Porous graft copolymer particles, method for producing same, and adsorbent material using same

Related application

The application that the Japanese application 30 October 2012 hopes especially 2012-238998,2012 years 11 month 15 hopes especially application Japan 2012-250757,2012 years 11 month 15 hopes especially application Japan 2012-250758,2013 years 1 month 23 hopes especially application Japan 2013-10411,2013 years 3 month 14 hopes especially application Japan 2013-51931 and the Japanese applications 31 July 2013 hopes especially 2013-158515 priority, the application specification and referenced by reference to all of the content as a part of this application.

Technical Field

The present invention relates to porous graft copolymer particles, using the same method of manufacturing the same and the adsorption material, the porous graft copolymer particles in the grafted chain can be high-efficiently the adsorption and the recovery of platinum group metal is representative in various metal adsorbing functional group.

Background Art

In recent years, the rare metal, and the like with the increasing demand for the metal resources by resource nationalist (  nationalism resource) restrictions caused by under the action of the supply of, lead to instability of the supply, such as prices in market unstable. In this case, positive on the use of the re-use of the product, the construction of the structure, and in the recovery, smelting process to reduce the loss in the development of technology.

From the metal-containing material as in the method of separating and recovering the metallic, known electrolytic refining method, coherencies precipitation method, solvent extraction method, the adsorption method. Wherein recovery of the opinion that the use of the adsorbing material of the adsorption process is suitable for implementation in the industry, for the various studies.

As the adsorbing material, the extensive use of the metal recovery high affinity to the ion-exchange groups, or chelate compound to form a group of high molecular substrate is introduced into the adsorption material, however, the adsorption material has the following problems: high molecular matrix usually reactive is low, and the number of the functional group can be introduced, such as types of restrictions.

In order to overcome this problem, the known radiation through the use of the graft polymerization of the porous polyolefin sheet introduced in the grafted chain containing adsorptive functional group as the ion exchange group or method for forming group of the chelate compound obtained by the method of example of adsorption material (Patent literature 1). Furthermore, known the following example: the function of with load extracting reagent in the graft polymerization of a polymerizable monomer to a substrate surface, in the porous film so as to obtain the extraction reagent load on the metal ion adsorption material (Patent literature 2).

Furthermore, known through the following through the polymer blend method of direct into adsorptive functional group to obtain particulate metal (in particular, the platinum group metal) examples of ion adsorbing material, through the polymer blend to the adsorptive functional group is introduced into the method is as follows: through the comprising polyethylene imine, ethylene-vinyl alcohol copolymer composition, or containing polyethylene imine, ethylene-vinyl alcohol copolymer and amine polymer composition is extruded and formed into a linear, then crushed processing (Patent document 3).

Furthermore, in Patent literature 4 discloses a kind of anionic permutoid, the ethylene-vinyl alcohol copolymer is introduced into the irradiation of ionizing radiation graft chain having quaternary ammonium groups. In the literature of the embodiment, the ethylene-vinyl alcohol copolymer irradiation of ionizing radiation, the result of grafting to 60% quaternary ammonium group is introduced.

Literature of the prior art

Patent literature

Patent literature 1: Japanese opens especially 2009-101289, the

Patent document 2: Japanese opens especially 2005-331510, the

Patent literature 3: Japanese opens especially 2012-67267, the

Patent literature 4: Japan opens especially 2010-1392, the

Content of the invention

Subject to be solved by the invention

However, Patent literature 1 absorption material is recorded on the sheet, therefore is not suitable for use in filling, for example, of to the column, a restricted mode in use. Furthermore, the use of sheet korematsu a relatively low density of the hollow fiber sheet, the introduction amount of the functional group per unit volume is less, in adsorption performance are not fully.

Furthermore, in Patent literature 2 is recorded in terms of the adsorption material, the extracting agent is supported by the chemical bonding with the substrate not, therefore, exist because of the different conditions of dissolving the extracting agent, the adsorption performance is reduced. Moreover, the absorption material is originally of a film, based on the above-mentioned same reasons, a restricted mode in use.

In Patent literature 3 is recorded in terms of metal ion adsorption material, in order to impart to the adsorbent durability, need to mix the ethylene-vinyl alcohol copolymer 60 mass % or more, but also, the functional group of a metal ion absorption by melt mixing in an ethylene-vinyl alcohol copolymer, the contact with the metal ion is not full, it is not possible to demonstrate sufficient adsorption performance.

Furthermore, Patent document 4 anionic permutoid obtained in not demonstrate sufficient adsorption performance. Also, a quaternary ammonium salt in the case of as the adsorbing group, if in order to demonstrate sufficient increase the performance of the functional group, the hydrophilic increase in resin swelling occurs, there is the following problem: the manufacturing not only of the adsorbing material is difficult, and even can be made also containing metal ions would be difficult to use in the aqueous solution.

Therefore, the purpose of this invention is to provide a porous graft copolymer particles, using the same method of manufacturing the same and porous graft copolymer particle adsorbing material, the porous graft copolymer particles readily introduced into the ion-exchange group or chelating group introduction amount and realizing high functional group, but also has to be absorb metal contact with the porous structure, and is easy to fill the shape of particle in the column, as an ion exchange resin or chelate resin is useful.

Method of solving the subject

The inventor of this invention in order to achieve the above goals, such as conducted in-depth research, found that the same, by high moldability through the resin particles of the porous substrate obtained by irradiation of ionizing radiation into the grafted chain obtained porous graft copolymer particles, excellent operability can be obtained, has the high absorbability of the graft copolymer particles, thereby completing the present invention.

The invention section 1 is a multi-hole of a graft copolymer particles, it is selected from the group consisting of olefin resin, the non-water-soluble-modified vinyl alcohol resin, amide resin, cellulose resin, chitosan resin and (meth) acrylic acid ester resin, at least 1 kind of the above-mentioned resin in the graft copolymer which is obtained grafted chain, and the porous copolymer states the stem grafting particulate, having an average of the surface of the particle a pore size of 0.01 the the m-50   m microporous.

In the present invention, the particle in the porous means there are a plurality of micro-pores. Need to prove, the microporous may be a continuous structure, also can be an independent structure.

Furthermore, in the present invention, the concept of including powder particles are.

In the above-mentioned hole in the graft copolymer particles, the above-mentioned non-water-soluble-modified vinyl alcohol resin is preferably ethylene-vinyl alcohol copolymer.

In the above-mentioned hole in the graft copolymer particles, the grafted chain having the functional group preferably containing the structural unit.

In the above-mentioned hole in the graft copolymer particles, the above-mentioned graft chain is preferably selected from the group consisting of the following functional groups comprising at least one of the structure unit of the above functional group, the functionalized group including: amino, amide, ether, carboxyl, thioureido group, isothiourea base , phosphoric acid group, a phosphonic acid group, amidoxime group, cyano, sulfonyl, N-methyl glucose amidogen , epoxy group and mercat. Wherein preferably, the grafted chain selected from the group consisting of the following functional groups comprising at least one of the structure unit of the above functional group, the functionalized group including: amino, ether, and thioureido isothioureido.

In the above-mentioned hole in the graft copolymer particles, is preferably introduced to the above-mentioned functional group 1.0mmol/g.

In the above-mentioned hole in the graft copolymer particles, preferably, the particles have a particle size from 10 the the m-2000  m.

The invention section 2 form is a multi-hole method for producing graft copolymer particles, the porous graft copolymer particles has a surface average pore diameter is 0.01 the the m-50 microporous   m,

The method comprises:

Process I: the selected from the group consisting of olefin resin, the non-water-soluble-modified vinyl alcohol resin, amide resin, chitosan resin, cellulose resin and (meth) acrylic acid ester resin, at least 1 kind of the above resin (the following, sometimes referred to as high-molecular polymer A) A different from the high-molecular polymer resin (the following, sometimes referred to as high-molecular polymer B) by melt-mixing, and the resultant melt is cooled and solidified to obtain complex;

Process II: extracted from the above-mentioned complex high molecular polymer B, is formed of high-molecular polymer A porous body;

Process III: in the above-mentioned process after I or II, comprising the above-mentioned porous body; and

Procedure IV:in the above-mentioned porous body comprising the introduction of grafted chain.

In the above-mentioned manufacturing method, preferably, the high molecular polymer A is ethylene-vinyl alcohol copolymer, the above-mentioned high-molecular polymer B of a water-soluble polymer, more preferably a water-soluble polymer is polyvinyl alcohol.

In the above-mentioned manufacturing method, preferably through the use of an ionizing radiation to the radiation graft polymerization into the grafted chain.

In the above-mentioned manufacturing method, comprising a grafted chain of the structure unit has functional groups, the graft polymerization can be also carried out after the conversion of the functional group.

The invention section 3 by the above-mentioned is recorded in the form of porous graft copolymer particles adsorbing material, said adsorption material is used for absorbing metal adsorption material.

It should be explained that, the invention also includes the claims and/or disclosed in the specification of at least 2 of the elements of a arbitrary combination. In particular, the invention comprises a right recorded in claim 2 or any combination of the claim.

Effect of the invention

The porous graft copolymer particles with porous high molecular polymer as the substrate, can be introduced into the adsorptive functional group of the grafted chain a, therefore, a large number of adsorptive functional group introduced, excellent adsorbability of the metal, and the like, in addition, due to the particle shape, can be effectively filled with the column as the metal in the excellent serviceability of the adsorbing material. By using the metal adsorption material, recovery of metals can be produced in high yield.

In this invention the porous graft copolymer particles in the method of manufacturing, the formability of the specific high molecular polymer (high molecular polymer A) resin with other ingredients (high molecular polymer B) mixture is, the high-molecular polymer that does not dissolve but A B can dissolve the high molecular polymer solvent extraction of the high molecular polymer B, porous high molecular polymer particles obtained, of a polymerizable monomer having a functional group of the graft polymerization into the porous particles into the grafted chain and, therefore, capable of introducing a functional group in a large amount, but also, to be adsorbed to the metal of the contact, excellent adsorbability can be manufactured of porous graft copolymer particles.

Using this invention a porous graft copolymer particles of the adsorption material has the following characteristics: the porous substrate as the graft copolymer particles has a large number of functional groups can be introduced into the porous structure, the metal adsorption is excellent, and, as a particulate, so column are good.

Mode of execution

(Porous graft copolymer particles)

Porous of the invention the grafted chain graft copolymer particles is introduced into the porous particulate high molecular polymer A (is selected from olefin resin, amide resin, the non-water-soluble-modified vinyl alcohol resin, cellulose resin, chitosan resin and (meth) acrylic acid ester resin, at least 1 kind of the above-mentioned resin) and (dry polymer) porous graft copolymer particles, the particles having an average surface of a pore size of 0.01 the the m-50   m microporous.

(Dry polymer)

In this invention is the high-molecular polymer A formability excellent high molecular polymer, is selected from olefin resin, amide resin, the non-water-soluble-modified vinyl alcohol resin, chitosan resin, cellulose resin and (meth) acrylic acid ester resin, at least 1 kind of the above-mentioned resin. The resin as a dry polymer (substrate), the functional group of the has the following record of unsaturated monomer to form a grafted chain graft polymerization, can be obtained by graft copolymer of this invention.

As used in the present invention of an olefin resin, can be enumerated polyethylene, polypropylene, ethylene-propylene copolymer, halogenated polyolefins, polyvinylidene fluoride and the like.

As a non-water-soluble-modified vinyl alcohol resin, is through the back of the water-soluble polymer dissolving out of the way of the porous structure is modified in order to non-water-soluble vinyl alcohol resin, can cite ethylene-vinyl alcohol copolymer, polyvinyl butyral, polyvinyl acetal, and the like. Usually, these modified vinyl alcohol resin can be in the 100 [...] keep the structure in the hot water.

As amide resin, can be enumerated: nylon 6, nylon 6, 6, nylon 6, 10, nylon 6, 12, nylon 11, nylon 12, nylon 4, 6, and the like.

As the cellulose-based resin, in addition to cellulose (pulp, cotton, regenerated cellulose and the like) other than, can also be enumerated: cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate and cellulose acylate.

As the (meth) acrylic acid ester resin, can be enumerated: poly (methyl) methacrylate, poly (meth) acrylic acid ethyl ester, poly (meth) acrylic acid propyl ester, (meth) acrylic ester and (meth) acrylic acid or styrene, such as the various copolymers.

As chitosan resin, can be enumerated: with (1 → 4)-2-acetamido-2-deoxy-β-D-glucan part of the chitin structure completely to acetylation structure, and by acylation reaction, etherification reaction, esterification reaction, other reaction to the structure obtained after acetylation the body goes a part of the amino group in the molecule or the same and a portion of the hydroxyl groups of a obtained by chemical modification, of chitosan derivatives.

(Ethylene-vinyl alcohol copolymer)

In the above-mentioned polymer, preferably ethylene-vinyl alcohol copolymer, the ethylene-vinyl alcohol copolymer can be formed of the particles with water resistance, but also because of the hydrophilic, the metal ion is easy to spread the resin.

