CN105924578A - Preparation of difunctional monomer magnetic molecularly-imprinted polymer and application of polymer in adsorption on bisphenol A in wastewater - Google Patents
Preparation of difunctional monomer magnetic molecularly-imprinted polymer and application of polymer in adsorption on bisphenol A in wastewater Download PDFInfo
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- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Abstract
The invention discloses a difunctional monomer magnetic molecularly-imprinted polymer. The difunctional monomer magnetic molecularly-imprinted polymer is prepared by taking ATP-Fe3O4 as a matrix, taking bisphenol A as a template and taking acrylamide and methacrylic acid as functional monomers under the action of a cross-linking agent and an initiating agent through a thermal polymerization method. Adsorption tests show that the prepared difunctional monomer magnetic molecularly-imprinted polymer shows the high selective recognition capacity on template molecule bisphenol A, has the high heat stability, has the specific adsorption effect on BPA in the wastewater, is used for detecting BPA in a water sample and has the advantages of the fast responsiveness, the predetermination property, the recognizability and the practicability, and therefore the difunctional monomer magnetic molecularly-imprinted polymer has the very good application prospect in detection and adsorption on bisphenol A (BPA) in the wastewater in wastewater treatment.
Description
Technical field
The invention belongs to detection and the processing technology field of Organic Pollutants in Wastewater, relate to a kind of with methacrylic acid and acrylamide the preparation method of the molecular imprinted polymer on surface as function monomer；The present invention also relates to the application of bisphenol-A in absorption waste water of this polymer.
Background technology
Bisphenol-A, also referred to as BPA, industrially bisphenol-A is used to the materials such as polycarbonate synthesis (PC) and epoxy resin.Just it is used for since the sixties manufacturing coating inside plastics (milk) bottle, the cup with sucking device of child, Food & Drink (milk powder) tank.BPA is ubiquitous, from mineral water bottle, medical apparatus and instruments to and packaging for foodstuff inside, have its figure.Every year, the produced worldwide 27,000,000 tons plastics containing BPA.But BPA can result in endocrine disturbance, threaten the health of fetus and child.The obesity that cancer and metabolic disturbance cause is recognized as relevant with this.European Union is thought can induce sexual precosity containing bisphenol-A feeding bottle, from 2 days March in 2011, forbids producing the baby bottle containing chemical substance bisphenol-A (BPA).Meanwhile, the natural water containing bisphenol-A may be produced through oxidation sterilizing the derivant of toxicity than bisphenol-A more intensity more own.Therefore, in the urgent need to develop method simple, quick, highly sensitive be used for identifying and determine environment and daily flat in the residual quantity of bisphenol-A.At present, the method measuring BPA mainly has chromatography and electrochemical analysis method.The pretreatment process of sample is required strict by chromatography, analyzes loaded down with trivial details time-consuming.Electrochemical methods has low cost, highly sensitive, it is easy to the advantages such as operation.But BPA electrochemical response on bare electrode is poor, and cause electrode surface to be passivated, electrode need to be carried out modification and realize enhanced sensitivity and antipollution etc..
Magnetic molecularly imprinted polymer is the material prepared that combined with magnetic material by molecular imprinting.Molecular imprinting is a kind of new and effective separation and molecular recognition technology, has special identity and selectivity；And magnetic material has superparamagnetism, can be by its sharp separation from solution under the effect of externally-applied magnetic field, it is also possible to make its surface have multiple reactive functionality by approach such as copolymerization or surface modifications, combine with target molecule in the way of absorption or covalent bonding.The magnetic molecularly imprinted polymer that both prepare after combining has had both the Common advantages of magnetic material and molecularly imprinted polymer, there is special identity and selectivity, it also avoid the shortcoming that molecularly imprinted polymer needs to be centrifuged or sucking filtration could be separated from solution simultaneously, there is the feature of sharp separation, thus magnetic molecularly imprinted material has been increasingly being applied to food, biology, environment and medicine and other fields.But current magnetic molecularly imprinted material is formed by single function monomer molecule aggregation, and adsorbance is little, and selectivity is low, it is impossible to meet the environmental monitoring requirement become increasingly complex.
Summary of the invention
The problem that the present invention seeks to exist for prior art, it is provided that the preparation of a kind of bi-functional monomer molecular imprinted polymer on surface, thus improve the performance of the single function monomer molecular imprinted polymer on surface of tradition；
It is a further object of the present invention to provide this bi-functional monomer magnetic molecularly imprinted polymer a kind of application of bisphenol-A in absorption waste water.
