CN104744634A - Method for preparation of lead ion imprinted polymer microspheres by use of bi-functional monomer synergistic effect - Google Patents
Method for preparation of lead ion imprinted polymer microspheres by use of bi-functional monomer synergistic effect Download PDFInfo
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- CN104744634A CN104744634A CN201310744172.5A CN201310744172A CN104744634A CN 104744634 A CN104744634 A CN 104744634A CN 201310744172 A CN201310744172 A CN 201310744172A CN 104744634 A CN104744634 A CN 104744634A
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Abstract
The invention belongs to the field of material science and engineering and environmental science, and particularly relates to a method for preparation of a lead ion imprinted polymer microspheres by use of bi-functional monomer synergistic effect. A lead ion is used as an imprinting ion (a template ion) of a polymer, methyl acrylic acid and 4-vinyl pyridine are used as functional monomers, and imprinted microspheres with uniform particle size can be prepared by suspension polymerization. The prepared imprinted microspheres have high lead ion adsorption capacity, good dynamic characteristics, high recognition selectivity and high repetition utilization. The microspheres achieve high selective enrichment of lead ions in natural water samples by combination of solid phase extraction. The method breaks through the traditional use of single functional monomers, and a new method for the preparation of an imprinted polymer by use of bi-functional monomers or multi-functional monomers is provided, and the method has the advantages of simple and rapid operation, low cost and good reproducibility, and has wide application prospect.
Description
Technical field
The invention belongs to Materials Science and Engineering and environmental science, specifically a kind of method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon.
Background technology
Lead is one of main heavy metal contaminants, has important environment, health and ecotoxicological meaning.Human body anemia, nervous function can be caused to lack of proper care and injury of the kidney, have carcinogenic, teratogenesis, mutagenic effect to human body.And plumbous is cumulative to the murder by poisoning of human body, is produced harm by the fishery products of Lead contamination and crop etc. by food chain enrichment to human body.Therefore, to be separated and trace lead in enrichment water is process lead waste water and the indispensable link of the leaded sample of analysis.
Molecular imprinting is a kind of novel Human serum protein technology, it mainly utilizes and adds template molecule in the course of the polymerization process, by template molecule elution after polymerization terminates, stay and the hole of template molecule space structure complementation and chemical bonding effect at polymeric inner, thus memory identification and absorption are carried out to template material.The polymkeric substance formed is referred to as molecularly imprinted polymer (Molecularly imprintedpolymers, MIPs), is widely used in the aspects such as extracting and separating, membrane separation technique, pharmaceutical analysis, Biomimic sensor at present, shows good prospect.Ion imprinted polymer (Ion imprintedpolymers, IIPs) is the important branch of MIPs, and trace object is ion, particularly metal ion.At present, have been reported employing and as function monomer synthesis, Cu is obtained to vinyl benzoic acid
2+, Zn
2+be the IIPs of template Deng metal ion, to corresponding metal ion, there is absorption and selectivity preferably.At present, the report utilizing lead ion to carry out imprinted polymer research for template is both at home and abroad also few, such as, utilizes surface imprinted technology to prepare, and having with methacrylic acid is monomer synthesize.But the monomer preparing ion imprinted polymer because existing is single, and title complex can be formed with different kinds of ions, so IIPs preparation is still faced with the huge challenge of poor selectivity.And, be nearly all adopt single function monomer to carry out imprinted polymer preparation at present.Therefore, utilize synergy that is two or multifunctional monomer to improve trace selectivity to be expected to become an effective way.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon.
For achieving the above object, the present invention adopts technical scheme to be:
A kind of method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon, polymkeric substance is using lead ion as trace ion (template ion), adopt methacrylic acid and tetravinyl pyridine as function monomer, the trace microballoon of the uniform particle diameter utilizing suspension polymerization to obtain.
Be specially:
(1) template lead ion and function monomer are dissolved in the mixing solutions of Natvosol (1wt.%) aqueous solution and toluene according to the amount of mol ratio 1:3-6, at the uniform velocity stir under mixing solutions room temperature, then add linking agent and initiator; Wherein methacrylic acid and the tetravinyl pyridine of function monomer to be mol ratio be 1:1, linking agent is ethylene glycol dimethacrylate, and initiator is Diisopropyl azodicarboxylate;
(2) after being sealed by mixed solution, ultrasonic and lead to nitrogen treatment through ice bath, adopt heated and stirred mode polyreaction to generate white powder shaped polymer, mixed solution reacts 10-18h at 40-70 DEG C;
(3) wash with the mixing solutions of acetone and water the white powder shaped polymer synthesized, with deionized water wash polymkeric substance to neutral;
(4), after extraction terminates, polymkeric substance is placed in vacuum drying oven and is dried to constant weight, finally obtain lead ion imprinted polymer.