As the graft copolymer of the present invention using the substrate of the ethylene-vinyl alcohol copolymer as long as they can obtain a graft copolymer of the above-mentioned nature there is no particular limitation, for example, the ethylene content can be as 10-60 mol % left and right, is preferably 20-50 mol % left and right. The ethylene content is less than 10 mol % of the cases, the graft copolymer of existence of the hidden danger of the loss of water resistance. On the other hand, if the ethylene content exceeds 60 mol %, it is difficult to obtain the manufacturing difficulties.

Furthermore, ethylene-vinyl alcohol copolymer is preferably a degree of saponification of 90 mol % or more, more preferably 95 mol % or more, especially preferably 99 mol % or more. The degree of saponification is less than 90 mol % under the condition of, existing poor moldability, or the obtained graft copolymer of hidden danger of the loss of water resistance.

Furthermore, ethylene-vinyl alcohol copolymer to the melt flow rate (MFR) (210 the [...] , load 2160g) there is no particular limitation, is preferably a 0.1g/min or more, more preferably 0.5g/min or more. In less than 0.1g/min under the condition of, water resistance, hidden danger of the loss of strength. It should be explained that, the upper limit of the melt flow rate in the range of usually used can be, for example, can be a 25g/min the following.

Without prejudice to the effects of this invention within the scope of, the invention of the ethylene-vinyl alcohol copolymer can also contain other unsaturated monomer unit. The unsaturated monomer unit content is preferably 10 mol % or less, more preferably 5 mol % the following.

Such ethylene-vinyl alcohol copolymer may be used alone, also can be combined to use 2 or more.

(Graft chain)

From the functional group of the grafted chain in the affinity of the metal, and the like, the viewpoint of metal absorption, in the present invention in a porous graft copolymer particles, preferably comprises a functional group selected from the group consisting of the following (adsorptive functional groups) of at least one functional group in the structural unit, to said functional group: amino, amide, ether, carboxyl, thioureido group, isothiourea base , phosphoric acid group, a phosphonic acid group, amidoxime group, cyano, sulfonyl, N-methyl glucose amidogen , epoxy group and mercat. In particular with a noble metal, and the like from the viewpoint of affinity, more preferably includes selected from the group consisting of amino, ether, and thioureido isothiourea base at least 1 more than the structure unit of a functional group of the graft copolymer particle. The above-mentioned functional group with the above-described functional groups of the unsaturated monomer graft polymerized to the above-mentioned dry polymer and introduced into the graft chain.

The introduction amount of the above-mentioned functional group, i.e., the graft copolymer particles per unit mass of the moles of the functional group is not particularly limited, but the adsorption of the metal, and the like from the viewpoint of performance, preferably 1.0mmol/g more, more preferably 2.0mmol/g the above, preferably further 4.0mmol/g the above. Lower than the introduction amount 1.0mmol/g circumstances, sometimes it is difficult to fully obtain the adsorption performance of the metal, and the like. On the other hand, more than the moles of the functional group 20mmol/g circumstances, it is difficult to control particle swelling, and it is difficult to make the most of the manufacture.

(Specific examples of functional group)

Is introduced into the graft chain functional group of the functional group having unsaturated monomer graft polymerized to the dry polymer is formed (substrate) having the functional group of the graft chain. For graft polymerization on the functional groups of the unsaturated monomer and specific examples, are described below.

(1. Amino)

As is used for graft polymerization of unsaturated monomers of amino, there is no particular limitation, can be used, for example, chemical formula (1) shown in the unsaturated monomer.

[Chemical formula 1]

Formula (1) in, Ra is hydrogen or methyl. Furthermore, X is carbonyl is formed and the adjacent components of an ester or amide linkage, from the viewpoint of chemical stability, preferably Ra is methyl.

Formula (1) in, as the Rb containing amino, for example, can be cited: amino, 1-amino-N-methylamino, N, N-dimethylamino, N-ethyl amino, N, N-diethyl amino, pyrrolidinyl, piperidinyl, piperazinyl, the carbon atom number 2-20 aliphatic amino; pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, [...] , [...] , benzocarbazoles [...] , indolyl, triazinyl, triazolyl, tetrazolyl, Azoly, heteroploid Oxazolyl, Oxadiazolyl, Triazolyl, purinyl, carbon atoms such as pteridyl 2-20 aromatic amino.

Furthermore, may also be used the carbon atom number Rb 2-20 and optionally the alkylene chain with substituent, and the illustration of the front of the aromatic nitrogen-containing heterocyclic structure of the compound.

As with amino unsaturated monomer, for example, can be instantiated the: amino alkyl (meth) acrylic acid [e.g., (meth) acrylic acid N, N-dimethyl amino ethyl ester, (meth) acrylic acid N, N-diethyl amino ethyl ester, (meth) acrylic acid N-single or two C_1-4 alkyl amino C_1-4 alkyl ester, etc.], amino alkyl (meth) acrylamide [for example, N, N-dimethyl amino ethyl (meth) acrylamide, N, N-diethyl amino ethyl (meth) acrylamide, N, N-dimethyl amino propyl (meth) acrylamide and other N-single or two C_1-4 alkyl amino C_1-4 alkyl (meth) acrylamide, and the like], vinyl pyridine (2-vinyl pyridine, 4-vinyl pyridine, etc.), N-vinyl carbazole, vinyl imidazole [(1-vinyl imidazole, 2-vinyl imidazole, 1-methyl-2-vinyl imidazole), and the like], vinyl triazole [(2-vinyl -1, 2, 4-triazole), and the like]_.

Furthermore, as to be graft polymerized unsaturated monomer, as long as the can after polymerization reactive group into the amino group can be, as such a monomer, using, for example, can be: glycidyl methacrylate, glycidyl acrylate, methacrylic acid chlorine ethyl ester , acrylic chlorine ethyl ester , chloromethyl styrene, and the like.

As the method for functional group conversion of the amino group, for example, can be cited: the addition of a compound having an amino group to the epoxy group, halogenated alkyl method. As a compound having an amino group, for example, can be cited: ethylene diamine, trimethylene diamine, 2-methyl -1, 3-propane diamine, propylene diamine, tetramethylene diamine, 3-methyl-amino-propylamine, 1, 3-diamino-2-propanol, 2-methyl -1, 2-propylene diamine, N-methyl ethylenediamin, N, N '-dimethyl-ethylenediamine, 1, 4-butanediamine, 1, 3- cadaverine , 1, 4-cyclohexanediamine, 1, 3-diaminocyclohexane, trans -1, 2-diaminocyclohexane, 2-methyl -1, 5- cadaverine , 1, 5- cadaverine , seven methylene diamine, eight sub-methyl diamine, nine-methylene diamine, ten methylene diamine, N-(2-aminoethyl) piperazine, diethylentriamine, triethylene tetramine, four subethyl five amines , pentaethylenehexamine, six subethyl seven amines , polyvinyl amines, polyallyl, polyethylene imine, 2-amino-benzylamine, 3-amino-benzylamine, 4-amino-benzylamine, benzylamine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 4-(dimethylamino) pyridine, 4-amino-2-methylpyridine, 4-amino-3-methyl pyridine, 2-ammonia methylpyridinio, 3-ammonia methylpyridinio, 4-aminomethyl-pyridine, 4-(ethylamino methyl) pyridine, 3-(2-amino-ethyl) pyridine, 2-(2-amino-ethyl) pyridine, b (3-pyridylmethyl) amine, di (2-pyridylmethyl) amine, 2-amino-4-methyl pyridine, 3-amino-4-methyl pyridine, imidazole compound (2-amino-imidazole, 1-(3-aminopropyl) imidazole, 2-amino-benzimidazole, and the like), triazole compound (4-amino -1, 2, 4-triazole, 3-amino -1H-1, 2, 4-triazole, and the like), benzo triazole compound (1-hydroxy benzotriazole, 1-amino-benzotriazole, etc.), 4-amino-indole, 5-amino-indole, 6-amino-indole, histamine, tryptamine, such as tryptophan. Wherein the easiness of the manufacture of the, metal ion adsorption of the viewpoint of performance, especially preferably the polyamine, imidazolates, triazole, benzotriazole compound.

In the above-mentioned the amino introduced into the grafted chain in the method of in, as a method of introducing amino group, preferably in the glycidyl methacrylate, glycidyl acrylate graft polymerization of the epoxy group into the amino group of the method. Furthermore, the epoxy group in the epoxy group or amino group into the ethylene-vinyl alcohol copolymer to the hydroxyl moiety cross-linking reaction, to give resistance to aqueous, from this context, to consider, preferably by glycidyl methacrylate, glycidyl acrylate amino group introduction method.

(2. Or thioureido isothiourea base)

In the graft copolymer of the present invention has in the grafted chain thiourea structure or isothiourea structure is not particularly limited, for example, may be cited the following formula (2)-(5) the structure of the shown.

[Chemical formula 2]

Formula (2)-(5) in, and * the chemically bonded to the grafted side chain.

Formula (5) in, R₁ expresses a carbon atom number 1-10 the carbon chain. Specifically, can cite methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, straight or branched chain alkyl, cyclohexyl, adamantyl, cycloalkyl, phenyl, naphthyl, aryl group, etc.. Furthermore, R₁ can also be a *.

In the present invention, in order to introduce at least having thiourea structure or isothiourea in the structure of the grafted chain at least one of, (1) can be used in or thioureido isothiourea base having at least at least any one group of the unsaturated monomer, or (2) can be used or thioureido isothiourea base to be capable of being converted into unsaturated monomer (in this specification, the thioureido and isothiourea base also referred to as the thioureido).

Or thioureido isothiourea base as having the unsaturated monomer, there is no particular limitation, for example, can use the following formula (6) shown in the unsaturated monomer. In the following formula (6) in, R₂ is hydrogen or methyl. Furthermore, X is carbonyl is formed and the adjacent components of an ester or amide linkage, from the viewpoint of chemical stability, R₂ is preferably methyl. R₃ are that the carbon atom number 2-10 and optionally the alkylene chain with substituent, at the end thereof having thiourea structure or isothiourea structure of the at least 1 kind of structural group. R₃ at the tail end is provided with the structure of the above-mentioned formula (2)-(5) in any of the structure, from the viewpoint of the easiness of the on, particularly preferred formula (2) structure.

[Chemical formula 3]

As carrying out the graft polymerization of an unsaturated monomer, as described above can be used with the monomer or isothiourea base thioureido group, can also be used after the graft polymerization or thioureido isothiourea base to be capable of being converted into reactive group-containing monomer. For example, can use glycidyl (meth) acrylate having an epoxy group such as an unsaturated monomer, chloromethyl styrene, (meth) acrylic acid with a halogenated alkyl such as chlorine ethyl ester unsaturated monomer.

In the case of converted to a thioureido group, can be introduced by, for example, the following manner: the glycidyl (meth) acrylate having an epoxy group such as an unsaturated monomer, chloromethyl styrene, (meth) acrylic acid with a halogenated alkyl such as chlorine ethyl ester of unsaturated monomer after carrying out the graft polymerization, the obtained amine of the graft is introduced into amino, then, further the amino and isosulfocyanate or sulfur cyanic acid acid and its salt, or the amino and carbon bisulfide generated from the reaction of the dithio Carbamic base and amine for reaction.

As the above-mentioned use of amine, for example, can be cited: ammonia, methylamine, dimethylamine, ethylamine, diethylamine, ethyl methylamine, propylamine, diisopropylamine, methyl propyl amine, methyl isopropyl group amine , ethyl propyl amine, ethyl isopropyl group amine , of tert-butyl amine, hydroxylamine, amino methanol, ethanolamine , alaninol, amino isopropanol, acetamide, carbamic acid methyl ester, ethylene diamine, trimethylene diamine, 2-methyl -1, 3-propane diamine, propylene diamine, tetramethylene diamine, 3-methyl-amino-propylamine, 1, 3-diamino-2-propanol, 2-methyl -1, 2-propylene diamine, N-methyl-ethylenediamine, 1, 4-butanediamine, 1, 3- cadaverine , 1, 4-cyclohexanediamine, 1, 3-diaminocyclohexane, trans -1, 2-diaminocyclohexane, 2-methyl -1, 5- cadaverine , 1, 5- cadaverine , seven methylene diamine, eight sub-methyl diamine, nine-methylene diamine, ten methylene diamine, diethylentriamine, triethylene tetramine, four subethyl five amines , pentaethylenehexamine, six subethyl seven amines , 2-amino-benzylamine, 3-amino-benzylamine, 4-amino-benzylamine and the like.

Isorhodanide as the above-mentioned use, for example, can be cited: isothiocyanic acid methylphenidates, ISO thiocyanate diethlyl, ISO propyl thiocyanate, ISO thiocyanate n-butyl, ISO-thiocyanate butylcyclohexyl acetate, phenyl ISO-thiocyanate, ISO thiocyanate jin'gang alkane ester , benzoyl isothiocyanate, different benzyl thiocyanate, phenylene di ISO thiocyanate, and the like. As the thiocyanate and its salt, for example, can be cited: thiocyanate, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, thiocyanate iron, zinc thiocyanate, and the like.

In the case of converted into isothiourea base , can be introduced by, for example, the following manner: the glycidyl (meth) acrylate having an epoxy group such as an unsaturated monomer, chloromethyl styrene, (meth) acrylic acid with a halogenated alkyl such as chlorine ethyl ester of unsaturated monomer after polymerization is carried out, so that the graft body and the thiourea, acetyl thiourea, thiourea compound reaction.

