CN102504115B - Preparation method of core-shell molecular print polymer for selectively separating clofibric acid (CA) and application thereof - Google Patents
Preparation method of core-shell molecular print polymer for selectively separating clofibric acid (CA) and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a core-shell molecular print polymer for selectively separating clofibric acid (CA) and an application thereof. Print and elution objects are CA, and the print physical dimension and binding site of the polymer are matched specifically with those of the CA; the CA molecular print polymer provided by the invention is easy and convenient to prepare; and polymer particles are uniform, and have large specific surface areas, large pore volumes, a special memory identifying function on the three-dimensional structure of a CA molecule, and high compatibility and selectivity for CA in water; and print polymer is used for selectively removing CA from surface water, and has a better effect than other adsorption materials.
Description
Technical field
The present invention relates to preparation method and the application of the core-shell type molecularly imprinted polymer of a kind of selective separation clofibric acid (CA), the present invention relates in addition the removal technical study of CA in Different Waters, the water body that polluted by CA as surface water, underground water, sewage, tap water etc.
Background technology
As a class " emerging pollutent ", medicine and personal care articles (Pharmaceutical and Personal Care Products, PPCPs) just continual, enter among the surrounding mediums such as water body, soil and atmosphere, and become continue typical environment pollution substance (PCBs, DDT, dioxy (mixing)) glutinous rehmannia and agricultural chemicals etc.) after the focus of another research.PPCPs is a very huge compound system, and the medical compounds kind surpasses kind more than 3000 at present, and the annual production of the medicinal chemicals whole world approaches 2 * 10
6Ton; The personal-care supplies classes of compounds is also more than several thousand kinds, and whole world annual production surpasses 1 * 10
6Ton.PPCPs and meta-bolites thereof enter municipal effluent by excretion or bathing, finally continually in the entered environment receiving water body.The present situation that PPCPs is used in a large number and special physicochemical characteristic, brought certain potential risk to ecotope and human health.At present, found more than 50 kind of PPCPs material in Sewage Plant Inlet and outlet water, surface water, underground water and tap water, concentration is up to μ gL
-1Level.
CA is the meta-bolites of fatty conditioning agent clofibric acid, etofibrate, is that in PPCPs, tool is typically a kind of.CA is also the strongest, the report of activity one of medicine the most widely in current water system residue, and this material has very strong polarity and very difficult biological degradation, it is reported that this material can be detained 21 years and not be degraded in environment.The people such as Buser are studied the CA in the North Sea and some lakes of Switzerland, and result shows that the concentration of CA in surface water environment has reached 1-2 ng/L.Stan and Heberer have detected the concentration of CA up to 165 ng/L in the tap water of Berlin.Heberer shows the research of underground water, and the tax of this material in underground water deposited concentration and reached 7300 ng/L.Result of study to CA in Mississippi and Lake Pontchartrain shows that concentration range is 6-10 ng/L.Existing research shows that conventional sewage treatment facility can't cut down such material, in the Lausanne of Switzerland and the data presentation CA of More sewage work, does not remove, and Heberer shows that to the monitoring result of CA in the Sewage treatment systems of Berlin clearance is almost nil.Therefore how effectively removing CA residual in water body has caused showing great attention to of research worker.