Described step 1) is by 1.5-3.0mmol lead nitrate and 3-6mmol methacrylic acid, 3-6mmol tetravinyl pyridine stirring and evenly mixing in Natvosol (1wt.%) aqueous solution of 30mL and the mixing solutions of 15mL toluene, add ethylene glycol dimethacrylate and the 30-50mg Diisopropyl azodicarboxylate of 15-30mmol, after ultrasonic ice bath leads to nitrogen treatment, react 4-8h at 40 DEG C-60 DEG C, then at 55-70 DEG C, react 6-10h.
Wherein, by the mixing solutions ultrasonic degas 8-15min made, ice bath reacts under nitrogen protection after leading to nitrogen 10-20min removing oxygen.
Wherein,
The volume ratio of acetone and water is 1:1, by polymkeric substance repetitive scrubbing repeatedly, removes template molecule, then be washed till pH6-8 with a large amount of deionized water, by final product vacuum-drying 18-26h with the salpeter solution of 0.3-0.6mmol/L.
Described trace microspherulite diameter is 300-400nm.
The advantage that the present invention has:
The present invention utilizes the synergistic effect of methacrylic acid and tetravinyl pyridine as function monomer, adopts the imprinted polymer of suspension polymerization synthesis lead ion to Pb simultaneously
2+demonstrate very high selective adsorption capacity.And deposit in case at other metal ions, relative to mass polymerization synthesis imprinted polymer to Pb
2+there are higher identification selection, binding capacity and absorption stability.On the other hand, by means of Pb
2+trace example, is expected to develop the platform of universal heavy metal identification, enrichment, removal and detection.
The present invention utilizes the synergy suspension polymerization of bi-functional monomer to prepare the method for lead ion imprinted polymer, simple to operate, favorable reproducibility, the uniform particle diameter prepared, Selective adsorption are strong, adsorption rate is fast, reproducible, and the lead ion imprinted polymer simultaneously prepared has more excellent trace performance compared to usually adopting the imprinted polymer of simple function monomer, combine solid phase extraction techniques, enrichment and purification can be carried out to the trace lead ion in water sample.
Accompanying drawing explanation
The experimental implementation process schematic that Figure 1A is prepared for the lead ion imprinted polymer that the embodiment of the present invention provides.
The trace principle schematic that Figure 1B provides for the embodiment of the present invention.
The scanning electron microscope (SEM) photograph that Fig. 2 A provides for the embodiment of the present invention.
The infrared spectrum that Fig. 2 B provides for the embodiment of the present invention.
The lead ion imprinted polymer that Fig. 3 provides for the embodiment of the present invention under other metal ions exist to the binding capacity histogram (wherein, S-IIPs prepares for adopting suspension polymerization, and B-IIPs prepares for adopting mass polymerization) of lead ion.
Embodiment
Embodiment 1
Be the amount of 1:4 by template ion lead ion and function monomer according to mol ratio, i.e. 2.5mmol and 10mmol, be dissolved in Natvosol (1wt.%) aqueous solution of 30mL and the mixing solutions of 15mL toluene, at the uniform velocity stir 3h under mixing solutions room temperature, then add linking agent and initiator.Wherein function monomer is methacrylic acid (5mmol) and tetravinyl pyridine (5mmol), and linking agent is ethylene glycol dimethacrylate (20mmol), and initiator is Diisopropyl azodicarboxylate (40mg).After being sealed by mixed solution, ultrasonic and lead to nitrogen treatment through ice bath, adopt heated and stirred mode polyreaction to generate white powder shaped polymer, mixed solution first reacts 6h under 50 DEG C of water-baths, then at 60 DEG C, reacts 8h.With the white powder shaped polymer that the acetone of volume ratio 1:1 and the mixing solutions washing of water are synthesized, removing tensio-active agent and linking agent, then repeatedly remove template Pb with the salpeter solution washing of 0.5mol/L
2+ion, finally uses deionized water wash polymkeric substance to neutral.After extraction terminates, polymkeric substance is placed in vacuum drying oven and is dried to constant weight, finally obtain lead ion imprinted polymer.Operating process is see Figure 1A.Trace principle is see Figure 1B, and under the synergy of two kinds of function monomers, namely tetravinyl pyridine is as the proton acceptor of methacrylic acid, promotes that the carboxyl of methacrylic acid is better dissociated by deprotonation, thus is beneficial to its carboxyl anion and Pb
2+positively charged ion combines, and prepares lead ion imprinted polymer.This suspension polymerization gained IIPs, is labeled as S-IIPs.
