CN114213562A - Preparation method of magnetic polystyrene microspheres with different particle sizes - Google Patents
Preparation method of magnetic polystyrene microspheres with different particle sizes Download PDFInfo
- Publication number
- CN114213562A CN114213562A CN202111515098.0A CN202111515098A CN114213562A CN 114213562 A CN114213562 A CN 114213562A CN 202111515098 A CN202111515098 A CN 202111515098A CN 114213562 A CN114213562 A CN 114213562A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- ferroferric oxide
- solution
- microspheres
- particle sizes
- 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
- 239000004005 microsphere Substances 0.000 title claims abstract description 41
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 28
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 28
- 239000002245 particle Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002086 nanomaterial Substances 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 26
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 14
- 239000005642 Oleic acid Substances 0.000 claims description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- HSBFHUOJEGKWRL-KVVVOXFISA-N ethanol;(z)-octadec-9-enoic acid Chemical compound CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O HSBFHUOJEGKWRL-KVVVOXFISA-N 0.000 claims description 8
- 238000007885 magnetic separation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229960000541 cetyl alcohol Drugs 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 6
- 239000000273 veterinary drug Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000000575 pesticide Substances 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 13
- 239000000523 sample Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 239000012491 analyte Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 102000012740 beta Adrenergic Receptors Human genes 0.000 description 2
- 108010079452 beta Adrenergic Receptors Proteins 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000018 receptor agonist Substances 0.000 description 2
- 229940044601 receptor agonist Drugs 0.000 description 2
- 238000000956 solid--liquid extraction Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 208000031295 Animal disease Diseases 0.000 description 1
- 206010013654 Drug abuse Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002222 matrix solid-phase dispersion Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
Classifications
-
- 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
- C08F112/00—Homopolymers 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 an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention relates to a preparation method of magnetic polystyrene microspheres with different particle sizes, and the structural formula is as follows. Firstly, preparing nano-level magnetic ferroferric oxide as a polystyrene-coated carrier by adopting a solvothermal method, and then preparing a series of magnetic polystyrene microspheres with different particle sizes by adopting an improved microsuspension method and controlling the ratio of a monomer to a magnetic nano material. The magnetic polystyrene microsphere has the characteristics of small particle size, large specific surface area, strong adsorption capacity, good dispersibility, easy modification and the like. The invention can be used as a carrier for functional modification, can be used for quickly adsorbing pesticide and veterinary drug residues in the pretreatment process of a food matrix, and has the advantages of high sensitivity, good selectivity, short time consumption and the like in the adsorption processIs characterized in that.
Description
Technical Field
The invention belongs to the field of food safety, and relates to a preparation method of magnetic polystyrene microspheres with different particle sizes.
Background
The veterinary drug plays an important role in preventing and treating animal diseases, improving production efficiency, improving quality of animal products and the like. However, the phenomenon of veterinary drug abuse is now widespread in animal husbandry due to the lack of scientific knowledge and the pursuit of economic interest for breeders. The abuse of veterinary drugs easily causes the residue of harmful substances in animal-derived foods, which not only causes direct harm to human health, but also causes great harm to the development of animal husbandry and ecological environment. Therefore, establishing a rapid and efficient veterinary drug residue detection method has important significance in the aspects of life science, environmental science, medical science, agricultural production and the like.
The instrumental technique is widely used in the analysis and treatment of samples as the method for detecting veterinary drug residues. At the same time, however, with the outbreak of various food safety incidents, the demand for sample analysis techniques has been increasing. And due to the complexity of the sample matrix, the detection of trace, trace and even ultra-trace pollutants in the sample is difficult to directly measure, the accuracy is difficult to meet the requirement, and the damage to the instrument is large. Therefore, the pretreatment processes of purification, decontamination, separation, enrichment and concentration before the sample is detected by the instrument are particularly important.
