CN112791674A - Core-shell micron-sized monodisperse silica gel microsphere and preparation method thereof - Google Patents
Core-shell micron-sized monodisperse silica gel microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention provides a core-shell micron-sized monodisperse silica gel microsphere and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing the polystyrene microsphere dispersion liquid with an acrylic monomer, swelling at 20-30 ℃ under an anaerobic condition, and reacting under initiation of a redox initiator; washing, air-drying and collecting the product carboxylated polystyrene microspheres; the particle size of the polystyrene microspheres in the polystyrene microsphere dispersion liquid is 2.0-2.5 microns; (2) dispersing the carboxylated polystyrene microspheres in an aqueous solution containing a polyether nonionic dispersing agent to obtain a carboxylated polystyrene microsphere dispersion, mixing tetraethoxysilane hydrolysate with the carboxylated polystyrene microsphere dispersion, and reacting at 50-60 ℃ for 80-160 hours; and washing and drying to obtain the core-shell type micron-sized monodisperse silica gel microspheres. The method can prepare the core-shell type micron-sized monodisperse silica gel microspheres with the average particle size of more than 3 mu m and higher uniformity.
Description
Technical Field
The invention relates to the technical field of high-molecular functional materials, in particular to a core-shell type micron-sized monodisperse silica gel microsphere and a preparation method thereof.
Background
The monodisperse silica gel microspheres can be used in the fields of photonic crystals, high performance liquid chromatography column packing, liquid crystal displays and the like. The method for industrially obtaining monodisperse silica gel microspheres is usually a sieving method, but the method is time-consuming and labor-consuming, and the particle size of the obtained silica gel microspheres cannot be strictly controlled. Can pass through a laboratory
Methods or modifications
The method (such as CN1011492164A) prepares monodisperse silica gel microspheres. According to the method, an organic silicon source is used as a precursor, ammonia water is used as a catalyst, ethanol and water are used as solvents, and hydrolysis and polymerization of the organic silicon source precursor are regulated and controlled according to reactant concentration and temperature, so that the nucleation and growth stages of silica gel are controlled, and the silica gel microspheres with uniform particle sizes are obtained. But instead of the other end of the tube
The method has strict requirements on reaction conditions, the particle size of the product is uneven due to slight changes of temperature, ionic strength and the like, and the method is limited by the influence of surface tension and gravity, and the silica gel microspheres prepared by the method are difficult to maintain high monodispersity when the particle size is over 2 mu m. The particle-type filler of the high performance liquid chromatography column needs the particle size of 3-10 mu m so as to ensure that the mobile phase has proper flow velocity in a normal pressure range. The ultrahigh pressure liquid phase can adopt filler with the particle size less than 3 μm, but the liquid chromatography has higher requirements on instruments and equipment and higher use and maintenance costs.
Except for the common gas phase method, the sol-gel method taking water glass as a precursor and the method taking an organic silicon source as a precursor
Methods, and other methods are also continually being explored. The patent CN102350325A takes monocrystalline silicon as a silicon source to prepare uniform silica gel microspheres with high purity and average particle size of 3 mu m, but the monodispersity is stillTo be improved. In patent CN104003410B, organosilane is used as a silica gel precursor, and a two-phase interface method is used to prepare monodisperse silica gel microspheres with controllable particle size, wherein the controllable particle size range is 0.27-1 μm, but the existing silica gel particle size does not meet the requirements of a high performance liquid chromatography column, and the uniformity needs to be improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a core-shell type micron-sized monodisperse silica gel microsphere and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of core-shell micron-sized monodisperse silica gel microspheres comprises the following steps:
(1) mixing the polystyrene microsphere dispersion liquid with an acrylic monomer, swelling at 20-30 ℃ under an anaerobic condition, and reacting under initiation of a redox initiator; washing, air-drying and collecting the product carboxylated polystyrene microspheres; the particle size of the polystyrene microspheres in the polystyrene microsphere dispersion liquid is 2.0-2.5 microns;
(2) dispersing the carboxylated polystyrene microspheres in an aqueous solution containing a polyether nonionic dispersing agent to obtain a carboxylated polystyrene microsphere dispersion, mixing tetraethoxysilane hydrolysate with the carboxylated polystyrene microsphere dispersion, and reacting at 50-60 ℃ for 80-160 hours; washing and drying to obtain the core-shell type micron-sized monodisperse silica gel microspheres; the weight ratio of the tetraethoxysilane to the carboxylated polystyrene microspheres is 1: (0.1 to 1).
