JPH02251504A - Preparation of aminopolycarboxylic acid type chelate resin - Google Patents

Abstract

PURPOSE:To provide the subject resin capable of combining with metal ions in high efficiency by carboxymethylating alpha-amino-epsilon-caprolactam, hydrolyzing the product and subsequently reacting the resultant lysine-N<alpha>,N<alpha>-diacetic acid with polystyrene resin having amine-reacting groups. CONSTITUTION:alpha-Amino-epsilon caprolactam is carboxymethylated to form alpha-amino-epsilon- caprolactam-N<alpha>,N<alpha>-diacetic acid, which is hydrolyzed into lysine-N<alpha>,N<alpha>-diacetic acid. The resultant lysine derivative directly reacted with polystyrene resin having amino-reacting groups to selectively introduce the lysine derivative to the resin matrix through the epsilon-amino group by the one stage polymeric reaction, thereby providing the objective aminopolycarboxylic acid type chelate resin to which the poly-coordinate ligand having a structure similar to a nitrilotriacetic acid of the formula at the terminal has been introduced.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for producing a novel chelate resin having excellent complex-forming ability and separation ability for metal ions. The present invention relates to a method for producing a novel aminopolycarboxylic acid type chelate resin, in which a polydentate ligand consisting of -diacetic acid is introduced into a polystyrene resin via its 7-mino group at the ε-position.

[Technical background of the invention and its problems] Since chelating polydentate ligands form more stable complexes with metal ions than monodentate ligands, the above-mentioned polydentate ligands were introduced. Chelate resins are good metal ion trapping materials and are extremely effective in treating metal ion-containing wastewater and recovering valuable metals.

Conventionally, among the monovalent polydentate ligands, iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), LfLt'
)7min-N,N,N',N'-four vinegar rli(E
Amine-N-polyacetic acids such as DTA) are known to be excellent ligands that form stable complexes with many metal ions.

Among these polydentate ligands, IDA groups are easy to introduce into polymer resins, and chelate resins containing IDA groups have a relatively high ability to trap heavy metal ions, so they are widely manufactured industrially. has been used.

However, the chelate stability constant of the above-mentioned chelate polydentate ligand for metal ions is generally I DA<N
The order is TA<EDTA ("5 tabilit").
y Con5tants of Metal-C
complexes J TbeCbea+1cal 5
ociety, London, 1971). In addition, ID8 is a royal ligand, and in order to successfully adsorb metal ions forming a hexacoordinated octahedral structure, multiple ligands must be close to each other within the rigid polymer skeleton. be. However, in the conventional KIRE-1 resin, since the IDA group is bonded close to the polymer skeleton, the degree of steric freedom is restricted, and there is a problem in forming such a stable complex. Therefore, the metal ion t# trapping ability of the IDA type KIRE-1 resin is not necessarily fully satisfactory.

For these reasons, NTA groups and EDTA groups, which can form more stable complexes with heavy metal ions, are preferable as chelating multidentate ligands to be introduced into polymer resins, and these chelating multidentate ligands have already been used. Chelate resins in which a ligand is introduced into polystyrene have been proposed, for example, J, Am,
Cbea+, Soc, vol. 81, p. 377, 1959, and MacroIIIol, CI+em, vol. 1
(Vol. 80, p. 2499, 1979) However, the NTA group and EDTA group in these methods are introduced through several steps of polymer reactions.

However, in general synthetic reactions, it is difficult to achieve both reaction rate and selectivity of 100%. This has a negative effect on the selectivity of metal ion adsorption. Furthermore, these methods have drawbacks such as problems in the steric freedom of the ligand and complicated reaction routes, and are not necessarily satisfactory as industrial production methods.

[Object of the Invention] In view of the above circumstances, the present inventors have developed a conventional IDA type cleaner.
1. N T can form more stable complexes than resins, etc.
A As a result of extensive research in order to obtain an aminopolycarboxylic acid type chelate resin by introducing a polydentate 2-position containing an El-like group without changing its molecular structure by a -step polymer reaction, we first developed α It was discovered that the object could be achieved by carboxymethylating -amino-ε-caprolactam and introducing acetic acid into a polymeric resin having an amine-reactive group, and based on this knowledge, the present invention was completed. It's arrived.

That is, the present invention uses α-amino-ε-caprolactam as a raw material, carboxymethylation, Through a homogeneous reaction such as hydrolysis, ricinol N,N-diacetic acid with a complete ligand structure, which has been synthesized and purified in advance, is converted into a polymer resin having an amine-reactive group through a -step polymer reaction. 7-minoboricarboxylic acid type Kir-1, which is characterized in that it is introduced into
-Provides a method for producing t1 fat.

