CN114146695A - Preparation method of phthalate magnetic molecularly imprinted polymer extraction material - Google Patents
Preparation method of phthalate magnetic molecularly imprinted polymer extraction material Download PDFInfo
- Publication number
- CN114146695A CN114146695A CN202111556425.7A CN202111556425A CN114146695A CN 114146695 A CN114146695 A CN 114146695A CN 202111556425 A CN202111556425 A CN 202111556425A CN 114146695 A CN114146695 A CN 114146695A
- Authority
- CN
- China
- Prior art keywords
- phthalate
- magnetic
- molecularly imprinted
- adsorption
- sio2
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 238000000605 extraction Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims description 35
- 239000000463 material Substances 0.000 title abstract description 15
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims abstract description 84
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229960001826 dimethylphthalate Drugs 0.000 claims abstract description 42
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000007613 environmental effect Effects 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 229910052681 coesite Inorganic materials 0.000 claims description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims description 17
- 229910052682 stishovite Inorganic materials 0.000 claims description 17
- 229910052905 tridymite Inorganic materials 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- -1 phthalate ester Chemical class 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 53
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 abstract 1
- 238000012673 precipitation polymerization Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 5
- 125000005498 phthalate group Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 241001326116 Ranunculus sceleratus Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- 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
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the new technical field of sample pretreatment and enrichment, and provides a preparation method of a dimethyl phthalate magnetic molecular imprinting polymer extraction material, which comprises the steps of firstly preparing a Ni0.5Zn0.5Fe2O4 magnetic core by a hydrothermal method, modifying and modifying the magnetic core by utilizing Tetraethoxysilane (TEOS) and 3- (methacryloyloxy) propyltrimethoxysilane (MPS), then preparing phthalate magnetic template molecular imprinting polymers (DMP-MMIPs) by adopting a precipitation polymerization method by utilizing dipropyl phthalate (DPRP) as template molecules, methacrylic acid (MAA) as a functional monomer, Ethylene Glycol Dimethacrylate (EGDMA) as a cross-linking agent and Azobisisobutyronitrile (AIBN) as an initiator, wherein the adsorption capacity of the phthalate magnetic molecular imprinting polymers prepared by the method on dimethyl phthalate can reach more than 2.50mg/g, can be applied to the targeted enrichment and the extraction of phthalate organic matters in an environmental water sample.
Description
Technical Field
The invention relates to the new technical field of sample pretreatment and enrichment, in particular to a preparation method of a phthalate magnetic molecular imprinting polymer extraction material.
Background
Phthalates (PAEs) are the most commonly used plasticizers in the world for flexible adhesives, sealants, found in food packaging materials, medical blood bags and hoses, vinyl flooring and wallpaper, waterproof films, power cable insulation protective covers, swimming pool liners, waterproof shoes and garden hoses, and the like. The phthalate plays a role similar to estrogen in human bodies and animal bodies, and can interfere endocrine, reduce the amount of sperms and the number of sperms in men, and the like. Therefore, the preparation of the solid phase extraction material with the functions of targeted adsorption and enrichment of phthalate in the environment is an important application direction in the field of environmental analysis.
The molecularly imprinted polymer is a high molecular material with a recognition site, and can be specifically combined with a target molecule. The phthalate template molecule and the functional monomer are assembled together through non-covalent bond interaction, a highly cross-linked polymer is formed through polymerization, then the template molecule is removed, and a cavity with the shape complementary to that of a target analyte and the same size and function is generated, so that the phthalate molecule can be specifically adsorbed.
