CN107200812A - A kind of preparation method of magnetic molecularly imprinted material - Google Patents
A kind of preparation method of magnetic molecularly imprinted material Download PDFInfo
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- B01J20/26—Synthetic macromolecular compounds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- C08K3/20—Oxides; Hydroxides
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- C08K2003/2272—Ferric oxide (Fe2O3)
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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Abstract
The invention discloses a kind of preparation method of magnetic molecularly imprinted material in chemical analysis test field.The magnetic nanoparticle that silica gel is wrapped up on surface is prepared first, modification then is carried out to its surface with modified Silica Gel agent, and magnetic molecularly imprinted material is finally made by the way of surface imprinted and thermal initiation.Magnetic molecularly imprinted material concentration and separation speed in the analysis detection of textile carcinogenic aromatic amine is fast, and selectivity is good, to target compound can specific recognition, stability is good, can Reusability, cost is more cheap, can put into industrial production.
Description
Technical field：
The invention belongs to chemical analysis test field, it is related to a kind of preparation method of magnetic molecularly imprinted material.
Background technology：
Azo compound is most, the most widely used class synthetic dyestuffs of kind, and research shows, many azo materials
With carcinogenesis, such as it is used for the butter yellow energy induced hepatocellular carcinoma that margarine is coloured, can causes wing as the methyl red of indicator
Skin and tumor of breast.Often there is false positive phenomenon in traditional detection method in aromatic amine in textile, and testing result is produced
Large effect.
Molecular engram technology of preparing (also referred to as molecular engram) (molecularly imprinting techniques, MIT)
Refer to obtain the polymer technology of preparing with template molecule matched on space structure and binding site, be one and come from height
The cross discipline of molecular chemistry, biochemistry, materials chemistry etc..In short, molecular engram is exactly the formation for copying Ag-Ab
Mechanism, forms the rigid macromolecule of high crosslinking around microsphere (imprinted molecule), removes after microsphere
The reactive group with binding ability is left in the network structure of polymer, the selection identification of height is shown to template molecule
Ability.Magnetic separation technique is a kind of new solid-liquid separation technique, is usually used in carrying for macromolecular substances such as DNA in biological sample
Take, separate, magnetic separation technique is gradually applied to the separation of pollutant in water body example in recent years.
At present, existing correlative study work is reported using magnetic nano ferroferric oxide as carrier, bisphenol-A, diethylstilbestrol,
The xenobiotics that estradiol etc. can produce influence to human body is template molecule, and preparing can under external magnetic field
To realize the material of fast and effectively separation of solid and liquid, but preparation technology is complex, and with the magnetic Nano of coated with silica
Particle (Fe3O4@SiO2) also relatively fewer for the research work of carrier, especially for the separation of carcinogenic aromatic amine in textile
The research of technology, current molecular imprinting technology there is no good application.Therefore, using the print for being wrapped in magnetic Nano material surface
Mark technology has important practical significance and extensively to the molecular recognition of carcinogenic aromatic amine, fast enriching, Separation Research in textile
General prospect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of magnetic molecularly imprinted material, comprise the following steps that：
(1) magnetic nanoparticle is prepared；
(2) the magnetic silica gel nano particle prepared on the basis of step (1)；
(3) using the magnetic silica gel nano material prepared by silica gel modifier modification step (2)：
(4) by the magnetic Nano material prepared by template molecule, function monomer, crosslinking agent, step (3), pore-foaming agent and draw
Agent reaction is sent out, magnetic molecularly imprinted material is obtained.
Magnetic nanoparticle described in step (1) is selected from Fe3O4With γ-Fe2O3Deng preferably Fe3O4。
Silica gel modifier described in step (3) is selected from alkenyl, aminopropyl, carboxyl, preferably alkenyl；It is highly preferred that described
Alkenyl derives from alkenyl silanes reagent.
Template molecule described in step (4) is 4,4 '-MDA, 3,3 '-dimethyl -4,4 '-diaminourea two
Phenylmethane or 4,4 '-methylene-two-(2- chloroanilines), molecular structure is respectively：
Function monomer described in step (4) is 2- vinylpyridines and 4-vinylpridine.
