CN102863579B - Barbituric acid chelating resin and preparation method and application thereof - Google Patents
Barbituric acid chelating resin and preparation method and application thereof Download PDFInfo
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- CN102863579B CN102863579B CN201210341949.9A CN201210341949A CN102863579B CN 102863579 B CN102863579 B CN 102863579B CN 201210341949 A CN201210341949 A CN 201210341949A CN 102863579 B CN102863579 B CN 102863579B
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Abstract
The invention discloses a barbituric acid chelating resin and a preparation method and the application of the resin. The method comprises the steps of: preparing low crosslinking degree macroporous styrene-divinyl benzene copolymer (that is a resin white ball) with the crosslinking degree of 2-12% by a suspension polymerization method; carrying out chloromethylation to obtain a resin chloride ball; and finally, grafting barbituric acid group on the resin chloride ball, wherein the content of the barbituric acid group is 1.12-2.56mol/g. The barbituric acid chelating resin is simple in synthesis, stable in performances, large in adsorption capacity for heavy metals such as Cu2+, Pb2+, and Hg2+ and high in selectivity, thus being used for treating and recycling the waste water containing the heavy metals.
Description
Technical field
The present invention relates to a kind of resin and synthetic method thereof, specifically, referred to a kind of barbituric acid resin and preparation method thereof.
Background technology
Development along with modern industry, its pollution that environment is produced more and more receives people's concern, in the middle of various pollutents, heavy metal contamination with its high toxicity, easily carcinogenic, not biodegradable, easily by features such as organism enrichment and amplifications, the mankind's health is produced to great threat, therefore heavy metal wastewater thereby effectively being processed is the prerequisite that guarantees human health and Sustainable development.
For the waste water that contains heavy metal ion, traditional treatment process mainly comprises the methods such as chemical precipitation, electrolysis, Mo Fen Li ﹑ ion-exchange, solvent extraction and biological treatment.Wherein macromolecule chelating resin is large with its adsorptive capacity, selectivity good, stability is high and the advantage such as favorable regeneration effect, and in heavy metal containing wastewater treatment field, application is more and more extensive.
Chelate resin be the polymkeric substance being cross-linked be the class functional polymer that skeleton (also claiming parent or carrier) connects special function base, can be from the aqueous solution that contains heavy metal ion selectively huge legendary turtle close specific heavy metal ion, by ionic linkage or coordinate bond, form polynary ring-type complex compound, and when condition is suitable by the Metal ion release of complexing out.At present, common resin has imine oxalic acid class, Schiff bases, hydroximic acid, amidoxim class, thio-alcohol, amine etc.Seeking the good resin of adsorptive capacity great ﹑ selectivity has become resin investigator's a target.
Summary of the invention
The object of this invention is to provide a kind of barbituric acid resin and its preparation method and application, by the present invention, can synthesize and there is barbituric acid group, divalence heavy metal is there is to the resin of selective adsorption.
Technical scheme of the present invention is as follows: a kind of barbituric acid resin, first adopting suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is resin Archon, through chloromethylation, obtain resin chlorine ball again, grafting barbituric acid group on resin chlorine ball, the structural formula of described barbituric acid group is:
The content of described barbituric acid group is 1.12 ~ 2.56mmol/g.
A kind of method of preparing described barbituric acid resin, first adopting suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is resin Archon, through chloromethylation, obtain resin chlorine ball again, resin chlorine ball is swollen in to N, in dinethylformamide, at 40 ~ 80 ℃, add barbituric acid saturated aqueous solution, stirring reaction 8 ~ 24h, obtains barbituric acid chelate resin.
Adding barbituric acid consumption is 1 ~ 5 times of resin chlorine ball quality.
The application of described barbituric acid resin in heavy metal wastewater thereby adsorption treatment.
Described heavy metal is divalence heavy metal.
Described heavy metal is Cu
2+﹑ Pb
2+, Hg
2+in any one or a few.
Beneficial effect
Barbituric acid is a kind of nitrogen heterocyclic, in its molecular structure, contains a large amount of can form nitrogen-atoms and the Sauerstoffatom of coordinate bond with heavy metal ion, and be a kind of good polydentate ligand, can form stable title complex with contents of many kinds of heavy metal ion.
Resin provided by the invention can be to as Cu
2+﹑ Pb
2+, Hg
2+in heavy metal, carry out selective adsorption, and adsorptive capacity is larger.
The chelate resin containing barbituric acid group that the present invention adopts barbituric acid modification to obtain, be easy to synthesize, stable performance, can form the complex compound that stability constant is higher with heavy metal cation, there is higher selectivity, can administer recovery to the heavy metal in waste water, and in the purification of the metallurgical mother liquor of mineral products, heavy metal in environmental analysis is separated and the field such as enrichment, be also with a wide range of applications.
