阅读说明：本技术 一种烯基磁性基球及其制备方法和应用 (Alkenyl magnetic base ball and preparation method and application thereof ) 是由 周丽 马春青 于 2021-08-11 设计创作，主要内容包括：本发明提供一种烯基磁性基球的制备方法,包括如下步骤：步骤一,通过乳液聚合合成单分散高分子微球,单分散高分子微球的粒径为200nm-800nm；步骤二,将磁性微粒沉积于步骤一中的单分散微球表面,形成磁性复合微球；步骤三,将纳米SiO-(2)附着于步骤二的磁性复合微球的外层,得到多层核壳磁性基球；步骤四,将所述步骤三中得到的多层核壳磁性基球通过氢氟酸或盐酸处理后,在甲苯中和烯基硅烷回流反应,得到乙烯基磁性复合微球。本发明的有益效果是：本发明的多层核壳磁性基核是将四氧化三铁(Fe-(3)O-(4))用碱共沉淀法将Fe-(3)O-(4)纳米粒子包覆于单分子的高分子微球外,避免了共沉淀法合成过程中导致的Fe-(3)O-(4)团聚。(The invention provides an alkenyl magnetThe preparation method of the sex base ball comprises the following steps: firstly, synthesizing monodisperse polymer microspheres through emulsion polymerization, wherein the particle size of the monodisperse polymer microspheres is 200nm-800 nm; depositing magnetic particles on the surfaces of the monodisperse microspheres obtained in the step one to form magnetic composite microspheres; step three, mixing the nano SiO 2 Attaching the magnetic composite microspheres to the outer layer of the magnetic composite microspheres in the second step to obtain a multilayer core-shell magnetic base sphere; and step four, treating the multilayer core-shell magnetic base ball obtained in the step three by hydrofluoric acid or hydrochloric acid, and then neutralizing alkenyl silane in toluene for reflux reaction to obtain the vinyl magnetic composite microsphere. The invention has the beneficial effects that: the multilayer core-shell magnetic base core is prepared by mixing ferroferric oxide (Fe) 3 O 4 ) Coprecipitation of Fe with alkali 3 O 4 The nano particles are coated outside the monomolecular polymer microspheres, so that Fe caused in the synthetic process of a coprecipitation method is avoided 3 O 4 And (4) agglomeration.)

1. An alkenyl magnetic base ball characterized in that: the magnetic microsphere comprises magnetic particles, wherein the magnetic particles are wrapped on the outer surface of a monodisperse polymer microsphere, and a hydrophobic monomer with double bonds is arranged on the outer surface of the magnetic particles; preferably, the alkenyl magnetic base sphere has a particle size of 500nm-2um and includes at least one or more double bonds.

2. The application of the alkenyl magnetic base ball is characterized in that: is used for synthesizing high polymer magnetic microspheres.

3. A preparation method of alkenyl magnetic base balls is characterized in that: the method comprises the following steps:

firstly, synthesizing monodisperse polymer microspheres through emulsion polymerization, wherein the particle size of the monodisperse polymer microspheres is 200nm-800 nm;

depositing magnetic particles on the surfaces of the monodisperse microspheres obtained in the first step to form magnetic composite microspheres, wherein the magnetic composite microspheres comprise at least 1 monodisperse polymer microsphere;

step three, mixing the nano SiO₂Attaching the magnetic composite microspheres to the outer layer of the magnetic composite microspheres obtained in the second step to obtain a multilayer core-shell magnetic base sphere;

step four, treating the multilayer core-shell magnetic base ball obtained in the step three by hydrofluoric acid or hydrochloric acid, and then neutralizing alkenyl silane in toluene for reflux reaction to obtain the vinyl magnetic composite microsphere.

4. The method for producing an alkenyl magnetic base ball according to claim 1, characterized in that: the monodisperse polymer microsphere prepared in the first step is synthesized by emulsion polymerization of one or two of styrene, divinylbenzene, chlorostyrene, methyl acrylate, methyl methacrylate and substituted acrylate.

