JPH0459326B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a chelate resin. More specifically, the present invention relates to a method for producing a chelate resin having excellent metal ion adsorption properties per unit weight from a resin having a nitrile group. Since chelate resins selectively remove certain metal ions from metal ion-containing liquids, they are extremely useful resins for industrial water purification and wastewater treatment. Conventionally,
Chelate resin made by chloromethylating a styrene-divinylbenzene copolymer and then reacting it with iminodiacetic acid {JCIA Monthly Report 25 [1], p. 24 (1972)},
An aminophosphoric acid group type chelate resin (French Patent No. 2279453) is known, in which a styrene-divinylbenzene copolymer is chloromethylated and aminated, and then reacted with an alkyl phosphorylating agent. Although these chelate resins have excellent adsorption performance,
Due to the low chloromethylation reaction rate in the chelate resin manufacturing process, the ratio of chelate functional groups introduced per unit monomer is as low as 40-50%, resulting in the inconvenience of having to use a large amount of chelate resin. There is. In order to improve these inconveniences, a method has been proposed in which the chloromethylation reaction is carried out in the presence of a swelling agent of styrene-divinylbenzene copolymer to increase the chloromethylation reaction rate. The introduction ratio of chelate functional groups per monomer is 50 to 80%, which is not necessarily fully satisfied. Furthermore, the above-mentioned chelate resin has the disadvantage that it is necessary to use a harmful reaction agent such as chloromethyl ether in its production. In view of these circumstances, the present inventors aimed to produce a chelate resin that does not use harmful reaction reagents such as chloromethyl ethyl ether in the production process of the chelate resin and has a high introduction rate of chelate functional groups per unit monomer. As a result of intensive research, the present invention was established. That is, the present invention involves (A) reacting a resin having a nitrile group with (B) an amino compound having a primary or secondary amino group, and then (C) reacting a chelate forming agent, or ( A method for producing a chelate resin, which comprises reacting a resin having a nitrile group with (D) a reaction product of the amino compound having a primary or secondary amino group and the chelate forming agent. It is. Examples of (A) resins having a nitrile group used in the method of the present invention include () acrylonitrile, a-chloroacrylonitrile, vinylidene cyanide, methacrylonitrile, fumardinitrile, crotonitrile, 2-cyanoethyl acrylate, 2- Polymers of vinyl cyanide monomers such as cyanoethyl methacrylate, or vinyl cyanide monomers and other ethylenically unsaturated monomers that can be copolymerized with these, such as divinylbenzene and diethylene glycoldi. Copolymers with methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, vinyl acetate, etc., () chloromethyl group, sulfonyl chloride group, carbonyl chloride group, isocyanate group, epoxy group, aldehyde group, chlorine, bromine,
Polymers such as phenolic resins, polyethylene, polypropylene or () polyvinyl chloride having amine-reactive groups such as halogen atoms such as iodine, () aminoacetonitrile, aminomalonitrile, diaminomaleonitrile, dicyandiamide, iminodiacetonitrile, Resins made by reacting nitrile compounds with amino groups or imino groups such as 1-amino-2-cyanoethane, 4-aminobenzonitrile, 1-amino-3-cyanopropane, etc. are used, but are limited to these. isn't it. Particularly preferred are acrylonitrile, methacrylonitrile, or vinylidene cyanide polymers, or these vinyl cyanide monomers and divinylbenzene, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, vinyl acetate, etc. A copolymer with is used. The degree of polymerization of (A) the resin having a nitrile group is not particularly limited as long as it is water-insoluble, but generally the degree of polymerization is approximately
More than 500 items are used. Furthermore, the shape of the resin having a nitrile group can be any shape such as powder, fiber, honeycomb, granule, spherical, liquid, etc., and the shape can be selected as appropriate depending on the purpose of use. However, in general, spherical and powdered resins are preferably used from the viewpoint of handling. Examples of the amino compound (B) in the present invention include ammonia, monomethylamine, monoethylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, diethylenetriamine, triethylene Aliphatic amines such as tetramine, tetraethylenepentamine, hydrazine, and guanidine; Aromatic amines such as toluylene diamine and phenylene diamine; Alicyclic amines such as diaminocyclobutane, diaminocyclopentane, diaminocyclohexane, diaminocycloheptane, and diaminocyclooctane Formula amine; diaminofuran,
