CN113817217A - Porous polymer microsphere for high selective adsorption of enrofloxacin and preparation method thereof - Google Patents
Porous polymer microsphere for high selective adsorption of enrofloxacin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of porous polymer microspheres for high selective adsorption of enrofloxacin, belonging to the technical field of preparation of porous adsorption materials. The porous polymer microsphere has the characteristics of porosity, large enrofloxacin adsorption capacity, high selectivity, fast mass transfer, good stability, simple preparation process and the like, and has wide application prospect in the fields of fast separation, enrichment and analysis of enrofloxacin in aquatic products, livestock and poultry meat, dairy and egg foods, environmental samples, biological samples, adsorption and removal of environmental enrofloxacin pollutants and the like.
Description
Technical Field
The invention relates to the technical field of preparation of porous adsorption materials, in particular to a porous polymer microsphere for high selective adsorption of enrofloxacin and a preparation method thereof.
Background
Enrofloxacin (Enrofloxacin) has the effects of inhibiting and killing gram-positive bacteria, gram-negative bacteria, mycoplasma bacteria and the like, has the characteristics of strong bactericidal activity, wide in-vivo distribution and the like, and is widely used for preventing and treating bacterial blight and mycoplasma infection of aquatic products and livestock and poultry animals, such as various bacterial infections of fish, gill rot and tail rot, chicken chronic respiratory disease, swine enzootic pneumonia, swine white dysentery, piglet yellow dysentery, swine edema disease and the like; it can also be illegally used as a growth promoter. Due to the extensive dosage form of enrofloxacin used in aquatic product and livestock and poultry breeding and the lack of medication guidance and supervision, the enrofloxacin preparation is abused greatly to pollute the environment, aquatic products, livestock and poultry meat and milk eggs. The long-term consumption of enrofloxacin residue can cause the drug resistance of microbial strains to be enhanced, allergy, gastrointestinal disorder and damage to liver and kidney, thus harming human health. How to remove enrofloxacin pollutants in the environment and quickly and sensitively detect enrofloxacin residues in food is a problem to be solved in the high-speed development of the current environment-friendly breeding industry.
At present, solvent extraction, ion exchange extraction, and the like are generally adopted for the separation and enrichment of enrofloxacin,The methods of activated carbon adsorption, membrane separation and the like have the defects of poor selectivity, low efficiency, environmental unfriendliness, high cost and the like. The enrofloxacin imprinted polymer prepared by the molecular imprinting technology has good selective adsorption capacity on enrofloxacin, and also has the advantages of high temperature resistance, acid and alkali resistance, organic solvent resistance, good mechanical strength, reproducibility and reusability, low cost and the like, so the enrofloxacin imprinted polymer is widely concerned in the field of separation, enrichment and analysis. For example, Caro et al (Ester Caro, Rosa M. Marce', Peter A. G. Cormack, et al. Analytica Chimica Acta,2006,562: 145-; wang et al (Wang J, Pan M, Fang G, et al. Microchimica Acta,2009,166: 295) adopt a sol-gel method, N dimethylformamide is taken as a pore-forming agent, enrofloxacin is taken as a template molecule, 3-aminopropyl triethoxysilane is taken as a functional monomer, tetraethoxy silica gel is taken as a cross-linking agent, and the prepared enrofloxacin imprinted polymer is applied to online adsorption monitoring of enrofloxacin residual quantity in fish and chicken; rodguez et al (rodri guez E, navaro-villosa F,
e, et al, analytical Chemistry,2011,83: 2046-; li et al (Xiao-Xia Li, Li-Hong Bai, Huang Wang, et al. journal of Chromatography A,2012,1251: 141-; he et al (Hai-Bo He, Chen Dong, Bin Li, et al. journal of Chromatography A,2014,1361: 23-33) chloroformPore-forming agent, enrofloxacin is used as template molecule, magnetic polyhedral oligomeric silsesquioxane Fe3O4The surface of the @ POSS matrix is copolymerized to prepare a magnetic imprinted polymer hybrid material which is applied to separation and detection of ofloxacin, enrofloxacin and danofloxacin in milk; wang et al (WANG X, ZHOU Y Q, NIU Y L, et al. International Journal of Analytical Chemistry,2019,5970754.DOI: org/10.1155/2019/5970754.) for cross-linking polymerized glycidyl methacrylate-ethylene glycol dimethacrylate microspheres (P. RTM. TM.)GMA-EDMA) Bonding 3-Methacryloxypropyltrimethoxysilane (MPS) on the surface of the substrate, and grafting methacrylic acid to obtain PGMA-EDMAThe @ MPS @ MAA microspheres are used as functional monomers, the enrofloxacin is used as a template molecule, and the enrofloxacin imprinted polymer is prepared by adopting a surface imprinting method and is applied to solid-phase extraction of enrofloxacin residue in milk; yan et al (Hongyua Yan, Fengxia Qiao, Kyung Ho Row. Chromatographia,2009,70(7-8): 1087-; xiao et al (Deli Xiao, Pierre Dramou, Nanqian Xiong, et al Analyst,2013,138: 3287-.