Conventional Molecularly Imprinted Polymers (MIPs) are time consuming to use, requiring complex separation steps such as centrifugation and filtration. The magnetic molecular imprinting technology can realize effective separation of an extraction material and a treated water sample through an external magnetic field, and the unique combination of the nano magnetic material and the MIPs opens a door for innovative application in the separation and purification field. A Fe3O4@ SiO2-MMIP magnetic PAEs isomer double-template molecularly imprinted polymer material which has the extraction capability on di (2-ethyl) hexyl phthalate (Daoshi paper of Chongqing university, 2019) is prepared by using silicon dioxide modified ferroferric oxide as a carrier. The poisonous buttercup (3) is used for preparing a novel material (Fe3O4@ void @ C-MIPs) of a yolk-egg shell type magnetic mesoporous carbon molecularly imprinted polymer, and can be applied to separation and enrichment of PAEs in an actual sample (Master thesis of Chinese university of science and technology, 2020). Lucellia bruguinii [4] and the like take Fe3O4@ SiO2 magnetic nano composite particles as carriers to prepare phthalate magnetic molecularly imprinted polymers, and the phthalate magnetic molecularly imprinted polymers are used for rapid separation and multi-residue detection of PAEs in complex samples (CN107189012B, 2019-03-22). However, the Fe3O4 used as the carrier has unstable soft magnetic performance and affects the repeated reuse of the solid phase extraction material, and the poor dispersibility of the Fe3O4 carrier also affects the coating of SiO2 and the combination of the molecular imprinting polymer. The problems of poor stability of repeated regeneration and utilization of the magnetic molecular polymer and poor compatibility with the molecularly imprinted polymer are solved by adopting Ni0.5Zn0.5Fe2O4 ferrite as a magnetic core. In addition, the molecularly imprinted polymer can selectively adsorb various phthalate molecules in the environment, and provides a new pretreatment method for rapidly analyzing the organic matters. Ni0.5Zn0.5Fe2O4@ SiO2@ APTES molecularly imprinted polymers (MMIPs) combine magnetic performance with selective adsorption capacity of the imprinted polymers, have good extraction efficiency and can be quickly separated from a complex sewage matrix, so that time-consuming filtration and centrifugation steps are avoided, and time and cost are saved.
Traditional solid phase extraction usually uses C18, HLB and other solid phase extraction columns for extraction, but the fillers in the extraction columns have poor selectivity and are not recyclable, and when a complex environmental sample is extracted, a large amount of impurities exist, which interfere with later-stage chromatographic analysis and increase the cost for processing the environmental sample. The Ni0.5Zn0.5Fe2O4@ SiO2@ APTES molecular imprinting technology can realize specific extraction of target molecules in a complex sample, reduce interference influence on later analysis and detection steps, and greatly improve the accuracy and sensitivity of sample pretreatment. Meanwhile, the excellent soft magnetic performance of the magnetic core can realize the quick separation of the solid-phase extraction material from the environmental sample, thereby realizing the repeated use for many times and reducing the pretreatment cost of the environmental sample. Therefore, the design of the invention can prepare the magnetic molecularly imprinted polymer material with selective and specific adsorption on the phthalate organic matter, and can be applied to targeted enrichment and purification of the phthalate organic matter in the environment.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of a phthalate ester magnetic molecularly imprinted polymer extraction material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a phthalate ester magnetic molecular imprinting polymer extraction material comprises the following steps:
(1) preparing Ni0.5Zn0.5Fe2O4 magnetic cores by a hydrothermal method: the reagent comprises ammonium ferrous sulfate hexahydrate, nickel nitrate hexahydrate and zinc nitrate hexahydrate; the precipitant comprises urea or ammonia water; the surfactant comprises cetyl trimethyl ammonium bromide or polyethylene glycol 400;
(2) carrying out surface coating on the Ni0.5Zn0.5Fe2O4 magnetic core obtained in the step (1) by adopting a sol-gel method or a hydrolytic precipitation method to obtain Ni0.5Zn0.5Fe2O4@ SiO2 nano-particles: the reagent comprises ethyl orthosilicate, ammonia water and hydrochloric acid; the surfactant comprises polyvinylpyrrolidone or polyethylene glycol 400;
(3) carrying out surface modification on the Ni0.5Zn0.5Fe2O4@ SiO2 nano-particles obtained in the step (2) by adopting a silane coupling agent to obtain a Ni0.5Zn0.5Fe2O4@ SiO2@ APTES magnetic carrier: the reagent comprises 3-Aminopropyltriethoxysilane (APTES);
(4) mixing dipropyl phthalate, a functional monomer and a pore-making agent, and carrying out prepolymerization reaction to obtain a mixed solution a;
(5) adding the magnetic carrier obtained in the step (3) and polyvinylpyrrolidone-K30 into the mixed solution a obtained in the step (4) to obtain a mixed solution b;
(6) and (3) mixing the mixed solution b obtained in the step (5) with a cross-linking agent and an initiator, carrying out ultrasonic deoxygenation, carrying out polymerization reaction, and removing template molecule dipropyl phthalate by using an eluting solvent after the reaction is finished to obtain the dimethyl phthalate magnetic pseudo template molecular imprinting polymer.
