CN1424127A - Preparation and use of functional polymer micro-balls for separating and determining heavy metal ions - Google Patents
Preparation and use of functional polymer micro-balls for separating and determining heavy metal ions Download PDFInfo
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- CN1424127A CN1424127A CN 02148580 CN02148580A CN1424127A CN 1424127 A CN1424127 A CN 1424127A CN 02148580 CN02148580 CN 02148580 CN 02148580 A CN02148580 A CN 02148580A CN 1424127 A CN1424127 A CN 1424127A
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Abstract
A functional high-molecular microsphere for detecting heavy metal ions and separating them from sewage is prepared through synthesizing the oligomer from N-vinyl acetylamine (NVA), preparing macro-molecular monomer, graft copolymerizing with styrene to obtain PNVA-g-PS microspheres, hydrolyzing in acid or alkaline solvent, and reacting on p-methyl azocarboxylate.
Description
Technical field
The methods for making and using same of the functionalized macromolecular microballoon of a kind of separation, detection heavy metal ion, the present invention is the surface-functionalized polymer microsphere of preparation, can detect, remove harmful metal ion, reaches harmless treatment and purposes such as fwaater resources protection, detection.The present invention relates to prepare the technical field of functionalized macromolecular material, processing and detection sewage.
Background technology
Environmental pollution is China's economic development, one of problem that social progress faced.Environmental pollution has not only destroyed the ecological balance, has wasted the resource and the energy, and serious harm mankind itself's healthy and existence, also can hinder further developing of industrial and agricultural production simultaneously.At present domestic to waste gas, the improvement of waste water is comparatively paid attention to, and common toxic heavy metal element has mercury, cadmium, lead, chromium, arsenic, selenium etc. in the waste water.Metamorphosis only takes place in these heavy metals and compound thereof in water body migration conversion process, can not disappear, and be cumulative toxicant, plant is still all had toxic action to human body.To plant mainly is to absorb by plant root to enter in the plant, and the excessive growth and development of plant that then directly influences causes the withered, dead of plant when serious.For human body, toxic heavy metal element is mainly by alimentary canal, respiratory tract, what have can also enter human body by approach such as skins, and mainly remain in organ-tissues such as liver, kidney, brain, then these human organs are caused murder by poisoning when excessive, cause functional lesion until completely losing when serious.In addition some element can also and the protein enzyme of human body and amino acid in functional groups, many biochemistry of interference body and physiological activity finally cause human body multiple disease to occur, and human health is caused great threat.Heavy metal ions in wastewater is dealt with improperly also can cause secondary pollution.
What the heavy metal ions in wastewater processing method was commonly used has: (1) chemical precipitation method; (2) absorption method; (3) air supporting method; (4) oxidation-reduction method; (5) ion-exchange; (6) membrane separation process etc. is looked into newly through consulting lot of documents and trust, the report that the functionalized macromolecular microballoon that not seeing has relevant being used to separate, detect heavy metal ion is both at home and abroad handled.
Summary of the invention
(1) technical problem that will solve
The invention provides a kind of methods for making and using same of functionalized macromolecular microballoon, remove harmful metal ion in the waste water, the purpose of protection environment to reach.
(2) technical scheme
Technical scheme of the present invention is a preparation functionalized macromolecular microballoon, and the polymer microsphere of this functionalization can remove the heavy metal ion in the waste water, and polymer microsphere can be reused.
A kind of preparation method of functionalized macromolecular microballoon, at first synthetic poly N-ethylene yl acetamide (PNVA) macromonomer; Then PNVA and styrene (S) are carried out dispersion copolymerization in alcohol or alcohol/water mixed solvent, one-step method obtains the polymer microsphere PNVA-g-PS that monodispersed surface has grafted chain; Again the PNVA-g-PS microballoon is added water decomposition in acid or basic solvent, get the surperficial polymer microsphere PVAm-g-PS that is rich in amido; The functionalized macromolecular microballoon that obtains separating, detecting heavy metal ion is reacted in adding to 2 bromopmethylazocarboxyl.This polymer microsphere can be reused.
Synthesizing of polymer microsphere
1.N-vinyl acetamide (NVA) oligomer is synthetic: with monomer NVA, initator azo two (2-(2-imidazoles)) propane (VA-061) and the adding of chain-transferring agent mercaptoethanol are equipped with in the there-necked flask of anhydrous ethanol solvent, prescription and process conditions that it is preferable are: filling a prescription is NVA: initator VA-061: chain-transferring agent is 10: 0.5～1: 1～3 (w/w), three mouthfuls connect condenser pipe respectively, nitrogen conduit and thermometer.The logical nitrogen 10min of elder generation's stirring at room is warming up to 60 ℃ of reaction 6h then.Product is splashed in the absolute ether again and also stir rapidly, the extracting waste precipitation is filtered in the adularescent flocculent deposit, and vacuum drying gets the NVA oligomer.
