CN101967209A - N-acetylethylenediamine chelate resin and preparation method thereof - Google Patents

Abstract

The invention discloses an N-acetylethylenediamine chelate resin and a preparation method thereof, belonging to the field of chelate resin. The constructional unit is shown in the specification, wherein the functional group is N-acetylethylenediamine; and the content of the functional group is 0.71-1.39mmol/g. The preparation method of the resin comprises the following steps: preparing a white ball; preparing a chlorine ball; extracting the chlorine ball through a soxhletextractor; then taking N,N-dimethylformamide as sweller, adding 2-aminothiazole-4-ethyl acetate potassium carbonate, and stirring for reaction to obtain faint yellow 2-aminothiazole-4-ethyl acetate based resin; washing the obtained resin; adding ethylenediamine solution; condensing and reacting; and filtering and drying to obtain the N-acetylethylenediamine chelate resin. The resin provided by the invention can selectively adsorb and separate heavy metal ions, such as Cu<2+> and the like, has wide applications in the fields of mining and metallurgy production mother solution extraction, production waste water management, heavy metal separation and preenrichment in the environmental analysis and the like.

Description

A kind of N-acetyl ethylenediamine chelating resin and preparation method thereof

technical field

The present invention relates to a kind of chelate resin and its synthetic method, specifically, refer to a kind of N-acetyl ethylenediamine chelate resin and its preparation method.

Background technique

Polyethylene polyamine chelating resin is a kind of high polymer coordinated by nitrogen atom. Through the interaction of lone pair electrons on nitrogen and metal ions, it can form complexes with various heavy metal ions, especially for transition group heavy metal ions. Superior adsorption performance and adsorption selectivity. The currently reported polyethylene polyamine resins have a large adsorption capacity for metal ions, but the adsorption selectivity for specific metal ions in multi-component solutions is insufficient. In China, Sun Xiangrong and others used epichlorohydrin to perform post-crosslinking reaction on triethylenetetraamine crosslinked polystyrene, and the selectivity of the obtained resin to copper ions was significantly improved. It has been reported in the literature that the adsorption performance of ethylenediamine resins with polyethylene glycol as chain units is better than that of amino resins with polyethylenediamine as units; increasing the number of ethoxy chain units and replacing oxygen atoms with sulfur atoms, the resin has a greater effect on gold The adsorption capacity was significantly increased. It can be seen that for polyethylene polyamine chelating resins, the length of the chain link between the substituent and the parent and the type of chain link have a significant impact on the adsorption performance of the resin, so the adsorption of heavy metals can be improved by adjusting the chain length and the type of chain unit performance, enrich the target heavy metals, and improve the adsorption selectivity of the resin.

Document search shows, take chlorine ball as substrate, the synthetic method of the chelating resin of bonding ethylenediamine by the ester group on the thiazole ring has not been reported.

Contents of the invention

The purpose of the present invention is to provide a kind of N-acetylethylenediamine chelating resin and preparation method thereof, can synthesize the chelating resin that has N-acetylethylenediamine structure, has special adsorption selectivity to copper ion by the present invention .

Technical scheme of the present invention is as follows:

A kind of N-acetyl ethylenediamine chelating resin, its structural unit is as follows:

It can be seen from the structural units that the resin contains functional groups: N-acetylethylenediamine and thiazole rings, and absorbs heavy metal ions through the chelation of nitrogen and oxygen atoms. The resin may form a cyclic chelate structure through the nitrogen atom and oxygen atom on the group:

The chemical functional group content of the N-acetylethylenediamine chelating resin is 0.71-1.39 mmol/g.

A kind of preparation method of N-acetyl ethylenediamine chelate resin, comprises the following steps:

(a) Styrene is used as a monomer, divinylbenzene is used as a crosslinking agent, one or both of liquid wax or No. 200 solvent oil is used as a porogen, and magnesium carbonate, gelatin, and polyvinyl alcohol are used. One or several kinds of mixtures are used as dispersant, benzoyl peroxide is used as initiator, and low-crosslinking macroporous styrene-divinylbenzene copolymer is prepared by suspension polymerization method. Steam distillation or ethanol, acetone, Industrial alcohol and low-boiling-point solvent gasoline are used as solvent extraction to remove the porogen remaining in the resin pores, and then air-dried to obtain low-crosslinked macroporous polystyrene-divinylbenzene resin, hereinafter referred to as white ball;

(b) Soak the white ball in chloromethyl ether 4 to 7 times its weight, add 20 to 50% of the weight of the white ball as zinc chloride as a catalyst, and carry out chloromethylation reaction at a temperature of 25 to 55°C until the chlorine When the content reaches more than 10%, the reaction is stopped, the resin spheres are filtered out, the remaining chlorinated mother liquor in the resin is washed with water or ethanol, and acetone, and air-dried to obtain chloromethylated low-crosslinked macroporous polystyrene-divinylbenzene resin, as follows Referred to as chlorine ball;

