CN103172513A - Uranyl ion imprinted polymer and preparation method and application thereof - Google Patents

Uranyl ion imprinted polymer and preparation method and application thereof Download PDF

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CN103172513A
CN103172513A CN2013100934187A CN201310093418A CN103172513A CN 103172513 A CN103172513 A CN 103172513A CN 2013100934187 A CN2013100934187 A CN 2013100934187A CN 201310093418 A CN201310093418 A CN 201310093418A CN 103172513 A CN103172513 A CN 103172513A
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uranyl
imprinted polymer
uranyl ion
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CN103172513B (en
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沈兴海
张红娟
陈庆德
梁和乐
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Peking University
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Abstract

The invention discloses a uranyl ion imprinted polymer and a preparation method and application thereof. The uranyl ion imprinted polymer is prepared by the steps of with a uranyl ion as a template and beta-diketone modified with acryloyl group or methacryloyl as a functional monomer, carrying out polymerization reaction under the actions of an initiator and a cross-linking agent, and removing the template uranyl ion from the obtained polymer after the reaction is ended. The imprinted polymer can compete to absorb uranyl ions from uranyl ammonium carbonate containing a lot of free carbonates, is high in adsorption capacity, and is not interfered by metal ions such as Li<+>, Na<+>, K<+> and Rb<+>. Therefore, the imprinted polymer can be used for adsorbing and extracting uranium form sea water with complicated ingredients and low uranium concentration.

Description

A kind of uranyl ion imprinted polymer and preparation method thereof and application
Technical field
The present invention relates to a kind of uranyl ion imprinted polymer and preparation method thereof and application.
Background technology
Uranium is a kind of topmost nuclear fuel in present Nuclear energy uses, and it exploits, extracts, separates great for the further Significance of Sustainable Development of nuclear energy.The mean concns of URANIUM IN SEAWATER is 3.3 μ g/L, approximately has 1.386 * 10 on the earth 14Ten thousand tons of seawater, the uranium resources in seawater has more than 40 hundred million tons (uranium is with UO 2(CO 3) 3 4-Form exists), be land more than 800 times of proven reserve.Extract efficiently, at an easy rate uranium from seawater, the Sustainable development of nuclear energy is significant.Ion imprinted polymer (Ionic Imprinted Polymer, IIP) enrichment that is used for metal ion with separate the action site with two obvious characteristics: the one, IIP template ion had very strong binding ability, can the very micro-object ion of enrichment; The 2nd, IIP can be under the condition that a large amount of interfering ions exist, highly selective enrichment and separate target metal ion.The These characteristics of IIP makes it to be expected to very micro-uranium is extracted from form complicated seawater efficiently.
The ion blotting technology is to mate experiment technology of preparing with the polymkeric substance of its selective adsorption for obtaining on space structure and binding site fully with a certain template ion.Ion imprinted polymer is used for the research of uranium extraction from seawater and reports relatively less.Singh seminar (Singh, D.K.; Mishra, S.Anal.Chim.Acta2009,644,42) utilize salicylaldoxime (SALO), 4-vinylpridine (4-VP), uranyl ion (UO 2 2+) form ternary complex, then prepare imprinted polymer with linking agent methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA) by organic method copolymerization, with UO 2 2+The maximum adsorption capacity of the IIP that obtains after wash-out is 559 μ mol/g, can be from Th 4+, Cu 2+, Co 2+, Ni 2+, Zn 2+And CrO 4 2-In the aqueous solution that coexists Deng interfering ion with UO 2 2+Enrichment out quantitatively.This synthetic imprinted polymer material loading capacity is high, and the rate of recovery of URANIUM IN SEAWATER reaches more than 95%, but best pH scope is 3.5～6.5.In addition, (Shamsipur, the M. such as Shamsipur; Fasihi, J.; Ashtari, K.Anal Chem2007,79,7116) with the polymerization process of inorganic polymer grafting, synthesized the uranyl ion imprinted polymer take methacrylic acid as function monomer, wash-out UO 2 2+After the maximum adsorption capacity of the IIP that obtains be 52.9 μ mol/g, can be from Fe 3+, Th 4+Deng with UO 2 2+In the aqueous solution of strong competitive adsorption interfering ion with UO 2 2+Enrichment out quantitatively.This IIP is very high in the rate of recovery of URANIUM IN SEAWATER, but its optimal ph is 3.0.Say seminar (Say, R.; Erosz, A.; Denizli, A.Separ Sci Technol2003,38,3431) pass through UO 2 2+Form complex compound with the methacryloyl Histidine, then itself and EGDMA copolymerization are obtained for UO 2 2+IIP.This IIP can contain Th 4+, Fe 3+Or Mn 2+Deng in the aqueous solution of interfering ion to UO 2 2+Carry out optionally enrichment; Optimal ph is 3.5.Other seminars have also synthesized with similar method can selective enrichment UO 2 2+IIP, the function monomer of wherein using has vinyl benzoic acid, β-chloroacrylic acid and Diethyl Allylnime etc.But above-mentioned IIP is to UO 2 2+The best pH scope of selective enrichment is not all in the pH of seawater scope (7.5-8.5).