Crosslinking agent described in step (4) is ethylene glycol dimethacrylate.
Pore-foaming agent described in step (4) is toluene.
A kind of preparation method of magnetic molecularly imprinted material, specific implementation steps are：
Step (1) prepares Fe using solvent-thermal method3O4Nano particle：By FeCl3·6H2O and NaAc are dissolved in ethylene glycol
In, formed in homogeneous yellow solution, the autoclave that solution is transferred to closed polytetrafluoroethyllining lining, in 200 DEG C
Under the conditions of react 8h, question response after the completion of, product is naturally cooled into room temperature, is separated under additional magnetic fields, uses second
Alcohol wash products repeatedly, vacuum drying obtains Fe under the conditions of 60 DEG C3O4Nano-particle.
Step (2) prepares magnetic silica gel nano particle：By obtained Fe in step (1)3O4It is molten that nano-particle is scattered in ethanol
In liquid, 1~5ml tetraethyl orthosilicates are added under agitation, is stirred at room temperature after 2h and 1~10mlNH is slowly added dropwise3·H2O,
Mixture obtains Fe after at the uniform velocity stirring 24h at ambient temperature3O4@SiO2Nano material, is divided under additional magnetic fields
From with ethanol wash products repeatedly, being dried in vacuo under the conditions of 60 DEG C.
Step (3) modified magnetic silica gel nano material：By the Fe in step (2)3O4@SiO2Nano material is scattered in purifying
In toluene, nitrogen protection is lower to be added with ethanol wash products repeatedly after silica gel modifier and triethylamine, back flow reaction 24h, in 60
Vacuum drying obtains modified magnetic silica gel nano-particle under the conditions of DEG C.
Magnetic molecularly imprinted material is made in step (4) by the way of surface imprinted and thermal initiation：By template molecule and work(
Energy monomer is 1 according to mol ratio:4 are scattered in toluene, and modified magnetic silica gel nano-particle and friendship are added after pre-assembled two hours
The ratio of connection agent, template molecule and crosslinking agent is 1:10~1:30, azodiisobutyronitrile progress is added under nitrogen protective condition
Polymerisation, initiation temperature is 55~75 DEG C, after the completion of reaction, product is naturally cooled into room temperature, under additional magnetic fields
Separated, with methanol, wash products are and true under the conditions of 60 DEG C to remove unreacted reactant and monomer autopolymer repeatedly
Sky is dried to obtain MIPs nano-particles.
The present invention compared with the existing technology has the advantages that：
1. it is environment-friendly, during the use of quick screening material, it is only necessary to consume less organic solvent, Bu Huiyin
Enter other poisonous and harmful substances, it is environmentally friendly.
2. easy to operate, enrichment rate is fast.On the one hand obtained Material Balance speed is fast, and on the other hand obtained magnetic is received
Rice magnetism of material is good, and quick screening material is realized in the presence of externally-applied magnetic field, in very short time and mother liquor is quick and complete separates.
3. selectivity is good, obtained nano material has imprinted cavity, there is higher selection to recognize energy template molecule
Power, reduces the false positive issue that carcinogenic aromatic amine occurs in traditional detection in textile.
4. stability is good, it can be used repeatedly.Adsorbing object on magnetic Nano material can be easy to having
Machine solvent is eluted, while ensure that its imprinted cavity is not destroyed, the quick screening available for object next time.In example
Middle performance, the maximal absorptive capacity of obtained nano material is more than the 80% of first time after reusing 4 times.
5. cost is more cheap, it can put into production use.
Brief description of the drawings：
Fig. 1 is the synthesis signal for the magnetic molecularly imprinted material that fast enriching of the present invention separates textile carcinogenic aromatic amine
Figure；
Fig. 2 is the infrared spectrum of the magnetic molecularly imprinted material of the embodiment of the present invention 2 and various intermediate products；
Fig. 3 is SEM the and TEM photos of the magnetic molecularly imprinted material of the embodiment of the present invention 2；
Fig. 4 is the hysteresis curve of the magnetic molecularly imprinted material of the embodiment of the present invention 2 and various intermediate products；
Fig. 5 is the magnetic molecularly imprinted material of the embodiment of the present invention 2 quick separating schematic diagram under additional magnetic fields.
