CN103626939B - The preparation method of a kind of selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer and application - Google Patents
The preparation method of a kind of selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer and application Download PDFInfo
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Abstract
The preparation method of a kind of selectivity of the present invention dynamic Solid-Phase Extraction cerium ion imprinted polymer and application, belong to material preparation technology and separation technology field.Refer in particular to ordered mesoporous material SBA-15 as substrate, with metallic cerium ion for template, 4-(chloromethyl) phenyltrimethoxysila,e is coupling agent, 4-vinylpridine is function monomer, Ethylene glycol dimethacrylate is linking agent, and Diisopropyl azodicarboxylate is initiator, and reversible addion-fragmentation chain transfer is polymerized to polymerization methods, prepare the method for cerium ion imprinted polymer, select dynamic adsorption experiment to study the Selective recognition performance of the sorbing material of preparation.The present invention uses RAFT to be polymerized synthesis of selective dynamic Solid-Phase Extraction cerium ion imprinted polymer first, and uses the separation condition of cerium ion in the dynamic adsorption experimental study aqueous solution.Result shows that the cerium ion imprinted polymer sorbing material utilizing the present invention to obtain has superior absorption and recognition performance to cerium ion.
Description
Technical field
The present invention relates to a kind of preparation method using reversible addion-fragmentation chain transfer polymerization technique synthesize meso-porous material surface ion imprinted polymer, particularly relate to the preparation method of a kind of selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer, and be applied to cerium ion in the Dynamic adsorption aqueous solution, belong to material preparation and separation technology field.
Background technology
The exploitation of nuclear raw material have driven the development in the world, but the harm simultaneously caused is also day by day serious.The exploitation of nuclear fuel and processing, the leakage of nuclear reactor, the reprocessing of nuclear fuel, the use etc. of Nuclear weapons become the main source of radioelement in environment.Europium, uranium, strontium, thorium, caesium, cerium etc. all belong to middle low-activity metallic element.Air, water and soil can be caused to pollute after radiation metallic element entered environment.Wherein radioelement cerium, long half time, not easily excretes in metabolic process, seriously jeopardizes HUMAN HEALTH, and its contaminated soil, water source matrix are complicated, many kinds of metal ions coexists, not easily separated.Therefore, be effectively separated thorium tool in the removal aqueous solution to be of great significance.Wherein conventional separation method has ion-exchange and adsorption solid phase abstraction technique, solvent extraction technology and chemical precipitation method etc.These methods respectively have particular advantages, but also respectively there is its limitation.As ion-exchange and adsorption solid phase abstraction technique poor heat stability, at high temperature easily lose cation exchange groups, degrade under radiation effect, loading capacity is low; Solvent extraction technology is a large amount of with an organic solvent, easily produces secondary pollution.Therefore develop the sorbent material that selectivity is good, loading capacity is high, simple to operate, regenerability is excellent, set up specificity nuclear waste transmutation sorbent material significant.
Molecular imprinting (MIT) is as the Molecular Recognization of enzyme-to-substrate, antibody and antigen etc. in simulating nature circle, take target molecule as template molecule preparation has the polymer imprinted polymer (MolecularlyImprintedPolymers, MIPs) of specific selectivity recognition function a kind of technology to this molecule.
The Application and Development of the surface molecule print technology produced that combined with substrate material by molecular imprinting is one of research of most magnetism.The problem such as molecular imprinted polymer on surface solves binding site heterogeneity that entrapping method brings, accessibility is poor, rate of mass transfer is slow, site utilization ratio is low, can realize combining fast between imprinted polymer with trace ion and being separated, reducing non-specific adsorption to optionally affecting, separating from the mixture of similar for specific molecular (ion) and providing feasible effective solution route.This also provides novel method for effectively removing low-activity element in the aqueous solution.