5. The method for producing an alkenyl magnetic base ball according to claim 2, characterized in that: the particle size of the monodisperse nanometer polymer microsphere in the step one is spherical particles.

6. The method for producing an alkenyl magnetic base ball according to claim 3, characterized in that: the magnetic particles in the second step can be selected from Fe₃O₄、Fe₂O₃、NiFe₂O₄、CuFe₂O₄And one or more of magnetic substances such as nickel and cobalt.

7. The method for producing an alkenyl magnetic base ball according to claim 4, characterized in that: nano SiO in the third step₂The method for attaching to the outer layer of the magnetic composite microsphere in the second step comprises the following steps:

step one, performing charge conversion on the surfaces of the magnetic particles in the step two by adopting polymer electrolyte;

second, electrostatically adsorbing nano silica gel particles to form nano SiO₂An outer layer of magnetic particles attached to said first step.

8. The method for producing an alkenyl magnetic base ball according to claim 5, characterized in that: the polymer electrolyte in the first step is a water-soluble cationic polyelectrolyte.

9. The method for producing an alkenyl magnetic base ball according to claim 6, characterized in that: the polymer electrolyte in the first step is any one of cetyltrimethylammonium bromide, polydidecyldimethylammonium chloride, polytrimethylallylammonium chloride, polydidecyldimethylammonium chloride.

10. The method for producing an alkenyl magnetic base ball according to claim 7, characterized in that: the second step is in nano SiO₂The particle diameter is 10nm-100 nm.

Technical Field

The invention relates to the field of composite material technology and magnetic material synthesis, in particular to an alkenyl magnetic base ball and a preparation method and application thereof.

Background

The molecular polymer (HLB) has adjustable surface functionalization and better chemical and physical stability, and can be applied to a plurality of special fields, such as food and environment detection, clinical detection and drug purification, the test and separation of samples can be realized only by installing a solid phase extraction column, a 96-pore plate, a Flash column, a DAC column and the like, the extraction column is used for filling an adsorption material into various extraction columns to form a stationary phase, and the analysis and the test of the samples are greatly influenced by the difference and the flow rate among the extraction columns. The magnetic high molecular polymer can directly use the magnetic material for extracting and separating organic substances in liquid or solution under the action of an external magnetic field, directly extracts and purifies the detected target substance by adopting specific adsorption, has convenient operation, good extraction efficiency, high efficiency and universality, and can eliminate errors and uncertainty caused by inter-column difference, column blockage and flow rate difference.

Due to the limitation of the traditional solid phase extraction column mode, the error caused by the flow rate difference and the risk of column blockage can not be overcome; and when the particle size is less than 30 microns, the flow rate is too slow, so that only materials with larger particle sizes can be used; the larger particle size in turn leads to longer mass transfer time, slow adsorption and desorption, and also leads to the fact that more solvent is needed for the target during desorption and cross with the interferents before and after.

The magnetic beads with specific extraction and adsorption are adopted to extract the target substance to be detected from the liquid and further purify the target substance, but the existing magnetic beads generally adopt a mode of coating a layer of polymer on the surface, and the magnetic beads do not have pore diameters, so that the adsorption and separation effects are not ideal.

Disclosure of Invention

The invention overcomes the defects in the prior art and provides an alkenyl magnetic base ball and a preparation method and application thereof.

The purpose of the invention is realized by the following technical scheme.

An alkenyl magnetic base ball characterized in that: the magnetic microsphere comprises magnetic particles, wherein the magnetic particles are wrapped on the outer surface of a monodisperse polymer microsphere, and a hydrophobic monomer with double bonds is arranged on the outer surface of the magnetic particles.

Preferably, the alkenyl magnetic base sphere has a particle size of 500nm-2um and includes at least one or more double bonds.

An application of alkenyl magnetic base ball in synthesizing high-polymer magnetic microsphere.

