CN103613722A - Method for preparing magnetic halloysite molecularly imprinted polymer with specific adsorption to 2,4-dichlorophenoxyacetic acid - Google Patents
Method for preparing magnetic halloysite molecularly imprinted polymer with specific adsorption to 2,4-dichlorophenoxyacetic acid Download PDFInfo
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- CN103613722A CN103613722A CN201310624108.3A CN201310624108A CN103613722A CN 103613722 A CN103613722 A CN 103613722A CN 201310624108 A CN201310624108 A CN 201310624108A CN 103613722 A CN103613722 A CN 103613722A
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- halloysite nanotubes
- halloysite
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 129
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 title claims abstract description 41
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 29
- HXKWSTRRCHTUEC-UHFFFAOYSA-N 2,4-Dichlorophenoxyaceticacid Chemical compound OC(=O)C(Cl)OC1=CC=C(Cl)C=C1 HXKWSTRRCHTUEC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002071 nanotube Substances 0.000 claims abstract description 81
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 9
- OVSKIKFHRZPJSS-DOMIDYPGSA-N 2-(2,4-dichlorophenoxy)acetic acid Chemical compound OC(=O)[14CH2]OC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-DOMIDYPGSA-N 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 238000005260 corrosion Methods 0.000 claims description 28
- 230000007797 corrosion Effects 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 150000002505 iron Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical group C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001338 self-assembly Methods 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 claims description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000004971 Cross linker Substances 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 238000000926 separation method Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 230000000274 adsorptive effect Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000006249 magnetic particle Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PNTSMIMYOILILJ-UHFFFAOYSA-N 2-(2-chloro-4-methylphenoxy)acetic acid Chemical compound CC1=CC=C(OCC(O)=O)C(Cl)=C1 PNTSMIMYOILILJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003534 oscillatory effect Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000002373 plant growth inhibitor Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing a magnetic halloysite molecularly imprinted polymer with specific adsorption to 2,4-dichlorophenoxyacetic acid. The preparation method comprises the following steps: preparing magnetic halloysite nano-tubes by using corroded halloysite nano-tubes by a coprecipitation method; reacting the magnetic halloysite nano-tubes and methacrylate in methylbenzene to obtain magnetic halloysite nano-tubes with double-bond-modified surfaces; after polymerizing the magnetic halloysite nano-tubes with double-bond-modified surfaces, the polymerized monomers and a crosslinker by taking the 2,4-dichlorophenoxyacetic acid as a template, then removing the 2,4-dichlorophenoxyacetic acid to obtain the magnetic halloysite molecularly imprinted polymer with specific adsorption to the 2,4-dichlorophenoxyacetic acid. The raw materials used in the preparation method are low in cost; the preparation method is easy to operate and easy to implement; the prepared magnetic halloysite molecularly imprinted polymer is stable in structure, has specific adsorption to the 2,4-dichlorophenoxyacetic acid, and can effectively separate and remove the 2,4-dichlorophenoxyacetic acid from a complex system.
Description
Technical field
The present invention relates to a kind of method 2,4 dichlorophenoxyacetic acid to the magnetic halloysite molecularly imprinted polymer of specific adsorption, function of dominant technical field of material prepared.
Background technology
Halloysite, a kind of aluminium silicon compound, chemical structure is similar to kaolin, i.e. Al
2si
2o
5(OH)
4nH
2o, but have again a little difference on pattern, halloysite has the tubular structure of hollow, and its structural unit is that water by unimolecular layer separates.The water of internal layer can cause physicochemical character to comprise organic interlayer and ion-exchange capacity.In addition, halloysite has two kinds of sizes, 10A and 7A, and wherein that moisture is 10A, water electrode is transformed into 7A after easily losing.Because the tubular structure that it is special, excellent performance, rich in natural resources and extremely low cost, halloysite all has very large potentiality and in recent years, has also won very large concern in a lot of fields.It is different from other unique tubular structure of aluminium silicon compound and good biocompatibility and very low toxicity makes it become a kind of very promising medicine supporting body.Halloysite is compared with carbon nanotube, and it is a kind of very economic starting material, can directly from clay raw ore, extract.The structure of halloysite is different from carbon nanotube and is, the latter is bar-shaped, and the former is the netted bar structure intermeshing, and this can be dissolved in solution or in polymeric web halloysite.Exactly because halloysite has so many excellent performance, for example, there are larger specific surface area, large aperture and abundant hydroxyl.