Research shows, silica-base material has that good mechanical property, sour environment stability are high, the not easily advantage such as swelling, is conventional surface imprinted substrate material.In recent years, ordered mesoporous silicon material, because having stable meso-hole structure, the aperture of modulation, good chemistry and mechanical stability, hole wall can there is the characteristics such as a large amount of modifiable Si-OH groups, is widely used in the research of solid support material.In polytype mesoporous material, SBA-15 has the homogeneous meso-hole structure of two-dimentional six side's shape, and specific surface area is large, aperture, pore volume are large, hole wall is thick, show fabulous surperficial mass transfer ability and chemical/mechanical stability, these character make SBA-15 become to have the modified surface substrate material of potential application foreground.
Activity/controllable free-radical polymerisation is the free radical polymerisation process that can control polymer architecture and performance, is still the study hotspot of radical polymerization so far.Reversible addion-fragmentation chain transfer (RAFT) radical polymerization is a kind of activity/controllable free-radical polymerisation.In RAFT reaction, chain transfer agents and growing chain free radical form the intermediate of dormancy, this intermediate can self-cleavage, discharge the living radical made new advances, form growing chain in conjunction with monomer, chain-transfer agent shifts rapidly between activity and dormancy free radical, the irreversible double-basis limited between growing chain free radical stops side reaction, polyreaction is effectively controlled, and relative molecular mass distribution reduces, and polymerization embodies activity/controllable characteristics.
The present invention is by the selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer of RAFT polymerization synthesis, activity/the controllable characteristics utilizing RAFT to be polymerized, mesoporous material specific surface area is large, machinery and thermal stability is good and the advantage such as highly selective, specific recognition of surface ion engram technology, use it in the fractionation by adsorption of low-activity metal pollutant, and use the dynamic adsorption experimental study absorption behavior of cerium ion, for low-activity metal pollutant in ion imprinted polymer selectivity Solid-Phase Extraction environmental sample provides new technique means.
Summary of the invention
The object of the invention is with sequential silicon-based mesoporous material (SBA-15) for substrate, in conjunction with RAFT polymerization synthesis, cerium ion is had to the ion imprinted polymer of single-minded evident characteristics, and be applied to the Optimum separation condition of cerium ion in dynamic adsorption experimental study mesopore surfaces ion imprinted polymer fractionate aqueous solutions.
A preparation method for selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer, carries out according to the following steps:
(1) get SBA-15 and be placed in round-bottomed flask, adding concentration is 3mol/L hydrochloric acid, and backflow 24h, then filters, and with secondary deionized water repetitive scrubbing to neutral, takes out after 80 DEG C of vacuum-drying 6h.
(2) SBA-15 and 4-(chloromethyl) phenyltrimethoxysila,e processed in step (1) is joined in toluene solution successively; and this mixing solutions is placed in 90 DEG C of oil baths; under nitrogen protection; magnetic agitation 24h; after reaction, product is respectively washed 5 times with toluene, methyl alcohol successively; with the unreacted 4-of wash-out (chloromethyl) phenyltrimethoxysila,e and toluene; at room temperature vacuum-drying; the mesoporous material of obtained chlorine functionalization, i.e. SBA-15-Cl.
(3) join in there-necked flask by phenylmagnesium bromide solution, oil bath is preheated to 40 ~ 60 DEG C, under nitrogen protection, dropwise adds dry dithiocarbonic anhydride (CS
2), under nitrogen protection, maintain oil bath temperature 40-60 DEG C reaction 1h.Then gained SBA-15-Cl in step (2) is added, under nitrogen protection, 70 DEG C of oil bath reaction 60h.Be cooled to room temperature after reaction terminates, add the hydrochloric acid that concentration is 1mol/L, continue stirring 5 ~ 10min, filter afterwards, and respectively wash 3 times with methyl alcohol and acetone successively, ambient temperature in vacuum is dry, obtain the SBA-15 that surperficial reversible addion-fragmentation chain transfer agent is modified, i.e. SBA-15-RAFT.
