JPH0623231B2 - Process for producing polymer having chelate forming ability - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polymer having a chelate-forming ability. More specifically, it relates to a method for producing a polymer having a novel chelate-forming ability, which is capable of effectively adsorbing and removing heavy metals from industrial wastewater and easily recovering the heavy metals.

[Conventional technology]

As pollution of rivers due to wastewater from factories and the like has become a problem in recent years, regulations for preventing pollution due to wastewater have been strengthened, and heavy metals contained in wastewater have been obliged to keep the concentration below a predetermined level. Mercury, cadmium, zinc,
Particularly strict regulations are set for harmful metals such as lead and copper chromium. A chelate resin is used as a method for removing heavy metals in such wastewater. For example, a styrene-divinylbenzene copolymer is added to an iminodiacetic acid group.
There are resins in which (1) or polyamine group (2) is introduced.

In addition, thiourea-type resins ((3) Safety Engineering 11, 85-92 (1972)) and dithiocarbamic acid-type resins ( (4) JP-A-49-99978) and the like are known. Recently, a polymer in which a mercapto group has been introduced into cellulose has also been reported ((5): Chemical Industry, July 1972 issue,
p. 941-945).

Further, as a chelate resin having an amidooxime group as a functional group, a method obtained by reacting a hydroxylamine with a resin having a nitrile structure has been reported ((6): JP-A-51-53598, (7): No. 53-126088, (8):
56-53106, (9): 59-41307).

[Problems to be solved by the invention]

However, the resins (1) and (2) have the drawbacks that the amount of heavy metals adsorbed (exchange capacity) is small and at the same time the adsorption rate is slow, and with regard to (1), there are many manufacturing processes and high manufacturing costs. In addition, the resins (3) and (4) were developed exclusively for the purpose of adsorbing and removing mercury and cadmium by giving selectivity to heavy metals, and the manufacturing process is simple and can be manufactured at low cost. However, there is a problem in the sanitary environment of workers because of the introduction of sulfur and the generation of odor due to sulfur compounds such as hydrogen sulfide.
Moreover, the polymer of (5) has not reached the practical stage yet.

All of the chelate resins (6) to (9) react a resin having a nitrile structure with hydroxylamine or the like, but all have low metal adsorption performance and a low recovery rate in recovering the adsorbed metal. Therefore, it has a drawback that the regeneration rate as a chelate resin becomes low, and as a result, the cost of treating wastewater becomes high.

In addition to the problems of conventional chelating resins as described above, there is a strong demand for chelating resins and polymers that can simultaneously remove many types of heavy metals at low cost, and not only harmful heavy metals but also gold, silver and other valuable heavy metals. Including such cases, there is an increasing demand that the adsorbed heavy metals can be easily recovered since they are often recovered and reused, and that the resins and polymers after recovery can be further recycled and used. As a result of an examination focusing on the above problems, the present invention has been achieved.

[Means for solving problems]

That is, the present invention provides (1) in the molecule as the substituent attached to the nitrogen, the formula - (CHR ') _n CN or and - (CH
R ') _n -COOR "(wherein R'is hydrogen or a carbon number of 1 to
An alkyl group of 3, n is an integer of 1 to 3, R ″ is a carbon number of 1 to
4 represents an alkyl group) 4) and a polyalkylene polyamine substitution product having at least one group having active hydrogen bonding to nitrogen (provided that alkylene is ethylene or propylene), A mixture containing an epoxy compound having at least two epoxy groups in the molecule,
(2) If necessary, after adding a curing agent for epoxy resin to the mixture, they are cured by heating as such, or they are suspended and dispersed in a water-soluble polymer compound or a surfactant aqueous solution, and cured by heating. A method for producing a polymer having a chelate-forming ability by reacting a cured resin obtained with hydroxylamine to introduce an amide oxime group and / or an oxime group, the mixture as it is or a water-soluble polymer thereof. Alternatively, a polymer having the same chelate-forming ability as described above can also be produced by using a prepolymer obtained by heating the mixture instead of the mixture when it is suspended and dispersed in an aqueous surfactant solution and cured. It is a manufacturing method that can be done.