However, most of imprinted polymers reported in the literature use organic small molecules such as dichloromethane, acetonitrile, chloroform and the like as pore-forming agents, the obtained polymers have small gaps and slow mass transfer, and the problems of low polymer adsorption capacity, template leakage and the like are often caused by the fact that recognition sites only exist on the surface of a material or the imprinting sites are embedded too deeply and the elution of template molecules is not complete, so that the application of the imprinted polymers in environmental pollution treatment and trace analysis is limited.
Disclosure of Invention
Aiming at the problems, the invention provides a porous polymer microsphere for adsorbing enrofloxacin with high selectivity, and a preparation method and application thereof.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of porous polymer microspheres for highly selective adsorption of enrofloxacin comprises the following steps:
(1) mixing and emulsifying a surfactant, hydrophobic ionic liquid and paraffin oil to obtain emulsion; weighing beta-cyclodextrin, dissolving the beta-cyclodextrin in hot water to obtain a beta-cyclodextrin solution, cooling, adding methacrylic acid, and uniformly mixing to obtain a continuous phase solution;
(2) mixing and emulsifying the continuous phase solution and the emulsion, adding a cross-linking agent and an initiator, introducing nitrogen, deoxidizing, sealing a reaction system, stirring and reacting at a constant temperature, and separating a white precipitate after the reaction is finished;
(3) washing the white precipitate with water and ethanol in sequence, leaching with an acetic acid ethanol solution, and drying after leaching to prepare the porous polymer microsphere.
Preferably, the surfactant is one or more of Span80, Tween80, cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate.
Preferably, the hydrophobic ionic liquid is one or more of 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 2-chloro-1, 3-dimethylimidazolium hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazolinium hexafluorophosphate, 1-butyl-4-methylpyridinium hexafluorophosphate and N-octylpyridinium hexafluorophosphate.
Preferably, the mixing mass ratio of the surfactant, the hydrophobic ionic liquid and the paraffin oil is (1-5): (10-25): (100-200).
Preferably, the concentration of the beta-cyclodextrin solution is 12-48 g/L; the molar ratio of the beta-cyclodextrin to the methacrylic acid in the continuous phase solution is 1: (8-10).
Preferably, the mixing volume ratio of the continuous phase solution to the emulsion is 1: (2-7).
Preferably, the cross-linking agent is one or more of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, trimethylolpropane trimethacrylate, N '-methylene bisacrylamide, N' -1, 4-phenyl bisacrylamide, pentaerythritol triacrylate and pentaerythritol tetraacrylate; the initiator is one or more of potassium persulfate, ammonium persulfate, persulfate-tetramethylethylenediamine and azodiisobutyronitrile.
Preferably, the reaction conditions of the constant-temperature stirring reaction are as follows: the reaction temperature is 70-75 ℃, and magnetic stirring is carried out for 1h at 1000 r/min.
The invention also aims to provide a porous polymer microsphere for highly selectively adsorbing enrofloxacin, which is prepared by the preparation method.
The invention further aims to provide application of the porous polymer microspheres, and the porous polymer microspheres are particularly used for detecting, enriching and/or separating enrofloxacin in samples to be detected, such as aquatic products, livestock and poultry meat, dairy and egg foods, environmental samples, biological samples and the like.