Examples include oxygen-containing, nitrogen, and ionic amines such as diaminothiophene, diaminopyran, diaminothiopyran, and diaminopyridine. In particular, ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehenxamine, hexamethylenediamine, guanidine, phenylenediamine, and hydrazine are preferably used. As the chelate forming agent (C) used in the present invention, any agent can be used as long as it reacts with a compound having a primary or secondary amino group to form a chelate group. Such chelating agents include monochloroacetic acid,
halogenated alkyl carboxylic acids such as monobromo, acetic acid, and monochloropropionic acid, polyfunctional compounds having two amine-reactive groups such as epichlorohydrin, epibromohydrin, hexamethylene diisocyanate, tolylene diisocyanate, phosgene or thiophosgene, and iminodiacetic acid. , alkyl carboxylic oxidizing agents such as mixtures with aminocarboxylic acids such as iminodipropionic acid; halogenated alkyl phosphoric acids such as chloromethyl phosphoric acid and chloroethyl phosphoric acid; polyfunctional compounds having the above two amine-reactive groups and aminomethyl phosphoric acid, aminoethyl phosphoric acid; Mixtures of amines such as phosphoric acid with alkyl phosphoric acids; mixtures of alkylating agents such as formalin and trioxymethylene with phosphorus compounds such as phosphorus trichloride, phosphorous acid, hypophosphorous acid, and ethyl phosphite; alkyl phosphorylating agents such as mixtures of the above two A thiocarboxylic oxidizing agent such as a mixture of a polyfunctional compound having an amine-reactive group and an aminothiocarboxylic acid such as diethylenetriaminodithiocarbamic acid, ethylenediaminodithiocarbamic acid, or dithiocarbamic acid; Carbon disulfide: a polyfunctional compound having the above two amine-reactive groups Amidoximating agents such as mixtures of compounds and amidoxime compounds such as 4-aminobenzamidoxime and 4-diethylenetriaminobenzamidoxime; 5-bromo-8-hydroxyquinoline, 5-
Chloromethyl-8-hydroxyquinoline, etc. or their alkyl, alkenyl, alkynyl derivatives and inorganic salts of these compounds; 2-amino-4-bromophenol, 3-amino-4-iodophenol, 2-amino-4-chloromethylphenol , 2-amino-4-hydroxybenzenesulfonyl chloride, 2-amino-4-hydroxybenzoic acid chloride, 1-amino-4-bromo-2-naphthol, 2-amino-4-bromthiophenol, 4-amino-3 -Aminophenols such as hydroxybenzenesulfonyl chloride; 5-bromo-2,2'-dihydroxy-N,N'-ethanediylidene dianiline, 5-bromo-2,2'-dimercapto-N,N'-ethanedianiline iridendianiline,
5-chloromethyl-2,2'-dihydroxy-N,
N'-ethanediylidene dianiline, 5-chloromethyl-2,2'-dimercapto-N,N'-ethanediylidene dianiline, 5-bromo-2,2'-dihydroxy-N,N'-(o, Schiff bases such as m- or p-xylene diylidene) dianiline; 3
- Esters such as ethyl acetylpropionate, ethyl acetylenedicarboxylate, ethyl acetoacetate, ethyl pyruvate, diethyl succinate, etc., and acid chlorides equivalent to these esters; polyfunctional compounds having the above two amine-reactive groups and diethylenetriamine , triethylenetetramine, tetraethylenepentamine, hexamethyleneheptamine,
Aminopyridine, diaminothiopyran, glutamic acid, aspartic acid, 5-amino-8-oxyquinoline, 5-diethyltriamino-8-oxyquinoline, 5-triethyltetraamino-8-oxyquinoline, aminoethanealdoxime, aminomethane Examples include amino compounds such as benzhydroxam or mixtures with derivatives thereof. In the present invention, the above (A), (B), and (C) are reacted as follows. () (A) a resin having nitrile groups is reacted with (B) an amino compound, and then (C) a chelating agent is reacted; or () (A) a resin having nitrile groups is reacted with (D) (B ) Reacting the reaction product of the amino compound and (C) the chelating agent. The reaction will be explained in detail below. (A) A resin having a nitrile group and (B) an amino compound are reacted without a solvent or in the presence of a solvent such as water, N,N-dimethylformamide, formamide, dimethyl sulfoxide, toluene, xylene, or ethyl alcohol. 50℃ or higher, preferably 70-150
Perform at ℃. A reaction temperature lower than 50° C. is not preferred because the reaction rate becomes slow and a long reaction time is required. The reaction is preferably carried out at a temperature of about 0.1 to 7
The optimum time within this range is determined depending on the reaction temperature, the concentration of the reaction solution, the solvent used, the type of amino compound, etc. However, longer reaction times can also be used. The reaction is generally carried out at normal pressure, but it is also possible to carry out the reaction under increased pressure. The reaction ratio of (B) amino compound to (A) nitrile group-containing resin may be 1/20 molar or more per equivalent of nitrile group in the resin, but using more amino compound than necessary is prohibited after the reaction. Since the treatment operation becomes complicated due to the recovery treatment of If the amount of the (B) amino compound used for the (A) resin is less than the above, substitution of amino groups will be reduced, which is undesirable because the resulting reaction-produced chelate resin will have a