CN100560617C - A kind of N, two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl) and preparation method thereof - Google Patents
A kind of N, two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl) and preparation method thereof Download PDFInfo
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- CN100560617C CN100560617C CNB2007100198084A CN200710019808A CN100560617C CN 100560617 C CN100560617 C CN 100560617C CN B2007100198084 A CNB2007100198084 A CN B2007100198084A CN 200710019808 A CN200710019808 A CN 200710019808A CN 100560617 C CN100560617 C CN 100560617C
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Abstract
The invention discloses a kind of N, the two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl), it contains functional group-N, two (carboxymethyl) the dithiocarbamate-based groups of N-, quantity is 1.15～2.85mmol/g, and the adsorptive capacity of heavy metal is counted 2.1～6mmol/g with Ni.Its preparation method is: prepare low cross-linking macroporous polystyrene-divinylbenzene resin earlier; Refabrication obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin; With N, dinethylformamide is a swelling agent, under 60～90 ℃, add N, two (carboxymethyl) nabams reactions of N-, consumption is heavy 1～3 times of resin, stirring reaction 5～10h can get N, the two resins that replace the modification of dithiocarbamate-based group of N-carboxymethyl.Resin provided by the invention can be to as Ni
2+, Zn
2+Carry out selective adsorption in heavy metal, and adsorptive capacity is bigger, contained group can form the higher complex compound of stability constant with some heavy metal, has higher selectivity.
Description
Technical field
The present invention relates to a kind of resin and synthetic method thereof, specifically, be meant a kind of N, two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl) and preparation method thereof.
Background technology
Contain dithio aminocarboxylic acid group resin be a class polygamy bit-type superpolymer, can generate complex compound with contents of many kinds of heavy metal ion by functional group and metal ion effect, heavy metal ion is had good adsorption performance and adsorption selectivity.The resin that different dithiocarbamic acid derivatives are modified, substituting group kind and position can influence the complex ability to different heavy metal species, therefore can separate the polycomponent heavy metal by regulating substituting groups different in the dithiocarbamate-based group, enrichment target heavy metal improves the selectivity of resin for heavy metal.Therefore, such resin possesses wide application prospect at aspects such as the enrichment that separates purification heavy metal, noble metal and recovery, solid phase extraction techniques, chromatographic separation.
Environment College, Nanjing Univ. has submitted patent application " a kind of N-methyl to August 18 in 2006, N-carboxymethyl dithio amidocarbonic acid chelating resin and preparation method thereof " (number of patent application: 200610041366.9), its main synthetic method is to be parent with chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, in the ethanol system under 50～90 ℃, adding consumption is 1～3 times heavy N-methyl of resin, N-carboxymethyl dithio carboxylamine sodium reagent, condensing reflux, stirring reaction, reaction finishes back methyl alcohol, water washing, can get functional group content is the N-methyl of 0.73～2.96mmol/g, N-carboxymethyl dithio carboxylamine base group modification resin.Find this N-methyl in property experiment, the resin of N-carboxymethyl dithio carboxylamine base group modification is for Ag
+And Cu
2+Show selectivity preferably, have much room for improvement but adsorptive capacity is still low.In addition, the N-methyl, the resin of N-carboxymethyl dithio carboxylamine base group modification is for some other heavy metal such as Ni
2+, Zn
2+Deng selectivity with to Ag
+And Cu
2+Selectivity big gap is arranged.Literature search shows, is matrix with the chlorine ball, N, and the synthetic of dithiocarbamate-based modified resins of the two replacements of N-two (carboxymethyl) do not appear in the newspapers.
Summary of the invention
The purpose of this invention is to provide a kind of N, two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl) and synthetic method thereof, can synthesize by the present invention and to have a kind of N, the dithiocarbamate-based group of the two replacements of N-two (carboxymethyl) has the resin of selective adsorption to the part heavy metal.