One, the preparation of bi-functional monomer magnetic molecularly imprinted polymer
The preparation of magnetic molecularly imprinted polymer of the present invention, with ATP/Fe3O4For substrate, bisphenol-A be template molecule, acrylamide and methacrylic acid be function monomer, under cross-linking agent and initiator effect, use thermal polymerization to be prepared.It is specifically prepared as it is shown in figure 1, specifically include following steps:
(1) substrate ATP/Fe3O4Preparation
By attapulgite (ATP), FeCl3·6H2O is dispersed in water, ultrasonic 15 ~ 30min, and magnetic agitation 10 ~ 12h obtains suspension under nitrogen protection；Add FeCl2·4H2O, is warming up to 85 ~ 90 DEG C, is subsequently adding ammonia to pH=12 ~ 13, and stirring generates black precipitate, is cooled to room temperature, with redistilled water washing to neutral, and vacuum drying, obtain ATP/Fe3O4Particle.Attapulgite and FeCl3·6H2The mass ratio of O is 1:0.5 ~ 1:2；Attapulgite and FeCl2·4H2The mass ratio of O is 1:0.5 ~ 1:2.
(2) preparation of magnetic molecularly imprinted polymer
By template molecule bisphenol-A, function monomer acrylamide and methacrylic acid, after porogen mixing, magnetic agitation makes monomer and the abundant self assembly of template molecule for 12 ~ 24 hours；Sequentially add substrate ATP/Fe3O4, cross-linking agent, initiator, dispersant, ultrasonic 10 ~ 15min, then reacts 2 ~ 3h at 55 ~ 60 DEG C, reacts 0.5 ~ 1h at 75 ~ 90 DEG C；Reaction is cooled to room temperature, Magneto separate after terminating, and obtains crude product, crude product with methanol/acetic acid mixed solution eluted template molecule, vacuum drying, obtains bi-functional monomer magnetic molecularly imprinted polymer polymer, be labeled as MMIPs (BPA).
In function monomer, the mol ratio of acrylamide and methacrylic acid is 1:1 ~ 1:3；
Template molecule is 1:2 ~ 1:4 with the mol ratio of function monomer；Template molecule and substrate ATP/Fe3O4Mass ratio be 3:1 ~ 1:1.
Porogen uses acetonitrile, and its consumption is 1 ~ 2 times of function monomer mole.
Cross-linking agent uses ethylene glycol dimethacrylate, and its consumption is 5 ~ 10 times of function monomer mole.
Initiator uses azo-bis-isobutyl cyanide, and its consumption is 0.5 ~ 0.6 times of function monomer mole.
Dispersant uses Polyethylene Glycol, and its consumption is 1 ~ 3 times of function monomer mole.
The dry of above steps is to carry out being vacuum dried 12 ~ 24 at 55 ~ 60 DEG C
h。
Two, the structure of bi-functional monomer molecularly imprinted polymer, morphology characterization
Below by scanning electron microscope (SEM), infared spectrum (FT-IR), thermogravimetric (TG), XRT analysis etc., structure, the pattern of bi-functional monomer molecular imprinted polymer on surface of the present invention are characterized.In order to the selection performance of microsphere polymer (being called for short MIP) prepared by the present invention is described, we are prepared for non-molecularly imprinted polymer (being called for short NIP) simultaneously, and compare.In the preparation process of non-molecularly imprinted polymer, in addition to without template molecule, preparation method with molecularly imprinted polymer is identical.
