and excellent acid resistance.
  • the ethylene content of the ethylene-vinyl alcohol copolymer may be about 10 to 60 mol%, preferably about 20 to 50 mol%. If the ethylene content is too low, the water resistance of the resulting graft copolymer may be reduced. On the other hand, when there is too much ethylene content, manufacture is difficult and acquisition is difficult.
  • the saponification degree of the ethylene-vinyl alcohol copolymer is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 99 mol% or more.
  • the degree of saponification is too low, moldability may be deteriorated or the water resistance of the obtained graft copolymer may be lowered.
  • melt flow rate (MFR) (210 ° C., load 2160 g) of the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more. preferable. If the melt flow rate is too small, water resistance and strength may be reduced. In addition, the upper limit of a melt flow rate should just be the range normally used, for example, may be 25 g / 10min or less.
  • the ethylene-vinyl alcohol copolymer of the present invention may contain other unsaturated monomer units as long as the effects of the present invention are not impaired.
  • the content of the unsaturated monomer unit is preferably 10 mol% or less, more preferably 5% mol or less.
  • Such ethylene-vinyl alcohol copolymers can be used alone or in combination of two or more.
  • the surface shape of the base material component is not particularly limited as long as graft polymerization is possible. From the viewpoint of improving the reactivity during graft polymerization, it is preferably a porous body that has been previously made porous.
  • the porous body only needs to have a plurality of holes formed on at least the surface thereof, and does not need to have holes formed therein.
  • the porous body has a structure including at least 10, preferably 100 or more, more preferably 1,000 or more pores having a major axis of 0.01 ⁇ m to 20 ⁇ m per 1 cm 2 of area. May be.
  • the porous base material component may physically form pores with respect to the base material component, or may be prepared by melting and mixing with a pore forming agent such as a foaming agent and the base material, or a solvent.
  • the polymer may be extracted by mixing by melt kneading or the like, and then the solvent extractable polymer may be extracted.
  • the pores formed on the surface of the porous body may have an average length of about 0.01 ⁇ m to 20 ⁇ m, preferably about 0.05 ⁇ m to 10 ⁇ m, more preferably about 0.1 ⁇ m to 5 ⁇ m. May be.
  • the average value of the major axis of these pores is a value measured by the method described in the examples described later.
  • a porous base material component made porous using a solvent-soluble polymer component is preferable in that the pore size can be easily controlled.
  • the substrate component and the solvent-soluble polymer component are mixed by melt-kneading, etc. It is preferably formed by a step of obtaining a composite obtained by cooling and solidifying a melt and a step of extracting a solvent-soluble polymer component from the composite with a solvent.
  • cooling and solidifying a melt means cooling and solidifying the melt without using a solidification bath or the like.
  • the solvent-soluble polymer used in the present invention is not particularly limited as long as it can be melt-mixed with the ethylene-vinyl alcohol copolymer, and is an organic solvent-soluble polymer (for example, polystyrene) or an alkali-soluble polymer (for example, polyester). Or the like, and is preferably a water-soluble polymer.
  • the water-soluble polymer is not particularly limited as long as it can be melt-mixed with the ethylene-vinyl alcohol copolymer, and generally known water-soluble polymers can be used.
  • water-soluble polymer examples include starch; gelatin; cellulose derivatives; water-soluble amine-based polymers such as polyvinylamine and polyallylamine; polyacrylic acid; polyacrylamide such as polyisopropylacrylamide; polyvinylpyrrolidone; Among these, polyvinyl alcohol is particularly preferably used because it is excellent in melt kneading with an ethylene-vinyl alcohol copolymer and easily controls the voids.
  • the ratio (mass ratio) between the base material component and the solvent-soluble polymer component can be appropriately determined according to the required degree of porosity.
  • the base material component: solvent-soluble polymer component is 100 : About 0 to 20:80, and preferably about 100: 0 to 30:70.
  • polyvinyl alcohol used as a water-soluble polymer can have structural units other than vinyl alcohol units and structural units derived from vinyl ester monomers as long as the effects of the present invention are obtained.
  • the structural unit includes, for example, ⁇ -olefins such as ethylene, propylene, n-butene, isobutylene and 1-hexene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, N-propyl acrylate, acrylic acid i Unsaturated monomers having an acrylate group such as -propyl, N-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid And salts thereof; methyl methacrylate, ethyl methacrylate, N-propyl methacrylate, i-propyl
  • Unsaturated monomer having a methacrylic acid ester group acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidopropyldimethylamine and its salt (For example, quaternary salt); methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and its salt, methacrylamidepropyldimethylamine and its salt (for example, quaternary salt); methyl vinyl ether, ethyl Vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether Vinyl ethers such as ether, stearyl vinyl ether and 2,3-diacetoxy-1-
  • the viscosity average polymerization degree (measured in accordance with JIS K6726) of the polyvinyl alcohol used in the present invention is not particularly limited, but is preferably 100 to 10,000, more preferably 200 to 7,000, still more preferably. Is 300 to 5,000. If the viscosity average degree of polymerization deviates from the above range, the surface area of the resulting porous body may be reduced.
