WO2015137451A1 - Polymère, adsorbant, et procédé de production dudit polymère - Google Patents

Polymère, adsorbant, et procédé de production dudit polymère Download PDF

Info

Publication number
WO2015137451A1
WO2015137451A1 PCT/JP2015/057308 JP2015057308W WO2015137451A1 WO 2015137451 A1 WO2015137451 A1 WO 2015137451A1 JP 2015057308 W JP2015057308 W JP 2015057308W WO 2015137451 A1 WO2015137451 A1 WO 2015137451A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
polymer
adsorbent
particles
group
Prior art date
Application number
PCT/JP2015/057308
Other languages
English (en)
Japanese (ja)
Inventor
雄介 天野
圭介 森川
拓未 高山
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Publication of WO2015137451A1 publication Critical patent/WO2015137451A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • 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
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated 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
    • 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
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated 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
    • 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
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
    • 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
    • B01J20/3231—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
    • 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
    • B01J20/3231—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
    • B01J20/3276—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
    • B01J20/30—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
    • B01J20/3278—Polymers being grafted on the carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/18—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to irradiated or oxidised macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/405—Impregnation with polymerisable compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/046—Elimination of a polymeric phase
    • C08J2201/0462—Elimination of a polymeric phase using organic solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/046—Elimination of a polymeric phase
    • C08J2201/0464—Elimination of a polymeric phase using water or inorganic fluids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00—Foams characterised by their intended use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/104—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/106—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a polymer into which a diglycolamide group is introduced that makes it possible to efficiently adsorb various rare earth elements, for example, an adsorbent containing the polymer, and a method for producing the same.
  • Rare earth magnets especially known as neodymium (Nd) magnets, are also in demand for various motors and sensors used in hybrid cars, and development of efficient recovery and recycling methods for rare earth elements from recovered products and scrap. Is desired.
  • Nd neodymium
  • a solvent extraction method is known as a method capable of mass processing, and in this processing method, several proposals have been made as a method for recovering rare earth metals.
  • a method of extracting a rare earth element with an extractant having a diglycolamide skeleton is known.
  • Patent Documents 1 and 2 the solvent extraction method requires a large amount of an organic solvent in the extraction layer and has a large environmental load.
  • the extraction efficiency from a processing solution having a low concentration of rare earth elements is very high in recovery efficiency. Have the fundamental problem of being bad.
  • Non-Patent Document 1 proposes a rare earth element adsorbent in which a diglycolamide skeleton is introduced into silica gel.
  • Non-Patent Document 1 is silica gel
  • the adsorbent is unsuitable for a method of burning the adsorbent together and recovering the target metal, and no elution method has been reported.
  • an object of the present invention is to provide an adsorbent capable of recovering adsorbed metal by combustion and having high adsorption performance. More specifically, the present invention provides a novel polymer useful as a rare earth element recovery material, an adsorbent containing the polymer, and a method for producing the same.
  • the inventors of the present invention have intensively studied to achieve the above object, and as a result, by obtaining a polymer in which a diglycolamide group is introduced into a specific resin, it is possible to recover the adsorbed metal by combustion and high
  • the present inventors have found that an adsorbent having rare earth element adsorption performance can be obtained, and have reached the present invention.