The above-mentioned, to the thioureido or isothioureido introduced into the graft chain having the functional group of the monomer into the situation, and to be capable of being converted into use or thioureido group with the functional group of isothiourea base of the monomer into the situation described, in that two factors, as can a large amount into the thiourea-based or isothiourea base method, preferably, in a having an epoxy group, a halogenated alkyl of unsaturated monomer for graft polymerization to the functional group conversion after or thioureido isothiourea base method. Furthermore, into the epoxy group, thioureido group or isothioureido introduced into the epoxy group, the ethylene-vinyl alcohol copolymer to the hydroxyl moiety cross-linking reaction, to give resistance to aqueous, from this context, to consider, preferably by glycidyl methacrylate, glycidyl acrylate thioureido or isothioureido introduction method. Furthermore, the introduction of the in or isothiourea base thioureido group, taking into account the stability, can also be by hydrochloric acid, nitric acid or the like in the state of in salt.

(3. Carboxyl (imino diacetoxy))

The grafted chain with imino diacetoxy can be used can be converted into a reactive group for imino diacetoxy of the unsaturated monomer, such as glycidyl (meth) acrylate having an epoxy group such as an unsaturated monomer, chloromethyl styrene, (meth) acrylic acid with a halogenated alkyl such as chlorine ethyl ester unsaturated monomer and the like. In the conversion to imino diacetoxy circumstances, can be introduced by, for example, the following manner: the glycidyl (meth) acrylate having an epoxy group such as an unsaturated monomer, chloromethyl styrene, (meth) acrylic acid with a halogenated alkyl such as chlorine ethyl ester of unsaturated monomer after polymerization, the graft copolymer and iminodiacetic acid or its salt reaction.

(4. Ether or amide)

As specific examples of ether groups, can be enumerated leaves oxygen Asia alkyl, furyl or tetrahydrofuryl, as oxygen alkyl, can cite: ethylene glycol alcohol-based, glycol alcohol, triethylene glycol poly equivalent, such as, propylene glycol based coolants is, b c b alcohol group, such as poly propylene glycol based coolants is three c glycol, these group single etherification the functional group of the a; as furyl, can cite: 2-furyl, 3-furyl; as tetrahydrofuryl, can cite: 2- [...] , 3- [...] , and the like. Furyl and tetrahydrofurl can be partly substituted. As concrete examples of the amido group, can cite: dimethyl amide, diethyl amide, methyl ethyl amide, pyrrolidine keto, and the like.

In order to introduce ether or amide, (1) can use the chloromethyl styrene, (meth) acrylic acid with a halogenated alkyl such as chlorine ethyl ester unsaturated monomer, or a glycidyl methacrylate having an epoxy group such as an unsaturated monomer. The method of pre-through the graft copolymerization of the unsaturated monomer into the as in the polymer of the substrate, the substrate with the reaction of a compound of the above-mentioned functional group, so as to with ether or amide into the grafted chain. (2) with the functional groups of the unsaturated monomer in the polymer as the base material (dry polymer) as a starting point for polymerization to form graft polymer, thus with ether or amide into the grafted chain.

In the application of the above-mentioned method (1), , of its reaction as the compound, preferably using, for example, the: three ethylene glycol monomethyl ether, diethylene glycol mono butyl ether, three ethylene glycol monobutyl ether, alkyl alcohols containing oxygen, furfural, tetrahydrofurfuroxy furfural, 1-(3-hydroxy-propyl)-2-pyrrolidone compounds.

In the application of the above-mentioned method (2), , of its reaction as the unsaturated monomer, preferably using, for example, the: methyl acrylic acid 2- methoxy ethyl ester , methyl acrylic acid 2- ethoxy group ethyl ester , methyl glycol monomethyl ether acrylate, polyethylene glycol methacrylate, polypropylene glycol methyl acrylate, polyethylene-polypropylene glycol methyl acrylate, and the like of the structure with continuous oxygen alkyl (meth) acrylic ester type monomer or (meth) acrylamide type monomer, methyl acrylic acid rice polishings ester , methyl acrylic acid four hydrogen rice polishings ester , or dimethyl acrylamide, diethyl acrylamide, dimethyl-methyl acrylamide, diethyl methyl acrylamide, N uncle amide monomer-vinyl pyrrolidone, and the like.

(5. Other functional groups)

In the adsorptive functional group of the metal other than those mentioned above into the graft chain, with the above-mentioned functional group by the graft polymerization of the monomer into the grafted chain directly, or can use, have can be transformed into the metal absorption, the reactive group of the functional monomer.

As the monomer having a metal absorption, can be enumerated : (meth) acrylic acid, fumaric acid, monomer having carboxyl group, acid phosphoric acid mono (2-methacryloxy ethyl) ester, phosphoric acid groups of the monomer, 4-sulfonyl styrene, 2-acrylamide-2-methylpropane-sulfonic acid and its salt, a monomer having a sulfonyl, thio acetic acid acetate, 1-acetyl thio-2-hydroxy-3-butene with a mercapto group, such as a monomer, the monomer has a nitrile group such as acrylonitrile and the like.

As a functional group can be converted into a metal absorption, the reactive group of the monomer, acrylonitrile can be to form the grafted chain graft polymerization, the graft after reaction with hydroxylamine to the cyano converted to amidoxime group, thus introducing metal adsorptive functional group. Furthermore, the glycidyl methacrylate graft polymerization to form the grafted chain, graft after the, the epoxy group reacts with the methyl-glucosamine, thus introduced into the metal or metalloid adsorptive functional group. Furthermore, the above-mentioned epoxy group can be the (amino-methyl) phosphonic acid to carry out the reaction, the adsorptive functional group introduced into the metal.

(Porous)

Porous graft copolymer of the present invention as long as at least the particles can be formed on the surface, can have been the interior of the structure is forming microporous. The capillary formed by the surface of the aperture can be an average of 0.01 the the m-50 about   m, preferably 0.05 the the m-20  m, more preferably 0.2 the the m-10  m. The average pore size of less than 0.01 the case of   m, impossible to obtain sufficient presence of the hidden danger of introduction amount of the functional group. The average diameter of the hole is larger than the 50 under the condition of   m, low mechanical strength of particles exist, the presence of the reactive substrate fall apart of the substrate. These microporous the average aperture through the latter embodiment is recorded in the determination of the value of the method.

(Particles)

The graft copolymer of the present invention the particle size of the particles can be adjusted through appropriate crushing, particle size is preferably 10 the the m-2000  m, more preferably 30 the the m-1500  m, most preferably 40 the the m-1000  m. Particle diameter lower than 10 the the   m, there are micro-powder is easily of operation become difficult. Particle size is more than 2000 the when   m, sometimes unable to fully obtain the adsorption performance of the metal, and the like.

(Porous graft copolymer particle manufacturing method)

As the porous graft copolymer particles of the invention method of manufacturing, there is no particular limitation, the following record a preferred example of the manufacturing method.

This manufacturing method is comprised of the following 4 a process.

Process I: the formability of high-molecular polymer A (is selected from olefin resin, the non-water-soluble-modified vinyl alcohol resin, amide resin, cellulose resin, chitosan resin and (meth) acrylic acid ester resin, at least 1 kind of the above-mentioned resin) and other components of high molecular polymer by melt-mixing B to make the predetermined shape (complex) of the molten mixture, the molten mixture by cooling and solidifying the mixture.

Process II: from the solvent used in the molten mixture obtained by extracting the high-molecular polymer B, porous high molecular polymer A obtained.

Process III: in the process I or process II by cutting off after, comprising crushing and the like, the cooling of the molten mixture or porous high molecular polymer A a particle of a given size.

Procedure IV: porous polymer particles through the graft polymerization of a polymerizable monomer having a functional group, to obtain the grafted chain having the functional group introduced into the porous graft copolymer particles.

It should be explained that, in the present invention, "melt cooling solidification" refers to the use of coagulating bath and the cooling and solidifying of the melt point.

(High-molecular polymer B)

In this invention the use of high molecular polymer B there is no particular limitation, can be used a generally known high-molecular polymer. Preferably the high molecular polymer A melt-mixing, for example, can be cited: starch; gelatin ; cellulose derivatives; polyvinyl amines, water-soluble amines, such as polyallylamine polymer; polyacrylic acid; poly isopropyl acrylamide, polyacrylamide; polyvinylpyrrolidone ; polyvinyl alcohol; polyethylene glycol, polypropylene glycol, ether polymer; styrene resin; a phenolic resin; polyvinyl butyral acetal resin; carbonic acid ester resin and the like. Furthermore, if different A with the high-molecular polymer, olefin resin can be used; amide resin ; (meth) acrylic acid ester resin.

Can be porous according to the needs to properly determine the degree of high molecular polymer B A and high polymer mass ratio of, for example, high-molecular polymer A: high molecular polymer can be B 99.9: 0.1-20:80, preferably 99.9: 0.1-30:70.

(Procedure I)

The high molecular polymer and other ingredients A B high molecular polymer melt mixing method is not particularly limited, can use a single screw extruder, double-screw extruder, burra the [...] (Brabender), kneading machine, the known mixing machine. After milling the melt of a high molecular polymer B A and high polymer to complex shape such as out of the strip, and is cooled and solidified.

(Procedure II)

For the purposes of the complex cooling and solidifying, the high-molecular polymer can be dissolved not A but is capable of dissolving the solvent of high molecular polymer B the high-molecular polymer B to extract processing, can obtain high-molecular polymer A of the porous body.

Used in the present invention there is no particular limitation to the extraction solvent, is preferably a high molecular polymer A and is a poor solvent of the high molecular polymer B good solvent, and with high molecular polymer A and high molecular polymer for B inert reaction solvent. The solvent can be used alone, also can be used as a mixed solvent. As the solvent, for example, can be cited: water, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, tetrahydrofuran, 1, 4-II Alkanes, ether, chloroform, dichloromethane, methyl acetate, ethyl acetate, acetonitrile, acetone, dimethyl formamide, dimethyl sulfoxide, benzene, toluene, xylene, hexane or heptane, and the like.

Especially high molecular polymer is a hydrophilic B under the condition of high molecule, preferably use water, alcohol as a solvent. Extracting the solvent temperature is preferably of the 40-120 the [...][...] , more preferably the 50-100 the [...][...].

(Step III)

In the step I (obtain molten curing stage of the complex) or process II (obtain porous high molecular polymer phase) then, the above-mentioned complex or the above-mentioned porous high molecular polymer A cut-off, comprising of crushing.

(Step IV)

With functional group by the graft polymerization of the polymerizable monomer to the process III the obtained porous high molecular polymer A particles, the grafted chain A introduced in to the high-molecular polymer.

As a lead-in having the functional group of the grafted chain method, there are various well-known method, for example, can be cited: the use of the polymerization initiator into the grafted chain to free radical polymerization method, the use of ionizing radiation into the grafted chain to free radical generating method. Wherein the introduction of grafted chain from the viewpoint of high efficiency, can be preferably the use of ionizing radiation into the grafted chain to the method. Especially through the use of porous substrate, graft polymerization can be high-efficiently by introducing a functional group.

A ionizing radiation α-ray, β-ray, ray γ, accelerated electron beams, ultraviolet and the like, preferably from the accelerated electron beams or γ-ray.

The use of ionizing radiation as the unsaturated monomer graft polymerized to the porous resin particle method on a substrate, the following method can be used in any one of: the substrate and unsaturated monomers under the condition of coexistence of mixed irradiation of radioactive ray, and radiation is irradiated only to the substrate in advance and then the unsaturated monomer is contacted with the base material of the front radiation method, a method of the pre-irradiation graft polymerization is not easily generated, other than the characteristic of the side reaction.

In graft polymerization, as the unsaturated monomer with the substrate contact method, including the liquid unsaturated monomers or unsaturated monomer solution the liquid phase polymerization direct contact, with the unsaturated monomer and the vapor contacts a gaseous state or in the gas phase graft polymerization, can be selected according to purposes.

As to the above-mentioned porous graft copolymer particles into the grafted chain method, can use various well-known method, for example, can be cited: the use of the polymerization initiator into the grafted chain to free radical polymerization method, the use of ionizing radiation into the grafted chain to free radical generating method. Wherein the introduction of grafted chain from the viewpoint of high efficiency, can be preferably the use of ionizing radiation into the grafted chain to the method. Especially through the use of porous substrate, graft polymerization can be high-efficiently by introducing a functional group.

As the irradiation dose of ionizing radiation, there is no particular limitation, is preferably 5-230kGy, more preferably 10-190kGy, further preferably 15-140kGy. Most preferably 20-100kGy. In less than 5kGy under the condition of, grafting due to reduce the dosage, unable to obtain the target metal ion adsorption capacity. A dose exceeding the 230kGy circumstances, increase the cost of the processing procedure, while illuminating the hidden danger of the resin becomes poor and the like.

In the case of the functional group of the grafted chain, with the adsorptive functional groups can be unsaturated monomer graft, the ionizing radiation may also be used with a reactive group of unsaturated monomer and then converting the after graft the adsorptive functional group.