Preferably, the magnetic carrier in the step (3) is Ni0.5Zn0.5Fe2O4@ SiO2@ MPS nanoparticles.
Preferably, the dipropyl phthalate in the step (4) has a molar ratio of the functional monomers of 1:2-1: 8.
Preferably, the molar ratio of the functional monomers to the cross-linking agent in the step (4) is 1:3-1: 6.
Preferably, the amount of dipropyl phthalate material in said step (4) is from 0.25 to 1.00 mmol.
Preferably, the crosslinking agent in the step (6) is ethylene glycol dimethacrylate or methyl methacrylate.
Preferably, the initiator in the step (6) is azobisisobutyronitrile or azobisisoheptonitrile.
Preferably, the elution solvent in the step (6) is methanol or dichloromethane.
(III) advantageous effects
Compared with the prior art, the invention provides a preparation method of a dimethyl phthalate template magnetic molecular imprinting polymer, which has the following beneficial effects:
according to the preparation method of the dimethyl phthalate template magnetic molecular imprinting polymer, a Ni0.5Zn0.5Fe2O4 magnetic core is prepared by a hydrothermal method, and a reagent comprises urea, hexadecyl trimethyl ammonium bromide, ammonium ferric sulfate (II) hexahydrate, nickel nitrate hexahydrate and zinc nitrate hexahydrate; carrying out surface coating and modification on the obtained magnetic core to obtain a Ni0.5Zn0.5Fe2O4@ SiO2@ APTES magnetic carrier, wherein the reagent comprises tetraethoxysilane, ammonia water, ethanol, polyethylene glycol 400 and 3-Aminopropyltriethoxysilane (APTES); mixing dimethyl phthalate or dipropyl phthalate, a functional monomer and a pore-making agent, and carrying out prepolymerization reaction to obtain a mixed solution a; adding the obtained magnetic carrier and polyvinylpyrrolidone K30 into the mixed solution a to obtain a mixed solution b; and mixing the obtained mixed solution b with a cross-linking agent and an initiator, carrying out ultrasonic deoxygenation, carrying out polymerization reaction, and removing phthalate template molecules after the reaction is finished to obtain the dimethyl phthalate template magnetic molecularly imprinted polymer. Experimental results show that the adsorption capacity of the dimethyl phthalate template magnetic molecularly imprinted polymer prepared by the method can reach more than 2.50mg/g for dimethyl phthalate.
Drawings
FIG. 1 is an XRD pattern of magnetic nuclei obtained in example 1 of the present invention;
FIG. 2 is a graph of the magnetic properties of magnetic cores made in example 1 of the present invention;
FIG. 3 is a graph showing the adsorption kinetics of DMP-MMIPs and DMP-MNIPs obtained in example 1 of the present invention;
FIG. 4 is a graph showing the adsorption amounts of the dimethyl formate-based template magnetic molecularly imprinted polymers prepared in examples 1 to 4 of the present invention;
FIG. 5 is a graph showing the adsorption amounts of the dimethyl formate-based template magnetic molecularly imprinted polymers prepared in examples 1, 5 to 7 of the present invention;
FIG. 6 is a graph showing the adsorption amounts of the dimethyl formate-based template magnetic molecularly imprinted polymers prepared in examples 1, 8 to 10 of the present invention;
FIG. 7 is a thermodynamic diagram of the adsorption of DMP-MMIPs and DMP-MNIPs prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
(1) 2.2500g of urea and 0.8325g of CTAB are weighed and added into 140mL of deionized water to be subjected to ultrasonic treatment until the solution is clear, 3.6000g of (NH4)2Fe (SO4) 2.6H 2O is added and stirred, 0.6674g of Ni (NO3) 2.6H 2O and 0.6827g of Zn (NO3) 2.6H 2O are added respectively under stirring, and after stirring for 10min, the mixture is transferred to a 200mL hydrothermal reaction kettle and reacted for 6H at 160 ℃. The obtained Ni0.5Zn0.5Fe2O4 magnetic core is washed 3 times by ethanol and deionized water respectively, and the product is collected by a magnet and dried for 12h under vacuum at 80 ℃.