Embodiment
The present invention provides a kind of preparation method of magnetic molecularly imprinted material, with reference to the accompanying drawings and examples to the present invention
It is further described.
Embodiment 1
The preparation method of the magnetic molecularly imprinted material of fast enriching separation textile carcinogenic aromatic amine of the present invention, with 4,
Exemplified by 4 '-MDA
The synthesis of the magnetic molecularly imprinted material of fast enriching separation textile carcinogenic aromatic amine provided by the present invention is shown
It is intended to as shown in Fig. 2 its specific preparation method can be divided into following four step：
First, Fe is prepared by solvent-thermal method3O4Nano-particle：By 2.7g FeCl3·6H2O and 7.2g NaAc are dissolved in
In 100ml ethylene glycol, stir, until forming homogeneous yellow solution, solution is transferred in closed polytetrafluoroethylene (PTFE) energetically
In the autoclave of lining, reacted under the conditions of 200 DEG C after the completion of 8h, question response, product is naturally cooled into room temperature, additional
Separated under magnetic fields, with ethanol wash products repeatedly, vacuum drying obtains Fe under the conditions of 60 DEG C3O4Nano-particle.
Secondly, by Fe3O4Nano-particle gel coated, is made embedding formula magnetic silica gel particle.Weigh 0.1g Fe3O4Receive
Rice corpuscles in 90ml ethanol solutions, ultrasonic disperse 30min after under 300rpm at the uniform velocity stirring add 5ml tetraethyl orthosilicates,
It is stirred at room temperature after 2h and 10ml NH is slowly added dropwise3·H2O, mixture is obtained after at the uniform velocity stirring 24h at ambient temperature
Fe3O4@SiO2Nano material, is separated under additional magnetic fields, true under the conditions of 60 DEG C with ethanol wash products repeatedly
Sky is dried.
Again, with silica gel modifier modified magnetic silica gel particle.Above-mentioned magnetic silica gel particle 0.1g is taken to be scattered in 50ml pure
In toluene solution after change, nitrogen is passed through into solution to exclude moisture therein.Then 3ml vinyl three is added into system
Ethoxysilane, is added dropwise after 6ml triethylamines, ultrasonic disperse and leads to 10min N again2, back flow reaction 24h at 125 DEG C.Question response is completed
Afterwards, product is naturally cooled into room temperature, separated under additional magnetic fields, with ethanol wash products repeatedly, in 60 DEG C of bars
Vacuum drying obtains the magnetic silica gel nano-particle of modified by vinyl under part.
Finally, magnetic surface imprinted polymer is prepared.The 4,4 '-MDA for weighing 1mmol is purified in 50ml
In toluene afterwards, according to mol ratio 1:4 add 4-vinylpridine, and nitrogen is passed through into solution to exclude moisture therein, room
The lower stirring 2h of temperature, makes template molecule be sufficiently mixed with function monomer, carries out pre-assembled.Then modified Fe is added3O4@SiO2
Nano material, 15mmol crosslinking agent ethylene glycol dimethacrylates EGDMA and 40mg initiator azodiisobutyronitrile
(AIBN), ultrasound degassing 10min, nitrogen bubble 10min is being passed through into solution, to remove the oxygen in solution.Container is close
Envelope, under conditions of nitrogen protection, 6h is reacted at 55 DEG C, is warming up to 65 DEG C of reaction 24h, then be warming up to 75 DEG C of reaction 6h.Treat anti-
Should after the completion of, product is naturally cooled into room temperature, separated under additional magnetic fields, with methanol repeatedly wash products to go
Except unreacted reactant and monomer autopolymer, the elution of template molecule is then carried out using the method for surname extraction, and in 60
Vacuum drying obtains magnetic imprinted polymer (MIPs) nano-particle under the conditions of DEG C.
