CN105884985A - Magnetic cadmium ion-imprinted polymer and preparation method thereof - Google Patents

Magnetic cadmium ion-imprinted polymer and preparation method thereof Download PDF

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CN105884985A
CN105884985A CN201610314950.0A CN201610314950A CN105884985A CN 105884985 A CN105884985 A CN 105884985A CN 201610314950 A CN201610314950 A CN 201610314950A CN 105884985 A CN105884985 A CN 105884985A
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magnetic
sio
imprinted polymer
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cadmium ion
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徐小艳
王梅
吴青
田兴国
徐莉
张燚
黄樱
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South China Agricultural University
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Abstract

The invention discloses a magnetic cadmium ion-imprinted polymer and a preparation method thereof. The magnetic cadmium ion-imprinted polymer is prepared by taking vinyl-modified Fe3O4@SiO2 as a magnetic carrier, Cd<2+> as a template, a combination of any two of methacrylic acid, acrylamide and vinyl pyridine as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, and azodiisobutyronitrile (AIBN) as an initiator. The magnetic cadmium ion-imprinted polymer is capable of carrying out enrichment and separation on trace cadmium in an agricultural product sample, and is high in detection sensitivity and accuracy; furthermore, the magnetic cadmium ion-imprinted polymer has the advantages of being simple in preparation method and low in cost and operation requirement, having higher selectivity for template ions, and the like; the product also can be rapidly separated in presence of an external magnetic field, so that the tedious operation such as centrifugation and filtration are avoided, and enrichment and separation efficiencies are improved; the magnetic cadmium ion-imprinted polymer has a wider and good application prospect in the field of detection of food and agricultural product samples.

Description

A kind of magnetic cadmium ion imprinted polymer and preparation method thereof
Technical field
The invention belongs to technical field of food safety.More particularly, to being a kind of magnetic cadmium ion imprinted polymer and preparation method thereof.
Background technology
Cadmium is the metallic element that a kind of toxicity is the strongest, and cadmium pollution has extremely strong accumulative and irreversibility, can enter internal by smoking and diet, threaten the biggest to health.Therefore the detection of cadmium pollution processes and has great importance.
But, in general agricultural samples, the content of cadmium is the lowest and sample matrices complicated, and directly detection Determination of Trace Amount Cadmium element there be difficulties involved when, in order to avoid the interference of matrix effect, improve the sensitivity of analysis method, cadmium must be separated, purify and be enriched with before detection is analyzed.
At present, the most conventional metal ion analysis pre-treating method has SPE, liquid-liquid extraction, coprecipitation and ion-exchange etc..These methods are respectively arranged with pluses and minuses, and because having, the rate of recovery is high, save solvent in SPE, easily and the advantage such as Modern Analytical Instrument combination and be widely used in separating and enriching trace element.Traditional solid phase extraction adsorbents is mainly chelating resin, bonded silica gel, activated carbon etc., because needing to fill post, cross the operation of post and make that process is loaded down with trivial details, waste time and energy, have that adsorption capacity is little, material requested spends high, to deficiencies such as the adsorptive selectivity differences of ion simultaneously.Current exploitation has high selectivity, the solid extracting agent of high specific becomes the focus of research.
In recent years, domestic ionic imprinting technique has had a lot of reports, but, mainly Ni, Pb plasma that report is relatively more, the report of magnetic ion trace is little, in particular for the magnetic ion imprinted polymer of cadmium ion.
Summary of the invention
The technical problem to be solved in the present invention is defect and the deficiency overcoming above-mentioned prior art, with the Fe of modified by vinyl3O4@SiO2For magnetic carrier, Cd2+Being function monomer for template, methacrylic acid (MAA) and acrylamide (AM), ethylene glycol dimethacrylate (EGDMA) is crosslinking, and azodiisobutyronitrile (AIBN) is initiator, prepares a kind of Cd2+Imprinted polymer microballoon；Determination of Trace Amount Cadmium in agricultural samples can be enriched with and separates, reduce the matrix impact on testing result, improve the accuracy of detection.And, ion imprinted polymer has the advantages such as preparation is simple, low cost, the selectivity higher to template ion tool, magnetic nano-particle is combined with engram technology the magnetic ion imprinted polymer of preparation, not only there is the advantage that ion imprinted polymer is the highest, quick separating can also be realized under additional magnetic fields, improve enrichment and the efficiency separated.