In order to introduce into the grafted chain with absorption functional group by the graft polymerization of, as the unsaturated monomer, not only can only use having the functional group of the unsaturated monomer, can also be without prejudice within the range of the performance of the combined use of the above-mentioned unsaturated monomer other than unsaturated monomer. For example, in order to inhibit graft the chain dissolves the bulge , can use divinyl benzene, ethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, four ethylene glycol (meth) acrylate, 1-(acyloxy)-3-(methacryloxy)-2-propanol, methylene-bis-acrylamide, and the like as the polyfunctional unsaturated monomer.

In the substrate and irradiating the ionizing radiation is irradiated, is generated from the activity of the substrate of the viewpoint of stability, in order to stably addition unsaturated monomer, at low temperature the substrate under processing is effective, in the case of radiation graft polymerization, polymerization initiation of the solvent temperature is preferably the 20 [...] the following, more preferably the 10 [...] the following. More than 20 the the [...] , the presence of unsaturated monomers the stable possibility of the introduction amount, or unable to ensure that the possibility of sufficient introduction amount. It should be explained that, if the back surface of the substrate is ethylene-vinyl alcohol copolymer under the circumstances, does not need to initiate the polymerization as described above reduce the temperature of the solvent.

(Grafting)

Through the above-mentioned graft polymerization, the porous high molecular polymer formed on the particle A with the above-mentioned functional group of the polymerizable monomer to form a graft chain.

Introduced by graft polymerization of unsaturated monomer (grafting rate) the amount of no particular limitation, porous polymer A particles relative to 100 parts by mass, preferably 30-900 parts by mass (30-900%), more preferably 90-800 parts by mass (90-800%), preferably further 120-700 parts by mass (120-700%), especially preferably 150-600 parts by mass (150-600%). Grafting is less than 30 parts by mass of the time, the metal of the adsorption performance is insufficient. Grafting more than 900 the quality, are usually difficult to be synthetic.

Without prejudice to within the range of the effects of this invention, the graft copolymer of the present invention can also contain cross-linking agent particles, inorganic fine particles, light stabilizer, antioxidant and other additives.

(Porous ethylene-vinyl alcohol copolymer particle)

The following is related to the present invention is preferably used in the ethylene-vinyl alcohol copolymer (the following, sometimes referred to as EVOH), and the method of obtaining porous particles of the record.

In the process I, preferably by melt mixing the ethylene-vinyl alcohol copolymer is mixed with the water soluble polymer, then, in the process II, preferably by using an aqueous solvent is extracted from the above-mentioned complex water-soluble polymer to form a porous body.

Used in the present invention so long as the water-soluble polymer with the ethylene-vinyl alcohol copolymer melt-mixing there is no particular limitation, can be used a water-soluble polymer generally known. The water-soluble polymer can be cited such as: starch; gelatin ; cellulose derivatives; polyvinyl amines, water-soluble amines, such as polyallylamine polymer; polyacrylic acid; poly isopropyl acrylamide, polyacrylamide; polyvinylpyrrolidone ; polyvinyl alcohol, and the like. Wherein the ethylene-vinyl alcohol copolymer is excellent degree of melting, mixing, and in terms of easy control of the gap, the polyvinyl alcohol is preferably used.

Used in the present invention having a viscosity average degree of polymerization of polyvinyl alcohol (according to JIS   K6726 measuring) there is no particular limitation, is preferably 100-10,000, more preferably 200-7,000, further preferably 300-5,000. If deviating from the above-mentioned range having a viscosity average degree of polymerization, the presence of the hidden danger of the loss of the surface area of the porous body.

The polyvinyl alcohol used in the present invention the degree of saponification is not particularly limited, is preferably 50 mol % or more, more preferably 60-98 mol %, especially preferably 70-95 mol %. If the saponification degree is less than 50 mol %, water-soluble reduce the is, after molding of deterioration taking samples of extracted by hot water. Saponification is higher than 98 mol % of polyvinyl alcohol is difficult to melt-mixing.

Can be porous according to the needs to properly determine the degree of ethylene-vinyl alcohol copolymer with a mass ratio of water-soluble polymer, for example: ethylene-vinyl alcohol copolymer: water-soluble polymer can be 99.9: 0.1-20:80, preferably 99.9: 0.1-30:70.

Extracting water-soluble polymer as a solvent, as long as they do not dissolve the ethylene-vinyl alcohol copolymer and can extract the water-soluble polymer, the solvent used in extracting the there is no particular limitation, water may be used, the kind of organic solvent, a mixture of water and organic solvent and so on, from using the viewpoint of the water-soluble polymer, preferably water as a solvent, particularly preferably with the use of hot water. The temperature of the hot water is preferably 40 the the [...] -120 [...] , further preferably in the 50-100 the [...][...].

Water-soluble polymer obtained by removing the porous ethylene-vinyl alcohol copolymer is preferably subjected to crushing shaping is a particle shape.

As mentioned above, water-soluble polymer obtained by removing the porous ethylene-vinyl alcohol copolymer particles with other polymer particles similarly, the average value of its aperture can be 0.01 the the m-50  m, preferably 0.05 the the m-20  m, more preferably 0.2 the the m-10  m, ethylene-vinyl alcohol copolymer to the circumstances, can be further preferably 0.1 the the m-7  m, a step can also be more preferably 0.2 the the m-7  m. By having the particle diameter of within the range, the full adsorption quantity can be obtained.

(The ethylene-vinyl alcohol copolymer for graft polymerization)

The use of ethylene-vinyl alcohol copolymer as a substrate under the condition of the radiation graft polymerization, by the ionizing radiation irradiation in the ethylene-vinyl alcohol copolymer with the stability of the free radical is generated, even if the through the irradiation of the ethylene-vinyl alcohol copolymer is placed in air, 1-2 hours after contact with the unsaturated monomers, graft polymerizable, in essence, also does not change. Therefore, compared with other polymer, can be easily introduced by graft polymerization of graft chain.

(Multi-hole use of graft copolymer particles)

Graft copolymer particles of the present invention can be used for molding, coating, adhesive, such as the use of the adsorbing material, because of having excellent metal adsorption performance, therefore, is particularly preferred as the metal adsorption material.

(Metal recovery method)

The adsorbing material of this invention can be efficiently recovered by a simple operation of various metal (in particular, the platinum group metal), quasi-metal. As a recovery method, as long as the use of the adsorbing material of this invention there is no particular limitation. For example, metal recovery method can possess adsorption step, in the adsorption step in the adsorption material of the present invention containing the target metal contact with the metal-containing liquid phase, thus the metal adsorption to the above-mentioned adsorption material. In the process, also can be added as needed to the adsorption material in the liquid to stir.

As the recovery of the adsorbing material of the invention the object of the metal no particular limitation, can be enumerated: platinum group metal (ruthenium, rhodium, palladium, osmium, iridium, platinum), gold, silver, copper, nickel, chromium, vanadium, cobalt, lead, zinc, mercury, cadmium. Furthermore, as a recovery target's quasi-metallic, can be enumerated: boron, arsenic, germanium, selenium, antimony, and the like. The can according to the metal/metal is introduced into the appropriate selection of the functional group of the grafted chain.

With respect to the above-mentioned recovery method, can be in a very high efficiency adsorption metal, such as, for example, adsorption quantity of metal 20 mg/g or more, preferably 50 mg/g or more, more preferably 100 mg/g or more.

It should be explained that, adsorption by the following embodiment of a method of measuring the value of the record.

Embodiment

The following, the embodiment of the present invention by a more detailed explanation, but the invention is not subject to any limitation of the embodiment. It should be explained that, so long as there is no special note, embodiment, in the comparison example of " %" and "parts" are "mass %" and that "parts by mass".

[Calculation of the mean pore size]

The adsorption material in the 40 [...] , vacuum dry the 12 hours later, a scanning electron microscope is used for observing the particle surface. Arbitrary selection 50 formed by the surface of a microporous, measuring the diameter of the micropore. The 50 the average diameter of a, the mean value is derived as the average pore size. Wherein the major axis of 1 nm is below, and the flaw, to distinguish adhesive, therefore excluded from the selection.

[Grafting]

According to the calculation formula shown below.

Grafting =100 × [w/w (%)] (conferred by the weight of the grafted chain) / (the weight of the substrate)

[Functional groups]

(Embodiment A-1-A -10, B-1-B -4, F -2, F -5, G-1-G -4 and comparison example A-4)

Before and after the reaction will be carried out into the functional group is set to be the variation in quality of the W. According to the calculation formula shown below.

Functional groups [mmol/g] = (each 1 molecular reaction matrix nitrogen atom number × W[g]/ reaction matrix molecular weight [g/mol]) / (after the reaction the quality of the resin particle) × 1000

(Embodiment C-1-C -10, F -4 and comparison example F-3)

Before and after the reaction will be carried out into the functional group is set to be the variation in quality of the W. According to the calculation formula shown below.

Functional groups [mmol/g] = (each 1 molecular reaction matrix of sulfur atom number × W[g]/ reaction matrix molecular weight [g/mol]) / (after the reaction the quality of the resin particle) × 1000

(Embodiment D-1-D -5)

The into iminodiacetic acid of quality change of the before and after the reaction is set to be W. According to the calculation formula shown below.

Functional groups [mmol/g] = (W[g]/ reaction matrix molecular weight [g/mol]) / (after the reaction the quality of the resin particle) × 1000

Imino diacetoxy in 1 molecule having 2 carboxyl, therefore carboxyl functional groups according to the formula of calculation shown below.

Functional groups [mmol/g] = (W[g]/ reaction matrix molecular weight [g/mol]) / (after the reaction the quality of the resin particle) × 1000 × 2

(Embodiment E-1-E -6, F -1, F -3 and comparison example E-1-E -3, F-1-F -2)

Before and after the reaction will be carried out into the functional group is set to be the variation in quality of the W. According to the calculation formula shown below.

Functional groups [mmol/g] = (each 1 molecular reaction matrix functional group few × W[g]/ reaction matrix molecular weight [g/mol]) / (after the reaction the quality of the resin particle) × 1000

[Metal adsorption amount, elution rate metal adsorption rate and]

(Embodiment A-1-A -10 and comparison example A-1-A -7)

The adsorptive material 50 mg into the metal concentration is 100 mg/L of 1 equivalent hydrochloric acid solution 200 ml in, for 25 the stirring under [...] 60 minutes. Furthermore, heating solution 1 ml as the sample and diluted to 50 ml rear, by ICP emission spectral analysis device (Nippon   Jarrell   Ash manufacturing Company, IRIS-AP) determine, as the obtained metal concentration C (mg/L). Based on the following formula of metal adsorption quantity is determined.

Each 1g metal adsorption of the sample (mg/g) = (100-50 ×C)/ 0.25

The adsorption measurement sample after the sample is taken out from the solution, expunged attached liquid, an aqueous solution of thiourea in 20 ml in 25 the impregnated [...] 10 minutes to elute metal, taking eluant 1 ml as the sample and diluted to 50 ml rear, ICP emission spectral analysis device for measuring metal concentration, is set as the D (mg/L). elution rate is determined according to the following formulae.

elution rate =D / (20-10 ×C) × 100 (%)

(Embodiment B-1-B -4 and comparison example B-1-B -2)

The adsorptive material 50 mg into the palladium ion concentration is 50 mg/L of 0.2 equivalent of the nitric acid solution 100 ml in, for 25 the stirring under [...] 24 hours. Furthermore, heating solution 1 ml as the sample and diluted to 25 ml rear, by ICP emission spectral analysis device (Nippon   Jarrell   Ash manufacturing Company, IRIS-AP) determine, as the obtained metal concentration C (mg/L). Based on the following formula of metal adsorption quantity is determined.

Each 1g metal adsorption of the sample (mg/g) =100-50 × C

(Embodiment C-1-C -13 and comparative example C-1-C -3)

The adsorptive material 50 mg into the target metal ion concentration is 200 mg/L of 0.2 equivalent of the nitric acid solution 25 ml in, for 23 the stirring under [...] 24 hours. Furthermore, heating solution 1 ml as the sample and dilution to 100 ml rear, by ICP emission spectral analysis device (Nippon   Jarrell   Ash manufacturing Company, IRIS-AP) determine, as the obtained metal concentration C (mg/L). Based on the following formula of metal adsorption quantity is determined.

Each 1g metal adsorption of the sample (mg/g) = (2-C) × 50

(Embodiment D-1-D -5 and comparative example D-1-D -2)

The adsorptive material 50 mg into the target metal ion concentration is 30 mg/L of 0.001 equivalent sulphuric acid solution 150 ml in, for 23 the stirring under [...] 60 minutes. Furthermore, heating solution 1 ml as the sample and diluted to 50 ml rear, by ICP emission spectral analysis device (Nippon   Jarrell   Ash manufacturing Company, IRIS-AP) determine, as the obtained metal concentration C (mg/L). Based on the following formula of metal adsorption rate is determined.

Metal adsorption rate (%) = (30-C × 50)/ 30 × 100

(Embodiment E-1-E -6 and comparative example E-1-E -3)

The adsorption material of the sample 50 mg into the containing 1mmol/L concentration of metal ions the 23 of [...] 5N hydrochloric acid 20 ml in, the 24 hours. Furthermore, apply the supernatant fluid 1 ml as the sample and diluted to 50 ml rear, by ICP emission spectral analysis device (Nippon   Jarrell   Ash manufacturing Company, IRIS-AP) determine, as the obtained metal concentration C (mmol/L). Based on the following formula of metal adsorption rate is determined.