The existence that CA generally detected in water system has confirmed that traditional sewage work can not remove such material effectively, and in water system, the CA pollution problem has proposed new challenge to traditional water pollution control theory.Molecularly imprinted polymer (Molecularly imprinted polymer, MIP), due to its unique identity and selectivity, is that the water with applications well prospect pollutes the processing new technology.By preparing the molecular engram material of target contaminant, in the system coexisted at multi-pollutant, can preferential affine absorption target contaminant.Control by MIP for CA, can improve the selectivity of removal, and treatment effect is corresponding raising also.Meng Zihui etc. be take alpha-estradiol as template, has synthesized first a kind of estrogenic molecularly imprinted polymer by non-covalent engram technology, for the oestrogenic hormon of Adsorption water.17 beta-estradiol molecular engram polymers of the preparation such as Le Noir, trace 17 beta estradiols of water body are removed in success for selective adsorption, in the aqueous solution of 2 μ g/L target compound pollutents, the rate of recovery of pollutent reaches (100 ± 0.6) %, for removing contaminant trace species, provides an effective way.The method synthesis of bisphenol A molecular imprinting particle of sedimentation polymerization for Lin Yi etc., carried out the research of dihydroxyphenyl propane molecularly imprinted polymer selective removal phenols female hormone from different source waters, prove thus and take a kind of typical compound as the template Synthesis of Molecular Imprinting Polymers, and by the feasibility of similar compound in the different water bodys of this polymkeric substance selective removal.The employing sedimentation polymerizations such as Chaomeng Dai have been synthesized respectively the molecularly imprinted polymer of Carbamzepine and diclofenac, and successfully for the removal of actual water body Carbamzepine and diclofenac, confirmed that MIP is more suitable for removing the target contaminant situation of large volume lower concentration in water body, this conclusion has profound significance to the reduction that has persistence and the general pollutent on the low side of concentration in water body environment simultaneously.In this research, MIP reuses at least 10 times, and remove efficiency, does not obviously reduce.Above these researchs are repaired for molecular imprinting evident characteristics, the pollution of carrying out typical PPCPs in water body and control techniques provides scientific basis.
It is shell that the MAA/2VP/4VP – DVB-80/EDGMA multipolymer that the single DVB-80 of dispersion homopolymer is core, CA trace is take in the present invention, has synthesized the core-shell type molecular blotting polymer microsphere that CA is had to high selectivity by the sedimentation polymerization.By studying the specific recognition capability of this CSMIP to CA, inquire into the feasibility of its CA application in removing water body, thereby provide strong theoretical foundation and technical support for the selective removal of CA in following actual environment water body.
Summary of the invention
To overcome traditional homogeneous molecularly imprinted polymer inside because the template material can't arrive the afunction caused, the object of the present invention is to provide preparation method and the application thereof of the nucleocapsid molecularly imprinted polymer of CA in a kind of selective separation water body.
The preparation method of the nucleocapsid molecularly imprinted polymer of CA in the selective separation water that the present invention proposes, concrete steps are as follows:
(1) do not having under the condition of template molecule, in reaction vessel, adding 1-200 mmol linking agent, 0.01-2 mmol initiator and 20-200mL pore-creating agent, shaking up, under condition of ice bath, passing into nitrogen 10-30 minute and remove oxygen wherein in reaction solution; Reaction vessel is placed in to water-bath, according to 0.25-0.45 oC/min temperature rise rate, is warming up to 45-82 oC, and reacts 3-25h at this temperature; Generate monodisperse polymer body poly (DVB), form the core core of molecularly imprinted polymer;
(2) the monodisperse polymer body poly (DVB) step (1) obtained mixes with 0.01-3.0 mmol template molecule, 0.08-2.0 mmol functional monomer, 0.05-20 mmol linking agent, 0.01-0.9 mmol initiator and 10-200 mL pore-creating agent, passes into nitrogen 10-30min and remove oxygen wherein in reaction solution; Reaction vessel is placed in to water-bath, according to 0.2-0.5 oC/min temperature rise rate, is warming up to 45-82 oC, and reacts 8-45h at this temperature; Prepare the shell of core-shell type molecular imprinting, thereby form nucleocapsid molecular blotting polymer microsphere (CSMIP); Described template molecule is CA;
(3) solvent that the nucleocapsid molecular blotting polymer microsphere that step (2) obtains is placed in methyl alcohol and acetic acid composition adopts soxhlet extraction to remove template molecule, the time that Soxhlet is extracted is 10-120h, obtain nucleocapsid molecularly imprinted polymer (CSMIP), wherein: the volume ratio of methyl alcohol and acetic acid is (1-10): (10-1).
In the present invention, template molecule is CA, and competing compound is Carbamzepine (CBZ).
In the present invention, functional monomer is preferably acrylic acid or the like, pyridines or amides, as in vinylformic acid (AA), methacrylic acid (MAA), 4-vinylpridine (4-VP), 2-vinyl pyridine (2-VP) or acrylamide (AM) any.Further, functional monomer is selected from methacrylic acid (MAA), 2-vinyl pyridine (2-VP) or acrylamide (AM) any.