1, FT-IR analyzes
Fig. 2 is the FT-IR collection of illustrative plates of molecular imprinted polymer on surface prepared by the present invention.ATP/ Fe3O4(a)；b-MMIPs(BPA)(b) ；MMIPs(BPA)(c)；The infrared spectrogram of MNIPs (BPA) (d), in a, the peak at 3424 is ATP@Fe3O4In the stretching vibration absworption peak of-OH group, 573 cm-1、469 cm-1Place is Fe2+-O2-And Fe3+-O2-Absworption peak, 1034 cm-1With 977
cm-1Peak is the symmetrical stretching vibration peak of Si-O-Si, 1652 cm-1Place is the stretching vibration peak of Mg-O.Illustrate to be successfully prepared ATP Fe3O4.In (b) 3485,3552cm-1For free and the stretching vibration peak of associate hydrogen bond O-H, 3413cm-1Sharp-pointed absworption peak for associate-N-H stretching vibration.3200-3500cm in (c) and (d)-1For intermolecular hydrogen bonding O-H stretching vibration, for wide absworption peak, may be with the presence of absorption water；2960 cm-1For the stretching vibration peak of C-H, 1720 ~ 1740 cm-1For-C=O the stretching vibration in carboxylic acid, 1638cm-1Neighbouring is the-C=O stretching vibration in amide；1210cm-1For C-O stretching vibration, 1150 cm-1For C-N stretching vibration.1388cm-1Neighbouring is methyl C-H symmetry in-plane bending vibration.1445 cm in (d)-1For the skeletal vibration of aromatic ring, 619cm-1For the absorption in over-frequency of substituted benzene ring, after removing template molecule, these absworption peaks disappear.Analyze it is found that the infrared spectrum of MMIPs (BPA) and MNIPs (BPA) is much like further, illustrate that imprinted polymer and non-imprinted polymer are consistent in composition.
2, sem analysis
Fig. 3 is the SEM figure of the molecular imprinted polymer on surface (MMIPs (BPA)) prepared of the present invention and non-molecularly imprinted polymer (MNIPs (BPA)).As seen from Figure 3, by comparing matrix ATP/Fe3O4A () and bi-functional monomer molecularly imprinted polymer (b) and the scanning electron microscope (SEM) photograph of blank molecularly imprinted polymer (c), illustrate at ATP/Fe3O4Surface is successfully prepared the spheroidal particle shaped polymer with regular pattern and good dispersibility.
3, TG-DTA analyzes
Fig. 4 is MMIPs (BPA), MNIPs (BPA) and the present invention prepare the heat of bi-functional monomer molecularly imprinted polymer and analyze (TG-DTA).Left figure is the thermal multigraph of MMIPs (BPA), right figure is the TGA curve of MMIPs (BPA), from fig. 4, it can be seen that MMIPs (BPA) and MNIPs (BPA) weight-loss ratio in the range of 100 ~ 200 DEG C is less than 7.2%, for samples dried process；MMIPs (BPA) occurs second weightless platform in the range of 325 ~ 366 DEG C, and weight-loss ratio is 60.9%, comes from the decomposition of the molecularly imprinted polymer on MMIPs (BPA) surface；Occurring the 3rd weightless platform in the range of 366 ~ 497 DEG C, weight-loss ratio is about 15%, comes from ATP@Fe in MMIPs (BPA)3O4The decomposition of other organic principle on surface.The heat decomposition curve of MNIPs (BPA) is identical with MMIPs (BPA) before 200 DEG C, second weightless platform occurs in the range of 336 ~ 372 DEG C, weight-loss ratio is 78.6%, comes from the decomposition of the molecularly imprinted polymer on MNIPs (BPA) surface；3rd weightless platform occurs in the range of 372 ~ 650 DEG C, comes from ATP@Fe in MNIPs (BPA)3O4In structure, the hydroxyl of constitution water depigmentation or ATP internal structure goes to pot.The above results proves that imprinted polymer produced herein has good heat stability.
4, XRD figure analysis
Fig. 5 is respectively Fe3O4/ ATP (a), MMIPs (BPA), the XRD spectrum of MNIPs (BPA).The scope of 2 θ is at 20 ~ 70 °.ATP@ Fe3O4, MMIPs (BPA), and the XRD spectra of MNIPs (BPA) is respectively as in Fig. 5 (a), (b), shown in (c).In the range of 2 θ=10-80 °, observe ATP@Fe3O4XRD spectra, it is found that in 2 θ=13.6 °, occur in that the characteristic diffraction peak of three ATP at 19.7 ° and 27.28 ° of place, be respectively belonging to (200) of ATP, (040) and (400) crystal face diffraction.In 2 θ=30.23 °, 35.54 °, 43.10 °, 53.50 °, 57.23 °, at 62.82 ° and 74.35 °, occur in that 6 Fe3O4Characteristic diffraction peak, be attributed to respectively and Fe3O4(220), (311), (400), (422), (511), (440) and (533) crystal face diffraction, result and Fe3O4JCPDS card (19-0629) the most identical, and without other impurity peaks, the ATP that ATP@Fe3O4 composite nanometer particle is face-centered cubic spinel-type Fe3O4 cladding of preparation is described.Fe is occurred in that in the XRD figure of MMIPs (BPA) and MNIPs (BPA)3O4(220), (311), the characteristic peak of (511) crystal face, illustrate that the preparation process of MMIPs (BPA) and MNIPs (BPA) does not destroy the crystal structure of Fe3O4.