  • the saponification degree of the polyvinyl alcohol used in the present invention is not particularly limited, but is preferably 50 mol% or more, more preferably 60 to 98 mol%, and particularly preferably 70 to 95 mol%. If the degree of saponification is too low, the water solubility is lowered and the extractability after molding becomes worse. Polyvinyl alcohol having a too high degree of saponification is difficult to melt and mix.
  • the porous ethylene-vinyl alcohol copolymer used in the present invention is, for example, mixed by melt-kneading an ethylene-vinyl alcohol copolymer and a solvent-soluble polymer (preferably a water-soluble polymer). Then, after obtaining a composite (compound) in which the melt is cooled and solidified, a solvent-soluble polymer (preferably a water-soluble polymer) is extracted from the composite.
  • the method of melt kneading is not particularly limited, and a known kneader such as a single screw extruder, a twin screw extruder, a Brabender, or a kneader can be used. In order to obtain a target shape, pulverization or the like may be performed at each stage as necessary.
  • the solvent used for the extraction is not particularly limited, and water, various organic solvents, water and organic solvents A mixture or the like can be used, but when a water-soluble polymer is used, it is preferable to use water, particularly hot water, as the solvent.
  • the temperature of hot water is preferably 40 ° C to 120 ° C, more preferably 50 ° C to 100 ° C.
  • the base material component Prior to the functional group-introducing step, the base material component, by performing a graft chain formation step of introducing a polymer component P 0 as a graft chain, it is possible to obtain a graft copolymer.
  • the graft chain can be obtained by utilizing radical polymerization using a polymerization initiator. And a method of generating a radical with respect to a base material component using ionizing radiation and introducing a graft chain. Among these, from the viewpoint of high graft chain introduction efficiency, a method of introducing the polymer component P 0 as a graft chain using ionizing radiation is preferably used.
  • the polymer component P 0 is a radical addition polymerization of a reactive (meth) acrylate skeleton (hereinafter sometimes referred to as a reactive (meth) acrylate skeleton) monomer from a radical generated in the base component. Can be obtained.
  • a reactive (meth) acrylate skeleton hereinafter sometimes referred to as a reactive (meth) acrylate skeleton
  • Examples of the reactive (meth) acrylic acid ester skeleton include a skeleton in which a functional group (that is, a functional group having reactivity with an adsorbing functional group) is introduced into the alkoxy group in the (meth) acrylic acid ester.
  • Examples of such a skeleton include glycidyl (meth) acrylate, glyceryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, chloroethyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate.
  • These reactive (meth) acrylic acid ester skeletons may be used alone or in combination of two or more.
  • the polymer component P 0 requires other vinyl polymerizable monomers (for example, (meth) acrylate monomers in which no reactive group is introduced). It may be included accordingly. Further, as described later, when a cross-linked structure is introduced in the formation process of the polymer component P 0 , a structure derived from the cross-linked component may be included.
  • the polymer component P 0 is preferably composed of a (meth) acrylic acid ester skeleton having a highly reactive functional group at its terminal.
  • the reactive functional group present in the skeleton is described later.
  • the adsorbing functional group can be easily introduced.
  • Examples of the ionizing radiation include ⁇ rays, ⁇ rays, ⁇ rays, accelerated electron rays, ultraviolet rays, and the like. Practically, accelerated electron rays or ⁇ rays are preferable.
  • the unsaturated monomer used here includes, in addition to the monomer forming the reactive (meth) acrylate skeleton described above, other vinyl polymerizable monomers ((meth) acrylate esters as necessary). As such) and multifunctional monomers.
  • Polyfunctional monomers may be used in the case of introducing a crosslinked structure in the formation process of the polymer components P 0.
  • the polyfunctional monomer for example, divinylbenzene, methylenebisacrylamide, polyethylene glycol dimethacrylate and the like are preferably used.
  • the other vinyl polymerizable monomer may be contained in an amount of, for example, 50 mol% or less, preferably 30 mol% or less, and the polyfunctional monomer is, for example, It may be contained in an amount of 50 mol% or less, preferably 30 mol% or less.
  • the base component and the unsaturated monomer may be brought into contact with each other as a liquid phase graft polymerization method in which a liquid unsaturated monomer or an unsaturated monomer solution is brought into direct contact with the unsaturated monomer solution.
