JPS5820964B2 - Chelate resin manufacturing method - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for producing chelate resins.

More specifically, in a resin having primary and/or secondary amine groups in the prisoner molecule (hereinafter referred to as aminated resin), (B) a polyfunctional compound having at least two amine-reactive groups. (hereinafter referred to as a polyfunctional compound) and an amine compound having a primary and/or secondary amino group (hereinafter referred to as an amine compound), or a reaction product of the polyfunctional compound and the amine compound. This invention relates to a method for producing a new chelate resin.

In recent years, chelate resins have been widely used as agents for removing heavy metals from industrial waste liquids and as scavengers for valuable metals from solutions containing valuable metals.

For example, conventionally, in order to remove heavy metals from solutions containing heavy metals at a concentration of about 1/1 or less, chelate resin (1) was prepared by chloromethylating a styrene-divinylbenzene copolymer and then reacting it with iminodiacetic acid. JCIA Monthly Report 25 [1] p. 24 (1972)), iminodiacetic acid.

After performing Mannich reaction in the coexistence of phenols and aldehydes, aldehydes and phenols were added and polycondensed chelate resin (JP-A-50-107092, JP-A-50-101490, JP-A-50-101490, JP-A-50-101490) -10
3590) has been proposed.

However, all known chelate resins are easily affected by other coexisting ions present in wastewater.

Compared to laboratory-prepared liquids, they have disadvantages in that their adsorption capacity is significantly lower when using industrial wastewater, etc., and the equilibrium concentration of heavy metals adsorbed in high-salt aqueous solutions is high.

In view of these circumstances, the present inventors set out to find a chelate resin that is less affected by coexisting ions than the chelate resins that have already been proposed, and that can lower the equilibrium concentration of heavy metal adsorption in a high salt concentration aqueous solution. As a result of intensive research, we have arrived at the present invention.

That is, the present invention provides (a) a resin having primary and/or secondary amino groups in the molecule, and (B) a polyfunctional compound having at least two amine-reactive groups and a primary and/or secondary amino group. Another object of the present invention is to provide a novel method for producing a chelate resin by reacting an amino compound having 7 secondary amine groups or a reaction product of the polyfunctional compound and the amine compound.

The captive aminated resin used in carrying out the method of the present invention may be any aminated resin having primary and/or secondary amine groups in its molecule, but is not particularly limited. isn't it.

However, it is more preferable that a first
Aminated resins having primary and/or secondary amine groups are used.

Examples of resins containing halogen atoms include polyvinyl chloride, polyvinylidene chloride, and polyvinyl bromide.

Halogen-containing resins such as polyvinylidene bromide and polyvinyl iodide, or polyethylene1. Examples include resins in which halogen atoms are introduced by halogenating resins that do not contain halogen atoms, such as polypropylene.

Preferably, a resin containing a chlorine atom as a halogen atom, particularly a vinyl chloride resin, is preferable.

Of course, the above resin may be copolymerized with other ethylenically unsaturated monomers that can be copolymerized with the above resin component, such as acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, methacrylic ester, acrylic ester, olefin, etc. It may also be a polymer.

Examples of the usage form of such a resin include a single powder molded product, a fibrous shape, a film shape, a honeycomb molded product, and the like.

The halogen atom-containing resin is then aminated by a known method.

Usually, the amino compound is reacted at a ratio of 1/20 mole or more, preferably 1/10 to 6/1 mole, per gram of halogen atom in the resin.

The aminated resin produced as described above is suitably used as a raw material resin in the method of the present invention.

However, polyethyleneimine, aniline resin.

Of course, amino resins such as melamine resins can also be used.

In implementing the method of the present invention, (a) the aminated resin is reacted with (B) a polyfunctional compound and an amino compound or a reaction product of a polyfunctional compound and an amine compound.

In carrying out the method of the present invention, the ratio of the polyfunctional compound and amine compound to the aminated resin is n/20 equivalents of the polyfunctional compound per equivalent of amine group in the aminated resin (where n is 1 molecule of the polyfunctional compound). (indicating the number of amine-reactive groups contained therein) or more and 1/20 equivalent or more of the amino compound.

Preferably, the polyfunctional compound is used in the range of n/10 to 2n/1 equivalent (n is the same as above) and the amine compound is used in the range of 1/10 to 2/1 equivalent.