Technical scheme of the present invention is as follows:
A kind of N, the two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl), its structural unit is as follows:
Contain functional group-N from structural unit as can be seen, two (carboxymethyl) the dithiocarbamate-based groups of N-are by the dual function Adsorption of Heavy Metal Ions of chelating and ion-exchange.After this resin may form the ring-type chelating by the sulphur atom on the separate base and carboxymethyl and metal, remaining carboxyl carried out ion-exchange with adjacent carboxymethyl and the heavy metal ion that does not participate in into ring.Its adsorption mechanism can be expressed as follows (being example with the divalent heavy metal ions):
Described N, the quantity of the two replacement dithio amidocarbonic acid chelating resin of N-two (carboxymethyl) functional group is 1.15～2.85mmol/g, is 2.1～6mmol/g (is that benchmark characterizes thing with Ni) to the adsorptive capacity of heavy metal.
A kind of N, the preparation method of the two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl) comprises following step:
(a) utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilize one or both the mixed pore-creating agents of doing in liquid wax or No. 200 solvent oils, use magnesiumcarbonate, gelatin, the mixed dispersion agent of doing of in the polyvinyl alcohol one or more, make initiator with benzoyl peroxide, adopt suspension polymerization, preparation low crosslinking degree macropore styrene-divinylbenzene copolymer, select steam distillation or ethanol for use, acetone, industrial spirit, low boiling point solvent gasoline is made solvent extraction, remove residual pore-creating agent in the resin duct, obtain low cross-linking macroporous polystyrene-divinylbenzene resin, following abbreviation Archon through air stream drying again;
(b) Archon is soaked in the chloromethyl ether of 4～7 times of its weight, 20～50% the zinc chloride that adds Archon weight is made catalyzer, under 25～55 ℃ of temperature, carry out chloromethylation, reach 10% above stopped reaction up to cl content, leach the resin spheroid, water or ethanol, acetone are washed chlorination mother solution remaining in the most resin, and air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, following abbreviation chlorine ball;
(c) after step (b) reaction, take out most reaction mother liquor, generally through Soxhlet extractor extracting 4～8 hours, then with N, dinethylformamide is a swelling agent, under 60～90 ℃, add N, two (carboxymethyl) nabam reactions of N-, consumption is heavy 1～3 times of resin, stirring reaction 5～10h can get N, the two resins that replace the modification of dithiocarbamate-based group of N-carboxymethyl.
The preparation method of above-mentioned a kind of resin, in the step (a), dosage of crosslinking agent is 4～12% of monomer and a linking agent total amount, and the pore-creating agent consumption is 40～100% of a monomer weight, and the degree of crosslinking of the low cross-linking macroporous polystyrene that makes is 2～10%.Preparation low crosslinking degree Archon former because: the high Archon of degree of crosslinking may influence the chelating with metal can the space swing of restriction group on modifier bit after the modification.The Archon of mentioning among the above-mentioned preparation method, chlorine ball can be for now disclosed preparation method is prepared.
Described a kind of N, the two preparation methods that replace dithio amidocarbonic acid chelating resin of N-carboxymethyl, it is characterized in that in the step (c), add N, the time of two (carboxymethyl) nabams reactions of N-added N at 5～10 hours by control, the consumption of two (carboxymethyl) nabam reagent of N-and reaction times and be parent with the chlorine ball of different cl contenies, can make series and contain N, the two resins that replace dithiocarbamate-based group of N-carboxymethyl.Usually determining other conditions, is in the parent building-up process with the chlorine ball of different cl contenies, and cl content is height more, and the surface group number of the resin of gained the more; Only change N, under the condition of the consumption of two (carboxymethyl) nabam reagent of N-, the consumption of reagent is bigger, and the surface group of the resin of gained the more; And the reaction times is longer, and then the surface group number is bigger.
