CN102863579A - 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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- CN102863579A CN102863579A CN2012103419499A CN201210341949A CN102863579A CN 102863579 A CN102863579 A CN 102863579A CN 2012103419499 A CN2012103419499 A CN 2012103419499A CN 201210341949 A CN201210341949 A CN 201210341949A CN 102863579 A CN102863579 A CN 102863579A
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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 the characteristics such as organism enrichment and amplification the mankind's health is produced 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.The advantages such as wherein macromolecule chelating resin is large with its adsorptive capacity, selectivity good, the high and favorable regeneration effect of stability are used more and more extensive in the heavy metal containing wastewater treatment field.
Chelate resin is a class functional polymer that (also claims parent or carrier) take crosslinked polymkeric substance as skeleton and connect special function base, can be from the aqueous solution that contains heavy metal ion selectively huge legendary turtle close specific heavy metal ion, form polynary ring-type complex compound by ionic linkage or coordinate bond, and when condition is suitable with 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 Da ﹑ selectivity has become resin investigator's a target.
Summary of the invention
The purpose of this invention is to provide a kind of barbituric acid resin and its preparation method and application, can synthesize by the present invention and have the barbituric acid group, the divalence heavy metal is had the resin of selective adsorption.
Technical scheme of the present invention is as follows: a kind of barbituric acid resin, adopting first suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is the resin Archon, obtain resin chlorine ball through chloromethylation 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 for preparing described barbituric acid resin, adopting first suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is the resin Archon, obtain resin chlorine ball through chloromethylation again, resin chlorine ball is swollen in N, in the dinethylformamide, under 40 ~ 80 ℃, add the barbituric acid saturated aqueous solution, stirring reaction 8 ~ 24h gets the 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 the heavy metal wastewater thereby adsorption treatment.
Described heavy metal is the 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, contains a large amount of nitrogen-atoms and the Sauerstoffatom that can form with heavy metal ion coordinate bond in its molecular structure, is 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 such as Cu
2+﹑ Pb
2+, Hg
2+Carry out selective adsorption in heavy metal, and adsorptive capacity is larger.
The present invention adopts barbituric acid to modify the chelate resin that contains the barbituric acid group that obtains, be easy to synthesize, stable performance, can form the higher complex compound of stability constant with heavy metal cation, has higher selectivity, can administer recovery to the heavy metal in the waste water, and separate and the field such as enrichment at the purification of the metallurgical mother liquor of mineral products, heavy metal in the environmental analysis, also be with a wide range of applications.
Embodiment
Further specify by the following examples the present invention.
A kind of barbituric acid resin, its structural unit is as follows:
Can find out from its structural unit, its functional group is the barbituric acid group:
Nitrogen-atoms and carbonylic oxygen atom in the 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: adopting first suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is the resin Archon, obtain resin chlorine ball through chloromethylation again, resin chlorine ball is swollen in N, in the dinethylformamide, under 40 ~ 80 ℃, add the barbituric acid saturated aqueous solution, stirring reaction 8 ~ 24h gets the barbituric acid chelate resin.Add the barbituric acid reagent dosage (amount that refers to the barbituric acid solid, be made into the reaction of the aqueous solution and chlorine ball) be 1 ~ 5 times of resin chlorine ball quality, the time of reaction was at 8 ~ 24 hours, cl content, barbituric acid reagent dosage and reaction times by control resin chlorine ball, can make the chelate resin that series contains the barbituric acid group.Determining other conditions, is in the parent building-up process with the chlorine ball of different cl contenies, and resin chlorine ball cl content is higher, the 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.
Adopting first suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is the resin Archon, obtain resin chlorine ball through chloromethylation 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 that strong anion-exchange resin is housed.
In the 250mL beaker, add 88g vinylbenzene, the 12g divinylbenzene, the 100g whiteruss stirs rear for subsequent use.In the 1000mL three-necked flask, add 450g distilled water, the 3.75g gelatin, be warming up to 40 ℃, under agitation add above-mentioned vinylbenzene, divinylbenzene and whiteruss mixed solution, add the 1g benzoyl peroxide, speed with 0.5 ℃/min is warming up to 75 ℃, and insulation 5h slowly is warming up to 85 ℃, insulation 4h, reaction finishes, and leaches the resin spheroid, hot wash, the apparatus,Soxhlet's of packing into after draining selects ethanol to make solvent extraction clean, then warm air drying is sieved, and the resin of getting suitable particle size is for subsequent use.
(b) chloromethylation
In the 500mL there-necked flask, add 50g macroporous St-DVB copolymer Archon, the 200g chloromethyl ether, in 30 ℃ of lower 2h that soak, under the mechanical stirring, adding 15g Zinc Chloride Anhydrous carries out chloromethylation 10h under 30 ℃ of temperature.Reaction leaches chloromethylation macroporous St-DVB copolymer spheroid after finishing, and water and ethanol are washed chlorination mother solution remaining in the most spheroid respectively, and then warm air drying obtains resin chlorine ball, and gained chloromethylation macroporous polystyrene chlorinity is 10%.