In the present invention, initiator described in step (1) and step (2) is water soluble starter or oil-soluble initiator as Diisopropyl azodicarboxylate (AIBN), ammonium persulphate, is preferably Diisopropyl azodicarboxylate (AIBN).
In the present invention, pore-creating agent described in step (1) and step (2) is in acetonitrile, methyl alcohol, toluene, methylene dichloride, trichloromethane or tetracol phenixin any.Further, be selected from acetonitrile or toluene.
In the present invention, described in step (1) and step (2), linking agent is selected from trimethylolpropane trimethacrylate (TRIM), ethylene glycol dimethacrylate (EGDMA), Vinylstyrene-80(DVB-80), N, in 0-bis-acryloyls-L-phenylalaninol or pentaerythritol triacrylate (PETRA) any.Further, be selected from ethylene glycol dimethacrylate (EGDMA) or Vinylstyrene-80(DVB-80).
In the present invention, described in step (1), the add-on of linking agent is 3-18 mmol, and the add-on of initiator is 0.01-0.09 mmol, and the add-on of pore-creating agent is for being 30-100 mL.
In the present invention, described in step (2), the add-on of template molecule is 0.1-1.5 mmol, and the add-on of functional monomer is 0.1-1.2 mmol, and the add-on of linking agent is 1-10 mmol, the add-on of initiator is 0.01-0.12 mmol, and the add-on of pore-creating agent is 20-90 mL.
In the present invention, described in step (1), temperature of reaction is 50-75oC, and the reaction times is 5-20h.
In the present invention, the described temperature of reaction of step (2) is 50-75oC, and the reaction times is 12-35h.
In the present invention, in step (2), the diameter of the nucleocapsid molecular blotting polymer microsphere of gained is 1～8 μ m.
In the present invention, described in step (3), the volume ratio of methyl alcohol and acetic acid is (7-9): (3-1), the time that Soxhlet is extracted is 12-72 h.
In the present invention, described in step (1), pore-creating agent is acetonitrile or toluene.
It is core that monodisperse polymer body poly (DVB) is take in the present invention, with MAA or 2VP, take acetonitrile or methyl alcohol as pore-creating agent, take EGDMA or DVB-80 as linking agent, take drug target as template molecule carries out ion blotting to its surface, prepare and there is optionally nucleocapsid molecular engram material.
The core-shell type molecularly imprinted polymer that utilizes the inventive method to prepare is for removing water body CA.
The core-shell type molecularly imprinted polymer that utilizes the inventive method to prepare is for the selective separation of water system trace medicine.
The present invention also aims to utilize this material to remove the method for CA in water body.The method can be used for the selective separation of trace medicine in water system, and has sharp separation ability and higher selectivity, and immunity from interference is strong, and the CA after enrichment can use the organic solvent wash-out.
Beneficial effect of the present invention:
The present invention is molecular imprinting, utilizes the specific selectivity of molecularly imprinted polymer to the template material, and pollutent is separated from water body.The synthetic CSMIP of this technology has regeneration performance preferably, this molecularly imprinted polymer Reusability is also obviously decay of generation of trace ability afterwards repeatedly, this technology not only means the feasibility of CSMIP technology application in water treatment, has more shown the feasibility with respect to the Economic Application of traditional sorbing materials such as business gac.This technology has solved conventional sorbing material target contaminant is not optionally adsorbed and separates simultaneously.
The accompanying drawing explanation
Fig. 1 core-shell type clofibric acid molecularly imprinted polymer synthesizes schematic diagram.
Fig. 2 core-shell type clofibric acid molecularly imprinted polymer model structure schematic diagram.
The SEM figure of Fig. 3 core-shell type clofibric acid molecularly imprinted polymer.
Embodiment
Further illustrate the present invention below by embodiment.
Embodiment 1
The synthetic method of core-shell type CA molecularly imprinted polymer of the present invention is as follows:
(1) AIBN that accurately takes the Vinylstyrene-80 of 5 mmol and 0.07 mmol, in 300-500 mL tool plug screw socket vial, then adds 50 mL acetonitriles, shakes up gently.Under condition of ice bath, pass into nitrogen 10 min and remove above the oxygen of dissolving and vial the oxygen of trace in air in reaction solution, finally by bottle sealing.Reaction vessel is placed in to water-bath, makes temperature rise to 60oC from room temperature slowly within two hours, and under the condition of 60oC constant temp. heating polymerization 10h.The synthetic list obtained disperses homopolymer, is the core of molecularly imprinted polymer.