Three, the absorption property of molecularly imprinted polymer
Pipette 5mL concentration and be respectively 1,2,3,4,5,6,7,8 × 10-4 mol.L-1BPA solution, be respectively placed in conical flask；Weigh 8 parts of 20mg MMIPs (BPA) or MNIPs (BPA), be scattered in the above-mentioned BPA aqueous solution of variable concentrations.With Magnet, particle is inhaled in bottom after 25 DEG C of constant temperature water bath vibration 10h, at 278nm, measure the absorbance of supernatant.Fig. 6 is the absorption property figure of molecular imprinted polymer on surface.A is dynamic absorption curve, and b is Thermodynamic Adsorption curve, and Fig. 6 result shows, the adsorbance of MMIPs (BPA) reaches 3110.2ug/A, and the adsorbance of MNIPs (BPA) only has 1069.2ug/g.MMIPs (BPA) and MNIPs (BPA)
Relatively big to the adsorbance difference of the BPA solution of variable concentrations, illustrate that MMIPs (BPA) is bigger to the adsorbance of template molecule.
Four, the selection performance of molecularly imprinted polymer
Choose biphenol, phenol and P-hydroxybenzoic acid as chaff interference, analyze the MMIPs (BPA) selectivity to BPA.Fig. 7 is that trace particle and non-trace particle are to 5mg/L BPA and the adsorption capacity of chaff interference.As can see from Figure 7, MMIPs (BPA) is maximum to the adsorbance (3110.2ug/g) of BPA, differs bigger with to the adsorbance of chaff interference.Illustrate that the molecularly imprinted polymer prepared has selective absorption to BPA.And MNIPs (BPA) does not has big difference to BPA and chaff interference phenol, hydroquinone, the adsorbance (873.04ug/g, 1085.25ug/g, 997.21ug/g, 385.7ug/g) of P-hydroxybenzoic acid and do not has rule, illustrate that template molecule BPA is not had selectivity.
Five, the recycling performance of molecularly imprinted polymer
Fig. 8 is the recycling figure of MIP adsorbing material.It can be seen that MIP material reuses 8 times, the highest to the absorbability of template molecule BPA.Therefore, this function adsorbing material has good adsorption activity and stability.
In sum, bi-functional monomer magnetic molecularly imprinted polymer prepared by the present invention shows higher Selective recognition ability to template molecule bisphenol-A, and there is higher heat stability, in waste water, BPA is had Specific adsorption effect, for detecting BPA in water sample, there is fast-response, precordainment, identity and the feature of practicality, therefore, the bisphenol-A in the treatment of waste water (BPA) in detection and absorption waste water has good application prospect.
Accompanying drawing explanation
Fig. 1 is the synthesis schematic diagram of molecular imprinted polymer on surface.
Fig. 2 is the infrared absorpting light spectra of molecular imprinted polymer on surface.
Fig. 3 is the scanning electron microscope (SEM) photograph of molecular imprinted polymer on surface.
Fig. 4 is the TG-DTA curve of molecular imprinted polymer on surface.
Fig. 5 is the XRD figure of molecular imprinted polymer on surface.
Fig. 6 is the absorption property figure of molecular imprinted polymer on surface.
Fig. 7 is the selection performance map of molecular imprinted polymer on surface.
Fig. 8 is the recycling figure of molecular imprinted polymer on surface.
Detailed description of the invention
Below by specific embodiment, the preparation of MIP of the present invention and the absorption property of template molecule are described further.
Embodiment one
1、ATP/Fe3O4The preparation of particle
Take 1.50g attapulgite (ATP) to be scattered in bis-water of 100mL；4.4gFeCl3·6H2O is scattered in bis-water of 100ml, and after the two being mixed after ultrasonic disperse 30min, magnetic agitation 12h obtains suspension under nitrogen protection.Take 1.6 gFeCl2·4H2O adds suspension, is heated to 90 DEG C and adds ammonia (25%, w:w) 6mL, stirs rapidly 1h, generates black precipitate, is cooled to room temperature, with redistilled water washing to neutral, and is vacuum dried 12h in 60 DEG C, obtains ATP/Fe3O4Particle, standby.