Molecular imprinting (MIT) is first template molecule and selected function monomer to be interacted and form mixture in suitable solvent, under linking agent effect, form again high cross-linked polymer, finally by specific means, remove after template molecule, in the molecularly imprinted polymer of acquisition (MIPs), leave binding site template molecule to specific recognition.MIPs, owing to having precordainment, identity and the large feature of practicality three, is widely used in many research fields such as chromatographic separation, Solid-Phase Extraction, mimetic enzyme catalysis, natural antibody simulation and membrane separation technique.The combination of magnetic-particle and molecularly imprinted polymer can be provided to the instrument of simple, quick a, high efficiency separation, like this can be so that original complicated filtering separation or centrifugation become simply, also actual being applied in separation.
At present, the preparation method of molecular imprinting is quite ripe, but it is rare to take the method that magnetic halloysite nanotubes prepares molecular imprinted polymer on surface as carrier.Although existing, utilize simple solvent thermal reaction to prepare halloysite Magnetic nano-pipe, it is only to load on halloysite surface, and the Z 250 particle unstable ferric oxide that easily changes into very makes part particle lose magnetism or occur leakage field.Conventional is surperficial at halloysite nanotubes by Fe 3 O 4 magnetic particle load, can be by the silicon-dioxide (SiO on halloysite nanotubes surface
2) cover, so direct modification that affects methacrylic acid, and affect synthesizing and adsorption selectivity energy of molecularly imprinted polymer.
2,4 dichlorophenoxyacetic acid (2,4-D) as plant growth inhibitor or agricultural chemicals, in world's agricultural planting technique, have a wide range of applications.2,4-D has been used a lot of years, although it is very poisonous for a lot of biologies.2,4 dichlorophenoxyacetic acid has non-volatile and solubility, and is difficult to biological degradation and directly photodissociation.Due to 2,4 dichlorophenoxyacetic acid can be in stratum infiltration migration, existing detection in underground water and surface water.2,4 dichlorophenoxyacetic acid is proved to be environment incretion interferent, and its chloride metabolic intermediate is accumulation in vivo easily, is typical three to cause pollutent.So specificity is selected very important of 2,4 dichlorophenoxyacetic acid.
Summary of the invention
The present invention is directed in prior art in traditional environment system 2,4-dichlorphenoxyacetic acid (2, the defect such as removal method 4-D) is time-consuming, effort, and removal efficiency is low, object is to be to provide a kind of Stability Analysis of Structures, 2,4-D is had to specific adsorption, and effectively 2 in complex system removed in separation, the preparation method of the magnetic halloysite molecularly imprinted polymer of 4-D, this preparation method's raw material is cheap, simple to operate, easy to implement.
The invention provides preparation to 2,4-D has the method for the magnetic halloysite molecularly imprinted polymer of specific adsorption, this preparation method obtains corroding halloysite nanotubes with sulfuric acid by halloysite nanotubes corrosion, described corrosion halloysite nanotubes and trivalent iron salt and divalent iron salt make magnetic halloysite nanotubes by coprecipitation method, described magnetic halloysite nanotubes and methacrylic acid react in toluene, obtain the magnetic halloysite nanotubes of the two keys of finishing; The magnetic halloysite nanotubes of the two keys of described finishing and polymerization single polymerization monomer and linking agent be take 2,4 dichlorophenoxyacetic acid after template is carried out polymerization, remove 2,4 dichlorophenoxyacetic acid, obtain;
Described 2,4-dichlorphenoxyacetic acid, polymerization single polymerization monomer, linking agent three's mol ratio is 1:2～6:16～24, wherein, polymerization single polymerization monomer is one or more in 4-vinylpridine, 2-vinyl pyridine, vinyl benzyl chloride, and linking agent is Vinylstyrene or ethylene glycol dimethacrylate;
The two magnetic halloysite nanotubes of key of described finishing and the mass ratio of polymerization single polymerization monomer are 1:1～2;
The proportionlity of described magnetic halloysite nanotubes, toluene, methacrylic acid three usage quantity is 1g:25～35mL:3～8mL.
The sulphuric acid soln that described corrosion halloysite nanotubes is is 0.5～2mol/L by concentration, under 55～65 ℃ of conditions, by halloysite nanotubes corrosion 12～15h, prepares.