(2) accurately taking 0.8 mmol CA, 0.08 mmol methacrylic acid, 5.0 mmol Vinylstyrenes-80 and 0.08 mmol AIBN is dissolved in 60 mL acetonitriles, after mixing, mixed reaction solution is transferred in the reaction flask in step (1), pass into the oxygen that nitrogen 20 min remove trace in the oxygen of dissolving and vial top air, then by bottle sealing.Reaction vessel is placed in to water-bath, makes temperature rise to 60 oC from room temperature slowly within two hours, and under the condition of 60 oC constant temp. heating polymerization 20 h.After polyreaction is complete, the CSMIP particle of generation is placed in to methyl alcohol/acetic acid=6/4 mixed solution Soxhlet and extracts 36 h, to remove template molecule; And then wash to remove acetic acid residual in particulate matter with a small amount of methyl alcohol, finally that the CSMIP particle vacuum-drying under 60 oC conditions obtained is standby.
Synthetic core-shell type clofibric acid molecularly imprinted polymer is carried out to the indices experiment:
Configuration of surface to core-shell type clofibric acid molecularly imprinted polymer characterizes as shown in Figure 3, and CSMIP is creamy white or transparent spherical small-particle, smooth surface, and particle diameter is even.
1) accurately take some parts of 10-100mg CSMIP, be placed in tool plug Erlenmeyer flask, add respectively 0～1500 mg/L CA aqueous solution 5-10 mL, Static Adsorption for some time in constant temperature oscillator, carry out the Scatchard matching, can be calculated the apparent binding capacity Q of maximum of specific binding site
Max1Be respectively 150 mg/g-430 mg/g.
2) 10-100 mg CSMIP is respectively charged in the tool plug Erlenmeyer flask of 10-30 mL, then adds respectively the CA aqueous solution that 2-30 mL concentration is 500-1000 mg/L, the binding kinetics character of Study Polymer Melts.After experimental results show that 10-15min, absorption reaches balance basically.
3) take the tool plug vial that 10-100 mg CSMIP is placed in 10-30 mL, then add respectively 2-30 mL, the CA/CBZ mixed solution of 50-200 mg/L.After sealing on the 25oC constant temperature oscillator with the velocity fluctuation 2-6 h of 200 rpm, then regularly take out reaction flask, the specific selectivity of research CSMIP to CA.Result show CSMIP to the absorption property of CA far above CBZ, proved that there are the specificitys such as obligate bonding reaction of memory hole, binding site, template molecule and the binding site of fixed size and shape in CSMIP itself.
4) take 10-100 mg CSMIP, before reusing at every turn in methyl alcohol/acetic acid=6/4 mixed solution ultrasonic extraction for several times, until can't detect CA in filtrate, and then use methyl alcohol drip washing, vacuum-drying, carry out the Study on reuse of CSMIP.Result prove this molecularly imprinted polymer Reusability 20 times after the trace ability do not decay yet.
Embodiment 2
The synthetic method of core-shell type CA molecularly imprinted polymer of the present invention is as follows:
(1) AIBN that accurately takes the DVB-80 of 18.3 mmol and 0.2562 mmol, in 300-500 mL tool plug screw socket vial, then adds 120 mL toluene, shakes up gently.Under condition of ice bath, pass into nitrogen 10 min and remove above the oxygen of dissolving and vial the oxygen of trace in air in reaction solution, finally by bottle sealing.Reaction vessel is placed in to water-bath, makes temperature rise to 65oC from room temperature slowly within two hours, and under the condition of 65oC constant temp. heating polymerization 10 h.The synthetic list obtained disperses homopolymer, is the core of molecularly imprinted polymer.