2, the preparation of MMIPs (BPA) molecularly imprinted polymer
The template molecule bisphenol-A of 1.0mmol, 1.0mmol monomer methacrylic acid, the porogen acetonitrile of 1.0mmol acrylamide and 90mL, magnetic agitation 12h is added so that monomer and the abundant self assembly of template molecule in 250mL round-bottomed flask；State then up in solution and be sequentially added into 0.1gATP/Fe3O4, 10mmol cross-linking agent ethylene glycol dimethacrylate, the initiator azo-bis-isobutyl cyanide of 100mg and 0.1g Polyethylene Glycol are as dispersant, and ultrasonic 10min, nitrogen reacts 3h in 60 DEG C of oil baths under protecting, reacts 1h at 90 DEG C.After reaction terminates, being cooled to room temperature, Magnetic Isolation obtains b-MMIPs (BPA), then with ethanol/acetic acid (9:1, v/v) mixed solution eluted template molecule, and is vacuum dried 24h in 60 DEG C, obtains product MMIPs (BPA).
MMIPs (BPA) reaches 2805.9ug/g to the adsorbance of BPA.
Embodiment two
1、ATP-Fe3O4The preparation of particle: with embodiment one；
2, the preparation of MMIPs (BPA) molecularly imprinted polymer: the addition 15 of ethylene glycol dimethacrylate
Mmol, other is with embodiment one.MMIPs (BPA) reaches 2988.7ug/g to the adsorbance of BPA.
Embodiment three
1、ATP-Fe3O4The preparation of particle: with embodiment one；
2, the preparation of MMIPs (BPA) molecularly imprinted polymer: the addition 20 of ethylene glycol dimethacrylate
Mmol, other is with embodiment one.MMIPs (BPA) reaches 2903.5ug/g to the adsorbance of BPA.
Embodiment four
1、ATP-Fe3O4The preparation of particle: with embodiment one；
2, the preparation of MMIPs (BPA) molecularly imprinted polymer: addition 15mmol of ethylene glycol dimethacrylate, the consumption of initiator is 80 mg, and other is with embodiment one.MMIPs (BPA) reaches 2701.5ug/g to the adsorbance of BPA.
Embodiment five
1、ATP-Fe3O4The preparation of particle: with embodiment one；
2, the preparation of MMIPs (BPA) molecularly imprinted polymer: addition 15mmol of ethylene glycol dimethacrylate, the consumption of initiator is 100 mg, and other is with embodiment one.MMIPs (BPA) reaches 2700.3ug/g to the adsorbance of BPA.
Embodiment six
1、ATP-Fe3O4The preparation of particle: with embodiment one；
2, the preparation of MMIPs (BPA) molecularly imprinted polymer: addition 15mmol of ethylene glycol dimethacrylate, the consumption of initiator is 80 mg, reacts 3h, react 1h at 75 DEG C after ultrasonic 15min under air atmosphere in 60 DEG C of oil baths.Other is with embodiment one.MMIPs (BPA) reaches 3000.7ug/g to the adsorbance of BPA.
Embodiment seven
1、ATP-Fe3O4The preparation of particle: with embodiment one；
2, the preparation of MMIPs (BPA) molecularly imprinted polymer: addition 15mmol of ethylene glycol dimethacrylate, the consumption of initiator is 80 mg, reacts 3h, react 1h at 100 DEG C after ultrasonic 15min under air atmosphere in 60 DEG C of oil baths.Other is with embodiment one.MMIPs (BPA) reaches 3100.3ug/g to the adsorbance of BPA.
Claims (10)
1. a preparation method for bi-functional monomer magnetic molecularly imprinted polymer, with ATP/Fe3O4For substrate, bisphenol-A be template molecule, acrylamide and methacrylic acid be function monomer, under cross-linking agent and initiator effect, use thermal polymerization to be prepared.
2. the preparation method of bi-functional monomer magnetic molecularly imprinted polymer as claimed in claim 1, it is characterised in that: by template molecule, function monomer, after porogen mixing, magnetic agitation makes monomer and the abundant self assembly of template molecule for 12 ~ 24 hours；Sequentially add substrate ATP/Fe3O4, cross-linking agent, initiator, dispersant, ultrasonic 10 ~ 15min, then reacts 2 ~ 3h at 55 ~ 60 DEG C, reacts 0.5 ~ 1h at 75 ~ 90 DEG C；Reaction is cooled to room temperature, Magneto separate after terminating, and obtains crude product, crude product with methanol/acetic acid mixed solution eluted template molecule, vacuum drying, obtains bi-functional monomer magnetic molecularly imprinted polymer polymer.
