CN109180864B - Molecularly imprinted polymer material for purifying sulfonamides in water and application thereof - Google Patents
Molecularly imprinted polymer material for purifying sulfonamides in water and application thereof Download PDFInfo
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- CN109180864B CN109180864B CN201810790112.XA CN201810790112A CN109180864B CN 109180864 B CN109180864 B CN 109180864B CN 201810790112 A CN201810790112 A CN 201810790112A CN 109180864 B CN109180864 B CN 109180864B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 38
- 239000002861 polymer material Substances 0.000 title claims abstract description 37
- 229940124530 sulfonamide Drugs 0.000 title claims abstract description 28
- 150000003456 sulfonamides Chemical class 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 229960002135 sulfadimidine Drugs 0.000 claims abstract description 18
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 13
- 231100000719 pollutant Toxicity 0.000 claims abstract description 13
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 238000010556 emulsion polymerization method Methods 0.000 claims abstract description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 13
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000012719 thermal polymerization Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 abstract description 5
- 229960004306 sulfadiazine Drugs 0.000 abstract description 5
- GPTONYMQFTZPKC-UHFFFAOYSA-N sulfamethoxydiazine Chemical compound N1=CC(OC)=CN=C1NS(=O)(=O)C1=CC=C(N)C=C1 GPTONYMQFTZPKC-UHFFFAOYSA-N 0.000 abstract description 4
- 229960002229 sulfametoxydiazine Drugs 0.000 abstract description 4
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 abstract description 4
- NHUHCSRWZMLRLA-UHFFFAOYSA-N Sulfisoxazole Chemical compound CC1=NOC(NS(=O)(=O)C=2C=CC(N)=CC=2)=C1C NHUHCSRWZMLRLA-UHFFFAOYSA-N 0.000 abstract description 3
- -1 sulfamethoxyzine Chemical compound 0.000 abstract description 3
- 229960001544 sulfathiazole Drugs 0.000 abstract description 3
- 229940124350 antibacterial drug Drugs 0.000 abstract description 2
- 229960000654 sulfafurazole Drugs 0.000 abstract description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000003814 drug Substances 0.000 description 12
- 229940079593 drug Drugs 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 241000282414 Homo sapiens Species 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000273 veterinary drug Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000003640 drug residue Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000000777 hematopoietic system Anatomy 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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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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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/40—Organic compounds containing sulfur
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Abstract
The invention relates to a molecularly imprinted polymer material for purifying sulfonamides in water, which is prepared by carrying out free radical polymerization on a template molecule, a functional monomer and a cross-linking agent under the action of an initiator and forming a microsphere molecular polymer with high cross-linking degree by an emulsion polymerization method. The molecularly imprinted polymer material for purifying the sulfonamides in the water has high adsorption capacity and good selectivity for 7 sulfanilamide antibacterial drugs such as sulfamethazine, sulfadiazine, sulfamethoxyzine, sulfisoxazole, sulfathiazole, sulfamethoxydiazine, sulfamethazine and the like which are pollutants in the water by enriching and purifying target pollutants.
Description
Technical Field
The invention belongs to the technical field of environmental protection and purification, and particularly relates to a molecularly imprinted polymer material for enriching and purifying sulfonamides in water and application thereof.
Background
In recent years, negative effects caused by mass production and abuse of veterinary drugs are increasingly remarkable, which not only affect agricultural production and destroy ecological environment, but also seriously harm human health. With the mass production and abuse of the agricultural and veterinary drugs, a large amount of drug residues are caused, and the water body pollution is serious. Therefore, the development of a simple, rapid and efficient method for purifying and removing the pollutants of the veterinary drugs in the water body is of great significance.
Sulfonamides are artificially synthesized antibacterial and bactericidal drugs, have the characteristics of convenient use, low price, good curative effect and the like, are widely applied to livestock breeding and human clinical medicine, but due to the phenomena of unreasonable use, abuse and the like of human, a large amount of pesticide and veterinary drug residues enter a water body to seriously pollute a water source. After being ingested by human body, the water source affects the hematopoietic system, urinary system, digestive system and kidney of human body, and is harmful to human health. And when the residue in the body reaches a certain level, it can cause cancer, teratogenesis and mutation. The focus of attention has been always focused on ensuring the health safety of human beings, ensuring the safety of drinking water, and efficiently purifying and removing the residual drug pollutants in the water.