(c) After step (b), it is generally extracted by Soxhlet extractor for 4 to 8 hours, and then N, N-dimethylformamide is used as a swelling agent, and 2-aminothiazole-4 - Ethyl acetate and potassium carbonate are reacted, the amount of 2-aminothiazole-4-ethyl acetate is 2 to 5 times the weight of the resin, the amount of potassium carbonate is 1 to 2 times the weight of the resin, and the reaction is stirred for 6 to 24 hours. A light yellow chelating resin was obtained.

(d) After washing and drying the resin obtained in step (c), add ethylenediamine solution 15 to 30 times the weight of the resin, react at 125°C for 24 to 30 hours, filter with suction, wash and dry to obtain N-acetylethylenediamine Amine Chelating Resin.

In the preparation method of the resin, it is characterized in that step (c) the reaction time is controlled at 85°C, and (d) the reaction time is 24-30h, and the reaction temperature is controlled at 125°C. A series of chelating resins can be prepared by controlling the amount of reagents added in the reaction and the reaction time. Usually other conditions are determined, the longer the reaction time, the larger the number of surface groups; the larger the amount of reagent used, the more surface groups of the resin obtained.

Beneficial effect

The invention discloses an N-acetylethylenediamine chelating resin and a preparation method thereof. The resin provided by the invention can selectively adsorb and separate heavy metal ions such as Cu2+. The contained N, O and other atoms play a chelating and coordinating role on heavy metals. The N-acetylethylenediamine chelating resin obtained by modifying 2-aminothiazole-4-ethyl acetate and ethylenediamine in the present invention contains groups that can form complexes with higher stability constants with certain heavy metals. With high adsorption selectivity, it is widely used in the fields of purification of mother liquor in mining and metallurgy production, treatment of production wastewater, and separation and pre-enrichment of heavy metals in environmental analysis.

Detailed ways

The present invention is further illustrated by the following examples.

Example 1

(a) suspension polymerization

Add a certain amount of dilute sodium hydroxide solution to the styrene monomer or directly filter the monomer through a resin column equipped with a strong base anion exchange resin to remove the polymerization inhibitor.

In a 1000mL beaker, add 210g styrene, 26g divinylbenzene, and 140g liquid paraffin, stir well and set aside.

In a 1000mL three-neck flask, add 600g of distilled water and raise the temperature to 40°C, then add 6g of gelatin, stir until completely dissolved, and at the same time raise the temperature to 50°C, add 2mL of methylene blue, stir well, add the above-mentioned styrene, divinylbenzene and liquid Add the initiator benzoyl peroxide 4.0g to the wax mixture; adjust the stirring speed to make the oil droplet size appropriate, gradually raise the temperature to 80°C at a speed of 1°C/6min, keep it warm for 4 hours, and then gradually raise the temperature to 85°C Keep warm for 3 hours, keep warm at 90°C for 2 hours, keep warm at 95°C for 4 hours, after the reaction is completed, filter out the resin, wash it with hot water first, filter out the resin, dry it, put it into a Soxhlet extractor, extract it with acetone, and air-dry it. Sieve, and take the resin with suitable particle size for later use.

(b) Chloromethylation

In a 2000mL three-neck flask, add 300g of white balls and 1200g of chloromethyl ether, soak at 20-25°C for more than 2 hours, add 150g of zinc chloride under stirring, control the temperature not higher than 25°C, stir for 1 hour, then raise the temperature to 38°C, Insulate for 8-12 hours and control the chlorine content above 10%, then the reaction can be ended.

After the reaction, filter out the resin spheres, wash with water and extract the resin, then wash with water until neutral, and air-dry to obtain chlorine spheres.

(c) Nucleophilic substitution reaction

In a 250mL three-necked flask, add 8g of chloromethylated resin prepared in step (b), and swell with 150ml of DMF for 4h; add 20g of ethyl 2-aminothiazole-4-acetate, 10g of anhydrous potassium carbonate, and then heat up to 65 ℃, stirred, reacted for 20 hours, filtered out the resin, washed with water, acetone and water in turn, and dried to obtain the resin with ester group structure.

(d) Nucleophilic substitution reaction

Into a 250mL three-neck flask, add 8g of the resin prepared in step (c), 150mL of ethylenediamine, condense and reflux for 30h at 115°C, filter with suction and wash with water, acetone, and water, and dry to obtain N-acetylethylenediamine Amine Chelating Resin.

