CN103881023A - Method for preparing magnetic molecularly imprinted polymer through suspension polymerization - Google Patents
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Abstract
The invention relates to a method for preparing magnetic molecularly imprinted polymers (MIPs) through suspension polymerization, belonging to the technical field of preparation of environmental functional materials. In particular, in the method for preparing the magnetic MIPs through suspension polymerization, Fe3O4 magnetic particles are synthesized through a hydrothermal synthesis method, methacrylic acid is taken as a functional monomer, 2,4,6-trichlorophenol (2,4,6-TCP) is taken as template molecules, azodiisobutyronitrile is taken as an initiator, methylbenzene is taken as a pore-foaming agent, ethylene glycol dimethacrylate is taken as a crosslinking agent, and polyvinyl alcohol is taken as a stabilizing agent. The obtained MIPs are regular spheres, holes of specific shapes and sizes left by a plurality of template molecules are formed in the surfaces of the polymers, and specifically-arranged binding sites are arranged in the holes. By adopting the MIPs, highly-selective adsorption of a target pollutant, namely, 2,4,6-trichlorophenol can be realized.
Description
Technical field
The invention belongs to environment functional material preparing technical field, relate to a kind of method of preparing magnetic molecularly imprinted polymer by suspension polymerization, and be applied to the chlorophenol pollutant in selective adsorption Separation of Water environment.
Background technology
Chlorophenol pollutant is multi-usage starting material conventional in chemical industry, and from twentieth century thirties, chlorophenol has been widely used as Insecticides (tech) & Herbicides (tech) and wood preservative.The waste water that comes from agricultural chemicals, timber, pharmacy, dyestuff manufacture, paper and paper pulp industry is most important chlorophenol pollution source.Chlorophenol pollutant can cause a lot of human diseasess, and as respiratory tract disease, cardiovascular disorder and gastrointestinal tract disease etc., and most chlorophenol pollutant is considered to the mankind's carcinogens.Environment protection tissue (EPA) classifies chlorophenol and derivative thereof as toxic pollutant as.The concentration of the World Health Organization (WHO) suggestion chlorophenol in tap water is 0.1 μ g/L.Therefore, from the aqueous solution, effectively remove the important topic that chlorophenol is field of environment protection.
Various water technologies have been widely used in administering the chlorophenol pollutant in water surrounding, biological example degraded, photocatalytic degradation, chemical oxidation, membrane sepn and adsorption technology.Wherein, adsorption technology is not only economy but also effective method of one.At present, polymeric sorbent is because its good physical and chemical stability, remarkable loading capacity and the characteristic such as renewable have caused increasing concern.But the selectivity of this polymeric sorbent is poor, do not possess single-minded recognition capability, therefore, realizing highly selective absorption is one of difficulties in sorbent material production process.
Recently, molecular imprinting has obtained everybody extensive concern.In molecularly imprinted polymer, contain a lot of specified shapes and big or small hole, in hole, there is the binding site of particular arrangement, and the structure of template molecule is had to certain memory and recognition function.Molecularly imprinted polymer can be realized highly selective absorption to target contaminant.By magnetic nano-particle being incorporated into the magnetic molecularly imprinted polymer that molecular imprinting prepares.Its binding site by molecularly imprinted polymer surface pollutent that unbinds, and utilize the magnetic particle of polymkeric substance inside to realize efficient magnetic response.Magnetic particle has shown high-performance in sepn process, and this sorbent material is highly susceptible to separating, and no longer needs extra centrifugal or filtration.
The method of preparing magnetic molecularly imprinted polymer has a variety of, comprises suspension polymerization, letex polymerization and dispersion polymerization etc., and wherein suspension polymerization is the common method of preparing magnetic molecularly imprinted polymer.Suspension polymerization is simple to operate, and the product purity obtaining is also very high.The magnetic molecularly imprinted polymer microballoon of preparing by suspension polymerization not only has higher specific surface area, remarkable absorption property, and can under the effect of externally-applied magnetic field, realize separation efficiently.