The invention has the beneficial effects that:
aiming at least one of the defects of poor selectivity, low efficiency, slow mass transfer, low adsorption capacity and the like of a separation and enrichment method for enrofloxacin in the prior art, the invention provides a preparation method of porous polymer microspheres with high selective adsorption for enrofloxacin, and the porous polymer microspheres are prepared by adopting an emulsion polymerization method, wherein ternary mixed liquid consisting of hydrophobic ionic liquid, paraffin oil and a surfactant is used as emulsion, beta-cyclodextrin is used as a template pore-forming agent, and methacrylic acid is used as a functional monomer. The porous polymer microsphere has the characteristics of porosity, large enrofloxacin adsorption capacity, high selectivity, fast mass transfer, good stability, simple preparation process and the like, and has wide application prospect in the fields of fast separation, enrichment and analysis of enrofloxacin in aquatic products, livestock and poultry meat, dairy and egg foods, environmental samples, biological samples, adsorption and removal of environmental enrofloxacin pollutants and the like.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a scanning electron micrograph of a porous polymeric microsphere according to example 1 of the present invention;
FIG. 2 is a static adsorption curve of porous polymeric microspheres according to example 1 of the present invention;
FIG. 3 is a static adsorption curve of porous polymeric microspheres according to example 3 of the present invention;
FIG. 4 is a dynamic adsorption curve of porous polymeric microspheres according to example 1 of the present invention;
FIG. 5 is a thermogravimetric analysis curve of the porous polymeric microspheres described in examples 2 and 3 of the present invention.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A preparation method of porous polymer microspheres for highly selective adsorption of enrofloxacin comprises the following steps:
(1) adding 1.0g of span80 and 10g of 1-hexyl-3-methylimidazolium hexafluorophosphate ionic liquid into 100g of paraffin oil, and performing ultrasonic emulsification for 20min to obtain an emulsion;
(2) weighing 0.6g of beta-cyclodextrin, dissolving in 25mL of 80 ℃ hot water, cooling to room temperature, adding 0.4mL of methacrylic acid into the solution, and uniformly stirring to obtain a continuous phase solution;
(3) slowly adding the continuous phase solution into the emulsion, stirring and emulsifying in a constant-temperature water bath at 40 ℃ for 1h, and keeping the stirring speed at 1000 r/min; then adding 4.0mL of ethylene glycol dimethacrylate and 0.12g of potassium persulfate into the emulsification system, carrying out ultrasonic treatment for 20min, introducing nitrogen for 20min, and sealing; stirring in a 70 ℃ constant temperature water bath for 24 hours, and keeping the stirring speed at 1000 r/min; filtering to obtain white precipitate after the reaction is finished;
(4) and (3) carrying out ultrasonic treatment on the white precipitate for 10min by using purified water at 85 ℃, then carrying out ultrasonic treatment for 10min by using ethanol, repeating the process for 4 times, carrying out Soxhlet extraction for 48h by using 20% acetic acid ethanol solution (glacial acetic acid and ethanol in a volume ratio of 2:8), and finally drying for 12h in a vacuum drying oven at 70 ℃ to obtain the porous polymer microspheres.
Example 2
A preparation method of porous polymer microspheres for highly selective adsorption of enrofloxacin comprises the following steps:
(1) adding 0.5g of hexadecyl trimethyl ammonium bromide and 10g of 2-fluoro-1, 3-dimethyl imidazoline hexafluorophosphate ionic liquid into 100g of paraffin oil, and performing ultrasonic emulsification for 20min to obtain emulsion;
(2) weighing 1.2g of beta-cyclodextrin, dissolving in 25mL of 70 ℃ hot water, cooling to room temperature, adding 0.85mL of methacrylic acid into the solution, and uniformly stirring to obtain a continuous phase solution;
(3) slowly adding the continuous phase solution into the emulsion, stirring and emulsifying in a constant-temperature water bath at 40 ℃ for 1h, and keeping the stirring speed at 1000 r/min; then adding 4.0mL of polyethylene glycol diacrylate and 0.12g of azobisisobutyronitrile into the emulsification system, carrying out ultrasonic treatment for 20min, introducing nitrogen for 20min, and sealing; stirring in 75 deg.C constant temperature water bath for 24h, and maintaining stirring speed at 1000 r/min; filtering to obtain white precipitate after the reaction is finished;
(4) and (3) carrying out ultrasonic treatment on the white precipitate for 10min by using purified water at 85 ℃, then carrying out ultrasonic treatment for 10min by using ethanol, repeating the process for 4 times, carrying out Soxhlet extraction for 48h by using 20% acetic acid ethanol solution (glacial acetic acid and ethanol in a volume ratio of 2:8), and finally drying for 12h in a vacuum drying oven at 70 ℃ to obtain the porous polymer microspheres.