The core-shell micron-sized monodisperse silica gel microspheres take polystyrene microspheres as microsphere seeds, and are mixed with acrylic monomers for swelling polymerization, so that the acrylic monomers are grafted on the surfaces of the polystyrene microspheres to prepare monodisperse carboxylated polystyrene microspheres; finally, taking the monodisperse carboxylated polystyrene microspheres as a core, and carrying out in-situ hydrolytic polymerization on the surface of the monodisperse carboxylated polystyrene microspheres by carboxyl on the core, namely hydrolytic polymerization on an acidic solid-liquid interface, so that the polymerization of tetraethoxysilane and hydrolysis products thereof in a water phase is reduced, and thus, the generation of over-small silicon dioxide particles in a system is avoided, and the core-shell structure silica gel microspheres with uniform particle size are prepared; the particle size is regulated and controlled by the size of the core and the mass ratio of tetraethoxysilane to carboxylated polystyrene microspheres, and the core-shell micron-sized monodisperse silica gel microspheres with the average particle size of more than 3 mu m and higher uniformity can be prepared.
Preferably, in the step (1), the weight ratio of the polystyrene microspheres to the acrylic monomers is (2-5): 2.
The inventor discovers that when the weight ratio of the polystyrene microspheres to the acrylic monomers is (2-5): 2, the acrylic monomers can be grafted on the surfaces of the polystyrene microspheres more uniformly, and the uniformity of the core-shell type micron-sized monodisperse silica gel microspheres is improved.
Preferably, in the step (1), the mass concentration of the polystyrene microspheres in the polystyrene microsphere dispersion liquid is 3-5%; the redox initiator comprises the following components in parts by weight: 3.5-4.5 parts of K2S2O81-2 parts of NaHSO3And 0.0006 to 0.0007 part of FeCl3The weight ratio of the redox initiator to the polystyrene microsphere dispersion liquid is (0.0165-0.165): 100.
preferably, the redox initiator comprises 4 parts of K2S2O81.5 parts of NaHSO3And 0.0006 to 0.0007 part of FeCl3。
Preferably, the preparation method of the tetraethoxysilane hydrolysate comprises the following steps: mixing tetraethoxysilane and water according to a weight ratio of 1: (9-10) mixing, and hydrolyzing at 45-55 ℃ for 2.5-3.5 hours.
Preferably, in the step (2), the mass concentration of the polyether dispersant in the carboxylated polystyrene microsphere dispersion is 0.25-0.35%, and the mass concentration of the carboxylated polystyrene microsphere in the carboxylated polystyrene microsphere dispersion is 0.25-3%.
Preferably, in the step (1), the acrylic monomer is at least one of methacrylic acid and acrylic acid.
The inventor finds that when the acrylic monomer is methacrylic acid or acrylic acid, in-situ hydrolytic polymerization of tetraethoxysilane on the surface of the monodisperse carboxylated polystyrene microsphere can be better realized, and the improvement of the uniformity of the core-shell micron-sized monodisperse silica gel microsphere is facilitated.
Preferably, in the step (1), the anaerobic condition is an inert gas atmosphere, swelling is carried out under the stirring condition of 100-300 RPM, and the swelling time is 3-5 h; and adding a redox initiator after swelling, and reacting for 20-24 hours under the stirring condition of 100-300 RPM.
Preferably, in the step (1), the product is washed by ethanol and deionized water in sequence;
in the step (2), the product is washed by ethanol and deionized water in sequence.
Preferably, in the step (2), the tetraethoxysilane hydrolysate and the carboxylated polystyrene microsphere dispersion liquid are mixed, and the mixture is stirred and reacted for 140 to 160 hours at the temperature of 50 to 60 ℃ and the stirring speed is 15 to 60 RPM.
The invention also provides the core-shell type micron-sized monodisperse silica gel microsphere prepared by the preparation method of any core-shell type micron-sized monodisperse silica gel microsphere, the average particle size of the core-shell type micron-sized monodisperse silica gel microsphere is 2.7-4.0 mu m, and the variation coefficient C of the core-shell type micron-sized monodisperse silica gel microspherevIs 0.018-0.042.
The invention has the beneficial effects that: the invention provides a core-shell micron-sized monodisperse silica gel microsphere and a preparation method thereof, the core-shell micron-sized monodisperse silica gel microsphere takes a polystyrene microsphere as a microsphere seed, and is mixed with an acrylic monomer for swelling polymerization, so that the acrylic monomer is grafted on the surface of the polystyrene microsphere to prepare the monodisperse carboxylated polystyrene microsphere; finally, taking the monodisperse carboxylated polystyrene microspheres as a core, and carrying out in-situ hydrolytic polymerization on the surface of the monodisperse carboxylated polystyrene microspheres by carboxyl on the core, namely hydrolytic polymerization on an acidic solid-liquid interface, so that the polymerization of tetraethoxysilane and hydrolysis products thereof in a water phase is reduced, and thus, the generation of over-small silicon dioxide particles in a system is avoided, and the core-shell structure silica gel microspheres with uniform particle size are prepared; the monodispersity of the prepared core-shell structure silica gel microspheres is determined by the uniformity of the adopted cores, the particle size is regulated and controlled by the size of the cores and the mass ratio of tetraethoxysilane to carboxylated polystyrene microspheres, and the core-shell structure micron-sized monodisperse silica gel microspheres with the average particle size of 3 mu m and higher uniformity can be prepared.