In addition, the ratio of the reactants of the polyfunctional compound and the amine compound to the aminated resin is 1 amine group in the aminated resin.
1/20 mole or more per equivalent, preferably 1/10 to 2/2 mole
It is used in a range of 1 mol.

In this case, the reaction ratio of the polyfunctional compound and the amine compound is 0.1 to 1 mol of the amino compound per 1 mol of the polyfunctional compound.

The amount is preferably 0.5 to 1 mole.

A polyfunctional compound that reacts with aminated resin.

If the ratio of the reactant between the amine compound or the polyfunctional compound and the amine compound is lower than the above, the heavy metal scavenging ability of the resulting chelate resin will decrease, and the heavy metal adsorption equilibrium concentration will not be able to be lowered, which is not preferable.

The reaction between the captive aminated resin and (B) the polyfunctional compound and the amine compound or the reaction product of the polyfunctional compound and the amine compound is generally carried out at about 30 to 200°C, preferably 40 to 15°C.
It is carried out at a temperature of 0°C.

If the reaction temperature is lower than 30°C, the reaction will take a long time, whereas if it is higher than 200°C, decomposition reactions of functional groups will occur, which is not preferable.

The reaction time is generally about 5 minutes to 24 hours, and the reaction pressure can be any of reduced pressure, normal pressure, and increased pressure.

The reaction between the aminated resin and (B) the polyfunctional compound and the amino compound or their reactants can be carried out without a solvent or in water or N,N-dimethylformamide.

N-N dimethyl sulfoxide, chloroform, tetracarbon L 1 , 2-dichloroethane, perchlorethylene, dioxane, methyl alcohol, ethyl alcohol,
This may be carried out in the presence of a solvent such as furopanol, phthanol, benzene, toluene, or chlorobenzene.

In carrying out the present invention, (A) the polyfunctional compound having at least two amine-reactive groups used to react with the aminated resin should contain a small amount of halogen, epoxy group, incyanato group, etc. in one molecule. Those containing two or more of both are used.

for example. Epichlorohydrin, epibromohydrin, epiiodohydrin, ■, 2-epoxy-4-chlorobutane, 1,2-epoxy-4-bromobutane, 1,2-epoxy-4-iodobutane, 2,3-epoxy-4-chlorobutane , 2,3-epoxy-4-bromobutane, 2
23-epoxy-4-iodobutane, 2,3-epoxy-5-chloropentane, 2,3-epoxy-5-bromopentane.

Epihalohydrins such as 1.2-epoxy-5-chlorobencune, 2,2-bis(p-1,2-epoxypropoxyphenyl)propane, and 1,4-bis(1,2-epoxypropoxy)benzene.

N,N'-bis(2,3-epoxypropyl)piperazine, ethylene glycol diglycidyl ether, propylene gellicol diglycidyl ether, glycerol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 2゜ Epoxy compounds such as 3.4-jepoxybutane, thiophosgene, glycerine dichlorohydrin, halides such as phthaloyl chloride, succinic acid chloride, chloroacetyl chloride, chlorosuccinic acid chloride, ketones such as chloroacetone, bromoacetone, glyoxal, Examples include incyanates such as hexamethylene diisocyanate, tolylene diisocyanate, metaxylylene diisocyanate, cyclohexylmethane-4,4-diisocyanate, and derivatives thereof.

Particularly preferred are epihalohydrins such as epichlorohydrin, epibromohydrin, or ebiodohydrin.

The amine compound used to react with the aminated resin, polyfunctional compound, or polyfunctional compound in carrying out the method of the present invention is ammonia.

Monomethylamine, monoethylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine,
Pentamethylenediamine, hexamethylenediacine, octamethylenediamine, nonamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine.

□Aliphatic amines such as hydrazine, dimethylamine, and diethylamine; alkanolamines such as ethanolamine and jetanolamine; aromatic amines such as aniline and paraphenylenediamine; cyclohexylamine, piperidine, piperazine, pyrrolidine, diaminocyclobutane, and diaminocyclopene. Kun, diaminocyclohexane,
Alicyclic amines such as diaminocyclohebutane and diaminocyclooctane, diaminofuran, and diaminothiophene.