Prepared by non-imprinted polymer (NIPs): according to aforesaid operations code, except not adding template ion Pb
2+outside ion, other steps are the same.
The preparation of the ion imprinted polymer (B-IIPs) of mass polymerization: adopt identical template ion, function monomer, linking agent and initiator and consumption thereof with suspension polymerization, just pore-creating agent is the dimethyl formamide of volume ratio 1:1 and the mixing solutions of acetone.Similar with suspension polymerization, mixed solution first reacts 6h under 50 DEG C of water-baths, then at 60 DEG C, reacts 8h.Products therefrom is ground, then adopts the processing modes such as identical cleaning-drying.Gained lead ion imprinted polymer is labeled as B-IIPs.
The above-mentioned gained S-IIPs for preparing carries out electron-microscope scanning, and shown in Fig. 2 A, above-described embodiment adopts suspension polymerization to prepare the microsphere particle of 300-400nm uniform particle diameter, pattern rule.Shown in Fig. 2 B infrared spectrum, showing is interacted by interionic has successfully prepared Pb
2+s-IIPs.
Embodiment 2
According to the working specification preparing S-IIPs in embodiment 1, simple function monomer is just used to prepare lead ion imprinted polymer, wherein, function monomer is respectively the methacrylic acid of 10mmol or the tetravinyl pyridine of 10mmol, and namely obtaining with methacrylic acid is the suspension polymerization lead ion imprinted polymer of function monomer or the suspension polymerization lead ion imprinted polymer that is function monomer with tetravinyl pyridine.
To get bi-functional monomer suspension polymerization IIPs prepared by 20mg above-described embodiment 1 and corresponding NIPs and bi-functional monomer mass polymerization IIPs, methacrylic acid be respectively the suspension polymerization IIPs of function monomer and tetravinyl pyridine be the suspension polymerization IIPs(of function monomer contrast also have other except polymkeric substance of the present invention and above-mentioned two single functions? answer: yes), be scattered in the different concns (0 of 5mL, 10,20,40,60,80,100,120ppm) Pb
2+in solution, mixed solution is placed in continuous oscillation 3h under the centrifuge tube room temperature of 10mL.Then by mixed solution centrifugal treating under the rotating speed of 7000r/min.Get the concentration that supernatant liquor atomic absorption instrument surveys residual lead ion.According to formula Q=(C
0-C) m/V tries to achieve loading capacity Q, thus draws Static Adsorption curve.Dynamic adsorption process, with Static Adsorption similar process, just gets the different polymkeric substance of 20mg and the lead ion solution of 60ppm, at different time (0,20 all simultaneously, 40,60,80,100,120min) record plumbum ion concentration, calculate loading capacity Q, thus draw dynamic adsorption curve.Found that, the S-IIPs adopting bi-functional monomer suspension polymerization to obtain has the highest loading capacity and rate of mass transfer, and its Static Adsorption meets Langmuir model, and dynamic adsorption meets particle internal diffusion kinetic model.
Embodiment 3
Getting 20mg bi-functional monomer suspension polymerization imprinted polymer (S-IIPs) and bi-functional monomer mass polymerization imprinted polymer (B-IIPs) respectively, to be scattered in 5mL concentration be in the lead ion solution of 60ppm, wherein the pH of lead ion solution is respectively 2.0,2.5,3.0,4.0,5.0,6.0,6.5 and 7.0.Then by mixed solution centrifugal treating under the rotating speed of 7000r/min.Get the concentration that supernatant liquor atomic absorption instrument surveys residual lead ion.According to formula Q=(C
0-C) m/V tries to achieve loading capacity Q, thus draws the influence curve of pH to imprinted polymer absorption property.Found that, S-IIPs and B-IIPs has identical trend, but S-IIPs adsorptive capacity is higher than B-IIPs; In acid range, raise with pH, loading capacity increases gradually, and when pH reaches neutrality, adsorptive capacity reaches maximum.Final selection pH value be 7 solution carry out related experiment.