  • a liquid phase graft polymerization method in which a liquid unsaturated monomer or an unsaturated monomer solution is brought into direct contact with the unsaturated monomer solution.
  • vapor-phase graft polymerization methods in which the monomer vapor or vaporized contact is made, but it can be selected according to the purpose.
  • the reaction conditions such as the concentration of the unsaturated monomer to be contacted and the polymerization treatment time can be appropriately set by those skilled in the art depending on the required graft rate and the like. it can.
  • the dose of ionizing radiation is not particularly limited, but is preferably 5 to 230 kGy, more preferably 10 to 190 kGy, still more preferably 15 to 140 kGy, and most preferably 20 to 120 kGy. If the dose is too small, the graft rate may decrease and the desired adsorption capacity may not be obtained. When the dose is too high, there is a concern that the treatment process is costly and the resin deteriorates during irradiation.
  • the amount of the unsaturated monomer introduced by graft polymerization is not particularly limited, but is preferably, for example, 30 to 900 parts by mass (30 to 900%) with respect to 100 parts by mass of the base material. It is more preferably 60 to 800 parts by mass (60 to 800%), further preferably 120 to 700 parts by mass (120 to 700%), and 150 to 700 parts by mass (150 to 700%). Is more preferably 200 to 600 parts by mass (200 to 600%). If the graft rate is too small, the adsorption performance to the adsorbed material such as metal ions is often insufficient. When the graft rate is too high, synthesis is generally difficult. In addition, a graft rate shows the value measured by the method described in the Example mentioned later.
  • an adsorptive functional group is introduced into the polymer component P 0 having at least a reactive (meth) acrylate skeleton as a structural unit.
  • the polymer component P 1 can be obtained by introducing an adsorptive functional group to the polymer component P 0 obtained as described above.
  • a compound having an adsorptive functional group may be dissolved in a good solvent of this compound and brought into contact with the polymer component P 0 and reacted, and the reaction conditions such as the compound concentration and reaction time are the types of the polymer component P 0 .
  • the reaction conditions such as the compound concentration and reaction time are the types of the polymer component P 0 .
  • it can be appropriately selected by those skilled in the art.
  • the polymer component P 1 has a (meth) acrylic acid ester skeleton as a structural unit, and has an adsorptive functional group having an adsorptivity to an adsorbent, and thus has a highly polar structure, It becomes a polymer with excellent affinity.
  • the adsorptive functional group to be introduced into the polymer component P 1 can be selected according to the type of the target adsorbate, and is, for example, a chelate-forming group because of its high adsorptivity to metal ions.
  • Glucamine group, diol group, polyol group, group composed of polyol and nitrogen atom, iminodiacetic acid group, amino group, ammonium group, amidoxime group, dithiocarbamic acid group, thiourea group, isothiourea group, phosphoric acid group, phosphonic acid Groups and the like are preferred.
  • These adsorbing functional groups may be used alone or in combination of two or more.
  • the adsorbing functional group may be a functional group introduced by, for example, hydrolysis of a reactive functional group.
  • the complex of polymeric components P 1 and the substrate the above components, for example, there adsorptive functional group is 1.5 mmol / g or more It may be.
  • 2.0 mmol / g or more, more preferably 3.0 mmol / g or more may be introduced.
  • the upper limit can be set as appropriate, but may be about 30 mmol / g from the viewpoint of suppressing swelling.
  • the amount of the adsorbing functional group indicates a value measured by the method described in Examples described later.
  • the polymer component P 0 or P 1 can be crosslinked.
  • a monomer case as described above, to form in the step of forming the polymeric component P 0, with a reactive (meth) acrylic ester backbone of performing crosslinking treatment (I) relative to the polymer component P 0
  • a crosslinked structure can be introduced into the polymer component P 0 .
  • a polymer component P 1 e.g., A part of the adsorptive functional group
  • the cross-linking component may cross-link a part of the adsorptive functional group and cross-link groups other than the other adsorptive functional group in the graft copolymer.
  • the crosslinking treatment (I) in the technique in which a divinyl compound is present as a copolymerization component at the time of radical polymerization of the vinyl compound and the crosslinking treatment is performed simultaneously with the polymerization, the polymerization control is difficult depending on the polymerization method and the shape of the adsorbent to be obtained. Since there is a possibility of inducing problems such as gelation, the method of crosslinking the adsorption functional group of the polymer component P 1 by the crosslinking treatment (II) is more preferable.
  • the crosslinking treatment (II) will be described in detail.
  • the polymer component P 1 is preferably treated by being immersed and stirred in a treatment solution in which a crosslinking agent is dissolved or dispersed.
  • a crosslinking agent is dissolved or dispersed.