Embodiment 2
The preparation method of the magnetic molecularly imprinted material of fast enriching separation textile carcinogenic aromatic amine of the present invention, with 4,
Exemplified by 4 '-methylene-two-(2- chloroanilines)
Specific preparation method can be divided into following four step：
First, Fe is prepared by solvent-thermal method3O4Nano-particle：By 2.7g FeCl3·6H2O and 7.2g NaAc are dissolved in
In 100ml ethylene glycol, stir, until forming homogeneous yellow solution, solution is transferred in closed polytetrafluoroethylene (PTFE) energetically
In the autoclave of lining, 8h is reacted under the conditions of 200 DEG C.After the completion of question response, product is naturally cooled into room temperature, additional
Separated under magnetic fields, with ethanol wash products repeatedly, vacuum drying obtains Fe under the conditions of 60 DEG C3O4Nano-particle.
Secondly, by Fe3O4Nano-particle gel coated, is made embedding formula magnetic silica gel particle.Weigh 0.1g Fe3O4Receive
Rice corpuscles in 90ml ethanol solutions, ultrasonic disperse 30min after under 300rpm at the uniform velocity stirring add 5ml tetraethyl orthosilicates,
It is stirred at room temperature after 2h and 10ml NH is slowly added dropwise3·H2O, mixture is obtained after at the uniform velocity stirring 24h at ambient temperature
Fe3O4@SiO2Nano material, is separated under additional magnetic fields, true under the conditions of 60 DEG C with ethanol wash products repeatedly
Sky is dried.
Again, with silica gel modifier modified magnetic silica gel particle.Above-mentioned magnetic silica gel particle 0.1g is taken to be scattered in 50ml pure
In toluene solution after change, nitrogen is passed through into solution to exclude moisture therein.Then 3ml vinyl three is added into system
Ethoxysilane, is added dropwise after 6ml triethylamines, ultrasonic disperse and leads to 10min N again2, back flow reaction 24h at 125 DEG C.Question response is completed
Afterwards, product is naturally cooled into room temperature, separated under additional magnetic fields, with ethanol wash products repeatedly, in 60 DEG C of bars
Vacuum drying obtains the magnetic silica gel nano-particle of modified by vinyl under part.
Finally, magnetic surface imprinted polymer is prepared.Weigh 1mmol 4,4 '-methylene-two-(2- chloroanilines) in
In the toluene of 50ml after purification, according to mol ratio 1:4 add 2- vinylpyridines, nitrogen are passed through into solution therein to exclude
Moisture, stirs 2h at room temperature, template molecule is sufficiently mixed with function monomer, carries out pre-assembled.Then add modified
Fe3O4@SiO2Nano material, 20mmol crosslinking agent ethylene glycol dimethacrylates EGDMA and 40mg initiator azo two is different
Butyronitrile (AIBN), ultrasound degassing 10min, nitrogen bubble 10min is being passed through into solution, to remove the oxygen in solution.It will hold
Device is sealed, and under conditions of nitrogen protection, 6h is reacted at 55 DEG C, is warming up to 65 DEG C of reaction 24h, then be warming up to 75 DEG C of reaction 6h.
After the completion of question response, product is naturally cooled into room temperature, separated under additional magnetic fields, with methanol wash products repeatedly
To remove unreacted reactant and monomer autopolymer, the elution of template molecule is then carried out using the method for surname extraction, and
Vacuum drying obtains magnetic imprinted polymer (MIPs) nano-particle under the conditions of 60 DEG C.
Embodiment 3
The structural characterization of the magnetic molecularly imprinted material of quick screening textile carcinogenic aromatic amine of the invention
The present embodiment is that structural characterization is carried out to magnetic molecularly imprinted material obtained in embodiment 2, specific as follows：
1. Fourier's infrared spectrum
Using FTIS to magnetic nanoparticle, magnetic silica gel nano particle, modified by vinyl after
Magnetic silica gel nano particle and magnetic molecularly imprinted polymer are characterized, and the preparation of sample is carried out using pellet technique.