Described polymerization is first by polymerization single polymerization monomer and 2,4-dichlorphenoxyacetic acid carries out self-assembly 6～12h at 0～5 ℃, obtain assembling liquid, in described assembling liquid, add magnetic halloysite nanotubes and the linking agent of the two keys of finishing first at 45～52 ℃ of pre-polymerization 3～7h, again at 53～65 ℃ of polymerization 18～22h, then at 75～85 ℃ of further polyase 13～7h.
Described polymerization adds a small amount of azo-bis-isobutyl cyanide or azo two cyanogen in different heptan as initiator.
Described reaction is to stir 18～24h at 65～70 ℃.
The described 2,4 dichlorophenoxyacetic acid that removes is to adopt methyl alcohol and the acetic acid mixed solvent that volume ratio is 8～9:1～2 to extract 1～2d.
Described method, corrosion halloysite nanotubes, trivalent iron salt and divalent iron salt three's reaction mass ratio is 0.2～0.5:0.6～0.9:0.50; Described trivalent iron salt is a kind of in Anhydrous Ferric Chloride, Iron(III) chloride hexahydrate, ferric sulfate; Described divalent iron salt is a kind of in four ferrous sulfate hydrates, Iron dichloride tetrahydrate, ferrous sulfate.
Described coprecipitation method reaction conditions: first, at 50～60 ℃, react after 0.5～1h, regulating pH is 9～11, then at 80～90 ℃, aging 4～5h.
The preparation method that 2,4-D is had to the magnetic halloysite molecularly imprinted polymer of specific adsorption of the present invention, comprises following concrete steps:
(1) coprecipitation method is prepared magnetic halloysite nanotubes (HNTS-Fe
3o
4):
Halloysite nanotubes is dispersed in the dilution heat of sulfuric acid that concentration is 0.5～2mol/L, after ultrasonic dispersion, in 55～65 ℃ of water-baths, stirring reaction 12～15h, filters, extremely neutral to pH with a large amount of distilled water washs, 40～60 ℃ of vacuum-dryings, obtain corroding halloysite nanotubes (HNTS);
Gained is corroded to halloysite nanotubes, trivalent iron salt and divalent iron salt iron to be dissolved in deionized water according to mass ratio 0.2～0.5:0.6～0.9:0.5, add a small amount of (take mixture total mass suitably add for benchmark) dispersion agent, ultrasonic dispersion, after under nitrogen protection, magnetic agitation 0.5～1h in 50～60 ℃ of water-baths; 6～12mL strong aqua is added dropwise to said mixture, control time for adding is 20～30min, the pH value of rear regulator solution is 9～11, rising temperature to 80～90 ℃, keep the aging 4～5h of temperature, finish reaction, thing to be mixed carries out after magnetic separation separation with magnet after being chilled to room temperature, with deionized water and dehydrated alcohol, respectively wash 3 times, vacuum-drying at 50～70 ℃, obtains HNTS-Fe
3o
4nanotube;
(2) prepare the magnetic halloysite nanotubes (MH-C=C) of the two keys of finishing:
Ratio in magnetic halloysite nanotubes, toluene, methacrylic acid three raw material usage quantity is that 1g:25～35mL:3～8mL adds, first be scattered in toluene magnetic halloysite nanotubes is ultrasonic, slowly drip methacrylic acid again, dropwise, 18～24h refluxes at 65～70 ℃; Reaction finishes with magnet, to carry out magnetic separation separation afterwards, uses successively toluene and absolute ethanol washing, and dry, obtains the magnetic halloysite nanotubes of the two keys of finishing;
(3) prepare magnetic halloysite molecularly imprinted polymer (MH-MIP):
By template molecule 2,4-D and polymerization single polymerization monomer in molar ratio 1:2～6 join in acetonitrile solution, pre-assembled 3～5h at 0～5 ℃; By the ratio of mol ratio 1:16～24 of 2,4-D:DVB, add DVB and a small amount of AIBN,
The magnetic halloysite nanotubes (mass ratio of its quality and polymerization single polymerization monomer is 1:1～2) that adds subsequently the two keys of finishing that make in step (2), ultrasonic dispersion, logical nitrogen half an hour, first at 45～52 ℃ of pre-polymerization 3～7h, again at 53～65 ℃ of polymerization 18～22h, then at 75～85 ℃ of further polyase 13～7h; After reaction finishes, products therefrom is carried out under externally-applied magnetic field to separation, after use acetone, alcohol and water repetitive scrubbing product, the final mixed solution with methyl alcohol/acetic acid (8～9:1～2, V:V) Soxhlet is extracted 1～2d, removes template molecule, vacuum-drying under room temperature, obtains magnetic halloysite molecularly imprinted polymer material.