  • the present invention relates to olefin resins, styrene resins, phenol resins, water-insoluble modified vinyl alcohol resins, amide resins, cellulose resins, chitosan resins, (meth) acrylic resins, and (meth). It is a polymer in which a diglycolamide group is introduced into at least one resin selected from the group consisting of acrylic ester resins.
  • the polymer of the present invention is preferably a graft polymer in which a diglycolamide group is introduced into a graft chain.
  • the polymer preferably has a diglycolamide group introduction amount of 1.0 mmol / g to 20.0 mmol / g.
  • the resin used for the polymer is preferably at least one resin selected from the group consisting of a cellulose resin, a chitosan resin, and a water-insoluble modified vinyl alcohol resin.
  • the water-insoluble modified vinyl alcohol resin is preferably an ethylene-vinyl alcohol copolymer.
  • the polymer is preferably an adsorbent.
  • the adsorbent preferably has a particle shape and a particle size of 10 ⁇ m to 2000 ⁇ m.
  • the adsorbent is preferably porous and has pores with an average pore diameter of 0.01 ⁇ m to 50 ⁇ m on the surface.
  • the adsorbent is preferably a rare earth element adsorbent.
  • the polymer production method of the present invention is preferably a production method in which a graft chain is introduced using ionizing radiation.
  • the polymer of the present invention can be processed into a desired shape such as particles, fibers, films, boards, etc., for example, solid phase extraction of metal ions, particularly rare earth elements, and recovery of the target metal by combustion after adsorption. Is possible. Moreover, according to the method for producing a polymer of the present invention, a polymer having excellent performance as described above can be produced efficiently.
  • the polymer of the present invention includes an olefin resin, a styrene resin, a phenol resin, a water-insoluble modified vinyl alcohol resin, an amide resin, a cellulose resin, a chitosan resin, a (meth) acrylic acid resin, and a (meta) ) It can be obtained by introducing a diglycolamide group using at least one resin selected from the group consisting of acrylic ester resins as a backbone polymer (base material).
  • olefin resin used in the present invention examples include halogenated polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and polyvinylidene fluoride.
  • styrene resin examples include polystyrene and crosslinked polystyrene.
  • Cross-linked polystyrene is a cross-linked copolymer of monovinyl aromatic compounds such as styrene, vinyl xylene, vinyl naphthalene and chloromethyl styrene and polyvinyl aromatic compounds such as divinyl benzene, divinyl toluene, divinyl xylene, divinyl naphthalene and trivinyl benzene. It is a coalescence.
  • Phenol resins include phenols such as phenol, ethylphenol, propylphenol, isopropylphenol, t-butylphenol, t-amylphenol, n-hexylphenol, phenylphenol, o-, m-, and p-cresol, benzaldehyde, It is a polycondensate with aldehydes such as naphthylaldehyde and biphenylaldehyde.
  • the water-insoluble modified vinyl alcohol resin is a water-insoluble modified vinyl alcohol resin, and examples thereof include ethylene-vinyl alcohol copolymers, polyvinyl acetals such as polyvinyl butyral, and the like.
  • these modified vinyl alcohol resins are insoluble in hot water at 100 ° C.
  • the amide resin include nylon 6; nylon 6,6; nylon 6,10; nylon 6,12; nylon 11; nylon 12;
  • the cellulose resin include cellulose (pulp, cotton linter, regenerated cellulose, etc.) and cellulose acylates such as cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, and cellulose acetate propionate.
  • Chitosan-based resins include (1 ⁇ 4) -2-acetamido-2-deoxy- ⁇ -D-glucan partially partially deacetylated structures of chitin, and deacetylated amino groups of the structures Or a chitosan derivative in which a part of the hydroxyl group in the same molecule is chemically modified by an acylation reaction, an etherification reaction, an esterification reaction, or other reactions.
  • the (meth) acrylic resin include poly (meth) acrylic acid or a neutralized salt thereof, and various copolymers such as (meth) acrylic acid and styrene.
  • (meth) acrylic acid ester resins include poly (meth) acrylic acid methyl, poly (meth) acrylic acid ethyl, poly (meth) acrylic acid propyl, (meth) acrylic acid ester and (meth) acrylic acid, styrene, etc. And various copolymers.
