CN114106254B - Method for preparing functionalized magnetic polymer microsphere by miniemulsion polymerization method using porous microsphere as template - Google Patents
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Abstract
The invention discloses a method for preparing functionalized magnetic polymer microspheres by a miniemulsion polymerization method by taking porous microspheres as templates, which comprises the following steps: synthesizing porous template polymer microspheres; preparing uniform and stable magnetic fluid; dispersing the magnetic fluid into an aqueous phase containing a surfactant, adding porous template polymer microspheres and an initiator, and preparing the magnetic polymer microspheres by a miniemulsion polymerization method. The method changes multiple steps into one step, thereby avoiding the problem that magnetic substances in the magnetic polymer microspheres are easy to leak and the subsequent additional encapsulation and function modification steps. Meanwhile, the porous microspheres with uniform particle size are used as templates, so that the problems of non-uniform and uncontrollable sizes of the magnetic polymer microspheres, low magnetic substance content in the microspheres and large difference of magnetic substance coating rate are solved. The method can be used for preparing the magnetic polymer microsphere with uniform and controllable particle size, high magnetic substance content and different functionalized surfaces.
Description
Technical Field
The invention belongs to a preparation method of magnetic polymer microspheres, and in particular relates to a method for preparing functionalized magnetic polymer microspheres by using a miniemulsion polymerization method with porous microspheres as templates.
Background
The magnetic polymer microsphere not only has the characteristics of non-toxicity and superparamagnetism of the magnetic inorganic nano particles, but also has the characteristics of polarity, biocompatibility, easy surface functionalization and the like of the polymer, and has wide application in a plurality of fields, in particular biological detection and in-vitro diagnostic reagents. The magnetic microsphere for diagnostic reagent is required to have uniform particle size, fast magnetic response, good suspension property and low nonspecific adsorption to biomacromolecule such as protein, nucleic acid, etc.
The preparation method of the magnetic polymer microsphere mainly comprises four steps: a monomer polymerization method, a template assembly method, a template in-situ generation method and a solvothermal method. Patent document US8038987B2 discloses a preparation method of coated magnetic polymer particles, which uses nitrified porous polystyrene microspheres as a template, and then coprecipitates ferric salt and manganese salt into the porous microspheres to prepare the magnetic polymer microspheres. The magnetic polymer microsphere prepared by the method has the advantages of simple preparation process, and additional polymer encapsulation and functional modification steps. Patent document CN106867021a discloses a preparation method of a magnetic porous polymer microsphere, which adopts oleic acid to wrap magnetic ferric oxide nano particles, and then swells the magnetic nano particles into pore channels of the porous polymer microsphere crosslinked by glycidyl methacrylate and ethylene glycol dimethacrylate, thus obtaining the magnetic porous polymer microsphere. The magnetic polymer microsphere prepared by the method still has a pore canal structure, so that magnetic substances are easy to leak, and the pore canals are easy to generate nonspecific adsorption on biological macromolecules such as proteins in subsequent biological detection experiments, so that higher background noise is caused. Patent document CN113351182a discloses a preparation method of magnetic microsphere modified by surface zwitterionic polymer, dispersing magnetic fluid into water phase containing surfactant, preparing magnetic microsphere by reverse microemulsion method, and modifying by silica and functional monomer to obtain magnetic microsphere coated by surface zwitterionic polymer. However, the method is not only cumbersome, but also the particle size of the obtained magnetic polymer microsphere is not uniform and controllable, and the coating rate of the magnetic substances in the microsphere is greatly different. Therefore, there is still a need to develop a new method for preparing magnetic polymer microspheres with uniform and controllable particle size, high magnetic substance content, and different functionalized surfaces.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for preparing functionalized magnetic polymer microspheres by using a miniemulsion polymerization method with porous microspheres as templates.