Optimal pH scope and the seawater pH scope of the ion imprinted polymer for preparing as function monomer with piroxicam (Pir), succsinic acid (SA), DCQ and HEMA and 4-VP approach, but their loading capacity is not high, and the rate of recovery of URANIUM IN SEAWATER is low, can not extract well uranium (Metilda, P. from seawater; Gladis, J.M.; Venkateswaran, G.; Rao, T.P.Anal Chim Acta2007,587,263).Therefore, present ion imprinted polymer can adsorb the uranium of trace from seawater, but it will realize the industrial applications of uranium extraction from seawater, also need to solve the loading capacity of ion imprinted polymer and the problem of the URANIUM IN SEAWATER rate of recovery, and seek suitable function monomer and make its optimal pH in seawater pH scope, to reach the optimal adsorption effect.
Be that under 1～4 acidic conditions, the uranium in the aqueous solution is with UO in the pH value 2 2+The form stable existence; And when the pH value was higher, uranyl ion can be hydrolyzed and generate UO 2OH +, (UO 2) 2(OH) 2 2+Or (UO 2) 3(OH) 5+In oxyhydroxide and unstable (Anirudhan, T.S.; Radhakrishnan, P.G.J Environ Radioactiv2009,100,250), thereby affect ion imprinted polymer to the concentration and separation of uranyl ion.Energy and UO 2 2+The ligand species of complexing is a lot, and different ligands and UO 2 2+The pH scope of complexing is different, therefore the selection of part is most important.Therefore, filter out in weakly alkaline (pH7.5～9.0) scope and UO 2 2+The part of complexing, and prepare the ion imprinted polymer of high efficiency extraction uranium in weakly alkaline (pH7.5～9.0) scope accordingly, significant for the extraction of URANIUM IN SEAWATER.
Summary of the invention
The purpose of this invention is to provide a kind of uranyl ion imprinted polymer and preparation method thereof.
Uranyl ion imprinted polymer provided by the present invention is that compound is function monomer take uranyl ion as template, shown in formula I, carry out polyreaction under the effect of initiator and linking agent, remove the template uranyl ion in resulting polymers after reaction finishes, namely obtain the uranyl ion imprinted polymer.
Figure BDA00002951161900021
(formula I)
In described formula I, R 1, R 2Identical or different, all be independently selected from any one in following radicals: C1-C6 alkyl and thienyl that phenyl, C1-C6 alkyl, halogen replace;
R is hydrogen or methyl.
Described uranyl ion specifically can be provided by the solubility uranyl salt, as uranyl nitrate, uranyl chloride, perchloric acid uranyl etc.
Described linking agent specifically can be the compound that contains two and two above carbon-carbon double bonds, as ethylene glycol dimethacrylate (EGDMA), Vinylstyrene, pentaerythritol acrylate trimethyl, N, N '-methylene-bisacrylamide etc.
Described initiator (for example: benzoyl peroxide), persulphate specifically can be Diisopropyl azodicarboxylate (AIBN), organo-peroxide.
The mol ratio of the compound shown in described uranyl ion, formula I, linking agent and initiator is 1: (2～4): (12～20): (0.05～0.15); Further can be 1: (2～4): 16: 0.12.
Described polyreaction is carried out under oxygen free condition, and temperature of reaction is 60～90 ℃, specifically can be 70 ℃, and the reaction times was more than 12 hours, as 24 hours.
Described polymer reaction carries out in organic solvent.This organic solvent also can play pore-creating agent simultaneously.Described organic solvent specifically can be selected from following at least a: Isosorbide-5-Nitrae-oxygen six rings, 2-methyl cellosolve, methyl alcohol, tetrahydrofuran (THF), acetic acid, ethylene dichloride, DMF and toluene.
Prepare the method for described uranyl ion imprinted polymer, specifically comprise the steps:
1) compound shown in formula I and solubility uranyl salt are dissolved in organic solvent, then add linking agent and initiator, carry out polyreaction under oxygen free condition, obtain polymer solids;
2) described polymer solids is ground, with the hydrochloric acid soln washing, remove the template uranyl ion, wash away residual organism with acetone again, wash at last to neutrality drying with water, sieving out particle diameter is 80～200 purpose polymers solid particulates, is the uranyl ion imprinted polymer.
Another object of the present invention is to provide the application of above-mentioned uranyl ion imprinted polymer.
The application of uranyl ion imprinted polymer provided by the present invention is that it adsorbs uranyl ion from contain the uranyl deionized water solution.
Also can contain Li described containing in the uranyl deionized water solution +, Na +, K +And Rb +Deng metal ion.
The described uranyl deionized water solution that contains is weakly alkaline, and its pH value is 7.5～9.0.
The described uranyl deionized water solution that contains specifically can be seawater, and it is pH value 7.5-8.5.
The beta-diketon function monomer that acryl shown in above-mentioned formula I or methacryloyl are modified also belongs to protection scope of the present invention.
The preparation method of this function monomer comprises the steps:
1) beta-diketon shown in formula II and N-bromo-succinimide are reacted, obtain the compound shown in formula III;
Figure BDA00002951161900031
(formula II) (formula III)
Wherein, R in formula II, formula III 1, R 2Definition cotype I;
2) under triethylamine exists, compound shown in formula III and acrylic or methacrylic acid are reacted, reaction removes by filter triethylamine salt after finishing, and obtains the function monomer shown in formula I.
The mol ratio of the beta-diketon shown in formula II wherein, step 1) and N-bromo-succinimide is 1: 1.Step 1) described reaction is carried out in methylene dichloride.
