spherical nanometer magnetons with stable solution dispersibility and preparation method thereof
阅读说明：本技术 一种具有稳定溶液分散性的球形纳米磁子及其制备方法 (spherical nanometer magnetons with stable solution dispersibility and preparation method thereof ) 是由 王飞 孙梦婷 张国栋 陈宸 于 2019-10-25 设计创作，主要内容包括：本发明属于磁力搅拌技术领域,涉及一种具有稳定溶液分散性的球形纳米磁子及其制备方法,以在微纳尺度下和限域微空间内实现磁力搅拌,球形纳米磁子是在水溶性聚合物纳米球载体表面通过静电吸附-原位还原生成的磁性Fe<Sub>3</Sub>O<Sub>4</Sub>纳米粒子,球形纳米磁子制备方法工艺过程包括制备聚合物纳米球水溶液和制备纳米磁子共两个步骤,通过静电吸附-原位还原生长的方式将Fe<Sub>3</Sub>O<Sub>4</Sub>纳米粒子固载于可在水中稳定分散的水溶性聚合物纳米球表面,使制备的纳米磁子在水中具有稳定分散性,并通过控制Fe<Sub>3</Sub>O<Sub>4</Sub>纳米粒子在水溶性聚合物纳米球表面的尺寸和分布密度,控制纳米磁子的磁性可控。(The invention belongs to the technical field of magnetic stirring, and relates to spherical nano-magnetons with stable solution dispersibility and a preparation method thereof, wherein magnetic stirring is realized under the micro-nano scale and in a limited domain micro-space, and the spherical nano-magnetons are magnetic Fe generated on the surface of a water-soluble polymer nanosphere carrier through electrostatic adsorption-in-situ reduction 3 O 4 The preparation method of the nano-particle and the spherical nano-magneton comprises two steps of preparing a polymer nano-sphere aqueous solution and preparing the nano-magneton, and Fe is prepared by a mode of electrostatic adsorption-in-situ reduction growth 3 O 4 The nano particles are fixed on the surface of the water-soluble polymer nano sphere which can be stably dispersed in water, so that the prepared nano magnetons have stable dispersibility in water and Fe is controlled 3 O 4 The size and distribution density of the nano particles on the surface of the water-soluble polymer nano sphere control the magnetism of the nano magnetons to be controllable.)
1, kinds of stable solventThe liquid-dispersible spherical nanomagnet is characterized in that magnetic Fe generated on the surface of a water-soluble polymer nanosphere carrier through electrostatic adsorption-in-situ reduction3O4Nanoparticles.
2. The spherical nanomagnet with stable solution dispersibility of claim 1, wherein the water-soluble polymer nanospheres are polymer nanospheres obtained by soap-free emulsion polymerization of hydrophilic monomers and hydrophobic monomers.
3. The spherical nanomagnetic particles with stable solution dispersibility according to claim 2, characterized in that the hydrophilic monomer is a mixture of carboxylate-type comonomer and sulfonate-type comonomer; the hydrophobic monomer is a mixture of styrene and acrylate monomers; the mass ratio of the hydrophilic monomer to the hydrophobic monomer is 1:2-1: 10; the mass ratio of the carboxylate comonomer to the sulfonate comonomer is 1:1-1: 5; the mass ratio of the styrene to the acrylate monomer is 1:1-9: 1.
4. The spherical nanomagnet with stable solution dispersibility according to claim 3, characterized in that the acrylate monomer is preferably methyl acrylate, ethyl acrylate or butyl acrylate.
5. The spherical nanomagnet with stable solution dispersibility according to claim 3, characterized in that the carboxylate-type comonomer has the formula:
6. The spherical nanomagnet with stable solution dispersibility according to claim 3 or 5, characterized in that the carboxylate-type comonomer is acrylic acid, crotonic acid, methacrylic acid, or methylcrotonic acid.
7. The spherical nanomagnet of claim 3, wherein the sulfonate-type comonomer has the formula:
8. The spherical nanomagnet with stable solution dispersibility according to claim 3 or 7, characterized in that the sulfonate-type comonomer is sodium p-styrene sulfonate, sodium allyl sulfonate, sodium methallyl sulfonate, sodium ethyl methacrylate sulfonate, or sodium propyl methacrylate sulfonate.