(2) accurately taking 2.93 mmol CA, 0.293 mmol MAA, 18.3 mmol DVB-80 and 0.293 mmol AIBN is dissolved in 180 mL toluene, after mixing, mixed reaction solution is transferred in the reaction flask in step (1), pass into the oxygen that nitrogen 20 min remove trace in the oxygen of dissolving and vial top air, then by bottle sealing.Reaction vessel is placed in to water-bath, makes temperature rise to 65 oC from room temperature slowly within two hours, and under the condition of 65oC constant temp. heating polymerization 20 h.After polyreaction is complete, the CSMIP particle of generation is placed in to methyl alcohol/acetic acid=9/1 mixed solution Soxhlet and extracts 72 h, to remove template molecule; And then wash to remove acetic acid residual in particulate matter with a small amount of methyl alcohol, finally that the CSMIP particle vacuum-drying under 60 ℃ of conditions obtained is standby.
Synthetic core-shell type clofibric acid molecularly imprinted polymer is carried out to the indices experiment:
1) accurately take some parts of 5-80mg CSMIP, be placed in tool plug Erlenmeyer flask, add respectively 5～2000 mg/L CA aqueous solution 5-10 mL, Static Adsorption for some time in constant temperature oscillator, carry out the Scatchard matching, can be calculated the apparent binding capacity Q of maximum of specific binding site
Max1Be respectively 130 mg/g-450 mg/g.
2) 10-100 mg CSMIP is respectively charged in the tool plug Erlenmeyer flask of 10-30 mL, then adds respectively the CA aqueous solution that 2-30 mL concentration is 500-1000 mg/L, the binding kinetics character of Study Polymer Melts.After experimental results show that 15min, absorption reaches balance basically.
3) take the tool plug vial that 10-100 mg CSMIP is placed in 10-30 mL, then add respectively 2-30mL, the CA/CBZ mixed solution of 50-200 mg/L.After sealing on the 25oC constant temperature oscillator with velocity fluctuation 3 h of 300 rpm, then regularly take out reaction flask, the specific selectivity of research CSMIP to CA.Result show CSMIP to the absorption property of CA far above CBZ, proved that there are the specificitys such as obligate bonding reaction of memory hole, binding site, template molecule and the binding site of fixed size and shape in CSMIP itself.
4) take 10-100 mg CSMIP, before reusing at every turn in methyl alcohol/acetic acid=6/4 mixed solution ultrasonic extraction for several times, until can't detect CA in filtrate, and then use methyl alcohol drip washing, vacuum-drying, carry out the Study on reuse of CSMIP.Result prove this molecularly imprinted polymer Reusability 35 times after the trace ability do not decay yet.
Embodiment 3
Core-shell type clofibric acid molecularly imprinted polymer of the present invention is in the application of removing surface water mark-on CA: the surface water water sample is taken from Huangpu River, and the surface water water sample is obtained to a series of water samples, a series of concentration of CA mark-on in all water samples with the deionized water dilution.The different surface water water samples of 5.0-10 mL are placed in to the 10-20 mL tool plug vial that contains 10-100 mg CSMIP, after sealing on the 25oC constant temperature oscillator with velocity fluctuation 5 h of 300 rpm, then regularly take out reaction flask, with connecing millipore filtration (Φ=0.3 μ m) under 5-50 mL syringe, filter, in filtrate, the free concentration of CA is measured with HPLC.This research is the removal for surface water CA by synthetic CSMIP, has assessed CSMIP and has removed the feasibility of polluted water body CA for obligate.According to the difference of surface water and deionized water ratio, CA adds the target clearance and reaches 80-95%.
Embodiment 4
Core-shell type clofibric acid molecularly imprinted polymer of the present invention is in the application of removing underground water mark-on CA: the underground water water sample is taken from Chongming Island, the underground water water sample is spent to the ionized water dilution and obtain a series of water samples, a series of concentration of CA mark-on in all water samples.The different surface water water samples of 5.0-10 mL are placed in to the 10-20 mL tool plug vial that contains 10-100 mg CSMIP, after sealing on the 25oC constant temperature oscillator with velocity fluctuation 5 h of 300 rpm, then regularly take out reaction flask, with connecing millipore filtration (Φ=0.3 μ m) under 5-50 mL syringe, filter, in filtrate, the free concentration of CA is measured with HPLC.This research is the removal for underground water CA by synthetic CSMIP, has assessed CSMIP and has removed the feasibility of Polluted Groundwater CA for obligate.According to the difference of underground water and deionized water ratio, CA adds the target clearance and reaches 85-99%.