Oxygen-containing, nitrogen, and sulfur amines such as diaminopyran, diaminothiopyran, aminopyridine, and diaminopyridine, iminodiacetic acid, iminodipropionic acid, iminodi(
α-methyl)propionic acid.

Amino acids such as glutamic acid and aspartic acid, and their sodium, potassium, and lithium.

Examples include ammonium salts and alkyl esters thereof such as methyl, ethyl, and propyl.

Especially diethylamine, aminopyridine, jetanolamine, aniline, paraphenylenediamine.

Iminodiacetic acid, iminodiacetic acid methyl ester, iminodipropionic acid, and iminodipropionic acid methyl ester are preferably used.

The reason why the chelate resin produced by the method of the present invention exhibits an excellent heavy metal trapping effect is not clear, but it is due to the interaction between the nitrogen, oxygen, or sulfur atoms of the polyfunctional compound and the nitrogen atoms of the amino groups in the aminated resin. We believe that this occurs due to an increase in chelate binding strength.

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 is extremely effective for removing and recovering heavy metals such as mercury, cadmium, lead, chromium, zinc, copper, gold, silver, platinum, and uranium from aqueous solutions containing these metals.

It can also be suitably used for recovery of valuable metals such as uranium from seawater; uranium extraction and nuclear fuel manufacturing process wastewater.

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 above, the chelate resin of the present invention is less affected by coexisting ions than known chelate resins.
This method has the advantage that it can significantly reduce the equilibrium concentration of heavy metal adsorption in a high salt concentration aqueous solution, and that it can be manufactured easily and at low cost.

The method of the present invention will be explained in more detail with reference to Examples below, but the present invention does not go beyond the gist thereof.

The following examples are not intended to be limiting.

Example 1 Emulsion polymerized vinyl chloride resin 12 with a mesh particle size of 10 to 60
240 parts by weight of ethylenediamine and 80 parts by weight of water were added to 4 parts by weight, and the mixture was reacted at 110 to 132°C for 4 hours.

Filter the reaction product and wash with water. Upon drying, 108.4 parts by weight of brown aminated resin was obtained.

Next, 25 parts by weight of the obtained aminated resin, 11.8 parts by weight of 3-aminopyridine, and shrimp chlorhydride.

11.8 parts by weight of phosphorus and 94 parts by weight of water were charged into a reaction vessel, and the reaction was carried out at 60 to 70°C for 1 hour.

When the resin component was washed with water, filtered, and dried, 29.7 parts by weight of a brown chelate resin was obtained.

From the results of elemental analysis of the resin, 3.
It was found that 2.9 parts by weight of 3-aminopyridine had reacted.

Example 2 170 parts by weight of diethylenetriamine and 43 parts by weight of water were added to 76 parts by weight of chlorinated polyethylene with a particle size of 22 to 48 mesh containing 53% by weight of chlorine atoms in the resin, and 1
The reaction was carried out at 20-140°C for 3 hours.

The reaction product was filtered, washed with water, and dried to obtain 69 parts by weight of a brown aminated resin.

Next, 25 parts by weight of the obtained aminated resin, 22.3 parts by weight of disodium iminodipropionic acid, 11.5 parts by weight of epichlorohydrin, and 100 parts by weight of water were charged into a reaction vessel and reacted at 50 to 100°C for 3 hours. I did it.

The resin component was washed with water, filtered, and dried to obtain 31 parts by weight of a yellowish brown chelate resin.

From the results of elemental analysis of the resin, 3.
9 parts by weight, 36 parts by weight of iminodipropionic acid disodium salt
It was found that 4 parts by weight had reacted.

Example 3 150 parts by weight of triethylenetetramine and 17 parts by weight of water were added to 100 parts by weight of chlorinated polypropylene with a particle size of 10 to 60 mesh containing 45% by weight of chlorine atoms in the resin at 120 to 155°C for 4 hours. The reaction was carried out.

The reaction product was filtered, washed with water, and dried to obtain 97 parts by weight of a brown aminated resin.

Then, 25 parts by weight of the obtained aminated resin, 4.6 parts by weight of aniline, 7.5 parts by weight of epibromohydrin and 1
00 parts by weight of ethyl alcohol solvent was charged into a reaction vessel and the reaction was carried out at 60 to 75°C for 3 hours.

When the resin was washed with water, filtered, and dried, 32 parts by weight of a brown chelate resin was obtained.