The molar ratio of compound shown in formula III step 2), acrylic or methacrylic acid, triethylamine is 1: 1.2: 1.2.
The diphenylpropane-1,3-dione(DPPO) that the present invention modifies take acryl or methacryloyl is as function monomer, itself and template UO 2 2+Form complex compound under proper condition and realize self-assembly; Then add linking agent, cause copolymerzation with cross-linking, obtain cross-linked polymer, the wash-out template ion obtains for UO 2 2+Ion imprinted polymer.This ion imprinted polymer can be from the uranyl ammonium carbonate that contains a large amount of uncombined carbon acid groups the competitive adsorption uranyl ion, loading capacity is high, and can be from Li +, Na +, K +, Rb +Deng selective adsorption UO in metal ion 2 2+Therefore, this imprinted polymer can be used for adsorbing and extracting uranium from complicated component, seawater that uranium concentration is low.
Description of drawings
Fig. 1 is the chemical reaction flow process figure of the methacrylic acid (1,3-phenylbenzene-1,3-dicarbapentaborane)-2-propyl ester function monomer of embodiment 1 preparation.
Fig. 2 is the synthetic schematic diagram of the uranyl ion imprinted polymer of embodiment 1 preparation.
Fig. 3 is the ion imprinted polymer adsorption effect comparison diagram of the different proportionings of embodiment 1 preparation.
Fig. 4 is the wash-out of embodiment 1 preparation, the infrared analysis figure of wash-out IIP2 and CP2 not.
Fig. 5 is the thermogravimetric analysis figure of DBM-MAA function monomer, IIP2 and the CP2 of embodiment 1 preparation.
Fig. 6 is the IIP2 of embodiment 1 preparation and the curve of adsorption kinetics of CP2.
Fig. 7 is the IIP2 of embodiment 1 preparation and the loading capacity curve of CP2.
Fig. 8 is the loading capacity curve of IIP2 under differing temps of embodiment 1 preparation.
Fig. 9 is the reusing of the uranyl ion imprinted polymer (IIP2) of embodiment 1 preparation.
Figure 10 is the IPM of embodiment 3 preparations and the loading capacity curve of CPM.
Figure 11 is the reusing of the uranyl ion imprinted polymer (IPM) of embodiment 3 preparations.
Embodiment
The present invention will be described below by specific embodiment, but the present invention is not limited thereto.
Experimental technique described in following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Concentration to uranium in the aqueous solution and other ion in following embodiment detects with inductively coupled plasma atomic emission spectrometry (ICP-AES).U, Li, Na, the operation wavelength of K and Rb is respectively 393.202nm, 610.364nm, 589.592nm, 766.491nm and 780.027nm.
The related key instrument of following embodiment is as follows: ASAP2010 specific surface pore distribution determinator (MICROMETER); Q600SDT TGA-DTA-DSC Simultaneous Determination instrument (U.S. Thermal Analysis company); ARX400 nuclear magnetic resonance spectrometer (400MHZ, Switzerland Bruker company); Elementar Vario EL (Germany); Nicolet iN10 MX FT-IR (U.S. Thermo-Fischer company).
Synthesizing of embodiment 1, uranyl ion imprinted polymer
1, the synthetic and sign of the methacrylic acid shown in formula I-1 (1,3-phenylbenzene-1,3-dicarbapentaborane)-2-propyl ester function monomer
Figure BDA00002951161900051
(formula I-1)
Diphenylpropane-1,3-dione(DPPO) (4.48g, 20mmol) and N-bromo-succinimide (NBS, 3.56g, 20mmol) stirring reaction in the 30mL methylene dichloride, then the sherwood oil recrystallization obtains the bromo diphenylpropane-1,3-dione(DPPO).Methacrylic acid and triethylamine react 3h in acetone (wherein molar ratio is n (bromo diphenylpropane-1,3-dione(DPPO)): n (triethylamine): n (methacrylic acid)=1: 1.2: 1.2), the methacrylic acid group and the bromo diphenylpropane-1,3-dione(DPPO) generation esterification that form, (v/v=5: 3) purify and obtain methacrylic acid (1 by recrystallization through ether-sherwood oil for thick product, the sterling of 3-phenylbenzene-1,3-dicarbapentaborane)-2-propyl ester function monomer.Chemical reaction flow process figure as shown in Figure 1.
Structural identification is as follows:
The nmr analysis result is: δ H(400MHZ, CDCl 3, Me 4Si) 1.98 (s, 3H, CH 3), 5.69 (s, 1H, C=CH), 6.24 (s, 1H, C=CH), 7.01 (s, 1H, CHO), 7.45-7.49 (d, 4H, ArH), 7.57-7.61 (d, 2H, ArH), 8.06-8.08 (t, 4H, ArH).Results of elemental analyses is C:74.03%; (theoretical value is C:74.03% to H:5.23%; H:5.19%).
Really be target compound methacrylic acid (1,3-phenylbenzene-1,3-dicarbapentaborane)-2-propyl ester through the compound that Structural Identification synthesized.