Beneficial effect of the present invention: the present invention carrys out supported magnetic ferroferric oxide particle by the corrosion halloysite nanotubes making through sulfuric acid corrosion halloysite nanotubes first, and further at the two keys of finishing and adopt surface imprinted technology with 2,4-D is that template is synthetic to 2,4-D has specific adsorption, and effectively separation is removed 2 in complex system, the magnetic halloysite molecularly imprinted polymer of 4-D.The present invention adopts dilute sulphuric acid by halloysite nanotubes inner wall corrosion to a certain extent, enriched the aperture of halloysite nanotubes inwall, then utilizing coprecipitation method is that magnetic ferroferric oxide between 20～30nm is embedded in halloysite inwall by the yardstick of generation, greatly increased the stability of magnetic halloysite nanotubes material structure, in the life-span of reusing that is conducive to magnetic halloysite molecularly imprinted polymer, also reduced because Fe 3 O 4 magnetic particle load is at the surperficial modification rate that affects methacrylic acid of halloysite nanotubes simultaneously; Secondly, the present invention has selected suitable polymerization single polymerization monomer and linking agent, with the magnetic halloysite nanotubes with certain two key amount modification of surfaces, with 2,4-D for template molecule, the magnetic halloysite molecularly imprinted polymer that polymerization obtains is to 2,4-D has special structure matching and stronger Intermolecular Forces, fast specific recognition and in conjunction with 2,4-D, improved the selective adsorption efficiency to 2,4-D.The magnetic halloysite molecularly imprinted polymer structure making by the inventive method is stable especially, and reusability is good, good to the specific recognition of 2,4-D, can well use magnetic and carry out efficient selective separation; And its preparation method is simple, raw material is cheap and easy to get, technique is simple, easy to implement.
Accompanying drawing explanation
[Fig. 1] is corrosion halloysite nanotubes and the two magnetic halloysite nanotubes of key of finishing and the infrared spectra comparison diagram of magnetic halloysite molecularly imprinted polymer of embodiment 1 preparation.
[Fig. 2] is that the corrosion magnetic halloysite nanotubes of embodiment 1 preparation contrasts figure with the transmission electron microscope of magnetic halloysite molecularly imprinted polymer: left figure is corrosion magnetic halloysite nanotubes; Right figure is magnetic halloysite molecularly imprinted polymer.
[Fig. 3] is the X-ray diffraction comparison diagram of the corrosion magnetic halloysite nanotubes of pure magnetic ferroferric oxide nano-particles and embodiment 1 preparation: a is magnetic ferroferric oxide; B is corrosion magnetic halloysite nanotubes.
The non-molecularly imprinted polymer of magnetic halloysite that [Fig. 4] makes for embodiment 1 and the dynamic adsorption curve comparison figure of magnetic halloysite molecularly imprinted polymer.
The non-molecularly imprinted polymer of magnetic halloysite that [Fig. 5] makes for embodiment 1 and the adsorption isothermal line comparison diagram of magnetic halloysite molecularly imprinted polymer.
The non-molecularly imprinted polymer of magnetic halloysite that [Fig. 6] makes for embodiment 1 and the specific selectivity comparison diagram of magnetic halloysite molecularly imprinted polymer.
Embodiment
Following examples are to further illustrate of the present invention, rather than restriction protection domain of the present invention.
(1) kinetics absorption is investigated: by 2,4-D molecularly imprinted polymer joins 2 of concentration known, in 4-D sample solution, then be transferred on vibrator, and be oscillatory reaction 70min under 200rmp～300rmp at vibration rotating speed, interval sampling, the rear magnet that utilizes carries out magnetic resolution, get solution testing absorbancy and calculate the concentration after adsorption equilibrium, according to the concentration difference of front and back, obtain adsorptive capacity Q.