Example 2

The synthetic steps of another embodiment of the present invention are as follows:

(a) suspension polymerization

Using styrene as a monomer, divinylbenzene as a crosslinking agent, using No. 200 solvent oil as a porogen, using gelatin as a dispersant, using benzoyl peroxide as an initiator, and adopting a suspension polymerization method to synthesize low crosslinking Macroporous polystyrene-divinylbenzene copolymer, using ethanol (or acetone, industrial alcohol, low boiling point solvent gasoline) as solvent extraction to remove the residual porogen in the resin channels, and then air drying to obtain low crosslinking Macroporous polystyrene-divinylbenzene resin, that is, white balls.

Wherein the dosage of the crosslinking agent is 7% of the total amount of the monomer and the crosslinking agent, the dosage of the porogen is 100% of the weight of the monomer, and the crosslinking degree of the low crosslinking macroporous polystyrene is 10%.

(b) Chloromethylation

Soak the white ball in chloromethyl ether that is 4 times its weight, add 20% of the weight of the white ball to zinc chloride as a catalyst, and carry out chloromethylation reaction at a temperature of 35°C until the chlorine content reaches more than 10% to stop the reaction, filter The resin spheres are taken out, the remaining chlorinated mother liquor in the resin is washed with water, and air-dried to obtain chloromethylated low-crosslinked macroporous polystyrene-divinylbenzene resin, namely chlorine spheres.

(c) Nucleophilic substitution reaction

Swell 15g of chlorine balls prepared in step (b) with 300ml of DMF; add 42g of ethyl 2-aminothiazole-4-acetate and 15g of anhydrous potassium carbonate after 4h, heat up to 85°C, stir, react for 8h, and filter out the resin , washed with water, acetone, and water successively.

(d) Nucleophilic substitution reaction

Add 15g of the resin prepared in step (c) and 300mL of ethylenediamine solution to a 500mL three-neck flask, then raise the temperature to 125°C and condense and reflux for 24h, filter with suction, wash with water, wash with acetone, wash with water, and dry to obtain N-acetyl ethyl Diamine chelating resin.

Example 3:

The synthetic steps of another embodiment of the present invention are as follows:

(a) suspension polymerization

Using styrene as a monomer, divinylbenzene as a cross-linking agent, using No. 200 solvent oil as a porogen, magnesium carbonate as a dispersant, and benzoyl peroxide as an initiator, a low cross-linking agent was synthesized by suspension polymerization. Linked macroporous polystyrene-divinylbenzene copolymer, steam distillation is used to remove the porogen remaining in the resin channels, and then air-dried to obtain low-crosslinked macroporous polystyrene-divinylbenzene resin, that is, white ball .

Wherein the dosage of the crosslinking agent is 8% of the total amount of the monomer and the crosslinking agent, the dosage of the porogen is 40% of the weight of the monomer, and the crosslinking degree of the low crosslinking macroporous polystyrene is 2%.

(b) Chloromethylation

Soak the white ball in chloromethyl ether which is 7 times its weight, add 50% of the weight of the white ball with zinc chloride as a catalyst, and carry out chloromethylation reaction at a temperature of 40°C until the chlorine content reaches more than 10% to stop the reaction, filter The resin spheres were taken out, the remaining chlorinated mother liquor in the resin was washed with acetone, and air-dried to obtain chloromethylated low-crosslinked macroporous polystyrene-divinylbenzene resin, namely chlorine spheres.

(c) Nucleophilic substitution reaction

In a 500mL three-neck flask, add 10g of chlorine balls, and swell with 250ml of DMF for 4h; add 20g of ethyl 2-aminothiazole-4-acetate, 12g of anhydrous potassium carbonate, then heat up to 80°C, stir, react for 6h, and filter out the resin. Wash with water, acetone, and water successively.

(d) Nucleophilic substitution reaction

Into a 250mL three-necked flask, add 10g of the resin prepared in step (c), 200mL of ethylenediamine, condense and reflux for 30h at 120°C, filter with suction, wash with water, wash with acetone, wash with water, and dry to obtain N-acetylethylenediamine Amine Chelating Resin.

The structural characteristics of the N-acetylethylenediamine chelating resin synthesized by this process are as follows:

The main technical indicators are as follows: (resins A, B and C correspond to the resins prepared in cases 1, 2 and 3 respectively)

Example 4:

The synthetic steps of another embodiment of the present invention are as follows:

(b) suspension polymerization

Using styrene as a monomer, divinylbenzene as a crosslinking agent, liquid wax as a porogen, polyvinyl alcohol as a dispersant, benzoyl peroxide as an initiator, and suspension polymerization to synthesize low crosslinking The macroporous polystyrene-divinylbenzene copolymer is extracted with ethanol as a solvent to remove the porogen remaining in the resin channels, and then air-dried to obtain a low-crosslinked macroporous polystyrene-divinylbenzene resin, namely White ball.