The technical scheme is as follows: the invention relates to a method for preparing functionalized magnetic polymer microspheres by using a miniemulsion polymerization method with porous microspheres as templates, which comprises the following steps:
(1) Synthesizing and hydrolyzing porous template polymer microspheres;
(2) Synthesizing uniform and stable magnetic fluid;
(3) Dispersing the magnetic fluid prepared in the step (2) into a water phase containing a surfactant, adding the porous template polymer microsphere prepared in the step (1) and an initiator, and preparing the magnetic polymer microsphere by using a miniemulsion polymerization method.
The method simplifies the synthesis steps, avoids the problem that magnetic substances in the magnetic polymer microspheres are easy to leak, and the subsequent additional steps of polymer encapsulation and functional modification, and solves the problems that the magnetic polymer microspheres are nonuniform and uncontrollable in size, low in magnetic substance content and large in difference of magnetic substance coating.
Further, the method for synthesizing the porous template polymer microsphere in the step (1) comprises the following steps: the seed microsphere is firstly swelled in a first step in an aqueous solution containing a swelling agent and a surfactant, swelled for 12-14 h at 30-50 ℃, then swelled in a second step in an aqueous solution containing a functional monomer, an initiator and the surfactant, swelled for 6-8 h at 30-50 ℃, finally heated to 60-80 ℃ for polymerization for 14-18 h, washed, hydrolyzed and dried to obtain the porous template polymer microsphere. The method for preparing the seed microsphere can be precipitation polymerization, emulsion polymerization, dispersion polymerization or soap-free emulsion polymerization.
Further, the surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the concentration of the aqueous solution is 0.15-0.25 wt%; the swelling agent is selected from one or more of dibutyl phthalate, toluene, acetone, cyclohexanol or n-heptane, and the addition amount of the swelling agent is 20-30 times of that of the seed microsphere; the functional monomer is 2-3 of methyl methacrylate, glycidyl methacrylate or divinylbenzene, and the dosage is 20-30 times of that of the seed microsphere; the initiator comprises potassium persulfate, ammonium persulfate, azodiisobutyronitrile or benzoyl peroxide, and the dosage of the initiator is 3-4wt% of the functional monomer. The hydrolysis is that firstly, the hydrolysis is carried out for 10 to 16 hours under the alkaline condition of 40 to 60 ℃, and then the hydrolysis is carried out for 8 to 10 hours under the acidic condition of 60 to 80 ℃.
Further, the preparation method of the magnetic fluid comprises the steps of coating magnetic nanoparticles with oleic acid and dispersing the magnetic nanoparticles into an oily functional monomer to obtain the magnetic fluid; the preparation method of the magnetic nano particles is a coprecipitation method, a thermal oxidation method or a high temperature pyrolysis method.
Further, the particle diameter of the magnetic nano particles is 8-10 nm, and the mass concentration of the magnetic particles in the magnetic fluid is 5% -50%; the functional monomer for dispersing the nano particles is any one or a combination of at least two of styrene, divinylbenzene, methyl methacrylate and glycidyl methacrylate.
The method prepares the functionalized magnetic polymer microsphere by using a miniemulsion polymerization method with the porous microsphere as a template, combines multiple steps into one step, and avoids the problem that magnetic substances in the magnetic polymer microsphere are easy to leak in the traditional template method and the subsequent additional encapsulation and functional modification steps. Meanwhile, the porous microspheres with uniform particle size are used as templates, so that the problems that the sizes of the magnetic polymer microspheres prepared by the traditional miniemulsion polymerization method are not uniform and controllable, the content of magnetic substances in the microspheres is low, and the coating difference of the magnetic substances is large are solved. In addition, the method has strong universality, so that the size of the porous microsphere and the types of functional monomers used in the magnetic fluid can be changed according to actual needs, various functional magnetic polymer microspheres can be prepared, and the application range of the magnetic polymer microspheres is greatly expanded. Therefore, the method has wide application prospect.
The technical effects are as follows: compared with the prior art, the invention has the following advantages:
1. the method changes multiple steps into one step, and the preparation process is simple and quick;
2. the porous microspheres are used as templates for miniemulsion polymerization, so that the uniform and controllable particle size of the magnetic polymer microspheres is realized;
3. the encapsulation of the magnetic nanoparticles is realized while the magnetic nanoparticles are dissolved in the porous template, and the modification of functional groups on the surfaces of the magnetic polymer microspheres is also realized.