(c) functionalizing reaction
In the 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 the flask, stirring reaction 8h leaches resin, successively water, diluted sodium hydroxide solution, water washing, the dehydrated alcohol extracting, warm air drying can make the 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 the 250mL beaker, add 96g vinylbenzene, the 4g divinylbenzene, the 50g whiteruss stirs rear for subsequent use.In the 1000mL three-necked flask, add 450g distilled water, the 3.75g gelatin, be warming up to 45 ℃, under agitation add above-mentioned vinylbenzene, divinylbenzene and whiteruss mixed solution, add the 1g benzoyl peroxide, speed with 0.5 ℃/min is warming up to 78 ℃, and insulation 5h slowly is warming up to 85 ℃, insulation 4h, reaction finishes, and leaches diameter polystyrene spheres, hot wash, select ethanol to make solvent extraction after draining, then warm air drying.
(b) the macroporous polystyrene spheroid is soaked in the chloromethyl ether of 6 times of its weight, in 30 ℃ of immersion 2h, the Zinc Chloride Anhydrous that adds polymer weight 60% is made catalyzer, carries out chloromethylation 12h under 50 ℃ of temperature.Stopped reaction leaches chloromethylation macroporous polystyrene spheroid, and water and ethanol are washed chlorination mother solution remaining in the most spheroid, then warm air drying respectively; Gained chloromethylation macroporous polystyrene chlorinity is 19.5%.
(c) in the 500mL there-necked flask, add the prepared chloromethyl resin 30g of step (b), DMF swelling 12h with 60mL is warming up to 80 ℃, 80 ℃ 300g barbituric acid saturated aqueous solution of pre-in advance preparation is added in the flask, stirring reaction 24h leaches resin, successively water, diluted sodium hydroxide solution, water washing, the dehydrated alcohol extracting, warm air drying can make the 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 the 500mL there-necked flask, add the prepared chloromethyl resin 30g of step (b), DMF swelling 12h with 60mL is warming up to 60 ℃, 60 ℃ 200g barbituric acid saturated aqueous solution of pre-in advance preparation is added in the flask, stirring reaction 16h leaches resin, successively water, diluted sodium hydroxide solution, water washing, the dehydrated alcohol extracting, warm air drying can make the 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 the 500mL there-necked flask, add the prepared chloromethyl resin 30g of step (b), DMF swelling 12h with 60mL is warming up to 70 ℃, 70 ℃ 250g barbituric acid saturated aqueous solution of pre-in advance preparation is added in the flask, stirring reaction 16h leaches resin, successively water, diluted sodium hydroxide solution, water washing, the dehydrated alcohol extracting, warm air drying can make the barbituric acid chelate resin.Gained barbituric acid resin functional group content is 2.12mmol/g.
The barbituric acid resin is to the adsorptive capacity (mg/g) of three heavy metal species
| 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. barbituric acid resin, it is characterized in that, adopting first suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is the resin Archon, obtain resin chlorine ball through chloromethylation 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. method for preparing barbituric acid resin claimed in claim 1, adopting first suspension polymerization to prepare degree of crosslinking is that 2 ~ 12% low crosslinking degree Macroporous styrene-divinybenzene copolymers is the resin Archon, obtain resin chlorine ball through chloromethylation again, it is characterized in that, resin chlorine ball is swollen in the DMF, under 40 ~ 80 ℃, add the barbituric acid saturated aqueous solution, stirring reaction 8 ~ 24h gets the barbituric acid chelate resin.
3. the method for preparing the barbituric acid chelate resin 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 the heavy metal wastewater thereby adsorption treatment.
5. application claimed in claim 4 is characterized in that, described heavy metal is the 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104946138A (en) * | 2014-03-27 | 2015-09-30 | 苏州吉利鼎海洋生物科技有限公司 | Method for removing heavy metal ions by using gelatin |
| CN105293643A (en) * | 2014-07-11 | 2016-02-03 | 中国石油化工股份有限公司 | Method for treating sewage through electrolytic catalysis oxidation |
| 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 |
| CN116239720A (en) * | 2023-02-06 | 2023-06-09 | 四川大学 | Hg having double base surface recognition 2+ Temperature-sensitive linear polymer material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461219A (en) * | 2000-07-26 | 2003-12-10 | 塔罗制药工业有限公司 | Non-sedating barbiturate compounds as neuroprotective agents |
| 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 |
-
2012
- 2012-09-14 CN CN201210341949.9A patent/CN102863579B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461219A (en) * | 2000-07-26 | 2003-12-10 | 塔罗制药工业有限公司 | Non-sedating barbiturate compounds as neuroprotective agents |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| BO-BIN JANG ETAL: "Binding of Uranyl Ion by 2,2"-Dihydroxyazobenzene Attached to a Partially Chloromethylated Polystyrene", 《JOURNAL OF POLYMER SCIENCE:PART A:POLYMER CHEMISTRY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946138A (en) * | 2014-03-27 | 2015-09-30 | 苏州吉利鼎海洋生物科技有限公司 | Method for removing heavy metal ions by using gelatin |
| CN105293643A (en) * | 2014-07-11 | 2016-02-03 | 中国石油化工股份有限公司 | Method for treating sewage through electrolytic catalysis oxidation |
| 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 |
| CN116239720A (en) * | 2023-02-06 | 2023-06-09 | 四川大学 | Hg having double base surface recognition 2+ Temperature-sensitive linear polymer material and preparation method thereof |
| CN116239720B (en) * | 2023-02-06 | 2024-05-31 | 四川大学 | Hg having double base surface recognition2+Temperature-sensitive linear polymer material and preparation method thereof |
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