Beneficial effect
The invention discloses a kind of N, resin that the dithiocarbamate-based group of the two replacements of N-two (carboxymethyl) modifies and preparation method thereof, resin provided by the invention can be to as Ni
2+, Zn
2+Carry out selective adsorption in heavy metal, and adsorptive capacity is bigger.Atom pairs heavy metals such as contained N, S, O have the dual function of chelating and ion-exchange.The present invention adopts N, two (carboxymethyl) nabams of N-are modified the N that contains that obtains, the chela of the dithiocarbamate-based group of the two replacements of N-two (carboxymethyl) is resinous, contained group can form the higher complex compound of stability constant with some heavy metal, have higher selectivity, mineral products metallurgical production mother liquor purify and the improvement recovery of factory effluent, environmental analysis in fields such as the separation of heavy metal and pre-concentration have been widely used.
Embodiment
Further specify the present invention by the following examples.
Embodiment 1
(a) suspension polymerization.
Styrene monomer adds a certain amount of diluted sodium hydroxide solution or monomer is directly filtered to remove stopper through the resin column that strong anion-exchange resin is housed.
In the 1000mL beaker, add 210g vinylbenzene, the 26g divinylbenzene, the 140g whiteruss, the back that stirs is standby.
In the 1000mL there-necked flask, add 600g distilled water and be warming up to 40 ℃, add the 6g gelatin again, be stirred to dissolving fully, be warming up to 50 ℃ simultaneously, add the 2mL methylene blue, stir, add the mixed liquid of above-mentioned vinylbenzene, divinylbenzene and liquid wax, add initiator benzoyl peroxide 4.0g; Adjust suitable stirring velocity and make the oil droplet size to fit, progressively be warming up to 80 ℃ with the speed of 1 ℃/6min, and insulation 4h, progressively be warming up to 85 ℃ of insulation 3h again, 90 ℃ of insulation 2h, 95 ℃ of insulation 4h, reaction finishes, and leaches resin, uses earlier hot wash, leach resin, dry, the Soxhlet extractor of packing into, clean with the acetone extracting, air stream drying sieves, and the resin of getting suitable particle size is standby.
(b) chloromethylation.
In the 2000mL there-necked flask, add the 300g Archon, the 1200g chloromethyl ether soaks more than the 2h down in 20-25 ℃, stir down, add the 150g zinc chloride, controlled temperature is not higher than 25 ℃, behind the stirring 1h, be warming up to 38 ℃, insulation 8～12h, the control cl content can finish reaction more than 10%.
Reaction leaches the resin spheroid after finishing, and washing back extracting resin washes with water to neutrality again, and air stream drying obtains the chlorine ball.
(c) nucleophilic substitution reaction
In the 1000mL there-necked flask, add the prepared chloromethyl resin 30g of step (b), with the DMF swelling 4h of 100ml; To contain 31gN, the 150mlDMF of two (carboxymethyl) nabam reagent of N-adds in the flask, is warming up to 60 ℃ then, stirs, and reaction 5h leaches resin, water successively, methyl alcohol, water washing.Can make N, the resin that two (carboxymethyl) dithiocarbamic acids of N-are modified.
This technology synthetic N, constitutional features such as following table that the two replacement dithiocarbamic acids of N-two (carboxymethyl) are modified resin:
The key technical indexes is as follows: (Resin A, B and C are respectively that the chlorine ball with different cl contenies 10%, 18% and 20% is the parent preparation, all the other parameters obtain for embodiment 1)
Embodiment 2
The synthesis step of another embodiment of the present invention is as follows:
(a) utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilize liquid wax to make pore-creating agent, make dispersion agent, make initiator with benzoyl peroxide with magnesiumcarbonate, adopt suspension polymerization, synthetic low crosslinking degree macroporous polystyrene-divinylbenzene copolymer is selected wet distillation for use or is made solvent extraction with ethanol, removes residual pore-creating agent in the resin duct, obtain low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. Archon through air stream drying again.
Wherein dosage of crosslinking agent is 4% of monomer and a linking agent total amount, and the pore-creating agent consumption is 40% of a monomer weight, and the degree of crosslinking of low cross-linking macroporous polystyrene is 2%.