  • concentration, temperature, liquid volume and treatment time of the crosslinking treatment liquid having a crosslinking agent are determined based on the polymer component P 1 (and necessary Depending on the kind of the base material component to be added according to the above, it can be appropriately set.
  • the solvent is not particularly limited, and a solvent in which the crosslinking agent is easily dissolved or dispersed can be selected as appropriate. However, an aqueous solvent (particularly water) is preferably used because post-treatment is easy.
  • the reaction temperature can be appropriately set.
  • the temperature for performing the crosslinking treatment may be, for example, about 30 to 100 ° C., preferably about 35 to 90 ° C.
  • cross-linking agents can be used as long as they have cross-linkability to the adsorptive functional group.
  • cross-linking agents having any one or more of amino group, isocyanate group, epoxy group, carbodiimide group, and azetidinium group ( Or a crosslinking component).
  • azetidinium group, isocyanate group, amino group, epoxy group and the like are particularly preferably used because of excellent reactivity with general adsorption functional groups.
  • a crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
  • crosslinking agent having an amino group examples include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, isophoronediamine, 1,3-bisaminomethylcyclohexane.
  • Diamine compounds such as diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, dicyandiamide; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyvinylamine, polyallylamine, polyethyleneimine, polyamidoamine
  • Polyamine compounds such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, 1,3 Bis (hydrazinocarboethyl) -5-isopropyl hydantoin, polyacrylic acid hydrazide, and hydrazine compounds such as hydrazine carbonate is.
  • TDI Tolylene diisocyanate
  • Hydrogenated TDI Trimethylolpropane-TDI adduct for example, “DesmodurL” manufactured by Bayer
  • triphenylmethane triisocyanate methylenebisdiphenyl isocyanate
  • MDI methylenebisdiphenyl isocyanate
  • hydrogenated MDI polymerized MDI; hexamethylene diisocyanate; xylylene diisocyanate; -Dicyclohexylmethane diisocyanate; isophorone diisocyanate and the like.
  • Isocyanates dispersed in water using an emulsifier can also be used.
  • crosslinking agent having an epoxy group examples include “Denacol” (EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, manufactured by Nagase ChemteX Corporation.
  • crosslinking agent having a carbodiimide group examples include “Carbodilite” (SV-02, V-02, V-02-L2, V-04, E-01, E-02) manufactured by Nisshinbo Chemical Co., Ltd.
  • crosslinking agent having an azetidinium group examples include polyamide / epichlorohydrin resin, polyamine / epichlorohydrin resin, and the like, for example, manufactured by Seiko PMC Co., Ltd. (WS4002, WS4020, WS4024, WS4030, WS4046, WS4010, CP8970). ) And the like.
  • the adsorbent of the present invention has an ethylene-vinyl alcohol copolymer as a base material, and a polymer component P 1 having a (meth) acrylate skeleton as a structural unit as a graft unit and having an adsorptive functional group is introduced into the base material. are, the polymer component P 1 is crosslinked by a crosslinking component.
  • the degree of swelling represented by the following formula (I) may be, for example, 50 to 200% from the viewpoint of controlling swelling under hot water while maintaining affinity with water.
  • Swelling degree ⁇ (mass after the adsorbent is shaken in hot water at 70 ° C. for 10 minutes to contain water) ⁇ (absolute dry mass of the adsorbed adsorbent) ⁇ / (absorption of the adsorbed adsorbent) (Dry mass) x 100 (%)
  • the degree of swelling is 150% or less, more preferably 130% or less.
  • the degree of swelling is preferably 60% or more, and more preferably 70% or more. In addition, this swelling degree shows the value measured by the method described in the Example mentioned later.
  • the reason for swelling the adsorbent with hot water of about 70 ° C. is as follows. That is, in the adsorption and recovery operation, it may be brought into contact with a high-temperature medium such as hot water, and the resin is most easily swollen during the operation. For this reason, it is important to control the swelling characteristics at high temperatures from the viewpoint of improving the adsorption and recovery efficiency.
  • the shape of the adsorbent of the present invention is not particularly limited, depending on the application location, from various shapes such as fibers and aggregates of woven and knitted fabrics and nonwoven fabrics, particles, sheets, hollow fibers, and films or processed products thereof. You can choose.
  • the particles are preferably in the form of particles from the viewpoint of improving the adsorptivity with an object to be adsorbed such as metal ions and being easily packed in a closed space such as a column.
  • the adsorbent may be spherical or non-spherical (for example, irregularly shaped particles).
  • the adsorbent When the adsorbent is in the form of particles, it may be appropriately adjusted to the desired particle size by pulverization or the like, but the particle size is preferably 10 ⁇ m to 2000 ⁇ m, more preferably 30 ⁇ m to 1500 ⁇ m, and most preferably 40 ⁇ m to 1000 ⁇ m.