The pollution components brought by the agricultural and veterinary medicines are complex, the treatment is difficult and the like, the existing water purification technology can not filter the agricultural and veterinary medicines in water completely, and membrane pollution is easy to cause for a long time, thus threatening the safety of drinking water. The molecular imprinting technology is a preparation technology for obtaining a polymer which is completely matched with a target molecule on a space structure and a binding site, and is a novel interdisciplinary subject which integrates the advantages of a plurality of subjects such as polymer synthesis, molecular design and recognition, bionic bioengineering and the like. The molecularly imprinted polymer is a high molecular material tailored for target molecules of drug pollutants, so the molecularly imprinted polymer has the advantages of good selectivity, good physical and chemical stability, strong anti-interference capability, long service life, wide application range and the like, and has wide application prospects in the fields of materials, chemistry, medicine, biology, environmental engineering and the like.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a molecularly imprinted polymer material for purifying sulfonamides in water, aiming at the defects in the prior art, the molecularly imprinted polymer material has high adsorption capacity and good selectivity on sulfonamide antibacterial drugs which are water pollutants, can thoroughly filter the pollutants in water, achieves the effect of purifying water and ensures the safety of domestic water.
The invention provides a molecularly imprinted polymer material for purifying sulfonamides in water, which is prepared by carrying out free radical polymerization on a template molecule, a functional monomer and a cross-linking agent under the action of an initiator, and forming a microsphere molecular polymer with high cross-linking degree by an emulsion polymerization method, wherein the template molecule, the functional monomer, the cross-linking agent and the initiator are added in the following proportions: (0.2-0.4) mol (0.6-0.7) mol (1.1-1.3) mol (61-68) g.
Preferably, the template molecule is sulfadimidine.
Preferably, the functional monomers comprise methacrylic acid and hydroxyethyl methacrylate, and the molar mass addition ratio of the functional monomers is (1-1.1): 1.
preferably, the crosslinking agent is triallyl isocyanurate.
Preferably, the initiator is azobisisobutyronitrile.
A preparation method of a molecularly imprinted polymer material for purifying sulfonamides in water comprises the following steps:
s1: dissolving sulfamethazine serving as a template molecule in acetonitrile, performing ultrasonic dispersion for 15-25min, adding a functional monomer methacrylic acid, and oscillating on a table concentrator for 1.5-2.5h to form a prepolymerization solution;
s2: then adding hydrophilic functional monomer hydroxyethyl methacrylate to continue shaking for 1-2h, adding the cross-linking agent to fully stir for 1-2h, adding the initiator to stir for 0.5 h;
s3: heating under the water bath condition of 60-65 ℃ under the protection of nitrogen to carry out thermal polymerization, and carrying out water bath for 23-25h to obtain the target molecular polymer material.
Further, the stirring rate in S2 is 400-600 rpm.
The molecularly imprinted polymer material for purifying the sulfonamides in the water is applied to sewage treatment.
The molecularly imprinted polymer material provided by the invention can be used for preparing a filter tube applied to sewage treatment according to the following steps:
(1) grinding the synthesized molecularly imprinted polymer into powder, sieving, wrapping the 600-800 mesh polymer with filter paper, transferring the wrapped polymer into a Soxhlet extractor, and extracting for 80 hours, wherein an extraction solvent is methanol: formic acid (v: v, 9:1) until no template molecule is detected.
(2) Then washing with 20ml of 1mol/L hydrochloric acid and 20ml of methanol for 2 hours, and finally repeatedly washing with 0.25mol/L sodium hydroxide and water until the mixture is neutral. And then placing the mixture in a 75 ℃ oven to dry the mixture to constant weight, thus obtaining the sulfamethazine molecularly imprinted polymer particles.
(3) 300g of adsorbing material is weighed and filled in an empty tube, and two ends of the adsorbing material are compressed by pressing sheets and vacuumized for standby. .