2.NVA macromonomer is synthetic: get the NVA oligomer, KI (KI), p-chloromethyl styrene is dissolved in the dimethyl formamide (DMF), prescription and process conditions that it is preferable are: filling a prescription is NVA oligomer: KI: p-chloromethyl styrene is 10: 1: 1 (w/w), at 30 ℃ of following stirring reaction 72h.Filter out sediment, filtrate splashed in the absolute ether and stir rapidly, filter flocky precipitate.With a small amount of anhydrous alcohol solution sediment, splash into once more in the absolute ether and stir rapidly, refilter flocky precipitate, vacuum drying gets the PNVA macromonomer.
3.PNVA grafted polystyrene microballoon (PNVA-g-PS) is synthetic: get the PNVA macromonomer respectively, styrene and azodiisobutyronitrile (AIBN) are dissolved in the mixed solvent (V of anhydrous ethanol solvent or ethanol and water
Ethanol/ V
Water=14～20/6～0) in, carry out the grafting dispersion copolymerization, prescription and process conditions that it is preferable are: proportioning is PNVA: S: AIBN=2: 2～20: 0.01～0.5, and packing into is connected to water condensing tube respectively, in the 50ml there-necked flask of thermometer and nitrogen conduit.Earlier logical nitrogen bubble 10min is warming up to 60 ℃ of stirring reaction 24h again.After the reaction product was dialysed in deionized water 5 days, to give contained organic solvent in the microballoon dispersion liquid.
By the size that the proportioning of control graft copolymerization thing is regulated product P NVA-g-PS microballoon, control PNVA macromonomer and cinnamic proportioning are 1: 1～10, and then diameter of micro ball is adjustable in 200nm to 1000nm scope.
The functionalization of polymer microsphere
4. the hydrolysis of microballoon: drip concentrated hydrochloric acid in PNVA-g-PS microballoon aqueous dispersions, preferable condition is: concentration of hydrochloric acid drips and reaches 4mol/L, is heated to 80 ℃ again, constantly stirs condensing reflux reaction 24h down.After hydrolysis finished, directly dialysing in deionized water was neutral to dispersion, gets the PVAm-g-PS microballoon.Or it is also passable to be hydrolyzed in basic solvent.
5. reaction kinetic: get PVAm-g-PS microballoon dispersion liquid, add 1-ethyl-3-(3-is to the methylamino propyl group) carbodiimides and (be called for short water-soluble carbodiimide, WSC), add potassium dihydrogen phosphate again, preferable condition is: stir-activating 30min at room temperature, add 2 bromopmethylazocarboxyl, microballoon (doing meter): to 2 bromopmethylazocarboxyl is 5: 0.3～2 (W/W), (0～5 ℃) stirring reaction 24h in the refrigerator cold-storage case again.(15000r/min 10min), is colourless with the clear liquid of ultra-pure water cyclic washing microballoon to the centrifugation, and microballoon is dark reddish purple look with reacted dispersion liquid centrifugation.
Used to 2 bromopmethylazocarboxyl, be that we oneself synthetic a kind of structure is
Compound, its name relatively the difficulty and complicated, so we get the CH in its structure
3-,-N=N-,-COOH and custom is called 2 bromopmethylazocarboxyl.Since in its structure-N=N-and-SO
3The acting in conjunction of H, energy and Pb
2+, Sr
2+, Cu
2+, Mn
2+, Ba
2+Form stable compound Deng metal ion, and good selectivity is arranged, so it is imported on the polymer microsphere as functional group.
The application of functionalized macromolecular microballoon
6, heavy metal ion adsorbed, desorption
Polymer microsphere is containing the trace level metal ions M
N+Waste water in, can the enrichment absorption and the metal ion of microballoon (doing meter) equal mass, i.e. microballoon: M
N+=1: 1 (W/W).When metal ion content is lower than this enrichment absorption limit value, i.e. M
N+/ microballoon is during smaller or equal to 1 (W/W), and then the ionic adsorption rate reaches 100%.
