JPS61283605A - Chelate resin and its production - Google Patents

Abstract

PURPOSE:To facilitate the formation of a chelate resin excellent in physical strength, chemical strength and chelate exchange capacity, by reacting a crosslinked polymer consisting of structural units of 2,3-epithiopropyl (meth) acrylate with hydrazine. CONSTITUTION:A chelate resin having functional groups of the formula is produced by reacting a crosslinked polymer consisting of structural units of 2,3-epithiopropyl methacrylate and/or 2,3-epithiopropyl acrylate with hydrazine. In the formula, R<1> is methyl or H. Said reaction is performed by heating while agitating the both in the presence or absence of a solvent. The reaction temperature is 20-120 deg.C, preferably, 40-100 deg.C. The reaction time varies with a solvent and a reaction temperature and a time of 2-4hr suffices when methanol is used with the reaction temperature of 60-80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel chelate resin and a method for producing the same. The present invention relates to a novel chelate resin of the 3,N coordination type, which is based on a crosslinked polymer having thiopropyl acrylate as a constituent unit, and a method for producing the same.

Chelate resins have the ability to selectively capture specific metal ions from solutions containing metal ions, and can be used to remove harmful heavy metals and recover useful heavy metals during the manufacturing process of various industrial wastewater, chemical products, foods, etc. It has a wide range of applications, including the concentration and recovery of useful metals from dilute solutions, and the separation of individual metals from multi-component metal systems.

[Conventional technology]

A large number of chelate resins have been known in the past, and the main ones include iminodiacetic acid, polyalkylene polyamines, dithiocarbamic acids, thiols, amidoximes, and other coordinating groups. / - introduced into a substrate such as resin or vinyl chloride resin.

[Purpose of the invention]

An object of the present invention is to provide a new chelate resin that has good physical strength and chemical strength, has a large chelate exchange capacity, and can be easily synthesized by a simple reaction, and a method for producing the same.

[Structure of the invention]

The present invention will be explained in detail below.

The present invention relates to a chelate resin having a structural unit represented by formula (1) (wherein R1 is a methyl group or a hydrogen atom), and a method for producing the backing thereof.

The chelate resin of the present invention is produced by reacting a crosslinked polymer containing co-, 3-evithioglobil methacrylate and /i or 2,3-evithiopropyl acrylate as a constituent unit with hydrazine according to the reaction of the following formula. be done.

-CH, -C! The reaction between the crosslinked polymer containing i or co, 3-evithiopropyl acrylate as a constituent unit and hydrazine is carried out by heating the two while stirring and mixing them in the presence or absence of a solvent. When used, it is preferable to use a solvent that is inert to the crosslinked polymer, dissolves hydrazide, and swells the crosslinked polymer, such as methanol,
Examples include alcohols such as ethanol, aromatic hydrocarbons such as benzene and toluene, acetone, dioxane, methyl ethyl ketone, ether, tetrahydrofuran, and dimethylformamide.

As a solvent, it is also possible to use solvents that react with human didine such as acetone and methyl ethyl keto 7 to form hydrazo/.
In this case, the hydrazo/crosslinked copolymer reacts. For example, when the solvent was aceto/, it was produced according to the reaction of the following formula.

This resin becomes a chelate resin having a structural unit represented by the formula (1) by treatment with an acid or alkaline aqueous solution.

■SH The combination of reaction temperature and reaction time is selected as appropriate, but the reaction temperature is from 20°C to 120°C, preferably from Hiroo°C to io
It is 0°C. The reaction time varies depending on the reaction temperature of the solvent, but when methanol is used, a reaction time of 2 to 10 hours is sufficient at a reaction temperature of 10°C to 10°C. As hydrazine, both anhydrous hydrazino and water-containing hydrazine can be used. It is best to use hydrazi/ in an amount equal to or more than θ, j equivalent to the episulfide group, but if it is too much, there will be waste, so
Preferably it is double equivalent of 1-. If the amount of solvent used is too excessive, the concentration of hydrazine, which is a reaction reagent, will decrease, so an appropriate amount is naturally present. When the solvent is methanol, the hydrazi/concentration is! ~≠0 volume The amount of methanol is good.

The cross-linked polymer having 2,3-evithioprobyl methacrylate and/or co,3-evithioprobyl acrylate as a constituent unit used in the present invention can be produced according to a known method. For example, 2.3
- Obtained by a copolymerization reaction of shrimp thio methacrylate and/or λ,3-evithio acrylate and a crosslinkable monomer.