2, UO 2 2+-IIP's is synthetic
Take Isosorbide-5-Nitrae-dioxane as pore-creating agent, with uranyl nitrate (template uranyl ion) and methacrylic acid (1,3-phenylbenzene-1,3-dicarbapentaborane)-2-propyl ester function monomer is dissolved in Isosorbide-5-Nitrae-oxygen six rings, then add linking agent EGDMA and initiator A IBN, stirring and dissolving.Pass into high pure nitrogen 30min deoxygenation, polyreaction is 24 hours in 70 ℃ of waters bath with thermostatic control, obtains bulk polymer, and the preparation formula sees Table 1.Bulk polymer is ground to form particulate, with the HCl solution washing of 0.05mol/L 24 hours, to remove the template uranyl ion, wash away residual organism with acetone again, wash with water at last to neutrality, dry in 70 ℃ of vacuum drying ovens, sieve out the polymer solid particles of 80～200 order sizes, namely obtain can be used for adsorbing the imprinted polymer of uranyl ion.Do not add the template uranyl ion, synthetic non-imprinted polymer (Control Polymer, CP) under identical experiment condition.Its building-up process as shown in Figure 2.
The preparation formula of table 1 uranyl ion imprinted polymer (IIPs) and non-imprinted polymer (CPs)
Figure BDA00002951161900052
Figure BDA00002951161900061
The uranyl ion imprinted polymer UO of embodiment 2, embodiment 1 preparation 2 2+The absorption property of-IIP
1, the preparation of uranyl ammonium carbonate mother liquor
The sal volatile of 100mL 6mM dropwise adds 100mL 2mM uranyl nitrate solution, solution turned yellow in stirring.Add again the sal volatile of 44mL 0.1M after dripping, after continuing to stir, namely make the uranyl ammonium carbonate mother liquor.Contain excessive volatile salt in this mother liquor, its pH is 9; Dilute with water, its pH value is substantially constant.The concentration that ICP records uranium in the uranyl ammonium carbonate mother liquor is 200ppm.
2, the absorption property of imprinted polymer
Uranyl ion imprinted polymer (UO 2 2+-IIP) the main experimentation of adsorption uranium is as follows: taking the uranyl ion imprinted polymer solid of 10mg, is vibration absorption uranyl ion in the uranyl carbonate ammonium solution of 2～20 μ g/mL at the 10mL uranium concentration.After vibration finished, the centrifuging and taking supernatant liquid was surveyed the concentration of residue uranium in the rear solution of absorption with ICP-AES.The wash-out uranyl ion but absorption post polymerization thing vibrates in the HCl of 10mL 0.01M solution.
The adsorptive capacity of ion imprinted polymer can be calculated and get with following this formula:
Q＝(c 0-c e)V/m
Wherein, Q is the adsorptive capacity (mg/g) of ion imprinted polymer; c 0Initial uranium concentration (mg/L) for adsorption liquid; c eFor adsorbing the residue uranium concentration (mg/L) of the rear upper strata stillness of night; V is the volume (L) of adsorption liquid; M is the quality (g) of polymkeric substance.
3, result
3.1 the ion imprinted polymer adsorption effect contrast that different proportionings are synthetic
Will be respectively according to the template uranyl ion: the function monomer mol ratio be 1: 2, the uranyl ion imprinted polymer of 1: 3 and 1: 4 preparation and corresponding non-imprinted polymer carry out the absorption property test according to the method under 2, and (actual conditions is: the 10mg polymer solids, 10mL12ppm uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibration 9h).Adsorption effect as shown in Figure 3.
As can be seen from Figure 3, the synthetic imprinted polymer of these three kinds of proportionings can be from the uranyl carbonate ammonium solution competitive adsorption uranyl ion.Wherein, n (uranyl ion): n (function monomer) is that the adsorptive capacity of 1: 3 synthetic IIP2 is the highest, and imprinted polymer IIP2 improves at most for the adsorptive capacity of corresponding non-imprinted polymer CP2, and its trace effect is better than the synthetic imprinted polymer of other proportioning.Therefore, selecting n (uranyl ion): n (function monomer) is that 1: 3 synthetic ion imprinted polymer (IIP2) is furtherd investigate.
3.2 the phenetic analysis of IIP2 and CP2
3.2.1 Fourier transform infrared spectroscopy (FT-IR) is analyzed
Wash-out (IIP2) and not the ion imprinted polymer of wash-out (unleached IIP2) and non-imprinted polymer (CP2) infrared spectra as shown in Figure 4.
As can be seen from Figure 4, the main infrared absorption peak of three kinds of polymkeric substance is basic identical, and this is because the content of linking agent EGDMA in polymkeric substance is very high.Be 1728cm in wave number -1The strong absorption peak at place is the stretching vibration peak of carbonyl in EGDMA, another one 1153cm -1Absorption peak be the stretching vibration peak of C-O key in EGDMA.At 1637cm -1The stretching vibration peak of the C=C of place disappears substantially, and this is crosslinking reaction to have occured and primitive reaction is complete due to two keys in polymerization process.In the imprinted polymer of wash-out not, at 920cm -1There is a small peak at the place, and this is the stretching vibration peak of uranyl ion; Disappear in the imprinted polymer of this peak after wash-out.
3.2.2 thermogravimetric analysis
The thermogravimetric analysis curve of methacrylic acid (1,3-phenylbenzene-1,3-dicarbapentaborane)-2-propyl ester function monomer (DBM-MAA), uranyl ion imprinted polymer (IIP2) and non-imprinted polymer (CP2) as shown in Figure 5.