  • cellulose resins cellulose resins, chitosan resins, and water-insoluble vinyl alcohol resins having excellent hydrophilicity are preferable. Since these resins have high hydrophilicity, when used as a rare earth element adsorbing material according to one aspect of the present invention, the rare earth metal elements in the treatment liquid are easily diffused inside the resin, which is advantageous for adsorption.
  • an ethylene-vinyl alcohol copolymer that is excellent in water resistance, moldability, and combustibility is more preferable.
  • the ethylene-vinyl alcohol copolymer used as the resin of the present invention is not particularly limited.
  • the ethylene content may be about 10 to 60 mol%, preferably about 20 to 50 mol%.
  • the water resistance of the obtained rare earth element adsorbent may be lowered.
  • the ethylene content exceeds 60 mol%, it is difficult to produce and difficult to obtain.
  • 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 less than 90 mol%, the moldability may be deteriorated or the water resistance of the obtained rare earth element adsorbent 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 / min or more, and more preferably 0.5 g / min or more. If it is less than 0.1 g / min, 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, 25 g / min or less may be sufficient.
  • 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.
  • a diglycolamide group is introduced as an adsorption functional group. Due to the high adsorption performance of the functional group, the polymer of the present invention can adsorb the target metal ion efficiently from the treatment liquid when used, for example, for extraction of metal ions.
  • the diglycolamide group may be directly introduced into the above resin, but from the viewpoint of adsorption performance, the above resin is used as a backbone polymer to introduce a graft chain into the side chain, and the diglycolamide group is introduced into the graft chain. It is preferable to do.
  • the functional groups By introducing diglycolamide groups into the graft chain, the functional groups can be densely packed and the adsorption efficiency can be increased.
  • the graft chain can be formed by the method described later.
  • the amount of diglycolamide group introduced in the present invention is not particularly limited, but from the viewpoint of adsorption performance, 1.0 mmol / g to 20.0 mmol / g It is preferably 2.0 mmol / g to 10.0 mmol / g, more preferably 3.0 mmol / g to 7.0 mmol / g.
  • the introduction amount is less than 1.0 mmol / g, the adsorption performance may not be sufficiently obtained.
  • the number of moles of the functional group exceeds 20.0 mmol / g, it is difficult to suppress swelling of the polymer, and it is often difficult to manufacture.
  • a method of introducing a graft chain using radical polymerization using a polymerization initiator, or generation of a radical using ionizing radiation As the method for high graft chain introduction efficiency, a method of introducing a graft chain using ionizing radiation is preferably used. In particular, by using a porous trunk polymer, a functional group can be efficiently introduced by graft polymerization.
  • 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.
  • a mixed irradiation method of irradiating radiation in the presence of the trunk polymer and unsaturated monomers, or radiation to only the trunk polymer in advance is possible, the pre-irradiation method, which is the latter method, has a feature that it is difficult to generate side reactions other than graft polymerization.
  • a liquid phase polymerization method in which a liquid unsaturated monomer or an unsaturated monomer solution is brought into direct contact with the unsaturated monomer
  • a gas phase graft polymerization method in which the body is contacted in a vapor or vaporized state, but it can be selected according to the purpose.
  • the dose of ionizing radiation is not particularly limited, but is preferably 5 to 230 kGy, more preferably 10 to 190 kGy, further preferably 15 to 140 kGy, and most preferably 20 to 100 kGy. If the dose is less than 5 kGy, the dose is too small and the graft rate may decrease, and the desired adsorption performance may not be obtained. In the case of 230 kGy or more, there are concerns that the treatment process is costly and the resin deteriorates during irradiation.
  • an unsaturated monomer having a diglycolamide group may be grafted, or an unsaturated monomer having a reactive group may be grafted using ionizing radiation. May be converted to a diglycolamide group.
  • graft polymerization When graft polymerization is performed, other unsaturated monomers may be used in addition to the target unsaturated monomer as long as the performance is not impaired.
  • unsaturated monomers for example, divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, bismethylene acrylamide and the like can be used.