[Summary of the Invention] In the present invention, first, using a known carboxymethylation reaction of amine, α-amino-ε-caprolactam and halogenated acetic acid are reacted to form α-°amino-ε-caprolactam-N,N- Obtain disaudonic acid. After the carboxymethylation reaction, this caprolactam derivative can be easily isolated and purified as crystals by adjusting the pH of the reaction aqueous solution to 1.8 using hydrochloric acid. As the halogenated acetic acid, chloroacetic acid and bromoacetic acid are used, and chloroacetic acid is preferably used because of its high isolation yield. The caprolactam derivative is easily hydrolyzed by heating under reflux in an alkaline aqueous solution to give lysine-N,N-diacetic acid. As the alkali, sodium hydroxide and potassium hydroxide are used. The amount of alkali added is 6 to 6 for the caprolactam derivative.
12 equivalents are used, and an aqueous solution of about 2M to 4M is preferably used at one time.

Instead, it can be used directly as an aqueous solution for the next reaction with a polymer resin.

In the present invention, as the polystyrene base resin, styrene i monopolymers, copolymers of styrene and other vinyl compounds, or crosslinked products of these can be used, but styrene-divinylbenzene copolymers are particularly suitable. Polymers are preferred. The amine-reactive group of the resin matrix is not particularly limited as long as it can react with an amino group, but a chloromethyl group is preferably used. However, since the lysine derivative is soluble only in water, it is difficult to react with hydrophobic or lolomethylated polystyrene. In order to facilitate the reaction, chloromethyl groups can be reacted with dimethyl sulfite to form sulfonium, or reacted with trimethylamine, dimethyl 7-niline, etc. to form quaternary groups.
Known methods such as ammonium formation (for example, J,
Am, Cben+, Soc.

, Vol. 94, p. 2660, 1972, and Ind.
Eng, Cbem, Vol. 59, p. 147, 1967.
(2007) to impart hydrophilicity to the resin matrix. From the relationship of reaction temperature and introduction rate, C is particularly preferred.
A sulfonated resin is used.

The reaction of the lysine derivative with the sulfonated resin is achieved by adding the resin and the lysine derivative to water, adjusting the pH to 11, and then heating to reflux with stirring.

Through this reaction, the amine-reactive group of the resin selectively reacts only with the 7-mino group at the ε-position of the lysine derivative, and is introduced into the resin matrix via this amino group.I of the reaction solution
H needs to be controlled to 10~12. pH below this
Protonation of amine groups occurs in this region, and further I
In the JH region, the sulfonium group of the resin is decomposed and a good introduction rate cannot be obtained. 1) (1) Use for control. Sodium hydroxide or potassium hydroxide should be used as the alkaline solution. Further, the reaction temperature is preferably in the range of 50 to 100°C, and the reaction time is preferably in the range of 12 to 72 hours.

Furthermore, the amount of the lysine derivative to be added is preferably 1 to 2 equivalents based on the amine-reactive group in the resin matrix.

[Effects of the Invention] The chelate resin of the present invention thus obtained has no crosslinked structure and has a nitrilotriacetic acid-like group at the end. This coordination group is introduced into the polymer resin matrix via a spacer made of tetramethylene 7 amine, and has a high degree of steric freedom. Also, since this coordination group acts as a tetradentate site, it can be used for various metal ions. and form an extremely stable 1:1i'1 body. Therefore, the present KIRE-1 resin can selectively remove and recover metal ions from an aqueous solution containing metal ions with high efficiency. In particular, the KIRE-1 resin of the present invention can remove and recover metal ions from an aqueous solution containing metal ions. ), nickel (I
I), zinc (11), Kobal 1-(II>, lead ((1)
, removal of heavy metal ions such as cadmium (11) ions,
It is also extremely effective in collecting gallium (Ill), indium (Ill), and rare earth metal (Ill) ions.

[Embodiments of the invention] Next, the present invention will be explained in more detail with reference to Examples.

The sulfonated polystyrene tM resin used in the examples was divinylhensen crosslinked porous MR type a-romethylated polystyrene (32-6° mesh, C+
It was synthesized from 5 meq/g-resin) and dimethyl 7-niline by a known method as follows.

Dimethyl sulfide 26g, dichloromethane 150m
Add 50 g of the above chloromethylated polystyrene resin to a mixed solution of 1 and 150 ml of water, and stir at 25°C for 4 days.
, S content 11.1%).