The sample pretreatment is the basis for analyzing food complex matrix, and can enrich and separate target analytes, thereby reducing matrix effect and interference on target components, and being an important link in food sample analysis. Two operations of extraction and purification are often adopted for animal tissue samples, and common extraction and purification methods include solid-liquid extraction, liquid-liquid extraction, solid-phase extraction, matrix solid-phase dispersion extraction, immunoaffinity extraction and the like. The solid-liquid extraction has higher requirements on samples, the substance to be detected has higher solubility and dispersibility in a solvent, and three methods of shaking extraction, homogenization and ultrasonic extraction are simultaneously used; the liquid-liquid extraction is simple, quick, easy to operate and good in reproducibility, but a large amount of organic solvent is used, and some compounds are adsorbed to cause loss and easy to generate emulsification when a glass container is used; although the SPE method has high selectivity and strong specificity, the SPE method is expensive and cannot be reused, only can purify one or one type of beta-receptor agonist, and meanwhile, the adsorbent has a certain adsorption effect on part of target objects, so that the recovery rate of part of beta-receptor agonist is low.
The Magnetic Solid Phase Extraction (MSPE) technology is a SPE sample preparation technology based on magnetic interaction, in the MSPE process, a magnetic adsorbent is dispersed in a sample solution or suspension containing a target analyte, under the extraction conditions of ultrasound, high-speed homogenization or vortex oscillation and the like, the magnetic adsorbent enriches the analyte to be detected in the sample solution on the surface of the magnetic adsorbent, then the magnetic adsorbent containing the analyte to be detected is separated under the action of an externally applied magnetic field, the target analyte is eluted from the magnetic adsorbent through an eluant such as methanol/acetonitrile and the like, and then the detection is carried out through a chromatographic analysis technology. Based on the unique discrete property of the magnetic adsorbent, researchers can promote phase separation by enhancing intermolecular diffusion of the target analyte and the magnetic adsorbent, so that phase transfer of the target analyte is completed more quickly, and extraction efficiency is improved. The magnetic adsorbent is separated from the sample solution by using an external magnetic field instead of filtration or high-speed centrifugation, so that the pretreatment process of the sample is simple and convenient. In addition, such magnetic adsorbents are easily functionalized, thereby increasing the selectivity of the magnetic adsorbent for a target analyte. The research of the subject aims to prepare the stable magnetic nano-adsorbent, apply the stable magnetic nano-adsorbent to the MSPE technology, expand the range of target detection objects, inhibit the influence of a sample matrix, and improve the accuracy of an experiment and the efficiency of sample pretreatment.
At present, the most widely used magnetic solid phase extraction adsorption material is prepared by coating a polymer or an inorganic material on the surface of a magnetic nano material and functionalizing different groups to prepare microspheres with different effects. The functionalization method of the microsphere is mainly to modify through the reaction of benzene ring, the reaction of double bond of olefin, the reaction of specific functional group, etc., and the surface modified magnetic polystyrene microsphere also comprises amino modified, sulfonated modified and carboxylated modified polystyrene microsphere, etc. The magnetic polystyrene microsphere is a high-quality magnetic substance, has excellent magnetism, and can quickly separate solid from liquid by using a magnetic separation technology.
Disclosure of Invention
The invention aims to provide a preparation method of magnetic polystyrene microspheres with different particle sizes.
In order to achieve the purpose, the invention adopts the following technical scheme:
respectively mixing ferric chloride hexahydrate, polyethylene glycol 2000 and sodium acetate according to a certain molar ratio, fully heating and dissolving by taking a mixed solution of diethylene glycol and ethylene glycol as a solvent, placing the mixture in a high-temperature reaction kettle under a certain pressure condition to react for 8-12h at the temperature of 110-.
Dissolving oleic acid in absolute ethyl alcohol to prepare an oleic acid-ethyl alcohol solution with a certain concentration, and taking Fe3O4Placing the powder and oleic acid-ethanol solution in a three-neck flask, heating in water bath at 30-50 deg.C for a certain time, filtering, and drying.
Taking a certain amount of oleic acid-coated and modified Fe3O4Dispersing the powder in styrene of different proportions, adding benzoyl peroxide as an initiator, and swelling for 12-14 hours. 0.2-0.4g of hexadecanol, 80-100mL of deionized water, 5-10mL of 5% PVA solution and 1-2mL of 5% SDS-PEG solution (the ratio of SDS to PEG4000 is 3: 2) were weighed and mixed uniformly in a 250mL three-necked flask. Then adding Fe which is ultrasonically dispersed for 40min3O4St solution, stirred at moderate speed. Placing in a water bath thermostatic bath, condensing and refluxing, heating to 70-75 deg.C, reacting for 4-6h, heating to 80-85 deg.C, reacting for 3-4h, vacuum filtering, vacuum drying to obtain brown powder product, and sieving. Soaking in dilute hydrochloric acid overnight, washing to neutral, drying, and separating magnetic substance with magnetic separation rack.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto.