lower metal-trapping ability. The aminated resin obtained by reacting the (A) nitrile group-containing resin with the (B) amino compound is then used as it is, after separating and removing the solvent and unreacted amino compound, or after washing and drying as necessary. After (C) reacting with a chelating agent. The reaction between the aminated resin and the chelate forming agent (C) can be carried out by a known method. Although reaction conditions vary depending on the type of chelate forming agent used, the reaction is usually carried out under the following conditions. Alkyl phosphorylating agents such as chloromethyl phosphoric acid and chloroethyl phosphoric acid, alkyl carboxylic oxidizing agents such as monochloroacetic acid, monochloropropionic acid, and monobromoacetic acid, thiocarboxylic oxidizing agents such as carbon dioxide, 8-hydroxyquinoline derivatives,
When aminophenol derivatives, Schiff bases, ketoesters, etc. are used as chelate forming agents, they can be used without catalyst or with pyridine, N,N-dimethylaniline, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium In the presence of a basic catalyst such as methoxide, at least 1/10 mole of chelating agent, preferably 1 mole or more, per equivalent of nitrile group in the resin containing nitrile groups.
The reaction may be carried out using ~5 mol. The reaction generally involves water, methyl alcohol, ethyl alcohol, propyl alcohol, N,N'-dimethylformamide, N,N-dimethylsulfoxide, 1,2-
It is carried out in the presence of a solvent such as dichloroethane, 1,1,2-trichloroethane, or pyridine. The reaction temperature is generally room temperature to 150°C, and the reaction time is generally 0.1 to 24 hours. In addition, when using an alkylating agent such as formaldehyde or trioxymethylene and a phosphorus compound such as phosphorous trichloride, phosphorous acid, hypophosphorous acid, methyl phosphite, or ethyl phosphite as a chelate forming agent, hydrochloric acid as a catalyst may be used. , except that an acidic catalyst such as sulfuric acid is used, the reaction molar ratio, use of solvent, reaction temperature, reaction time, etc. may be within substantially the same ranges as above. In addition, the (D) reaction product used to react with the resin (A) having a nitrile group is an amino compound having (B) a primary or secondary amino group and (C) an amino compound having a primary or secondary amino group.
The chelate-forming agent is added to 1/10 to 1 equivalent of the amino compound having an amino group.
The reaction may be carried out using moles. Regarding the use of a solvent, reaction temperature, reaction time, etc., it is sufficient to adopt substantially the same range as for the reaction between the above amino compound and (C) chelate forming agent. (D) The reaction product of the amino compound and the chelate forming agent is then reacted with (A) the resin having a nitrile group. The reaction conditions vary depending on the type of reaction product between (D) the amino compound and (C) the chelate-forming agent, but usually the reaction conditions are the same as in the case of the reaction between (A) the resin having a nitrile group and (B) the amino compound. Approximately similar ranges may be adopted for the ratio, use of solvent, reaction temperature, reaction time, etc. The chelate resin produced as described above can be used for appropriate purposes as it is or after washing and drying, but if necessary, the chelate resin can be further treated with a base or acid before use. The chelate resin produced by the method of the present invention has different adsorption properties for metal ions depending on the functional group.
Extremely effective in removing and recovering metal ions such as heavy metal ions such as silver, platinum, and uranium, and metal ions such as calcium, magnesium, barium, and iron in aqueous solutions of alkaline chlorides such as sodium chloride and potassium chloride. It is. It can also be suitably used to recover valuable metals such as uranium from seawater. The chelate resin produced by the method of the present invention can be used in addition to collecting heavy metals, for example, for analysis, for separating and purifying organic substances, for catalysts, and as a raw material for producing chemical-resistant resins. As described in detail above, the method for producing a chelate resin of the present invention has the effect that the number of chelate functional groups per unit monomer is large compared to known methods for producing a chelate resin, so that a large amount of metal ions can be adsorbed per resin. demonstrate. Furthermore, by the reaction of (A) a resin having a nitrile group with (B) an amino compound or (D) a reaction product, a group having a chelating agent and an imino group or a carbonyl group are formed around the carbon atom of the nitrile group. Perhaps because these two groups mutually act as chelate-forming agents, the amount of metal ion adsorption is lower than that of chelate resins with approximately the same number of chelate functional groups per unit monomer produced by known production methods. It has the advantage that it can significantly reduce the metal adsorption equilibrium concentration in a high salt concentration aqueous solution, and that it can be manufactured easily and at a low cost. The method of the present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless the gist of the invention is exceeded. Example 1 120 parts by weight of ethylenediamine and 40 parts by weight of water were added to 60 parts by weight of acrylonitrile-divinylbenzene copolymer resin with a degree of crosslinking of 4 mol%, and the mixture was heated at 110 to 132°C.