(2) Weighing 700mg of the magnetic core synthesized in the step (1), ultrasonically dispersing the magnetic core in 50mL of a mixed solution of deionized water and ethanol (1:4, V/V), stirring after ultrasonic treatment for 20min, adding 5mL of ammonia water and 4mL of ethyl orthosilicate under stirring, continuously stirring for 6h at room temperature, separating the obtained product by using a magnet, washing for 3 times by using ethanol and deionized water respectively, and drying for 12h under vacuum at 50 ℃ to obtain Ni0.5Zn0.5Fe2O4@ SiO2 nanoparticles.
(3) Adding 5mL of 3-Aminopropyltriethoxysilane (APTES) into 40mL of ethanol/water (3:1, V/V) mixed solution (pH is 4.0), hydrolyzing at room temperature for 1h, continuously adding 200mg of Ni0.5Zn0.5Fe2O4@ SiO2 nano particles obtained in the step (2), ultrasonically dispersing, transferring into a round bottom flask after ultrasonic treatment, stirring and reacting at 50 ℃ for 6h, collecting a product by using a magnet, washing with deionized water and ethanol for several times, and drying in vacuum for 12h to obtain the Ni0.5Zn0.5Fe2O4@ SiO2@ APTES magnetic carrier.
(4) Adding 0.75mmol DPRP and 3.0mmol MAA into 20mL acetonitrile, and stirring at room temperature for 1h to obtain a mixed solution a; wherein the molar ratio of the dimethyl phthalate to the functional monomer (methacrylic acid) is 1: 4.
(5) And (4) weighing 100mg of the magnetic carrier synthesized in the step (3) and 20mg of PVP-K30, adding into the mixed solution a obtained in the step (4), and continuing stirring for 2 hours to obtain a mixed solution b.
(6) Adding 30mg AIBN and 10mmol EGDMA into the mixed solution b obtained in the step (5), carrying out ultrasonic treatment for 30min, sealing, and reacting for 24h at 65 ℃; wherein the molar ratio of the functional monomer (methacrylic acid) in the step (4) to the EGDMA in this step is 1: 5.
(7) And (3) collecting the product obtained in the step (6) by a magnet, ultrasonically eluting the template molecules by using methanol/acetic acid (9:1, V/V), and repeating for multiple times until the template molecules cannot be detected in the eluent by HPLC (high performance liquid chromatography), so as to obtain dimethyl phthalate magnetic molecularly imprinted polymers (DMP-MMIPs). Dimethyl phthalate magnetic non-imprinted polymers (DMP-MNIPs) without template molecules were synthesized in the same manner.
FIG. 1 is an XRD pattern of magnetic nuclei obtained in example 1. The characteristic peaks of the Ni0.5Zn0.5Fe2O4 cubic system are obvious and sharp diffraction peaks at the 2 theta of 35 degrees, 43 degrees, 56 degrees and 62 degrees.
FIG. 2 is a graph of magnetic properties of the magnetic core obtained in example 1, from which the magnetic core has excellent soft magnetic properties.
The preparation process of the dimethyl phthalate magnetic non-imprinted polymer is completed according to the following steps:
(1) same as example 1, step (1).
(2) Same as example 1, step (2).
(3) Same as example 1, step (3).
(4) 3.0mmol MAA was added to 20mL acetonitrile and stirred at room temperature for 1h to obtain a mixture a.
(5) Same as example 1, step (5).
(6) Same as example 1, step (6).
(7) And (3) collecting the product obtained in the step (6) by a magnet, ultrasonically eluting the template molecules by using methanol/acetic acid (9:1, V/V), and repeating the steps for multiple times until the template molecules cannot be detected in the eluent by HPLC (high performance liquid chromatography), so as to obtain dimethyl phthalate magnetic non-imprinted polymers (DMP-MNIPs).
Example 2
The difference from the example 1 is that the molar ratio of the template molecule (dimethyl phthalate or dipropyl phthalate) to the functional monomer (methacrylic acid) is 1:2, the molar ratio of the functional monomer to the crosslinking agent is the same as that of the example 1, the molar ratio of the template molecule to the functional monomer to the crosslinking agent is 1:2:10, and the rest is the same as that of the example 1.