Another object of the present invention is to provide a kind of magnetic cadmium ion imprinted polymer.
Another object of the present invention is to provide the preparation method of described magnetic cadmium ion imprinted polymer.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of magnetic cadmium ion imprinted polymer, is the Fe with modified by vinyl3O4@SiO2For magnetic carrier, Cd2+For template, in methacrylic acid, acrylamide and vinylpyridine any two kinds be combined as function monomer, ethylene glycol dimethacrylate (EGDMA) is crosslinking agent, and azodiisobutyronitrile (AIBN) is that initiator prepares.
Particularly preferably, the preparation method of described magnetic cadmium ion imprinted polymer comprises the steps:
S1. Fe is prepared by coprecipitation3O4Magnetic carrier；
S2. polyethylene glycol PEG200 is passed through as dispersant to improve Fe3O4The dispersion stabilization of particle, utilizes the hydrolysis of tetraethyl orthosilicate at Fe3O4Particle surface superscribes silica (SiO2) layer, define Fe3O4@SiO2Particulate；
S3. vinyltrimethoxy silane and cetyl trimethylammonium bromide are passed through to Fe3O4@SiO2Particulate is modified, and has obtained Fe3O4@SiO2-C=C；
S4. with Cd2+For template, in methacrylic acid, acrylamide and vinylpyridine any two kinds be combined as function monomer, after carrying out prepolymerization in acetonitrile/water mixed solution, add Fe3O4@SiO2-C=C(i.e. the Fe of magnetic carrier modified by vinyl3O4@SiO2), crosslinking agent ethylene glycol dimethacrylate (EGDMA) and initiator azodiisobutyronitrile (AIBN), refluxing at 80～90 DEG C 8～12h(is preferably at 85 DEG C backflow 10h), prepare magnetic cadmium ion imprinted polymer (i.e. Cd2+Imprinted polymer microballoon).
It addition, as a kind of concrete the most preferably can embodiment, the preparation method of described magnetic cadmium ion imprinted polymer comprises the steps:
S1. Fe is prepared3O4Particle:
S11. under logical condition of nitrogen gas, by Fe3Cl3·6H2O and FeCl2·4H2O is dissolved in ultra-pure water, adds thermal agitation to 70～90 DEG C under the conditions of temperature constant magnetic stirring；Add ammoniacal liquor and PEG200, add thermal agitation 2～4h；
S12. the reaction of step S1 terminates, and is cooled to room temperature, separates with magnet after removing supernatant, and ethanol and ultra-pure water respectively wash 2～4 times, are dried in 50～70 DEG C, grind and obtain Fe3O4Powder；
S2. Fe is prepared3O4@SiO2:
Weigh Fe3O4Powder is distributed in the mixed solution of distilled water, ethanol and ammoniacal liquor, then drips TEOS, stirs 5～7h, i.e. can get Fe under normal temperature3O4@SiO2Particle；
S3. Fe is prepared3O4@SiO2-C=C:
S31. by Fe3O4@SiO2Particle redisperse, in the mixed solution of distilled water and ethanol, adds the ammoniacal liquor containing CTAB, adds TEOS and VTES afterwards, stirs 5～7h；
S32. by the product Magneto separate of step S31 and after washing removing CTAB, 70～90 DEG C of acetone solns reflux 20～30h, i.e. can get Fe3O4@SiO2-C=C(i.e. the Fe of modified by vinyl3O4@SiO2Microballoon), with ethanol and distilled water cyclic washing, and it is dried；
S4. magnetic ion trace polymers is prepared:
S41. by CdCl2·5/2H2O, function monomer are distributed in the mixed solution of pore-foaming agent and water, stir 80～100min and carry out prepolymerization, add Fe under room temperature3O4@SiO2The Fe of-C=C(modified by vinyl3O4@SiO2Microsphere powder), EGDMA and AIBN, return stirring 8～12h at 80～90 DEG C；
S42. step S41 product Magneto separate and with ethanol washing remove unreacted reactant, elute with HCl solution, more repeatedly wash with distilled water, at 65 DEG C be dried, obtain magnetic cadmium ion imprinted polymer (M-IIP).