9, preparation method of spherical nanometer magnetons with stable solution dispersibility, which is characterized in that the process comprises two steps of preparing polymer nanometer sphere water solution and preparing nanometer magnetons:
(1) preparation of aqueous polymer nanosphere solution: under the protection of nitrogen and the condition of constant stirring, sequentially adding deionized water, hydrophilic monomers and hydrophobic monomers with set mass, uniformly mixing, heating to 70-80 ℃, dropwise adding an initiator aqueous solution with set solubility at a constant speed, reacting for 3-5h at the constant temperature of 70-80 ℃, naturally cooling to room temperature, and polymerizing soap-free emulsion to obtain a polymer nanosphere aqueous solution which takes the hydrophobic monomer as a core, is coated with hydrophilic groups at the periphery, has an average particle size of 30-200nm and has stable dispersibility in water;
(2) preparing nano magnetons: diluting the mass percent concentration of the polymer nanosphere water solution to 0.1-10%, and dropwise adding FeCl at the speed of 1-5 drops/10 s under the stirring condition of the rotation speed of 100-500rpm3Aqueous solution of Fe3+The mol ratio of the polymer nanosphere surface sulfonic acid radical or carboxylic radical type hydrophilic group is 1:1-1:6, and the mixture is dripped and stirred at a constant speed for 1-2h to ensure that Fe3+Adsorbed on the surface of a hydrophilic group under the electrostatic adsorption effect with a sulfonate group or a carboxylate group,then dropwise adding sodium borohydride aqueous solution, sodium borohydride aqueous solution and FeCl at the speed of 1-5 drops/10 s3The molar concentration ratio of the aqueous solution is 2:1-6:1, and the mixture is stirred at a constant speed for 1-2h after being dripped to obtain the Fe solid carried on the surface3O4Spherical nanomagnets of particles.
10. The method of claim 9, wherein the initiator is ammonium persulfate or potassium persulfate.
The technical field is as follows:
the invention belongs to the technical field of magnetic stirring, and relates to spherical nano magnetons with stable solution dispersibility and a preparation method thereof, so as to realize magnetic stirring under a micro-nano scale and in a confined micro space.
Background art:
magnetic stirring is a principle that like poles repel and opposite poles attract of a magnetic field, magnetic particles placed in a container are pushed to move by the aid of the magnetic field, so that stirring is achieved, magnetic stirring can achieve non-mechanical contact type power transmission of a driving device and a stirring device, and has important application value in a closed system (such as a high-pressure container)3O4Magnetic particles are deposited on the surface of a compound of graphene and carbon nano tubes, lysine is modified on a magnetic hybrid body through a surface grafting technology to prepare a magnetic biological adsorption material, the preparation method of nano magnetic liquids disclosed in Chinese patent 200510041150.8 uses a coprecipitation method to prepare Fe3O4Particles, then by the reaction of Fe3O4The particles are peptized under acidic condition to obtain Fe3O4A transparent colloidal solution; chinese patent 200910197295.5 discloses a method for preparing water-soluble amino-functionalized Fe nano magnetic particles by iron-based coordination reaction-high-temperature pyrolysis-deamination protection reaction3O4The preparation method of nano-magnetic polymer composite microspheres disclosed in Chinese patent 200810227202.4 and the preparation method of nano-magnetic polymer composite microspheres disclosed in Chinese patent 201019114005.6 are both characterized in that Fe subjected to hydrophobic treatment is added in the emulsion polymerization process3O4Preparing nanometer polymer magnetic microsphere with particles, preparing magnetic nanometer Fe coated with polyaniline derivative through distribution and interpenetration reaction with polyaniline derivatives disclosed in Chinese patent 201310576592.73O4The water-soluble ferroferric oxide nano-magnetic fluid disclosed in Chinese patent 201410152393.8 is prepared by carrying out sealed reflux on trivalent ferric salt, urea and tartaric acid polyalcohol-water solution at the temperature of 100-200 ℃ to prepare Fe with the diameter of 3-5 nanometers3O4A nanometer fluid, nanometer magnetic particles for sewage treatment disclosed in Chinese patent 201811050455.9, and Fe3O4The nanometer magnetons are treated with alkali solution, then treated with tetramethylsiloxane and coupled with PEG polymerization to prepare PEG magnetic nanoparticles, the high-stability water-based nanometer magnetic fluids disclosed in Chinese patent 201910025790.1 are prepared by coprecipitation method under the dispersion action of macromolecular surfactant to obtain Fe with good water solubility3O4Magnetic nanoparticles; although the above reports all provide methods for the preparation of magnetic nanoparticles, it is by the use of Fe3O4The magnetic particles are obtained by modification, and enrichment and purification under the magnetic field condition ensure that the dispersion stability of the magnetic particles under the action of a magnetic field is lower and the magnetic stirring under the micro-nano scale and in a limited space is difficult to meet, so that spherical nano magnetons with stable solution dispersibility and a preparation method thereof are researched and developed, and the method has very high social significance and practical value.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and aims to research, develop and design spherical nano magnetons with stable solution dispersibility and a preparation method thereof, so that magnetic stirring under nano-micro scale and in a confined micro space can be realized.