(2) equilibrium adsorption is investigated: magnetic halloysite molecularly imprinted polymer material (MH-MIP) and the non-molecularly imprinted polymer of magnetic halloysite (MH-NIP) (are made according to the preparation method of MH-MIP, just do not add 2,4-D template molecule) join respectively the series 2 of concentration known, in 4-D sample solution, in constant temperature oscillator, shake 24h, after utilize magnet to carry out magnetic separation separation, get supernatant liquid, test absorbancy calculates the concentration after adsorption equilibrium, according to the concentration difference of front and back, obtains adsorptive capacity Q.
(3) specific selectivity is investigated: the MH-MIP of equivalent is joined respectively to 2 of same concentrations, in 4-D and analog phenoxy acetic acid thereof and 4-methyl-2-chlorophenoxyacetic acid, in constant temperature oscillator, shake 24h, after utilize magnet to carry out magnetic resolution, get supernatant liquid, test respectively absorbancy and calculate the concentration after adsorption equilibrium, according to the concentration difference of front and back, obtain adsorptive capacity Q; The specific selectivity experiment of MH-NIP is identical with above-mentioned steps.
Embodiment 1
(1) coprecipitation method preparation corrosion magnetic halloysite nanotubes (HNTS-Fe
3o
4)
2g halloysite nanotubes particle is dispersed in the dilution heat of sulfuric acid of 100mL2mol/L, after ultrasonic, in 60 ℃ of water-bath magnetic agitation 12h, filter, with a large amount of distilled water washs to PH=7,50 ℃, vacuum is dry, obtains the corrosion halloysite nanotubes (HNTS) of the rear dilatation of inner wall section corrosion.
Corrosion halloysite nanotubes, FERRIC CHLORIDE ANHYDROUS, Iron dichloride tetrahydrate are dissolved in 200mL deionized water according to mass ratio 0.2:0.69:0.51, add after the ultrasonic dispersion of polyvinyl alcohol (PVA) of 5wt% (take mixture total mass as benchmark), under nitrogen protection, magnetic agitation 1h in 60 ℃ of water-baths; 12mL strong aqua is added dropwise to said mixture, control time for adding is 30min, the pH value of rear regulator solution is 11, rising temperature to 80 ℃, keeps aging 4h, finishes reaction, thing to be mixed carries out magnetic resolution with magnet after being chilled to room temperature, with deionized water and dehydrated alcohol, respectively wash 3 times afterwards, vacuum-drying at 60 ℃, obtains HNTS-Fe
3o
4nanotube.
(2) preparation of the magnetic halloysite nanotubes (MH-C=C) of the two keys of finishing
Get corrosion halloysite Magnetic nano-pipe 1g and add 30mL dry toluene; ultrasonic 30min; add again 3mL to remove the methacrylic acid (MMA) of stopper; under nitrogen protection; in 70 ℃ of backflow 24h; reaction finishes with magnet, to carry out separation afterwards, respectively washs 3 times successively, and be dried in 60 ℃, vacuum with toluene, dehydrated alcohol.The magnetic halloysite nanotubes (MH-C=C) of the two keys of finishing that obtain can well be dissolved in the organic solvents such as ethanol, chloroform, acetonitrile.
(3) preparation of magnetic halloysite molecularly imprinted polymer (MH-MIP)
First, get template molecule 2,4 dichlorophenoxyacetic acid 0.11g (0.5mmol) and add 10mL acetonitrile and 0.17mL (2mmol) monomer 4-vinylpridine (4-VP) self-assembly 12h at 4 ℃, obtain pre-assembled solution.
Then, by magnetic halloysite nanotubes (MH-C=C), the 1.9mL(20mmol of the two keys of the 0.2g finishing of preparation in step (2)) linking agent Vinylstyrene (DVB) joins pre-assembled solution, letting nitrogen in and deoxidizing, stir the mixed solution that the polyvinylpyrrolidone adding after 30min by 0.1g is dissolved in the acetonitrile of 30mL and form small molecular weight polymer at 0.02g initiator azo-bis-isobutyl cyanide (AIBN) prepolymerization reaction 5h at 50 ℃, being warmed up to 60 ℃ continues, after reaction 20h, to continue to be warmed up at 80 ℃ and react 3h.After reaction finishes, be cooled to room temperature, with magnet, carry out separation, with methyl alcohol, wash away the complete monomer of unreacted and linking agent, 60 ℃, vacuum is dry.