A preparation method of high polymer magnetic microspheres comprises the following steps:

step one, acetonitrile, polymer monomer, alkenyl magnetic base ball and AIBN are mixed evenly;

and secondly, placing the mixture obtained in the first step in a constant temperature oscillator, and carrying out precipitation polymerization for 6-24h at 70-90 ℃ to obtain the high polymer magnetic microspheres.

A preparation method of an alkenyl magnetic base ball comprises the following steps:

firstly, synthesizing monodisperse polymer microspheres through emulsion polymerization, wherein the particle size of the monodisperse polymer microspheres is 200nm-800 nm;

depositing magnetic particles on the surfaces of the monodisperse microspheres obtained in the first step to form magnetic composite microspheres, wherein the magnetic composite microspheres comprise at least 1 monodisperse polymer microsphere;

step three, mixing the nano SiO₂Attaching the magnetic composite microspheres to the outer layer of the magnetic composite microspheres obtained in the second step to obtain a multilayer core-shell magnetic base sphere;

step four, treating the multilayer core-shell magnetic base ball obtained in the step three by hydrofluoric acid or hydrochloric acid, and then neutralizing alkenyl silane in toluene for reflux reaction to obtain the vinyl magnetic composite microsphere.

Preferably, the monodisperse polymer microsphere prepared in the first step is synthesized by emulsion polymerization of one or two of styrene, divinylbenzene, chlorostyrene, methyl acrylate, methyl methacrylate and substituted acrylate.

Preferably, in any of the above schemes, the particle size of the monodisperse nano polymer microsphere in the step one is spherical.

Preferably, in any of the above embodiments, the magnetic particles in the second step may be selected from Fe₃O₄、Fe₂O₃、NiFe₂O₄、CuFe₂O₄And one or more of magnetic substances such as nickel and cobalt.

Preferably, in any of the above schemes, the step three is nano SiO₂The method for attaching to the outer layer of the magnetic composite microsphere in the second step comprises the following steps:

step one, performing charge conversion on the surfaces of the magnetic particles in the step two by adopting polymer electrolyte;

second, electrostatically adsorbing nano silica gel particles to form nano SiO₂An outer layer of magnetic particles attached to said first step.

In any of the above embodiments, preferably, the polymer electrolyte in the first step is a water-soluble cationic polyelectrolyte.

Preferably, in any of the above embodiments, the polymer electrolyte in the first step is any one of cetyltrimethylammonium bromide, polydidecyldimethylammonium chloride, polytrimethylallylammonium chloride, and polydidecyldimethylammonium chloride.

Preferably, in any of the above schemes, the second step is performed by using nano SiO₂The particle diameter is 10nm-100 nm.

The invention has the beneficial effects that:

the invention provides a 500nm-2um alkenyl magnetic base ball which can be used for synthesizing magnetic high molecular polymer, and the alkenyl magnetic base core is used for synthesizing high polymer magnetic microspheres, so that basic filler used for solid phase extraction, preparation and purification has magnetism.

The multilayer core-shell magnetic base core is prepared by mixing ferroferric oxide (Fe)₃O₄) Coprecipitation of Fe with alkali₃O₄The nano particles are coated outside the monomolecular polymer microspheres, so that Fe caused in the synthetic process of a coprecipitation method is avoided₃O₄Agglomerating, and then passing through polymer electrolyte to Fe₃O₄And SiO₂Surface charge conversion is carried out to realize multilayer SiO₂And then silane modification is carried out to enable the magnetic core to be provided with alkenyl. The magnetic-based core containing alkenyl further initiates precipitation polymerization with methyl acrylate, styrene and divinylbenzene again, and further synthesizes magnetic beads such as polystyrene magnetic beads, carboxyl magnetic beads and polyacrylates for detection.

Drawings

FIG. 1 is vinyl @ SiO₂@Fe₃O₄The structure of the @ Polymer magnetic composite microsphere is shown schematically.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples.