Example: To 200 ml of aqueous IF containing 83 g of monochloroacetic acid,
Water-soluble Iα200 containing 35g of sodium hydroxide under water cooling
1 was gradually added dropwise to neutralize the mixture, and then 51 g of α-amino-ε-caprolactam was added. The I)H of the reaction solution was maintained at 9 to 11 with 1rR of sodium hydroxide solution, and heated at 40°C for 12 hours. Stirred. After the reaction is complete, adjust the pH of α to 1.8 with 6N hydrochloric acid to obtain α-
Amino-ε-caprolactam-Na, 6-diacetic acid 83
g was isolated as crystals (73% yield). Then, 57 g of the caprolactam derivative was added to an aqueous solution of 3001 containing 84 g of sodium dispersion, and the mixture was heated and stirred at 80° C. for 24 hours. After the reaction is complete, use 6N hydrochloric acid to
+H adjusted to 12, sulfonated resin 180ml
added. Adjust the pH of reaction lα to 10~ with thorium hydroxide solution! 2, and heated and stirred at 80° C. for 24 hours. The obtained reaction product was filtered, washed with 2N hydrochloric acid, and then dried with water to obtain 62.4 g of a resin into which lysine-Na1+-diacetic acid was introduced.

The elemental analysis value of this product was N: 2.94%, and the ligand content was 1.05+amol/g-resin.

Application example 1 500tmg of the chelate resin obtained in the example was added to 20a+
In addition to the aqueous Iα containing M steel (11) ions, a predetermined p
After stirring at room temperature for 24 hours, the resin was separated. Next, the metal ions adsorbed on this resin are
By eluating with normal hydrochloric acid and measuring the concentration of metal ions in the eluate, the amount of m adsorbed per 1 g of resin was determined.
(11) The amount of adsorbed ions (in millimoles) was determined. Adsorption of gallium (Ill) and nickel (11) ions was attempted using a similar method, and the relationship between the amount of metal ions adsorbed per gram of resin and Ill was determined. The results are shown in FIG. In Figure 1, the beak axis represents the pH of the I8 liquid, the vertical axis represents the adsorption amount of metal ions (in millimoles) per resin 18, the solid line represents m(11) ions, the broken line represents gallium (Ill), and the dotted line represents nickel. (11) It is an ion.

Application example 2 Using 500+ ng of Kire-1 resin obtained in the example,
Indium (Ill) ions,
Aluminum (Ill) ion, zinc (11) ion,
An attempt was made to adsorb cobal (I+) ions, and the relationship between the maximum amount of metal ions adsorbed per gram of resin and pH was determined.

The results are shown in Table 1.

COMPARATIVE EXAMPLE 500 grams of Kirey-1 resin synthesized in Example or commercially available iminoniacetic acid type Kirey-1 Jun FvI was added to 100 a+l of an aqueous solution containing copper (11) ions or gallium (1) ions at a concentration of 1 to 1. In addition, adjust to the specified pH,
After shaking at room temperature for 7 days, the residual metal ions in the solution were measured once, and the distribution coefficient of the resin for metal ions (
Kd> (Metal ions adsorbed per gram of resin ffi
/lc+a3 amount of metal ions remaining in the solution) and 11
) 1 was found. The results are shown in FIG.

In Figure 12, the inertial axis represents the IIH of melt α, the vertical axis represents the common logarithm of the distribution coefficient, the solid line represents the chelate resin of the present invention and copper (11) ions, and the broken line represents the chelate resin of the present invention and gallium. (Ill) ion, the dotted line shows the relationship between the commercially available iminonilocic acid type chelate resin and m(11) ion, and the - dotted line shows the relationship between the commercially available iminodiacetic acid type chelate resin and gallium (l l +) ion. be.

As can be seen from FIG. 2, the chelate resin of the present invention has a higher distribution coefficient than commercially available iminodiacetic acid type resins, and therefore adsorbs metal ions well even in a pH range of 1°C.

[Brief explanation of drawings]

Figure 1 shows the relationship between the adsorption amount of metal ions of the KIRE-1 resin of the present invention and the pH of the solution in Application Example 1, and Figure 2 shows the relationship between the KIRE-1 resin of the present invention and the commercially available KIRE-1 resin in a comparative example. 3 is a graph showing the relationship between the distribution coefficient of the iminodiacetic acid type chelate resin for metal ions and the pH of dissolved i7I. July 1989

Claims (1)

[Claims] 1. A polystyrene resin matrix having the formula ▲ represented by the following formula,
Chemical formulas, tables, etc. are available ▼ To produce an aminopolycarboxylic acid type chelate resin that has a multidentate ligand with a structure similar to nitrilotriacetic acid introduced at the end, α-amino-ε-caprolactam is first converted to carboxymethyl. α-amino-ε-
Caprolactam-N^α,N^α-diacetic acid is obtained, which is then hydrolyzed to obtain lysine-N^α,N^α-diacetic acid, and further a polystyrene resin having an amine-reactive group and the lysine are obtained. A method for producing an aminopolycarboxylic acid type chelate resin, which comprises directly reacting the derivative and selectively introducing the lysine derivative into the resin matrix via the amino group at the ε-position through a one-step polymer reaction. 2. The manufacturing method according to claim 1, wherein the polystyrene resin having an amine-reactive group is a sulfonated resin obtained by reacting a chloromethylated polystyrene resin with dimethyl sulfide.