(4) by the SBA-15-RAFT in step (3), cerous nitrate (Ce (III)), 4-vinylpridine (4-VP), Ethylene glycol dimethacrylate (EGDMA) and Diisopropyl azodicarboxylate (AIBN) mixing are added in the mixed solution of first alcohol and water; And this mixing solutions is placed in 60 DEG C of oil baths, and under nitrogen protection, reaction 24h.5 times are respectively washed with methyl alcohol, deionized water successively after reaction, to remove the template ion cerium ion (Ce (III)) of unreacted monomer 4-vinylpridine, initiator Diisopropyl azodicarboxylate and non-trace, vacuum-drying at 60 DEG C, then 250 ~ 1000mL concentration is used to be that 2mol/L hydrochloric acid washes away template ion, and be washed till neutrality with deionized water, then vacuum-drying obtains mesoporous material surface ion imprinted polymer (IIP) at 60 DEG C.
Wherein, the massfraction of the SBA-15 described in step (1) is 0.15 ~ 1.5%.
Wherein, SBA-15,4-(chloromethyl) phenyltrimethoxysila,e described in step (2) and the ratio of toluene solution are 1g:1mL:40mL.
Wherein, the phenylmagnesium bromide solution described in step (3) is that phenyl-magnesium-bromide is present in the solution in super dry tetrahydrofuran with the concentration of 1.0mol/L; The volume ratio of the described dithiocarbonic anhydride that adds and phenylmagnesium bromide solution is 1:16; The amount of the described SBA-15-Cl added is 0.125-0.5g; The amount adding hydrochloric acid is 12.5 ~ 25mL.
Wherein, in the mixed solution of first alcohol and water described in step (4), the volume ratio of methyl alcohol and water is 4:1, the massfraction of described SBA-15-RAFT is 0.23 ~ 0.7%, the concentration of cerium ion Ce (III) is 5 ~ 15mmol/L, the concentration of 4-VP is 20 ~ 60mmol/L, the concentration of EGDMA is the concentration of 26 ~ 78mmol/L, AIBN is 0.6 ~ 2.5mmol/L.
In above-mentioned technical scheme, SBA-15 is impregnated in the solution of hydrochloric acid to make its surface hydroxyl be activated.
Cerous nitrate described in technique scheme, it act as template ion.
4-vinylpridine described in technique scheme, it act as function monomer.
Ethylene glycol dimethacrylate described in technique scheme, it act as linking agent.
Diisopropyl azodicarboxylate described in technique scheme, it act as initiator.
SBA-15 described in technique scheme, it act as substrate material.
4-(chloromethyl) phenyltrimethoxysila,e described in technique scheme, it act as silane coupling agent.
Phenyl-magnesium-bromide described in technique scheme and dithiocarbonic anhydride, it act as RAFT transfer agent compound agent.
RAFT polymerization methods described in such scheme, its role is to obtain that controlled, the adsorptive capacity of polymer thickness is comparatively large, adsorption rate surface ion imprinted polymer faster.
Above-mentioned selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer is applied to the method for cerium ion in the dynamic separation aqueous solution, carries out according to following step:
(1) the dynamic adsorption experimental apparatus of self-control is selected, first the ion imprinted polymer of 0.1g is loaded ready dynamic adsorption post, then with pH be the deionized water of 5.0 by adsorption unit 10 ~ 30min, its object is to get rid of experiment outside influence factor, thus reduce experimental error.Finally by control loading flow velocity, by the solution for preparing by adsorption column, and connect effluent liquid continuously with 5mL tool plug centrifuge tube, survey its concentration in conjunction with inductively coupled plasma atomic emission spectrum (ICP-AES);
(2) dynamic adsorption laboratory method is to the research of cerium ion separation condition in the aqueous solution
Choose temperature, sample concentration and loading flow velocity as influence factor, with cerium ion equilibrium adsorption capacity for evaluation index response value, determine temperature 25 ~ 45 DEG C, cerium ion concentration at 3 ~ 8mg/L, flow velocity is 1.5 ~ 3.5mL/min, by analyze obtain Optimum separation condition.
(3) dynamic adsorption laboratory method is to the research of cerium ion selective separation in the aqueous solution
Under Optimum separation condition, choosing different metal ions and cerium ion forms mixing solutions, is response value with selectivity coefficient, by analytical calculation, thus obtains ion imprinted polymer that the present invention obtains to the selectivity coefficient of cerium ion.