That is, the present invention substitutes at least one active hydrogen bonded to a nitrogen atom of a polyalkylene polyamine with a cyanoalkyl group or an alkyl ester group of carboxyalkyl, and at the same time, at least two active hydrogens in the molecule. A mixture of the remaining polyalkylene polyamine derivative and an epoxy compound having at least two epoxy groups in the molecule, or a mixed solution obtained by dissolving it in an organic solvent (hereinafter referred to as "mixture (A ) '')
If necessary, a curing agent for epoxy resin is added to cause a curing reaction. It is also possible to heat the mixture (A) or a mixture thereof with a curing agent for epoxy resin to carry out a polyaddition reaction to produce a prepolymer and then to carry out a curing reaction to obtain a cured resin. Further, if necessary, a curing agent for an epoxy resin is added to either the mixture (A) or the prepolymer, and the mixture is dropped and suspended in an aqueous solution in which a water-soluble polymer or a surfactant is dissolved under heating and stirring. A cured resin can be obtained by carrying out a curing reaction. The cured resin thus obtained is reacted with hydroxylamine to introduce an amide oxime group and / or an oxime group. The amide oxime group can be obtained by reacting a hydroxylamine with a cyanoalkyl group which has been introduced by substituting the active hydrogen of the polyalkylenepolyamine structure. Similarly, the oxime group can be obtained by reacting a hydroxyamine with an alkyl ester group of carboxyalkyl which is introduced by substitution with active hydrogen.

As the polyalkylene polyamines used in the present invention,
Ethylenediamine, propylenediamine, phenylenediamine, hexamethylenediamine, metaxylenediamine, 1.3-bis (aminomethyl) cyclohexane, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, 3-
(2-Aminoethyl) aminopropylamine, N, N '
-Bis (3-aminopropyl) ethylenediamine, 1.14
-Diamino-4,8,11-triazatetradecane, 1.18-diamino-4,8,11,15-tetraazaoctadecane, pentapropylhexamine, iminobislopyramine, polyethyleneimine (molecular weight 300 to 100,000) and the like,
Further, a mono- or poly-N-alkyl-substituted product of the above polyalkylene polyamines (wherein the alkyl group is an alkyl group having 1 to 24 carbon atoms or a 2-hydroxyalkyl group having 2 to 30 carbon atoms), the polyalkylene polyamines and epichlorohydrin are It also includes a condensation reaction product and a condensation reaction product of a mono- or poly-N-alkyl substitution product of the above polyalkylene polyamines with epichlorohydrin, and each of the substitution product, the condensation reaction product or the condensation reaction product of the substitution product described above. It can be used in place of the polyalkylene polyamines. (These are collectively referred to as the “polyalkylene polyamine of the present invention”.) Next, at least one active hydrogen bonded to the nitrogen atom of the “polyalkylene polyamine of the present invention” is represented by the general formula — (CH
R ') _n CN or and-(CHR') _n -COOR "(however,
R'is hydrogen or a methyl group, n is an integer of 1 to 3, R "is an alkyl group having 1 to 4 carbon atoms), and a carboxyalkyl alkyl ester group and / or a carboxyalkyl alkyl ester group is substituted. The method is a monohaloacetonitrile, a monohalopropionitrile, a monohalobutyronitrile, an alkyl monohaloacetate, an alkyl monohalopropionate, an alkyl monohalobutyrate, an acrylonitrile, a methacrylonitrile, an alkyl acrylate in the “polyalkylene polyamine of the present invention”, It can be obtained by addition reaction with acrylic methacrylate, alkyl crotonic acid, or the like. The halogen of the monohalo compound shown here is any of chlorine, bromine and iodine, and alkyl is an alkyl group having 1 to 4 carbon atoms. The reaction product obtained here has at least 2 active hydrogens bonded to nitrogen in the molecule.
Substituent is introduced so that The reaction here is performed as follows.