Summary of the invention
Technical scheme of the present invention refers to the synthetic Fe of hydrothermal synthesis method
3o
4magnetic particle, and taking methacrylic acid as function monomer, with 2,4,6-Trichlorophenol (2,4,6-TCP) be template molecule, taking Diisopropyl azodicarboxylate as initiator, taking toluene as pore-creating agent, taking ethylene glycol dimethacrylate as linking agent, taking polyvinyl alcohol as stablizer, adopt the method preparation of suspension polymerization to generate magnetic molecularly imprinted polymer (MIPs), and be applied to selective adsorption separation 2 in water surrounding, 4,6-Trichlorophenol.
technical scheme
Utilize suspension polymerization to prepare the method for magnetic molecularly imprinted polymer, carry out according to the following steps:
(1) the synthetic Z 250 (Fe of hydrothermal synthesis method
3o
4) magnetic nano-particle:
Ferric chloride (FeCl36H2O) (FeCl
36H
2o) and sodium acetate, anhydrous (NaAc) be dissolved in ethylene glycol solution, wherein control FeCl
36H
2o, the ratio of NaAc and ethylene glycol is (1.3-1.4): (7-8): (40-50) (g/mL/mL).Mixing solutions speed with 800 rpm/min under the protection of nitrogen stirs 1-2 h in the water bath with thermostatic control of 160 DEG C; then mixing solutions is transferred in the reactor of 50 mL; temperature is controlled at 200 DEG C; reaction times is 10 h; after taking-up, be cooled to room temperature; suspension is cleaned to 3-5 time with ethanolic soln, the product of acquisition is dried under the vacuum environment of 60 DEG C, finally in mortar, pulverize and grind.
(2) oleic acid is to Fe
3o
4magnetic nano-particle carries out finishing
In step (1), prepare the Fe of gained
3o
4nanoparticle mixes with oleic acid, continues to stir 1-2 h with the speed of 200 rpm/min, forms dark-brown Fe
3o
4magnetic fluid, wherein controls the Fe in step (1)
3o
4the ratio of nanoparticle and oleic acid is 0.1:4 (g/mL).
(3) suspension polymerization synthesizing magnetic molecularly imprinted polymer
Solvent 1: by 2,4,6-Trichlorophenol, methacrylic acid is dissolved in toluene solution, at room temperature stir 10-30 min, wherein control 2,4,6-Trichlorophenol: methacrylic acid: the ratio of toluene is (0.2-0.3): (0.35-0.45): (5-7) (g/mL/mL);
Solvent 2: prepare the Fe after the oleic acid modification of gained in step (2)
3o
4magnetic fluid, Diisopropyl azodicarboxylate and toluene are dissolved in ethylene glycol dimethacrylate solution.Wherein control the Fe in step (2)
3o
4magnetic fluid: Diisopropyl azodicarboxylate: toluene: the ratio of ethylene glycol dimethacrylate is 4:(0.15-0.2): (2-3): (3.5-4) (mL/g/mL/mL);
Solvent 3: polyvinyl alcohol is added in deionized water, temperature is controlled at 80 DEG C, stirring velocity is 400 rpm/min, reaction times is 30-60 min, be cooled to room temperature, the ratio of wherein controlling polyvinyl alcohol and deionized water is (3-4): (130-150) (g/mL) again;
Solvent 4: sodium lauryl sulphate is added in deionized water, and under room temperature, 600 rpm/min stir 10 min, the ratio of wherein controlling sodium lauryl sulphate and deionized water is 1:20 (g/mL).
Solvent 1 and solvent 2 are mixed to form to solution a, and solvent 1 is (5-7) with the volume ratio of solvent 2: (9.5-11), stir 2 h under room temperature, rotating speed is 400 rpm/min.Solvent 3 and solvent 4 are mixed to form to solution b, and solvent 3 is (130-150) with the volume ratio of solvent 4: 20, under room temperature, stir 2 h, and rotating speed is 400 rpm/min.Solution a is mixed with solution b, and the volume ratio of solution a and solution b is (14.5-18): (150-170).At room temperature, controlling stirring velocity is 600 rpm/min, and under nitrogen protection, reaction continues 1 h, then temperature is risen to 60 DEG C, and stirring velocity is 600 rpm/min, and under nitrogen protection, 24 h are carried out in reaction, obtain molecularly imprinted polymer.