Metal adsorption rate = (1-C × 50) × 100 (%)

The adsorption measurement sample after the sample is taken out from the solution, expunged attached liquid, in ion-exchange water 20 ml in 80 the impregnated [...] 3 hours to elute metal, taking eluant 1 ml as the sample and diluted to 50 ml rear, ICP emission spectral analysis device for measuring metal concentration, is set as the D (mg/L). elution rate is obtained through the following formula.

elution rate =D / (3.94-197 ×C) × 100 (%)

(Embodiment F-1-3, 5 and comparative example F-1, 2)

The adsorptive material 50 mg into the target metal ion concentration is 100 mg/L of 1 equivalent hydrochloric acid solution 200 ml in, for 25 the stirring [...] 60 minutes. Furthermore, heating solution 1 ml as the sample and diluted to 50 ml rear, by ICP emission spectral analysis device (Nippon   Jarrell   Ash manufacturing Company, IRIS-AP) determine, as the obtained metal concentration C (mg/L). Based on the following formula of metal adsorption rate is determined.

Metal adsorption rate = 100-C × 50 (%)

(Embodiment F-4 F-3 and comparison example)

The adsorptive material 50 mg into the target metal ion concentration is 200 mg/L of 0.2 equivalent of the nitric acid solution 25 ml in, for the 23 [...] stirring 24 hours. Furthermore, heating solution 1 ml as the sample and dilution to 100 ml rear, by ICP emission spectral analysis device (Nippon   Jarrell   Ash manufacturing Company, IRIS-AP) determine, as the obtained metal concentration C (mg/L). Based on the following formula of metal adsorption rate is determined.

Metal adsorption rate = 100-C × 50 (%)

(G-1-4 embodiment)

The adsorption material 100 mg inputs to boron concentration is 100 mg/L and pH=8 aqueous sodium hydroxide solution of 40 ml in, for the 25 [...] stirring 24 hours. Furthermore, the solution sampling, using ICP emission spectral analysis device (Nippon   Jarrell   Ash manufacturing Company, IRIS-AP) carry out the measurement, as will be the boron density of C (mg/L). Based on the following formula of metal adsorption quantity is determined.

Each 1g (mg/g) =40-C × 0.4 the boron attractsattaches the quantity of the sample

(G-5 embodiment)

The adsorptive material 50 mg inputs to arsenic the concentration of 20 mg/L and pH=3 nitric acid solution of 100 ml in, for the 25 [...] stirring 24 hours. Furthermore, the solution sampling, atom is used for absorbing light instrument (Corporation Hitachi manufacturing, Z-5000) determine, as the obtained arsenic concentration C (mg/L). Based on the following formula of metal adsorption quantity is determined.

Each 1g arsenic adsorptive capacity (mg/g) =40-C × 2 of the sample

(To EVOH into the aliphatic amino examples of grafted chain)

[A-1 embodiment]

For test (Labo-plastomill) plasticator for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size using the screen 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.60  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the use of methanol to wash and dry particles, then evaluation of the grafting, its result is 281%. Further the adjustment to the 80 [...] of diethylentriamine of 53% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing with methanol and dried the particles, obtained by grafting the amino group of the ethylene-vinyl alcohol copolymer to form a resistance to aqueous metal ion adsorption material. The screen for the obtained metal ion adsorption material grading as the particle size of 425 the the m-710 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material of an average pore size of the micropore to the 0.51  m, for functional group quantity 9.6mmol/g.

[A-2 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, E105) 50 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 50 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size using the screen 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 1.56  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the methanol used for the cleaning and drying of the particles, evaluation of the grafting, its result is 216%. Further the adjustment to the 80 [...] of diethylentriamine of 53% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading as the particle size of 425 the the m-710 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the average pore diameter of the micropore the 1.45  m, for functional group quantity 8.8mmol/g.

[A-3 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, L104) 60 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA217) 40 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size using the screen 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.83  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the methanol used for the cleaning and drying of the particles, evaluation of the grafting, its result is 366%. Further in the adjusted to 80 the ethylenediamine [...] of 40% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading as the particle size of 425 the the m-710 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the average pore diameter of the micropore the 0.71  m, for functional group quantity 7.7mmol/g.

[A-4 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, G156) 70 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA403) 30 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size using the screen 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.95  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the methanol used for the cleaning and drying of the particles, evaluation of the grafting, its result is 174%. Further the adjustment to the 80 [...] of diethylentriamine of 53% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading to particle size 212 the the m-500 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the average pore diameter of the micropore the 0.84  m, for functional group quantity 8.5mmol/g.

[A-5 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 99 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 1 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size using the screen 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore of the 0.15  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 278%. Further in the adjusted to 80 the ethylenediamine [...] of 40% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading to particle size 212 the the m-500 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the average pore diameter of the micropore of the 0.10  m, for functional group quantity 7.2mmol/g.

[A-6 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 40 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA203) 60 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size using screen 425 the the m-710   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 3.46  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 303%. Further in the adjusted to 80 the ethylenediamine [...] of 40% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading to particle size 1000 the the m-1400 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the average pore diameter of the micropore the 2.85  m, for functional group quantity 7.4mmol/g.

[A-7 embodiment]

A-1 to the embodiment of the porous ethylene-vinyl alcohol copolymer particle irradiation 30kGy the γ-ray, is placed in the air 1 hour, then impregnating after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 10% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 132%. Further the adjustment to the 80 [...] of diethylentriamine of 53% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading as the particle size of 425 the the m-710 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the capillary, the mean pore size of 0.58 the  m, for functional group quantity 6.2mmol/g.

[A-8 embodiment]

A-1 the embodiment of the graft copolymer particles (grafting 281%)is impregnated in the adjusted to 80 the of [...] N, N '-dimethyl-ethylenediamine of 49% isopropanol solution quality, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading as the particle size of 425 the the m-710 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the average pore diameter of the micropore of the 0.46  m, for functional group quantity 6.5mmol/g.

[A-9 embodiment]

A-1 the embodiment of the ethylene-vinyl alcohol copolymer and the vinyl alcohol polymer melt mixture crushing, the use of screen the production of particle size 150 the the m-300   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.60  m. To the porous particle irradiation 60kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of glycidyl methacrylate 60% of the quality of 80 the isopropanol solution [...] , stirring 120 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 389%. Further the adjustment for the 80 of [...] N-(2-amino ethyl) piperazine 65% isopropanol solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading to particle size 212 the the m-425 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the average pore diameter of the micropore of the 0.49  m, for functional group quantity 9.1mmol/g.

[A-10 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 60 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 40 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size using the screen 106 the the m-212   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles of an average pore size of the micropore in the 1.37  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour, then impregnating after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 30% isopropanol solution quality, stirring 120 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 364%. Further the adjustment to the 80 [...] polyethylene imine (Corporation Japan catalyst manufacturing,   SP-200 EPOMIN) of 50% isopropanol solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the graft with amino ethylene-vinyl alcohol copolymer of the water resistance of the formed metal ion adsorption material. The screen for the obtained metal ion adsorption material grading of particle size 150 the the m-300 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1. Need to prove, the adsorption material for the average pore diameter of the micropore the 1.09  m, for functional group quantity 4.5mmol/g.

[Comparison example A-1]

Commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) after crushing (non-porous), the particle size using sieves the graduation 425 the the m-710 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1.

[Comparison example A-2]

The commercial vinyl alcohol polymer (Kuraray Company manufacturing, PVA117) after crushing (non-porous), making particle size using the screen 212 the the m-425   m of the particles. To the particle irradiation 30kGy the γ-ray, is placed in air and the 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 0%, completely not carrying out the graft polymerization. The use of the particle and the adsorption rate of Pd elution rate , but particle severe swelling, cannot be accessed.

[Comparison example A-3]

For test for the commercial plasticator the vinyl alcohol polymer (Kuraray Company manufacturing, PVA117) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size using the screen 212 the the m-425   m particles (non-porous). Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, at this moment, dissolving substantially all of the, particles cannot be taken out.

[Comparison example A-4]

A-2 the example of the particle size of the obtained 425 the the m-710   m ethylene-vinyl alcohol copolymer irradiation 100kGy electron beam, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 70 [...] vinyl benzyl trimethyl ammonium chloride of 30% in the quality of the aqueous solution, the stirring 24 hours, the implementation of the graft polymerization. Furthermore, the obtained particles after washing with water and drying, evaluation of the grafting, its result is 33% (functional groups: 1.2mmol/g). The use of screen will be resistance to aqueous metal ion adsorption material grading as the particle size of 425 the the m-710 particle   m, and adsorption of the Pd elution rate. The results are shown in table 1.

[Comparison example A-5]

A-1 to the embodiment of the particle size of the obtained 425 the the m-710   m ethylene-vinyl alcohol copolymer irradiation 30kGy electron beam, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 70 [...] vinyl benzyl trimethyl ammonium chloride of 30% in the quality of the aqueous solution, the stirring 24 hours, the implementation of the graft polymerization, at this time, particles of severe swelling, cannot be accessed.

[Comparison example A-6]

The use of anion exchange resin (Mitsubishi chemical Corporation manufacturing,   SA10A DIAION) as a metal ion adsorption material, and adsorption of the Pd elution rate. The results are shown in table 1.

[Comparison example A-7]

The use of anion exchange resin (Mitsubishi chemical Corporation manufacturing,   WA20 DIAION) as a metal ion adsorption material, and adsorption of the Pd elution rate. The results are shown in table 1.

-A-1-A by the embodiment 10 can be known, the adsorbing material of this invention can absorb metal ion, and can effectively elute, therefore the separation and recovery of the metal ion is a very effective.

Such that the comparison is an example A-1 as, ethylene-vinyl alcohol copolymer is not of itself exhibit metal ion adsorption performance. On the other hand, such that the comparison is an example A-2, A -3 as, the vinyl alcohol polymer used as the substrate, poor water resistance. On the other hand, to the quaternary ammonium salt as the adsorbing group, such as comparison example A-4 introduction amount of the functional group, as in the case of relatively small, insufficient adsorption, such as comparison example A-5 increase of the adsorption group, as in the case of introduction amount, swelling serious and can not be taken out in a particle shape. Furthermore, for comparative example A-6, A -7 of the commercial shown in the case of an anion exchange material, is not able to meet the adsorption, these two properties to elute performance.

(To EVOH into the aromatic amino group of the grafted chain examples)

[B-1 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size using sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.60  m. To the porous particle irradiation 30kGy the γ-ray, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 247%. Further the adjustment for the 80 of [...] 4-amino -1, 2, 4-triazole 20% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the aromatic nitrogen-containing heterocycle is introduced into the graft chain in the ethylene-vinyl alcohol copolymer of the water resistance of the formed adsorption material. The screen will be used for grading the particle size of the absorption material 212 the the m-500   m particles, adsorption of the Pd. The results are shown in table 2. Need to prove, the adsorption material for the capillary, the mean pore size of 0.58 the  m, for functional group quantity 11.5mmol/g.

[B-2 embodiment]

B-1 the embodiment of the graft of the glycidyl methacrylate graft copolymer particles which are impregnated in the adjusted to 80 the of [...] 3-amino -1H-1, 2, 4-triazole 20% isopropanol solution quality, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the aromatic nitrogen-containing heterocycle is introduced into the graft chain in the ethylene-vinyl alcohol copolymer of the water resistance of the formed adsorption material. The screen will be used for grading the particle size of the absorption material 212 the the m-500   m particles, adsorption of the Pd. The results are shown in table 2. Need to prove, the adsorption material for the average pore diameter of the micropore of the 0.50  m, for functional group quantity 10.1mmol/g.

[B-3 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 80 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 20 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore of the 0.43  m. To the porous particle irradiation 30kGy the γ-ray, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 270%. Further the adjustment to the 80 of [...] 1-(3-aminopropyl) imidazole 20% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target by the aromatic nitrogen-containing heterocycle is introduced into the graft chain in the ethylene-vinyl alcohol copolymer of the water resistance of the formed adsorption material. The screen will be used for grading the particle size of the absorption material 212 the the m-500   m particles, adsorption of the Pd. The results are shown in table 2. Need to prove, the adsorption material for the average pore diameter of the micropore the 0.40  m, for functional group quantity 8.5mmol/g.

[B-4 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, E105) 60 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA217) 40 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 1.46  m. To the porous particle irradiation 30kGy the γ-ray, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 223%. Further the adjustment for the 80 of [...] 1-Aminobenzimidazoles triazole 20% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 4 hours. After the reaction, the methanol used for cleaning the particle and drying, to obtain the target by the aromatic nitrogen-containing heterocycle is introduced into the graft chain of the ethylene-vinyl alcohol copolymer to form the water resistance of the adsorbing material. The screen will be used for grading the particle size of the absorption material 212 the the m-500   m particles, adsorption of the Pd. The results are shown in table 2. Need to prove, the adsorption material for the average pore diameter of the micropore the 1.39  m, for functional group quantity 10.1mmol/g.