Example 3
A preparation method of porous polymer microspheres for highly selective adsorption of enrofloxacin comprises the following steps:
(1) adding 0.5g of span80 and 10g of 1-hexyl-3-methylimidazolium hexafluorophosphate ionic liquid into 100g of paraffin oil, and performing ultrasonic emulsification for 20min to obtain an emulsion;
(2) adding 0.4mL of methacrylic acid into 25mL of purified water, and uniformly stirring to obtain a continuous phase solution;
(3) slowly adding the continuous phase solution into the emulsion, stirring and emulsifying in a constant-temperature water bath at 40 ℃ for 1h, and keeping the stirring speed at 1000 r/min; then adding 4.0mL of ethylene glycol dimethacrylate and 0.12g of potassium persulfate into the emulsification system, carrying out ultrasonic treatment for 20min, introducing nitrogen for 20min, and sealing; stirring in a 70 ℃ constant temperature water bath for 24 hours, and keeping the stirring speed at 1000 r/min; filtering to obtain white precipitate after the reaction is finished;
(4) and (2) carrying out ultrasonic treatment on the white precipitate for 10min by using purified water at 85 ℃, then carrying out ultrasonic treatment for 10min by using ethanol, repeating the process for 4 times, carrying out Soxhlet extraction for 48h by using 20% acetic acid ethanol solution (glacial acetic acid and ethanol in a volume ratio of 2:8), and finally drying for 12h in a vacuum drying oven at 70 ℃ to obtain the blank porous polymer microspheres.
Examples of the experiments
1. Topography characterization
The porous polymer microspheres prepared in example 1 are observed by a scanning electron microscope, and a scanning electron microscope image is shown in fig. 1, so that the polymer is agglomerated together by a plurality of spheres with nonuniform particle size distribution, the diameter is about 500-600 nm, the surface is rough, and the polymer has porosity.
2. Static adsorption experiment
30mg of each of the porous polymers prepared in examples 1 and 3 was weighed accurately, 10mL of a 10.0, 100.0, 200.0, 300.0, 400.0, 500.0, 600.0, 800.0, 1000.0. mu.g/mL difloxacin acetonitrile solution, an enrofloxacin acetonitrile solution, a sarafloxacin acetonitrile solution and a ciprofloxacin acetonitrile solution were added, the mixture was put into a constant temperature oscillator and oscillated at 150rpm for 1 hour at 25 ℃, standing and separated, a supernatant was taken, absorbances of Difloxacin (DIF), enrofloxacin (SAR), Sarafloxacin (SAR) and Ciprofloxacin (CIP) in the solution were measured with an ultraviolet spectrophotometer, and an adsorption amount Q (mg/g) of the polymer to difloxacin, enrofloxacin, sarafloxacin and ciprofloxacin was calculated from changes in the concentrations of the solution before and after adsorption. The calculation results are shown in fig. 2 and 3.
The experimental results show that: the porous polymer microsphere prepared in the embodiment 1 has high adsorption selectivity on enrofloxacin, and the adsorption capacity reaches 138.8mg/g at most; the blank porous polymer microspheres prepared in example 3 have no significant difference in adsorption capacity for difloxacin, enrofloxacin, sarafloxacin and ciprofloxacin, and the adsorption capacity is low, namely 20.2, 21.5, 18.3 and 18.6 mg/g.