Furthermore, in order to improve the strength of the resin, monomers that can be copolymerized with these monomers, such as styrene, α-methylstere, methyl methacrylate, methyl acrylate, vinyl acetate, acrylonitrile, etc., may be copolymerized. It is possible.

Examples of crosslinkable monomers include divinylbenzene, divinyltoluene/, ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, propylene/glycol dimethacrylate, propyle/glycol diacrylate, and propanetriol triacrylate. , propanetriol triacrylate, and other polyvinyl monomers.

The crosslinking monomer is 0.0% based on the total monomers. It is preferably used in a ratio of 1 to 30 volumes.

The preferred method of polymerization is suspension polymerization to produce spherical polymers. Suspension polymerization is carried out by adding a monomer mixture and a radical polymerization initiator to an aqueous medium containing a suspension stabilizer.
This is carried out by polymerization at 20° C. with stirring. The polymerization initiator may be appropriately selected from those commonly used in vinyl polymerization; for example, benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide, tertiary butyl peroxide, etc. may be used alone or in combination. .

Suspension stabilizers include gelatin, sodium polyacrylate, and sodium polymethacrylate.

polyvinyl alcohol, hydroxyethyl cellulose,
Water-soluble polymer substances such as calcium carbonate, barium sulfate, pet/tonite, and hydroxyapatite, and water-insoluble inorganic compounds are used alone or in combination.

In some cases, calcium chloride, sodium sulfate, etc. are added to the aqueous medium to prevent the monomer from dissolving in the aqueous medium.

Also used in the present invention. A cross-linked polymer containing 2.3-evithiopropyl acrylate and/or 2.3-evithiopropyl acrylate as a constituent unit is macrobo-2.
Macroporous type resins are preferably produced according to known methods. That is, in the above-mentioned polymerization, a solvent is added to the monomer, which acts as a solvent for the monomer and as a non-swelling agent for the polymer. Examples of such solvents include paraffins such as n-hebutane and isooctane, and higher alcohols such as octatool and heptatool, and mixed solvents include petroleum base, petroleum naphthe, and the like.

Alternatively, it can be produced by adding a suitable linear polymer soluble in the monomer mixture to the monomers, polymerizing them, and then extracting and removing them from the resulting copolymer with a solvent. Examples of such linear polymers include linear polymers of acrylic esters, methacrylic esters, styrene, and the like.

The chelate resin of the present invention contains many types of heavy metal ions, such as Ag+, Hg2+, Cu2+, N12+, and C02+.

a62+, zrn2+, Mn2+, AIJ+
, CrJ + , CrA + , pb2 +.

It shows a large adsorption capacity for AuJ +, U022+, etc., and also has a high adsorption rate.

Also, the adsorbed metal ions are eluted with an acid or alkaline solution depending on their properties.

When using the resin of the present invention to separate a specific metal ion, a solution containing the target metal ion is passed through a resin column filled with the resin of the present invention to adsorb the target metal ion, and then an appropriate The target metal ion is extracted by treatment with a suitable eluent such as sulfuric acid, hydrochloric acid, nitric acid, cyanic acid, cyanate, alkali hydroxide, or a solution containing thiourea, alkali hydrosulfide, etc. /elute. Alternatively, the resin can be directly mixed with a solution containing metal ions to effect adsorption, separated, and then eluted using an eluent. The resin from which the metal ions have been eluted can be used again for adsorption after washing with water. The eluent is treated in a conventional manner to recover each metal.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

<Production of crosslinked copolymer of λ,3-evithiomethacrylate> j 00d To a three-necked flask were added 2 tOy1 g of water, 10 tnl of a 1% gelatin aqueous solution as a suspension stabilizer, 3 f1 sodium sulfate, and 1 L1 calcium carbonate.

Furthermore, in a mixed solution 20d (the mixing ratio is written in the column) of t/C2,3-evithio methacrylate and purity CH ve = s, ``''''ze' part is ``CH'' = 9 rubenzene), A solution in which the polymerization initiator azobisisobutyronitrile O6λ2 was dissolved and 10 txl of inoctane were mixed and added. After stirring the liquid and dispersing the organic solvent phase so that the droplet size is about 3λ to tO mesh, it takes about 1 hour to raise the liquid temperature to 70°C and maintain this state for 1 hour. The mixture was then kept at 0° C. for 2 hours to complete the polymerization. After heating in water to remove the solvent, the resulting spherical copolymer is separated, the calcium carbonate is decomposed with hydrochloric acid, other suspension stabilizers are removed by water washing, and the 32-2θ mesh is dried. A spherical polymer was obtained.