[Comparison example B-1]

Commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, E105) crushing, the particle size for the sieves the graduation 425 the the m-710   m particles (non-porous). Use of the particle to evaluate the adsorption of the Pd. The results are shown in table 2.

[Comparison example B-2]

B-1 the embodiment of the screen will be recorded in the glycidyl methacrylate graft of the graft copolymer particle classification for particle size 212 the the m-500   m particles, adsorption of the Pd. The results are shown in table 2.

[Table 2]

-B-1-B by the embodiment 4 can be known, the adsorbing material of this invention can absorb metal ion, therefore, for example, in the separation and recovery of the metal ion is a very effective.

Such that the comparison is an example B-1 as, ethylene-vinyl alcohol copolymer is not of itself exhibit metal ion adsorption performance. Such that the comparison is an example B-2 that, in the absence of the amino group introduced into the graft chain, does not show a metal ion adsorption performance.

(To EVOH into the thioureido or isothiourea base examples of the grafted chain)

[C-1 embodiment]

(1) for test for the commercial plasticator ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 50 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 50 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, to sieves the graduation particle size for 106 the the m-212   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 1.56  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol wash and dry, then evaluation of the grafting, its result is 210%.

(2) then, the adjusted to a 50 the thiourea [...] the 7% in the quality of the aqueous solution, the thiourea to 0.1 equivalent hydrochloric acid to dissolve, further impregnating the above-mentioned (1) particle in, to enable its reaction 3 hours. After the reaction, the particle washing with water and drying, sieves the graduation to particle size for 106 the the m-500 particle   m, to obtain the target resistance to dryness metal ion adsorption material. The functional group introduction amount 1.4mmol/g, the average pore diameter of the micropore the 1.53  m. The results are displayed in table 3-1.

[C-2 embodiment]

In addition of the isothiourea the base leadshydrochloric acid quantity relative to thiourea as a 0.7 equivalent outside, C-1 with the embodiment to operate the same, the drying-resistant metal ion adsorption material. The functional group introduction amount 2.2mmol/g, the average pore diameter of the micropore the 1.51  m. The results are displayed in table 3-1.

[C-3 embodiment]

In addition of the isothiourea the base leadshydrochloric acid quantity relative to thiourea as a 1.4 equivalent outside, C-1 with the embodiment to operate the same, the drying-resistant metal ion adsorption material. The functional group introduction amount 2.3mmol/g, the average pore diameter of the micropore the 1.50  m. The results are displayed in table 3-1.

[C-4 embodiment]

(1) for test for the commercial plasticator ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 60 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 40 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles of an average pore size of the micropore in the 1.37  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 407%.

(2) then, the adjusted to 80 the thiourea [...] of 12% in the quality of the aqueous solution, the thiourea to 0.7 equivalents of hydrochloric acid to dissolve, further impregnating the above-mentioned (1) particle in, to enable its reaction 3 hours. After the reaction, the particle washing with water and drying, the particle size for the sieves the graduation 425 the the m-710 particle   m, by the drying-resistant metal ion adsorption material. The functional group introduction amount 2.8mmol/g, the average pore diameter of the micropore the 1.30  m. The results are displayed in table 3-1.

[C-5 embodiment]

(1) for test for the commercial plasticator ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, E105) 60 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA217) 40 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore of the 1.40  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 223%.

(2) then, the adjusted to 80 the thiourea [...] of 12% in the quality of the aqueous solution, the thiourea to 1.4 equivalents of hydrochloric acid to dissolve, further impregnating the above-mentioned (1) particle in, to enable its reaction 3 hours. After the reaction, the particle washing with water and drying, the particle size for the sieves the graduation 425 the the m-710 particle   m, by the drying-resistant metal ion adsorption material. The functional group introduction amount 2.5mmol/g, the average pore diameter of the micropore the 1.34  m. The results are displayed in table 3-1.

[C-6 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.27  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 274%. Further the adjustment to the 80 [...] of diethylentriamine of 53% isopropyl alcohol solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing the particles with methanol and dried, to obtain the graft copolymer with amino. Further the adjustment to the 80 of methyl isothiocyanate [...] 40 mass % b Impregnating the particles in alkane solution , to enable its reaction 3 hours. After reaction, washing with methanol and drying the particles, the particle size for the sieves the graduation 212 the the m-500 particle   m, by the drying-resistant metal ion adsorption material. The functional group introduction amount 1.5mmol/g, the average pore diameter of the micropore the 0.21  m. The results are displayed in table 3-1.

[C-7 embodiment]

(1) for test for the commercial plasticator ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.27  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 274%.

(2) then, the adjusted to 80 the thiourea [...] of 12% in the quality of the aqueous solution, the thiourea to 1.4 equivalents of hydrochloric acid to dissolve, further impregnating the above-mentioned (1) particle in, to enable its reaction 3 hours. After the reaction, the particle washing with water and drying, the particle size for the sieves the graduation 425 the the m-710 particle   m, by the drying-resistant metal ion adsorption material. The functional group introduction amount 2.6mmol/g, an average pore size of the microporous of the 0.23  m. The results are displayed in table 3-1.

[C-8 embodiment]

Methacrylic acid is added to the reactor 3- bromine propyl ester 100 parts by mass, thiourea 31 parts by mass, ethanol 1200 parts by mass, in the heating to reflux the reaction of 14 hours. After removing the solvent by distillation, crystallization in isopropanol in purification, the obtained 3-( ureido-Dcarbamido sulfo-) propyl methyl acrylic acid ester hydrobromide 112 parts by mass. Furthermore, the commercial plasticator for testing for the ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 80 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 20 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore of the 0.43  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 the [...] 3-( ureido-Dcarbamido sulfo-) propyl methyl acrylic acid ester hydrobromide of 10% in the quality of the aqueous solution, mixing 90 minutes, the implementation of the graft polymerization. Evaluation of the grafting, its result is 53%. Furthermore, the mixed solution of water/methanol for cleaning and drying of the particles, the particle size for the sieves the graduation 300 the the m-500 particle   m, by the drying-resistant metal ion adsorption material. The functional group introduction amount 1.5mmol/g, the average pore diameter of the micropore the 0.40  m. The results are displayed in table 3-1.

[C-9 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.27  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 274%. Then the particle is impregnated in adjusted to 80 the diethylentriamine [...] of the 53% isopropanol solution quality, to enable its reaction 3 hours. After reaction, washing the particles with methanol and dried, to obtain the graft copolymer with amino. Further the adjustment for the 100 [...] the particles with the water of reaction ammonium thyiocyanate 12 hours. After the reaction, the particle washing with water and drying, the particle size for the sieves the graduation 212 the the m-500 particle   m, by the drying-resistant metal ion adsorption material. The functional group introduction amount 1.3mmol/g, the average pore diameter of the micropore the 0.25  m. The results are displayed in table 3-1.

[C-10 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, the particle size for the sieves the graduation 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.27  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 274%. Further in the adjusted to 80 the ethylenediamine [...] of 50% isopropanol solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing the particles with methanol and dried, to obtain the graft copolymer with amino. Further the adjustment for the 20 the [...] 10 mass % sodium hydroxide aqueous solution in the reaction with carbon disulfide the particle 2 hours, then add butylamine, in 40 the reaction [...] 1 hour. After reaction, washing with methanol and drying the particles, the particle size for the sieves the graduation 212 the the m-500 particle   m, by the drying-resistant metal ion adsorption material. The functional group introduction amount 1.2mmol/g, the average pore diameter of the micropore the 0.22  m. The results are displayed in table 3-1.

[C-11 embodiment]

C-1 embodiment of use of the metal ion adsorption material, the adsorption quantity of Pt evaluation. The results are displayed in table 3-2.

[C-12 embodiment]

C-2 embodiment of use of the metal ion adsorption material, the adsorption quantity of Pt evaluation. The results are displayed in table 3-2.

[C-13 embodiment]

C-3 embodiment of use of the metal ion adsorption material, the adsorption quantity of Pt evaluation. The results are displayed in table 3-2.

[Comparison example C-1]

Commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) after grinding, the particle size for the sieves the graduation 425 the the m-710   m particles (non-porous), the evaluation of the adsorption rate of Pt. The results are displayed in table 3-2.

[Comparison example C-2]

As a metal ion adsorption material chelating resin (Ajinomoto Company   Fine-Techno manufacturing, MA-A) vacuum drying at room temperature 12 hours later, the adsorption quantity of Pt evaluation. The results are displayed in table 3-2.

[Comparison example C-3]

As a metal ion adsorption material chelating resin (Purolite   International Company manufacturing, Purolite   S920) vacuum drying at room temperature 12 hours later, the adsorption quantity of Pt evaluation. The results are displayed in table 3-2.

[Table 3-1]

[Table 3-2]

Accurately construct C-1-C -10 is shown, according to the manufacturing method of the invention, can be obtained with thiourea structure or isothiourea structure of an ethylene-vinyl alcohol graft copolymer. Furthermore, -C-11-C from the embodiment 13 resin after drying is shown in the adsorption test can be known, the adsorbing material of this invention in the separation and recovery of the metal ions is very effective.

Such that the comparison is an example C-1 as, ethylene-vinyl alcohol copolymer is not of itself exhibit metal ion adsorption performance. Furthermore, for comparative example C-2, C -3 shown in the case of commercial chelating resin, evaluation is after drying the adsorption performance of the adsorption characteristic of adequate performance.

(To EVOH into a carboxyl group (imino diacetoxy) examples of the grafted chain)

[D-1 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 50 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 50 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making the particle size of the screen used for 106 the the m-212   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 1.56  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 40% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 175%. Further the adjustment for the 80 [...] of iminodiacetic acid disodium 30% aqueous solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing with water and drying the particles, obtained in the target by the grafted chain with imino diacetoxy ethylene-vinyl alcohol copolymer-shaped metal ion adsorption material. The screen for the obtained metal ion adsorption material grading as the particle size is 300 the the m-500 particle   m, to evaluate the cu, Co, the adsorption performance of Ni. Table displayed in the particle 4-1, the results of the performance evaluation shown in table 4-2. Need to prove, the adsorption material for the average pore diameter of the micropore the 1.45  m, for functional group quantity 2.1mmol/g (to carboxylic acid group as 4.2mmol/g).

[D-2 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making the particle size of the screen used for 106 the the m-212   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.27  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 60% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 374%. Further the adjustment for the 80 [...] of iminodiacetic acid disodium 30% aqueous solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing with water and drying the particles, obtained in the target by the grafted chain with imino diacetoxy ethylene-vinyl alcohol copolymer of a metal ion adsorption material. The screen for the obtained metal ion adsorption material grading as the particle size is 300 the the m-500 particle   m, to evaluate the cu, Co, the adsorption performance of Ni. Table displayed in the particle 4-1, the results of the performance evaluation shown in table 4-2. Need to prove, the adsorption material of an average pore size of the micropore to the 0.20  m, for functional group quantity 2.3mmol/g (to carboxylic acid group as 4.6mmol/g).

[D-3 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, E105) 70 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA217) 30 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making the particle size of the screen used for 106 the the m-212   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore of the 0.46  m. To the porous particle irradiation 30kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 15% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 87%. Further the adjustment for the 80 [...] of iminodiacetic acid disodium 30% aqueous solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing with water and drying the particles, obtained in the grafted chain of the targets with imino diacetoxy ethylene-vinyl alcohol copolymer of a metal ion adsorption material. The screen for the obtained metal ion adsorption material grading as the particle diameter of the 106 m-212 the the particle   m, to evaluate the cu, Co, the adsorption performance of Ni. Table displayed in the particle 4-1, the results of the performance evaluation shown in table 4-2. Need to prove, the adsorption material for the average pore diameter of the micropore of the 0.37  m, for functional group quantity 1.2mmol/g (to carboxylic acid group as 2.4mmol/g).

[D-4 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 60 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 40 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 1180 the the m-1400   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles of an average pore size of the micropore in the 1.37  m. To the porous particle irradiation 100kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 60% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 407%. Further the adjustment for the 80 [...] of iminodiacetic acid disodium 30% aqueous solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing with water and drying the particles, obtained in the target by the grafted chain with imino diacetoxy ethylene-vinyl alcohol copolymer of a metal ion adsorption material. The screen for the obtained metal ion adsorption material grading to particle size 2360 the the m-2800 particle   m, to evaluate the cu, Co, the adsorption performance of Ni. Table displayed in the particle 4-1, the results of the performance evaluation shown in table 4-2. Need to prove, the adsorption material for the average pore diameter of the micropore of the 1.16  m, for functional group quantity 2.5mmol/g (to carboxylic acid group as 5.0mmol/g).