Embodiment
Further illustrate by the following examples the present invention.
A resin, its structural unit is as follows:
From its structural unit, can find out, its functional group is barbituric acid group:
Nitrogen-atoms and carbonylic oxygen atom in barbituric acid resin functional group can provide lone-pair electron, can form coordinate bond with heavy metal ion, it is a kind of good polydentate ligand, can form stable title complex with contents of many kinds of heavy metal ion, thereby this resin have higher adsorptive capacity and good selectivity to heavy metal ion.
Described its functional group content of barbituric acid resin is 1.12 ~ 2.56mmol/g.
A kind of preparation method of barbituric acid resin, comprise following step: first adopting suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is resin Archon, through chloromethylation, obtain resin chlorine ball again, resin chlorine ball is swollen in to N, in dinethylformamide, at 40 ~ 80 ℃, add barbituric acid saturated aqueous solution, stirring reaction 8 ~ 24h, obtains barbituric acid chelate resin.Add the barbituric acid reagent dosage (amount that refers to barbituric acid solid, being made into the aqueous solution reacts with chlorine ball) be 1 ~ 5 times of resin chlorine ball quality, the time of reaction was at 8 ~ 24 hours, by controlling cl content, barbituric acid reagent dosage and the reaction times of resin chlorine ball, can make series containing the chelate resin of barbituric acid group.Determining other conditions, is in parent building-up process with the chlorine ball of different cl contenies, and resin chlorine ball cl content is higher, barbituric acid reagent dosage is larger, the reaction times is longer, and the surface functional group quantity of the chelate resin of gained the more.
First adopting suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is resin Archon, through chloromethylation, obtain resin chlorine ball again, concrete preparation method can be with reference to < < JornaI of PoIymer Science, Part A:PoIymer Chemistry > > 15August 1999 Binding of uranyl ion by 2, 2 '-dihydroxyazobenzene attached to a partially chloromethylated polystyrene JangB.B., LeeK., Kwon W.J..
Embodiment 1
(a) low crosslinking degree macroporous St-DVB copolymer Archon preparation.
Styrene monomer adds a certain amount of diluted sodium hydroxide solution or monomer is directly filtered to remove stopper through the resin column of strong anion-exchange resin is housed.
In 250mL beaker, add 88g vinylbenzene, 12g divinylbenzene, 100g whiteruss, standby after stirring.In 1000mL three-necked flask, add 450g distilled water, 3.75g gelatin, be warming up to 40 ℃, under agitation add above-mentioned vinylbenzene, divinylbenzene and whiteruss mixed solution, add 1g benzoyl peroxide, speed with 0.5 ℃/min is warming up to 75 ℃, and insulation 5h, is slowly warming up to 85 ℃, insulation 4h, reaction finishes, and leaches resin spheroid, hot wash, packs apparatus,Soxhlet's into after draining, and selects ethanol to make solvent extraction clean, then warm air drying, sieves, and the resin of getting suitable particle size is standby.
(b) chloromethylation
In 500mL there-necked flask, add 50g macroporous St-DVB copolymer Archon, 200g chloromethyl ether soaks 2h at 30 ℃, under mechanical stirring, adds 15g Zinc Chloride Anhydrous, at 30 ℃ of temperature, carries out chloromethylation 10h.After reaction finishes, leach chloromethylation macroporous St-DVB copolymer spheroid, water and ethanol are washed chlorination mother solution remaining in most spheroid respectively, and then warm air drying obtains resin chlorine ball, and gained chloromethylation macroporous polystyrene chlorinity is 10%.
(c) functionalizing reaction
In 500mL there-necked flask, add the prepared chloromethyl resin 30g of step (b), DMF swelling 12h with 60mL, is warming up to 60 ℃, the 200g barbituric acid saturated aqueous solution that is preheated to 60 ℃ is added in flask, stirring reaction 8h, leaches resin, successively water, diluted sodium hydroxide solution, water washing, dehydrated alcohol extracting, warm air drying can make barbituric acid chelate resin.
The synthetic barbituric acid of this technique is modified the following structural features table of resin:
Embodiment 2
The synthesis step of another embodiment of the present invention is as follows:
(a) in 250mL beaker, add 96g vinylbenzene, 4g divinylbenzene, 50g whiteruss, standby after stirring.In 1000mL three-necked flask, add 450g distilled water, 3.75g gelatin, be warming up to 45 ℃, under agitation add above-mentioned vinylbenzene, divinylbenzene and whiteruss mixed solution, add 1g benzoyl peroxide, speed with 0.5 ℃/min is warming up to 78 ℃, and insulation 5h, is slowly warming up to 85 ℃, insulation 4h, reaction finishes, and leaches diameter polystyrene spheres, hot wash, after draining, select ethanol to make solvent extraction, then warm air drying.