`` Polyalkylene polyamine of the present invention '' and a monohalo compound or an unsaturated monomer in the presence or absence of a solvent such as benzene, toluene, xylene, chloroform, carbon tetrachloride, or the like, 30 to 120 ° C, preferably 60 to 80
The reaction is carried out at ℃ for 2 to 15 hours, preferably 3 to 5 hours.

Next, a mixture A obtained by adding a compound having at least two epoxy groups in the molecule to the addition reaction product of the “polyalkylene polyamine of the present invention” obtained above, and the mixture A containing an organic solvent, In the case where neither of them is contained, the reaction between the amine and the epoxy compound may occur with the passage of time to form a polymer, and therefore the mixture A exists as a mixture or a mixture containing a polymer.
Examples of the compound having at least two epoxy groups in the molecule used herein include 3-bis (1.2-epoxypropoxy) benzene, 1.4-bis (1.2-epoxypropoxy) benzene and 2.2. -Bis (p-1.2-epoxypropoxyphenyl) propane, N.N'-bis (2
・ 3-Epoxypropyl) piperazine, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol diglycidyl ether, pentaerythritol diglycidyl ether, sorbitol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1 1-bis (p-1.2-epoxypropoxyphenyl) 2,3-propanediol, vinylcyclohexene dioxide, butadiene dioxide, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, 1.1.2 2-
Tetrakis (p-1,2-epoxypropoxyphenyl) ethane, N, N, N ', N'-tetraglycidyl m
-Xylylenediamine, 1.3-bis (N, N-diglycidylaminomethyl) cyclohexane and the like,
These epoxy compounds may be used alone or in combination of two or more.

The organic solvent used here is benzene, toluene, xylene, chlorobenzene, O-dichlorobenzene, butyl cellosolve, isopropyl alcohol, DM.
F, DMSO, N-methylpyrrolidone, dioxane, carbon tetrachloride, chloroform, water and the like, and octylene oxide, butyl glycidyl ether, styrene oxide, phenyl glycidyl ether, p-butylphenol glycidyl ether, 3- ( It is also possible to use an epoxy resin diluent such as pentadecyl) phenyl glycidyl ether, allyl glycidyl ether, cyclohexene, α-pinene monoxide, fert-carboxylic acid glycidyl ester, and glycidyl methacrylate.
The above organic solvents may be used alone or in combination of two or more.

Next, there are the following two methods for curing the mixture A. In the first method, the mixture A or its prepolymer is used as it is, or an epoxy resin curing agent is added thereto, and the mixture is heated at 60 to 180 ° C. for 2 to 24 hours to carry out a curing reaction to obtain a cured resin. At that time, when an organic solvent is used for the mixture A, curing is performed while removing the solvent under reduced pressure.
A film-shaped or plate-shaped cured product is obtained. The second method is to add the mixture A or its prepolymer to an aqueous solution in which one or more kinds of water-soluble polymers or surfactants are dissolved, or to add a curing agent to the mixture A or its prepolymer. When it is added dropwise at -100 ° C and suspension polymerization is carried out, a spherical cured product having a substantially constant particle size is obtained.

The film-shaped or plate-shaped cured product obtained by the first method is used as it is or after being crushed into amorphous particles or powder, and then the following reaction step is performed. In addition, the spherical cured polymer obtained by the second method can freely control the particle size up to a powder form of 4 to 300 mesh or less,
There is no need to perform any special granulation process.

The curing reaction time in this case is 1 to 30 hours. As the epoxy resin curing agent used here, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaphenylenediamine, metaxylenediamine, heterocyclic diamine, N-aminoethylpiperazine, Diaminophenyl methane, diaminodiphenyl sulfone, phthalic anhydride, hexahydrophthalic anhydride, methylnadic acid anhydride, pyromellitic anhydride,
Examples thereof include, but are not limited to, dicyandiamide, BF ₃ , and monoethylamine. Examples of the water-soluble polymer include carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol (molecular weight: 400 to 6,000), sodium polyacrylate and the like. Examples of surfactants include anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants. Among these surfactants, particularly good sphericity is obtained when nonionic surfactants are used. A polymer is obtained.