Wherein it is preferred to, Fe described in step S113Cl3·6H2O and FeCl2·4H2O mol ratio is 1:0.1～1.
It is highly preferred that Fe described in step S113Cl3·6H2O and FeCl2·4H2The mol ratio of O is 1:0.6.
Preferably, Fe described in step S113Cl3·6H2O and ultra-pure water amount ratio are 0.005～0.02mol:50ml.
It is highly preferred that Fe described in step S113Cl3·6H2The amount ratio of O and ultra-pure water is 0.01mol:50ml.
Preferably, ultra-pure water described in step S11: ammoniacal liquor: PEG200 volume ratio is 40～60:3～6:1.
It is highly preferred that ultra-pure water described in step S11: the volume ratio of ammoniacal liquor: PEG200 is 50:5:1.
Preferably, under the conditions of temperature constant magnetic stirring, thermal agitation is added described in step S11 to 80 DEG C；After described addition ammoniacal liquor and PEG200, add thermal agitation 3h.
Preferably, ethanol described in step S12 and ultra-pure water respectively wash 3 times, are dried in 60 DEG C.
Preferably, Fe described in step S23O4Powder: distilled water: ethanol: ammoniacal liquor: TEOS=0.01～0.2g:15～25ml:5～15ml:1～3ml:0.01～0.2ml.
It is highly preferred that Fe described in step S23O4Powder: distilled water: ethanol: ammoniacal liquor: TEOS=0.1g:20ml:10ml:2ml:0.1ml.
Preferably, 6h is stirred described in step S2.
Preferably, distilled water described in step S31: ethanol: the volume ratio containing the ammoniacal liquor of CTAB: TEOS:VTES is 90～110:40～60:8～12:3～5:3～4.
It is highly preferred that distilled water described in step S31: ethanol: the volume ratio containing the ammoniacal liquor of CTAB: TEOS:VTES is 100:50:10:4:3.7.
Preferably, distilled water described in step S2: the volume ratio of distilled water described in step S31 is 0.5～2:0.5～2.
It is highly preferred that distilled water described in step S2: the volume ratio of distilled water described in step S31 is 1:1.
Preferably, containing the concentration of CTAB in the ammoniacal liquor of CTAB described in step S31 is 0.1～0.3g/ml.
It is highly preferred that containing the concentration of CTAB in the ammoniacal liquor of CTAB described in step S31 is 0.2g/ml.
Preferably, 6h is stirred described in step S31.
Preferably, reflux described in step S32 in 80 DEG C of acetone solns 24h.
Preferably, CdCl described in step S412·5/2H2O: function monomer: pore-foaming agent: water=0.4～0.6mmol:3～5mmol:30～50ml:5～15ml.
It is highly preferred that CdCl described in step S412·5/2H2O: function monomer: pore-foaming agent: water=0.5mmol:4mmol:40ml:10ml.
Preferably, CdCl described in step S412·5/2H2O:Fe3O4@SiO2The mass ratio of-C=C:EGDMA:AIBN is 0.05～0.1:0.5～0.75:1.5～2:0.1～0.2.
It is highly preferred that CdCl described in step S412·5/2H2O:Fe3O4@SiO2The mass ratio of-C=C:EGDMA:AIBN is 0.092:0.5:1.98:0.15.
Preferably, the combination of any two kinds in being methacrylic acid, acrylamide and vinylpyridine of function monomer described in step S41.
It is highly preferred that the combination that function monomer described in step S41 is methacrylic acid and acrylamide.
Preferably, the mol ratio of described methacrylic acid and acrylamide is 3:1.
Preferably, pore-foaming agent described in step S41 is acetonitrile/water solution or acetonitrile/DMF/ aqueous solution.
It is highly preferred that pore-foaming agent described in step S41 is acetonitrile/water solution.
Preferably, stir 90min under room temperature described in step S41 and carry out prepolymerization.
Preferably, described in step S41 at 85 DEG C return stirring 10h.
Preferably, it is dried at step S42 is set forth in 65 DEG C.