  • the particle diameter When the particle diameter is 10 ⁇ m or less, it is difficult to handle because the fine powder is likely to fly.
  • the particle size is 2000 ⁇ m or more, sufficient adsorption performance may not be obtained.
  • a particle diameter shows the value classified by sieving.
  • the adsorbent may be a porous body.
  • the pores formed on the surface may have an average value of the major axis of about 0.01 ⁇ m to 20 ⁇ m, preferably 0.05 ⁇ m to It may be about 10 ⁇ m, more preferably about 0.1 ⁇ m to 5 ⁇ m, still more preferably about 0.2 ⁇ m to 5 ⁇ m.
  • the average value of the major axis of these pores is a value measured by the method described in the examples described later.
  • the adsorbent of the present invention may contain various additives such as inorganic fine particles, light stabilizers, antioxidants and the like within a range not impairing the effects of the present invention.
  • the adsorbent of the present invention can adsorb various objects to be adsorbed according to the type of adsorbing functional group, and can then efficiently elute and recover the objects to be adsorbed.
  • Preferred adsorbents include, for example, various metals (for example, platinum group metals, gold, silver, copper, nickel, chromium, vanadium, cobalt, lead, zinc, etc.) or valuable metals from solutions containing these metal compounds. It can be used for recovery and removal of harmful metals (for example, mercury, cadmium, etc.) contained in factory wastewater, mine wastewater, hot spring water, and the like.
  • Adsorption functional group amount [mmol / g] ⁇ (Number of adsorption functional groups possessed by reaction substrate) ⁇ (W [g] / reaction substrate molecular weight [g / mol]) ⁇ 1000 ⁇ / resin particle mass after reaction [g]
  • Example 1 90 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., F101) and 10 parts by mass of vinyl alcohol polymer (Kuraray Co., Ltd., PVA205) at a temperature of 210 ° C. using a lab plast mill. Then, the compound obtained by cooling and solidifying the melt was pulverized and classified into particles having a particle diameter of 106 ⁇ m to 212 ⁇ m using a sieve. Further, the obtained particles were stirred in hot water at 100 ° C. for 2 hours to extract only the vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles.
  • a commercially available ethylene-vinyl alcohol copolymer Kuraray Co., Ltd., F101
  • vinyl alcohol polymer Kuraray Co., Ltd., PVA205
  • the average value of the major axis of the pores of the porous particles was 0.27 ⁇ m.
  • the porous particles were irradiated with 100 kGy of ⁇ rays, immersed in an isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 150 minutes for graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and the graft ratio was evaluated to be 351%. Further, the particles were immersed in an aqueous disodium iminodiacetate adjusted to 100 ° C. and reacted for 9 hours.
  • the particles were washed with water and dried to obtain an adsorbent complex (polymer complex P1 and substrate component complex) having an iminodiacetic acid group.
  • the amount of functional groups introduced into the adsorptive complex was 4.6 mmol / g, and the degree of swelling before the crosslinking treatment was 445%.
  • the obtained adsorptive complex was immersed in an aqueous solution of polyamide / epichlorohydrin resin (cross-linking agent “WS4020” manufactured by Seiko PMC Co., Ltd.) adjusted to 60 ° C. and reacted for 1 hour. After the reaction, the particles were washed with water and dried to obtain the target adsorbent.
  • the average value of the long diameter of the pores of the adsorbent was 0.21 ⁇ m.
  • the obtained adsorbent was classified into particles having a particle diameter of 106 ⁇ m to 425 ⁇ m using a sieve, and the degree of swelling was evaluated.
  • a Cu adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 2 A commercially available ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., L104) 80 parts by mass and a vinyl alcohol polymer (Kuraray Co., Ltd., PVA205) 20 parts by mass were tested at a temperature of 210 ° C. using a lab plast mill. Then, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle diameter of 212 ⁇ m to 425 ⁇ m were classified using a sieve. Further, the obtained particles were stirred in hot water at 100 ° C. for 2 hours to extract only the vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles.
  • the average value of the major axis of the pores of the porous particles was 0.41 ⁇ m.
  • the porous particles were irradiated with 30 kGy of ⁇ rays, immersed in an isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 90 minutes to carry out graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated and found to be 258%. Further, the particles were immersed in an aqueous disodium iminodiacetate adjusted to 100 ° C. and reacted for 9 hours.
  • the particles were washed with water and dried to obtain an adsorbent complex having an iminodiacetic acid group.
  • the amount of functional groups introduced into the adsorptive complex was 3.8 mmol / g, and the degree of swelling before the crosslinking treatment was 290%.