3. Dynamic adsorption experiment
Respectively taking 10.0mL of a difloxacin acetonitrile solution with the concentration of 500.0 mu g/mL, an enrofloxacin acetonitrile solution, a sarafloxacin acetonitrile solution and a ciprofloxacin acetonitrile solution, adding 30.0mg of the porous polymer prepared in the example 1, oscillating and adsorbing for different time (2-30 mim) in a constant temperature oscillator at 25 ℃, standing and separating, taking a supernatant, measuring the absorbance of the difloxacin, the enrofloxacin, the sarafloxacin and the ciprofloxacin in the solution by using an ultraviolet spectrophotometer, and calculating the adsorption capacity of the polymer. The results are shown in FIG. 4.
Experimental results show that the porous polymer microsphere achieves balance in absorption of sarafloxacin and bifloxacin for 5min and balance in absorption of enrofloxacin and ciprofloxacin for 10min, and the polymer absorption mass transfer is fast.
4. Thermogravimetric experiments
Thermogravimetric analysis curves of the porous polymer microspheres in examples 2 and 3 are shown in fig. 5, wherein the polymer starts to decompose at 250 ℃ and completely decomposes at about 450 ℃, which indicates that the polymer has good stability.
5. Repeated use experiment
0.1g of the porous polymer prepared in example 1 was weighed in 10.0mL of enrofloxacin acetonitrile solution with a concentration of 500.0. mu.g/mL to perform 10 times of static adsorption and elution cycle experiments. After each static adsorption experiment, the polymer is washed by 0.5mol/L hydrochloric acid and purified water in sequence, and is dried in vacuum at 70 ℃ for regeneration. And adsorbing the enrofloxacin by the regenerated polymer again, and calculating the adsorption recovery rate (%) of the enrofloxacin by the polymer, wherein the test results are shown in table 1. The stability is good and the service life is long.
TABLE 1 Effect of the number of reuses on the adsorption Performance
| Number of repeated use | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Recovery (%) | 99.5 | 98.7 | 96.4 | 94.2 | 91.6 | 88.8 | 85.4 | 82.2 | 79.6 | 76.4 |
6. Application in aquatic product detection
The porous polymer microspheres prepared in example 1 were used to detect the content of 4 FQs in different batches of tilapia mossambica sold in the farmer market in east post of the district of the end state of Zhaoqing.
Preparation of a sample solution: taking a proper amount of fish meat, homogenizing, accurately weighing 5.000g of homogenized fish meat, placing the homogenized fish meat into a 50mL polypropylene centrifuge tube, adding 10mL of 1% formic acid acetonitrile solution, carrying out vortex oscillation for 2min, carrying out ultrasonic extraction for 10min, centrifuging for 5min under the condition of 10000r/min, transferring supernatant into another polypropylene centrifuge tube, repeatedly extracting fish residues for 2 times, combining extracting solutions, carrying out rotary evaporation, and then diluting to a constant volume of 5.00mL by using 1% formic acid acetonitrile solution to obtain a sample solution.
Filling a solid phase extraction column: 50.0mg of the porous polymer powder prepared in example 1 was weighed, charged into a solid-phase extraction cartridge, and packed with absorbent cotton over the packing to prepare a porous polymer solid-phase extraction cartridge.
The solid phase extraction method comprises the following steps: activating with 3.0mL of methanol, controlling flow rate at 0.5mL/min, adding 5.00mL of sample solution, washing with 2.0mL of 5% methanol water, eluting with 10.0mL of 5% methanol-ammonia water (V: 95:5), collecting eluate, and eluting with N2Blow-drying, dissolving the residue with 1.00mL of mobile phase, filtering with 0.45 μm organic membrane, and performing UPLC-MS/MS analysis.
UPLC-MS/MS analysis conditions: ACQUITY UPLCBEHC18A column (50 mm. times.2.1 mm, 1.7 μm, Waters Corp.); mobile phase: methanol-0.1% formic acid water (gradient elution see table 2); the flow rate is 0.25 mL/min; the sample injection amount is 10 mu L.