Then, the granular, powdery or spherical cured polymer obtained above is reacted with hydroxylamine to form an amide oxime group or an oxime group. At 40-150 ° C, preferably 50,
When the reaction is carried out at -100 ° C for 1-10 hours, preferably 2-5 hours, a polymer having a chelate-forming ability is obtained. Hydroxylamine is obtained by neutralizing a hydroxylamine salt such as hydrochloride, sulfate or acetate with an alkali, and is used as a solution of water or a solvent containing water. The concentration of hydroxylamine is 1 to 6% by weight. , Preferably 2
4%. As the alkali, sodium hydroxide, potassium hydroxide or the like is used. As the solvent used in the reaction, water, dimethyformamide, dimethyl sulfoxide, tetrahydrofuran, alcohols such as methanol and ethanol can be used alone or in admixture of two or more.

The polymer having a chelate-forming ability obtained in the present invention can be used for adsorption removal of various heavy metals and valuable metals, and recovery, and as heavy metals, mercury, cadmium, lead, copper, zinc, chromium, manganese, and the like, It can be effectively used for adsorption removal and recovery of valuable metals such as gold, silver, platinum, nickel, cobalt, gallium and indium.

〔Example〕

 The present invention will be described below with reference to examples.

Example 1 Polyethyleneimine (average molecular weight 30,000) 100 parts, methyl acrylate 120 parts, ethanol-toluene (1: 1) 1
Charge 50 parts, conduct Michael addition reaction at 75-85 ° C for 4 hours, cool to 40 ° C, add 175 parts 2.2-bis (p-1.2-epoxypropoxyphenyl) propane, and add nitrogen. Conduct polyaddition reaction at 80-85 ℃ for 8 hours, then 30
Cool to ~ 40 ° C, form into a film, slowly heat while removing ethanol and toluene, and at 150-170 ° C.
Curing reaction was carried out for 20 hours. A hard, elastic, pale yellow transparent cured film was obtained. The cured film was ground to 20-100 mesh.

The crushed resin thus obtained is immersed in a 4 wt% hydroxylamine hydrochloride water-methanol solution (water: methanol = 0.5: 1 weight ratio) neutralized with potassium hydroxide, and reacted at 50 ° C. for 4 hours, A resin having chelating ability was obtained. 20
Resin classified to ~ 48 mesh was subjected to adsorption experiments.

Example 2 65 parts of ethylenediamine 2 butyl propionate, sorbitol diglycidyl ether (epoxy equivalent: 150) 82.6
Parts, charged with nitrogen and subjected to polyaddition reaction at 70 to 80 ° C for 1.5 hours, cooled to 30 to 40 ° C, added with 2.85 parts of diethylenetriamine to form a film, and added to 60 to 100
Cured under reduced pressure at 15 ° C for 15 hours. Cured film is 10-100
Crushed into a mesh.

The ground resin thus obtained is immersed in a 3 wt% hydroxylamine hydrochloride water-methanol solution (water: methanol = 1: 1 weight ratio) neutralized with potassium hydroxide, and reacted at 60 ° C. for 2 hours. A resin having a chelating property classified into 20 to 48 mesh was obtained.

Example 3 100 parts of polyethyleneimine (average molecular weight 10,000), 140 parts of methyl acrylate and toluene-ethanol (1:
1) Charge 150 parts, carry out Michael addition reaction at 70-80 ° C for 3 hours, then add 74.0 parts of 1.3-bis (1.2-epoxypropoxy) benzene, and flush with nitrogen at 70-80 ° C. While carrying out the polyaddition reaction for 3 hours. 200% 0.5 wt% polyvinyl alcohol aqueous solution that has been preheated to about 70 ° C
When the prepolymer solution prepared above was slowly added dropwise to 0 part with stirring, the solution was suspended in an aqueous system, and further heated in this state.
A cured product of 20 to 100 mesh was obtained.