From the results of elemental analysis of the resin, 6.
It was found that 6 parts by weight and 4.1 parts by weight of aniline had reacted.

Example 4 700 parts by weight of hexamethylene diamine and 70 parts by weight of water were added to 214 parts by weight of vinyl bromide resin having a particle size of 10 to 60 mesh, and the mixture was reacted at 80 to 95°C for 15 hours.

When the reaction product was filtered and washed with water, 317 parts by weight (undried) of brown aminated resin was obtained.

50 parts by weight of the obtained aminated resin (undried) was mixed with 4.7 parts by weight of epichlorohydrin and 100 parts by weight of N,N
-3 at 50-60°C in the presence of dimethylformamide solvent
After 0 minutes of reaction, 8 parts by weight of methyl iminodiacetate was added and the reaction was carried out at 60 to 70°C for 2 hours.
13 parts by weight of an OH aqueous solution was added, and the reaction was further carried out at 80 to 100°C for 1 hour.

Filter the resin content. After washing with water, 57 parts by weight (undried) of brown chelate resin was obtained.

From the results of elemental analysis of resin. epichlorohydrin 3
．． It was found that 5 parts by weight of methyl iminodiacetate and 4.3 parts by weight of methyl iminodiacetate had reacted.

Examples 5-10 Emulsion polymerized vinyl chloride resin 12 with mesh particle size of 10-60
1,890 parts by weight of tetraethylenepentamine and 210 parts by weight of water were added to 40 parts by weight, and the mixture was reacted at 130 to 170°C for 1 hour.

When the reaction product was filtered, washed with water, and dried, 1030 parts by weight of a brown aminated resin was obtained.

Next, 25 parts by weight of the obtained aminated resin was reacted in the same manner as in Example 1 under the reaction conditions shown in Table 4, and brown chelate resins were obtained in all cases.

Example 11 9.3 weight of aniline was added dropwise to a mixture of 8.6 parts by weight of 1,2,3,4-jepoxybutane and 100 parts by weight of ethanol solvent, and after reaction at 70 to 78°C for 30 minutes, Example 5 After adding 25 parts by weight of the same aminated resin used in Example 1 and carrying out a reaction at 70 to 78°C for 4 hours, the mixture was filtered, washed with water, and dried.

32.2 parts by weight of chelate resin was obtained.

The results of elemental analysis of the resin revealed that 3.6 parts by weight of 1,2,3,4-jepoxybutane and 3.7 parts by weight of aniline were reacted.

Example 12 16.1 parts by weight of methyl iminodiacetate and 1 part of ethanol solvent
13 parts by weight of thiophosgene was added dropwise to 00 parts by weight of the mixture, and the mixture was reacted at 60 to 73°C for 1 hour.

Then the same aminated resin 25 used in Example 5
After adding an air volume part and continuing to react at 70 to 80°C for 1 hour, add 770 parts by weight of 50 parts by weight of a 30% aqueous solution of caustic soda.
The reaction was further carried out at 70-80°C for 1 hour.

After reaction, filtered, washed with water, and dried. 33.4 parts by weight of brown chelate resin was obtained.

The results of elemental analysis of the resin revealed that 4.4 parts by weight of thiophosgene and 6.0 parts by weight of methyl iminodiacetate were reacted.

Example 13 25 parts by weight of the same aminated resin used in Example 5 and 15.5 parts by weight of succinic acid chloride.

Add 100 parts by weight of tetrachlorethylene solvent and 20.2 parts by weight of triethylamine reaction promoter, and heat to 70 to 90°C.
After 3 hours of reaction, 16.2 parts by weight of p-phenylenediamine was added to 770°C, and the reaction was carried out at 70 to 90°C for 5 hours, filtered, washed with water, and dried, resulting in 34.3 parts by weight of brown. A chelate resin was obtained.

From the results of elemental analysis of the resin, 8.1 of succinic acid chloride
It was found that 5.6 parts by weight of p-phenylenediamine had reacted.

Example 14 15.6 parts by weight of hexamethylene diisocyanate was added to 25 parts by weight of the same aminated resin used in Example 5, 8.6 parts by weight of piperazine, and 100 parts by weight of an aqueous solvent, and 5 parts by weight of hexamethylene diisocyanate were added.
After carrying out the reaction at 0 to 80°C for 8 hours, the mixture was filtered, washed, and dried to obtain 34.7 parts by weight of a brown chelate resin.