As can be seen from Figure 2 Fe3O4After nano particle cladding silica gel, 1450cm-1Locate peak to disappear, in 1662cm–1Place goes out
Existing characteristic peak is H-O-H flexural vibrations peak, 1078cm-1Locate the symmetrical stretching vibration absworption peak for Si-O-Si, 780cm-1
The weak absorbing at place is Si-O-Si antisymmetric stretching vibration absworption peak and 480cm-1Locate the flexural vibrations absworption peak for Si-O-Si.
After alkenyl modification, 3470cm-1The peak at place reduces, and illustrates that-the OH of silicon ball surface is reduced；In 1658,1412cm-1The feature at place is inhaled
Receive stretching vibration peak, the vinylic end group=CH of C=C keys2Scissoring vibration peak.After magnetic molecularly imprinted polymer is modified compared with alkenyl
Fe3O4@SiO2 3446cm-1Place is compared with 3470cm-1Contain-OH and-NH in the peak enhancing at place, MIPs2, 2989cm-1、1391cm-1
Locate as-CH3Stretching vibration and flexural vibrations, 1728cm-1The sharp strong peak in place is the absworption peak of carbonyl, 1637cm-1The suction at place
Receive the stretching vibration that peak is C=C, 1453cm-1The absworption peak of the moderate strength at place is the absworption peak of carboxylic acid.The change explanation of spectrogram
Imprinted polymer is successfully grafted to Fe3O4@SiO2Surface.
2.SEM and TEM photos
Using SEM (SEM) and transmission electron microscope (TEM) to obtained magnetic molecule silver and material
The structure of material carry out analysis sample making course be by sample in ethanol in proper amount solution ultrasonic disperse, be then added dropwise on copper mesh, treat
Ethanol evaporate into it is dry after can carry out the measure of sample.
As can be seen from Figure 3 the particle of magnetic molecularly imprinted polymer is substantially spherical in shape, and particle size is left in 300nm
The right side, even particle size, dispersiveness is very good；The internal color of polymeric material is deep compared with outer rim color, and demonstrating polymer is
Formed on magnetic Nano material surface.
3. hysteresis curve
Fe is characterized by hysteresis curve3O4Nano material, Fe3O4@SiO2With MIPs saturation magnetization intensity, contrast
Fe3O4Nano material cladding silica gel, surface form the change of magnetic intensity after imprinted polymer.
It was found from from Fig. 4 left figures, Fe3O4, Fe3O4@SiO2Hysteresis curve spectrogram with tri- kinds of materials of MIPs is on origin
Symmetrically, and shape is similar.In figure, Fe3O4, Fe3O4@SiO2Reduced successively with MIPs saturation magnetization, its value is respectively
84.04emu/g, 14.10emu/g and 6.60emu/g, although Fe3O4@SiO2With MIPs compared with Fe3O4Saturation magnetization reduction
A lot, but MIPs polymer still have good magnetic response.
It can be seen from Fig. 5 in the presence of no magnetic field, MIPs polymer is uniformly dispersed in the solution；Additional magnetic
After field action, MIPs polymer is attracted to the side of magnet；After externally-applied magnetic field effect is removed, under oscillating condition, magnetic
Molecularly imprinted polymer is uniformly dispersed again in the solution.
Claims (10)
1. a kind of preparation method of magnetic molecularly imprinted material, it is characterised in that comprise the following specific steps that：
(1) magnetic nanoparticle is prepared；
(2) the magnetic silica gel nano particle prepared on the basis of step (1)；
(3) using the magnetic silica gel nano material prepared by silica gel modifier modification step (2)；
(4) by magnetic Nano material, pore-foaming agent and the initiator prepared by template molecule, function monomer, crosslinking agent, step (3)
Reaction, obtains magnetic molecularly imprinted material.