Embodiment 4
Get 20mg bi-functional monomer suspension polymerization imprinted polymer (S-IIPs) and bi-functional monomer mass polymerization imprinted polymer (B-IIPs), add the Pb containing 20ppm respectively
2+with the Fe of 200ppm
3+, Cd
2+, Mn
2+, Cu
2+, Zn
2+, Ca
2+or K
+the mixing solutions of ion, measures the immunity from interference of lead ion imprinted polymer to other metal ions with this, and vibrate under mixed solution being placed in the centrifuge tube room temperature of 10mL 3h.Then by mixed solution centrifugal treating under the rotating speed of 7000r/min.Get the concentration that supernatant liquor atomic absorption instrument surveys residual lead ion.According to formula Q=(C
0-C) m/V tries to achieve loading capacity Q, thus draws the immunity from interference of lead ion imprinted polymer.As shown in Figure 3, suspension polymerization gained IIPs is adopted to have excellent immunity from interference.
Claims (6)
1. the method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon, it is characterized in that: polymkeric substance is using lead ion as trace ion (template ion), adopt methacrylic acid and tetravinyl pyridine as function monomer, the trace microballoon of the uniform particle diameter utilizing suspension polymerization to obtain.
2., by the method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon according to claim 1, it is characterized in that:
Be specially
(1) template lead ion and function monomer are dissolved in the mixing solutions of Natvosol (1wt.%) aqueous solution and toluene according to the amount of mol ratio 1:3-6, at the uniform velocity stir under mixing solutions room temperature, then add linking agent and initiator; Wherein methacrylic acid and the tetravinyl pyridine of function monomer to be mol ratio be 1:1, linking agent is ethylene glycol dimethacrylate, and initiator is Diisopropyl azodicarboxylate;
(2) after being sealed by mixed solution, ultrasonic and lead to nitrogen treatment through ice bath, adopt heated and stirred mode polyreaction to generate white powder shaped polymer, mixed solution reacts 10-18h at 40-70 DEG C;
(3) wash with the mixing solutions of acetone and water the white powder shaped polymer synthesized, with deionized water wash polymkeric substance to neutral;
(4), after extraction terminates, polymkeric substance is placed in vacuum drying oven and is dried to constant weight, finally obtain lead ion imprinted polymer.
3. by the method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon according to claim 2, it is characterized in that: by 1.5-3.0mmol lead nitrate and 3-6mmol methacrylic acid, 3-6mmol tetravinyl pyridine stirring and evenly mixing in Natvosol (1wt.%) aqueous solution of 30mL and the mixing solutions of 15mL toluene, add ethylene glycol dimethacrylate and the 30-50mg Diisopropyl azodicarboxylate of 15-30mmol, after ultrasonic ice bath leads to nitrogen treatment, react 4-8h at 40 DEG C-60 DEG C, then at 55-70 DEG C, react 6-10h.
4. by the method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon according to claim 3; it is characterized in that: by the mixing solutions ultrasonic degas 8-15min made; ice bath reacts under nitrogen protection after leading to nitrogen 10-20min removing oxygen.
5. by the method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon according to claim 2, it is characterized in that: the volume ratio of acetone and water is 1:1, by polymkeric substance repetitive scrubbing repeatedly, template molecule is removed with the salpeter solution of 0.3-0.6mmol/L, pH6-8 is washed till again, by final product vacuum-drying 18-26h with a large amount of deionized water.
6., by the method utilizing bi-functional monomer synergy to prepare lead ion imprinted polymer microballoon according to claim 2, it is characterized in that: described trace microspherulite diameter is 300-400nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945580A (en) * | 2015-07-16 | 2015-09-30 | 江苏大学 | Manufacturing method and application of Cr(VI) anion imprinted material |
| CN106977639A (en) * | 2017-03-14 | 2017-07-25 | 嘉兴学院 | It is a kind of that there is porous microsphere shape polymeric adsorbent of selective absorption and preparation method thereof to lead ion |
| CN108503749A (en) * | 2018-03-28 | 2018-09-07 | 天津城建大学 | A kind of preparation method of uranyl ion imprinted polymer material |
-
2013
- 2013-12-30 CN CN201310744172.5A patent/CN104744634A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 蔡晓强等: "Pb2+印迹聚合物的制备及其应用", 《第七届全国仪器分析及样品预处理学术研讨会论文集》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945580A (en) * | 2015-07-16 | 2015-09-30 | 江苏大学 | Manufacturing method and application of Cr(VI) anion imprinted material |
| CN106977639A (en) * | 2017-03-14 | 2017-07-25 | 嘉兴学院 | It is a kind of that there is porous microsphere shape polymeric adsorbent of selective absorption and preparation method thereof to lead ion |
| CN108503749A (en) * | 2018-03-28 | 2018-09-07 | 天津城建大学 | A kind of preparation method of uranyl ion imprinted polymer material |
| CN108503749B (en) * | 2018-03-28 | 2020-09-08 | 天津城建大学 | Preparation method of uranyl ion imprinted polymer material |
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Application publication date: 20150701 |