Example 3
The difference from the example 1 is that the molar ratio of the template molecule (dimethyl phthalate or dipropyl phthalate) to the functional monomer (methacrylic acid) is 1:6, the molar ratio of the functional monomer to the crosslinking agent is the same as that of the example 1, the molar ratio of the template molecule to the functional monomer to the crosslinking agent is 1:6:30, and the rest is the same as that of the example 1.
Example 4
The difference from the example 1 is that the molar ratio of the template molecule (dimethyl phthalate or dipropyl phthalate) to the functional monomer (methacrylic acid) is 1:8, the molar ratio of the functional monomer to the crosslinking agent is the same as that of the example 1, the molar ratio of the template molecule to the functional monomer to the crosslinking agent is 1:8:40, and the rest is the same as that of the example 1.
Example 5
The difference from example 1 is that the molar ratio of the functional monomer (methacrylic acid) to the crosslinking agent (EGDMA) is 1:3, the molar ratio of the template molecule, the functional monomer and the crosslinking agent is the same as that of example 1, the molar ratio of the template molecule, the functional monomer and the crosslinking agent is 1:4:12, and the rest is the same as that of example 1.
Example 6
The difference from example 1 is that the molar ratio of the functional monomer (methacrylic acid) to the crosslinking agent (EGDMA) is 1:4, the molar ratio of the template molecule, the functional monomer and the crosslinking agent is the same as that of example 1, the molar ratio of the template molecule, the functional monomer and the crosslinking agent is 1:4:16, and the rest is the same as that of example 1.
Example 7
The difference from example 1 is that the molar ratio of the functional monomer (methacrylic acid) to the crosslinking agent (EGDMA) is 1:6, the molar ratio of the template molecule, the functional monomer and the crosslinking agent is the same as that of example 1, the molar ratio of the template molecule, the functional monomer and the crosslinking agent is 1:4:24, and the rest is the same as that of example 1.
Example 8
The difference from example 1 is that the amount of dimethyl phthalate or dipropyl phthalate as template molecule is 0.25mmol, the molar ratio of template molecule, methacrylic acid and EGDMA is 1:4:20, and the rest is the same as example 1.
Example 9
The difference from example 1 is that the amount of dimethyl phthalate or dipropyl phthalate as template molecule is 0.50mmol, the molar ratio of template molecule, methacrylic acid and EGDMA is 1:4:20, and the rest is the same as example 1. .
Example 10
The difference from example 1 is that the amount of the template molecule dimethyl phthalate or dipropyl phthalate material is 1.00mmol, the molar ratio of the template molecule, methacrylic acid and EGDMA is 1:4:20, and the rest is the same as example 1. .
Adsorption test of phthalate template magnetic molecularly imprinted polymer
Test 1: adsorption kinetics test
Weighing 20mg of DMP-MMIPs and 20mg of DMP-MNIPs respectively, adding into a 25mL sample bottle containing 20mL of 40mg/L dimethyl phthalate solution, placing in a water bath constant temperature oscillation box at 25 ℃ for oscillation adsorption, separating the solution by using a magnet after 1, 2, 4, 8, 10, 20, 30, 60 and 120min respectively, taking supernatant, and measuring the concentration of dimethyl phthalate in the solution by using HPLC. The adsorption amount was calculated according to formula 1.
Q＝(C0-Ce)V/m (1)
Wherein Q is the adsorption capacity (mg/g) of the adsorbent; c0 is the initial concentration (mg/L) of the adsorption solution; ce is the equilibrium concentration (mg/L) of the adsorption solution; v is the volume of adsorption solution (mL); and m is the mass (mg) of the adsorbing material.
The calculated adsorption kinetics of DMP-MMIPs and DMP-MNIPs are shown in FIG. 3. As can be seen from FIG. 3, the adsorption amounts of DMP-MMIPs and DMP-MNIPs to dimethyl phthalate rapidly increased within the first 30min, and equilibrium was gradually reached after 30 min. When the reaction starts, the adsorption sites of the polymer are not occupied, the adsorption can be quickly carried out, the adsorption sites are gradually reduced along with the progress of the adsorption process, the adsorption rate is reduced, and the adsorption gradually reaches an equilibrium state. In addition, the adsorption capacity of DMP-MMIPs to dimethyl phthalate is greater than that of DMP-MNIPs to dimethyl phthalate, which indicates that the DMP-MMIPs have binding sites and holes matched with template molecules and can realize specific selective adsorption on target molecules.