  • the solvent temperature at the start of polymerization is preferably 20 ° C. or less, and more preferably 10 ° C. or less. If the temperature exceeds 20 ° C., the amount of unsaturated monomer introduced may not be stable, or a sufficient amount introduced may not be ensured.
  • the trunk polymer is an ethylene-vinyl alcohol copolymer, it is not necessary to lower the solvent temperature at the start of polymerization as described above.
  • the polymer of the present invention can be used as an adsorbent for organic bases, polymers, metal ions, etc., because diglycolamide groups having excellent adsorption properties for various target substances are introduced. Further, among the above-mentioned adsorption target substances, since they are excellent in adsorption characteristics of rare earth elements such as scandium (Sc), neodymium (Nd), dysprosium (Dy), they are particularly preferably used as a rare earth element adsorbent.
  • rare earth elements such as scandium (Sc), neodymium (Nd), dysprosium (Dy)
  • the adsorbent of the present invention can be used in a state of being processed into various shapes. Specific examples include particles, fibers, films, and boards. If the adsorbent is in the form of particles, after the adsorbent particles are packed in the column and passed through the solution containing the adsorption target substance or put into the solution containing the adsorption target substance, the adsorption target substance is adsorbed Use it by pulling it up. When the adsorbent is fibrous, the adsorbent fibers are wound around a cylindrical core having a hole on the side, and the solution containing the substance to be adsorbed is passed from the inside of the cylinder to the outside or vice versa.
  • the material fibers into appropriate lengths and fill the column, and pass the solution containing the substance to be adsorbed, or process the adsorbent fibers into sheets of paper, nonwoven fabric, woven fabric, etc.
  • the column is packed and used by passing a solution containing the substance to be adsorbed.
  • the adsorbent is a film or a board, the adsorbent is cut into a desired length, put into a solution containing the substance to be adsorbed, pulled up after adsorbing the substance to be adsorbed, etc.
  • the adsorbent is preferably particulate.
  • the particle diameter is preferably 10 ⁇ m to 2000 ⁇ m, more preferably 30 ⁇ m to 1500 ⁇ m, and even more preferably 50 ⁇ m to 1200 ⁇ m.
  • the particle diameter is less than 10 ⁇ m, it is difficult to handle, for example, the fine powder easily floats.
  • the particle diameter is larger than 2000 ⁇ m, the adsorption performance of the substance to be adsorbed may not be sufficiently obtained.
  • a particle diameter shows the value classified by sieving.
  • the term “particulate” is a concept including powder.
  • the adsorbent of the present invention may be a porous body from the viewpoint of adsorption performance.
  • the term “porous” means that a plurality of pores are present in the polymer molded product.
  • the pores may have a continuous structure or an independent structure. Furthermore, the pore does not need to be formed to the inside of the adsorbent.
  • the pores formed on the surface may have an average pore diameter of about 0.01 ⁇ m to 50 ⁇ m, preferably 0.05 ⁇ m to 20 ⁇ m, more preferably about 0.2 ⁇ m to 10 ⁇ m. When the average pore diameter is less than 0.01 ⁇ m, there is a possibility that sufficient adsorption performance cannot be obtained. If the average pore diameter is larger than 50 ⁇ m, the mechanical strength of the adsorbent is low and the adsorbent may collapse. The average pore diameter of these pores is a value measured by the method described in the examples described later.
  • adsorbent of the present invention Since the adsorbent of the present invention is excellent in combustibility, when recovering the adsorption target substance, a method of combusting and ashing the adsorbent and taking out the adsorption target substance is preferably used. A method in which a high eluent and an adsorbent are brought into contact with each other to elute and recover the substance to be adsorbed from the adsorbent can also be applied.
  • the polymer of the present invention may contain additives such as a crosslinking agent, inorganic fine particles, a light stabilizer, and an antioxidant as long as the effects of the present invention are not impaired.
  • Metal adsorption rate 100 mg of the adsorbent is put into 20 mL of a 3N nitric acid solution having a target metal concentration of 0.02 mmol / L and stirred at 25 ° C. for 60 minutes. Thereafter, 1 mL of the solution is sampled and made up to 50 mL, and the metal concentration measured with an ICP emission analyzer (manufactured by Niger Jarrel Ash, IRIS-AP) is defined as C (mmol / L).