Additionally; the magnetic cadmium ion imprinted polymer prepared by above-mentioned preparation method; and this magnetic cadmium ion imprinted polymer cadmium in cadmium pollution sample (especially Determination of Trace Amount Cadmium) detection, be enriched with and/or application in terms of separation, the most all within protection scope of the present invention.
The method have the advantages that
The present invention is with the Fe of modified by vinyl3O4@SiO2For magnetic carrier, Cd2+Being best-of-breed functionality combination of monomers for template, methacrylic acid (MAA) and acrylamide (AM), ethylene glycol dimethacrylate (EGDMA) is crosslinking, and azodiisobutyronitrile (AIBN) is initiator, prepares a kind of Cd2+Imprinted polymer microballoon；Determination of Trace Amount Cadmium in agricultural samples can be enriched with and separates, reduce the matrix impact on testing result, improve the accuracy of detection, and owing to the cadmium in sample is not free state, can use the method after digesting agricultural samples, the detection field at food, agricultural samples has relatively broad good application prospect.
This patent can improve by the solid extracting agent specific adsorption ability to cadmium ion, when being combined modern instrument and detecting, can avoid the interference of matrix effect, and the sensitivity and the detection that accuracy is Determination of Trace Amount Cadmium that improve detection provide reference frame.
And, ion imprinted polymer has that preparation is simple, low cost, operation require the advantages such as low, higher to template ion tool selectivity, magnetic nano-particle is combined with engram technology the magnetic ion imprinted polymer of preparation, not only there is the advantage that ion imprinted polymer is the highest, quick separating can also be realized under additional magnetic fields, avoid the troublesome operation such as centrifugal, filtration, improve enrichment and the efficiency separated.
Accompanying drawing explanation
Fig. 1 is the comparison of the unit adsorbance of the function monomer of various combination.
Fig. 2 is metering system and the acrylamide impact on adsorbance of different proportion.
Fig. 3 is the comparison of the unit adsorbance of different pore-foaming agent.
Fig. 4 is template molecule and the monomer impact on adsorbance of different proportion.
The impact on adsorbance of the amount of Fig. 5 difference crosslinking agent.
Fig. 6 is the impact on adsorbance of the consumption of different magnetic material.
Fig. 7 is Fe3O4(A) hysteresis curve and M-IIP(B).
Fig. 8 is the comparison of the adsorbance of the different initial concentration cadmium of magnetic cadmium ion imprinted polymer (M-IIP).
Detailed description of the invention
Further illustrate the present invention below in conjunction with Figure of description and specific embodiment, but the present invention is not limited in any form by embodiment.Unless stated otherwise, the present invention uses reagent, method and apparatus are the art conventional reagent, method and apparatus.
Unless stated otherwise, following example agents useful for same and material are commercial.
Instrument: Atomic Absorption Spectrometer (AA800), magnetic stirring apparatus (ZNCL-G-C), air dry oven (SFG-02.400), constant-temperature table (ZWY-100H ), vibrating specimen magnetometer YPC7-VSM-130, ultrasonic washing instrument (SB-4200DTD)；
It is pure that following reagent is analysis: caddy, methacrylic acid (MAA), acrylamide (AM), acetonitrile, ethylene glycol dimethacrylate (EGDMA), azodiisobutyronitrile (AIBN), iron chloride, frerrous chloride, ammoniacal liquor, ethylene glycol (PEG200), tetraethyl orthosilicate (TEOS), vinyltrimethoxy silane (VTES), cetyl trimethylammonium bromide (CTAB), ethanol.
Cadmium standard liquid (standard items).