The obtained spherical cured product was thoroughly washed with hot water, then washed with methanol and air dried.

The spherical cured product thus obtained is immersed in a 3% hydroxylamine methanol solution and reacted at 60 ° C. for 3 hours,
Classifying to 20 to 48 mesh, a resin having chelating performance was obtained.

Example 4 Methyl ethylenediamine diacetate (50 g, 0.245 mol) and 2,2-bis (p-1,2-epoxypropoxyphenyl) propane (epoxy equivalent = 186.3), 136.9 g (0.
To 367 mol), 50 g of toluene as a solvent and 8.3 g (0.061 mol) of metaxylenediamine as a curing agent were added and mixed. A 0.3 wt% polyoxyethylene lauryl ether aqueous solution prepared in advance was heated to about 70 ° C., and the mixture containing the curing agent was slowly added dropwise under stirring, and the cured product was suspended in an aqueous system, and then 80 to 100. When the curing reaction was continued while the solvent was removed from the system at 5 ° C for 5 hours, a white 10-100 mesh spherical cured polymer was obtained.

The obtained spherical cured polymer was treated in the same manner as in Example 3 and then reacted with hydroxylamine to give 20-48.
The resin was classified into a mesh to obtain a chelating resin.

Example 5 Polyethyleneimine (average molecular weight 600) 50 parts, crotonmethyl 92.9 parts and toluene-ethanol (1: 1) 10
Charge 0 parts and carry out addition reaction at 70-80 ℃ for 8 hours.
After cooling to 0 ° C, 81.0 parts of 2.2-bis (p-1.2-epoxypropoxyphenyl) propane was added, and polyaddition reaction was carried out at 70 to 80 ° C for 2.5 hours while flowing nitrogen.
The reaction solution was cooled to 30 to 40 ° C, 5 parts of diethylenetriamine was added to form a film, and a curing reaction was carried out at 120 to 130 ° C for 6 hours while removing toluene-ethanol and the like. The obtained cured film tended to be light yellow, transparent, hard and slightly brittle, so that it could be easily crushed to 40 to 100 mesh.

The obtained pulverized resin was reacted with hydroxylamine in the same manner as in Example 1 and classified into 20 to 48 mesh to obtain a resin having chelating ability.

Example 6 N- (2-hydroxyoctyl) -N′-propionitrile) ethylenediamine 100 parts, polypropylene glycol diglycidyl ether (epoxy equivalent: 190.0) 15
7.4 parts and 100 parts of isopropanol were charged, and polyaddition reaction was performed at 80 to 85 ° C. for 3 hours while flowing nitrogen to obtain a cured film. The obtained film was pulverized to 20 to 60 mesh, hydroxylamine was reacted by the same method as in Example 3, and classified to 20 to 48 mesh to obtain a resin having chelating performance.

Example 7 100 parts of triethylenetetramine tripropionitrile,
Charge 184 parts of 2,2-bis (p-1.2-epoxypropoxyphenyl) propane and 150 parts of benzene and carry out a polyaddition reaction under nitrogen at 80 to 90 ° C for 2 hours.
The polymer solution was added dropwise to 2,000 parts of a 1 wt% aqueous solution of carboxymethyl cellulose that had been cooled to about 65 ° C and was heated to about 65 ° C with stirring, and toluene was distilled off at 85 to 100 ° C in a suspended state. While performing the curing reaction for 7 hours. The obtained spherical cured product (10 to 100 mesh) was reacted with hydroxylamine by the same method as in Example 3 and classified into 20 to 48 mesh to obtain a resin having a chelating property.