Drawings
FIG. 1 is a scanning electron microscope image of polystyrene seed microspheres prepared by a dispersion polymerization method in example 1 of the present invention;
FIGS. 2 (a) and (b) are a scanning electron microscope and a transmission electron microscope, respectively, of porous crosslinked poly (methyl methacrylate-glycidyl methacrylate) microspheres prepared by the two-step seed swelling method of example 1 of the present invention;
FIGS. 3 (a) and (b) are a scanning electron microscope image and a transmission electron microscope image, respectively, of a functional porous polymer microsphere prepared by the two-step seed swelling method in example 1 of the present invention after acid-base hydrolysis of the porous crosslinked poly (methyl methacrylate-glycidyl methacrylate) microsphere;
FIG. 4 is a transmission electron microscope image of oleic acid modified ferroferric oxide nanoparticles prepared by the coprecipitation method in example 1 of the present invention;
FIGS. 5 (a) and (b) are, respectively, scanning electron microscopy and transmission electron microscopy images of functionalized magnetic polymer microspheres prepared by miniemulsion polymerization using porous microspheres as templates in example 1 of the present invention;
FIG. 6 is a transmission electron microscope image of an ultrathin slice of the functionalized magnetic polymer microsphere prepared by the miniemulsion polymerization method using the porous microsphere as a template in example 1 of the present invention after embedding the epoxy resin.
Detailed Description
The ferroferric oxide nanoparticles used in the following examples, oleic acid as a ligand, were prepared as follows:
(1) 5.2g of FeCl 3 ·6H 2 O and 2.0g FeCl 2 ·4H 2 O was dissolved in 20mL of distilled water, and added to a 50mL three-necked flask, and the temperature was raised to 70℃under nitrogen protection.
(2) Adding 10mL of ammonia water, reacting for 1h, magnetically separating after the reaction is finished, and washing for multiple times to obtain the ferroferric oxide nano particles.
(3) The ferroferric oxide nano particles synthesized in the step (2) are dispersed in a three-neck flask filled with 30mL of distilled water, heated to 85 ℃,3mL of oleic acid is added, and the reaction is carried out for 30min.
(4) Cooling to room temperature, magnetically separating, and repeatedly washing with ethanol for several times to obtain oleic acid modified ferroferric oxide nano particles.
Example 1
(1) Synthesis of polystyrene seed microspheres: firstly, adding isopropanol and distilled water with the mass ratio of 3:2 into a 50mL three-neck flask, and stirring to uniformly mix the materials. Then, 0.375g of polyvinylpyrrolidone, 2.5mL of styrene and 0.04g of azobisisobutyronitrile were added thereto, and stirring was continued to mix them uniformly. The reaction solution was heated to 75℃under nitrogen protection and reacted for 12 hours. And (3) centrifugally washing the product with deionized water for multiple times, and vacuum drying the product for 12 hours to obtain the polystyrene seed microspheres with the particle size of about 1 mu m.
(2) Synthesis and hydrolysis of porous polymer microspheres:
a. and (3) synthesis: 0.6mL of toluene and 1.8mL of dibutyl phthalate were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. 0.1 g of the polystyrene seed microsphere prepared in the step (1) is added, and the mixture is swelled for 12 hours at room temperature. Similarly, 2.5mL of methyl methacrylate, 0.5mL of divinylbenzene, 0.5mL of glycidyl methacrylate, and 0.12g of benzoyl peroxide were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. The emulsified solution was added to the reaction solution after swelling for 12 hours, and swelling was continued for 6 hours. Finally, the polymer microspheres are polymerized for 16 hours under the protection of nitrogen atmosphere at 70 ℃, centrifuged, washed three times by ethanol and water respectively, and dried in a vacuum drying oven to obtain the porous polymer microspheres with the particle size of about 3 mu m.
b. Hydrolysis: 1g of the porous polymer microspheres was hydrolyzed with 50ml of 10% aqueous sodium hydroxide at 60℃for 8 hours, and after the hydrolysis, washed with distilled water to neutrality. And then, condensing and refluxing 50ml of 0.2mol/L dilute sulfuric acid aqueous solution for 4 hours at the temperature of 80 ℃, washing to be neutral by distilled water after the hydrolysis is finished, and drying for 16 hours in a vacuum drying oven to obtain the twice hydrolyzed functionalized porous polymer microsphere.