3. the preparation method of bi-functional monomer magnetic molecularly imprinted polymer as claimed in claim 1, it is characterised in that: ATP/Fe3O4The preparation of particle: attapulgite, FeCl3·6H2O is dispersed in water, ultrasonic 15 ~ 30min, and magnetic agitation 10 ~ 12h obtains suspension under nitrogen protection；Add FeCl2·4H2O, is warming up to 85 ~ 90 DEG C, is subsequently adding ammonia to system pH=12 ~ 13, and stirring generates black precipitate, is cooled to room temperature, with redistilled water washing to neutral, and vacuum drying, obtain ATP-Fe3O4Particle；Attapulgite and FeCl3·6H2The mass ratio of O is 1:0.5 ~ 1:2；Attapulgite and FeCl2·4H2The mass ratio of O is 1:0.5 ~ 1:2.
4. the preparation method of any bi-functional monomer magnetic molecularly imprinted polymer as described in claim 1-3, it is characterised in that: in function monomer, the mol ratio of acrylamide and methacrylic acid is 1:1 ~ 1:3.
5. the preparation method of any bi-functional monomer magnetic molecularly imprinted polymer as described in claim 1-3, it is characterised in that: template molecule is 1:2 ~ 1:4 with the mol ratio of function monomer, template molecule and substrate ATP/Fe3O4Mass ratio be 3:1 ~ 1:1.
6. the preparation method of any bi-functional monomer magnetic molecularly imprinted polymer as described in claim 1-3, it is characterised in that: porogen is acetonitrile, and its consumption is 1 ~ 2 times of function monomer mole.
7. the preparation method of any bi-functional monomer magnetic molecularly imprinted polymer as described in claim 1-3, it is characterised in that: cross-linking agent is ethylene glycol dimethacrylate, and its consumption is 5 ~ 10 times of function monomer mole.
8. the preparation method of any bi-functional monomer magnetic molecularly imprinted polymer as described in claim 1-3, it is characterised in that: initiator is azo-bis-isobutyl cyanide, and its consumption is 0.2 ~ 0. 6 times of function monomer mole.
9. the preparation method of any bi-functional monomer magnetic molecularly imprinted polymer as described in claim 1-3, it is characterised in that: dispersant is Polyethylene Glycol, and its consumption is 1 ~ 3 times of function monomer mole.
10. the kind bi-functional monomer magnetic molecularly imprinted polymer that as claimed in claim 1 prepared by method is for the bisphenol-A adsorbing in waste water.
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| CN106378097A (en) * | 2016-10-11 | 2017-02-08 | 常州大学 | Preparation method of molecularly imprinted silica magnetic attapulgite and application of molecularly imprinted silica magnetic attapulgite to identification of tyrosine enantiomer |
| CN106633056A (en) * | 2016-12-22 | 2017-05-10 | 西安交通大学 | Preparation method of bromelain molecularly imprinted polymer on surface of magnetic carbon material |
| CN107837799A (en) * | 2017-11-16 | 2018-03-27 | 河南永泽环境科技有限公司 | A kind of magnetic for phenol wastewater of degrading strengthens flyash trace photochemical catalyst |
| CN110684157A (en) * | 2019-08-16 | 2020-01-14 | 浙江海洋大学 | Preparation method of dendrimer-modified magnetic attapulgite surface imprinted polymer |
| CN114057965A (en) * | 2021-12-17 | 2022-02-18 | 中国地质大学（武汉） | Magnetic molecularly imprinted polymer material for targeted extraction of bisphenol A in sewage |
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| CN107837799A (en) * | 2017-11-16 | 2018-03-27 | 河南永泽环境科技有限公司 | A kind of magnetic for phenol wastewater of degrading strengthens flyash trace photochemical catalyst |
| CN107837799B (en) * | 2017-11-16 | 2020-06-23 | 河南永泽环境科技有限公司 | Magnetic reinforced fly ash imprinted photocatalyst for degrading phenol-containing wastewater |
| CN110684157A (en) * | 2019-08-16 | 2020-01-14 | 浙江海洋大学 | Preparation method of dendrimer-modified magnetic attapulgite surface imprinted polymer |
| CN110684157B (en) * | 2019-08-16 | 2022-02-18 | 浙江海洋大学 | Preparation method of dendrimer-modified magnetic attapulgite surface imprinted polymer |
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