  • the metal adsorption rate is obtained from the following equation.
  • thermogravimetric measuring device “Thermo Plus TG8120” manufactured by Rigaku Denki Co., Ltd.
  • the reduction rate was 95% or more as A, 80 to 95% as B, 50 to 80% as C, and 50% or less as D and used as a combustibility index.
  • Example 1 After melt-kneading 90 parts by mass of commercially available polyethylene (7000F manufactured by Prime Polymer Co., Ltd.) and 10 parts by mass of polyvinylpyrrolidone (manufactured by BASF, Kollidon CL-M) at a temperature of 230 ° C. for 3 minutes, The compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle size of 212 ⁇ m to 425 ⁇ m were prepared using a sieve. Further, the obtained particles were stirred in isopropanol at 80 ° C. for 2 hours to extract only polyvinylpyrrolidone to obtain porous polyethylene polymer particles.
  • the porous particles were irradiated with ionizing radiation of 100 kGy, immersed in a 20% by mass isopropanol solution of glycidyl methacrylate substituted with nitrogen at 0 ° C., stirred for 60 minutes, and then heated to 80 ° C. to carry out graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and the graft ratio was evaluated to be 206%. Furthermore, this particle
  • the particles were washed with methanol and dried, then immersed in a dioxane solution of diglycolic anhydride adjusted to 80 ° C., and reacted for 2 hours. After the reaction, the particles were washed with methanol and dried to obtain a polymer having a diglycolamide group introduced.
  • the average pore diameter of the particles was 2.4 ⁇ m, and the functional group amount was 2.3 mmol / g.
  • Example 2 Commercially available nylon 6 (manufactured by Selva, polyamide-6-powder) was melt-kneaded at a temperature of 230 ° C. for 3 minutes in a lab plast mill, then the compound obtained by cooling and solidifying the melt was pulverized and sieved Particles having a particle size of 300 ⁇ m to 500 ⁇ m were prepared. The particles were irradiated with ionizing radiation of 100 kGy, immersed in a 40% by mass isopropanol solution of glycidyl methacrylate substituted with nitrogen at 0 ° C., stirred for 60 minutes, and then heated to 80 ° C. to carry out graft polymerization.
  • the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated to be 94%. Furthermore, this particle
  • Example 3 A commercially available ethylene-vinyl alcohol copolymer (F101, manufactured by Kuraray Co., Ltd.) was pulverized, and particles having a particle diameter of 106 ⁇ m to 212 ⁇ m were prepared using a sieve. The particles were irradiated with 100 kGy of ionizing radiation, immersed in a 40% by mass isopropanol solution of glycidyl methacrylate substituted with nitrogen at 70 ° C., and graft polymerization was performed for 300 minutes. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated and found to be 171%.
  • F101 ethylene-vinyl alcohol copolymer
  • the particles were immersed in a 40% by mass isopropanol solution of diethylenetriamine adjusted to 80 ° C. and reacted for 2 hours. After the reaction, the particles were washed with methanol and dried, then immersed in a dioxane solution of diglycolic anhydride adjusted to 80 ° C., and reacted for 2 hours. After the reaction, the particles were washed with methanol and dried to obtain a rare earth element adsorbent containing a polymer having a diglycolamide group introduced. The functional group amount of the particles was 4.9 mmol / g.
  • Example 4 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) were used at a temperature of 210 ° C. at a lab plast mill. After melt-kneading for 3 minutes, the compound obtained by cooling and solidifying the melt was pulverized and classified into particles having a particle diameter of 150 ⁇ m to 300 ⁇ 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 porous particles were irradiated with 150 kGy of ⁇ rays, immersed in a 60% by mass isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and graft polymerization was performed for 300 minutes. 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 a 40% by mass isopropanol solution of diethylenetriamine adjusted to 80 ° C. and reacted for 2 hours.
  • the particles were washed with methanol and dried, then immersed in a dioxane solution of diglycolic anhydride adjusted to 80 ° C., and reacted for 2 hours. After the reaction, the particles were washed with methanol and dried to obtain a rare earth element adsorbent containing a polymer having a diglycolamide group introduced.
  • the average pore diameter of the particles was 0.2 ⁇ m, and the functional group amount was 5.3 mmol / g.