The action principle is as follows:
the molecular imprinting is to take target pollutant molecules as templates, combine functional monomers with the template molecules in a covalent bond or non-covalent bond mode, add a cross-linking agent for polymerization reaction, and then extract the template molecules to form high molecules of the template molecules with cavities and capable of being recognized, wherein the high molecules are called as molecular imprinting polymers.
The microsphere molecularly imprinted polymer with high crosslinking degree is prepared by reaction in a large amount of medium, the medium of the reaction system is greatly higher than the dosage of the block polymer, and the molecularly imprinted polymer is synthesized by taking sulfadimidine as template molecule. The recognition ability of the imprinted polymer is determined by the stability of the complex formed by the template molecule and the functional monomer before polymerization, and the action form between the template molecule and the functional monomer. Because the pyridine ring of the sulfadiazine drug is an electron-withdrawing group, -NH2Has stronger basicity, so when the complex is formed with MAA (with pKa of 4.6), the synergy of static electricity and hydrogen bond can be generated simultaneously, and the figure is shown in figure 2.
Firstly, according to the polymerization theory, the polymerization reaction starts from the mixture of homogeneous functional monomers, template molecules, a cross-linking agent and an initiator; the initiator initiates free radical polymerization of the functional monomer and the cross-linking agent to form the microsphere molecular polymer with high cross-linking degree, and the polymer prepared by the method is different from a suspension polymerization method in stability by adding stabilizing agents such as polyethylene glycol and the like, and the polymer prepared by the method does not need to be added with the stabilizing agent, so that non-selective adsorption of the stabilizing agent on template molecules can be avoided; then the template molecule is taken out by an elution method, so that the sulfonamide residues in the water can be adsorbed and enriched, and the effect of purifying the water is achieved.
Compared with the prior art, the invention has the beneficial effects that:
compared with the prior art, the molecularly imprinted polymer has the characteristics of predetermination, identification, practicability and the like on target molecules, and is widely applied to the research in the fields of chemical bionic sensors, solid-phase extraction, simulated enzyme catalysis, enantiomer separation, membrane separation technology and the like. The recognition sites generated by the molecularly imprinted polymer in the molecular imprinting process are usually selectively combined with the template molecules by means of the acting forces of ions, hydrogen bonds, metal coordination and the like. The molecularly imprinted polymer material forms binding sites on the surface of molecules, so that the polymer material has the characteristics of large adsorption capacity, high adsorption and resolution speed, high specificity, good selectivity, long service life, capability of realizing reutilization and the like.
The molecular imprinting polymer provided by the invention is a microspheric molecular imprinting polymer material with relatively good monodispersity, and has the advantages of high molecular recognition efficiency, convenience for functional design and more convenience for preparation and application. The existing molecularly imprinted polymer is in a block shape and is used after being ground and sieved, but the subsequent treatment process of the method is complicated and time-consuming, the product loss is easy to cause in the grinding and sieving process, the product shape is irregular, the dispersibility is poor, and the chromatographic efficiency is low.
The molecularly imprinted polymer material for purifying the sulfonamides in water has high adsorption capacity and good selectivity on residues of 7 sulfonamides such as sulfamethazine, sulfadiazine, sulfamethoxyzine, sulfisoxazole, sulfathiazole, sulfamethoxydiazine, sulfamethazine and the like through enrichment and purification of target pollutants. The activated material thoroughly filters sulfonamide pollutants in water, achieves the effect of purifying water, and ensures the safety of domestic water. Meanwhile, the polymer material can be cleaned by methanol for a long time and can be recycled. The molecularly imprinted polymer material has the advantages of high selectivity, good specificity, long service life, reusability and the like for target molecular drug pollutants.
Drawings
FIG. 1 is an electron microscope scanning image of the molecularly imprinted polymer material prepared by the present invention;
FIG. 2 is a diagram showing the formation process and identification process of imprinted polymers.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
A molecularly imprinted polymer material for purifying sulfonamides in water comprises the following components: 0.2mol of azobisisobutyronitrile, 1.1mol of triallyl isocyanurate, 61g of azobisisobutyronitrile and 0.6mol of functional monomers, wherein the functional monomers comprise 0.3mol of methacrylic acid and 0.3mol of hydroxyethyl methacrylate.