The ethanolic soln for molecularly imprinted polymer obtaining in step (3) (ethanol: deionized water (V:V)=1:1) is cleaned 3 times, then use washed with de-ionized water 2 times.
(4) wash-out template molecule
With the preparation of acetic acid and methyl alcohol eluent, wherein acetic acid: the ratio of methyl alcohol is 10:90 (V/V), and the magnetic molecularly imprinted polymer preparing in step (3) is cleaned to 5-7 days in apparatus,Soxhlet's, then be washed till neutrality with deionized water.
Pay special attention to, the preparation method of the non-imprinted polymer of magnetic (MNIPs) is identical with the preparation method of above-mentioned magnetic molecularly imprinted polymer, just in the solvent 1 of step (3), does not add 2,4,6-Trichlorophenol, and does not have step (4).
The polymerization process adopting in above-mentioned technical scheme is suspension polymerization.
Described in above-mentioned technical scheme 2,4,6-Trichlorophenol, it act as template molecule.
Methacrylic acid described in above-mentioned technical scheme, it act as function monomer.
Diisopropyl azodicarboxylate described in above-mentioned technical scheme, it act as initiator.
Toluene described in above-mentioned technical scheme, it act as pore-creating agent.
Ethylene glycol dimethacrylate described in above-mentioned technical scheme, it act as linking agent.
Polyvinyl alcohol described in above-mentioned technical scheme, it act as stablizer.
Sodium lauryl sulphate described in above-mentioned technical scheme, it makes promising tensio-active agent.
Technological merit of the present invention: this product is magnetic molecularly imprinted polymer, prepare by suspension polymerization, present the spherical of rule, contain specified shape that multiple template molecules stay and big or small hole at polymer surfaces, in hole, have the binding site of particular arrangement, molecularly imprinted polymer can be realized highly selective absorption to target contaminant.Fe
3o
4nanoparticle has good magnetic response performance, in strengthening the physical strength of polymkeric substance, can realize the sharp separation in adsorption process.This polymkeric substance, as sorbent material, has stronger absorption property and thermal stability.
Brief description of the drawings
Fig. 1 is the magnetic Fe of preparation in embodiment 1
3o
4the scanning electron microscope (SEM) photograph of nanoparticle and magnetic molecularly imprinted polymer can be found out magnetic Fe from a figure
3o
4nanoparticle is high dispersive, average particle diameter is about 255nm, b figure and c figure are the configurations of surface of the magnetic molecularly imprinted polymer under different amplification, in b figure, polymkeric substance presents spherical, in c figure, can obviously find out that surface exists a lot of holes, d figure is the energy spectrogram of polymkeric substance, therefrom can find out carbon, the existence of the elements such as iron, has proved that polymkeric substance is that tool is magnetic.
Fig. 2 is the infrared spectrogram of embodiment 2, wherein (a). ferriferrous oxide nano-particle; (b). imprinted polymer; (c). non-imprinted polymer; Contrast magnetic Fe_3O_4 nanoparticle, the infrared spectrogram of magnetic molecularly imprinted polymer and the non-imprinted polymer of magnetic.As can be seen from the figure, the Fe-O peak that 599 cm-1 places occur in magnetic Fe_3O_4 nanoparticle, appear at equally in the non-imprinted polymer of magnetic molecularly imprinted polymer and magnetic, but intensity is compared with weakening slightly in magnetic Fe_3O_4 nanoparticle, this be due in magnetic Fe_3O_4 nanoparticle outer cladding the reason of polymkeric substance.At the peak of magnetic molecularly imprinted polymer and the non-imprinted polymer 1732 cm-1 places appearance of magnetic, also prove the existence of carbonyl compound.
Embodiment
Absorption property analysis test method described in technique scheme is specially:
(1) Static Adsorption test
To 2 of 10 mL different concns be housed, 4,6-TCP solution joins in colorimetric cylinder, add respectively 10 mg magnetic molecularly imprinted polymers and the non-imprinted polymer of magnetic, be placed on and in the water bath with thermostatic control of differing temps, leave standstill 12 h, investigate in test soln 2,4, the impact on sorbent material absorption property of the starting point concentration of 6-TCP and temperature of reaction; After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, not 2,4 of absorption, the concentration ultraviolet spectral analysis of 6-TCP, and according to result calculate loading capacity (
q e, mg/g):
Wherein
c 0(mg/L) and
c e(mg/L) be respectively absorption front and back 2,4, the concentration of 6-TCP,
w(g) be sorbent material consumption,
v(mL) be test fluid volume.