  • Example 5 60 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., L104) and 40 parts by mass of a vinyl alcohol polymer (Kuraray Co., Ltd., PVA217) were heated at 210 ° C. using a lab plast mill. After melt-kneading at temperature for 3 minutes, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle diameter of 710 ⁇ m to 1100 ⁇ 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.
  • the porous particles were irradiated with 60 kGy of ⁇ rays, immersed in a 60% by mass isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and graft polymerization was performed for 300 minutes. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated to be 498%. Furthermore, this particle
  • the particles were washed with methanol and dried, then immersed in a dioxane solution of diglycolic anhydride adjusted to 80 ° C., and reacted for 2 hours. After the reaction, the particles were washed with methanol and dried to obtain a rare earth element adsorbent containing a polymer having a diglycolamide group introduced.
  • the average pore diameter of the particles was 2.6 ⁇ m, and the functional group amount was 2.6 mmol / g.
  • Example 6 A commercially available weakly basic ion exchange resin of styrene resin (WA20 manufactured by Mitsubishi Chemical Corporation) was dried at 40 ° C. overnight with a vacuum dryer. The obtained dried particles were immersed in a dioxane solution of diglycolic anhydride adjusted to 80 ° C. and reacted for 2 hours. After the reaction, the particles were washed with methanol and dried to obtain a polymer having a diglycolamide group introduced. The average pore diameter of the particles was 0.05 ⁇ m, and the functional group amount was 2.0 mmol / g.
  • Table 1 shows the results of evaluating the metal adsorption performance and the combustibility after classifying the polymer of Example 1 into particles having a diameter of 425 ⁇ m to 710 ⁇ m using a sieve.
  • Example 8 Table 1 shows the results of evaluating the metal adsorption performance and flammability after classifying the polymer of Example 3 into particles having a diameter of 212 to 300 ⁇ m using a sieve.
  • Table 1 shows the results of evaluating the metal adsorption performance and flammability after classifying the polymer of Example 4 into particles having a diameter of 300 ⁇ m to 500 ⁇ m using a sieve.
  • Table 1 shows the results of evaluating the metal adsorption performance and flammability after classifying the polymer of Example 5 into particles having a diameter of 1200 ⁇ m to 1500 ⁇ m using a sieve.
  • Example 11 The polymer of Example 6 was classified into particles having a diameter of 710 ⁇ m to 1200 ⁇ m using a sieve, and the results of evaluating metal adsorption performance and combustibility are shown in Table 1.
  • Table 1 shows the results of evaluating the metal adsorption performance and the flammability after the polymer of Comparative Example 1 was classified into particles having a diameter of 50 ⁇ m to 106 ⁇ mm using a sieve.
  • the polymer having a diglycolamide group of the present invention exhibits excellent rare earth element adsorption performance and good combustibility. Therefore, when separating and recovering rare earth elements, It was very effective.
  • an ethylene-vinyl alcohol copolymer which is a water-insoluble modified vinyl alcohol resin, was used as the resin, the metal adsorption rate was high and the flammability was excellent (Examples 8 to 10).
  • Comparative Example 2 the polymer containing no diglycolamide group did not exhibit metal element adsorption performance. Further, as in Comparative Example 3, it was difficult for the adsorbent composed of silica to recover the target metal by combustion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Le problème abordé par la présente invention est de pourvoir à un polymère qui permet l'extraction en phase solide d'un ion métallique, en particulier d'un élément de terres rares, et à partir duquel un métal d'intérêt peut être récupéré par combustion du polymère après adsorption du métal d'intérêt sur le polymère. La solution selon l'invention porte sur un polymère obtenu par introduction d'un groupe amide de diglycol dans au moins une résine choisie dans le groupe constitué par une résine oléfinique, une résine styrénique, une résine phénolique, une résine alcool vinylique modifiée insoluble dans l'eau, une résine amide, une résine cellulosique, une résine chitosane, une résine acide (méth)acrylique et une résine ester d'acide (méth)acrylique.
PCT/JP2015/057308 2014-03-13 2015-03-12 Polymère, adsorbant, et procédé de production dudit polymère WO2015137451A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014050289 2014-03-13
JP2014-050289 2014-03-13