Claims (13)
1. the preparation method of the nucleocapsid molecularly imprinted polymer of clofibric acid in a selective separation water is characterized in that concrete steps are as follows:
(1) do not having under the condition of template molecule, in reaction vessel, adding 1-200 mmol linking agent, 0.01-2mmol initiator and 20-200mL pore-creating agent, shaking up, under condition of ice bath, passing into nitrogen 10-30min and remove oxygen wherein in reaction solution; Reaction vessel is placed in to water-bath, according to the 0.25-0.45oC/min temperature rise rate, is warming up to 45-82oC, and react 3-25h at this temperature; Generate the monodisperse polymer body, form the core core of molecularly imprinted polymer;
(2) monodisperse polymer body step (1) obtained mixes with 0.01-3.0 mmol template molecule, 0.08-2.0 mmol functional monomer, 0.05-20 mmol linking agent, 0.01-0.9 mmol initiator and 10-200 mL pore-creating agent, passes into nitrogen 10-30min and remove oxygen wherein in reaction solution; Reaction vessel is placed in to water-bath, according to the 0.2-0.5oC/min temperature rise rate, is warming up to 45-82oC, and react 8-45 hour at this temperature; Prepare the shell of core-shell type molecular imprinting, form the nucleocapsid molecular blotting polymer microsphere; Described template molecule is clofibric acid;
(3) solvent that the nucleocapsid molecular blotting polymer microsphere that step (2) obtains is placed in methyl alcohol and acetic acid composition adopts soxhlet extraction to remove template molecule, the time that Soxhlet is extracted is 10-120h, obtain the nucleocapsid molecularly imprinted polymer, wherein: the volume ratio of methyl alcohol and acetic acid is (1-10): (10-1).
2. preparation method according to claim 1, is characterized in that functional monomer is acrylic acid or the like, pyridines or amides.
3. preparation method according to claim 1, is characterized in that described in step (1) and step (2), initiator is water soluble starter or oil-soluble initiator.
4. preparation method according to claim 1, is characterized in that pore-creating agent described in step (1) and step (2) is in acetonitrile, methyl alcohol, toluene, methylene dichloride, trichloromethane or tetracol phenixin any.
5. preparation method according to claim 1, it is characterized in that described in step (1) and step (2), linking agent is trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, Vinylstyrene-80, N, in O-bis-acryloyls-L-phenylalaninol or pentaerythritol triacrylate any.
6. preparation method according to claim 1, the add-on that it is characterized in that linking agent described in step (1) is 3-18 mmol, and the add-on of initiator is 0.01-0.09 mmol, and the add-on of pore-creating agent is 30-100 mL.
7. preparation method according to claim 1, the add-on that it is characterized in that template molecule described in step (2) is 0.1-1.5 mmol, the add-on of functional monomer is 0.1-1.2 mmol, the add-on of linking agent is 1-10 mmol, the add-on of initiator is 0.01-0.12 mmol, and the add-on of pore-creating agent is 20-90 mL.
8. preparation method according to claim 1, is characterized in that described in step (1), temperature of reaction is 50-75oC, and the reaction times is 5-20h.
9. preparation method according to claim 1, is characterized in that the described temperature of reaction of step (2) is 50-75oC, and the reaction times is 12-35h.
10. preparation method according to claim 1, is characterized in that the diameter of the nucleocapsid molecular blotting polymer microsphere of gained in step (2) is 1～8 μ m.
11. preparation method according to claim 1, the volume ratio that it is characterized in that methyl alcohol described in step (3) and acetic acid is (7-9): (3-1), the time that Soxhlet is extracted is 12-72 h.
12. the core-shell type molecularly imprinted polymer that the preparation method obtains as claimed in claim 1 is for removing the clofibric acid of water body.
13. the core-shell type molecularly imprinted polymer that the preparation method obtains as claimed in claim 1 is for the selective separation of water system trace medicine.
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| CN101220187A (en) * | 2008-01-31 | 2008-07-16 | 复旦大学 | Magnetic composite microsphere with nucleocapsid structure and method for producing the same |
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