Finally use methyl alcohol: mixed solution Soxhlet acetic acid=9:1(V/V) is extracted template molecule 2,4 dichlorophenoxyacetic acid is removed, until detect without template molecule and wash out and stop wash-out by high performance liquid phase.Elution time is 48h.Make the molecularly imprinted polymer on magnetic halloysite nanotubes surface leave hole.60 ℃, last vacuum is dry.
MH-NIP preparation method is consistent with preparation MH-MIP method and consumption, but does not add template molecule.
Above-mentioned synthetic magnetic halloysite nanotubes marking Molecularly Imprinted Polymer is carried out to Infrared Characterization, as in the infared spectrum of Fig. 1 3693 and 3622cm
-1absorption peak belong to the hydroxyl peak of halloysite nanotubes inside, 560 and 480cm
-1absorption peak belong to iron oxygen absorption peak, 1600cm
-1absorption peak proved that the magnetic halloysite nanotubes that two keys are modified successfully makes, 2900cm
-1the absorption peak explanation polymkeric substance of left and right is successfully wrapped in magnetic halloysite nanotubes surface: Fig. 2 is known, left side halloysite internal diameter is 20～25nm, external diameter is 40～45nm, the Z 250 ball particle 15～20nm on surface, thickness after the coated polymer of the right is 35～40nm: in Fig. 3, a curve is pure ferriferrous oxide particles, and b curve is halloysite ferriferrous oxide nano pipe.Between 20 °～70 °, can know six characteristic peak (2 θ=30.15 seeing Z 250 2 θ
, 35.54
, 43.21
, 53.41
, 57.13
, and 62.34
) in magnetic ferroferric oxide and magnetic ferroferric oxide halloysite nanotubes mixture peak position in (220), (311), (400), (422), (511), and (440) occur, yet, magnetic ferroferric oxide halloysite nanotubes is in 2 θ=12 °, and 21 °, the Shang You peak, position of 25 ° is because halloysite starting material cause.Illustrate that magnetic particle is successfully embedded in halloysite inside.
(1) coprecipitation method preparation corrosion magnetic halloysite nanotubes (HNTS-Fe
3o
4)
2g halloysite nanotubes particle is dispersed in the dilution heat of sulfuric acid of 100mL 2mol/L, after ultrasonic, in 60 ℃ of water-bath magnetic agitation 12h, filter, with a large amount of distilled water washs to PH=7,50 ℃, vacuum is dry, obtains the corrosion halloysite nanotubes (HNTS) of the rear dilatation of inner wall section corrosion.
Corrosion halloysite nanotubes, Iron(III) chloride hexahydrate, ferrous sulfate are dissolved in 200mL deionized water according to mass ratio 0.25:0.466:0.3, the ultrasonic dispersion of Macrogol 2000 (PEG-2000) that adds 5wt% (take mixture total mass as benchmark), after under nitrogen protection, magnetic agitation 1h in 50 ℃ of water-baths; The strong aqua that is 28% by 12mL volume fraction is added dropwise to said mixture, controlling time for adding is 30 min, the pH value of rear regulator solution is 11, rising temperature to 80 ℃, keeps aging 4 h, finishes reaction, thing to be mixed carries out magnetic resolution with magnet after being chilled to room temperature, with deionized water and dehydrated alcohol, respectively wash 3 times afterwards, vacuum-drying at 60 ℃, obtains HNTS-Fe
3o
4nanotube.
(2) preparation of the magnetic halloysite nanotubes (MH-C=C) of the two keys of finishing
Get corrosion halloysite Magnetic nano-pipe 1g and add 30mL dry toluene; ultrasonic 30min; add again 3mL to remove the methacrylic acid (MMA) of stopper; under nitrogen protection; in 70 ℃ of backflow 24h; reaction finishes with magnet, to carry out separation afterwards, respectively washs 3 times successively, and be dried in 60 ℃, vacuum with toluene, dehydrated alcohol.The magnetic halloysite nanotubes (MH-C=C) of the two keys of finishing that obtain can well be dissolved in the organic solvents such as ethanol, chloroform, acetonitrile.