The reaction was carried out for 4 hours. When the reaction product was filtered and washed with water, 233 parts by weight (undried) of aminated resin was obtained. Next, a mixed solution of 66 parts by weight of phosphorous acid as an alkyl phosphorylating agent, 137 parts by weight of 36% hydrochloric acid, and 25 parts by weight of 95% paraformaldehyde was added to 98 parts by weight of the obtained aminated resin.
The reaction was carried out at ~100°C for 6 hours. Wash the resin with water,
As a result, a chelate resin having 89 mol % of aminomethylene phosphate groups based on 159 parts by weight (undried) of unit monomer was obtained. Example 2 310 parts by weight of diethylene triamine, 1200 parts by weight of water and 228 parts by weight of carbon disulfide were added to 94 parts by weight of vinylidene cyanide-tetraethylene glycol dimethacrylate copolymer resin with a degree of crosslinking of 4 mol%, and 80 parts by weight of carbon disulfide were added.
The reaction was carried out at ℃ for 6 hours. When the reaction product was filtered and washed with water, 546 parts by weight (undried) of a resin having dithiocarbamic acid groups was obtained. Example 3 300 parts by weight of triethylenetetramine and 75 parts by weight of water were added to 68 parts by weight of acrylonitrile-divinylbenzene copolymer resin with a degree of crosslinking of 8 mol%, and 110 to 120 parts by weight of water were added.
The reaction was carried out at ℃ for 2 hours. When the reaction product was filtered and washed with water, 276 parts by weight (undried) of aminated resin was obtained. Next, 28 parts by weight of monochloroacetic acid and sodium carbonate were added to 28 parts by weight of the obtained aminated resin.
32 parts by weight and 100 parts by weight of water were added and the reaction was carried out at 70 to 100°C for 2 hours. When the resin content was washed with water and filtered, 93
A chelate resin having parts by weight (undried) of aminoacetic acid groups was obtained. Example 4 A mixture of 136 parts by weight of hexamethylene diisocyanate and 1000 parts by weight of toluene held at 70°C was
58 parts by weight (dry) of the same aminated resin used in Example 1 was added, and the mixture was reacted at 40 to 80°C for 4 hours and then filtered. Add a 10% by weight aqueous aminoethylene phosphate aqueous solution to the total amount of the resin obtained by
1690 parts by weight was added and the reaction was carried out at 70 to 100°C for 6 hours. When the resin was washed with water and filtered, 386 parts by weight (undried) of a chelate resin having aminoethylene phosphate groups was obtained. Example 5 580 parts by weight of an 80% by weight aqueous pentaethylenehexamine solution was added to 62 parts by weight of methacrylonitrile-divinylbenzene copolymer resin with a degree of crosslinking of 6 mol%, and the mixture was reacted at 110 to 140°C for 2 hours and then filtered. As a result, 279 parts by weight (undried) of aminated resin was obtained. Next, 15 parts by weight of carbon disulfide as a chelate forming agent was added to 28 parts by weight (undried) of the aminated resin obtained.
3 parts by weight and 100 parts by weight of water as a solvent and heated at 43 to 46℃.
A time reaction was performed. When the reaction product was filtered and washed with water, 44% of the resin containing dithiocarbamic acid groups was found.
Part by weight (undried) was obtained. Examples 6-10 Same aminated resin 93 as used in Example 1
Part by weight (undried) was added to the first part in the same manner as in Example 5.
When the reaction was carried out with a chelate forming agent under the reaction conditions shown in Table 1, chelate resins shown in Table 1 were obtained. Examples 11 to 15 To 900 parts by weight of vinylidene cyanide-divinylbenzene copolymer resin with a degree of crosslinking of 8 mol%, 2000 parts by weight of an aqueous solution of ethylenediamine with a concentration of 60% by weight was added,
When the reaction was carried out at 100-114° C. for 6 hours and filtered, 2760 parts by weight (undried) of aminated resin was obtained. Next, 276 parts by weight (undried) of the obtained aminated resin was reacted in the same manner as in Example 1 under the reaction conditions shown in Table 2, and a chelate resin as shown in Table 2 was obtained. It was done.