Microballoon is scattered in contains ion M
N+(as Pb
2+, Sr
2+, Cu
2+, Mn
2+, Ba
2+) in the aqueous solution that waits, static 10min, (15000r/min 15min), gets supernatant liquor, adds NaOH solution, boils 10min in boiling water, adds Triton X-100 (OP) solution again, constant volume in centrifugation again.Measure the absorbance of this solution at 400～500nm place.Through calculating microsphere surface adion M
N+(as Pb
2+, Sr
2+, Cu
2+, Mn
2+, Ba
2+) adsorption rate can reach 100%.
With adion M
N+(as Pb
2+, Sr
2+, Cu
2+, Mn
2+, Ba
2+) aqueous dispersions of the microballoon that waits, centrifugation adds HCl solution, measures its absorbance again, and the desorption rate of microsphere surface adion reaches 99% as calculated.Microballoon can desorption, repeated use, uses adsorption rate also can reach more than 95% for the second time.
(3) beneficial effect
The polymer microsphere of hydrophilic shell-hydrophobic core has certain mechanical performance; it is centrifugation and dispersed with stirring repeatedly; and the hydrophilic chain tensible of its surface grafting is in water; both having played the protection polymeric microspheres stabilize disperses to prevent to condense; can fully occupy the space in the water again, have very high specific area.Thereby such microballoon can be made the adsorbent of the aqueous solution.As polymeric sorbent, its chemical composition and functional group are the most basic, also are most important structural factors.Because to 2 bromopmethylazocarboxyl energy and Cu
2+, Sr
2+, Mn
2+, Ba
2+, Pb
2+Synthetic functional polymer microballoon forms stable compound Deng metal ion, and good selectivity arranged, so 2 bromopmethylazocarboxyl is imported on the polymer microsphere as functional group, can be used for separating, detecting these metal ions.The functional polymer microballoon is made metal ion enrichment sorbing material, is used for gathering and measuring trace level metal ion or eliminates the influence of some toxic metals ion pair environment, has reached the purpose of protection water resource.
Effect of the present invention is to handle by the functional polymer microballoon that utilizes preparation to contain effluent containing heavy metal ions, can remove the heavy metal ion in the waste water, and the functionalized macromolecular microballoon can be recycled, and recyclable needed heavy metal.This method is a kind of efficient, simple, feasible process route, reaches wastewater treatment, reduces and pollutes, the purpose of protection environment.
The specific embodiment
Example example 1
With monomer NVA 10g, initator VA-061 0.6g and chain-transferring agent (mercaptoethanol) 2g is in being equipped with the 50ml there-necked flask of 30ml absolute ethyl alcohol, and three mouthfuls are connected to water condensing tube respectively, thermometer and nitrogen conduit, the logical nitrogen 10min of elder generation's stirring at room is warming up to 60 ℃ of reaction 6h then.Product is splashed in the absolute ether again and also stir rapidly, the extracting waste precipitation is filtered in the adularescent flocculent deposit, and vacuum drying gets the NVA oligomer.
Get gained NVA oligomer 10g, KI (KI) 1g, p-chloromethyl styrene 1g dissolves in the flask that 20ml dimethyl formamide (DMF) is housed, at 30 ℃ of following stirring reaction 72h.Filter out sediment, filtrate splashed in the absolute ether and stir rapidly, filter flocky precipitate.With a small amount of anhydrous alcohol solution sediment, splash into once more in the absolute ether and stir rapidly, refilter flocky precipitate, vacuum drying gets the PNVA macromonomer.
Get gained PNVA macromonomer 2g, styrene 2g and AIBN 0.03g are dissolved in the 20ml anhydrous ethanol solvent, and packing into is connected to water condensing tube respectively, in the 50ml there-necked flask of thermometer and nitrogen conduit.Logical nitrogen bubble 10min is warming up to 60 ℃ of stirring reaction 24h again.After the reaction product was dialysed in deionized water 5 days, to give contained solvent in the microballoon.
The hydrolysis of microballoon: in PNVA-g-PS microballoon aqueous dispersions, drip concentrated hydrochloric acid to concentration of hydrochloric acid and reach 4mol/L, be heated to 80 ℃ again, constantly stir condensing reflux reaction 24h down.After hydrolysis finished, directly dialysing in deionized water was neutral to dispersion, gets the PVAm-g-PS microballoon.
Reaction kinetic: get PVAm-g-PS microballoon dispersion liquid 150mg/20ml, add 1-ethyl-3-(3-is to the methylamino propyl group) carbodiimides (WSC) 40mg, add potassium dihydrogen phosphate again to 0.1mol/L, at room temperature stir-activating 30min, add again 2 bromopmethylazocarboxyl 10～60mg, at 0～5 ℃, stirring reaction 24h is with reacted dispersion liquid centrifugation (15000r/min, 10min), with ultra-pure water cyclic washing microballoon, the clear liquid to centrifugation is colourless, and microballoon is dark reddish purple look.Promptly get the functionalized macromolecular microballoon.