Embodiment 1 The preparation method of magnetic cadmium ion imprinted polymer
The preparation method of magnetic cadmium ion imprinted polymer, comprises the steps:
S1. Fe is prepared3O4Particle:
Weigh 0.02mol Fe3Cl3·6H2O、0.012mol FeCl2·4H2O is placed in 250ml triangular flask, it is dissolved in 100ml ultra-pure water under logical condition of nitrogen gas, add thermal agitation to 80 DEG C in constant temperature blender with magnetic force, add 10ml ammoniacal liquor and 2ml PEG200, add thermal agitation 3h, reaction terminates, being cooled to room temperature, separate with magnet after removing supernatant, ethanol and ultra-pure water respectively wash 3 times, in 60 DEG C of oven dryings, grind and obtain Fe3O4Powder；
S2. Fe is prepared3O4@SiO2:
Weigh 0.5g Fe3O4Powder is distributed in the mixed solution of 100ml distilled water, 50ml ethanol and 10ml ammoniacal liquor, then drips 0.5ml TEOS, stirs 6h, i.e. can get Fe under normal temperature3O4@SiO2Particle；
S3. Fe is prepared3O4@SiO2-C=C:
By Fe3O4@SiO2Particle redisperse, in the mixed solution of 100ml distilled water and 50ml ethanol, adds the ammoniacal liquor that 10ml contains 2g CTAB, adds 4ml TEOS and 3.7ml VTES afterwards, stirring 6h, by above-mentioned product Magneto separate and wash removing CTAB after, in 80 DEG C of acetone solns reflux 24h, i.e. can get Fe3O4@SiO2-C=C(i.e. the Fe of modified by vinyl3O4@SiO2Microballoon), with ethanol and distilled water cyclic washing, and it is dried；
S4. magnetic ion trace polymers is prepared:
Weigh 0.5mmol CdCl2·5/2H2In the solution of the water that O, a certain amount of bi-functional monomer methacrylic acid and acrylamide are distributed to 40ml pore-foaming agent and 10ml, stir 90min under room temperature and carry out prepolymerization, add a certain amount of Fe3O4@SiO2The Fe of-C=C(modified by vinyl3O4@SiO2Microsphere powder), ethylene glycol dimethacrylate (EGDMA) and 0.15g azodiisobutyronitrile (AIBN), return stirring 10h at 85 DEG C, product Magneto separate also removes unreacted reactant with ethanol washing, elute with HCl solution, repeatedly wash with distilled water again, it is dried at 65 DEG C, obtains magnetic cadmium ion imprinted polymer (M-IIP).
Embodiment 2 The selection of optimization function monomer (methacrylic acid and the acrylamide) kind of preparation technology
1, preparation method is with embodiment 1, and difference is the function monomer methacrylic acid used in step S4 and acrylamide, replaces with following different combination respectively:
(1) methacrylic acid；
(2) vinylpyridine；
(3) acrylamide；
(4) methacrylic acid and vinylpyridine；
(5) methacrylic acid and acrylamide；
(6) acrylamide and vinylpyridine.
By comparing various combination function monomer, function monomer is screened by the adsorbance of cadmium.
2, result is as shown in Figure 1, in the preparation of magnetic cadmium ion imprinted polymer (M-IIP), ion imprinted polymer adsorbance prepared by bi-functional monomer is above the adsorbance of ion blotting prepared by single function monomer, in the combination of bi-functional monomer, the adsorbance using methacrylic acid and acrylamide to prepare ion imprinted polymer is the highest.Therefore, the optimal selection of function monomer used by ion imprinted polymer is prepared in this experiment is methacrylic acid and acrylic acid.
Embodiment 3 Preparation technology optimizes methacrylic acid and the selection of acrylamide ratio
1, preparation method is with embodiment 1, and difference is that the function monomer methacrylic acid used in step S4 is different with the ratio of acrylamide, is respectively as follows: 1:1,1:3,3:1.
2, result is as shown in Figure 2, and when the ratio of methacrylic acid and acrylamide is 3:1, the adsorbance to cadmium is the highest.
Embodiment 4 The selection optimizing pore-foaming agent of preparation technology
1, preparation method is with embodiment 1, and difference is that used in step S4, pore-foaming agent is respectively acetonitrile/water, acetonitrile/two kinds of DMF/ water pore-foaming agent.
2, result is as shown in Figure 3, is used as the solvent adsorbance to cadmium apparently higher than the adsorbance with acetonitrile/DMF/ water mixed liquid by acetonitrile/water, so acetonitrile/water solution is optimal pore-foaming agent.
Embodiment 5 The optimization template of preparation technology CdCl2 · 5/2H2O Optimization with function monomer ratio
1, preparation method is with embodiment 1, and difference is template CdCl used in step S42·5/2H2O is different with the mol ratio ratio of function monomer (methacrylic acid and acrylamide), respectively 1:4,1:6,1:8,1:10,1:12.
2, result is as shown in Figure 4, and when the ratio of template Yu function monomer is 1:8, the adsorbance to cadmium is maximum.