Example 8 116 parts of pentaethylenehexamine and 159 parts of acrylonitrile were charged and addition reaction was carried out at 70 to 80 ° C. for 8 hours, and 165 parts of N · N′-bis (2.3-epoxypropyl) piperazine and 200 parts of toluene. Part, and polyaddition reaction was performed under nitrogen at 70-80 ° C for 4 hours, then again 30-
After cooling to 40 ° C, 10 parts of ethylenediamine was added as a curing agent. Subsequent spherical curing reaction was carried out in the same manner as in Example 8. However, 2,000 parts of 0.5 wt% polyoxyethylene nonylphenol (ethylene oxide 10 mol adduct) aqueous solution was used in the spherical curing reaction. A spherical cured resin of 10 to 100 mesh was obtained. The obtained spherical cured product was reacted with hydroxylamine in the same manner as in Example 2 and classified into 20 to 48 mesh to obtain a resin having chelating performance.

Example 9 100 parts of meta-xylenediamine di (2-methylpropionitrile), 181.8 parts of 2.2-bis (p-1.2-epoxypropoxyphenyl) propane and 150 of benzene
Part, charged with nitrogen under stirring, carried out polyaddition reaction at 70 to 8180 ° C for 4 hours, cooled to 30 to 40 ° C, added 4.6 parts of ethylenediamine to form a film, and removed benzene. Meanwhile, the curing reaction was performed at 100 to 120 ° C. for about 10 hours. A hard, but elastic, pale yellow transparent cured film was obtained. This was ground to 10-60 mesh and reacted with hydroxylamine in the same manner as in Example 3 to give 20-48
A resin having a chelating property was obtained by classifying into a mesh.

Example 10 100 parts of ethylenediamine diacetonitrile, 180 parts of 1.3-bis (1.2-epoxypropoxy) benzene, and 100 parts of toluene were charged, and the mixture was put under nitrogen at 80 to 90 ° C. for 4 hours.
A time-dependent polyaddition reaction was carried out, the mixture was cooled to 30 to 40 ° C., and 5 parts of diethylenetriamine was added as a curing agent. About 65 ℃
0.1 wt% polyvinyl alcohol aqueous solution heated to 1
When 500 parts of the above polymer solution was slowly dropped with stirring, the polymer was suspended in an aqueous system and further heated in this state, and a curing reaction was carried out for 5 hours while distilling toluene at 88 to 100 ° C. Continue to have a white spherical hard and strong elasticity 20
A ~ 100 mesh spherical resin was obtained. The polymer was further thoroughly washed with hot water to remove polyvinyl alcohol, and then reacted with hydroxylamine in the same manner as in Example 3 to classify it into 20 to 48 mesh to obtain a resin having a chelating property.

Example 11 Acrylonitrile 6 was added to 176.0 parts of a condensation reaction product of metaxylenediamine and epichlorohydrin (active hydrogen equivalent: 84.5).
6.2 parts of it was added dropwise at 50 ° C, addition reaction was carried out at 70 ° C for 3 hours, and 35.8 parts of methyl acrylate was further added dropwise at 75-85 ° C.
The addition reaction was carried out for 4 hours. Further, 173.0 parts of dimethylformamide and 87.5 parts of 2,2-bis (p-1,2-epoxypropoxyphenyl) propane were added, and the polyaddition reaction was carried out under nitrogen at 75 to 85 ° C for 3 hours. Further, the reaction solution was cooled to 30 to 40 ° C., 0.8 part of diethylenetriamine was added, and the mixture was molded into a film and cured at 100 to 180 ° C. for 6 hours while removing dimethylformamide. The obtained cured film was light yellow and hard. This cured film was ground to 20-60 mesh and reacted with hydroxylamine in the same manner as in Example 1 to give 20-48 mesh.
A resin having chelating ability on the mesh was obtained.

Example 12 Cu ²⁺ concentration: 35 ppm (pH: 3.8), Ca ³⁺ concentration: 60 ppm (pH:
After preparing two kinds of different simulated wastewaters such as 3.5), 1g of the adsorbents obtained in Examples 1 to 11 was added to the various simulated wastewaters 1, and after stirring for 1.5 hours, solid-liquid separation was performed and the residual metal concentration in the treated water was increased. Was measured by the atomic absorption spectrophotometry to determine the adsorption amount for these metals. The results are shown in Table-1. In the case of the polymer of Example 6, the residual metal ion concentration is shown.