Claims (9)
1, a kind of preparation method of functionalized macromolecular microballoon is characterized in that at first synthetic poly N-ethylene yl acetamide (PNVA) macromonomer; Then PNVA and styrene (S) are carried out dispersion copolymerization in alcohol or alcohol/water mixed solvent, one-step method obtains the polymer microsphere PNVA-g-PS that monodispersed surface has grafted chain; With the hydrolysis in acid or basic solvent of PNVA-g-PS microballoon, get the surperficial polymer microsphere PVAm-g-PS that is rich in amido again; Adding is reacted the functionalized macromolecular microballoon that obtains separating, detecting heavy metal ion to 2 bromopmethylazocarboxyl, and this polymer microsphere can be reused;
A. polymer microsphere is synthetic: at first be the synthetic of N-vinyl acetamide (NVA) oligomer, with monomer NVA, initator VA-061 and chain-transferring agent mercaptoethanol react in anhydrous ethanol solvent and generate product, splash in the absolute ether and rapidly and stir, the adularescent flocculent deposit, filtration extracting waste precipitation, vacuum drying; Next is too molecule monomer synthetic of NVA, gets the NVA oligomer, and KI, p-chloromethyl styrene are dissolved among the DMF, stirring reaction, the PNVA macromonomer; Be the synthetic of PNVA grafted polystyrene microballoon (PNVA-g-PS) at last, get the PNVA macromonomer respectively, styrene and AIBN are dissolved in the mixed solvent (V of anhydrous ethanol solvent or ethanol and water
Ethanol/ V
Water=14～20/6～0) in, carries out the grafting dispersion copolymerization, get product;
The functionalization of B, polymer microsphere: the hydrolysis that at first is microballoon, in PNVA-g-PS microballoon aqueous dispersions, drip acid or alkali, constantly stir condensing reflux reaction down, hydrolysis in acid or basic solvent, after hydrolysis finishes, directly dialysing in deionized water is neutral to dispersion, gets the PVAm-g-PS microballoon; Next is a reaction kinetic, get PVAm-g-PS microballoon dispersion liquid, adding 1-ethyl-3-(3-is to the methylamino propyl group) carbodiimides (is called for short water-soluble carbodiimide, WSC), adds potassium dihydrogen phosphate again, at room temperature first stir-activating, add again 2 bromopmethylazocarboxyl, at 0～5 ℃ of stirring reaction, with reacted dispersion liquid centrifugation, be colourless with the clear liquid of ultra-pure water cyclic washing microballoon to the centrifugation, microballoon is dark reddish purple look.
2. preparation method according to claim 1, it is characterized in that the synthetic of N-vinyl acetamide (NVA) oligomer, preferable prescription and process conditions are: NVA: initator VA-061: the chain-transferring agent mercaptoethanol is 10: 0.5～1: 1～3 (W/W), add and be equipped with in the there-necked flask of anhydrous ethanol solvent, three mouthfuls connect condenser pipe, nitrogen conduit and thermometer respectively, the logical nitrogen 10min of elder generation's stirring at room is warming up to 60 ℃ of reaction 6h then.
3. preparation method according to claim 1 is characterized in that the synthetic of NVA macromonomer, and preferable prescription and process conditions are: NVA oligomer: KI: p-chloromethyl styrene is 10: 1: 1 (W/W), at 30 ℃ of following stirring reaction 72h.
4. preparation method according to claim 1 is characterized in that the synthetic of PNVA-g-PS microballoon, and prescription and process conditions that it is preferable are: PNVA: S: AIBN is 2: 2～20: 0.01～0.5 (W/W), adds V is housed
Ethanol/ V
WaterIn the there-necked flask of=14～20/6～0 pure water mixed solvent, three mouthfuls connect condenser pipe, nitrogen conduit and thermometer respectively, and earlier logical nitrogen bubble 10min is warming up to 60 ℃ of stirring reaction 24h then.
5. preparation method according to claim 1 is characterized in that the hydrolysis of microballoon, and preferable condition is: concentration of hydrochloric acid drips and reaches 4mol/L, when being heated to 80 ℃ again, constantly stirs condensing reflux 24h down.
