CN104744634A - Method for preparation of lead ion imprinted polymer microspheres by use of bi-functional monomer synergistic effect - Google Patents
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- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
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- 239000007864 aqueous solution Substances 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 2
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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 the field of material science, engineering and environmental science, and particularly relates to a method for preparing a lead ion imprinted polymer microsphere by utilizing the synergistic effect of a bifunctional monomer.
Background
Lead is one of the main heavy metal pollutants, and has important environmental, health and ecological toxicological significance. Can cause anemia, nerve function disorder and kidney injury, and has carcinogenesis, teratogenesis and mutagenesis effects. Moreover, the poison of lead to human bodies is cumulative, and water products, crops and the like polluted by lead can be enriched and harmful to human bodies through food chains. Therefore, the separation and enrichment of trace lead in water is an indispensable link for the treatment of lead-containing wastewater and the analysis of lead-containing samples.
The molecular imprinting technology is a new type affinity separation technology, it mainly utilizes that the template molecule is added in the course of polymerization, after the polymerization is completed, the template molecule is eluted, and the cavity complementary with space structure of template molecule and chemical bonding action are remained in the interior of polymer so as to make memorability identification and adsorption of template substance. The polymer formed is calledAs Molecular Imprinted Polymers (MIPs), the molecular imprinted polymers are widely used in the aspects of extraction separation, membrane separation technology, drug analysis, biomimetic sensors and the like at present, and show good prospects. Ion Imprinted Polymers (IIPs) are important branches of MIPs, and the imprinted objects are ions, particularly metal ions. At present, the synthesis of Cu by taking p-vinylbenzoic acid as a functional monomer has been reported2+、Zn2+The IIPs using the plasma metal ions as templates have better adsorption and selection performance for the corresponding metal ions. At present, few reports are reported on the study of imprinted polymers by using lead ions as templates at home and abroad, for example, the imprinted polymers are prepared by using a surface imprinting technology and synthesized by using methacrylic acid as a monomer. However, the preparation of IIPs still faces a great challenge of poor selectivity because the existing monomers for preparing ion imprinted polymers are single and can form complexes with various ions. Moreover, at present, the imprinted polymer is almost prepared by adopting a single functional monomer. Therefore, the synergistic effect of the double or multifunctional monomers is expected to be an effective way to improve the imprinting selectivity.
Disclosure of Invention
The invention aims to provide a method for preparing lead ion imprinted polymer microspheres by utilizing the synergistic effect of bifunctional monomers.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing a lead ion imprinted polymer microsphere by utilizing the synergistic effect of bifunctional monomers is disclosed, wherein the polymer is an imprinted microsphere with uniform particle size, which is prepared by taking lead ions as imprinted ions (template ions), adopting methacrylic acid and tetravinylpyridine as functional monomers and utilizing suspension polymerization.
The method specifically comprises the following steps:
(1) dissolving template lead ions and functional monomers into a mixed solution of hydroxyethyl cellulose (1 wt.%) aqueous solution and toluene according to a molar ratio of 1:3-6, uniformly stirring the mixed solution at a constant speed at room temperature, and then adding a cross-linking agent and an initiator; wherein the functional monomers are methacrylic acid and tetravinylpyridine in a molar ratio of 1:1, the crosslinking agent is ethylene glycol dimethacrylate, and the initiator is azobisisobutyronitrile;
(2) sealing the mixed solution, performing ultrasonic treatment, introducing nitrogen through ice bath, performing polymerization reaction in a heating and stirring mode to generate a white powdery polymer, and reacting the mixed solution at 40-70 ℃ for 10-18 h;
(3) washing the synthesized white powdery polymer with a mixed solution of acetone and water, and washing the polymer to neutrality with deionized water;
(4) and after the extraction is finished, putting the polymer in a vacuum drying oven to dry to constant weight, and finally obtaining the lead ion imprinted polymer.
Step 1) stirring and uniformly mixing 1.5-3.0mmol of lead nitrate, 3-6mmol of methacrylic acid and 3-6mmol of tetravinylpyridine in a mixed solution of 30mL of hydroxyethyl cellulose (1 wt.%) aqueous solution and 15mL of toluene, adding 15-30mmol of ethylene glycol dimethacrylate and 30-50mg of azobisisobutyronitrile, introducing nitrogen through an ultrasonic ice bath, reacting at 40-60 ℃ for 4-8h, and then reacting at 55-70 ℃ for 6-10 h.