(b) Archon is soaked in the chloromethyl ether of 4 times of its weight, 20% the zinc chloride that adds Archon weight is made catalyzer, when 35 ℃ of temperature, carry out chloromethylation, reach 10% above stopped reaction up to cl content, leach the resin spheroid, wash chlorination mother solution remaining in the most resin with water, air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. chlorine ball.
(c) with DMF be swelling agent swelling 30g chlorine ball, add 61gN, two (carboxymethyl) nabam reagent of N-are dissolved among the 300mlDMF, are warming up to 60 ℃, and stirring reaction 5h leaches resin, water successively, methyl alcohol, water washing.Can get N, the resin that the dithiocarbamate-based group of the two replacements of N-two (carboxymethyl) modifies, the amount of contained functional group is 2.34mmol/g, is 4.27mol/g (is that benchmark characterizes thing with Ni) to the adsorptive capacity of heavy metal.
Embodiment 3
Concrete steps are with embodiment 2, and just dosage of crosslinking agent is 12% of monomer and a linking agent total amount in the step (a), and the pore-creating agent consumption is 60% of a monomer weight, and the degree of crosslinking of low cross-linking macroporous polystyrene is 6%.Carry out chloromethylation in the step (b) during 40 ℃ of temperature.The N that makes, the amount of the contained functional group of N-two (carboxymethyl) two replacement dithiocarbamic acid resin is 2.17mmol/g, is 3.96mmol/g (is that benchmark characterizes thing with Ni) to the adsorptive capacity of heavy metal.
Embodiment 4:
The synthesis step of another embodiment of the present invention is as follows:
(a) utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilize No. 200 solvent oils to make pore-creating agent, with gelatin (or polyvinyl alcohol, or magnesiumcarbonate, gelatin, several mixing in the polyvinyl alcohol) make dispersion agent, make initiator with benzoyl peroxide, adopt suspension polymerization, synthetic low crosslinking degree macroporous polystyrene-divinylbenzene copolymer, select ethanol (or acetone for use, industrial spirit, low boiling point solvent gasoline) make solvent extraction, remove residual pore-creating agent in the resin duct, obtain low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. Archon through air stream drying again.
Wherein dosage of crosslinking agent is 7% of monomer and a linking agent total amount, and the pore-creating agent consumption is 100% of a monomer weight, and the degree of crosslinking of low cross-linking macroporous polystyrene is 10%.
(b) Archon is soaked in the chloromethyl ether of 7 times of its weight, 50% the zinc chloride that adds Archon weight is made catalyzer, in 40 ℃ of temperature, carry out chloromethylation, reach 10% above stopped reaction up to cl content, leach the resin spheroid, wash chlorination mother solution remaining in the most resin with ethanol (or acetone), air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, i.e. chlorine ball.
(c) add 30g chlorine ball in the 1000ml there-necked flask, add N, two (carboxymethyl) nabam reagent of N-, consumption is 3 times of weight resin, reagent is dissolved in 300mlDMF adds in the flask, be warming up to 60 ℃, stirring reaction 5h leaches resin, water successively, methyl alcohol, water washing.Making functional group content is 2.47mmol/g, and counterweight metal adsorption amount is the N of 4.51mmol/g (is that benchmark characterizes thing with Ni), and resin is modified by the dithiocarbamate-based group of the two replacements of N-two (carboxymethyl).