A preparation method of a molecularly imprinted polymer material for purifying sulfonamides in water comprises the following steps:
s1: dissolving sulfamethazine serving as a template molecule into 120mL of acetonitrile, performing ultrasonic dispersion for 15min, adding a functional monomer methacrylic acid, and oscillating on a table concentrator for 2.5h to form a prepolymerization solution;
s2: then adding a hydrophilic functional monomer hydroxyethyl methacrylate to continue shaking for 2h, then adding a cross-linking agent to fully stir for 2h, and then adding an initiator to stir for 0.5h at the speed of 400 rpm;
s3: and (3) heating under the water bath condition of 62 ℃ under the protection of nitrogen to carry out thermal polymerization, and carrying out water bath for 23 hours to obtain the target molecular polymer material.
Example 2
A molecularly imprinted polymer material for purifying sulfonamides in water comprises the following components: 0.4mol of azobisisobutyronitrile, 1.3mol of triallyl isocyanurate, 68g of azobisisobutyronitrile and 0.7mol of functional monomers, wherein the functional monomers comprise 0.36mol of methacrylic acid and 0.34mol of hydroxyethyl methacrylate.
A preparation method of a molecularly imprinted polymer material for purifying sulfonamides in water comprises the following steps:
s1: dissolving sulfamethazine serving as a template molecule into 120mL of acetonitrile, performing ultrasonic dispersion for 25min, adding a functional monomer methacrylic acid, and oscillating on a table concentrator for 1.5h to form a prepolymerization solution;
s2: then adding a hydrophilic functional monomer hydroxyethyl methacrylate to continue shaking for 2h, then adding a cross-linking agent to fully stir for 2h, and then adding an initiator to stir for 0.5h at the speed of 600 rpm;
s3: and (3) heating under the water bath condition of 65 ℃ under the protection of nitrogen to carry out thermal polymerization, and carrying out water bath for 25h to obtain the target molecular polymer material.
Example 3
A molecularly imprinted polymer material for purifying sulfonamides in water comprises the following components: 0.3mol of azobisisobutyronitrile, 1.2mol of triallyl isocyanurate, 65g of azobisisobutyronitrile and 0.65mol of functional monomers, wherein the functional monomers comprise 0.34mol of methacrylic acid and 0.31mol of hydroxyethyl methacrylate.
A preparation method of a molecularly imprinted polymer material for purifying sulfonamides in water comprises the following steps:
s1: dissolving sulfamethazine serving as a template molecule into 120mL of acetonitrile, performing ultrasonic dispersion for 20min, adding a functional monomer methacrylic acid, and oscillating on a table concentrator for 2h to form a prepolymerization solution;
s2: then adding a hydrophilic functional monomer hydroxyethyl methacrylate to continue shaking for 1h, then adding a cross-linking agent to fully stir for 1h, and then adding an initiator to stir for 0.5h at the speed of 500 rpm;
s3: and (3) heating under the water bath condition of 60 ℃ under the protection of nitrogen to carry out thermal polymerization, and carrying out water bath for 24 hours to obtain the target molecular polymer material.
Example 4
A molecularly imprinted polymer material for purifying sulfonamides in water comprises the following components: 0.2mol of azobisisobutyronitrile, 1.3mol of triallyl isocyanurate, 66g of azobisisobutyronitrile and 0.7mol of functional monomers, wherein the functional monomers comprise 0.35mol of methacrylic acid and 0.35mol of hydroxyethyl methacrylate.
A preparation method of a molecularly imprinted polymer material for purifying sulfonamides in water comprises the following steps:
s1: dissolving sulfamethazine serving as a template molecule into 120mL of acetonitrile, performing ultrasonic dispersion for 20min, adding a functional monomer methacrylic acid, and oscillating on a table concentrator for 1.5h to form a prepolymerization solution;
s2: then adding a hydrophilic functional monomer hydroxyethyl methacrylate to continue shaking for 1.5h, then adding a cross-linking agent to fully stir for 1h, and then adding an initiator to stir for 0.5h at the speed of 400 rpm;
s3: and (3) heating under the water bath condition of 60 ℃ under the protection of nitrogen to carry out thermal polymerization, and carrying out water bath for 23-25h to obtain the target molecular polymer material.