(1) The method for preparing the magnetic ferroferric oxide microspheres comprises the following steps: respectively mixing ferric chloride hexahydrate, polyethylene glycol 2000 and sodium acetate according to a certain molar ratio, fully heating and dissolving by taking a mixed solution of diethylene glycol and ethylene glycol as a solvent, placing the mixture in a high-temperature reaction kettle under a certain pressure condition for a period of time, washing the mixture for a plurality of times by using absolute ethyl alcohol after the reaction is finished, and drying the mixture in vacuum to constant weight to obtain the magnetic ferroferric oxide microspheres.
(2) The method for preparing the magnetic polystyrene microspheres with different particle sizes comprises the following steps: mixing and swelling magnetic ferroferric oxide microspheres with an initiator and a certain amount of styrene monomer for 12-14h after being modified by oleic acid, adding a dispersant, an insoluble assistant and a compounded surfactant into a flask according to a certain molar ratio, adding ultrapure water, heating, stirring, refluxing, reacting for a period of time, raising the temperature, continuing to perform heat preservation reaction for a period of time, washing reactants with the ultrapure water after the reaction is finished, re-dispersing the reactants in distilled water after secondary distillation after magnetic separation and extraction, soaking the reactants in dilute hydrochloric acid overnight, and performing vacuum drying to obtain the magnetic polystyrene microspheres.
Example 1
(1) Magnetic ferroferric oxide Fe3O4Synthesis of (2)
Respectively mixing ferric chloride hexahydrate, polyethylene glycol 2000 and sodium acetate according to a certain molar ratio, fully heating and dissolving by taking a mixed solution of diethylene glycol and ethylene glycol as a solvent, placing the mixture in a high-temperature reaction kettle under a certain pressure condition, reacting for 8-12h at the temperature of 121 ℃, washing for several times by absolute ethyl alcohol after the reaction is finished, and drying in vacuum to constant weight to obtain the magnetic ferroferric oxide microspheres.
(2) Oleic acid modified magnetic ferroferric oxide Fe3O4Synthesis of-OA-1
Dissolving oleic acid in anhydrous ethanol to obtain 3% oleic acid-ethanol solution, and collecting 0.27g Fe3O4Placing the powder and oleic acid-ethanol solution in a three-neck flask, heating to 40-50 deg.C in water bath, maintaining for about 3-4 hr, filtering, and drying.
(3) Micron-sized magnetic polystyrene microsphere Fe3O4Synthesis of @ PS-1
Mixing and swelling magnetic ferroferric oxide microsphere oleic acid modified and initiator benzoyl peroxide and 10mL of styrene monomer for 12-14h, then weighing 0.2-0.4g of hexadecanol, 80-100mL of deionized water, 5-10mL of 5% PVA solution and 1-2mL of 5% SDS-PEG solution (the ratio of SDS to PEG4000 is 3: 2), and adding the mixture into 250mL of three-layer polymer emulsionThe mixture in the flask was mixed well. Then adding Fe which is subjected to ultrasonic dispersion for 40-60min3O4St solution, stirred at moderate speed. Placing in a water bath thermostatic bath, condensing and refluxing, heating to 70 deg.C, reacting for 4 hr, heating to 80 deg.C, reacting for 3-4 hr, vacuum filtering, vacuum drying to obtain brown powder product, and sieving. Soaking in 1M hydrochloric acid for 18-24 hr, washing to neutrality, drying, separating magnetic substance with magnetic separation rack to obtain nanometer magnetic polystyrene microsphere Fe3O4@PS-1。
Example 2
(1) Magnetic ferroferric oxide Fe3O4Synthesis of (2)
Respectively mixing ferric chloride hexahydrate, polyethylene glycol 2000 and sodium acetate according to a certain molar ratio, fully heating and dissolving by taking a mixed solution of diethylene glycol and ethylene glycol as a solvent, placing the mixture in a high-temperature reaction kettle under a certain pressure condition, reacting for 8-12h at the temperature of 121 ℃, washing for several times by absolute ethyl alcohol after the reaction is finished, and drying in vacuum to constant weight to obtain the magnetic ferroferric oxide microspheres.