Claims (4)
1, a kind of N, the preparation method of the dithiocarbamate-based resin of the two replacements of N-two (carboxymethyl) is characterized in that comprising following step:
(a) utilize vinylbenzene to make monomer, divinylbenzene is made linking agent, utilize one or both the mixed pore-creating agents of doing in liquid wax or No. 200 solvent oils, use magnesiumcarbonate, gelatin, the mixed dispersion agent of doing of in the polyvinyl alcohol one or more, make initiator with benzoyl peroxide, adopt suspension polymerization, preparation low crosslinking degree macropore styrene-divinylbenzene copolymer, select steam distillation or ethanol for use, acetone, industrial spirit or low boiling point solvent gasoline are made solvent extraction, remove residual pore-creating agent in the macropore styrene-divinylbenzene copolymer resin duct, obtain low cross-linking macroporous polystyrene-divinylbenzene resin through air stream drying again, hereinafter to be referred as Archon;
(b) Archon is soaked in its weight 4-7 chloromethyl ether doubly, 20～50% the zinc chloride that adds Archon weight is made catalyzer, under 25～55 ℃ of temperature, carry out chloromethylation, reach stopped reaction on 10% up to cl content, leach the resin spheroid, water, ethanol or acetone are washed chlorination mother solution remaining in the most resin, and air stream drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resin, hereinafter to be referred as the chlorine ball;
(c) after step (b) reaction, take out most reaction mother liquor, through Soxhlet extractor extracting 4～8 hours, then with N, dinethylformamide was a swelling agent, under 60～90 ℃, add N, two (carboxymethyl) nabam reactions of N-, consumption is 1～3 times of weight resin, can get N, the two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl).
2, according to a kind of N described in the claim 1, the preparation method of the two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl), it is characterized in that in step (a), dosage of crosslinking agent is 4～12% of monomer and a linking agent total amount, the pore-creating agent consumption is 40～100% of a monomer weight, and the degree of crosslinking of the low cross-linking macroporous polystyrene that makes is 2～10%.
3, according to a kind of N described in the claim 1, the preparation method of the two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl) is characterized in that controlling different reaction times 8～18h in the step (b), and the chlorine ball that obtains has different chlorinity.
4, according to a kind of N described in the claim 1, the preparation method of the two replacement dithio amidocarbonic acid chelating resins of N-two (carboxymethyl), it is characterized in that in the step (c), add N, the time of two (carboxymethyl) nabam reagent reacts of N-is 5～20h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9708202B2 (en) | 2012-04-28 | 2017-07-18 | Nanjing University | Electroplating waste water treatment method |
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| CN102295723B (en) * | 2011-05-24 | 2013-03-27 | 南京大学 | 6-aminopyridine-3-carboxylic acid chelating resin and its preparation method |
| CN104923163B (en) * | 2014-03-20 | 2017-03-29 | 长沙文晟生物科技有限责任公司 | A kind of silica gel absorber of Adsorption of Heavy Metal Ions and preparation method thereof |
| CN107376874A (en) * | 2017-08-18 | 2017-11-24 | 江苏海普功能材料有限公司 | Heavy metal absorbent and preparation method thereof |
| CN114272959B (en) * | 2021-12-30 | 2023-11-03 | 江苏金杉新材料有限公司 | Preparation method of chelate resin for hydrometallurgy |
| CN115672287B (en) * | 2022-09-16 | 2024-02-09 | 苏州博进生物技术有限公司 | Modified chelating resin for heavy metal ion adsorption |
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Non-Patent Citations (4)
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| Crosslinked polystyrene-supported dithiocarbamates as metalcomplexing agents. Beena Mathew,V. N. Rajasekharan Pillai.Eur. Polym. J.,Vol.30 No.1. 1994 |
| Crosslinked polystyrene-supported dithiocarbamates as metalcomplexing agents. Beena Mathew,V. N. Rajasekharan Pillai.Eur. Polym. J.,Vol.30 No.1. 1994 * |
| Reaction with metal ions of chloromethylated polystyrene resincontaining dithiocarbamate group. KAZUHISA HIRATANI, et al.Journal of applied polymer science,Vol.26 . 1981 |
| Reaction with metal ions of chloromethylated polystyrene resincontaining dithiocarbamate group. KAZUHISA HIRATANI, et al.Journal of applied polymer science,Vol.26 . 1981 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9708202B2 (en) | 2012-04-28 | 2017-07-18 | Nanjing University | Electroplating waste water treatment method |
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