Publications (1)

Publication Number Publication Date
WO2015137451A1 true WO2015137451A1 (fr) 2015-09-17

Family

ID=54071888

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/057308 WO2015137451A1 (fr) 2014-03-13 2015-03-12 Polymère, adsorbant, et procédé de production dudit polymère

Country Status (1)

Country Link
WO (1) WO2015137451A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016047705A1 (fr) * 2014-09-24 2016-03-31 日東電工株式会社 Monomère de vinyle ayant un ligand de type acide diglycolamidique
WO2020251000A1 (fr) * 2019-06-13 2020-12-17 昭和電工マテリアルズ株式会社 Particules adsorbantes, particule de base, colonne garnie, et procédé de récupération d'élément des terres rares

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070163957A1 (en) * 2002-09-30 2007-07-19 Horwitz E P Multivalent metal ion extraction using diglycolamide-coated particles
JP2008529014A (ja) * 2005-01-31 2008-07-31 ベックマン コールター インコーポレイテッド 添加物含有シリカを用いたマイクロスフェア型光イオン・センサ
JP2009503054A (ja) * 2005-08-04 2009-01-29 コミサリア ア レネルジィ アトミーク フルオレセイン系化合物およびペプチド合成のためのその使用
JP2010515762A (ja) * 2007-01-16 2010-05-13 エンゾン ファーマスーティカルズ インコーポレイテッド ポサコナゾール−ポリマー複合体、並びに、ポサコナゾールおよびそのポリマー複合体を使用した治療方法
JP2012012369A (ja) * 2010-07-05 2012-01-19 Shin-Etsu Chemical Co Ltd 希土類金属抽出剤の合成方法
JP2013533459A (ja) * 2010-04-30 2013-08-22 アルゲッタ エイエスエイ 同位体の製造方法
WO2014157225A1 (fr) * 2013-03-25 2014-10-02 独立行政法人産業技術総合研究所 Adsorbant pour un élément des terres rares et procédé de récupération d'un élément des terres rares

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070163957A1 (en) * 2002-09-30 2007-07-19 Horwitz E P Multivalent metal ion extraction using diglycolamide-coated particles
JP2008529014A (ja) * 2005-01-31 2008-07-31 ベックマン コールター インコーポレイテッド 添加物含有シリカを用いたマイクロスフェア型光イオン・センサ
JP2009503054A (ja) * 2005-08-04 2009-01-29 コミサリア ア レネルジィ アトミーク フルオレセイン系化合物およびペプチド合成のためのその使用
JP2010515762A (ja) * 2007-01-16 2010-05-13 エンゾン ファーマスーティカルズ インコーポレイテッド ポサコナゾール−ポリマー複合体、並びに、ポサコナゾールおよびそのポリマー複合体を使用した治療方法
JP2013533459A (ja) * 2010-04-30 2013-08-22 アルゲッタ エイエスエイ 同位体の製造方法
JP2012012369A (ja) * 2010-07-05 2012-01-19 Shin-Etsu Chemical Co Ltd 希土類金属抽出剤の合成方法
WO2014157225A1 (fr) * 2013-03-25 2014-10-02 独立行政法人産業技術総合研究所 Adsorbant pour un élément des terres rares et procédé de récupération d'un élément des terres rares