(3) preparation of magnetic halloysite molecularly imprinted polymer (MH-MIP)
First, get template molecule 2,4 dichlorophenoxyacetic acid 0.11g (0.5mmol) and add 10mL acetonitrile and 0.17mL (2mmol) to locate monomer 4-vinylpridine (4-VP) self-assembly 12h at 4 ℃ of stopper, obtain pre-assembled solution.
Then, by magnetic halloysite nanotubes (MH-C=C), the 1.9mL(20mmol of the two keys of the 0.2g finishing of preparation in step (2)) join pre-assembled solution except stopper linking agent Vinylstyrene (DVB), letting nitrogen in and deoxidizing, stir the mixed solution that the polyvinylpyrrolidone adding after 30min by 0.1g is dissolved in the acetonitrile of 30mL and form small molecular weight polymer at 0.02g initiator azo-bis-isobutyl cyanide (AIBN) prepolymerization reaction 5h at 50 ℃, being warmed up to 60 ℃ continues, after reaction 20h, to continue to be warmed up at 80 ℃ and react 3h.After reaction finishes, be cooled to room temperature, with magnet, carry out separation, with methyl alcohol, wash away the complete monomer of unreacted and linking agent, 60 ℃, vacuum is dry.
Finally use methyl alcohol: mixed solution Soxhlet acetic acid=9:1(V/V) is extracted template molecule 2,4 dichlorophenoxyacetic acid is removed, until detect without template molecule and wash out and stop wash-out by high performance liquid phase.Elution time is 48h, makes the molecularly imprinted polymer on magnetic halloysite nanotubes surface leave hole.60 ℃, last vacuum is dry.MH-NIP preparation method is consistent with preparation MH-MIP method and consumption, but does not add template molecule.
Embodiment 3
Magnetic halloysite nanometer molecular imprinting polymer to embodiment 1 carries out adsorptive capacity detection: process is as follows: by the magnetic halloysite structure nano molecularly imprinted polymer of the embodiment of 5mg 1, to put into the concentration of substrate of 5mL be 80mg/L 2, in 4-D solution, being placed on vibration on Clothoid type vibrator mixes, in oscillatory process respectively at 5min, 10min, 15min, 20min, 30min, 40min, 50min, 60min, during 80min different time interval, with magnet, carry out separation, get supernatant liquid, test absorbancy calculates the concentration after adsorption equilibrium, according to the concentration difference of front and back according to formula Q
e=(C
o-C
e) * V/m, wherein C
oand C
ebe the starting point concentration of 2,4-D and the concentration after absorption, V is liquor capacity, and m is Polymer adsorption quality of materials.As shown in Figure 4, adsorption time comparatively fast just can reach adsorption equilibrium at 40min, can be calculated and obtains adsorptive capacity Q
max=34.9mg/g.
Magnetic halloysite nanometer molecular imprinting polymer to embodiment 1 carries out equilibrium adsorption detection: process is as follows: get each 5mg of MH-MIP and MH-NIP in ground flask, add 2 of different concns (25-400mg/L), 4-D solution 5mL, in constant temperature oscillator, shake 24h, with magnet, carry out separation, get supernatant liquid, test absorbancy calculate the concentration after adsorption equilibrium, according to the concentration difference of front and back according to the concentration difference of front and back according to formula Q
e=(C
o-C
e) * V/m, wherein C
oand C
ebe the starting point concentration of 2,4-D and the concentration after absorption, V is liquor capacity, and m is Polymer adsorption quality of materials.As shown in Figure 5, imprinted polymer Yu Fei imprinted polymer army is along with concentration rising adsorptive capacity increases.But can reach adsorption equilibrium under 400mg/L condition.Can be calculated and obtain adsorptive capacity Q.
The magnetic halloysite nanometer molecular imprinting polymer specificity of embodiment 1 is selected: get with phenoxy acetic acid and 4 – methyl-2-chlorophenoxyacetic acid of 2,4-D similar and test its specificity, compound concentration is the solution of 0.36mol/L.Accurately take MH-MIP and, each 5mg of MH-NIP is in ground flask, add respectively the above-mentioned solution of 2mL, in thermostat container at 25 ℃, after Static Adsorption 24h, with magnet, carry out separation, get supernatant liquid, test absorbancy calculates the concentration after adsorption equilibrium, obtains adsorptive capacity Q by following formula, obtain Qi, Qj in selection factor-alpha=Qi/Qj formula and represent that respectively molecularly imprinted polymer is to template molecule and substrate molecule adsorptive capacity separately according to the concentration difference of front and back.α is larger, and expression molecularly imprinted polymer is better to the selectivity of substrate molecule, and when α > 1.35, it has been generally acknowledged that imprinted polymer can be separated from blending ingredients by template molecule.Result shows to corrode magnetic halloysite molecularly imprinted polymer (MH-MIP) 2,4 dichlorophenoxyacetic acid is had to good selectivity.