The results of elemental analysis of the resin revealed that 6.3 parts by weight of hexamethylene diisocyanate and 3.4 parts by weight of piperazine were reacted.

Example 15 80 to 46.4 parts by weight of aniline and 376 parts by weight of water solvent
Heat to 100°C, then add Epicrono, Rehydrin 46
After adding parts by weight and subsequently reacting at 80 to 100°C for 1 hour, 100 parts by weight of the same aminated resin used in Example 5 was added and reacting at 80 to 99°C for 3 hours, followed by filtration. After washing with water and drying, 154.6 parts by weight of a brown chelate resin was obtained.

Elemental analysis of the resin showed that 34 parts by weight of epichlorohydrin and 33 parts by weight of aniline had reacted.

Example 16 Emulsion polymerized vinyl chloride resin 62 with mesh particle size of 10 to 35
To the weight parts, 120 parts by weight of ethylenediamine and 40 parts by weight of water were added, and the reaction was carried out at 110 to 132°C for 4 hours.

Filter the reaction product and wash with water. Upon drying, 54.2 parts by weight of brown aminated resin was obtained.

Next, 25 parts by weight of the obtained aminated resin, 17.8 parts by weight of iminodiacetic acid, 18.6 parts by weight of epichlorohydrin and 195 parts by weight of water were charged into a reaction vessel, and 80 to 9
The reaction was carried out at 0°C for 1 hour, and then 55 parts by weight of a 30% by weight aqueous solution of potassium hydroxide was added, followed by base treatment at 90 to 40°C for 1 hour.

The reaction product was washed with water, filtered, and dried to obtain 29.5 parts by weight of a brown chelate resin.

Based on the results of elemental analysis of the resin, epichlorohydrin was 1.8
It was found that 2.5 parts by weight of iminodiacetic acid had reacted.

Example 17 400 parts by weight of triethylenetetramine and 45 parts by weight of water were added to 111 parts by weight of a chlorinated vinyl chloride resin with a particle size of 10 to 28 mesh containing 63% by weight of chlorine atoms in the resin, and the mixture was heated at 140 to 160°C. The reaction was carried out for 4 hours.

The reaction product was filtered, washed with water, and dried to obtain 103 parts by weight of a brown aminated resin.

Next, 50 parts by weight of the obtained aminated resin was added to a mixture in which 26.7 parts by weight of iminodiacetic acid and 23 parts by weight of epichlorohydrin were reacted in advance at 40 to 60°C for 1 hour in 400 parts by weight of an aqueous solvent.

The reaction was carried out at 60-70°C for 60 minutes.

The reaction product was filtered and washed with water to remove unreacted iminodiacetic acid and epichlorohydrin.

The reaction product was then immersed in 54 parts by weight of a 15% by weight aqueous sodium hydroxide solution at room temperature for 1 hour to perform a base treatment.

After that, 1 reaction product was washed with water, filtered, and dried, and 5
8 parts by weight of brown chelate resin was obtained.

Based on the results of elemental analysis of the resin, epichlorohydrin was found to be 3.2
It was found that 4.4 parts by weight of iminodiacetic acid had reacted.

Application example 1 0.25 parts by weight of each of the chelate resin obtained in each example, the phenolic resin-based chelate resin, and the aminated resin obtained in Example 1 in terms of dry resin was added to 1077Q-Cd/
13 CdCl2 and 39.3, S'-Na/I! was added to 50 parts by weight of an aqueous solution containing NaC11 at pH 5.5 and brought into contact for 1 hour with shaking.

As a result, the Cd concentration in the aqueous solution after treatment was as shown in Table 2.

*A mixed aqueous solution of 47.0 parts by weight of phenol, 66.5 parts by weight of iminodiacetic acid, and 40.5 parts by weight of 37% formalin was heated from room temperature to 70°C in 40 minutes, and heated at 70 to 73°C for 2 hours. After stirring, the temperature was lowered to 40°C, and a solution of 60 parts by weight of caustic soda dissolved in 100 parts by weight of ion-exchanged water was added to adjust the pH of the reaction system to 12.8.