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1:
1, utilize suspension polymerization to prepare the method for magnetic molecularly imprinted polymer, its preparation method carries out according to following step:
(1) the synthetic Z 250 (Fe of hydrothermal synthesis method
3o
4) magnetic nano-particle:
Ferric chloride (FeCl36H2O) (FeCl
36H
2o) and sodium acetate, anhydrous (NaAc) be dissolved in ethylene glycol solution, wherein control FeCl
36H
2o, the ratio of NaAc and ethylene glycol be (1.3:7:40) (g/mL/mL).Mixing solutions speed with 800 rpm/min under the protection of nitrogen stirs 1 h in the water bath with thermostatic control of 160 DEG C; then mixing solutions is transferred in the reactor of 50ml; temperature is controlled at 200 DEG C; reaction times is 10 h; after taking-up, be cooled to room temperature;, by suspension cleaning 3 times the product of acquisition is dried under the vacuum environment of 60 DEG C with ethanolic soln, finally in mortar, pulverize and grind.
(2) oleic acid is to Fe
3o
4magnetic nano-particle carries out finishing
In step (1), prepare the Fe of gained
3o
4nanoparticle mixes with oleic acid, continues to stir 1 h with the speed of 200 rpm/min, forms dark-brown Fe
3o
4magnetic fluid, wherein controls the Fe in step (1)
3o
4the ratio of nanoparticle and oleic acid is 0.1:4 (g/mL).
(3) suspension polymerization synthesizing magnetic molecularly imprinted polymer
Solvent 1: by 2,4,6-Trichlorophenol, methacrylic acid is dissolved in toluene solution, at room temperature stirs 10 min, wherein controls 2,4,6-Trichlorophenol: methacrylic acid: the ratio of toluene be (0.2:0.35:5) (g/mL/mL);
Solvent 2: prepare the Fe after the oleic acid modification of gained in step (2)
3o
4magnetic fluid, Diisopropyl azodicarboxylate and toluene are dissolved in ethylene glycol dimethacrylate solution.Wherein control the Fe in step (2)
3o
4magnetic fluid: Diisopropyl azodicarboxylate: toluene: the ratio of ethylene glycol dimethacrylate be (4:0.15:2:3.5) (mL/g/mL/mL);
Solvent 3: polyvinyl alcohol is added in deionized water, temperature is controlled at 80 DEG C, and stirring velocity is 400 rpm/min, reaction 30 min, be cooled to again room temperature, the ratio of wherein controlling polyvinyl alcohol and deionized water for (3:130) (g/mL);
Solvent 4: sodium lauryl sulphate is added in deionized water, stir 10 min under room temperature, the ratio of wherein controlling sodium lauryl sulphate and deionized water is 1:20 (g/mL).
Solvent 1 and solvent 2 are mixed to form to solution a, and solvent 1 is 5:9.5 with the volume ratio of solvent 2, stirs 2 h under room temperature, and rotating speed is 400 rpm/min.Solvent 3 and solvent 4 are mixed to form to solution b, and solvent 3 is 130:20 with the volume ratio of solvent 4, stirs 2 h under room temperature, and rotating speed is 400 rpm/min.Solution a is mixed with solution b, and the volume ratio of solution a and solution b is 14.5:150.At room temperature, controlling stirring velocity is 600 rpm/min, and under nitrogen protection, reaction continues 1 h, then temperature is risen to 60 DEG C, and stirring velocity is 600 rpm/min, and under nitrogen protection, 24 h are carried out in reaction.
The ethanolic soln for molecularly imprinted polymer obtaining in step (3) (ethanol: deionized water (V:V)=1:1) is cleaned 3 times, then use washed with de-ionized water 2 times.