As can be seen from Figure 5, function monomer (DBM-MAA) decomposes in the time of 160～400 ℃ fully substantially; Uranyl ion imprinted polymer (IIP2) is 200～450 ℃ of decomposition; Non-imprinted polymer (CP2) begins to decompose at 250 ℃, and 470 ℃ are decomposed fully.Function monomer and linking agent in trace or non-imprinted polymer have been cross-linked to form network structure, and the heat that decomposition needs is than the height of monomer.The decomposition starting temperature of non-imprinted polymer is higher than imprinted polymer, this is due to metal ion and function monomer coordination, to can stay imprinted sites after the template ion wash-out in imprinted polymer, the duct of imprinted polymer is opened, structure is more loose with respect to non-imprinted polymer, heat transfer between solid is better, begins to decompose in lower temperature.
3.2.3 BET analyzes
The BET analytical results of IIP2 and CP2 is listed in table 2.As can be seen from Table 2, the BET surface-area of uranyl ion imprinted polymer is obviously large than non-imprinted polymer.
The BET analytical results of table 2 IIP2 and CP2
Figure BDA00002951161900071
3.3 kinetics of adsorption
Will be according to the template uranyl ion: the function monomer mol ratio be that the uranyl ion imprinted polymer (IIP2) of preparation in 1: 3 and corresponding non-imprinted polymer (CP2) carry out the kinetics of adsorption test according to the method under 2 (actual conditions is: the 10mg polymer solids, 10mL 20ppm uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibrations).UO 2 2+-IIP2 curve of adsorption kinetics, namely adsorptive capacity Q in time t change curve as shown in Figure 6.
As can be seen from Figure 6, the adsorptive capacity Q of uranyl ion imprinted polymer t in time increases, and progressively reaches a platform, and namely polymkeric substance reaches adsorption equilibrium.According to the curve of adsorption kinetics of intending second-order kinetic equation match polymkeric substance, wherein:
The plan second-order kinetic equation is:
t/Q t＝1/(k 2Q max 2)+t/Q max
The fit equation supplemental characteristic of uranyl ion trace and non-imprinted polymer is listed in table 3.The curve correlation coefficient R that table 3 is listed 2Absorption maximum value Q with curve calculation maxQ with the experiment gained maxMatching degree show that all the kinetics of adsorption process of uranyl ion imprinted polymer satisfy to intend the second-order kinetics model.
Table 3 IIP2 and CP2 absorption UO 2 2+The kinetic parameter of plan secondary rate process
Figure BDA00002951161900081
3.4 loading capacity
Will be according to the template uranyl ion: the function monomer mol ratio be that the uranyl ion imprinted polymer (IIP2) of preparation in 1: 3 and corresponding non-imprinted polymer (CP2) carry out capacity indicator according to the method under 2 (actual conditions is: the 10mg polymer solids, 10mL uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibration 9h).The loading capacity curve of IIP2 and CP2 as shown in Figure 7.
As can be seen from Figure 7, the adsorptive capacity Q of uranyl ion trace and non-imprinted polymer increases with uranyl ammonium carbonate adsorption liquid concentration c, reaches at last a platform, the absorption that namely reaches capacity, and its maximum adsorption capacity is 10.1mg/g.Fig. 8 is the loading capacity curve of uranyl ion imprinted polymer (IIP2) under differing temps.The loading capacity of uranyl ion imprinted polymer increases with the rising of temperature T, and this explanation uranyl ion imprinted polymer competitive adsorption uranyl ion from uranyl ammonium carbonate is an endothermic process, and it is chemisorption.
Langmuir adsorption isotherm equation is:
Q e＝Q m?c e/(K d+c e)
In formula: Q eAnd c eIt is respectively the equilibrium concentration of equilibrium adsorption capacity and the solution of polymkeric substance; Q mBe theoretical maximal absorptive capacity; K dDissociation constant during for adsorption equilibrium.
The loading capacity curve of Langmuir isothermal adsorpting equation match IIP2 under differing temps, the match value of each parameter of equation is listed in table 4.The adsorption process of IIP2 meets the Langmuir isothermal adsorption.
The parameter of each temperature of table 4 Langmuir equation model IIP2 absorption uranyl ion
3.5 adsorption selectivity
Will be according to the template uranyl ion: the function monomer mol ratio be that the uranyl ion imprinted polymer (IIP2) of preparation in 1: 3 and corresponding non-imprinted polymer (CP2) carry out the adsorption selectivity test according to the method under 2 (actual conditions is: 100 μ g metal ions, 0.01g polymer solids, 10mL 10ppm uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibration 9h).
Uranyl ion imprinted polymer (IIP2) listed by table 5 and non-imprinted polymer (CP2) is adsorbing UO 2 2+In process with seawater in the result of content some metal ion competitive adsorption of Duoing than uranium.Wherein:
Partition ratio D=c p/ c e, c wherein pPolymer adsorption UO during for balance 2 2+Concentration, c eRemaining UO in solution during for balance 2 2+Concentration.