Technological merit of the present invention:
(1) printing process occurs in silicon-based mesoporous material surface, avoids conventional template molecule dark and cannot the problem of wash-out because embedding.
(2) utilize reversible addion-fragmentation chain transfer to be polymerized, synthesized selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer first, for the metal ion in selectivity Solid-Phase Extraction environment provides novel method.
(3) it is large that the selectivity utilizing the present invention to obtain dynamic Solid-Phase Extraction cerium ion imprinted polymer has specific surface area, the advantage of good mechanical property and thermostability etc., superior cerium ion recognition performance.
(4) selectivity utilizing the present invention to obtain dynamic Solid-Phase Extraction cerium ion imprinted polymer, first time by dynamic adsorption experimental study its to the Optimum separation condition of metal ion in the aqueous solution, apply further for industry and foundation be provided.
Accompanying drawing explanation
Fig. 1 is raw material and polymkeric substance infared spectrum: in figure, a is SBA-15; B is SBA-15-Cl; C is SBA-15-RAFT; D is IIP.As can be seen from the figure, at 1083cm
-1, 805cm
-1, 461cm
-1place can observe the stretching vibration of silicon-based mesoporous material Si-O-Si and the absorption peak of formation vibration, and the skeleton structure all maintaining SBA-15 is described.Polymerisate IIP, 1424cm
-1for the C-H flexural vibration on pyridine ring, 1509cm
-1, 1601cm
-1near there is the weak absorbing of the flexural vibration absorption peak (C=C, C=N) of pyridine ring, prove that 4-vinylpridine successful polymerization is to SBA-15-RAFT surface.The successful synthesis of selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer is described.
Fig. 2 is selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer transmission electron microscope picture.Substrate material is order mesoporous silica-base material (SBA-15) as we can see from the figure, the crosslinking reaction of its surface due to polymkeric substance and the formation of ion imprinted polymer, what substrate material was become is coarse, and the successful synthesis of selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer is described.
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1
(1) get 0.25gSBA-15 and be placed in round-bottomed flask, adding 150mL concentration is 3mol/L hydrochloric acid, and backflow 24h, then filters, and with secondary deionized water repetitive scrubbing to neutral, takes out after 80 DEG C of vacuum-drying 6h.
(2) getting SBA-15 and 0.25mL4-(chloromethyl) phenyltrimethoxysila,e processed in 0.25g step (1) is added in the solution of 10mL toluene successively; and this mixing solutions is placed in 90 DEG C of oil baths; under nitrogen protection; magnetic agitation 24h; toluene, methyl alcohol is adopted by product respectively to wash 5 times after reaction successively; with the unreacted 4-of wash-out (chloromethyl) phenyltrimethoxysila,e and toluene, the mesoporous material (SBA-15-Cl) of the chlorine functionalization that at room temperature vacuum-drying obtains.
(3) join in there-necked flask by 8mL phenyl-magnesium-bromide (PMB), oil bath is preheated to 40 DEG C, under nitrogen protection, dropwise adds the dithiocarbonic anhydride (CS of 0.5mL drying
2), under nitrogen protection, maintain oil bath temperature reaction 1h.Then gained SBA-15-Cl in 0.125g step (2) is added, under nitrogen protection, 70 DEG C of oil bath reaction 60h.Be cooled to room temperature after reaction terminates, add 12.5mL1mol/LHCl, continue to stir 5min, filter afterwards, and respectively washing 3 times with methyl alcohol and acetone successively, ambient temperature in vacuum is dry, obtains the SBA-15 (SBA-15-RAFT) that surperficial reversible addion-fragmentation chain transfer agent is modified.
(4) 0.05gSBA-15-RAFT is got, 0.128mmol cerous nitrate (Ce (III)), 0.512mmol4-vinyl pyridine (4-VP), 0.6656mmol Ethylene glycol dimethacrylate (EGDMA) and 2.5mg Diisopropyl azodicarboxylate (AIBN) mixing are added in the mixing solutions of 25mL methanol-water.And this mixing solutions is placed in 60 DEG C of oil baths, and under nitrogen protection, reaction 24h.5 times are respectively washed with methyl alcohol, deionized water successively after reaction, to remove the template ion (Ce (III)) of unreacted monomer 4-vinylpridine, initiator Diisopropyl azodicarboxylate and non-trace, vacuum-drying at 60 DEG C, then template ion is washed away with 250mL2mmol/L hydrochloric acid, and be washed till neutrality with deionized water, then vacuum-drying obtains mesoporous material surface ion imprinted polymer at 60 DEG C.