(3) Synthesis of magnetic polymer microspheres: 0.5g oleic acid modified ferroferric oxide nanoparticles were dispersed in 2mL methyl methacrylate, 0.5mL divinylbenzene and 2mL glycidyl methacrylate to form a uniform magnetic fluid, then 60mL0.15% aqueous solution of sodium dodecyl sulfate was added thereto, and the above solution was emulsified completely by sonication. And finally, adding 0.5g of the functionalized porous microsphere obtained in the step (2) and 0.16g of benzoyl peroxide into the mixture, swelling the mixture at room temperature for 6 hours, and heating the mixture to 70 ℃ for reaction for 16 hours to obtain the magnetic polymer microsphere.
Example 2
(1) Synthesis of polystyrene seed microspheres: firstly, adding isopropanol and distilled water with the mass ratio of 3:2 into a 50mL three-neck flask, and stirring to uniformly mix the materials. Then, 0.375g of polyvinylpyrrolidone, 2.5mL of styrene and 0.04g of azobisisobutyronitrile were added thereto, and stirring was continued to mix them uniformly. The reaction solution was heated to 75℃under nitrogen protection and reacted for 12 hours. And (3) centrifugally washing the product with deionized water for multiple times, and vacuum drying the product for 12 hours to obtain the polystyrene seed microspheres with the particle size of about 1 mu m.
(2) Synthesis of porous polymer microspheres: 0.6mL of toluene and 1.8mL of dibutyl phthalate were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. 0.1 g of the polystyrene seed microsphere prepared in the step (1) is added, and the mixture is swelled for 12 hours at room temperature. Similarly, 2mL of styrene, 0.6mL of divinylbenzene, and 0.12g of benzoyl peroxide were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was sonicated to complete emulsification. The emulsified solution was added to the reaction solution after swelling for 12 hours, and swelling was continued for 6 hours. Finally, the temperature is raised to 70 ℃ and the polymerization is carried out for 16 hours under the protection of nitrogen atmosphere. After the reaction, the mixture was centrifuged, washed three times with ethanol and water, and dried in a vacuum oven to obtain porous polymer microspheres having a particle size of about 3. Mu.m.
(3) Synthesis of magnetic polymer microspheres: 0.5g oleic acid modified ferroferric oxide nanoparticles were dispersed in 2mL methyl methacrylate, 0.5mL divinylbenzene and 2mL glycidyl methacrylate to form a uniform magnetic fluid, then 60mL0.15% aqueous solution of sodium dodecyl sulfate was added thereto, and the above solution was emulsified completely by sonication. Finally, adding 0.5g of the porous microsphere obtained in the step (2) and 0.16g of benzoyl peroxide into the mixture, swelling the mixture at room temperature for 6 hours, and then heating the mixture to 70 ℃ for reaction for 16 hours to obtain the magnetic polymer microsphere.
Example 3
(1) Synthesis of polystyrene seed microspheres: firstly, adding isopropanol and distilled water with the mass ratio of 3:2 into a 50mL three-neck flask, and stirring to uniformly mix the materials. Then, 0.375g of polyvinylpyrrolidone, 2.5mL of styrene and 0.04g of azobisisobutyronitrile were added thereto, and stirring was continued to mix them uniformly. The reaction solution was heated to 75℃under nitrogen protection and reacted for 12 hours. And (3) centrifugally washing the product with deionized water for multiple times, and vacuum drying the product for 12 hours to obtain the polystyrene seed microspheres with the particle size of about 1 mu m.