  • the obtained adsorptive complex was immersed in an aqueous solution of polyamide / epichlorohydrin resin (cross-linking agent “WS4020” manufactured by Seiko PMC Co., Ltd.) adjusted to 60 ° C. and reacted for 1 hour. After the reaction, the particles were washed with water and dried to obtain the target adsorbent. The average value of the long diameters of the pores of the adsorbent was 0.39 ⁇ m.
  • the obtained adsorbent was classified into particles having a particle diameter of 300 ⁇ m to 500 ⁇ m using a sieve, and the degree of swelling was evaluated.
  • a Cu adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 3 90 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., F101) and 10 parts by mass of a vinyl alcohol polymer (Kuraray Co., Ltd., PVA403) were heated at 210 ° C. using a lab plast mill. After melt-kneading for 3 minutes at a temperature, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle diameter of 212 ⁇ m to 425 ⁇ m were classified using a sieve. Further, the obtained particles were stirred in hot water at 100 ° C. for 2 hours to extract only the vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles.
  • a commercially available ethylene-vinyl alcohol copolymer Kuraray Co., Ltd., F101
  • a vinyl alcohol polymer Kuraray Co., Ltd., PVA403
  • the average value of the major axis of the pores of the porous particles was 0.23 ⁇ m.
  • the porous particles were irradiated with 60 kGy of ⁇ -rays, immersed in an isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 140 minutes for graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated and found to be 310%. Further, the particles were immersed in an isopropanol solution of ethylenediamine adjusted to 80 ° C. and reacted for 1 hour. After the reaction, the particles were washed with water and dried to obtain an adsorptive complex having an amino group.
  • the amount of functional groups introduced into the adsorbent complex was 6.0 mmol / g, and the degree of swelling before the crosslinking treatment was 258%.
  • the obtained adsorptive complex was immersed in an aqueous ethylene glycol diglycidyl ether solution adjusted to 40 ° C. and allowed to react for 1 hour. After the reaction, the particles were washed with water and dried to obtain the target adsorbent. The average value of the long diameter of the pores of the adsorbent was 0.14 ⁇ m.
  • the obtained adsorbent was classified into particles having a particle diameter of 300 ⁇ m to 500 ⁇ m using a sieve, and the degree of swelling was evaluated. In addition, a Pt adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 4 70 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., E105) and 30 parts by mass of vinyl alcohol polymer (Kuraray Co., Ltd., PVA217) were heated at 210 ° C. using a lab plast mill. After melt-kneading for 3 minutes at a temperature, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle size of 106 ⁇ m to 212 ⁇ m were classified using a sieve. Further, the obtained particles were stirred in hot water at 100 ° C. for 2 hours to extract only the vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles.
  • the average value of the major axis of the pores of the porous particles was 0.89 ⁇ m.
  • the porous particles were irradiated with 60 kGy of ⁇ rays, immersed in an isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 90 minutes to carry out graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated to be 323%. Further, the particles were immersed in an isopropanol solution of N- (2-aminoethyl) piperazine adjusted to 80 ° C. and reacted for 1 hour.
  • the particles were washed with water and dried to obtain an adsorptive complex having an amino group.
  • the amount of the functional group introduced into the adsorptive complex was 7.9 mmol / g, and the degree of swelling before the crosslinking treatment was 321%.
  • the obtained adsorptive complex was immersed in an aqueous ethylene glycol diglycidyl ether solution adjusted to 40 ° C. and allowed to react for 1 hour.
  • the particles were washed with water and dried to obtain the target adsorbent.
  • the average value of the long diameter of the pores of the adsorbent was 0.71 ⁇ m.
  • the obtained adsorbent was classified into particles having a particle diameter of 425 ⁇ m to 710 ⁇ m using a sieve, and the degree of swelling was evaluated.
  • a Pt adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 5 90 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., F101) and 10 parts by mass of a vinyl alcohol polymer (Kuraray Co., Ltd., PVA205) were heated at 210 ° C. using a lab plast mill. After melt-kneading for 3 minutes at a temperature, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle size of 106 ⁇ m to 212 ⁇ m were classified using a sieve. Further, the obtained particles were stirred in hot water at 100 ° C. for 2 hours to extract only the vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles.
  • a commercially available ethylene-vinyl alcohol copolymer Kuraray Co., Ltd., F101
  • a vinyl alcohol polymer Kuraray Co., Ltd., PVA205
  • the average value of the major axis of the pores of the porous particles was 0.27 ⁇ m.
  • the porous particles were irradiated with 100 kGy of ⁇ rays, immersed in an isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 150 minutes for graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated and found to be 374%. Further, the particles were immersed in an isopropanol solution of diethylenetriamine adjusted to 80 ° C. and reacted for 1 hour. After the reaction, the particles were washed with water and dried to obtain an adsorptive complex having an amino group.