TABLE 2 mobile phase ratio of ultra high performance liquid chromatography corresponding to different times
| Time (min) | Methanol (%) | 0.1% aqueous formic acid (%) |
| 0 | 30 | 70 |
| 1 | 50 | 50 |
| 3 | 95 | 5 |
| 8 | 30 | 70 |
TABLE 3 Retention time, qualitative ion pairs, quantitative ion pairs, Collision gas energy and declustering Voltage of the quinolone drugs
The results are shown in Table 4. No 4 FQs were detected in 10 spot-checked batches of tilapia samples. In the tilapia sample labeling experiment, 0.20, 2.0 and 10.0 mu g/kg of quinolone with different concentration levels is added, each concentration is 5 parts in parallel, extraction is carried out under the optimized solid phase extraction condition, UPLC-MS/MS measurement is combined, continuous measurement is carried out for 3 days, and the results of the labeling recovery rate and the relative standard deviation are shown in Table 4. The recovery rate of the 4 types of FQs with the added standard is 77.0-101%, and the RSD is 4.0-8.7%. The method has the advantages of good precision and high accuracy, and can be applied to actual sample detection.
Table 4 tilapia samples with 4 FQs remaining amount test results (n ═ 5)
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of porous polymer microspheres for highly selective adsorption of enrofloxacin is characterized by comprising the following steps:
(1) mixing and emulsifying a surfactant, hydrophobic ionic liquid and paraffin oil to obtain emulsion; weighing beta-cyclodextrin, dissolving the beta-cyclodextrin in hot water to obtain a beta-cyclodextrin solution, cooling, adding methacrylic acid, and uniformly mixing to obtain a continuous phase solution;
(2) mixing and emulsifying the continuous phase solution and the emulsion, adding a cross-linking agent and an initiator, introducing nitrogen, deoxidizing, sealing a reaction system, stirring and reacting at a constant temperature, and separating a white precipitate after the reaction is finished;
(3) washing the white precipitate with water and ethanol in sequence, leaching with an acetic acid ethanol solution, and drying after leaching to prepare the porous polymer microsphere.
2. The method for preparing the porous polymer microspheres for highly selective adsorption of enrofloxacin according to claim 1, wherein the surfactant is one or more of Span80, Tween80, cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate.
3. The method for preparing porous polymer microspheres for highly selective adsorption of enrofloxacin according to claim 1, wherein the hydrophobic ionic liquid is one or more of 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 2-chloro-1, 3-dimethylimidazolium hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazoline hexafluorophosphate, 1-butyl-4-methylpyridine hexafluorophosphate and N-octylpyridinium hexafluorophosphate.
4. The preparation method of the porous polymer microsphere for highly selective adsorption of enrofloxacin according to claim 1, wherein the mixing mass ratio of the surfactant, the hydrophobic ionic liquid and the paraffin oil is (1-5): (10-25): (100-200).
5. The preparation method of the porous polymer microsphere for high selective adsorption of enrofloxacin according to claim 1, wherein the concentration of the beta-cyclodextrin solution is 12-48 g/L; the molar ratio of the beta-cyclodextrin to the methacrylic acid in the continuous phase solution is 1: (8-10).
6. The method for preparing the porous polymer microspheres for highly selective adsorption of enrofloxacin according to claim 1, wherein the mixing volume ratio of the continuous phase solution to the emulsion is 1: (2-7).
7. The method for preparing the porous polymer microsphere capable of adsorbing enrofloxacin with high selectivity according to claim 1, wherein the cross-linking agent is one or more of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, trimethylolpropane trimethacrylate, N '-methylenebisacrylamide, N' -1, 4-phenylbisacrylamide, pentaerythritol triacrylate and pentaerythritol tetraacrylate; the initiator is one or more of potassium persulfate, ammonium persulfate, persulfate-tetramethylethylenediamine and azodiisobutyronitrile.
8. The preparation method of the porous polymer microsphere for highly selective adsorption of enrofloxacin according to claim 1, wherein the reaction conditions of the constant temperature stirring reaction are as follows: the reaction temperature is 70-75 ℃, and magnetic stirring is carried out for 1h at 1000 r/min.
9. A porous polymer microsphere for adsorbing enrofloxacin with high selectivity, which is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the porous polymer microspheres of claim 9 for the detection, enrichment and/or separation of enrofloxacin in a sample to be tested.
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| CN117966296A (en) * | 2024-03-29 | 2024-05-03 | 浙江伊诺环保集团股份有限公司 | Water treatment filter material and preparation method thereof |
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