(4) wash-out template molecule
With the preparation of acetic acid and methyl alcohol eluent, wherein acetic acid: the ratio of methyl alcohol is 10:90 (V/V), the magnetic molecularly imprinted polymer preparing is cleaned 5 days in apparatus,Soxhlet's, then be washed till neutrality with deionized water in step (3).
Pay special attention to, the preparation method of the non-imprinted polymer of magnetic (MNIPs) is identical with the preparation method of above-mentioned magnetic molecularly imprinted polymer, just in the solvent 1 of step (3), does not add 2,4,6-Trichlorophenol, and does not have step (4).
Fig. 1 is the magnetic Fe of preparation in embodiment 1
3o
4the scanning electron microscope (SEM) photograph of nanoparticle and magnetic molecularly imprinted polymer, microballoon is the spherical of rule as seen from the figure, and is distributed with a large amount of holes.
2, absorption property analytical test:
(1) Static Adsorption test 1
To 2,4 of 10 mL different concns be housed, 6-TCP solution joins in colorimetric cylinder, concentration is respectively 10,30, and 50,80,100,150,200,300 and 400 mg/L add respectively 10 mg magnetic molecularly imprinted polymers and the non-imprinted polymer of magnetic in colorimetric cylinder, be placed on standing 12h in 25 DEG C of waters bath with thermostatic control, investigate in test soln 2,4, the impact of the starting point concentration of 6-TCP on Polymer adsorption performance; After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, and not 2,4 of absorption, the concentration ultraviolet spectral analysis of 6-TCP, according to formula calculation result.
Result show: magnetic molecularly imprinted polymer in the time of 25 DEG C to the saturated adsorption capacity of 2,4,6-TCP apparently higher than the non-imprinted polymer of magnetic.
embodiment 2:
1, utilize suspension polymerization to prepare the method for magnetic molecularly imprinted polymer, carry out according to the following steps:
(1) the synthetic Z 250 (Fe of hydrothermal synthesis method
3o
4) magnetic nano-particle:
Ferric chloride (FeCl36H2O) (FeCl
36H
2o) and sodium acetate, anhydrous (NaAc) be dissolved in ethylene glycol solution, wherein control FeCl
36H
2o, the ratio of NaAc and ethylene glycol be (1.4:8:50) (g/mL/mL).Mixing solutions speed with 800 rpm/min under the protection of nitrogen stirs 2 h in the water bath with thermostatic control of 160 DEG C; then mixing solutions is transferred in the reactor of 50 mL; temperature is controlled at 200 DEG C; reaction times is 10 h; after taking-up, be cooled to room temperature;, by suspension cleaning 5 times the product of acquisition is dried under the vacuum environment of 60 DEG C with ethanolic soln, finally in mortar, pulverize and grind.
(2) oleic acid is to Fe
3o
4magnetic nano-particle carries out finishing
In step (1), prepare the Fe of gained
3o
4nanoparticle mixes with oleic acid, continues to stir 2 h with the speed of 200 rpm/min, forms dark-brown Fe
3o
4magnetic fluid, wherein controls the Fe in step (1)
3o
4the ratio of nanoparticle and oleic acid is 0.1:4 (g/mL).
(3) suspension polymerization synthesizing magnetic molecularly imprinted polymer
Solvent 1: by 2,4,6-Trichlorophenol, methacrylic acid is dissolved in toluene solution, at room temperature stirs 30 min, wherein controls 2,4,6-Trichlorophenol: methacrylic acid: the ratio of toluene is (0.3:0.45: 7) (g/mL/mL);
Solvent 2: prepare the Fe after the oleic acid modification of gained in step (2)
3o
4magnetic fluid, Diisopropyl azodicarboxylate and toluene are dissolved in ethylene glycol dimethacrylate solution.Wherein control the Fe in step (2)
3o
4magnetic fluid: Diisopropyl azodicarboxylate: toluene: the ratio of ethylene glycol dimethacrylate is 4:(0.2:3:4) (mL/g/mL/mL);
Solvent 3: polyvinyl alcohol is added in deionized water, temperature is controlled at 80 DEG C, and stirring velocity is 400rpm/min, reaction 60 min, be cooled to again room temperature, the ratio of wherein controlling polyvinyl alcohol and deionized water for (4:150) (g/mL);
Solvent 4: sodium lauryl sulphate is added in deionized water, stir 10 min under room temperature, the ratio of wherein controlling sodium lauryl sulphate and deionized water is 1:20 (g/mL).