【table】

[Table] Example 16 The same procedure as in Example 1 was used except that 40 parts by weight of phosphorous acid, 82 parts by weight of 36% by weight hydrochloric acid and 15 parts by weight of formaldehyde at 95% by weight were used as the alkyl phosphorylating agent. A chelate resin having 54 mol % of aminomethylene phosphate groups per unit monomer was obtained. Application example 1 Chelate resin obtained in Examples 1, 3, 4, 7, 8, 9, 10, 11, styrene resin-based chelate resin, phenolic resin-based chelate resin, and aminated resin obtained in Example 1 0.25 The parts by weight (in terms of dry resin) are 100 mg-Cd/CdCl ₂ and 40 g-Na/
was added to 50 parts by weight of an aqueous solution of PH4 containing NaCl, and 1
Contacted for an hour. As a result, in the aqueous solution after treatment,
The Cd concentration was as shown in Table 2.

【table】

[Table] Application example 2 100mg/Cd/CdCl ₂ and 11.79g-Na/
PH containing NaCl and 500 mg-Cd/NaClO
Examples 1, 3, 4, 7, and 100 parts by weight of the aqueous solution of 5.51
Chelate resins Nos. 8, 9, 10, 11, and 16, the styrene resin-based chelate resin, the phenol resin-based chelate resin, and the aminated resin obtained in Example 1 were each added in an amount of 0.5 parts by weight in terms of dry resin, and the mixture was shaken. The contact was continued for 1 hour. As a result, the Cd concentrations in the aqueous solution after treatment were as shown in Table 3.

[Table] Application example 3 100mg-U/Na ₄ (UO) ₂ (CO ₃ ) ₂ and 13.1g-
The chelate resins of Examples 1, 4, 8, 9, 11, 12, and 13 were added to 100 parts by weight of an aqueous solution of pH 8.2 containing NaCl, the phenolic resin-based chelate resin, and the amino acid obtained in Example 4. 0.5 parts by weight of each resin was added, and the mixture was allowed to come into contact with the mixture for 1 hour while being shaken. As a result, the U concentrations in the aqueous solutions after treatment were as shown in Table 4.

[Table] Application example 4 Examples 1, ₃ , 4, 7, 8, 9,
Chelate resins Nos. 10, 11, 14, and 15, the phenolic resin-based chelate resin, and the aminated resin obtained in Example 1 were each added in an amount of 0.5 part by weight in terms of dry resin, and were brought into contact with each other for 1 hour while shaking. As a result, the Cu concentrations in the aqueous solutions after treatment were as shown in Table 5.

【table】

[Table] Application example 5 13.20mg/concentration of Hg and 30g/concentration of NaCl
Example 2 to 100 parts by weight of an aqueous solution of PH7.8 containing
0.5 parts by weight of each of the chelate resins Nos. 5 and 6, a commercially available dithizone-type mercury adsorption resin, the phenol resin-based chelate resin, and the aminated resin obtained in Example 1 were added in terms of dry weight, and the mixture was contacted for 1 hour with shaking. I let it happen. As a result, the Hg concentration in the aqueous solution after treatment was as shown in Table 6.

[Table] Application example 6 Examples 1 and 16 were added to 50 parts by weight of a pH 9 aqueous solution containing 63 mg/concentration of Ca and 300 g/concentration of NaCl.
The chelate resin and the styrene resin-based chelate resin were each added in an amount of 0.5 parts by weight in terms of dry resin, and were brought into contact with each other for 1 hour while being shaken. As a result, the Ca concentration in the aqueous solution after treatment was as shown in Table 7.