Product performance experiment
Grinding the synthesized molecularly imprinted polymer into powder, sieving, wrapping the 600-800 mesh polymer with filter paper, transferring the wrapped polymer into a Soxhlet extractor, and extracting for 80 hours, wherein an extraction solvent is methanol: formic acid (v: v, 9:1) until no template molecule is detected. Then washing with 20mL of 1mol/L hydrochloric acid and 20mL of methanol for 2h, and finally repeatedly washing with 0.25mol/L sodium hydroxide and distilled water until the solution is neutral. And then placing the mixture in a 75 ℃ oven to dry the mixture to constant weight, thus obtaining the sulfamethazine molecularly imprinted polymer particles. 300g of adsorbing material is weighed and filled in an empty tube, and two ends of the adsorbing material are compressed by pressing sheets and vacuumized for standby. The material is activated by 200mL of methanol, and is repeatedly eluted by distilled water for 5 times, so that the purification treatment of trace pollutants in water can be realized.
Preparing 7 drug sample solutions of 50mg/L, adsorbing the drug samples by using a spare molecular imprinting packed column in sequence, and finally eluting with methanol: formic acid (v: v, 9:1) was eluted, concentrated and finally the sample was analyzed and tested by HPLC, the experimental results are shown in Table 1.
TABLE 1 results of treatment
| Medicine | Before treatment (mg/L) | After treatment (mg/L) | Removal rate% |
| Sulfamethazine | 50 | 4.2×10-1 | 99.2 |
| Sulfadiazine | 50 | 3.7 | 92.6 |
| Sulfamethoxyzine | 50 | 2.1 | 95.8 |
| Sulfasoxazole | 50 | 5.3 | 89.4 |
| Sulfathiazole | 50 | 1.1 | 97.8 |
| Sulfamethoxydiazine | 50 | 6.4×10-1 | 98.7 |
| Sulfamethopyrimidine | 50 | 4.8 | 90.4 |
By enriching and purifying target molecules, the polymer material has high adsorption capacity and good selectivity to sulfamethazine, sulfadiazine, sulfamethoxazole, sulfthiazole, sulfamethoxydiazine and sulfamethazine, and the activated material thoroughly filters sulfonamide pollutants in water to achieve the effect of purifying water.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A preparation method of a molecularly imprinted polymer material for purifying sulfonamides in water is characterized in that a template molecule, a functional monomer and a cross-linking agent are subjected to free radical polymerization under the action of an initiator, and a microsphere molecular polymer with high cross-linking degree is formed by an emulsion polymerization method, wherein the template molecule, the functional monomer, the cross-linking agent and the initiator are added in the following proportion: (0.2-0.4) mol (0.6-0.7) mol (1.1-1.3) mol (61-68) g; the template molecule is sulfamethazine; the functional monomer comprises methacrylic acid and hydroxyethyl methacrylate, and the molar mass addition ratio of the functional monomer to the hydroxyethyl methacrylate is (1-1.1): 1;
the preparation method comprises the following steps:
s1: dissolving sulfamethazine serving as a template molecule in acetonitrile, performing ultrasonic dispersion for 15-25min, adding a functional monomer methacrylic acid, and oscillating on a table concentrator for 1.5-2.5h to form a prepolymerization solution;
s2: then adding hydrophilic functional monomer hydroxyethyl methacrylate to continue shaking for 1-2h, adding the cross-linking agent to fully stir for 1-2h, adding the initiator to stir for 0.5 h;
s3: heating under the water bath condition of 60-65 ℃ under the protection of nitrogen to carry out thermal polymerization, and carrying out water bath for 23-25h to obtain the target molecular polymer material.
2. The preparation method of the molecularly imprinted polymer material for purifying sulfonamides in water as claimed in claim 1, wherein said cross-linking agent is triallyl isocyanurate.
3. The preparation method of the molecularly imprinted polymer material for purifying sulfonamides in water as claimed in claim 1, wherein the initiator is azobisisobutyronitrile.
4. The method as claimed in claim 1, wherein the stirring speed in S2 is 400-600 rpm.
5. The molecularly imprinted polymer material for purifying the sulfonamides which are pollutants in water prepared by the method according to any one of claims 1-4 is applied to sewage treatment.
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