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANYUN ZHANG ET AL.: "Preparation of a Novel Macroporous Silica-based Diglycolamide Derivative-impregnated Polymeric Composite and its Adsorption Mechanism for Rare Earth Metal Ions", ADSORPTION SCIENCE & TECHNOLOGY, vol. 25, no. 5, pages 257 - 272 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016047705A1 (fr) * 2014-09-24 2016-03-31 日東電工株式会社 Monomère de vinyle ayant un ligand de type acide diglycolamidique
JP2016065134A (ja) * 2014-09-24 2016-04-28 日東電工株式会社 ジグリコールアミド酸型配位子を有するビニルモノマー
WO2020251000A1 (fr) * 2019-06-13 2020-12-17 昭和電工マテリアルズ株式会社 Particules adsorbantes, particule de base, colonne garnie, et procédé de récupération d'élément des terres rares
CN113993618A (zh) * 2019-06-13 2022-01-28 昭和电工材料株式会社 吸附材料粒子、基材粒子、填充柱及回收稀土元素的方法
JP7476894B2 (ja) 2019-06-13 2024-05-01 株式会社レゾナック 吸着材粒子、基材粒子、充填カラム、及び、希土類元素を回収する方法
CN113993618B (zh) * 2019-06-13 2024-05-24 株式会社力森诺科 吸附材料粒子、基材粒子、填充柱及回收稀土元素的方法

Similar Documents

Publication Publication Date Title
Wang et al. Enhanced selective removal of Cu (II) from aqueous solution by novel polyethylenimine-functionalized ion imprinted hydrogel: Behaviors and mechanisms
KR100861452B1 (ko) 중금속 이온의 선택적 분리를 위한 표면 각인된 코어-쉘형태의 폴리아크릴레이트 미소구체의 제조 방법
US9943825B2 (en) Porous graft copolymer particles, method for producing same, and adsorbent material using same
Liu et al. Synthesis of porous acrylonitrile/methyl acrylate copolymer beads by suspended emulsion polymerization and their adsorption properties after amidoximation
JP5590594B2 (ja) キレート性高分子化合物含有金属吸着材
Lin et al. Enhanced and selective adsorption of Hg2+ to a trace level using trithiocyanuric acid-functionalized corn bract
JP5045269B2 (ja) 粒子状セルロース系吸着材及びその製造方法
JP2010540714A (ja) 化学結合クラウンエーテルを有する非イオン性多孔性の小さい固体樹脂
WO2015137451A1 (fr) Polymère, adsorbant, et procédé de production dudit polymère
Yang et al. Preparation and evaluation of bis (diallyl alkyl tertiary ammonium salt) polymer as a promising adsorbent for phosphorus removal
JP2005097545A (ja) 多孔質樹脂ビーズおよびその製造方法
KR101016231B1 (ko) 선택적으로 중금속 이온을 분리할 수 있는 다공성 각인 고분자 입자의 제조방법
Ali et al. Study on the synthesis of a macroporous ethylacrylate‐divinylbenzene copolymer, its conversion into a bi‐functional cation exchange resin and applications for extraction of toxic heavy metals from wastewater
Hoai et al. Synthesis, structure, and selective separation behavior of copper‐imprinted microporous polymethacrylate beads
Huang et al. Preparation of ultrahigh‐water‐content nanofiber composite hydrogel for Cd2+ removal
Kaikake et al. Theophylline-bearing microspheres with dual features as a coordinative adsorbent and catalytic support for palladium ions
KR102325730B1 (ko) 보론 흡착능력이 향상된 보론 흡착용 랜덤 공중합 킬레이트 수지 및 이의 제조방법
JP2014198330A (ja) 金イオン吸着材、その製造方法及び金の回収方法
JP2014114436A (ja) エチレン−ビニルアルコール系共重合体のグラフト共重合体、その製造方法及びそれを用いた金属吸着材
JP6139962B2 (ja) エチレン−ビニルアルコール系共重合体のグラフト共重合体、その製造方法及びそれを用いた金属吸着材
KR101776369B1 (ko) 금속이온에 대한 흡착능이 우수한 고분자 및 그 제조방법
KR101776370B1 (ko) 금속이온에 우수한 흡착능을 가지고 재사용이 가능한 고분자 캡슐 흡착제 및 그 제조방법
JP6147175B2 (ja) エチレン−ビニルアルコール系グラフト共重合体粒子、その製造方法及び金属イオン吸着材
JP2001038202A (ja) ガス吸着剤
JP6147162B2 (ja) エチレン−ビニルアルコール系共重合体のグラフト共重合体、その製造方法及びそれを用いた金属イオン吸着材

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15762088

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15762088

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP