CN105693918B - A kind of preparation method of magnetic hollow structural molecule imprinted polymer - Google Patents
A kind of preparation method of magnetic hollow structural molecule imprinted polymer Download PDFInfo
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- CN105693918B CN105693918B CN201610062396.1A CN201610062396A CN105693918B CN 105693918 B CN105693918 B CN 105693918B CN 201610062396 A CN201610062396 A CN 201610062396A CN 105693918 B CN105693918 B CN 105693918B
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- imprinted polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008961 swelling Effects 0.000 claims abstract description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 6
- -1 iron ion Chemical class 0.000 claims abstract description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-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
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- JGAALXVSFDPKRK-UHFFFAOYSA-N CC(C=C)(C)C.C(O)C(CC)(CO)CO Chemical group CC(C=C)(C)C.C(O)C(CC)(CO)CO JGAALXVSFDPKRK-UHFFFAOYSA-N 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000005456 glyceride group Chemical group 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000006249 magnetic particle Substances 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ICFXCSLDPCMWJI-UHFFFAOYSA-N 2,3-dimethylbut-2-enoic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CC(C)=C(C)C(O)=O.CCC(CO)(CO)CO ICFXCSLDPCMWJI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 244000230342 green foxtail Species 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
Abstract
The present invention discloses a kind of preparation method of magnetic hollow structural molecule imprinted polymer, comprises the following steps：（1）Using hydroxyethyl methacrylate as function monomer, GMA is co-monomer, and the molecularly imprinted polymer with hollow structure of epoxy radicals has been prepared in surface graft using multistep seed swelling polymerization method；（2）Step（1）Molecularly imprinted polymer handled with perchloric acid, make the epoxy ring-opening on surface；（3）Through step（2）The molecularly imprinted polymer of processing is scattered with solvent, then by the mol ratio of iron ion and ferrous ion is 2:1 adds molysite and ferrous salt, and regulation to alkalescence, reaction obtains magnetic hollow structural molecule imprinted polymer.The present invention first prepares hollow imprinted polymer, then magnetic particle is grown in its surface in situ, so as to successfully prepare the molecularly imprinted polymer with magnetic hollow structure.It has high binding capacity and quick Magneto separate feature.
Description
Technical field
The invention belongs to molecularly imprinted polymer field, and in particular to a kind of magnetic hollow structural molecule imprinted polymer
Preparation method.
Background technology
Molecularly imprinted polymer is obtained extensively because of characteristics such as its selectivity height, chemically stables in terms of Chemical Decomposition and sensing
General application, but binding capacity is relatively low, the difficult development for limiting molecular imprinting technology of separation.Hollow imprinted polymer can be effective
Solve the problem of molecularly imprinted polymer binding capacity is low.Magneto separate is incorporated into molecular engram by magnetic molecularly imprinted polymer
In, the problem of effectively can solving to separate difficulty.Printed with reference to the magnetic hollow molecule of both Magneto separate and hollow imprinted polymer advantage
There is technical barrier in the preparation of mark polymer, there are no relevant report always.
Multistep seed swelling polymerization method is to prepare one of single dispersing polymeric hollow microsphere ideal method at present, such as《Print
The preparation of mark aquagel membrane and the hollow trace microballoon of single hole and its performance study》（Zhang Zhong, University Of Nanchang, 37-38 in 2012
Page）Disclosing first to add in the dispersion liquid of seed microballoon helps sweller dibutyl phthalate to carry out being swelled for the first step,
Add function monomer methacrylic acid, pore-foaming agent toluene and template molecule, be swelled again, then add crosslinking agent with
And initiator swollen-state polymerization, eventually pass appropriate solvent elution and remove pore-foaming agent, template molecule etc., obtain hollow trace polymerization
Thing microballoon.
The many progress by core of magnetic microsphere of the process route of traditional magnetic molecularly imprinted polymer are surface imprinted, so cause
Polymer is difficult to cavitation.
The content of the invention
The technical problem to be solved in the present invention is to overcome existing defect there is provided a kind of magnetic hollow structural molecule trace
The preparation method of polymer.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of preparation method of magnetic hollow structural molecule imprinted polymer, comprises the following steps：
（1）Using hydroxyethyl methacrylate as function monomer, GMA is co-monomer, using multistep
Seed swelling polymerization method has prepared in surface graft the molecularly imprinted polymer with hollow structure of epoxy radicals；
（2）Step（1）Molecularly imprinted polymer handled with perchloric acid, make the epoxy ring-opening on surface；
（3）Through step（2）The molecularly imprinted polymer of processing is scattered with solvent, then by iron ion and mole of ferrous ion
Than for 2:1 adds molysite and ferrous salt, and regulation to alkalescence, reaction obtains magnetic hollow structural molecule imprinted polymer.
Further, step（1）Two-step seed swelling polymerization using polystyrene microsphere as seed, first with helping sweller pair
Seed be swelled for the first time, is added function monomer, co-monomer, pore-foaming agent and template molecule and is swelled again, then
Add crosslinking agent and initiator carries out swollen-state polymerization, finally elution removes pore-foaming agent, template molecule, obtains surface graft epoxy
The molecularly imprinted polymer with hollow structure of base.
Further, described to help sweller for dibutyl phthalate, pore-foaming agent is generally non-（It is weak）Polar organic solvent,
Such as toluene or acetonitrile；Crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, trimethylol propane trimethyl acrylic acid
Ester or N, N- methylene diacrylamine；Initiator is that oil-soluble initiator just can be with such as azodiisobutyronitrile or peroxidating two
Benzoyl.
Further, step（2）In, preferably using water-ethanol mixed liquor it is anti-when molecularly imprinted polymer is handled with perchloric acid
Answer medium.
Further, GMA consumption very little, causes the hydroxyl value on surface after open loop few, is unfavorable for original
Position growth magnetic particle, too many to cause magnetic particle too many again, cover aggregation thing surface causes the combination of imprinted polymer to be held
The volume ratio of amount reduction, hydroxyethyl methacrylate and GMA is 1:（08-1.2）It can receive,
Preferably 1:1.
Further, the molysite is iron chloride, and the ferrous salt is frerrous chloride.
Further, step（3）Reaction temperature there is no particularly severe requirement, typically control 70-85 DEG C.
The present invention first prepares hollow imprinted polymer, then magnetic particle is grown in its surface in situ, so as to successfully prepare
Provide the molecularly imprinted polymer for the hollow structure that is magnetic.It has high binding capacity and quick Magneto separate feature.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and constitutes a part for specification, the reality with the present invention
Applying example is used to explain the present invention together, is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the electron microscope of magnetic hollow structural molecule imprinted polymer of the present invention and its precursor；
Fig. 2 is present invention process route map；
Fig. 3 is the magnetic property curve of magnetic hollow structural molecule imprinted polymer of the present invention；
Fig. 4 is the capacity curve of magnetic hollow structural molecule imprinted polymer of the present invention.
Embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that preferred reality described herein
Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment 1
1. the preparation of polystyrene seed uses dispersion copolymerization method, process is as follows：Added in 100 mL ethanol 20 mL go from
Sub- water, 1.4 g polyvinylpyrrolidones（PVP）Ultrasonic disperse is uniform.It is under fast stirring that 80 mg initiators azos two are different
Butyronitrile（AIBN）It is added dropwise to the mixed solution of 10 mL monomer styrenes in dispersion, after the min of letting nitrogen in and deoxidizing 30, by system
Seal, 24 h are reacted at 60 DEG C.Polymerization is centrifuged after terminating, and gained polystyrene microsphere is cleaned into 40 DEG C of vacuum after three times with ethanol
It is dried overnight standby, pattern is as shown in Figure 1a.
2. multistep seed swelling polymerization method prepares molecular blotting polymer microsphere：By 0.125 g lauryl sodium sulfate
（SDS）It is added to 100 mL deionized waters in 250 mL there-necked flasks, then adds 0.2g polystyrene microspheres, ultrasonic disperse
After uniform；First add 0.7mL dibutyl phthalates（DBP）24h is swelled at room temperature；Add 10 mL toluene, 1.0 mL first
Base hydroxy-ethyl acrylate（), HEMA 1.0 mL GMAs（GMA）, 2 mmol (0.43g) atrazine,
It is swelled 24 h again at room temperature；Then 2.0 mL divinylbenzenes are added（DVB）The 3rd step is swelled at room temperature with 60 mg AIBN
After 24 h, 70 DEG C, the lower reaction 24h of nitrogen protection are warming up to.After reaction terminates, polymer is collected by filtration, is first washed with dichloromethane
De- polystyrene seed, again with methanol/acetic acid（9:1）Elution removes template molecule atrazine, obtains surface graft epoxy radicals
The molecularly imprinted polymer with hollow structure, pattern is as shown in Figure 1 b.
3. epoxy ring-opening：400 mg molecularly imprinted polymers are added in 25 mL 10vt% high chloro acid solutions, room
Temperature reaction 24h.To improve open loop effect, 5 mL ethanol are added in high chloro acid solution.Filtering, water is cleaned to neutrality, obtained
The hollow imprinted polymer of surface hydroxylation.
4. growth in situ magnetic nano-particle：By the 200 hollow imprinted polymers of mg surface hydroxylations and 20 mL water-first
Alcohol（4:1) mixed solution is added in 100 mL three-neck flasks, then adds 0.02 mmol FeCl3·6H2O ultrasonic disperses are equal
It is even, 30 min are stirred at room temperature, are passed through nitrogen and are continued the min of stirring reaction 10, then toward adding 0.01mmol in solution
FeCl2·4H2O, dissolving.Continue logical nitrogen, and temperature is risen to after 80 DEG C, 10 min, 3 mL ammoniacal liquor are added dropwise, and not
It is disconnected to be stirred and maintaining nitrogen purge.1h is reacted at 80 DEG C.Magnetic hollow structural molecule imprinted polymer is divided using magnet
Separate out and, dried with after secondary deionized water and ethanol cyclic washing to neutrality, obtain magnetic hollow structural molecule trace polymerization
Thing, pattern is as illustrated in figure 1 c.
The process route of magnetic hollow structural molecule imprinted polymer is as shown in Figure 2.
The preparation method of the non-imprinted polymer of magnetic hollow ibid, is differed only in, and during multistep seed swelling polymerization, is not added with
Enter template molecule.
Fig. 3 is the magnetic property curve of magnetic hollow structural molecule imprinted polymer.As seen from the figure, highest is magnetized to
2.75 emu/g, dispersed polymer can illustrate that the material prepared has magnetic under the effect of extraneous magnet with rapid aggregation
Property, it is possible to achieve Magneto separate.Prove simultaneously, magnetic particle growth in situ is on imprinted polymer surface.
Binding capacity is tested
20 mg imprinted polymers（MIPs）It is added in 5 mL scale test tubes, adds the green bristlegrass of 2 mL various concentrations
Tianjin acetonitrile solution is removed, at room temperature after 24 h of vibration absorption, centrifuges, supernatant is quantified with high performance liquid chromatography.Knot
Capacity is closed to be calculated using following equation：Determine.MIPs adsorbanceQCalculated with below equation：
Q=(C 0 -C F )V/m
Wherein,C 0 （mg/mL）WithC F （mg/mL）For the initial concentration and ultimate density of atrazine acetonitrile solution,V（mL）It is
The volume of solution,m（g）For the quality of polymer.Each sample parallel determination three times, average.
With the non-imprinted polymer of magnetic hollow as a comparison.Binding capacity curve is as shown in figure 4, magnetic hollow trace polymerization
Many high to the binding capacity imprinted polymer more non-than magnetic hollow of atrazine of thing, illustrate the presence of trace binding site.Trace
The factor, is defined as the binding capacity and accordingly the ratio between non-imprinted polymer binding capacity of imprinted polymer.In this experiment, reach
During adsorption equilibrium, imprinting factor is 5.2.High imprinting factor illustrates the presence of high binding capacity.
The magnetic hollow trace of table 1（Non- trace）The binding capacity Q (mg/g) of polymer
。
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or to which part technical characteristic progress equivalent.
Within the spirit and principles of the invention, any modifications, equivalent substitutions and improvements made etc., should be included in the present invention's
Within protection domain.
Claims (6)
1. a kind of preparation method of magnetic hollow structural molecule imprinted polymer, comprises the following steps：
（1）Using hydroxyethyl methacrylate as function monomer, GMA is co-monomer, using multistep seed
Swollen-state polymerization method has prepared in surface graft the molecularly imprinted polymer with hollow structure of epoxy radicals；
（2）Step（1）Molecularly imprinted polymer handled with perchloric acid, make the epoxy ring-opening on surface；
（3）Through step（2）The molecularly imprinted polymer of processing is scattered with solvent, then is by the mol ratio of iron ion and ferrous ion
2:1 adds molysite and ferrous salt, and regulation to alkalescence, reaction obtains magnetic hollow structural molecule imprinted polymer；
Step（1）Multistep seed swelling polymerization method using polystyrene microsphere as seed, first with helping sweller to carry out to seed
Once it is swelled, adds function monomer, co-monomer, pore-foaming agent and template molecule and be swelled again, then add crosslinking agent
Swollen-state polymerization is carried out with initiator, finally elution removes pore-foaming agent, template molecule, obtains in the having of surface graft epoxy radicals
The molecularly imprinted polymer of hollow structure；
The volume ratio of the hydroxyethyl methacrylate and GMA is 1:（0.8-1.2）.
2. preparation method according to claim 1, it is characterised in that：It is dibutyl phthalate, pore to help sweller
Agent is toluene or acetonitrile；Crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, trimethylol propane trimethyl propylene
Acid esters or N, N- methylene diacrylamine；Initiator is azodiisobutyronitrile or dibenzoyl peroxide.
3. preparation method according to claim 1, it is characterised in that：Hydroxyethyl methacrylate and Glycidyl methacrylate
The volume ratio of glyceride is 1:1.
4. preparation method according to claim 1, it is characterised in that：Step（2）In, molecularly imprinted polymer perchloric acid
Using water-ethanol mixed liquor as reaction medium during processing.
5. preparation method according to claim 1, it is characterised in that：The molysite is iron chloride, and the ferrous salt is chlorine
Change ferrous.
6. preparation method according to claim 1, it is characterised in that：Step（3）Reaction temperature be 70-85 DEG C.
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| CN102585119A (en) * | 2012-02-23 | 2012-07-18 | 宁波市疾病预防控制中心 | Preparation method of magnetic nanometer molecular imprinting composite material related to estrogen |
| CN104140501A (en) * | 2014-07-22 | 2014-11-12 | 中国科学院烟台海岸带研究所 | Thermosensitive bisphenol A (BPA) imprinted polymeric microsphere and application thereof |
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| CN102585119A (en) * | 2012-02-23 | 2012-07-18 | 宁波市疾病预防控制中心 | Preparation method of magnetic nanometer molecular imprinting composite material related to estrogen |
| CN104140501A (en) * | 2014-07-22 | 2014-11-12 | 中国科学院烟台海岸带研究所 | Thermosensitive bisphenol A (BPA) imprinted polymeric microsphere and application thereof |
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