Claims (7)
1. preparation is to 2,4-dichlorphenoxyacetic acid has the method for the magnetic halloysite molecularly imprinted polymer of specific adsorption, it is characterized in that, with sulfuric acid, halloysite nanotubes corrosion is obtained corroding halloysite nanotubes, described corrosion halloysite nanotubes and trivalent iron salt and divalent iron salt make magnetic halloysite nanotubes by coprecipitation method, described magnetic halloysite nanotubes and methacrylic acid react in toluene, obtain the magnetic halloysite nanotubes of the two keys of finishing; The magnetic halloysite nanotubes of the two keys of described finishing and polymerization single polymerization monomer and linking agent be take 2,4 dichlorophenoxyacetic acid after template is carried out polymerization, then remove 2,4 dichlorophenoxyacetic acid, obtain;
Described 2,4-dichlorphenoxyacetic acid, polymerization single polymerization monomer, linking agent three's mol ratio is 1:2～6:16～24, wherein, polymerization single polymerization monomer is one or more of 4-vinylpridine, 2-vinyl pyridine, vinyl benzyl chloride, and linking agent is Vinylstyrene or ethylene glycol dimethacrylate;
The two magnetic halloysite nanotubes of key of described finishing and the mass ratio of polymerization single polymerization monomer are 1:1～2;
The proportionlity of described magnetic halloysite nanotubes, toluene, methacrylic acid three usage quantity is 1g:25～35mL:3～8mL.
2. the method for claim 1, is characterized in that, the sulphuric acid soln that described corrosion halloysite nanotubes is is 0.5～2mol/L by concentration, under 55～65 ℃ of conditions, by halloysite nanotubes corrosion 12～15h, prepares.
3. the method for claim 1, it is characterized in that, described polymerization is first by polymerization single polymerization monomer and 2,4-dichlorphenoxyacetic acid carries out self-assembly 6～12h at 0～5 ℃, obtain assembling liquid, in described assembling liquid, add magnetic halloysite nanotubes and the linking agent of the two keys of finishing first at 45～52 ℃ of pre-polymerization 3～7h, then at 53～65 ℃ of polymerization 18～22h, then at 75～85 ℃ of further polyase 13～7h.
4. the method for claim 1, is characterized in that, described reaction is to stir 18～24h at 65～70 ℃.
5. the method for claim 1, is characterized in that, the described 2,4 dichlorophenoxyacetic acid that removes is to adopt methyl alcohol and the acetic acid mixed solvent that volume ratio is 8～9:1～2 to extract 1～2d.
6. the method for claim 1, is characterized in that, corrosion halloysite nanotubes, trivalent iron salt and divalent iron salt three's reaction mass ratio is 0.2～0.5:0.6～0.9:0.50.
7. the method for claim 1, is characterized in that, described coprecipitation method reaction conditions: first, at 50～60 ℃, react after 0.5～1h, regulating pH is 9～11, then at 80～90 ℃, aging 4～5h.
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| CN104844768A (en) * | 2015-04-22 | 2015-08-19 | 中南大学 | Preparation method and application of core-shell structure temperature sensitive magnetic protein imprinted microspheres |
| CN104844768B (en) * | 2015-04-22 | 2017-09-29 | 中南大学 | A kind of preparation method and applications of the Thermo-sensitive magnetic Western blotting microballoon of core shell structure |
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| CN106525948B (en) * | 2016-10-31 | 2019-04-19 | 扬州大学 | A kind of preparation method and application of molecular engram detection 2,4-d sensor |
| CN108435147A (en) * | 2018-05-16 | 2018-08-24 | 武汉霖泉环保科技有限公司 | A kind of preparation method of magnetic material |
| CN111978469A (en) * | 2019-05-21 | 2020-11-24 | 中国药科大学 | Preparation and application of mycotoxin and concealed toxin magnetic halloysite nanotube/molecularly imprinted polymer |
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