Wherein, the prepared mixed solution is degassed by ultrasonic for 8-15min, and is introduced with nitrogen in ice bath for 10-20min to remove oxygen, and then reacts under the protection of nitrogen.
Wherein,
the volume ratio of acetone to water is 1:1, the polymer is repeatedly washed for a plurality of times, the template molecules are removed by using a nitric acid solution of 0.3-0.6mmol/L, then the polymer is washed by using a large amount of deionized water until the pH value is 6-8, and the final product is dried for 18-26h in vacuum.
The particle size of the imprinting microsphere is 300-400 nm.
The invention has the advantages that:
the invention utilizes methacrylic acid and tetraethylene pyridineThe synergistic effect of pyridine is used as a functional monomer, and the suspension polymerization is adopted to synthesize the imprinted polymer of lead ions for Pb2+Showing a high selective adsorption capacity. And in the presence of other metal ions, the imprinted polymer synthesized by bulk polymerization is opposite to Pb2+Has higher recognition selectivity, binding capacity and adsorption stability. On the other hand, with the aid of Pb2+And the imprinting example is expected to develop a general heavy metal identification, enrichment, removal and detection platform.
The method for preparing the lead ion imprinted polymer by suspension polymerization by utilizing the synergistic effect of the bifunctional monomers has the advantages of simple operation, good reproducibility, uniform particle size, strong selective adsorption, high adsorption rate and good repeatability, and the prepared lead ion imprinted polymer has more excellent imprinting performance compared with the imprinted polymer which usually adopts a single functional monomer, and can enrich and purify trace lead ions in a water sample by combining a solid phase extraction technology.
Drawings
Fig. 1A is a schematic diagram of an experimental operation process for preparing a lead ion imprinted polymer according to an embodiment of the present invention.
Fig. 1B is a schematic diagram of the imprinting principle provided in the embodiment of the present invention.
Fig. 2A is a scanning electron microscope image provided by the embodiment of the invention.
Fig. 2B is an ir spectrum provided by an embodiment of the present invention.
FIG. 3 is a bar graph of the binding capacity of the lead ion imprinted polymer provided in the example of the present invention to lead ions in the presence of other metal ions (where S-IIPs are prepared by suspension polymerization, and B-IIPs are prepared by bulk polymerization).
Detailed Description
Example 1
Dissolving template ion lead ions and functional monomers into a mixed solution of 30mL of hydroxyethyl cellulose (1 wt.%) aqueous solution and 15mL of toluene according to the molar ratio of 1:4, namely 2.5mmol and 10mmol, uniformly stirring the mixed solution at room temperature for 3 hours, and then adding a cross-linking agent and an initiator. Wherein the functional monomers are methacrylic acid (5 mmol) and tetravinylpyridine (5 mmol), the cross-linking agent is ethylene glycol dimethacrylate (20 mmol), and the initiator is azobisisobutyronitrile (40 mg). And sealing the mixed solution, performing ultrasonic treatment, introducing nitrogen through an ice bath, performing polymerization reaction in a heating and stirring mode to generate a white powdery polymer, and reacting the mixed solution in a water bath at 50 ℃ for 6 hours and then at 60 ℃ for 8 hours. Washing the synthesized white powdery polymer with a mixed solution of acetone and water in a volume ratio of 1:1 to remove the surfactant and the crosslinking agent, and then washing with a 0.5mol/L nitric acid solution for multiple times to remove the template Pb2+Deionized water and finally the polymer is washed to neutrality with deionized water. And after the extraction is finished, putting the polymer in a vacuum drying oven to dry to constant weight, and finally obtaining the lead ion imprinted polymer. The operation process is shown in fig. 1A. The imprinting principle, as shown in fig. 1B, under the synergistic effect of two functional monomers, namely, tetravinyl pyridine as the proton acceptor of methacrylic acid, promotes the better dissociation of the carboxyl group of methacrylic acid through deprotonation, thereby facilitating the carboxyl anion and Pb2+And (4) cation combination to prepare the lead ion imprinted polymer. IIPs obtained by the suspension polymerization method are marked as S-IIPs.