(5) the dynamic adsorption experimental apparatus of self-control is selected, first the 0.1g ion imprinted polymer that the present invention obtains is loaded ready dynamic adsorption post, then adsorption unit 10 ~ 30min is passed through with the deionized water of pH5.0, its object is to get rid of the influence factor outside experiment, thus reduce experimental error.Finally by control loading flow velocity, by the solution for preparing by adsorption column, and connect effluent liquid continuously with 5mL tool plug centrifuge tube, survey its concentration in conjunction with ICP-AES;
(6) dynamic adsorption laboratory method is to the research of cerium ion separation condition in the aqueous solution
Choose temperature, sample concentration and loading flow velocity as influence factor, with cerium ion equilibrium adsorption capacity for evaluation index response value, determine temperature 25 ~ 45 DEG C, cerium ion concentration at 3 ~ 8mg/L, flow velocity is 1.5 ~ 3.5mL/min, by analyze obtain Optimum separation condition.
Result shows, and optimal separation temperature is 25 DEG C, and loading flow velocity is 1.5mL/min, and cerium ion concentration is 5mg/L, and separating effect is best, and equilibrium adsorption capacity reaches 20.5mg/g.
(7) dynamic adsorption laboratory method is to the research of cerium ion selective separation in the aqueous solution
Under Optimum separation condition, choose Ce (III) and Fe (III), Ca (II), the competitive adsorption of binary system that Zn (II), Sr (II) mix, be 5.0 by dilute hydrochloric acid or weak ammonia adjust ph, then according to step (5), research ion imprinted polymer and non-imprinted polymer adsorb the dynamic competition of each binary solution respectively.The concentration ICP-AES of the Ce (III) in connect solution and other competitive adsorption ion is measured, calculates loading capacity according to result.
The mesopore surfaces ion imprinted polymer that result shows the present invention's acquisition shows good selectivity to Ce (III), wherein Ce (III) is respectively 3.21 relative to the selectivity coefficient of competitive adsorption ion Fe (III), Ca (II), Zn (II), Sr (II), 10.7,11.9 and 13.25.
embodiment 2
(1) get 1gSBA-15 and be placed in round-bottomed flask, adding 150mL concentration is 3mol/L hydrochloric acid, and backflow 24h, then filters, and with secondary deionized water repetitive scrubbing to neutral, takes out after 80 DEG C of vacuum-drying 6h.
(2) getting SBA-15 and 0.5mL4-(chloromethyl) phenyltrimethoxysila,e processed in 0.5g step (1) is added in the solution of 20mL toluene successively; and this mixing solutions is placed in 90 DEG C of oil baths; under nitrogen protection; magnetic agitation 24h; toluene, methyl alcohol is adopted by product respectively to wash 5 times after reaction successively; with the unreacted 4-of wash-out (chloromethyl) phenyltrimethoxysila,e and toluene, the mesoporous material (SBA-15-Cl) of the chlorine functionalization that at room temperature vacuum-drying obtains.
(3) join in there-necked flask by 16mL phenyl-magnesium-bromide (PMB), oil bath is preheated to 50 DEG C, under nitrogen protection, dropwise adds the dithiocarbonic anhydride (CS of 1mL drying
2), under nitrogen protection, maintain oil bath temperature reaction 1h.Then gained SBA-15-Cl in 0.25g step (2) is added, under nitrogen protection, 70 DEG C of oil bath reaction 60h.Be cooled to room temperature after reaction terminates, add 18.75mL1mol/LHCl, continue to stir 7.5min, filter afterwards, and respectively washing 3 times with methyl alcohol and acetone successively, ambient temperature in vacuum is dry, obtains the SBA-15 (SBA-15-RAFT) that surperficial reversible addion-fragmentation chain transfer agent is modified.