(2) Oleic acid modified magnetic ferroferric oxide Fe3O4Synthesis of-OA-2
Dissolving oleic acid in anhydrous ethanol to obtain 3% oleic acid-ethanol solution, and collecting 0.4g Fe3O4Placing the powder and oleic acid-ethanol solution in a three-neck flask, heating to 40-50 deg.C in water bath, maintaining for about 3-4 hr, filtering, and drying.
(3) Nano-scale magnetic polystyrene microsphere Fe3O4Synthesis of @ PS-2
Modifying magnetic ferroferric oxide microspheres with oleic acid, mixing the modified magnetic ferroferric oxide microspheres with an initiator benzoyl peroxide and 4mL of styrene monomer for swelling for 12-14h, weighing 0.2-0.4g of hexadecanol, 80-100mL of deionized water, 5-10mL of 5% PVA solution and 1-2mL of 5% SDS-PEG solution (the ratio of SDS to PEG4000 is 3: 2), and uniformly mixing in a 250mL three-neck flask. Then adding Fe which is ultrasonically dispersed for 40min3O4St solution, stirred at moderate speed. Placing in a water bath thermostatic bath, condensing and refluxing, heating to 70-75 deg.C, reacting for 4-6h, heating to 80 deg.C, reacting for 3-4h, vacuum filtering, vacuum drying to obtain brown powder product, and sieving. Soaking in 1M hydrochloric acid 18Washing for 24h to be neutral, drying, separating magnetic substances by using a magnetic separation frame to obtain the nanoscale magnetic polystyrene microsphere Fe3O4@PS-2。
Example 3
(1) Magnetic ferroferric oxide Fe3O4Synthesis of (2)
Respectively mixing ferric chloride hexahydrate, polyethylene glycol 2000 and sodium acetate according to a certain molar ratio, fully heating and dissolving by taking a mixed solution of diethylene glycol and ethylene glycol as a solvent, placing the mixture in a high-temperature reaction kettle under a certain pressure condition, reacting for 8-12h at the temperature of 121 ℃, washing for several times by absolute ethyl alcohol after the reaction is finished, and drying in vacuum to constant weight to obtain the magnetic ferroferric oxide microspheres.
(2) Oleic acid modified magnetic ferroferric oxide Fe3O4Synthesis of-OA-3
Dissolving oleic acid in anhydrous ethanol to obtain 2% oleic acid-ethanol solution, and collecting 0.4g Fe3O4Placing the powder and oleic acid-ethanol solution in a three-neck flask, heating to 40-50 deg.C in water bath, maintaining for about 3-4 hr, filtering, and drying.
(3) Micron-sized magnetic polystyrene microsphere Fe3O4Synthesis of @ PS-3
Modifying magnetic ferroferric oxide microspheres with oleic acid, mixing the modified magnetic ferroferric oxide microspheres with an initiator benzoyl peroxide and 8.9mL of styrene monomer for swelling for 12-14h, weighing 0.2-0.4g of hexadecanol, 80-100mL of deionized water, 5-10mL of 5% PVA solution and 1-2mL of 5% SDS-PEG solution (the ratio of SDS to PEG4000 is 3: 2), and uniformly mixing in a 250mL three-neck flask. Then adding Fe which is ultrasonically dispersed for 40min3O4St solution, stirred at moderate speed. Placing in a water bath thermostatic bath, condensing and refluxing, heating to 70-75 deg.C, reacting for 3-4 hr, heating to 80-85 deg.C, reacting for 3-4 hr, vacuum filtering, vacuum drying to obtain brown powder product, and sieving. Soaking in 1M hydrochloric acid for 18-24 hr, washing to neutrality, drying, separating magnetic substance with magnetic separation rack to obtain nanometer magnetic polystyrene microsphere Fe3O4@PS-3。
Finally, it is noted that the disclosed embodiments are intended to facilitate a further understanding of the invention. But those skilled in the art will understand that: various substitutions and modifications are possible without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the present invention should not be limited to the disclosure of the embodiment. The scope of the invention is defined by the appended claims.