[D-5 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, L104) 80 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA217) 20 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, screen for the production of particle size 150 the the m-300   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.63  m. To the porous particle irradiation 100kGy the γ-ray, is placed in the air 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] methyl glycidyl acrylate 60% isopropanol solution quality, mixing 90 minutes, the implementation of the graft polymerization. Furthermore, the obtained particles with methanol and dried after cleaning, evaluation of the grafting, its result is 365%. Further the adjustment for the 80 [...] of iminodiacetic acid disodium 30% aqueous solution impregnated in the quality of the particle, to enable its reaction 3 hours. After reaction, washing with water and drying the particles. Then the particle is added to the 5% aqueous solution of calcium chloride in quality, in the 40 [...] stirring 1 hour. Furthermore, washing with water and drying the particles, obtained in the target by the grafted chain with imino diacetoxy ethylene-vinyl alcohol copolymer of a metal ion adsorption material. The screen for the obtained metal ion adsorption material grading to particle size 212 the the m-425 particle   m, to evaluate the cu, Co, the adsorption performance of Ni. Table displayed in the particle 4-1, the results of the performance evaluation shown in table 4-2. Need to prove, the adsorption material of an average pore size of the micropore to the 0.57  m, for functional group quantity 2.0mmol/g (to carboxylic acid group as 4.0mmol/g).

[Comparison example D-1]

Commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, E105) crushing, making particle size by sieve 300 the the m-500   m particles (non-porous). The use of the particle evaluation cu, Co, the adsorption performance of Ni. The performance evaluation results shown in table 4-2.

[Comparison example D-2]

The commercial chelating resin (Purolite   International Company manufacturing, Purolite   S930) in 40 the vacuum drying under [...] 12 hours later, the evaluation cu, Co, the adsorption performance of Ni. The performance evaluation results shown in table 4-2.

[Table 4-1]

[Table 4-2]

Accurately construct D-1-D -5 shown, this invention has a carboxyl group (imino diacetoxy) ethylene-vinyl alcohol graft copolymer particles show excellent metal ion adsorption performance, therefore the separation and recovery of the metal ion is a very effective.

Such that the comparison is an example D-1 as, ethylene-vinyl alcohol copolymer is not of itself exhibit metal ion adsorption performance. Furthermore, for comparative example D-2 shown in the case of commercial chelating resin, the dryness is poor, therefore, adsorption performance evaluation after drying did not demonstrate sufficient absorption characteristics.

(To EVOH into the ether base or uncle examples of grafted chain amido group)

[E-1 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.27  m. To the porous particle irradiation 30kGy γ-ray after the, is impregnated in the after nitrogen replacement of the 80 the [...] N, N '-diethyl acrylamide 80% isopropanol solution quality, mixing 90 minutes, the implementation of graft polymerization, grafting of the 72% porous graft copolymer particles. Furthermore, methanol for cleaning the particle and drying, to obtain the target adsorption material. The screen will be used for grading the particle size of the absorption material 300 the the m-500 particle   m, evaluation on the Au, Pd, Rh and the performance of the elution of Au performance. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material for the average pore diameter of the micropore the 0.21  m, for functional group quantity 3.3mmol/g.

[E-2 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 10 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.27  m. To the porous particle irradiation 30kGy γ-ray after the, is impregnated in the after nitrogen replacement of the 80 four hydrogen rice polishings ester[...] of the methyl acrylic acid 60% isopropanol solution quality, mixing 90 minutes, the implementation of graft polymerization, grafting of the 87% porous graft copolymer particles. Furthermore, methanol for cleaning the particle and drying, to obtain the target adsorption material. The screen will be used for grading the particle size of the absorption material 300 the the m-500 particle   m, evaluation on the Au, Pd, Rh and the adsorption performance on the elution of Au. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material for the average pore diameter of the micropore the 0.19  m, for functional group quantity 2.7mmol/g.

[E-3 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 70 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA217) 30 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore the 0.88  m. To the porous particle irradiation 30kGy γ-ray after the, is impregnated in the after nitrogen replacement of the 80 of the methyl acrylic acid rice polishings ester[...] 60% isopropanol solution quality, mixing 90 minutes, the implementation of graft polymerization, grafting of the 65% porous graft copolymer particles. Furthermore, methanol for cleaning the particle and drying, to obtain the target adsorption material. The screen will be used for grading the particle size of the absorption material 300 the the m-500 particle   m, evaluation on the Au, Pd, Rh and the adsorption performance on the elution of Au. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material for the average pore diameter of the micropore the 0.79  m, for functional group quantity 2.3mmol/g.

[E-4 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, E105) 60 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA217) 40 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 1180 the the m-1400   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore of the 1.40  m. To the porous particle irradiation 100kGy γ-ray after the, is impregnated in the after nitrogen replacement of the 80 four hydrogen rice polishings ester[...] of the methyl acrylic acid 60% isopropanol solution quality, mixing 90 minutes, the implementation of graft polymerization, grafting of the 100% porous graft copolymer particles. Furthermore, methanol for cleaning the particle and drying, to obtain the target adsorption material. The screen will be used for the absorption material to particle size classification 2360 the the m-2880 particle   m, evaluation on the Au, Pd, Rh and the adsorption performance on the elution of Au. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material for the average pore diameter of the micropore the 1.19  m, for functional group quantity 3.9mmol/g.

[E-5 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 80 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 20 parts by mass for the 210 the temperature of the melt under [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles to the average pore diameter of the micropore of the 0.43  m. To the porous particle irradiation 30kGy γ-ray after the, is impregnated in the after nitrogen replacement of the 80 [...] N-vinyl pyrrolidone of 40% isopropanol solution quality, mixing 90 minutes, the implementation of graft polymerization, grafting of the 54% porous graft copolymer particles. Furthermore, methanol for cleaning the particle and drying, to obtain the target adsorption material. The screen will be used for grading the particle size of the absorption material 300 the the m-500 particle   m, evaluation on the Au, Pd, Rh and the adsorption performance on the elution of Au. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material for the average pore diameter of the micropore the 0.40  m, for functional group quantity 3.2mmol/g.

[E-6 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) 60 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA205) 40 parts by mass of the 210 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 212 the the m-425   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the vinyl alcohol polymer for extracting only, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles of an average pore size of the micropore in the 1.37  m. To the porous particle irradiation 30kGy γ-ray after the, impregnated after nitrogen replacement glycol monomethyl ether of methyl acrylate 60% isopropanol solution quality, mixing 90 minutes, the implementation of graft polymerization, grafting of the 107% porous graft copolymer particles. Furthermore, methanol for cleaning the particle and drying, to obtain the target adsorption material. The screen will be used for grading the particle size of the absorption material 300 the the m-500 particle   m, evaluation on the Au, Pd, Rh and the adsorption performance on the elution of Au. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material of an average pore size of the micropore to the 1.20  m, for functional group quantity 2.8mmol/g.

[Comparison example E-1]

Commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, F101) crushing, making particle size by sieve 212 the the m-425   m and substantially no microporous particles. To the particle irradiation 30kGy γ-ray after the, is impregnated in the after nitrogen replacement of the 80 hydrogen rice polishings ester[...] of four methacrylate of 50% isopropanol solution quality, mixing 90 minutes, the implementation of graft polymerization, grafting of the 29% of the graft copolymer particle. Furthermore, methanol for cleaning the particle and drying, to obtain the target adsorption material. The screen will be used for grading the particle size of the absorption material 300 the the m-500 particle   m, evaluation on the Au, Pd, Rh and the adsorption performance on the elution of Au. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material for functional group quantity 1.3mmol/g.

[Comparison example E-2]

The commercial polyethylene (Prime   Polymer manufacturing Company, 7000F) crushing, making particle size by sieve 212 the the m-425   m and substantially no microporous particles. To the particle irradiation 200kGy the γ-ray, is impregnated in the after nitrogen replacement of the 80 the [...] N, N '-diethyl acrylamide 80% isopropanol solution quality, mixing 90 minutes, the implementation of graft polymerization, grafting of the 25% of the graft copolymer particle. Furthermore, methanol for cleaning the particle and drying, to obtain the target adsorption material. The screen will be used for grading the particle size of the absorption material 300 the the m-500 particle   m, evaluation on the Au, Pd, Rh and the adsorption performance on the elution of Au. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material for functional group quantity 1.6mmol/g.

[Comparison example E-3]

The cross-linked polyvinyl chloride methyl styrene (chlorine methyl radical content is 6.55mmol/g) particles containing four hydrogen furol added to 20% of the quality of 2 mass % sodium hydroxide-isopropanol solution, and heating reflux for 5 hours. Furthermore, methanol for cleaning the particle and drying, to obtain a substantially no capillary adsorption material. The introduction amount of the functional group of the adsorbing material 2.0mmol/g. The screen will be used for grading the particle size of the absorption material 300 the the m-500 particle   m, evaluation on the Au, Pd, Rh and the adsorption performance on the elution of Au. Table displayed in the particle 5-1, the adsorption/elution performance evaluation result displayed in table 5-2. Need to prove, the adsorption material for functional group quantity 2.0mmol/g.

[Table 5-1]

[Table 5-2]

Accurately construct E-1-E -6 illustrated, the adsorbing material of this invention can selectively absorb only to the gold ion, and does not need special eluant, hot water can be simply and conveniently used for the adsorption of the gold ion to elute recovery, during the separation and recovery jin Shi is very effective.

Such that the comparison is an example E-1 such, the ethylene-vinyl alcohol copolymer under the condition of non-capillary, even if in the graft polymerization, functional groups are also less, therefore more difference, in addition, in polyethylene particle, cross-linked polyvinyl chloride methyl styrene particles under the condition of, the situation of the micropore-free compared with the case of a capillary, the result is also poor adsorption rate.

(To EVOH outside of an olefin resin, polyamide resin into the adsorptive functional group of the grafted chain examples)

[F-1 embodiment]

For test for the commercial plasticator polyethylene (Prime   Polymer manufacturing Company, 7000F) (PE) 90 parts by mass and polyvinyl pyrrolidone (BASF Company manufacturing, Kollidon   CL-M) (PVP) 10 parts by mass for 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 212 the the m-425   m of the particles. Then the obtained particles in the 80 [...] of isopropanol (iPrOH) stirring in 2 hours, the extracting only polyvinyl pyrrolidone, to obtain a porous polyethylene polymer particle. To the porous particle irradiation 100kGy of ionizing radiation, is impregnated in the after nitrogen replacement of the 0 [...] methyl acrylic acid (THFMA) of four hydrogen rice polishings ester 40% isopropanol solution quality, stirring 60 minutes later, the temperature is increased to 80 the [...] , implementation of graft polymerization. Furthermore, the methanol of the particles obtained after cleaning and drying, evaluation of the grafting, its result is 315%. The particles for the average pore diameter of the micropore of the 2.4  m, for functional group quantity 4.5mmol/g. Furthermore, by using a sieve the particle classification is a diameter 212 the the m-425 particle   m, the adsorption material grafted with ether groups. Au to the adsorbing material of the adsorption performance of the evaluation, the results shown in table 6.

[F-2 embodiment]

For test for the commercial plasticator polypropylene (Japan polypropylene Corporation manufacturing,   MA3 NOVATEC-PP) (PP) 90 parts by mass and polyvinyl pyrrolidone (BASF Company manufacturing, Kollidon   CL-M) 10 parts by mass for 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making the particle size of the screen used for 106 the the m-300   m of the particles. Then the obtained particles in the 80 in the isopropanol [...] stirring 2 hours, the extracting only polyvinyl pyrrolidone, to obtain a porous polypropylene polymer particles. To the porous particle irradiation 100kGy of ionizing radiation, is impregnated in the after nitrogen replacement of the 0 the [...] of glycidyl methacrylate (GMA) 40% isopropanol solution quality, stirring 60 minutes later, the temperature is increased to 80 the [...] , the implementation of the graft polymerization. Furthermore, the methanol of the particles obtained after cleaning and drying, evaluation of the grafting, its result is 545%. Then the particle is impregnated in adjusted to 80 the diethylentriamine [...] (DETA) of the 50% isopropanol solution quality, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target particle. The average pore diameter of the microporous particles in the 5.3  m, for functional group quantity 10.4mmol/g. Furthermore, the particles through the screen for grading the diameter of 106 the the m-300 particle   m, the adsorbing material of the graft with amino. The Pd to the adsorbing material of the adsorption performance evaluation, the results shown in table 6.

[F-3 embodiment]

For test for the commercial plasticator polypropylene (Japan polypropylene Corporation manufacturing,   MA3 NOVATEC-PP) 70 parts by mass and polyvinyl pyrrolidone (BASF Company manufacturing, Kollidon   CL-M) 30 parts by mass for 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, screen for the production of particle size of 425 the the m-710   m of the particles. Then the obtained particles in the 80 in the isopropanol [...] stirring 2 hours, the extracting only polyvinyl pyrrolidone, to obtain a porous polypropylene polymer particles. To the porous particle irradiation 100kGy of ionizing radiation, is impregnated in the after nitrogen replacement of the 0 the [...] N, N '-diethyl acrylamide (DEAA) of 40% isopropanol solution quality, stirring 60 minutes later, the temperature is increased to 80 the [...] , the implementation of the graft polymerization. Furthermore, the methanol of the particles obtained after cleaning and drying, evaluation of the grafting, its result is 105%. The particles for the average pore diameter of the micropore of the 7.5  m, for functional group quantity 4.0mmol/g. Furthermore, the screen for particle classification the diameter of 425 the the m-710 particle   m, grafted with amide by the adsorbing material. Au to the adsorbing material of the adsorption performance of the evaluation, the results shown in table 6.