(b) macroporous polystyrene spheroid is soaked in the chloromethyl ether of 6 times of its weight, in 30 ℃ of immersion 2h, adds the Zinc Chloride Anhydrous of polymer weight 60% to make catalyzer, at 50 ℃ of temperature, carry out chloromethylation 12h.Stopped reaction, leaches chloromethylation macroporous polystyrene spheroid, and water and ethanol are washed chlorination mother solution remaining in most spheroid, then warm air drying respectively; Gained chloromethylation macroporous polystyrene chlorinity is 19.5%.
(c) in 500mL there-necked flask, add the prepared chloromethyl resin 30g of step (b), DMF swelling 12h with 60mL, is warming up to 80 ℃, the pre-300g barbituric acid saturated aqueous solution of 80 ℃ of preparation is in advance added in flask, stirring reaction 24h, leaches resin, successively water, diluted sodium hydroxide solution, water washing, dehydrated alcohol extracting, warm air drying can make barbituric acid chelate resin.Gained barbituric acid resin functional group content is 2.56mmol/g.
Embodiment 3
Step (a) is (b) with embodiment 2.Be step (c): in 500mL there-necked flask, add the prepared chloromethyl resin 30g of step (b), DMF swelling 12h with 60mL, is warming up to 60 ℃, the pre-200g barbituric acid saturated aqueous solution of 60 ℃ of preparation is in advance added in flask, stirring reaction 16h, leaches resin, successively water, diluted sodium hydroxide solution, water washing, dehydrated alcohol extracting, warm air drying can make barbituric acid chelate resin.Gained barbituric acid resin functional group content is 1.95mmol/g.
Embodiment 4
Step (a) is (b) with embodiment 2.Be step (c): in 500mL there-necked flask, add the prepared chloromethyl resin 30g of step (b), DMF swelling 12h with 60mL, is warming up to 70 ℃, the pre-250g barbituric acid saturated aqueous solution of 70 ℃ of preparation is in advance added in flask, stirring reaction 16h, leaches resin, successively water, diluted sodium hydroxide solution, water washing, dehydrated alcohol extracting, warm air drying can make barbituric acid chelate resin.Gained barbituric acid resin functional group content is 2.12mmol/g.
Barbituric acid resin is to the adsorptive capacity of three heavy metal species (mg/g)
| Heavy metal | Hg | Pb | Cu |
| Adsorptive capacity | 92.3 | 71.2 | 58.1 |
(Application Example 4 gained resins, resin demand is 0.1g, and heavy metal solution concentration is 100mg/L, and consumption is 100mL, and temperature is 25 ℃, adsorption time is 10h).
Claims (6)
1. a barbituric acid resin, it is characterized in that, first adopting suspension polymerization to prepare degree of crosslinking is that 2～12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is resin Archon, through chloromethylation, obtain resin chlorine ball again, grafting barbituric acid group on resin chlorine ball, the structural formula of described barbituric acid group is:
The content of described barbituric acid group is 1.12～2.56mmol/g.
2. a method of preparing barbituric acid resin claimed in claim 1, first adopting suspension polymerization to prepare degree of crosslinking is that 2～12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is resin Archon, through chloromethylation, obtain resin chlorine ball again, it is characterized in that, resin chlorine ball is swollen in DMF, at 40～80 ℃, add barbituric acid saturated aqueous solution, stirring reaction 8～24h, obtains barbituric acid resin.
3. a kind of method of preparing barbituric acid resin claimed in claim 1 according to claim 2, is characterized in that, adding barbituric acid consumption is 1～5 times of resin chlorine ball quality.
4. the application of barbituric acid resin claimed in claim 1 in heavy metal wastewater thereby adsorption treatment.
5. application claimed in claim 4, is characterized in that, described heavy metal is divalence heavy metal.
6. application claimed in claim 4, is characterized in that, described heavy metal is Cu
2+﹑ Pb
2+, Hg
2+in any one or a few.
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| CN105293643B (en) * | 2014-07-11 | 2018-09-21 | 中国石油化工股份有限公司 | The method of catalytic and oxidative electrolysis technology treated sewage |
| CN104945550A (en) * | 2015-06-18 | 2015-09-30 | 东南大学 | Dicyclohexylamine modified ion exchange resin, and preparation method and application of ion exchange resin |
| CN105287640A (en) * | 2015-11-24 | 2016-02-03 | 江西中天医药生物有限公司 | Combined chelating resin method for removal of heavy metals in termite extract |
| CN112661561A (en) * | 2020-12-24 | 2021-04-16 | 广东金正大生态工程有限公司 | Slow-release water-retaining fertilizer and preparation method thereof |
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| EP1625848A1 (en) * | 2004-08-10 | 2006-02-15 | Taro Pharmaceuticals North America, Inc. | Composition and method for enhanced delivery of 5,5-diphenyl barbituric acid |
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