Solvent 1 and solvent 2 are mixed to form to solution a, and solvent 1 is 7:11 with the volume ratio of solvent 2, stirs 2 h under room temperature, and rotating speed is 400 rpm/min.Solvent 3 and solvent 4 are mixed to form to solution b, and solvent 3 is 150:20 with the volume ratio of solvent 4, stirs 2 h under room temperature, and rotating speed is 400 rpm/min.Solution a is mixed with solution b, and the volume ratio of solution a and solution b is 18:170.At room temperature, controlling stirring velocity is 600 rpm/min, and under nitrogen protection, reaction continues 1 h, then temperature is risen to 60 DEG C, and stirring velocity is 600 rpm/min, and under nitrogen protection, 24 h are carried out in reaction.
The ethanolic soln for molecularly imprinted polymer obtaining in step (3) (ethanol: deionized water (V:V)=1:1) is cleaned 3 times, then use washed with de-ionized water 2 times.
(4) wash-out template molecule
With the preparation of acetic acid and methyl alcohol eluent, wherein acetic acid: the ratio of methyl alcohol is 10:90 (V/V), the magnetic molecularly imprinted polymer preparing is cleaned 7 days in apparatus,Soxhlet's, then be washed till neutrality with deionized water in step (3).
Pay special attention to, the preparation method of the non-imprinted polymer of magnetic (MNIPs) is identical with the preparation method of above-mentioned magnetic molecularly imprinted polymer, just in the solvent 1 of step (3), does not add 2,4,6-Trichlorophenol, and does not have step (4).
Fig. 2 is the magnetic Fe of preparation in embodiment 1
3o
4nanoparticle, the infrared spectrogram of magnetic molecularly imprinted polymer and the non-imprinted polymer of magnetic.
2, absorption property analytical test:
(1) Static Adsorption test 1
Be 2 of 100 mg/L by 10 mL concentration, 4,6-TCP solution joins in colorimetric cylinder, add respectively 10 mg magnetic molecularly imprinted polymers and the non-imprinted polymer of magnetic, respectively at 15 DEG C, in 25 DEG C and 35 DEG C of waters bath with thermostatic control, leave standstill 12 h, investigate the impact of differential responses temperature on Polymer adsorption performance; After saturated adsorption, polymkeric substance is collected with Nd-Fe-B permanent magnet, and not 2,4 of absorption, the concentration ultraviolet spectral analysis of 6-TCP, according to formula calculation result.Result substitution Gibbs free energy formula calculates.
Result shows: by Gibbs free energy formula, the value of trying to achieve Δ Ho is 0.0047, Δ
sthe value of o is that Δ G corresponding under 0.029, three differing temps is respectively-5.178 ,-6.054 and-7.064.Δ Ho>0 explanation adsorption process is absorbed heat, Δ
g<0 shows that sorbent material is spontaneous to the absorption of 2,4,6-TCP.
(2) Static Adsorption test 2
Be 2 of 150 mg/L by 10 mL concentration, 4,6-TCP solution joins in colorimetric cylinder, add respectively 10 mg magnetic molecularly imprinted polymers and the non-imprinted polymer of magnetic, respectively at 15 DEG C, in 25 DEG C and 35 DEG C of waters bath with thermostatic control, leave standstill 12 h, investigate the impact of differential responses temperature on Polymer adsorption performance; After saturated adsorption, polymkeric substance is collected with Nd-Fe-B permanent magnet, and not 2,4 of absorption, the concentration ultraviolet spectral analysis of 6-TCP, according to formula calculation result.Result substitution Gibbs free energy formula calculates.
Result shows: by Gibbs free energy formula, the value of trying to achieve Δ Ho is 0.0072, and the value of Δ So is that Δ G corresponding under 0.026, three differing temps is respectively-7.313 ,-8.014 and-8.931.Δ Ho>0 explanation adsorption process is absorbed heat, and Δ G<0 shows that sorbent material is spontaneous to the absorption of 2,4,6-TCP.