(2) Synthesis and hydrolysis of porous crosslinked polymer microspheres:
a. and (3) synthesis: 0.6mL of toluene and 1.8mL of dibutyl phthalate were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. 0.1 g of the polystyrene seed microsphere prepared in the step (1) is added, and the mixture is swelled for 12 hours at room temperature. Similarly, 2.5mL of methyl methacrylate, 0.5mL of divinylbenzene, 0.5mL of glycidyl methacrylate, and 0.12g of benzoyl peroxide were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. The emulsified solution was added to the reaction solution after swelling for 12 hours, and swelling was continued for 6 hours. Finally, the temperature is raised to 70 ℃ and the polymerization is carried out for 16 hours under the protection of nitrogen atmosphere. After the reaction, the mixture was centrifuged, washed three times with ethanol and water, and dried in a vacuum oven to obtain porous polymer microspheres having a particle size of about 3. Mu.m.
b. Hydrolysis: 1g of the porous polymer microspheres described above was hydrolyzed with 50ml of 10% aqueous sodium hydroxide solution at 60℃for 8 hours. Washing with distilled water to neutrality after hydrolysis to obtain porous microsphere. Then, 50ml of a 0.2mol/L dilute aqueous sulfuric acid solution was refluxed at 80℃for 4 hours. And after the reaction is finished, washing with water to be neutral, and putting the mixture into a vacuum drying oven for drying for 16 hours to obtain the twice hydrolyzed functionalized porous microspheres.
(3) Synthesis of magnetic polymer microspheres: 0.5g oleic acid modified ferroferric oxide nanoparticles were dispersed in 2mL t-butyl methacrylate, 0.25mL divinylbenzene and 0.25mL glycidyl methacrylate to form a homogeneous magnetic fluid, then 30mL of 0.15% aqueous sodium dodecyl sulfate solution was added thereto, and the solution was completely emulsified by sonication. And finally, adding 0.2g of the functionalized porous microsphere obtained in the step (2) and 0.06g of benzoyl peroxide into the mixture, swelling the mixture at room temperature for 6 hours, and heating the mixture to 70 ℃ for reaction for 16 hours to obtain the magnetic polymer microsphere.
Example 4
(1) Synthesis of polystyrene seed microspheres: into a 50mL three-necked flask, 20mL of ethanol, 0.2g of polyvinylpyrrolidone, 3mL of styrene and 0.04g of azobisisobutyronitrile were added, and stirring was continued to mix them uniformly. The reaction solution was heated to 74℃under nitrogen protection and reacted for 24 hours. And (3) centrifugally washing the product with deionized water for multiple times, and vacuum drying the product for 12 hours to obtain the polystyrene seed microspheres with the particle size of about 2 mu m.
(2) Synthesis and hydrolysis of porous polymer microspheres:
a. and (3) synthesis: 0.6mL of toluene and 1.8mL of dibutyl phthalate were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. 0.1 g of the polystyrene seed microsphere prepared in the step (1) is added, and the mixture is swelled for 12 hours at room temperature. Similarly, 2.5mL of methyl methacrylate, 0.5mL of divinylbenzene, 0.5mL of glycidyl methacrylate, and 0.12g of benzoyl peroxide were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. The emulsified solution was added to the reaction solution after swelling for 12 hours, and swelling was continued for 6 hours. Finally, the temperature is raised to 70 ℃ and the polymerization is carried out for 16 hours under the protection of nitrogen atmosphere. After the reaction, the mixture is centrifuged, washed three times with ethanol and water, and dried in a vacuum drying oven to obtain porous polymer microspheres with the particle size of about 6 mu m.
b. Hydrolysis: 1g of the porous polymer microspheres described above was hydrolyzed with 50ml of 10% aqueous sodium hydroxide solution at 60℃for 8 hours. Washing with distilled water to neutrality after hydrolysis to obtain porous microsphere. Then, 50ml of a 0.2mol/L dilute aqueous sulfuric acid solution was refluxed at 80℃for 4 hours. And after the reaction is finished, washing with water to be neutral, and putting the mixture into a vacuum drying oven for drying for 16 hours to obtain the twice hydrolyzed functionalized porous microspheres.