Wherein the dosage of the crosslinking agent is 4% of the total amount of the monomer and the crosslinking agent, the dosage of the porogen is 40% of the weight of the monomer, and the crosslinking degree of the low crosslinking macroporous polystyrene is 2%.

(b) Chloromethylation

Soak the white ball in chloromethyl ether that is 4 times its weight, add 20% of the weight of the white ball to zinc chloride as a catalyst, and carry out chloromethylation reaction at a temperature of 35°C until the chlorine content reaches more than 10% to stop the reaction, filter The resin spheres are taken out, the remaining chlorinated mother liquor in the resin is washed with ethanol, and air-dried to obtain chloromethylated low-crosslinked macroporous polystyrene-divinylbenzene resin, namely chlorine spheres.

(c) Nucleophilic substitution reaction

Add 600ml of swelling agent DMF to a three-necked flask with 25g of chlorine balls, add reagent 2-aminothiazole-4-ethyl acetate 6h later, the dosage is twice the weight of the resin, 25g of anhydrous potassium carbonate, stir at 70°C After reacting for 12 hours, the resin was filtered out and washed with water, acetone and water successively.

(d) Nucleophilic substitution reaction

Into a 1000mL three-neck flask, add 20g of the resin prepared in step (c), 700mL of ethylenediamine, heat up to 110°C and condense and reflux for 20h, filter with suction, wash with water, wash with acetone, wash with water, and dry to obtain N-acetylethylenediamine Chelating resin.

Claims (6)

1. a N-acetylethylenediamine chelating resin is characterized in that its structural unit is as follows:

2. a kind of N-acetylethylenediamine chelating resin according to claim 1 is characterized in that functional group is N-acetylethylenediamine, and functional group content is 0.71～1.39mmol/g. 3. a kind of preparation method of N-acetylethylenediamine chelating resin is characterized in that comprising the following steps: (a) Styrene is used as a monomer, divinylbenzene is used as a crosslinking agent, one or two of liquid wax or 200# solvent oil is used as a porogen, and magnesium carbonate, gelatin, and polyvinyl alcohol are used One or several kinds of mixtures are used as dispersant, benzoyl peroxide is used as initiator, and low-crosslinking macroporous styrene-divinylbenzene copolymer is prepared by suspension polymerization method. Steam distillation or ethanol, acetone, Industrial alcohol and low-boiling-point solvent gasoline are used as solvent extraction to remove the porogen remaining in the resin pores, and then air-dried to obtain low-crosslinked macroporous polystyrene-divinylbenzene resin, hereinafter referred to as white ball; (b) Soak the white ball in chloromethyl ether 4 to 7 times its weight, add 20 to 50% of the weight of the white ball as zinc chloride as a catalyst, and carry out chloromethylation reaction at a temperature of 25 to 55°C until the chlorine When the content reaches more than 10%, the reaction is stopped, the resin spheres are filtered out, the remaining chlorinated mother liquor in the resin is washed with water or ethanol, and acetone, and air-dried to obtain chloromethylated low-crosslinked macroporous polystyrene-divinylbenzene resin, as follows Referred to as chlorine ball; (c) After step (b), extract by Soxhlet extractor for 4 to 8 hours, then use N,N-dimethylformamide as swelling agent, add 2-aminothiazole- 4-Ethyl acetate and 1-5 times of potassium carbonate are stirred and reacted at 40-100°C for 6-24 hours to obtain light yellow 2-aminothiazole-4-ethyl acetate-based resin; (d) After washing the resin obtained in step (c), add ethylenediamine solution in an amount of 20 to 50 times the weight of the resin, condense and react at 105 to 125°C for 20 to 30 hours, filter with suction, wash and dry to obtain N - Acetyl ethylenediamine chelating resin. 4. according to the preparation method of a kind of N-acetyl ethylenediamine chelating resin described in claim 3, it is characterized in that in step (a), cross-linking agent consumption is monomer and cross-linking agent total when preparing white ball The amount of the porogen is 4-12% of the weight of the monomer, and the amount of the porogen is 40-100% of the weight of the monomer, and the cross-linking degree of the obtained low cross-linked macroporous polystyrene is 2-10%. 5. according to the preparation method of a kind of N-acetylethylenediamine chelating resin described in claim 3 or 4, it is characterized in that in step (b), the control reaction time is 8～18h, obtains the different chlorine content chlorine balls. 6. according to the preparation method of a kind of N-acetyl ethylenediamine chelating resin described in claim 3 or 4, it is characterized in that in step (c), control reaction temperature is 40～85 ℃.