One-layer and multi-layer core-shell magnetic base ball and preparation method thereof

A preparation method of an alkenyl magnetic base ball comprises the following steps:

firstly, synthesizing monodisperse polymer microspheres through emulsion polymerization, wherein the particle size of the monodisperse polymer microspheres is 200nm-800 nm; the particle size of the monodisperse nano polymer microsphere in the step one is spherical particle, preferably, the particle size of the monodisperse polymer microsphere is 500-700 nm;

in the first step, the monodisperse polymer microsphere is prepared by emulsion polymerization of one or two of styrene, divinylbenzene, chlorostyrene, methyl acrylate, methyl methacrylate and substituted acrylate.

Step two, depositing magnetic particles in the step oneForming magnetic composite microspheres on the surfaces of the monodisperse microspheres, wherein the magnetic composite microspheres comprise at least 1 monodisperse polymer microsphere; the magnetic particles in the second step can be selected from Fe₃O₄、Fe₂O₃、NiFe₂O₄、CuFe₂O₄And one or more of magnetic substances such as nickel and cobalt.

The nano SiO₂The method for attaching to the outer layer of the magnetic composite microsphere in the second step comprises the following steps:

step one, performing charge conversion on the surfaces of the magnetic particles in the step two by adopting polymer electrolyte; the polymer electrolyte in the first step is a water-soluble cationic polyelectrolyte, and the polymer electrolyte in the first step is any one of cetyl trimethyl ammonium bromide, polydidecyl dimethyl ammonium chloride, polytrimethylallyl ammonium chloride and polydidecyl dimethyl ammonium chloride;

second, electrostatically adsorbing nano silica gel particles to form nano SiO₂An outer layer attached to the magnetic particles of the first step; the second step is in nano SiO₂The particle diameter is 10nm-100 nm.

The multilayer core-shell magnetic base ball comprises monodisperse polymer microspheres, magnetic particles are precipitated outside the monodisperse polymer microspheres, and nano SiO is adsorbed outside the magnetic particles₂. Preferably, the alkenyl magnetic base sphere has a particle size of 500nm-2um and includes at least one or more double bonds.

Step three, mixing the nano SiO₂And attaching the magnetic composite microspheres to the outer layer of the magnetic composite microspheres obtained in the second step to obtain the multilayer core-shell magnetic base sphere.

Step four, preparing the alkenyl magnetic base ball by using the multilayer core-shell magnetic base ball in the step three, wherein the specific method comprises the following steps:

step one, the multilayer core-shell magnetic base ball is treated by hydrofluoric acid or 1mol hydrochloric acid to further open Si-O-Si bonds on the surface;

and secondly, carrying out reflux reaction on the multilayer core-shell magnetic base spheres treated in the first step in toluene and alkenyl silane, screening a magnet, and drying a lotion to obtain the alkenyl magnetic micro-core.

Secondly, synthesizing high polymer magnetic microspheres by using alkenyl magnetic micronucleus

A preparation method of high polymer magnetic microspheres comprises the following steps:

step one, acetonitrile, polymer monomer, alkenyl magnetic base ball and AIBN are mixed evenly;

and secondly, placing the mixture obtained in the first step in a constant temperature oscillator, and carrying out precipitation polymerization for 6-24h at 70-90 ℃ to obtain the high polymer magnetic microspheres.

Preferably, the polymer monomers of the high polymer magnetic microspheres are: styrene, divinylbenzene, methyl acrylate, methyl methacrylate and N-vinyl pyrrolidone.

Example 1

Selecting Fe from magnetic particles₃O₄For example, the Fe₃O₄From FeCl₃·6H₂O and FeCl₂·4H₂O is synthesized by a coprecipitation method.