Next, 162.0 parts by weight of 37% by weight formalin was added, heated gradually, and after 40 minutes, the temperature was raised to 70°C, and after reacting at 70 to 90°C for 3 hours, 47.0 parts by weight of phenol was added, Subsequently, after reacting at 70 to 90°C for 1 hour, the reaction system was kept at 90 to 100°C and 115.0 parts by weight of water was distilled out under reduced pressure, yielding 249 parts by weight of a viscous reddish-brown resin composition. .

The resulting resin composition was cured by heating in a hot air dryer at 130°C for 3 hours, and then pulverized to obtain a phenolic resin-based chelate resin having a particle size of 10 to 35 mesh.

Application example 2 CdCl2 of 1007V-Cd/l and 11.79,9-
Na/i! NaC7 and 500 ■-CI! /l of Na
The chelate resins of Examples 2.4, 7, 8, 12, 16, and 17, the phenolic resin-based chelate resin, and the aminated resin obtained in Example 1 were added to 100 parts by weight of an aqueous solution containing C11O at pH 6.0. 0.5 part by weight of each was added in terms of dry resin, and the mixture was allowed to contact for 1 hour while being shaken.

As a result, the Cd concentration in the aqueous solution after treatment was as shown in Table 3.

Application example 3 1007Q-U/l! Na, (UO)2(CO3)2
Examples 1, 3, 5,
Chelate resin of 6,9°10.11,13,14,15.

0.5 parts by weight of each of the phenolic resin-based chelate resin and the aminated resin obtained in Example 4 were added.

Contact was allowed for 1 hour with shaking.

As a result, the U concentration in the aqueous solution after treatment was as shown in Table 4.

Application example 4 Examples 1, 2, 3,
4°16.17 chelate resin, phenol resin-based chelate resin, and aminated resin obtained in Example 1 were added in an amount of 0.5 parts by weight in terms of each dry resin, and the mixture was allowed to contact each other for 1 hour with shaking.

As a result, the Cu concentration in the aqueous solution after treatment was as shown in Table 5.

Application example 5 2Cr207 and 13.1.9 in 100m9 Cr/l
- aqueous solution 1 of pH 5.0 containing NaCl of Na/l
0.00 parts by weight of the chelate resins of Examples 1, 3, 5, and 6, the phenolic resin-based chelate resin, and the aminated resin obtained in Example 1 were added in an amount of 0.5 parts by weight in terms of each dry resin, and while shaking. It was left in contact for 1 hour.

As a result, the Cr concentration in the aqueous solution after treatment was as shown in Table 6.

From Application Examples 1, 2, 3, 4, and 5, the chelate resins produced by the method of the present invention have better heavy metal adsorption ability than known chelate resins, have less influence of coexisting salts on heavy metal adsorption, and are It is clear that the equilibrium concentration of heavy metal adsorption in aqueous solutions in the presence of oxidizing agents such as sodium chlorate can be lowered.

Claims (1)

[Claims] 1(A) Primary and/or secondary amide 7 in the molecule
(B) a polyfunctional compound having at least two amine-reactive groups and a primary and/or secondary
A method for producing a chelate resin, which comprises reacting an amino compound having a class amine group, or a reaction product of the polyfunctional compound and the amino compound. 2(A) Polyfunctional compound n per equivalent of amine 7 group in resin
1/20 equivalent or more (n indicates the number of amine-reactive groups contained in one molecule of the polyfunctional compound) and 1/20 equivalent or more of the amino compound. manufacturing method. 3(A) Polyfunctional compound n per equivalent of amine 7 group in the resin
2. The method for producing a chelate resin according to claim 1, characterized in that 1/10 to 2n/1 equivalent (n is the same as described in the previous section) and 1/10 to 2/1 equivalent of the amino compound are reacted. 4(A) Production of a chelate resin according to claim 1, characterized in that 1/20 mole or more of a reactant of a polyfunctional compound and an amine compound is reacted per ami/-tl equivalent in the resin. Law. 5(A) The chelate resin according to claim 1, characterized in that 1/1 to 2/1 mole of the reactant of the polyfunctional compound and the amino compound is reacted per equivalent of amino group in the resin. manufacturing method. 6(A) As a resin, primary and/or
or Claims 1, 2, and 3, characterized in that an aminated resin having a secondary amino group is used.
A method for producing a chelate resin according to item 4, item 5, or item 6.