Claims (6)
1. A preparation method of magnetic polystyrene microspheres with different particle sizes is characterized by comprising the following steps: the carrier is magnetic ferroferric oxide nano-microspheres, styrene monomers with different proportions are selected as coating materials, and a series of magnetic polystyrene microspheres with different particle sizes are prepared in one step by adopting an improved microsuspension method.
2. The magnetic polystyrene microsphere of claim 1, having the following structure:
wherein the content of the first and second substances,
is a magnetic ferroferric oxide nano material.
3. The magnetic ferroferric oxide nano material as claimed in claim 2 has the characteristics of narrow particle size distribution and good dispersibility in water solution; the magnetic polystyrene microsphere has the characteristics of small particle size, large specific surface area, strong adsorption capacity, good dispersibility, easy modification and the like.
4. The preparation method of magnetic polystyrene microspheres with different particle sizes as claimed in claim 2 has the following characteristics:
respectively mixing ferric chloride hexahydrate, polyethylene glycol 2000 and sodium acetate according to a certain molar ratio, fully heating and dissolving by taking a mixed solution of diethylene glycol and ethylene glycol as a solvent, placing the mixture in a high-temperature reaction kettle under a certain pressure condition to react for 8-12h at the temperature of 110 ℃., washing the mixture for several times by absolute ethyl alcohol after the reaction is finished, and drying the mixture in vacuum to constant weight to obtain magnetic ferroferric oxide microspheres;
dissolving oleic acid in absolute ethyl alcohol to prepare an oleic acid-ethyl alcohol solution with a certain concentration, and taking Fe3O4Placing the powder and oleic acid-ethanol solution in a three-neck flask, heating in water bath at 30-50 deg.C, maintaining for a certain time, filtering, and drying;
taking a certain amount of oleic acid coated and modified Fe3O4Dispersing the powder into styrene with different proportions, adding an initiator benzoyl peroxide to swell for 12-14 hours; cetyl alcohol, deionized water, 5-10% PVA solution, 5% SDS-PEG solution (ratio of SDS to PEG4000 3: 2) were weighed and mixed well in a 250mL three-necked flask. Then adding Fe which is subjected to ultrasonic dispersion for 40-60min3O4St solution, stirring at medium speed; placing in a water bath thermostatic bath, condensing and refluxing, heating to 70-75 deg.C, reacting for 4-6 hr, heating to 80-85 deg.C, reacting for 3-4 hr, vacuum filtering, vacuum drying to obtain brown powder product, and sieving; soaking in dilute hydrochloric acid overnight, washing to neutral, drying, and separating magnetic substance with magnetic separation rack.
5. The magnetic polystyrene microsphere of claim 1, having the following core-shell structure: the magnetic ferroferric oxide nano material is used as a core, and polystyrene formed by polymerizing styrene monomers with different concentrations is used as a shell.