  • the amount of functional groups introduced into the adsorptive complex was 8.7 mmol / g, and the degree of swelling before the crosslinking treatment was 389%.
  • the obtained adsorptive complex was immersed in an aqueous ethylene glycol diglycidyl ether solution adjusted to 40 ° C. and allowed to react for 1 hour. After the reaction, the particles were washed with water and dried to obtain the target adsorbent. The average long diameter of the adsorbent pores was 0.20 ⁇ m.
  • the obtained adsorbent was classified into particles having a particle diameter of 106 ⁇ m to 425 ⁇ m using a sieve, and the degree of swelling was evaluated.
  • a Pt adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 6 50 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., E105) and 50 parts by mass of vinyl alcohol polymer (Kuraray Co., Ltd., PVA205) were mixed at 210 ° C. with a lab plast mill. After melt-kneading for 3 minutes at a temperature, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle diameter of 1180 ⁇ m to 1400 ⁇ m were prepared using a sieve. Further, the obtained particles were stirred in hot water at 100 ° C. for 2 hours to extract only the vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles.
  • a commercially available ethylene-vinyl alcohol copolymer Kuraray Co., Ltd., E105
  • vinyl alcohol polymer Kuraray Co., Ltd., PVA205
  • the average pore diameter of the pores of the porous particles was 1.56 ⁇ m.
  • the porous particles were irradiated with 60 kGy of ⁇ rays, immersed in an isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 150 minutes for graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated and found to be 340%. Further, the particles were immersed in an isopropanol solution of diethylenetriamine adjusted to 80 ° C. and reacted for 4 hours. After the reaction, the particles were washed with water and dried to obtain an adsorptive complex having an amino group.
  • the functional group introduction amount of the adsorptive complex was 6.9 mmol / g, and the degree of swelling before the crosslinking treatment was 356%.
  • the obtained adsorptive complex was immersed in an aqueous ethylene glycol diglycidyl ether solution adjusted to 40 ° C. and allowed to react for 1 hour. After the reaction, the particles were washed with water and dried to obtain the target adsorbent. The average value of the major axis of the pores of the adsorbent was 1.42 ⁇ m.
  • the obtained adsorbent was classified into particles having a particle diameter of 2100 ⁇ m to 2400 ⁇ m using a sieve, and the degree of swelling was evaluated.
  • a Pt adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 7 The adsorptive complex having iminodiacetic acid groups obtained in the same manner as in Example 1 was immersed in an aqueous solution of polyamide / epichlorohydrin resin (cross-linking agent “WS4020” manufactured by Seiko PMC Co., Ltd.) adjusted to 60 ° C., The reaction was carried out for 1 hour. After the reaction, the particles were washed with water and dried to obtain the target adsorbent. The average long diameter of the adsorbent pores was 0.20 ⁇ m. The obtained adsorbent was classified into particles having a particle diameter of 106 ⁇ m to 425 ⁇ m using a sieve, and the degree of swelling was evaluated. In addition, a Cu adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 8 The adsorptive complex having an amino group obtained in the same manner as in Example 4 was immersed in an aqueous ethylene glycol diglycidyl ether solution adjusted to 40 ° C. and allowed to react for 1 hour. After the reaction, the particles were washed with water and dried to obtain the target adsorbent. The average value of the long diameters of the pores of the adsorbent was 0.69 ⁇ m. The obtained adsorbent was classified into particles having a particle diameter of 425 ⁇ m to 710 ⁇ m using a sieve, and the degree of swelling was evaluated. In addition, a Pt adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 1 The target adsorbent was obtained in the same manner as in Example 1 except that the crosslinking treatment was not performed (functional group introduction amount: 5.04.6 mmol / g). The average long diameter of the adsorbent pores was 0.20 ⁇ m. The obtained adsorbent was classified into particles having a particle diameter of 106 ⁇ m to 425 ⁇ m using a sieve, and the degree of swelling was evaluated. In addition, a Cu adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 2 The target adsorbent was obtained in the same manner as in Example 5 except that the crosslinking treatment was not performed (functional group introduction amount: 10.18.7 mmol / g). The average long diameter of the adsorbent pores was 0.19 ⁇ m. The obtained adsorbent was classified into particles having a particle diameter of 106 ⁇ m to 425 ⁇ m using a sieve, and the degree of swelling was evaluated. In addition, a Pt adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • Example 3 A commercially available ethylene-vinyl alcohol copolymer (E105, manufactured by Kuraray Co., Ltd.) was pulverized, and particles having a particle diameter of 425 ⁇ m to 710 ⁇ m were prepared using a sieve. The particles were irradiated with 10 kGy of ⁇ rays, immersed in an isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 90 minutes for graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and the graft ratio was evaluated to be 11%.