(3) Synthesis of magnetic polymer microspheres: 0.5g oleic acid modified ferroferric oxide nanoparticles were dispersed in 2mL methyl methacrylate, 0.5mL divinylbenzene and 2mL glycidyl methacrylate to form a uniform magnetic fluid, then 60mL0.15% aqueous solution of sodium dodecyl sulfate was added thereto, and the above solution was emulsified completely by sonication. And finally, adding 0.5g of the functionalized porous microsphere obtained in the step (2) and 0.16g of benzoyl peroxide into the mixture, swelling the mixture at room temperature for 6 hours, and heating the mixture to 70 ℃ for reaction for 16 hours to obtain the magnetic polymer microsphere.
Example 5
(1) Synthesis of polystyrene seed microspheres: firstly, adding a three-neck flask with 50mL into a three-neck flask with the mass ratio of 3:2 and distilled water, and stirring to mix them uniformly. Then, 0.4g of an aqueous solution of polyacrylic acid, 1mL of styrene and 0.025g of ammonium persulfate were added thereto, and stirring was continued to mix them uniformly. The reaction solution was heated to 75℃under nitrogen protection and reacted for 8 hours. And (3) centrifugally washing the product with deionized water for multiple times, and vacuum drying the product for 12 hours to obtain the polystyrene seed microspheres with the particle size of about 0.4 mu m.
(2) Synthesis and hydrolysis of porous polymer microspheres:
a. and (3) synthesis: 0.6mL of toluene and 1.8mL of dibutyl phthalate were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. 0.1 g of the polystyrene seed microsphere prepared in the step (1) is added, and the mixture is swelled for 12 hours at room temperature. Similarly, 2.5mL of methyl methacrylate, 0.5mL of divinylbenzene, 0.5mL of glycidyl methacrylate, and 0.12g of benzoyl peroxide were added to a 30mL aqueous solution containing 0.05g of sodium dodecyl sulfate, and the mixture was thoroughly emulsified by sonication. The emulsified solution was added to the reaction solution after swelling for 12 hours, and swelling was continued for 6 hours. Finally, the temperature is raised to 70 ℃ and the polymerization is carried out for 16 hours under the protection of nitrogen atmosphere. After the reaction, the mixture is centrifuged, washed three times with ethanol and water, and dried in a vacuum drying oven to obtain porous polymer microspheres with the particle size of about 1 μm.
b. Hydrolysis: 1g of the porous polymer microspheres described above was hydrolyzed with 50ml of 10% aqueous sodium hydroxide solution at 60℃for 8 hours. Washing with distilled water to neutrality after hydrolysis to obtain porous microsphere. Then, 50ml of a 0.2mol/L dilute aqueous sulfuric acid solution was refluxed at 80℃for 4 hours. And after the reaction is finished, washing with water to be neutral, and putting the mixture into a vacuum drying oven for drying for 16 hours to obtain the twice hydrolyzed functionalized porous microspheres.
(3) Synthesis of magnetic polymer microspheres: 0.5g oleic acid modified ferroferric oxide nanoparticles were dispersed in 2mL methyl methacrylate, 0.5mL divinylbenzene and 2mL glycidyl methacrylate to form a uniform magnetic fluid, then 60mL0.15% aqueous solution of sodium dodecyl sulfate was added thereto, and the above solution was emulsified completely by sonication. And finally, adding 0.5g of the functionalized porous microsphere obtained in the step (2) and 0.16g of benzoyl peroxide into the mixture, swelling the mixture at room temperature for 6 hours, and heating the mixture to 70 ℃ for reaction for 16 hours to obtain the magnetic polymer microsphere.