[Table] From Application Example 6, the chelate resin produced by the method of the present invention has a higher metal ion adsorption property than the known chelate resin having almost the same amount of aminomethylene phosphate groups per unit monomer. It is clear that it is superior. Example 17 206 parts by weight of diethylenetriamine and 40 parts by weight of water were added to 60 parts by weight of acrylonitrile-divinylbenzene copolymer resin with a degree of crosslinking of 4 mol%, and 110 parts by weight of diethylenetriamine and 40 parts by weight of water were added.
The reaction was carried out at ~120°C for 4 hours. When the reaction product was filtered and washed with water, 177 parts by weight of aminated resin was obtained. Next, 5-bromo-8 was added as a chelate forming agent to 129 parts by weight of the obtained aminated resin.
-Add 252 parts by weight of hydroxyquinoline hydrochloride, 131 parts by weight of pyridine and 2857 parts by weight of toluene to 80~
The reaction was carried out at 90°C for 4 hours. When the resin was filtered, washed with water, and then washed with ethanol, a chelate resin containing 89 mol % of 8-hydroxyquinoline groups per 235 parts by weight of unit monomer was obtained. Example 18 310 parts by weight of diethylenetriamine and 1200 parts by weight of water were added to 94 parts by weight of vinylidene cyanide-tetraethylene glycol dimethacrylate copolymer resin having a degree of crosslinking of 4 mol%, and a reaction was carried out at 110 to 120°C for 4 hours. When the reaction product was filtered and washed with water, 277
Parts by weight of aminated resin were obtained. Next, 2-amino-4-bromophenol hydrochloride was added to 129 parts by weight of the obtained aminated resin as a chelate forming agent.
222 parts by weight, 131 parts by weight of pyridine, and 2857 parts by weight of toluene.
Parts by weight were added and the reaction was carried out at 80 to 90°C for 4 hours.
When the resin was filtered, washed with water, and then washed with ethanol, a chelate resin containing 93 mol % of o-aminophenol groups per 213 parts by weight of unit monomer was obtained. Example 19 300 parts by weight of triethylenetetramine and 75 parts by weight of water were added to 63 parts by weight of acrylonitrile-divinylbenzene copolymer resin with a degree of crosslinking of 8 mol%, and 110 to 120 parts by weight were added.
The reaction was carried out at ℃ for 2 hours. When the reaction product was filtered and washed with water, 166 parts by weight of aminated resin was obtained. Then, to 129 parts by weight of the obtained aminated resin,
187 parts by weight of glyoxal-5-chloromethylbis(2-hydroxyanyl) as a chelate forming agent, 51 parts by weight of pyridine and 2857 parts by weight of toluene were added, and the reaction was carried out at 100-110°C for 4 hours. When the resin was filtered, washed with water, and then washed with ethanol, a chelate resin containing 87 mol % of glyoxal-bis(2-hydroxyanyl) groups based on 263 parts by weight of unit monomer was obtained. Example 20 Same aminated resin used in Example 17
To 129 parts by weight were added 73 parts by weight of ethyl acetoacetate as a chelate forming agent, 13 parts by weight of sodium methoxide, and 281 parts by weight of methanol, and the reaction was carried out at 60 to 70°C for 4 hours. When the resin was filtered, washed with water, and then washed with ethanol, a chelate resin containing 94 mol % of β-diketone groups per 163 parts by weight of unit monomer was obtained. Examples 21-30 Same aminated resin used in Example 17
When 129 parts by weight was reacted with a chelate forming agent as shown in Table 8 in the same manner as in Example 1 under the reaction conditions, chelate resins as shown in Table 8 were obtained.

[Table] 〓

〓

Claims (1)

[Claims] 1. (A) A resin having a nitrile group is reacted with (B) an amino compound having a primary or secondary amino group, and then (C) a resin having a primary or secondary amino group is reacted with the resin. (A) reacting with a chelating agent that reacts with a compound having an amino group to form a chelate group, or (A)
A method for producing a chelate resin, which comprises reacting a resin having a nitrile group with (D) a reaction product of the amino compound having a primary or secondary amino group and the chelate forming agent. 2. The method for producing a chelate resin according to claim 1, wherein (A) the resin having a nitrile group is a homopolymer or copolymer of acrylonitrile, methacrylonitrile, or vinylidene cyanide. 3 (C) the chelating agent is an alkyl phosphorylating agent,
Alkyl carbon oxidizing agent, thiocarboxylic oxidizing agent,
Claim 1, which is an amidoximating agent, an 8-hydroxyquinoline derivative, an aminophenol derivative, Schiff bases or ketoesters
A method for producing a chelate resin according to item 1 or 2. 4 (B) The amino compound having a primary or secondary amino group is ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, guanidine, phenylenediamine, or hydrazine. A method for producing a chelate resin according to claim 1, 2, or 3.