The dimethyl phthalate magnetic molecularly imprinted polymers prepared in examples 1 to 4 were tested by an adsorption test of the dimethyl phthalate magnetic molecularly imprinted polymers, and the adsorption amounts of the obtained magnetic molecularly imprinted polymers are shown in fig. 4. The experiment researches the influence of the prepared DMP-MMIPs on the adsorption quantity of dimethyl phthalate when the molar ratio of the template molecule DPRP to the functional monomer MAA is 1:2, 1:4, 1:6 and 1: 8. With the increase of the molar ratio of DPRP and MAA, the adsorption amounts of DMP-MMIPs to dimethyl phthalate are increased and then decreased, the specific adsorption amounts are respectively 0.21, 0.24, 0.14 and 0.17mg/g, and the highest adsorption amount is reached under the molar ratio of 1: 4. Thus, a DMP to MAA molar ratio of 1:4 was chosen as the optimal condition for preparing DMP-MMIPs.
The dimethyl phthalate magnetic molecularly imprinted polymers prepared in examples 1, 5 to 7 were tested by an adsorption test of the dimethyl phthalate magnetic molecularly imprinted polymer, and the adsorption amount of the obtained magnetic molecularly imprinted polymer is shown in fig. 5. The test researches the influence of DMP-MMIPs prepared when the molar ratio of the functional monomer MAA to the crosslinking agent EGDMA is 1:3, 1:4, 1:5 and 1:6 respectively on the adsorption quantity of dimethyl phthalate. The DMP-MMIPs have the DMP adsorption capacities of 0.16, 0.15, 0.24 and 0.02mg/g under different molar conditions, the DMP adsorption capacity is increased and then decreased along with the increase of MAA and EGDMA, and the adsorption capacity is maximum when the molar ratio is 1: 5. Thus, the molar ratio of MAA to EGDMA is determined to be 1:5 as the optimal ratio for preparing DMP-MMIPs.
The dimethyl phthalate magnetic molecularly imprinted polymers prepared in examples 1 and 8 to 10 were tested by an adsorption test of the dimethyl phthalate magnetic molecularly imprinted polymer, and the adsorption amount of the obtained magnetic molecularly imprinted polymer is shown in fig. 6. In the experiment, a series of DMP-MMIPs prepared by respectively using 0.25, 0.50, 0.75 and 1.00mmol of dipropyl phthalate as a template molecule are researched for the adsorption effect. When the amount of the template molecular substance was 0.75mmol, the adsorption amount of DMP-MMIPs prepared was the largest. Thus, DMP-MMIPs were prepared using 0.75 mol of template molecular species.
Test 2: thermodynamic test of adsorption
Preparing a series of dimethyl phthalate aqueous solutions with the concentrations of 5, 10, 20, 30, 40, 60, 80 and 100 mg/L. Weighing DMP-MMIPs and DMP-MNIPs respectively 20mg, respectively adding into a 25mL sample bottle containing 20mL of the above dimethyl phthalate solution, placing in a water bath constant temperature oscillation box at 25 ℃ and oscillating for 30min, after magnet adsorption, taking supernatant, and detecting the concentration of dimethyl phthalate in the solution by using HPLC. The adsorption amount was calculated according to formula 1.
The thermodynamic diagrams for adsorption of DMP-MMIPs and DMP-MNIPs are calculated and shown in FIG. 7. As can be seen from FIG. 7, the adsorption amount rapidly became larger as the initial concentration of DMP increased at room temperature, and the adsorption equilibrium was gradually reached as the concentration increased to 80 mg/L. The maximum adsorption of DMP-MMIPs is higher than that of DMP-MNIPs. The results show that the recognition sites on the surface of DMP-MMIPs are equivalent to DMP, and have better chemical and spatial matching degrees. In contrast, the interaction of DMP-MNIPs with dimethyl phthalate is mainly through non-specific adsorption.