(4) 0.1gSBA-15-RAFT is got, 0.256mmol cerous nitrate (Ce (III)), 1.024mmol4-vinyl pyridine (4-VP), 1.3312mmol Ethylene glycol dimethacrylate (EGDMA) and 5mg Diisopropyl azodicarboxylate (AIBN) mixing are added in the mixing solutions of 25mL methanol-water.And this mixing solutions is placed in 60 DEG C of oil baths, and under nitrogen protection, reaction 24h.5 times are respectively washed with methyl alcohol, deionized water successively after reaction, to remove the template ion (Ce (III)) of unreacted monomer 4-vinylpridine, initiator Diisopropyl azodicarboxylate and non-trace, vacuum-drying at 60 DEG C, then template ion is washed away with 500mL2mol/L hydrochloric acid, and be washed till neutrality with deionized water, then vacuum-drying obtains mesoporous material surface ion imprinted polymer at 60 DEG C.
(5) the dynamic adsorption experimental apparatus of self-control is selected, first the 0.1g ion imprinted polymer that the present invention obtains is loaded ready dynamic adsorption post, then adsorption unit 10 ~ 30min is passed through with the deionized water of pH5.0, its object is to get rid of the influence factor outside experiment, thus reduce experimental error.Finally by control loading flow velocity, by the solution for preparing by adsorption column, and connect effluent liquid continuously with 5mL tool plug centrifuge tube, survey its concentration in conjunction with ICP-AES;
(6) dynamic adsorption laboratory method is to the research of cerium ion separation condition in the aqueous solution
Choose temperature, sample concentration and loading flow velocity as influence factor, with cerium ion equilibrium adsorption capacity for evaluation index response value, determine temperature 25 ~ 45 DEG C, cerium ion concentration at 3 ~ 8mg/L, flow velocity is 1.5 ~ 3.5mL/min, by analyze obtain Optimum separation condition.
Result shows, and optimal separation temperature is 25 DEG C, and loading flow velocity is 1.5mL/min, and cerium ion concentration is 5mg/L, and separating effect is best, and equilibrium adsorption capacity reaches 19.8mg/g.
(7) dynamic adsorption laboratory method is to the research of cerium ion selective separation in the aqueous solution
Under Optimum separation condition, choose Ce (III) and Fe (III), Ca (II), the competitive adsorption of binary system that Zn (II), Sr (II) mix, be 5.0 by dilute hydrochloric acid or weak ammonia adjust ph, then according to step (5), research ion imprinted polymer and non-imprinted polymer adsorb the dynamic competition of each binary solution respectively.The concentration ICP-AES of the Ce (III) in connect solution and other competitive adsorption ion is measured, calculates loading capacity according to result.
The mesopore surfaces ion imprinted polymer that result shows the present invention's acquisition shows good selectivity to Ce (III), wherein Ce (III) is respectively 3.19 relative to the selectivity coefficient of competitive adsorption ion Fe (III), Ca (II), Zn (II), Sr (II), 11.03,10.84 and 13.02.
embodiment 3
(1) get 2.5gSBA-15 and be placed in round-bottomed flask, adding 150mL concentration is 3mol/L hydrochloric acid, and backflow 24h, then filters, and with secondary deionized water repetitive scrubbing to neutral, takes out after 80 DEG C of vacuum-drying 6h.
(2) getting SBA-15 and 1.0mL4-(chloromethyl) phenyltrimethoxysila,e processed in 1g step (1) is added in the solution of 40mL toluene successively, and this mixing solutions is placed in 90 DEG C of oil baths, under nitrogen atmosphere, magnetic agitation 24h, after reaction, product is adopted toluene successively, methyl alcohol divides each washing 5 times, with the unreacted 4-of wash-out (chloromethyl) phenyltrimethoxysila,e and toluene, the mesoporous material (SBA-15-Cl) of the chlorine functionalization that at room temperature vacuum-drying obtains.