Production Example 1 - Production of Hiroku Chelate Resin> A ≠θ% methanol solution of hydrazine hydrate J- was added to the 2.3-functional bithiomethacrylate crosslinked copolymer it,
9. Perform the Hiroki reaction at 10℃. After the reaction was completed, the resin was washed with pure water and immersed in a normal sodium hydroxide aqueous solution overnight to convert the resin into the 10H form. Thereafter, washing was performed again with pure water until the washing liquid became almost neutral. The nitrogen content of the obtained resin was determined by elemental analysis. The results were as follows.

Manufacturing example! ~r <Manufacture of chelate resin> Production example/-44 except that hydrazine hydrate was used instead of the hydrazine water-based methanol solution.
Chelate resin was produced in exactly the same manner as ~≠9. The nitrogen content of the obtained resin was as follows.

Table 3 Example 1 Dry resin 'o, i, z jy of production examples i and r θ, θ
Add 1 mol/l AgNO3 aqueous solution jOtttl,
After contacting for p and r hours at 27°C while stirring, Ag+ in the supernatant was determined by chelate titration method.
The adsorption amount was determined from the g+ concentration.

Example λ to Example λ To the crosslinked copolymer/f of 2,3-evithiomethacrylate prepared in Example λ, hydrazide/hydrate j, 10%, 20
%, to% methanol solution/Ottl fr added,
A chelate resin was produced in the same manner as Production Example 1 to Hiro.

Dry resin 0. / 2 t f to 0.0 / mol/l
AgN0g.

Add and Oml of HgC11 aqueous solution, and mix well! After contact at ℃ for an hour, the metal concentration in the supernatant liquid was determined by chelate titration method, and the amount of metal adsorption was determined from the metals before and after adsorption (from agricultural products).

Hg, 2 + , Ou2+ of the resin used in the example in Production Example λ
, p bj +.

The results of determining the relationship between (il-shown in Figures 1 and 2)

A metal ion bath solution of 0.0/mol/l is used, and the amount added is qoOrttl for resin f2. Resin and metal solution are here! The contact was carried out at ℃ for at hours. Hg-2+.

Ag 2 and Or 2 exhibit good selective adsorption in the low pH range and can be separated from other metals at pHJ or lower. Also,
In the column method, metal ions can be separated by changing the eluent composition stepwise.

Example 7~/3 Manufacturing example! Ag+ of about 2 positive O1/2 in Bunso manufactured by
The adsorbed material was washed with water, filtered, and air-dried. 0. / Add 0 thiourea to the normal H01 solution toOrtl,! ? ,/,
Or, /,! ? , 2. Of, 3. C2! , 0?
, / 0. An eluent in which C2 was dissolved and an Ag adsorption resin of approximately 0. / 2 j f to each! After adding 0rtl and shaking at 3°C for 1 hour, Ag+ eluted into the eluent was measured to determine the elution rate.

〔Effect of the invention〕

As mentioned above, according to the chelate resin of the present invention, various metal ions? Figure 1 shows the Hg -2+ , A g , U 0,2+ , cuj + , Oa-2+ of the chelate resin that can be efficiently separated.
, p d + O and adsorption to Zn2+ and p
It is a figure showing the relationship with H.

Figure 2 shows the AIJ + of the chelate resin produced in Example 6.
, Or3 + , O% + , Ca2+ ,
zn, 2+, H12+, Mnj+.

FIG. 2 is a diagram showing the relationship between adsorption for Ca2+ and Pb2+ and pH.

Applicant Hiroshi Egawa Masato Kiriyo
Patent attorney for private practice - 1 other person Figure 1 H

Claims (2)

[Claims] (1) A chelate resin that is a crosslinked polymer and is characterized by having a structural unit represented by the following general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1 represents a methyl group or a hydrogen atom) (2) A compound represented by the following general formula (1) characterized by reacting a crosslinked polymer having 2,3-epithiopropyl methacrylate and/or 2,3-epithiopropyl acrylate as a constituent unit with hydrazine. Manufacturing method of chelate resin with functional groups ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (1) (In the formula, R^1 represents a methyl group or a hydrogen atom.)