6. The magnetic polystyrene microsphere of claim 5, having the following characteristics: the prepared magnetic ferroferric oxide is in a nanometer level, and the particle size of the prepared magnetic polystyrene microsphere can be from the nanometer level to the micron level according to different addition proportions of the magnetic ferroferric oxide and monomer styrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111515098.0A CN114213562A (en) | 2021-12-13 | 2021-12-13 | Preparation method of magnetic polystyrene microspheres with different particle sizes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111515098.0A CN114213562A (en) | 2021-12-13 | 2021-12-13 | Preparation method of magnetic polystyrene microspheres with different particle sizes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114213562A true CN114213562A (en) | 2022-03-22 |
Family
ID=80701137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111515098.0A Pending CN114213562A (en) | 2021-12-13 | 2021-12-13 | Preparation method of magnetic polystyrene microspheres with different particle sizes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114213562A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115475656A (en) * | 2022-09-05 | 2022-12-16 | 河南科技大学 | Preparation method of magnetic solid acid and application of magnetic solid acid in biomass hydrolysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106434621A (en) * | 2016-10-28 | 2017-02-22 | 华北电力大学 | Method for immobilizing laccase on polyacrylamide-coated magnetic nano particles and application of method |
| CN107768061A (en) * | 2017-01-06 | 2018-03-06 | 华侨大学 | A kind of preparation method of bag silicon nanoscale magnetic bead |
-
2021
- 2021-12-13 CN CN202111515098.0A patent/CN114213562A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106434621A (en) * | 2016-10-28 | 2017-02-22 | 华北电力大学 | Method for immobilizing laccase on polyacrylamide-coated magnetic nano particles and application of method |
| CN107768061A (en) * | 2017-01-06 | 2018-03-06 | 华侨大学 | A kind of preparation method of bag silicon nanoscale magnetic bead |
Non-Patent Citations (2)
| Title |
|---|
| 丁玲等: "磁性微球与牛血清白蛋白的相互作用", 《化学研究》 * |
| 靳艳巧等: "微悬浮聚合法制备聚苯乙烯磁性微球的研究", 《高分子材料科学与工程》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115475656A (en) * | 2022-09-05 | 2022-12-16 | 河南科技大学 | Preparation method of magnetic solid acid and application of magnetic solid acid in biomass hydrolysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Recent advances and future trends in the detection of contaminants by molecularly imprinted polymers in food samples | |
| Chen et al. | A hollow visible-light-responsive surface molecularly imprinted polymer for the detection of chlorpyrifos in vegetables and fruits | |
| CN110204735B (en) | Preparation method and application of magnetic core-hollow porous molecularly imprinted polymer satellite assembly of macrolide antibiotics | |
| CN102516679B (en) | Magnetic microsphere resin with high specific surface area and preparation method and application thereof | |
| CN102964539B (en) | The preparation method of porous magnetic polystyrene microsphere | |
| Chen et al. | Microwave-assisted RAFT polymerization of well-constructed magnetic surface molecularly imprinted polymers for specific recognition of benzimidazole residues | |
| CN110586052B (en) | Preparation and application of magnetic composite porous network adsorption material | |
| JPH0737535B2 (en) | Shrinked polymer / metal composite particles, aqueous dispersions of the particles and processes for their preparation | |
| CN107200812A (en) | A kind of preparation method of magnetic molecularly imprinted material | |
| CN111821960A (en) | Liquid chromatography stationary phase based on metal organic framework composite material and preparation method thereof | |
| Wang et al. | Facile fabrication of snowman-like magnetic molecularly imprinted polymer microspheres for bisphenol A via one-step Pickering emulsion polymerization | |
| US20230234029A1 (en) | Zearalenone functionalized graphene surface molecularly imprinted material, preparation method therefor and use thereof | |
| CN107999019B (en) | Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof | |
| CN105153367A (en) | Preparation method of dicyandiamide mesoporous surface molecularly imprinted polymer microspheres | |
| CN109354657B (en) | Preparation and application methods of alkylphenol composite template molecularly imprinted polymer modified magnetic graphene oxide | |
| CN100395851C (en) | Size controllable molecular engram polymer magnetic composite nano particles and producing process thereof | |
| CN114213562A (en) | Preparation method of magnetic polystyrene microspheres with different particle sizes | |
| CN111909311B (en) | Corn gibberellin ketone functionalized graphene surface molecularly imprinted material and preparation method thereof | |
| CN114146696A (en) | Metal organic framework composite material chiral chromatography stationary phase based on post-modification technology | |
| CN105854844B (en) | Arteannuic acid magnetic blotting microballoon and its preparation method and application | |
| CN102698723A (en) | Preparation method and application of magnetic organophosphorus pesticide molecular imprinting nanometer microspheres | |
| CN112851848A (en) | Preparation method of temperature-sensitive magnetic molecularly imprinted polymer for selectively separating and enriching aristolochic acid I | |
| CN106905696B (en) | A kind of synthetic method of magnetism phosphorescence Microcystin imprinted material | |
| CN103086387B (en) | Porous silica microsphere preparation method | |
| CN117101616A (en) | Molecularly imprinted polymer adsorption material based on metal-organic framework, and preparation method and application thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220322 |