1. Synthesis of monodisperse nano polymer microsphere

And (3) synthesizing the monodisperse polystyrene-divinylbenzene emulsion microspheres by an emulsion polymerization method. Respectively measuring 10g to 100g of styrene with water and polymerization inhibitor removed, 0.5g to 1g of divinylbenzene with water and polymerization inhibitor removed, 0.1g to 1g of potassium persulfate added into 100ml to 1000ml of deionized water, stirring until the potassium persulfate is dissolved, introducing high-purity nitrogen for 30min to remove oxygen in the reaction system, adjusting the stirring of the reaction system to be 500r/min for 200 plus materials, stirring at normal temperature for 30min to 60min, heating in a water bath to 65 ℃ to 85 ℃, and reacting for 10 h. After the reaction is finished, cooling to room temperature for later use.

2、Fe₃O₄Preparation of @ Polymer magnetic composite microspheres

Taking 50-500ml of the monodisperse styrene emulsion obtained in the step 1, adding the monodisperse styrene emulsion into a 1-10L four-neck flask, adding 500-8000ml of deoxidized deionized water into a four-neck reaction bottle, and stirring for 30 min. Weighing 3.73-33.6mmol FeCl₃·6H₂O and 1.87-16.8mmol FeCl₂·₄H₂And adding O into the reaction styrene solution to dissolve. Molar concentration ratio of Fe₃+ and Fe₂2: 1, introducing high-purity nitrogen for 30min to remove oxygen in a reaction system, dropwise adding 5-50ml of 28% concentrated ammonia water or 10M 3-20ml of NaOH aqueous solution, and carrying out aging reaction at 40-80 ℃ for 30min-2 h. After the reaction is finished, cooling to room temperature, separating by a magnet, washing to be neutral by ultrapure water, washing for 3 times by methanol, and drying in vacuum at 40-60 ℃.

3、SiO₂@Fe₃O₄Preparation of @ Polymer magnetic composite microspheres

Taking 1-50g of ferroferric oxide magnetic composite microspheres obtained in the 2 steps, adding 50-500ml of polymer electrolyte aqueous solution with the mass percent of 0.2-2%, mixing for 10-30 minutes, separating by a magnet, and washing for 3 times by deionized water

Adding 10ml-500ml of silica sol after cleaning, adjusting the pH of the silica sol to 2.5-5.5 by using nitric acid, mixing for 30-60 minutes, and washing for 3 times by using magnet separation deionized water

Repeatedly adding electrolyte aqueous solution and silica sol, continuing coating for 5-20 times, separating with magnet, and drying to obtain SiO₂@Fe₃O₄@ Polymer magnetic composite microspheres.

4. Vinyl @ SiO₂@Fe₃O₄Preparation of @ Polymer magnetic composite microspheres

Mixing SiO₂@Fe₃O₄The @ Polymer magnetic composite microspheres were treated with 1mol of hydrochloric acid to open Si-O-Si bonds on the surface. The concentration of hydrofluoric acid can be generally between 0.5 and 2 mol/L; the acid treatment time can generally be from 5 to 24 hours at a temperature of from 50 to 100 ℃.

Taking hydrofluoric acid treated SiO₂@Fe₃O₄1-50g of @ Polymer magnetic composite microspheres, 5-500ml of toluene and 2-100g of alkenyl silane are added, reflux reaction is carried out for 5-36h, magnet screening is carried out, and lotion is dried to obtain vinyl @ SiO₂@Fe₃O₄@ Polymer magnetic composite microsphere

In particular, alkenyl @ SiO₂@Fe₃O₄The @ Polymer magnetic composite microsphere is prepared by adding double-bond silane coupling agent including vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriiso-trimethoxysilaneOne or more of propoxysilane.

5. Preparation of styrene-divinylbenzene magnetic microspheres

Adding acetonitrile, styrene, DVB, magnetic core and AIBN into a conical flask according to a certain proportion, mixing uniformly, charging nitrogen for 15min, plugging and sealing. Putting the conical flask into a constant temperature oscillator, controlling the temperature to react for 24h at 70 ℃, centrifugally separating the product, and distributing and washing with acetone and ethanol for three times to obtain the required styrene-divinylbenzene magnetic microspheres.

While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.