Select coefficient S U/M=D U/ D M
The trace COEFFICIENT K '=S Imprinted/ S Non-imprinted
As can be seen from Table 5, synthetic uranyl ion imprinted polymer can be from Li +, Na +, K +, Rb +Adsorption uranium optionally in plasma.IIP2 selective adsorption uranyl ion well from these monovalent metallic ions, and have good trace effect.Contain a large amount of free carbonates in the uranyl carbonate ammonium solution, common divalent-metal ion is as Mg 2+, Ca 2+, Cu 2+, Sr 2+And Ba 2+Can form carbonate deposition with carbonate Deng metal ion, and can not exert an influence to the absorption property of uranyl ion trace polymerization.The adsorption site of ion imprinted polymer is specific, can optionally adsorb metallic print ion.
The adsorption selectivity of table 5 uranyl ion trace and non-imprinted polymer
Figure BDA00002951161900092
3.6 reusing
The uranyl ion imprinted polymer is used the ion of the hydrochloric acid wash-out absorption of 0.01M after the absorption uranyl ion, and be recycled and reused for and adsorb uranyl ion from the aqueous solution, thus the reusing of examination ion imprinted polymer.
Each experimentation all carries out according to the method under 2, and actual conditions is: 10mg imprinted polymer solid, 10mL 10ppm uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibration 9h.3 times of uranyl ion imprinted polymer (IIP2) circulations to the adsorption rate of uranium as shown in Figure 9.
As can be seen from Figure 9, after recycling through 3 times, ion imprinted polymer still can keep higher adsorptive capacity to the adsorptive power of uranyl ion, and its recycling performance is good.
Modify diphenylpropane-1,3-dione(DPPO) by methacryloyl, then be linked in polymer network, it is not lost in elution process, guarantee its reusing.With the synthetic ion imprinted polymer of this function monomer can be from the uranyl ammonium carbonate that contains a large amount of uncombined carbon acid groups the competitive adsorption uranyl ion, its maximum adsorption capacity at 25 ℃ is 10.1mg/g, and can be from Li +, Na +, K +, Rb +Deng selective adsorption UO in metal ion 2 2+Therefore, this imprinted polymer can be used for adsorbing and extracting uranium from the low seawater of complicated component uranium concentration.
Synthetic and the absorption property of embodiment 3, uranyl ion imprinted polymer
1, the synthetic and sign of the methacrylic acid shown in formula I-2 (2,4-dicarbapentaborane)-3-pentyl ester function monomer
Figure BDA00002951161900101
Methyl ethyl diketone (2.00g, 20mmol) and N-bromo-succinimide (NBS, 3.56g, 20mmol) stirring reaction in the 30mL methylene dichloride, synthetic 3-bromo-2,4-diacetylmethane.(wherein molar ratio is n (3-bromo-2 to the methacrylic acid group generation esterification stirring at room reaction 3h that forms with triethylamine and methacrylic acid, the 4-diacetylmethane): n (triethylamine): n (methacrylic acid)=1: 1.2: 1.2), reaction removes by filter the by product triethylamine salt after finishing, the thick product that obtains obtains methacrylic acid (2,4-dicarbapentaborane)-3-pentyl ester monomer through the column chromatography separating-purifying.
Structural identification is as follows:
The nmr analysis result is: δ H(300MHZ, CDCl 3, Me 4Si) 2.02 (s, 3H, CH 3), 2.34 (s, 6H, CH 3), 5.76 (s, 1H, C=CH), 6.32 (s, 1H, C=CH), 5.55 (s, 1H, CHO).Results of elemental analyses is C:57.90%; (theoretical value is C:58.69% to H:6.54%; H:6.57%).Molecular ion peak m/z=207.06249 in high resolution mass spectrum is C 9H 12O 4The peak of+Na.
Really be target compound methacrylic acid (2,4-dicarbapentaborane)-3-pentyl ester through the compound that Structural Identification synthesized.
2, UO 2 2+-IIP's is synthetic
Take uranyl ion as template, the methyl ethyl diketone methacrylic ester as function monomer, ethylene glycol dimethacrylate as linking agent and Diisopropyl azodicarboxylate be initiator (n (UO wherein 2 2+): n (methacrylic acid (2, the 4-carbonyl)-3-pentyl ester): n (ethylene glycol dimethacrylate): n (Diisopropyl azodicarboxylate)=1: 3: 16: 0.12) at 10mL pore-creating agent 1, carry out mass polymerization in the 4-dioxane, obtain polymkeric substance.The solid that thermopolymerization generates is through grinding, the template uranyl ion in hydrochloric acid wash-out polymkeric substance, and acetone washes away residual organism, and sieves out the solid particulate of 80-200 order size, namely obtains the imprinted polymer of uranyl ion.
The uranyl ion imprinted polymer (IPM) of above-mentioned preparation and corresponding non-imprinted polymer (CPM) are carried out capacity indicator according to the method under in embodiment 22, and (actual conditions is: the 10mg polymer solids, 10mL uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibration 9h).The loading capacity curve of IPM and CPM as shown in figure 10.
As can be seen from Figure 10, the loading capacity of uranyl ion imprinted polymer can reach 15.3mg/g.
The maximal absorptive capacity of table 6 ion blotting/non-imprinted polymer
Figure BDA00002951161900111
Investigate the reusing of uranyl ion imprinted polymer (IPM).Experimentation all carries out according to the method under in embodiment 22, and actual conditions is: 10mg imprinted polymer solid, 10mL20ppm uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibration 9h.5 times of uranyl ion imprinted polymer (IPM) circulations to the adsorption rate of uranium as shown in figure 11.