It can be seen from the above examples that the dimethyl phthalate template magnetic molecularly imprinted polymer prepared by the method provided by the invention has higher selective adsorption capacity on dimethyl phthalate.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of phthalate ester magnetic molecular imprinting polymer comprises the following steps:
(1) preparing a Ni0.5Zn0.5Fe2O4 magnetic core by a hydrothermal method;
(2) carrying out surface coating on the Ni0.5Zn0.5Fe2O4 magnetic core obtained in the step (1) by adopting a sol-gel method to obtain Ni0.5Zn0.5Fe2O4@ SiO2 nano particles;
(3) carrying out surface modification on the Ni0.5Zn0.5Fe2O4@ SiO2 nano-particles obtained in the step (2) by adopting a silane coupling agent to obtain a Ni0.5Zn0.5Fe2O4@ SiO2@ APTES magnetic carrier;
(4) mixing dimethyl phthalate or dipropyl phthalate, a functional monomer and a pore-making agent, and carrying out prepolymerization reaction to obtain a mixed solution a;
(5) adding the Ni0.5Zn0.5Fe2O4@ SiO2@ APTES magnetic carrier obtained in the step (3) and polyvinylpyrrolidone K30 into the mixed solution a obtained in the step (4) to obtain a mixed solution b;
(6) and (3) mixing the mixed solution b obtained in the step (5) with a cross-linking agent and an initiator, carrying out ultrasonic deoxygenation, carrying out polymerization reaction, and removing template molecules of phthalate by using an eluting solvent after the reaction is finished to obtain the phthalate magnetic molecular imprinting polymer.
2. The preparation method of claim 1, wherein the magnetic carrier in the step (3) is Ni0.5Zn0.5Fe2O4@ SiO2@ APTES nanoparticles.
3. The method according to claim 1, wherein the molar ratio of the dimethyl phthalate or the dipropyl phthalate in the step (4) to the functional monomers is 1:2 to 1: 8.
4. The method according to claim 1, wherein the molar ratio of the functional monomers to the crosslinking agent in step (4) is 1:3 to 1: 6.
5. The method according to claim 1, wherein the amount of the phthalate ester compound in the step (4) is 0.25 to 1.00 mmol.
6. The method according to claim 1, wherein the crosslinking agent in the step (6) is ethylene glycol dimethacrylate or methyl methacrylate.
7. The method according to claim 1, wherein the initiator in the step (6) is azobisisobutyronitrile or azobisisoheptonitrile.
8. The method according to claim 1, wherein the eluting solvent in the step (6) is methanol or dichloromethane.
9. The method for preparing the magnetic molecularly imprinted polymer of phthalate according to claim 1 to 8, wherein the magnetic molecularly imprinted polymer can be applied to targeted enrichment and extraction of phthalate organic matters in environmental water samples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111556425.7A CN114146695A (en) | 2021-12-17 | 2021-12-17 | Preparation method of phthalate magnetic molecularly imprinted polymer extraction material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111556425.7A CN114146695A (en) | 2021-12-17 | 2021-12-17 | Preparation method of phthalate magnetic molecularly imprinted polymer extraction material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114146695A true CN114146695A (en) | 2022-03-08 |
Family
ID=80452147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111556425.7A Pending CN114146695A (en) | 2021-12-17 | 2021-12-17 | Preparation method of phthalate magnetic molecularly imprinted polymer extraction material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114146695A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905166A (en) * | 2010-07-27 | 2010-12-08 | 中国地质大学（武汉） | Magnetically separable nitrogen-doped TiO2 photocatalyst and preparation method thereof |
| WO2016058561A1 (en) * | 2014-10-13 | 2016-04-21 | 中国环境科学研究院 | Magnetic nanomaterial solid phase extraction agent, and preparation method and use therefor |
| CN107189012A (en) * | 2017-07-03 | 2017-09-22 | 长江师范学院 | The preparation method and product of phthalate molecularly imprinted polymer and application |
| CN107999019A (en) * | 2017-11-30 | 2018-05-08 | 西安交通大学 | A kind of amphipathic magnetic nano-balls and preparation method thereof and adsorption applications |
-
2021
- 2021-12-17 CN CN202111556425.7A patent/CN114146695A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905166A (en) * | 2010-07-27 | 2010-12-08 | 中国地质大学（武汉） | Magnetically separable nitrogen-doped TiO2 photocatalyst and preparation method thereof |