Example 13 After preparing an aqueous sodium aluminate solution consisting of Ga: 53 ppm, Al: 20,000 ppm, and NaOH: 18%, 200 ml of this aqueous solution
To the adsorbents obtained in Examples 1 to 11 (excluding Example 6)
After adding 0.3 g and shaking for 1.5 hours, the gallium ion concentration in the aqueous solution was measured to determine the adsorption amount. The results are shown in Table-2.
Shown in.

Example 14 After preparing two kinds of simulated wastewaters having different Cu ²⁺ concentration: 200ppm, Ca ³⁺ concentration: 400ppm, etc., 20ml of the adsorbents obtained in Examples 1, 2, 6 and 9 were prepared in various simulated wastewaters 1. Add
After stirring for 5 hours, solid-liquid separation was performed, and the resin was washed with water to prepare a Cu ²⁺ or Ca ³⁺ adsorption resin.

The next resin with adsorbed Cu ²⁺ or Ca ^3+, was filled into 10ml column (inner diameter having a diameter of 15 mm) as the volume before the adsorption, and liquid passing the 1NHCl aqueous solution 30ml passed through speed SU _2, in downflow Cu ²⁺ or C
The a ³⁺ ion was recovered by elution.

Table 3 shows the adsorption amount of Cu ²⁺ or Ca ³⁺ adsorbed on the resin and the recovery rate of Cu ²⁺ or Ca ³⁺ recovered by elution.

Comparative Example 1 Acrylonitrile-divinylbenzene (8 wt%) was added to n-
A 10-100 mesh spherical resin was obtained by suspension polymerization in a 0.1 wt% polyvinyl alcohol aqueous solution in the presence of hexane. The spherical resin was immersed in a water-methanol solution of hydroxylamine in which 4 wt% hydroxylamine hydrochloride was neutralized with potassium hydroxide (water: methanol = 0.5: 1 weight ratio), and the mixture was reacted at 50 ° C. for 4 hours with stirring to form an amide. A resin having an oxime group was obtained. This was classified to obtain 20 to 48 mesh.

〔The invention's effect〕

As described above, a polymer having a novel chelate-forming ability can be produced, and the obtained polymer having a chelate-forming ability can be used in industrial wastewater in comparison with conventional polymers having the same purpose. Heavy metals and valuable metals can be effectively adsorbed and removed, and the adsorbed metals can be easily recovered.

Continuation of the front page (56) Reference JP-A-51-71400 (JP, A) JP-A-51-71399 (JP, A) JP-A-53-10699 (JP, A) JP-A-53-10698 (JP , A) JP-A-51-91998 (JP, A) JP-A-53-126088 (JP, A) JP-A-59-41307 (JP, A) JP-A-59-41307 (JP, A)

Claims (2)

[Claims] (1) In the molecule, as a substituent bonded to nitrogen, a compound represented by the general formula-(CHR ') _n CN or-(CHR') _n
-COOR "(provided that R'is hydrogen or an alkyl group having 1 to 3 carbon atoms, n is an integer of 1 to 3 and R" is an alkyl group having 1 to 4 carbon atoms) And a polyalkylenepolyamine derivative having at least two active hydrogens bonded to nitrogen (provided that alkylene is ethylene,
A mixture of any of propylene) with an epoxy compound having at least two epoxy groups in the molecule, then
(2) If necessary, after adding a curing agent for epoxy resin to the mixture, they are cured by heating as such, or they are suspended and dispersed in a water-soluble polymer compound or a surfactant aqueous solution, and cured by heating. A method for producing a polymer having a chelate-forming ability by reacting the obtained cured resin with hydroxylamine to introduce an amide oxime group and / or an oxime group. 2. The method for producing a polymer having chelating ability according to claim 1, wherein a prepolymer obtained by heating the mixture is used instead of the mixture.