In order to achieve the aim, the spherical nano magnetons with stable solution dispersibility are magnetic Fe generated on the surface of a water-soluble polymer nanosphere carrier through electrostatic adsorption-in-situ reduction3O4Nanoparticles.
The water-soluble polymer nanospheres are polymer nanospheres obtained by carrying out soap-free emulsion polymerization on hydrophilic monomers and hydrophobic monomers, wherein the hydrophilic monomers are a mixture of carboxylate type comonomers and sulfonate type comonomers; the hydrophobic monomer is a mixture of styrene and an acrylate monomer, and the acrylate monomer is preferably methyl acrylate, ethyl acrylate or butyl acrylate; the mass ratio of the hydrophilic monomer to the hydrophobic monomer is 1:2-1: 10; the mass ratio of the carboxylate comonomer to the sulfonate comonomer is 1:1-1: 5; the mass ratio of the styrene to the acrylate monomer is 1:1-9: 1.
The structural formula of the carboxylate comonomer related by the invention is as follows:
The structural formula of the sulfonate comonomer related by the invention is as follows:
The invention relates to a method for preparing spherical nano magnetons with stable solution dispersibility, which comprises the following two steps:
(1) preparation of aqueous polymer nanosphere solution: under the protection of nitrogen and under the condition of constant-speed stirring, sequentially adding deionized water, hydrophilic monomers and hydrophobic monomers with set mass, uniformly mixing, heating to 70-80 ℃, dropwise adding an initiator aqueous solution with set solubility at a constant speed, reacting for 3-5h at the constant temperature of 70-80 ℃, naturally cooling to room temperature, and polymerizing soap-free emulsion to obtain a polymer nanosphere aqueous solution which takes the hydrophobic monomer as a core, is coated with hydrophilic groups (sulfonate or carboxylate) at the periphery, has an average particle size of 30-200nm and has stable dispersibility in water;
(2) preparing nano magnetons: diluting the mass percent concentration of the polymer nanosphere water solution to 0.1-10%, and dropwise adding FeCl at the speed of 1-5 drops/10 s under the stirring condition of the rotation speed of 100-500rpm3Aqueous solution of Fe3+The mol ratio of the polymer nanosphere surface sulfonic acid radical or carboxylic radical type hydrophilic group is 1:1-1:6, and the mixture is dripped and stirred at a constant speed for 1-2h to ensure that Fe3+Is adsorbed on the surface of a hydrophilic group under the electrostatic adsorption effect between the hydrophilic group and a sulfonic acid group or a carboxylic acid group, and then sodium borohydride aqueous solution, sodium borohydride aqueous solution and FeCl are dropwise added at the speed of 1-5 drops/10 s3The molar concentration ratio of the aqueous solution is 2:1-6:1, and the mixture is stirred at a constant speed for 1-2h after being dripped to obtain the Fe solid carried on the surface3O4Spherical nanomagnets of particles.
The initiator is ammonium persulfate or potassium persulfate.
Compared with the prior art, the method provided by the invention has the advantages that Fe is subjected to electrostatic adsorption-in-situ reduction growth3O4The nano particles are fixed on the surface of the water-soluble polymer nano sphere which can be stably dispersed in water, so that the prepared nano magnetons have stable dispersibility in water and Fe is controlled3O4The size and distribution density of the nano particles on the surface of the water-soluble polymer nano sphere control the magnetism of the nano magnetons to be controllable.
Description of the drawings:
fig. 1 is a process flow diagram of a method for preparing nano-sized magnetons according to embodiment 1 of the present invention.
Fig. 2 is a transmission electron micrograph of the nanomagnet according to example 1 of the present invention.
The specific implementation mode is as follows:
the invention is further illustrated by way of example and with reference to the accompanying drawings.
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