As can be seen from Figure 11, after recycling through 5 times, ion imprinted polymer still can keep more than 80% the loading capacity of uranyl ion, and its recycling performance is good.
Synthetic and the absorption property of embodiment 4, uranyl ion imprinted polymer
1, the synthetic and sign of the methacrylic acid shown in formula I-3 (1-phenyl-1,3-dicarbapentaborane)-2-butyl ester function monomer
Figure BDA00002951161900112
Benzoyl acetone (3.24g, 20mmol) and N-bromo-succinimide (NBS, 3.56g, 20mmol) stirring reaction in the 30mL methylene dichloride, synthetic 1-bromobenzene formyl acetone.(wherein molar ratio is n (1-bromobenzene formyl acetone): n (triethylamine): n (methacrylic acid)=1: 1.2: 1.2) with methacrylic acid stirring at room reaction 3h under the triethylamine condition, reaction removes by filter the by product triethylamine salt after finishing, the thick product that obtains obtains methacrylic acid (1-phenyl-1,3-dicarbapentaborane)-2-butyl ester monomer through the column chromatography separating-purifying.
Structural identification is as follows:
The nmr analysis result is: δ H(300MHZ, CDCl 3, Me 4Si) 2.01 (s, 3H, CH 3), 2.77 (s, 3H, CH 3), 5.84 (s, 1H, C=CH), 6.30 (s, 1H, C=CH), 6.37 (s, 1H, CHO), 7.44-7.50 (d, 2H, ArH), 7.55-7.66 (d, 1H, ArH), 7.92-7.97 (t, 2H, ArH).Results of elemental analyses is C:68.28%; (theoretical value is C:68.28% to H:5.72%; H:5.73%).Molecular ion peak m/z=269.07778 in high resolution mass spectrum is C 14H 14O 4The peak of+Na.
Really be target compound methacrylic acid (1-phenyl-1,3-dicarbapentaborane)-2-butyl ester through the compound that Structural Identification synthesized.
2, UO 2 2+-IIP's is synthetic
Take uranyl ion as template, the benzoyl acetone methacrylic ester as function monomer, ethylene glycol dimethacrylate as linking agent and Diisopropyl azodicarboxylate be initiator (n (UO wherein 2 2+): n (methacrylic acid (1-phenyl-1, the 3-dicarbapentaborane)-2-butyl ester): n (ethylene glycol dimethacrylate): n (Diisopropyl azodicarboxylate)=1: 3: 16: 0.12) at 10mL pore-creating agent 1, carry out mass polymerization in the 4-dioxane, obtain polymkeric substance.The solid that thermopolymerization generates is through grinding, the template uranyl ion in hydrochloric acid wash-out polymkeric substance, and acetone washes away residual organism, and sieves out the solid particulate of 80-200 order size, namely obtains the imprinted polymer of uranyl ion.
The uranyl ion imprinted polymer of above-mentioned preparation is carried out capacity indicator (actual conditions is: 10mg polymer solids, 10mL uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibration 9h) according to the method under in embodiment 22.The loading capacity of uranyl ion imprinted polymer can reach 9.8mg/g.
Synthesizing of embodiment 5, uranyl ion imprinted polymer
1, the synthetic and sign of the thenoyltrifluoroacetone methacrylic ester function monomer shown in formula I-4
Figure BDA00002951161900121
Thenoyltrifluoroacetone (4.44g, 20mmol) and N-bromo-succinimide (NBS, 3.56g, 20mmol) stirring reaction in the 30mL methylene dichloride, synthetic 1-bromothiophene formyl trifluoroacetone.(wherein molar ratio is n (1-bromothiophene formyl trifluoroacetone): n (triethylamine): n (methacrylic acid)=1: 1.2: 1.2) with methacrylic acid stirring at room reaction 3h under the triethylamine condition, reaction removes by filter the by product triethylamine salt after finishing, and the thick product that obtains obtains the thenoyltrifluoroacetone methacrylate monomer through the column chromatography separating-purifying.
Structural identification is as follows:
The nmr analysis result is: δ H(300MHZ, CDCl 3, Me 4Si) 1.90 (s, 3H, CH 3), 5.57 (s, 1H, C=CH), 6.13 (s, 1H, C=CH), 5.71 (s, 1H, CHO), 7.44-7.50 (d, 1H, ArH), 6.92-7.01 (t, 1H, ArH), 7.53-7.55 (d, 1H, ArH).Results of elemental analyses is C:43.28%; (theoretical value is C:43.25% to H:2.22%; H:2.27%).Molecular ion peak m/z=244.98521 in high resolution mass spectrum is C 8H 5F 3O 2The peak of S+Na.
Really be target compound thenoyltrifluoroacetone methacrylic ester through the compound that Structural Identification synthesized.
2, UO 2 2+-IIP's is synthetic
Take uranyl ion as template, the thenoyltrifluoroacetone methacrylic ester as function monomer, ethylene glycol dimethacrylate as linking agent and Diisopropyl azodicarboxylate be initiator (n (UO wherein 2 2+): n (thenoyltrifluoroacetone methacrylic ester): n (ethylene glycol dimethacrylate): n (Diisopropyl azodicarboxylate)=1: 3: 16: 0.12) at 10mL pore-creating agent 1, carry out mass polymerization in the 4-dioxane, obtain polymkeric substance.The solid that thermopolymerization generates is through grinding, the template uranyl ion in hydrochloric acid wash-out polymkeric substance, and acetone washes away residual organism, and sieves out the solid particulate of 80-200 order size, namely obtains the imprinted polymer of uranyl ion.