6. preparation method according to claim 1, it is characterized in that the preferable condition of reaction kinetic is: stir-activating 30min at room temperature, add 2 bromopmethylazocarboxyl, microballoon (doing meter): to 2 bromopmethylazocarboxyl is 5: 0.3～2 (W/W), at 0～5 ℃ of stirring reaction 24h again.
7. preparation method according to claim 1 is characterized in that the PNVA-g-PS diameter of micro ball is adjustable, and control PNVA macromonomer: styrene is 1: 1～10 o'clock, and diameter of micro ball is adjustable in 200nm to 1000nm scope.
8. according to the application process of the functionalized macromolecular microballoon of the described method of claim 1 preparation, it is characterized in that can be used for heavy metal ion adsorbed, desorption, microballoon is scattered in contains ion M
N+The aqueous solution in, static, supernatant liquor is got in centrifugation again, adds NaOH solution, boils, and adds OP solution again, constant volume is worked as M
N+/ microballoon (W/W) was smaller or equal to 1 o'clock, and by the absorbance analysis, the ionic adsorption rate reaches 100%; With adion M
N+The aqueous dispersions of microballoon, centrifugation adds HCl solution, the ion desorption rate reaches 99%, and the handled aqueous solution that contains harmful metal ion obtains adsorption rate by the absorbance experiment and reaches 100%, microballoon can desorption, repeated use, uses desorption rate to reach more than 95% for the second time.
9. application process according to claim 8 is characterized in that metal ions M
N+Can be Pb
2+, Sr
2+, Cu
2+, Mn
2+, Ba
2+
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440168B (en) * | 2007-11-20 | 2011-11-09 | 中国科学院过程工程研究所 | Method for surface hydrophilic modification of polystyrene material and product |
| CN102335576A (en) * | 2011-08-25 | 2012-02-01 | 江南大学 | Preparation and application of sulfonitride heavy metal ion chelating polymer microspheres |
| CN101745116B (en) * | 2008-12-17 | 2012-02-01 | 中国科学院大连化学物理研究所 | Preparation method for copper ion chelate adsorbing medium used for curing Wilson's disease |
| CN102391407A (en) * | 2011-09-26 | 2012-03-28 | 南京大学 | Ultrahigh crosslinked resin for separating and recovering medium and high concentration volatile organic compounds (VOCs), and preparation method and application of resin |
| CN102504150A (en) * | 2011-11-23 | 2012-06-20 | 江南大学 | Reversible addition fragmentation chain transfer preparation method of amphiphilic PVAc-b-PNVA segmented copolymers |
| CN103613718A (en) * | 2013-10-23 | 2014-03-05 | 江南大学 | Polyvinyl alcohol macromonomer based method for preparing functional microsphere |
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| US7323110B1 (en) * | 2006-12-11 | 2008-01-29 | The Hong Kong Polytechnic University | Wastewater treatment process using core-shell particles |
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2002
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440168B (en) * | 2007-11-20 | 2011-11-09 | 中国科学院过程工程研究所 | Method for surface hydrophilic modification of polystyrene material and product |
| CN101745116B (en) * | 2008-12-17 | 2012-02-01 | 中国科学院大连化学物理研究所 | Preparation method for copper ion chelate adsorbing medium used for curing Wilson's disease |
| CN102335576A (en) * | 2011-08-25 | 2012-02-01 | 江南大学 | Preparation and application of sulfonitride heavy metal ion chelating polymer microspheres |
| CN102391407A (en) * | 2011-09-26 | 2012-03-28 | 南京大学 | Ultrahigh crosslinked resin for separating and recovering medium and high concentration volatile organic compounds (VOCs), and preparation method and application of resin |
| CN102391407B (en) * | 2011-09-26 | 2013-08-28 | 南京大学 | Ultrahigh crosslinked resin for separating and recovering medium and high concentration volatile organic compounds (VOCs), and preparation method and application of resin |
| CN102504150A (en) * | 2011-11-23 | 2012-06-20 | 江南大学 | Reversible addition fragmentation chain transfer preparation method of amphiphilic PVAc-b-PNVA segmented copolymers |
| CN102504150B (en) * | 2011-11-23 | 2014-04-30 | 江南大学 | Reversible addition fragmentation chain transfer preparation method of amphiphilic PVAc-b-PNVA segmented copolymers |
| CN103613718A (en) * | 2013-10-23 | 2014-03-05 | 江南大学 | Polyvinyl alcohol macromonomer based method for preparing functional microsphere |
| CN103613718B (en) * | 2013-10-23 | 2015-12-30 | 江南大学 | A kind of method preparing functional microsphere based on polyvinyl alcohol macromonomer |
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