(3) join in there-necked flask by 32mL phenyl-magnesium-bromide (PMB), oil bath is preheated to 60 DEG C, under nitrogen protection, dropwise adds the dithiocarbonic anhydride (CS of 2mL drying
2), under nitrogen protection, maintain oil bath temperature reaction 1h.Then gained SBA-15-Cl in 0.5g step (2) is added, under nitrogen protection, 70 DEG C of oil bath reaction 60h.Be cooled to room temperature after reaction terminates, add 25mL1mol/LHCl, continue to stir 10min, filter afterwards, and respectively washing 3 times with methyl alcohol and acetone successively, ambient temperature in vacuum is dry, obtains the SBA-15 (SBA-15-RAFT) that surperficial reversible addion-fragmentation chain transfer agent is modified.
(4) 0.15gSBA-15-RAFT is got, 0.383mmol cerous nitrate (Ce (III)), 1.532mmol4-vinyl pyridine (4-VP), 1.9921mmol Ethylene glycol dimethacrylate (EGDMA) and 10mg Diisopropyl azodicarboxylate (AIBN) mixing are added in the mixing solutions of 25mL methanol-water.And this mixing solutions is placed in 60 DEG C of oil baths, and under nitrogen protection, reaction 24h.5 times are respectively washed with methyl alcohol, deionized water successively after reaction, to remove the template ion (Ce (III)) of unreacted monomer 4-vinylpridine, initiator Diisopropyl azodicarboxylate and non-trace, vacuum-drying at 60 DEG C, then template ion is washed away with 1000mLmol/L hydrochloric acid, and be washed till neutrality with deionized water, then vacuum-drying obtains mesoporous material surface ion imprinted polymer at 60 DEG C.
(5) the dynamic adsorption experimental apparatus of self-control is selected, first the 0.1g ion imprinted polymer that the present invention obtains is loaded ready dynamic adsorption post, then adsorption unit 10 ~ 30min is passed through with the deionized water of pH5.0, its object is to get rid of the influence factor outside experiment, thus reduce experimental error.Finally by control loading flow velocity, by the solution for preparing by adsorption column, and connect effluent liquid continuously with 5mL tool plug centrifuge tube, survey its concentration in conjunction with ICP-AES;
(6) dynamic adsorption laboratory method is to the research of cerium ion separation condition in the aqueous solution
Choose temperature, sample concentration and loading flow velocity as influence factor, with cerium ion saturated extent of adsorption for evaluation index response value, determine temperature 25 ~ 45 DEG C, cerium ion concentration at 3 ~ 8mg/L, flow velocity is 1.5 ~ 3.5mL/min, by analyze obtain Optimum separation condition.
Result shows, and optimal separation temperature is 25 DEG C, and loading flow velocity is 1.5mL/min, and cerium ion concentration is 5mg/L, and separating effect is best, and equilibrium adsorption capacity reaches 21.2mg/g.
(7) dynamic adsorption laboratory method is to the research of cerium ion selective separation in the aqueous solution
Under Optimum separation condition, choose Ce (III) and Fe (III), Ca (II), the competitive adsorption of binary system that Zn (II), Sr (II) mix, be 5.0 by dilute hydrochloric acid or weak ammonia adjust ph, then according to step (5), research ion imprinted polymer and non-imprinted polymer adsorb the dynamic competition of each binary solution respectively.The concentration ICP-AES of the Ce (III) in connect solution and other competitive adsorption ion is measured, calculates loading capacity according to result.
The mesopore surfaces ion imprinted polymer that result shows the present invention's acquisition shows good selectivity to Ce (III), wherein Ce (III) is respectively 3.13 relative to the selectivity coefficient of competitive adsorption ion Fe (III), Ca (II), Zn (II), Sr (II), 9.81,11.91 and 12.96.