The uranyl ion imprinted polymer of above-mentioned preparation is carried out capacity indicator (actual conditions is: 10mg polymer solids, 10mL uranyl ammonium carbonate adsorption liquid, 25 ℃ of vibration 9h) according to the method under in embodiment 22.The loading capacity of uranyl ion imprinted polymer can reach 10.8mg/g.
Embodiment 6, uranyl ion imprinted polymer adsorb recovery uranium from seawater
(the pH value is 7.7 to seawater, and the major metal ion has Na +, K +, Mg 2+, Ca 2+, Fe 3+, Cu 2+, Sr 2+And Ba 2+Deng) take from the Qingdao seashore, adopt the UO of embodiment 3 preparations 2 2+-IIP (IPM) adsorbs the uranium in above-mentioned seawater, and is specific as follows: get the 10mg IPM polymer solids 24h that vibrates in 10mL contains the seawater of 30 μ g uranium.After finishing, vibration uses the HCl eluant solution UO of 10mL 50mM 2 2+, with the concentration of ICP-AES survey wash-out uranium.Experimental result shows, the rate of recovery of uranium is 93.8 ± 5.4%.Result shows, the IIP that the present invention synthesizes can adsorb from seawater and reclaims uranium.
By above-described embodiment as can be known, with UO 2 2+The beta-diketon of modifying for template, acryl or methacryloyl is function monomer copolymerzation with cross-linking under the effect of initiator and linking agent, obtains cross-linked polymer, and the wash-out template ion obtains the uranyl ion imprinted polymer.This imprinted polymer can be from the uranyl ammonium carbonate that contains a large amount of uncombined carbon acid groups the competitive adsorption uranyl ion, and have significant adsorption selectivity.Therefore, this imprinted polymer can be used for adsorbing and extracting uranium from the low seawater of complicated component uranium concentration.
Although the present invention is illustrated with reference to preferred embodiments and drawings,, for a person skilled in the art, the present invention can have various modifications and variations, as the substituent variation of beta-diketon of acryl or methacryloyl modification.Various change of the present invention, variation and equivalent are contained by the content of appending claims.

Claims (10)

1. the compound shown in formula I:
Figure FDA00002951161800011
(formula I)
In formula I, R 1, R 2Identical or different, all be independently selected from any one in following radicals: C1-C6 alkyl and thienyl that phenyl, C1-C6 alkyl, halogen replace;
R is hydrogen or methyl.
2. prepare the method for compound shown in claim 1 Chinese style I, comprise the steps:
1) beta-diketon shown in formula II and N-bromo-succinimide are reacted, obtain the compound shown in formula III;
Figure FDA00002951161800012
(formula II) (formula III)
Wherein, R in formula II, formula III 1, R 2Definition cotype I;
2) under triethylamine exists, compound shown in formula III and acrylic or methacrylic acid are reacted, reaction removes by filter triethylamine salt after finishing, and obtains the compound shown in formula I.
3. method for preparing the uranyl ion imprinted polymer, that compound take uranyl ion as template, shown in claim 1 Chinese style I is function monomer, carry out polyreaction under the effect of initiator and linking agent, remove the template uranyl ion in resulting polymers after reaction finishes, namely obtain described uranyl ion imprinted polymer.
4. method according to claim 3, it is characterized in that: described method specifically comprises the steps:
1) compound and the solubility uranyl salt shown in claim 1 Chinese style I are dissolved in organic solvent, then add linking agent and initiator, carry out polyreaction under oxygen free condition, obtain polymer solids;
2) described polymer solids is ground, with the hydrochloric acid soln washing, remove the template uranyl ion, then wash away residual organism with acetone, wash with water at last to neutrality, drying namely gets the uranyl ion imprinted polymer.
5. according to claim 3 or 4 described methods, it is characterized in that: described uranyl ion is provided by the solubility uranyl salt;
Described linking agent is the compound that contains two and two above carbon-carbon double bonds;
Described initiator is Diisopropyl azodicarboxylate, organo-peroxide or persulphate;
The mol ratio of the compound shown in described uranyl ion, formula I, linking agent and initiator is 1: (2～4): (12～20): (0.05～0.15).
6. the described method of any one according to claim 4-5, it is characterized in that: described polyreaction is carried out under oxygen free condition, and temperature of reaction is 60～90 ℃, and the reaction times is more than 12 hours.
7. the described method of any one according to claim 4-6, it is characterized in that: described polymer reaction carries out in organic solvent; Described organic solvent is selected from following at least a: Isosorbide-5-Nitrae-dioxane, 2-methyl cellosolve, methyl alcohol, tetrahydrofuran (THF), acetic acid, ethylene dichloride, DMF and toluene.
8. the uranyl ion imprinted polymer that in claim 4-7, the described method of any one prepares.
9. uranyl ion imprinted polymer claimed in claim 8 contains the application in uranyl ion in the uranyl deionized water solution in absorption.
10. application according to claim 9 is characterized in that: the described pH value that contains the uranyl deionized water solution is 7.5-9; The described uranyl deionized water solution that contains is specially seawater.
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