  • E105 ethylene-vinyl alcohol copolymer
  • the particles were immersed in an isopropanol solution of ethylenediamine adjusted to 80 ° C. and reacted for 1 hour. After the reaction, the particles were washed with water and dried to obtain the target adsorbent. The amount of functional group introduced into the adsorbent was 1.2 mmol / g. The obtained adsorbent was classified into particles having a particle diameter of 500 to 710 ⁇ m using a sieve, and the degree of swelling was evaluated. In addition, a Pt adsorption test was performed to evaluate metal adsorption performance. Table 1 shows the particle composition and performance evaluation results.
  • the adsorbent of the present invention exhibits good adsorptivity to metal ions.
  • the swelling property is highly controlled while increasing the amount of the adsorptive functional group, particularly good adsorptivity to metal ions is shown. From the results of these examples, the adsorbent of the present invention is very effective when separating and recovering an adsorbed material such as metal ions.
  • the adsorbent that has not been subjected to the crosslinking treatment is swelled by water absorption, and the amount of adsorbent that can be filled is reduced, so that the adsorption performance per unit volume is significantly reduced.
  • the amount of the adsorbing functional group is reduced as in Comparative Example 3, it is easy to control the swelling, but the adsorption performance is remarkably lowered.
  • the present invention it is possible to provide a new adsorbent that can be used industrially and has high adsorbability while highly controlling resin swelling due to water absorption.
  • the adsorbent can efficiently recover various objects to be adsorbed, such as ions of platinum group metals, gold, silver, copper, nickel, chromium, vanadium, cobalt, lead, zinc, mercury, cadmium and the like.

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Abstract

L'invention concerne un adsorbant capable d'adsorber efficacement des éléments à adsorber tels que ions métalliques et similaires, ainsi qu'un procédé de fabrication d'un tel adsorbant. Cet adsorbant possède: un copolymère de type éthylène - alcool vinylique en tant que matériau de base et un squelette ester d'acide (métha) acrylique en tant qu'unité structurelle, comme branche greffée sur le matériau de base. Un composant polymère possédant un groupe fonctionnel adsorbant est introduit, et ce composant polymère (P1) est réticulé. En outre, un tel adsorbant peut avoir un taux de gonflement, représenté par exemple par la formule (1), compris entre 50 et 200 %.　Taux de gonflement = {(quantité d'adsorbant obtenue après introduction dans une eau à 70℃, cette introduction dans l'eau étant suivie de l'application de secousses pendant 10 min.) - (masse sèche absolue de l'adsorbant introduit dans l'eau) } / (masse sèche absolue de l'adsorbant introduit dans l'eau) x 100 (%) ...(1).
PCT/JP2014/069362 2013-08-01 2014-07-22 Adsorbant et son procédé de fabrication WO2015016103A1 (fr)

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JP2018080329A (ja) * 2016-11-04 2018-05-24 学校法人福岡大学 共重合体および共重合体の製造方法、ならびに前記共重合体を含有するメッキ助剤、ポリエチレン系樹脂の成形品
WO2019131629A1 (fr) * 2017-12-25 2019-07-04 日産化学株式会社 Agent d'élimination de métal et procédé d'élimination de métal pour éliminer les impuretés métalliques en solution
US20210130522A1 (en) * 2019-10-31 2021-05-06 Daikin Industries, Ltd. Graft copolymer and soil resistant composition
WO2023149153A1 (fr) * 2022-02-01 2023-08-10 三菱瓦斯化学株式会社 Agent de récupération de métal du groupe du platine et procédé de récupération de métal du groupe du platine

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Publication number Priority date Publication date Assignee Title
JP2018080329A (ja) * 2016-11-04 2018-05-24 学校法人福岡大学 共重合体および共重合体の製造方法、ならびに前記共重合体を含有するメッキ助剤、ポリエチレン系樹脂の成形品
JP7090869B2 (ja) 2016-11-04 2022-06-27 学校法人福岡大学 樹脂成形品のメッキ処理方法、およびメッキ助剤、ならびにポリエチレン系樹脂の成形品
WO2019131629A1 (fr) * 2017-12-25 2019-07-04 日産化学株式会社 Agent d'élimination de métal et procédé d'élimination de métal pour éliminer les impuretés métalliques en solution
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US20210130522A1 (en) * 2019-10-31 2021-05-06 Daikin Industries, Ltd. Graft copolymer and soil resistant composition
US11566095B2 (en) * 2019-10-31 2023-01-31 Daikin Industries. Ltd. Graft copolymer and soil resistant composition
WO2023149153A1 (fr) * 2022-02-01 2023-08-10 三菱瓦斯化学株式会社 Agent de récupération de métal du groupe du platine et procédé de récupération de métal du groupe du platine

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