Embodiment 6 The optimization template of preparation technology CdCl2 · 5/2H2O Optimization with crosslinker ratio
1, preparation method is with embodiment 1(with template and methacrylic acid and acrylamide as function monomer, and template and function monomer ratio are 1:8, and acetonitrile/water is pore-foaming agent), difference is template CdCl used in step S42·5/2H2O and crosslinking agent ethylene glycol dimethacrylate (EGDMA) Mol ratio ratio different, respectively 1:8,1:12,1:16,1:20,1:24.
2, result is as shown in Figure 5, and when the ratio of template Yu crosslinking agent is 1:20, the adsorbance to cadmium is maximum.
Embodiment 7 The optimization of the amount optimizing magnetic carrier of preparation technology
1, preparation method is with embodiment 1, and with methacrylic acid and acrylamide as function monomer, template and function monomer are 1:8, and template is 3:1 with the ratio that ratio is 1:20, methacrylic acid and acrylamide of crosslinking agent, control magnetic carrier (Fe3O4@SiO2The Fe of-C=C, i.e. modified by vinyl3O4@SiO2)) amount 0.25,05,0.75,1.00g.
2, result is as shown in Figure 6, and the amount of the carrier when with 0.5～0.75g can be satisfied with the requirement of adsorbance and magnetic.
Embodiment 8 Magnetic cadmium ion imprinted polymer ( M-IIP ) magnetic properties research
1, vibrating specimen magnetometer (VSM) is utilized to measure Fe3O4With the hysteresis curve of M-IIP, Fe prepared by research institute3O4Magnetic properties with M-IIP.Test temperature is 300K, is 0～20000H in south poles magnetic field intensity scope.
2, result is as shown in Figure 7, and the hysteresis curve of the two has similar shape, coercivity and remanent magnetization all close to zero, illustrate that both has paramagnetism, can have strong magnetic responsiveness under magnetic fields, it is simple to the gathering of particle.
Embodiment 8 Magnetic cadmium ion imprinted polymer ( M-IIP ) application study
1, the M-IIP of many parts of 20mg is weighed, add the cadmium standard liquid that 20ml concentration range is 30～90ug/ml, it is placed in constant-temperature table concussion absorption 2h, separate with magnet, take a certain amount of supernatant, measure the concentration of wherein cadmium after dilution with AAS, investigate the saturated absorption adsorbance of magnetic ion imprinted polymer.
2, result is as shown in Figure 8, Cd2+Ion concentration is in the range of 30～80 μ g/ml, and along with cadmium-ion solution degree increases, the adsorbance of magnetic cadmium ion imprinted polymer (M-IIP) all increases, and tends to saturated when 75 μ g/ml, and saturated extent of adsorption is 46.80mg/g.

Claims (10)

1. a magnetic cadmium ion imprinted polymer, it is characterised in that be the Fe with modified by vinyl3O4@SiO2For magnetic carrier, Cd2+For template, in methacrylic acid, acrylamide and vinylpyridine any two kinds be combined as function monomer, ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is that initiator prepares.
2. the preparation method of magnetic cadmium ion imprinted polymer described in claim 1, it is characterised in that comprise the steps:
S1. Fe is prepared by coprecipitation3O4Magnetic carrier；
S2. polyethylene glycol PEG200 is passed through as dispersant to improve Fe3O4The dispersion stabilization of particle, utilizes the hydrolysis of tetraethyl orthosilicate at Fe3O4Particle surface superscribes silicon dioxide layer, defines Fe3O4@SiO2Particulate；
S3. vinyltrimethoxy silane and cetyl trimethylammonium bromide are passed through to Fe3O4@SiO2Particulate is modified, and has obtained Fe3O4@SiO2-C=C；
S4. with Cd2+For template, in methacrylic acid, acrylamide and vinylpyridine any two kinds be combined as function monomer, after carrying out prepolymerization in acetonitrile/water mixed solution, add Fe3O4@SiO2-C=C, crosslinking agent ethylene glycol dimethacrylate and initiator azodiisobutyronitrile, at 80～90 DEG C, backflow 8～12h, prepares magnetic cadmium ion imprinted polymer.