[F-4 embodiment]

For test for the commercial plasticator nylon 6 (manufacturing Company SERVA, polyamide-6-powder) 80 parts by mass and polyethylene glycol (and optical Corporation manufacturing, polyvinyl alcohol 20000) 20 parts by mass for 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, screen for the production of particle size of 425 the the m-710   m of the particles. Then the obtained particles in the 100 the stirring in the hot water [...] 2 hours, the extracting only polyvinyl alcohol, the obtained porous nylon 6 polymer particles. To the porous particle irradiation 100kGy of ionizing radiation, is impregnated in the after nitrogen replacement of the 0 [...] methyl glycidyl acrylate 40% isopropanol solution quality, stirring 60 minutes later, the temperature is increased to 80 the [...] , the implementation of the graft polymerization. Furthermore, the methanol of the particles obtained after cleaning and drying, evaluation of the grafting, its result is 250%. The particle is impregnated in the adjusted to the 80 [...] of diethylentriamine of 50% isopropanol solution quality, reaction 4 hours later, methanol for cleaning the particle, the particle is impregnated in the further adjusted to the 80 [...] of methyl isothiocyanate (MeNCS) of 40 mass % b In alkane solution , to enable its reaction 3 hours. After reaction, washing the particles with methanol and dried, thioureido group has been grafted with the adsorption material. The adsorption material of an average pore size of the microporous of the 1.8  m, for functional group quantity 5.0mmol/g. Furthermore, the particles through the screen for grading the diameter of 425 the the m-710 particle   m, thioureido group has been grafted with the adsorption material. Pt to the adsorbing material of the adsorption performance of the evaluation, the results shown in table 6.

[F-5 embodiment]

For test for the commercial plasticator polypropylene (Japan polypropylene Corporation manufacturing,   MA3 NOVATEC-PP) (PP) 90 parts by mass and polyvinyl pyrrolidone (BASF Company manufacturing, Kollidon   CL-M) 10 parts by mass for 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making the particle size of the screen used for 106 the the m-300   m of the particles. Then the obtained particles in the 80 in the isopropanol [...] stirring 2 hours, the extracting only polyvinyl pyrrolidone, to obtain a porous polypropylene polymer particles. To the porous particle irradiation 100kGy of ionizing radiation, is impregnated in the after nitrogen replacement of the 80 the [...] of glycidyl methacrylate (GMA) 40% isopropanol solution quality, the implementation of the graft polymerization. Furthermore, the methanol of the particles obtained after cleaning and drying, evaluation of the grafting, its result is 18%. Then the particle is impregnated in adjusted to 80 the diethylentriamine [...] (DETA) of the 50% isopropanol solution quality, to enable its reaction 4 hours. After reaction, washing the particles with methanol and dried, to obtain the target particle. The average pore diameter of the microporous particles in the 5.3  m, for functional group quantity 2.9mmol/g. Furthermore, the particles through the screen for grading the diameter of 106 the the m-300 particle   m, the adsorbing material of the graft with amino. The Pd to the adsorbing material of the adsorption performance evaluation, the results shown in table 6.

[Comparison example F-1]

For test for the commercial plasticator polyethylene (Prime   Polymer manufacturing Company, 7000F) in 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, making particle size by sieve 212 the the m-425   m particles (non-porous). To the particle irradiation 100kGy of ionizing radiation, is impregnated in the after nitrogen replacement of the 0 four hydrogen rice polishings ester[...] of the methyl acrylate 40% isopropanol solution quality, stirring 60 minutes later, the temperature is increased to 80 the [...] , the implementation of the graft polymerization. Furthermore, the methanol of the particles obtained after cleaning and drying, evaluation of the grafting, its result is 70%. The particles for functional group quantity 2.3mmol/g. Furthermore, by using a sieve the particle classification is a diameter 212 the the m-425 particle   m, the adsorption material grafted with ether groups. Au to the adsorbing material of the adsorption performance of the evaluation, the results shown in table 6.

[Comparison example F-2]

For test for the commercial plasticator polypropylene (Japan polypropylene Corporation manufacturing,   MA3 NOVATEC-PP) in 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, screen for the production of particle size of 425 the the m-710   m particles (non-porous). To the particle irradiation 100kGy of ionizing radiation, is impregnated in the after nitrogen replacement of the 0 the [...] N, N '-diethyl acrylamide 40% isopropanol solution quality, stirring 60 minutes later, the temperature is increased to 80 the [...] , the implementation of the graft polymerization. Furthermore, the methanol of the particles obtained after cleaning and drying, evaluation of the grafting, its result is 45%. The particles for functional group quantity 2.4mmol/g. Furthermore, the particles through the screen for grading the diameter of 425 the the m-710 particle   m, grafted with amide by the adsorbing material. Au to the adsorbing material of the adsorption performance of the evaluation, the results shown in table 6.

[Comparison example F-3]

For test for the commercial plasticator nylon 6 (manufacturing Company SERVA, polyamide-6-powder) in 230 the temperature of mixing the molten [...] 3 minutes, the melt is then cooled and solidified, and the obtained mixture, screen for the production of particle size is 300 the the m-500   m particles (non-porous). To the particle irradiation 100kGy of ionizing radiation, is impregnated in the after nitrogen replacement of the 0 [...] methyl glycidyl acrylate 40% isopropanol solution quality, stirring 60 minutes later, the temperature is increased to 80 the [...] , the implementation of the graft polymerization. Furthermore, the methanol of the particles obtained after cleaning and drying, evaluation of the grafting, its result is 95%. The particle is impregnated in the adjusted to 80 the of trimethylamine [...] of 50% isopropanol solution quality, reaction 4 hours later, methanol for cleaning the particle, the particle is impregnated in the further adjusted to the 80 of methyl isothiocyanate [...] 40 mass % b In alkane solution , to enable its reaction 3 hours. After the reaction, the methanol used for cleaning the particle and drying, thioureido group has been grafted with the particle. The particles for functional group quantity 2.8mmol/g. Furthermore, the particles through the screen for grading the diameter of 300 the the m-500 particle   m, obtained by grafting a thioureido the adsorbing material. Pt to the adsorbing material of the adsorption performance of the evaluation, the results shown in table 6.

-F-1-F by the embodiment 5 can be known, the invention has realized with high adsorptive functional groups, and the metal adsorption excellent porous graft copolymer particles.

By comparing example F-1-F -3 can be known, the use of a porous case of graft copolymer particles, the grafting rate of the to be fully, therefore, cannot obtain sufficient adsorptive functional groups, metal adsorption performance is poor.

(To EVOH into the methyl glucose amidogen examples of the grafted chain)

[G-1 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, "F101 the [...] , MFR3.8g/10 sub-) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing," the PVA205 [...]) 10 parts by mass of a molten milling, and then the molten material is cooled and solidified, and the obtained mixture, making particle size by sieve 1180-1400 the particle   m. Then the obtained particles processed in hot water, extract the vinyl alcohol polymer, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particle-diameter average value of the capillary of the 0.36  m. To the porous particle irradiation 60kGy of ionizing radiation, the air in 25 the placing [...] 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] glycidyl methacrylate and isopropanol solution of stirring, the implementation of the graft polymerization. Evaluation of the grafting of the particles obtained, its result is 407%. Further the particles in the 80 the impregnated in the under the condition of [...] N-methyl-glucosamine in aqueous solution and stirring, by addition reaction of N-methyl-glucosamine, the target is obtained by grafting a N-methyl-glucosamine-based ethylene-vinyl alcohol graft copolymer of a metal ion adsorption material. The porous particles for introduction amount of the functional group 2.6mmol/g, an average pore size of the microporous of the 0.32  m. The screen for the obtained ethylene-vinyl alcohol graft copolymer particle size classification to 2360 the the m-2800 particle   m, boron, the adsorption rate of the evaluation. Table displayed in the particle 7-1, the adsorption results shown table 7-2.

[G-2 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, " G156 the [...] , the MFR 15g/10 sub-) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing, PVA217) 10 parts by mass of a molten milling, and then the molten material is cooled and solidified, and the obtained mixture, making particle size by sieve 212 the the m-425   m of the particles. Then the obtained particles processed in hot water, extract the vinyl alcohol polymer, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles of the microporous-diameter average value of the the 0.95  m. To the porous particle irradiation 100kGy of ionizing radiation, the air in 25 the placing [...] 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] glycidyl methacrylate and isopropanol solution of stirring, the implementation of the graft polymerization. Evaluation of the grafting of the particles obtained, its result is 370%. Further the particles in the 80 the impregnated in the under the conditions of [...] N-methyl-glucosamine and stirs in aqueous solution, N-methyl-glucosamine of the addition reaction, the target is obtained by grafting a N-methyl-glucosamine-based ethylene-vinyl alcohol graft copolymer of a metal ion adsorption material. The porous particles for introduction amount of the functional group 2.3mmol/g, the average pore diameter of the micropore the 0.90  m. Through the sieve will be ethylene-vinyl alcohol graft copolymer particle size classification is 212 the the m-500 particle   m, boron, the adsorption rate of the evaluation. Table displayed in the particle 7-1, the adsorption results shown table 7-2.

[G-3 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, "F101 the [...] , the MFR 3.8g/10 sub-) 90 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing," the PVA205 [...]) 10 parts by mass of a molten milling, and then the molten material is cooled and solidified, and the obtained mixture, making the particle size of the screen used for 106 the the m-212   m of the particles. Then the obtained particles in the hot water extracting the vinyl alcohol polymer, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles of the microporous-diameter average value of the the 0.27  m. To the porous particle irradiation 100kGy of ionizing radiation, the air in 25 the placing [...] 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] glycidyl methacrylate and isopropanol solution of stirring, the implementation of the graft polymerization. Evaluation of the grafting of the particles obtained, its result is 371%. Further the particles in the 80 the impregnated in the under the conditions of [...] N-methyl-glucosamine and stirs in aqueous solution, N-methyl-glucosamine of the addition reaction, the target is obtained by grafting a N-methyl-glucosamine-based ethylene-vinyl alcohol graft copolymer of a metal ion adsorption material. The porous particles for introduction amount of the functional group 2.4mmol/g, the average pore diameter of the micropore the 0.24  m. The screen for the obtained ethylene-vinyl alcohol graft copolymer particle size classification is 212 the the m-500 particle   m, boron, the adsorption rate of the evaluation. Table displayed in the particle 7-1, the adsorption results shown table 7-2.

[G-4 embodiment]

plasticator for testing for commercially available ethylene-vinyl alcohol copolymer (Kuraray Company manufacturing, "L104 the [...] , the MFR 8.9g/10 sub-) 80 parts by mass and vinyl alcohol polymer (Kuraray Company manufacturing," the PVA205 [...]) 20 parts by mass of a molten milling, and then the molten material is cooled and solidified, and the obtained mixture, screen for the production of particle size is 300 the the m-500   m of the particles. Then the obtained particles in the hot water extracting the vinyl alcohol polymer, to obtain a porous ethylene-vinyl alcohol copolymer particle. The porous particles of the microporous-diameter average value of the the 0.41  m. To the porous particle irradiation 20kGy of ionizing radiation, the air in 25 the placing [...] 1 hour later, is impregnated in the after nitrogen replacement of the 80 [...] glycidyl methacrylate and isopropanol solution of stirring, the implementation of the graft polymerization. Evaluation of the grafting of the particles obtained, its result is 269%. Further the particles in the 80 the impregnated in the under the conditions of [...] N-methyl-glucosamine and stirs in aqueous solution, N-methyl-glucosamine of the addition reaction, the target is obtained by grafting a N-methyl-glucosamine-based ethylene-vinyl alcohol graft copolymer of a metal ion adsorption material. The porous particles for introduction amount of the functional group 2.1mmol/g, the average pore diameter of the micropore the 0.36  m. The screen for the obtained ethylene-vinyl alcohol graft copolymer particle size classification is 212 the the m-500 particle   m, boron, the adsorption rate of the evaluation. Table displayed in the particle 7-1, the adsorption results shown table 7-2.

[G-5 embodiment]

G-4 using embodiment of the use of metal ion adsorption material to evaluate the adsorption of arsenic. Table displayed in the particle 7-1, the adsorption results shown table 7-2.

[Table 7-1]

[Table 7-2]

Accurately construct 1-4 illustrated, the use of ethylene-vinyl alcohol copolymer through the ionizing radiation under the condition of the graft polymerization, even if the irradiation of the ionizing radiation is placed at the room temperature, the graft polymerization can be carried out more stably, can be introduced in the grafted chain N-methyl-glucosamine-based ethylene-vinyl alcohol graft copolymer. Furthermore, the ethylene-vinyl alcohol graft copolymer for boron, arsenic and other quasi-metal exhibit adsorbability.

Industrial practicability

According to the present invention, can be used on industrial can be provided a novel porous graft copolymer particles, the use of the particle and the metal, the absorption material to have the high absorbability. The adsorption material can be efficiently recovered, e.g., platinum group metal, gold, silver, copper, nickel, chromium, vanadium, cobalt, lead, zinc, mercury, cadmium metal, therefore with practicability in the industry.

As mentioned above, the preferred embodiment of this invention described, however, for the purposes of the technical personnel in this field, can be based on the records of the application specification, in easily within the range of that various changes and modifications.

Therefore, such changes and modification being interpreted as by the right request within the scope of the invention.