| WO2016058561A1 (en) * | 2014-10-13 | 2016-04-21 | 中国环境科学研究院 | Magnetic nanomaterial solid phase extraction agent, and preparation method and use therefor |
| CN107189012A (en) * | 2017-07-03 | 2017-09-22 | 长江师范学院 | The preparation method and product of phthalate molecularly imprinted polymer and application |
| CN107999019A (en) * | 2017-11-30 | 2018-05-08 | 西安交通大学 | A kind of amphipathic magnetic nano-balls and preparation method thereof and adsorption applications |
Non-Patent Citations (2)
| Title |
|---|
| 常梦珠等: ""磁性分子印迹聚合物制备及其对环境水样中雌二醇的特异性吸附性能研究"", 《安全与环境工程》 * |
| 徐婉珍等: ""表面接枝法制备磁性邻苯二甲酸二丁酯印迹聚合物及其识别性能研究"", 《分析化学( FENXI HUAXUE) 研究报告》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hoai et al. | Batch and column separation characteristics of copper-imprinted porous polymer micro-beads synthesized by a direct imprinting method | |
| CN103709342B (en) | A kind of preparation method of magnetic cadmium ion surface imprinted polymer | |
| CN103709341B (en) | A kind of preparation method of magnetic zine ion surface imprinted polymer | |
| CN110938282B (en) | Composite material with covalent organic framework and core-shell structure and preparation method and application thereof | |
| CN105498694B (en) | The metallic organic framework magnetic material of a kind of temperature sensitive polymer parcel and application thereof | |
| Liu et al. | Effect of anions on the polymerization and adsorption processes of Cu (II) ion-imprinted polymers | |
| Tan et al. | Development of surface imprinted core–shell nanoparticles and their application in a solid-phase dispersion extraction matrix for methyl parathion | |
| CN110527039B (en) | Magnetic surface molecularly imprinted polymer and preparation method and application thereof | |
| CN107200812A (en) | A kind of preparation method of magnetic molecularly imprinted material | |
| CN112808256B (en) | Magnetic core-shell mesoporous surface molecularly imprinted composite nanomaterial and preparation method thereof | |
| CN105693932A (en) | Preparation method of magnetic microsphere surface molecularly-imprinted polymer | |
| CN109354657B (en) | Preparation and application methods of alkylphenol composite template molecularly imprinted polymer modified magnetic graphene oxide | |
| Zhao et al. | Magnetic surface molecularly imprinted poly (3-aminophenylboronic acid) for selective capture and determination of diethylstilbestrol | |
| Chang et al. | One-pot synthesis of uniform and monodisperse superparamagnetic molecularly imprinted polymer nanospheres through a sol–gel process for selective recognition of bisphenol A in aqueous media | |
| Dolak | Ion imprinted affinity Cryogels for the selective adsorption uranium in real samples | |
| CN112007621A (en) | Preparation and application methods of tetracycline antibiotic multi-template molecularly imprinted magnetic composite material | |
| CN107930599B (en) | Magnetic material for pretreatment of aqueous solution drug test material and preparation method thereof | |
| Dolak | Selective separation and preconcentration of Thorium (IV) in bastnaesite ore using Thorium (IV)-Imprinted cryogel polymer | |
| CN106040204A (en) | Magnetic microporous organic nanotube hybrid material and preparation and application thereof | |
| CN108586660A (en) | The preparation method of TNT magnetic molecularly imprinted polymer microballoons | |
| CN112979893B (en) | Preparation of magnetic fluorescent material @ molecularly imprinted particle and method for preparing composite membrane by using same | |
| CN103613722A (en) | Method for preparing magnetic halloysite molecularly imprinted polymer with specific adsorption to 2,4-dichlorophenoxyacetic acid | |
| CN112552469B (en) | Preparation method of bisphenol A magnetic molecularly imprinted polymer and application of bisphenol A magnetic molecularly imprinted polymer in bisphenol A fluorescence detection | |
| CN114146695A (en) | Preparation method of phthalate magnetic molecularly imprinted polymer extraction material | |
| Dolak | Selective adsorption of U (VI) by using U (VI)-imprinted poly-hydroxyethyl methacrylate-methacryloyl-L-histidine (P-[HEMA-(MAH) 3]) cryogel polymer. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220308 |