Claims (6)
1. a preparation method for selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer, is characterized in that, carries out according to the following steps:
(1) get sequential silicon-based mesoporous material SBA-15 and be placed in round-bottomed flask, adding concentration is 3mol/L hydrochloric acid, and backflow 24h, then filters, and with secondary deionized water repetitive scrubbing to neutral, takes out after 80 DEG C of vacuum-drying 6h;
(2) SBA-15 and 4-(chloromethyl) phenyltrimethoxysila,e processed in step (1) is joined in toluene solution successively, and this mixing solutions is placed in 90 DEG C of oil baths, under nitrogen protection, magnetic agitation 24h, after reaction, product is respectively washed 5 times with toluene, methyl alcohol successively, with the unreacted 4-of wash-out (chloromethyl) phenyltrimethoxysila,e and toluene, at room temperature vacuum-drying, the mesoporous material SBA-15-Cl of obtained chlorine functionalization;
(3) join in there-necked flask by phenylmagnesium bromide solution, oil bath is preheated to 40 ~ 60 DEG C, under nitrogen protection, dropwise adds dry dithiocarbonic anhydride, under nitrogen protection, maintains oil bath temperature 40-60 DEG C reaction 1h; Then gained SBA-15-Cl in step (2) is added, under nitrogen protection, 70 DEG C of oil bath reaction 60h; Be cooled to room temperature after reaction terminates, add the hydrochloric acid that concentration is 1mol/L, continue stirring 5 ~ 10min, filter afterwards, and respectively wash 3 times with methyl alcohol and acetone successively, ambient temperature in vacuum is dry, obtain the SBA-15 that surperficial reversible addion-fragmentation chain transfer agent is modified, i.e. SBA-15-RAFT;
(4) by the SBA-15-RAFT in step (3), cerous nitrate, 4-vinylpridine, Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate mixing are added in the mixed solution of first alcohol and water; And this mixing solutions is placed in 60 DEG C of oil baths, and under nitrogen protection, reaction 24h; 5 times are respectively washed with methyl alcohol, deionized water successively after reaction, to remove the template ion cerium ion of unreacted monomer 4-vinylpridine, initiator Diisopropyl azodicarboxylate and non-trace, vacuum-drying at 60 DEG C, then 250 ~ 1000mL concentration is used to be that 2mol/L hydrochloric acid washes away template ion, and be washed till neutrality with deionized water, then vacuum-drying obtains mesoporous material surface ion imprinted polymer at 60 DEG C.
2. the preparation method of a kind of selectivity according to claim 1 dynamic Solid-Phase Extraction cerium ion imprinted polymer, is characterized in that, the massfraction of the SBA-15 described in step (1) is 0.15 ~ 1.5%.
3. the preparation method of a kind of selectivity according to claim 1 dynamic Solid-Phase Extraction cerium ion imprinted polymer, it is characterized in that, the ratio of SBA-15,4-(chloromethyl) phenyltrimethoxysila,e described in step (2) and toluene solution is 1g:1mL:40mL.
4. the preparation method of a kind of selectivity according to claim 1 dynamic Solid-Phase Extraction cerium ion imprinted polymer, it is characterized in that, the phenylmagnesium bromide solution described in step (3) is that phenyl-magnesium-bromide is present in the solution in super dry tetrahydrofuran with the concentration of 1.0mol/L; The volume ratio of the described dithiocarbonic anhydride that adds and phenylmagnesium bromide solution is 1:16; The amount of the described SBA-15-Cl added is 0.125-0.5g; The amount adding hydrochloric acid is 12.5 ~ 25mL.
5. the preparation method of a kind of selectivity according to claim 1 dynamic Solid-Phase Extraction cerium ion imprinted polymer, it is characterized in that, in the mixed solution of first alcohol and water described in step (4), the volume ratio of methyl alcohol and water is 4:1, the massfraction of described SBA-15-RAFT is 0.23 ~ 0.7%, the concentration of cerium ion is 5 ~ 15mmol/L, the concentration of the concentration of 4-VP to be the concentration of 20 ~ 60mmol/L, EGDMA be 26 ~ 78mmol/L, AIBN is 0.6 ~ 2.5mmol/L.
6. the preparation method of a kind of selectivity according to claim 1 dynamic Solid-Phase Extraction cerium ion imprinted polymer, is characterized in that, prepared selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer is applied to the cerium ion in the fractionation by adsorption aqueous solution.
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