Preparation method the most according to claim 2, it is characterised in that the condition of backflow described in step S4 is backflow 10h at 85 DEG C.
Preparation method the most according to claim 2, it is characterised in that comprise the steps:
S1. Fe is prepared3O4Particle:
S11. under logical condition of nitrogen gas, by Fe3Cl3·6H2O and FeCl2·4H2O is dissolved in ultra-pure water, adds thermal agitation to 70～90 DEG C under the conditions of temperature constant magnetic stirring；Add ammoniacal liquor and PEG200, add thermal agitation 2～4h；
S12. the reaction of step S1 terminates, and is cooled to room temperature, separates with magnet after removing supernatant, and ethanol and ultra-pure water respectively wash 2～4 times, are dried in 50～70 DEG C, grind and obtain Fe3O4Powder；
S2. Fe is prepared3O4@SiO2:
Weigh Fe3O4Powder is distributed in the mixed solution of distilled water, ethanol and ammoniacal liquor, then drips TEOS, stirs 5～7h, i.e. can get Fe under normal temperature3O4@SiO2Particle；
S3. Fe is prepared3O4@SiO2-C=C:
S31. by Fe3O4@SiO2Particle redisperse, in the mixed solution of distilled water and ethanol, adds the ammoniacal liquor containing CTAB, adds TEOS and VTES afterwards, stirs 5～7h；
S32. by the product Magneto separate of step S31 and after washing removing CTAB, 70～90 DEG C of acetone solns reflux 20～30h, i.e. can get Fe3O4@SiO2-C=C, with ethanol and distilled water cyclic washing, and is dried；
S4. magnetic ion trace polymers is prepared:
S41. by CdCl2·5/2H2During the combination of any two kinds is distributed to the mixed solution of pore-foaming agent and water in O, and methacrylic acid, acrylamide and vinylpyridine, stirs 80～100min under room temperature and carry out prepolymerization, add Fe3O4@SiO2The Fe of-C=C(modified by vinyl3O4@SiO2Microsphere powder), EGDMA and AIBN, return stirring 8～12h at 80～90 DEG C；
S42. step S41 product Magneto separate and with ethanol washing remove unreacted reactant, elute with HCl solution, more repeatedly wash with distilled water, at 65 DEG C be dried, obtain magnetic cadmium ion imprinted polymer.
Preparation method the most according to claim 4, it is characterised in that Fe described in step S113Cl3·6H2O and FeCl2·4H2The mol ratio of O is 1:0.1～1；Fe described in step S113Cl3·6H2The amount ratio of O and ultra-pure water is 0.005～0.02mol:50ml；The volume ratio of ultra-pure water described in step S11: ammoniacal liquor: PEG200 is 40～60:3～6:1.
Preparation method the most according to claim 4, it is characterised in that Fe described in step S23O4Powder: distilled water: ethanol: ammoniacal liquor: TEOS=0.01～0.2g:15～25ml:5～15ml:1～3ml:0.01～0.2ml；Distilled water described in step S31: ethanol: the volume ratio containing the ammoniacal liquor of CTAB: TEOS:VTES is 90～110:40～60:8～12:3～5:3～4.
Preparation method the most according to claim 4, it is characterised in that distilled water described in step S2: the volume ratio of distilled water described in step S31 is 0.5～2:0.5～2；Containing the concentration of CTAB in the ammoniacal liquor of CTAB described in step S31 is 0.1～0.3g/ml.
Preparation method the most according to claim 4, it is characterised in that CdCl described in step S412·5/2H2O: function monomer: pore-foaming agent: water=0.4～0.6mmol:3～5mmol:30～50ml:5～15ml；CdCl described in step S412·5/2H2O:Fe3O4@SiO2The mass ratio of-C=C:EGDMA:AIBN is 0.05～0.1:0.5～0.75:1.5～2:0.1～0.2.
9. the magnetic cadmium ion imprinted polymer prepared according to the arbitrary described preparation method of claim 2～8.
10. the detection of cadmium in cadmium pollution sample of magnetic cadmium ion imprinted polymer described in claim 9, it is enriched with and/or application in terms of separation.
CN201610314950.0A 2016-05-13 2016-05-13 Magnetic cadmium ion-imprinted polymer and preparation method thereof Pending CN105884985A (en)

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