Preparation of non-imprinted polymers (NIPs): following the above protocol, except that no template ion Pb was added2+Except for ions, other steps are the same as above.
Preparation of bulk polymerized ion imprinted polymers (B-IIPs): the same template ions, functional monomers, cross-linking agents and initiators and the amounts thereof are used for suspension polymerization, except that the pore-foaming agent is a mixture of 1:1 of dimethylformamide and acetone. Similar to suspension polymerization, the mixture was first reacted for 6h in a water bath at 50 ℃ and then for 8h at 60 ℃. The obtained product is ground and then treated by the same treatment modes of cleaning, drying and the like. The obtained lead ion imprinted polymer is marked as B-IIPs.
Scanning the prepared S-IIPs by an electron microscope, and as shown in FIG. 2A, the microsphere particles with uniform particle size of 300-400nm and regular morphology are prepared by suspension polymerization in the above embodiment. As shown in the IR spectrum of FIG. 2B, it was revealed that Pb was successfully produced by the interaction between ions2+S-IIPs of (1).
Example 2
According to the procedure for preparing S-IIPs in example 1, only a single functional monomer, namely 10mmol of methacrylic acid or 10mmol of tetravinylpyridine, is used to prepare the lead ion imprinted polymer, and thus the suspension polymerization lead ion imprinted polymer using methacrylic acid as the functional monomer or the suspension polymerization lead ion imprinted polymer using tetravinylpyridine as the functional monomer is obtained.
20mg of the bifunctional monomer suspension polymerization IIPs prepared in example 1 above, the corresponding NIPs and bifunctional monomer bulk polymerization IIPs, the suspension polymerization IIPs using methacrylic acid as a functional monomer, and the suspension polymerization IIPs using tetraethylene pyridine as a functional monomer (comparative responses: yes except for the polymer of the present invention and the two monofunctional monomers), respectively, were dispersed in 5mL of Pb at different concentrations (0, 10, 20, 40, 60, 80, 100, 120 ppm)2+To the solution, the mixture was placed in a 10mL centrifuge tube and shaken continuously at room temperature for 3 h. The mixture was then centrifuged at 7000 r/min. And taking the supernatant, and measuring the concentration of the residual lead ions by using an atomic absorption instrument. According to the formula Q = (C)0C) m/V to determine the adsorption capacity Q, and thus to obtain a static adsorption curve. The dynamic adsorption process is similar to the static adsorption process except that 20mg of different polymers and 60ppm of lead ion solution are taken simultaneously, the lead ion concentration is measured at different times (0, 20, 40, 60, 80, 100, 120 min), and the adsorption is calculatedAnd (4) the adsorption capacity Q, so that a dynamic adsorption curve is obtained. As a result, the S-IIPs prepared by the suspension polymerization of the bifunctional monomers have the highest adsorption capacity and mass transfer rate, the static adsorption of the S-IIPs conforms to a Langmuir model, and the dynamic adsorption of the S-IIPs conforms to an intra-particle diffusion kinetic model.
Example 3
20mg of bifunctional monomer suspension polymerization imprinted polymer (S-IIPs) and bifunctional monomer bulk polymerization imprinted polymer (B-IIPs) were respectively dispersed in 5mL of 60ppm lead ion solution, wherein the pH of the lead ion solution was 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 6.5 and 7.0, respectively. The mixture was then centrifuged at 7000 r/min. And taking the supernatant, and measuring the concentration of the residual lead ions by using an atomic absorption instrument. According to the formula Q = (C)0C) m/V, obtaining the adsorption capacity Q, and obtaining the influence curve of pH on the adsorption performance of the imprinted polymer. As a result, it was found that S-IIPs and B-IIPs had the same tendency, but the S-IIPs had a higher adsorption amount than the B-IIPs; in the acidic range, the adsorption capacity gradually increases with increasing pH, and the adsorption capacity reaches a maximum when the pH reaches neutral. Finally, a solution with a pH value of 7 was selected for the relevant experiments.