Claims (7)
1. A method for preparing functionalized magnetic polymer microspheres by a miniemulsion polymerization method using porous microspheres as templates, which is characterized in that: the method comprises the following steps:
(1) Synthesizing and hydrolyzing porous template polymer microspheres;
the seed microsphere is firstly swelled in a first step in an aqueous solution containing a swelling agent and a surfactant, swelled for 12-14 h at 30-50 ℃, then swelled in a second step in an aqueous solution containing a functional monomer, an initiator and the surfactant, swelled for 6-8 h at 30-50 ℃, finally heated to 60-80 ℃ for polymerization for 14-18 h, washed, hydrolyzed and dried to obtain the porous template polymer microsphere;
the functional monomer is 2-3 of methyl methacrylate, glycidyl methacrylate or divinylbenzene, and the dosage is 20-30 times of that of the seed microsphere;
(2) Synthesizing uniform and stable magnetic fluid;
the magnetic nanoparticles are coated by oleic acid and then dispersed into oily functional monomers to obtain magnetic fluid; the particle size of the magnetic nano particles is 8-10 nm, and the mass concentration of the magnetic particles in the magnetic fluid is 5-50%; the functional monomer for dispersing the nano particles is any one or a combination of at least two of styrene, divinylbenzene, methyl methacrylate and glycidyl methacrylate;
(3) Dispersing the magnetic fluid prepared in the step (2) into a water phase containing a surfactant, adding the porous template polymer microsphere prepared in the step (1) and an initiator, and preparing the magnetic polymer microsphere by using a miniemulsion polymerization method.
2. The method for preparing functionalized magnetic polymer microspheres by miniemulsion polymerization using porous microspheres as template according to claim 1, wherein the method comprises the steps of: the method for preparing the seed microsphere is a precipitation polymerization, emulsion polymerization, dispersion polymerization or soap-free emulsion polymerization method.
3. The method for preparing functionalized magnetic polymer microspheres by miniemulsion polymerization using porous microspheres as template according to claim 1, wherein the method comprises the steps of: the surfactant is one or more selected from sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the concentration of the aqueous solution is 0.15-0.25 wt%.
4. The method for preparing functionalized magnetic polymer microspheres by miniemulsion polymerization using porous microspheres as template according to claim 1, wherein the method comprises the steps of: the swelling agent is selected from one or more of dibutyl phthalate, toluene, acetone, cyclohexanol or n-heptane, and the addition amount of the swelling agent is 20-30 times of that of the seed microsphere.
5. The method for preparing functionalized magnetic polymer microspheres by miniemulsion polymerization using porous microspheres as template according to claim 1, wherein the method comprises the steps of: the initiator comprises potassium persulfate, ammonium persulfate, azodiisobutyronitrile or benzoyl peroxide, and the dosage of the initiator is 3-4wt% of the functional monomer.
6. The method for preparing functionalized magnetic polymer microspheres by miniemulsion polymerization using porous microspheres as template according to claim 1, wherein the method comprises the steps of: the hydrolysis is that firstly, the hydrolysis is carried out for 10 to 16 hours under the alkaline condition of 40 to 60 ℃, and then the hydrolysis is carried out for 8 to 10 hours under the acidic condition of 60 to 80 ℃.
7. The method for preparing functionalized magnetic polymer microspheres by miniemulsion polymerization using porous microspheres as template according to claim 1, wherein the method comprises the steps of: the preparation method of the magnetic nano particles is a coprecipitation method, a thermal oxidation method or a high-temperature thermal decomposition method.
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| CN101220187A (en) * | 2008-01-31 | 2008-07-16 | 复旦大学 | Magnetic composite microsphere with nucleocapsid structure and method for producing the same |
| CN102029133A (en) * | 2009-09-29 | 2011-04-27 | 北京万德高科技发展有限公司 | Porous polymer microsphere and functional composite polymer microsphere as well as preparation method and application thereof |
| CN106867021A (en) * | 2015-12-11 | 2017-06-20 | 北京大学深圳研究生院 | A kind of preparation method of magnetic porous polymer microsphere |
| CN110396148A (en) * | 2019-08-05 | 2019-11-01 | 东南大学 | A kind of magnetic polystyrene microsphere and preparation method thereof |
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| CN101220187A (en) * | 2008-01-31 | 2008-07-16 | 复旦大学 | Magnetic composite microsphere with nucleocapsid structure and method for producing the same |
| CN102029133A (en) * | 2009-09-29 | 2011-04-27 | 北京万德高科技发展有限公司 | Porous polymer microsphere and functional composite polymer microsphere as well as preparation method and application thereof |
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