2. the preparation method of a kind of magnetic molecularly imprinted material according to claim 1, it is characterised in that in step (1)
The magnetic nanoparticle is selected from Fe3O4Or γ-Fe2O3。
3. the preparation method of a kind of magnetic molecularly imprinted material according to claim 1, it is characterised in that in step (1)
The magnetic nanoparticle is preferably Fe3O4。
4. the preparation method of a kind of magnetic molecularly imprinted material according to claim 1, it is characterised in that in step (3)
The silica gel modifier is selected from alkenyl, aminopropyl, carboxyl.
5. the preparation method of a kind of magnetic molecularly imprinted material according to claim 1, it is characterised in that in step (3)
The silica gel modifier is preferably alkenyl, and the alkenyl derives from alkenyl silanes reagent.
6. the preparation method of a kind of magnetic molecularly imprinted material according to claim 1, it is characterised in that in step (4)
The template molecule is 4,4 '-MDA, 3,3 '-dimethyl -4,4 '-MDA or 4,4 '-methylene
Base-two-(2- chloroanilines), molecular structure is respectively：
7. the preparation method of a kind of magnetic molecularly imprinted material according to claim 1, it is characterised in that in step (4)
The function monomer is 2- vinylpyridines and 4-vinylpridine.
8. the preparation method of a kind of magnetic molecularly imprinted material according to claim 1, it is characterised in that in step (4)
The crosslinking agent is ethylene glycol dimethacrylate.
9. the preparation method of a kind of magnetic molecularly imprinted material according to claim 1, it is characterised in that in step (4)
The pore-foaming agent is toluene.
10. a kind of preparation method of magnetic molecularly imprinted material according to claim 1, it is characterised in that specific implementation
Mode is as follows：
(1) Fe is prepared using solvent-thermal method3O4Nano particle：By FeCl3·6H2O and NaAc are dissolved in ethylene glycol, are formed homogeneous
Yellow solution, in the autoclave that solution is transferred to closed polytetrafluoroethyllining lining, reacted under the conditions of 200 DEG C
After the completion of 8h, question response, product is naturally cooled into room temperature, separated under additional magnetic fields, is cleaned repeatedly with ethanol
Product, vacuum drying obtains Fe under the conditions of 60 DEG C3O4Nano-particle；
(2) magnetic silica gel nano particle is prepared：By obtained Fe in step (1)3O4Nano-particle is scattered in ethanol solution,
1~5ml tetraethyl orthosilicates are added under stirring condition, is stirred at room temperature after 2h and 1~10ml NH is slowly added dropwise3·H2O, mixture
At the uniform velocity obtain Fe after stirring 24h at ambient temperature3O4@SiO2Nano material, is separated under additional magnetic fields, uses second
Alcohol wash products repeatedly, are dried in vacuo under the conditions of 60 DEG C；
(3) modified magnetic silica gel nano material：By the Fe in step (2)3O4@SiO2Nano material is scattered in purifying toluene, nitrogen
Added under gas shielded with ethanol wash products repeatedly after silica gel modifier and triethylamine, back flow reaction 24h, it is true under the conditions of 60 DEG C
Sky is dried to obtain modified magnetic silica gel nano-particle；
(4) magnetic molecularly imprinted material is made by the way of surface imprinted and thermal initiation：Template molecule and function monomer are pressed
It is 1 according to mol ratio:4 are scattered in toluene, and modified magnetic silica gel nano-particle and crosslinking agent, template are added after pre-assembled two hours
The ratio of molecule and crosslinking agent is 1:10~1:30, azodiisobutyronitrile progress polymerisation is added under nitrogen protective condition,
Initiation temperature is 55~75 DEG C, and after the completion of reaction, product is naturally cooled into room temperature, separated under additional magnetic fields,
With methanol, wash products are obtained with removing unreacted reactant and monomer autopolymer, and being dried in vacuo under the conditions of 60 DEG C repeatedly
Magnetic molecularly imprinted material.
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| CN112844335A (en) * | 2020-12-30 | 2021-05-28 | 中南林业科技大学 | Acid-resistant magnetic nano adsorbent and preparation method thereof |
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