Example 4
20mg of bifunctional monomer suspension polymerization imprinted polymer (S-IIPs) and bifunctional monomer bulk polymerization imprinted polymer (B-IIPs) are respectively added with 20ppm of Pb2+And 200ppm of Fe3+，Cd2+，Mn2+，Cu2+，Zn2+，Ca2+Or K+And (3) measuring the anti-interference capability of the lead ion imprinted polymer on other metal ions by using the mixed solution of the ions, and placing the mixed solution in a 10mL centrifuge tube to oscillate for 3h at room temperature. The mixture was then centrifuged at 7000 r/min. And taking the supernatant, and measuring the concentration of the residual lead ions by using an atomic absorption instrument. According to the formula Q = (C)0C) m/V to obtain the adsorption capacity Q, thereby obtaining the resistance of the lead ion imprinted polymerInterference capability. As shown in FIG. 3, IIPs obtained by suspension polymerization have excellent anti-interference capability.
Claims (6)
1. A method for preparing a lead ion imprinted polymer microsphere by utilizing the synergistic effect of bifunctional monomers is characterized in that a polymer is an imprinted microsphere with uniform particle size, which is prepared by taking lead ions as imprinted ions (template ions), adopting methacrylic acid and tetravinylpyridine as functional monomers and utilizing suspension polymerization.
2. The method for preparing the lead ion imprinted polymer microsphere by utilizing the synergistic effect of the bifunctional monomers as claimed in claim 1, wherein:
in particular to
(1) Dissolving template lead ions and functional monomers into a mixed solution of hydroxyethyl cellulose (1 wt.%) aqueous solution and toluene according to a molar ratio of 1:3-6, uniformly stirring the mixed solution at a constant speed at room temperature, and then adding a cross-linking agent and an initiator; wherein the functional monomers are methacrylic acid and tetravinylpyridine in a molar ratio of 1:1, the crosslinking agent is ethylene glycol dimethacrylate, and the initiator is azobisisobutyronitrile;
(2) sealing the mixed solution, performing ultrasonic treatment, introducing nitrogen through ice bath, performing polymerization reaction in a heating and stirring mode to generate a white powdery polymer, and reacting the mixed solution at 40-70 ℃ for 10-18 h;
(3) washing the synthesized white powdery polymer with a mixed solution of acetone and water, and washing the polymer to neutrality with deionized water;
(4) and after the extraction is finished, putting the polymer in a vacuum drying oven to dry to constant weight, and finally obtaining the lead ion imprinted polymer.
3. The method for preparing the lead ion imprinted polymer microspheres by utilizing the synergistic effect of the bifunctional monomers as claimed in claim 2, is characterized in that 1.5-3.0mmol of lead nitrate, 3-6mmol of methacrylic acid and 3-6mmol of tetravinyl pyridine are uniformly stirred in a mixed solution of 30mL of hydroxyethyl cellulose (1 wt.%) aqueous solution and 15mL of toluene, 15-30mmol of ethylene glycol dimethacrylate and 30-50mg of azobisisobutyronitrile are added, and after the mixture is treated by introducing nitrogen through an ultrasonic ice bath, the mixture is reacted at 40-60 ℃ for 4-8h, and then the mixture is reacted at 55-70 ℃ for 6-10 h.
4. The method for preparing the lead ion imprinted polymer microsphere by utilizing the synergistic effect of the bifunctional monomers as claimed in claim 3, wherein the prepared mixed solution is subjected to ultrasonic degassing for 8-15min, nitrogen is introduced into an ice bath for 10-20min to remove oxygen, and then the reaction is carried out under the protection of nitrogen.
5. The method for preparing the lead ion imprinted polymer microsphere by utilizing the synergistic effect of the bifunctional monomers as claimed in claim 2, wherein the volume ratio of acetone to water is 1:1, the polymer is repeatedly washed for a plurality of times, a nitric acid solution of 0.3-0.6mmol/L is used for removing template molecules, a large amount of deionized water is used for washing until the pH value is 6-8, and the final product is dried for 18-26h in vacuum.
6. The method for preparing the lead ion imprinted polymer microsphere by utilizing the synergistic effect of the bifunctional monomers as claimed in claim 2, wherein the particle size of the imprinted microsphere is 300-400 nm.
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| 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 |
| CN115321695A (en) * | 2022-08-23 | 2022-11-11 | 浙江碧源环保科技有限公司 | Coagulation-aiding decoloration softening agent and preparation method and application thereof |
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| 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 |
| CN115321695A (en) * | 2022-08-23 | 2022-11-11 | 浙江碧源环保科技有限公司 | Coagulation-aiding decoloration softening agent and preparation method and application thereof |
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