Claims (1)
1. utilize suspension polymerization to prepare the method for magnetic molecularly imprinted polymer, carry out according to the following steps:
(1) the synthetic Z 250 (Fe of hydrothermal synthesis method
3o
4) magnetic nano-particle:
Ferric chloride (FeCl36H2O) (FeCl
36H
2o) and sodium acetate, anhydrous (NaAc) be dissolved in ethylene glycol solution, wherein control FeCl
36H
2o, the ratio of NaAc and ethylene glycol is (1.3-1.4): (7-8): (40-50) (g/mL/mL);
Mixing solutions speed with 800 rpm/min under the protection of nitrogen stirs 1-2 h in the water bath with thermostatic control of 160 DEG C, then mixing solutions is transferred in the reactor of 50 mL, temperature is controlled at 200 DEG C, reaction times is 10 h, after taking-up, be cooled to room temperature, suspension is cleaned to 3-5 time with ethanolic soln, the product of acquisition is dried under the vacuum environment of 60 DEG C, finally in mortar, pulverize and grind;
(2) oleic acid is to Fe
3o
4magnetic nano-particle carries out finishing
In step (1), prepare the Fe of gained
3o
4nanoparticle mixes with oleic acid, continues to stir 1-2 h with the speed of 200 rpm/min, forms dark-brown Fe
3o
4magnetic fluid, wherein controls the Fe in step (1)
3o
4the ratio of nanoparticle and oleic acid is 0.1:4 (g/mL);
(3) suspension polymerization synthesizing magnetic molecularly imprinted polymer
Solvent 1: by 2,4,6-Trichlorophenol, methacrylic acid is dissolved in toluene solution, at room temperature stir 10-30 min, wherein control 2,4,6-Trichlorophenol: methacrylic acid: the ratio of toluene is (0.2-0.3): (0.35-0.45): (5-7) (g/mL/mL);
Solvent 2: prepare the Fe after the oleic acid modification of gained in step (2)
3o
4magnetic fluid, Diisopropyl azodicarboxylate and toluene are dissolved in ethylene glycol dimethacrylate solution;
Wherein control the Fe in step (2)
3o
4magnetic fluid: Diisopropyl azodicarboxylate: toluene: the ratio of ethylene glycol dimethacrylate is 4:(0.15-0.2): (2-3): (3.5-4) (mL/g/mL/mL);
Solvent 3: polyvinyl alcohol is added in deionized water, temperature is controlled at 80 DEG C, stirring velocity is 400 rpm/min, reaction times is 30-60 min, be cooled to room temperature, the ratio of wherein controlling polyvinyl alcohol and deionized water is (3-4): (130-150) (g/mL) again;
Solvent 4: sodium lauryl sulphate is added in deionized water, and under room temperature, 600 rpm/min stir 10 min, the ratio of wherein controlling sodium lauryl sulphate and deionized water is 1:20 (g/mL);
Solvent 1 and solvent 2 are mixed to form to solution a, and solvent 1 is (5-7) with the volume ratio of solvent 2: (9.5-11), stir 2 h under room temperature, rotating speed is 400 rpm/min;
Solvent 3 and solvent 4 are mixed to form to solution b, and solvent 3 is (130-150) with the volume ratio of solvent 4: 20, under room temperature, stir 2 h, and rotating speed is 400 rpm/min;
Solution a is mixed with solution b, and the volume ratio of solution a and solution b is (14.5-18): (150-170);
At room temperature, controlling stirring velocity is 600 rpm/min, and under nitrogen protection, reaction continues 1 h, then temperature is risen to 60 DEG C, and stirring velocity is 600 rpm/min, and under nitrogen protection, 24 h are carried out in reaction, obtain molecularly imprinted polymer;
The ethanolic soln for molecularly imprinted polymer obtaining in step (3) (ethanol: deionized water (V:V)=1:1) is cleaned 3 times, then use washed with de-ionized water 2 times;
(4) wash-out template molecule
With the preparation of acetic acid and methyl alcohol eluent, wherein acetic acid: the ratio of methyl alcohol is 10:90 (V/V), and the magnetic molecularly imprinted polymer preparing in step (3) is cleaned to 5-7 days in apparatus,Soxhlet's, then be washed till neutrality with deionized water.
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