Drawings
FIG. 1 is a polarizing microscope photograph of polystyrene microspheres of examples 1-5 of the present invention;
FIG. 2 is a polarizing microscope photograph of core-shell type micron-sized monodisperse silica gel microspheres of example 1 of the present invention;
FIG. 3 is a polarizing microscope photograph of core-shell type micron-sized monodisperse silica gel microspheres of example 2 of the present invention;
FIG. 4 is a polarizing microscope photograph of core-shell type micron-sized monodisperse silica gel microspheres of example 3 of the present invention;
FIG. 5 is a polarizing microscope photograph of core-shell type micron-sized monodisperse silica gel microspheres of example 4 of the present invention;
FIG. 6 is a polarizing microscope photograph of core-shell type micron-sized monodisperse silica gel microspheres of example 5 of the present invention;
FIG. 7 is a polarizing microscope photograph of core-shell type micron-sized monodisperse silica gel microspheres of comparative example 1 of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the core-shell micron-sized monodisperse silica gel microspheres provided by the embodiment of the invention comprises the following steps:
(1) preparing polystyrene microspheres according to the method of the patent CN111019028A, obtaining the polystyrene microspheres with the average particle size of 2.2 mu m through particle size distribution detection, centrifuging, ultrasonically dispersing in deionized water, and preparing 3.8 wt% polystyrene microsphere dispersion liquid; adding 100g of the polystyrene microsphere dispersion and 3g of methacrylic acid into a reactor provided with a stirrer device, a nitrogen protection device and a temperature control device, and blowing nitrogen for 30minRemoving oxygen, and swelling at 25 deg.C for 5h under stirring at 300RPM in nitrogen atmosphere; adding K2S2O80.012g、NaHSO3 0.0045g、FeCl3·6H20.0033mg of O, and reacting for 20 hours at 25 ℃ under the stirring of 300 RPM; after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence, and air-drying at room temperature;
(2) hydrolyzing 0.99g of tetraethoxysilane and 9.01g of deionized water for 3 hours in advance at 50 ℃ under vigorous stirring to prepare hydrolysate of tetraethoxysilane; simultaneously dispersing 0.35g of carboxylated polystyrene microspheres in 35g of 0.3 wt% aqueous solution of polyether Pluronic P123 to prepare a carboxylated polystyrene microsphere dispersion, and heating to 50 ℃; then mixing the carboxylated polystyrene microsphere dispersion liquid with the prehydrolysis liquid of tetraethoxysilane, stirring at the speed of 30RPM, and reacting at the constant temperature of 55 ℃ for 100 hours; and after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence and drying to obtain the core-shell type micron-sized monodisperse silica gel microspheres.
FIG. 2 shows the measurement result of a polarizing microscope, and the average particle diameter was 3.0. mu.m, CvWas 0.0282.
Example 2
The preparation method of the core-shell micron-sized monodisperse silica gel microspheres provided by the embodiment of the invention comprises the following steps:
(1) preparing polystyrene microspheres according to the method of the patent CN111019028A, obtaining the polystyrene microspheres with the average particle size of 2.2 mu m through particle size distribution detection, centrifuging, ultrasonically dispersing in deionized water, and preparing 4 wt% polystyrene microsphere dispersion liquid; adding 100g of the polystyrene microsphere dispersion, 2g of methacrylic acid and 2g of acrylic acid into a reactor provided with a stirrer device, a nitrogen protection device and a temperature control device, blowing nitrogen for 30min to remove oxygen, and swelling for 4h at 25 ℃ under the stirring of 300RPM in the nitrogen atmosphere; adding K2S2O8 0.008g、NaHSO3 0.003g、FeCl3·6H2O0.0022 mg, stirring at 300RPM, reacting for 22h at 25 ℃; after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence, and air-drying at room temperature;
(2) hydrolyzing 0.99g of tetraethoxysilane and 9.01g of deionized water for 3 hours in advance at 50 ℃ under vigorous stirring to prepare hydrolysate of tetraethoxysilane; simultaneously dispersing 0.5g of carboxylated polystyrene microspheres in 35g of 0.4 wt% aqueous solution of polyether Pluronic P123 to prepare a carboxylated polystyrene microsphere dispersion, and heating to 50 ℃; then mixing the carboxylated polystyrene microsphere dispersion liquid with the prehydrolysis liquid of tetraethoxysilane, stirring at the speed of 30RPM, and reacting at the constant temperature of 55 ℃ for 140 hours; and after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence and drying to obtain the core-shell type micron-sized monodisperse silica gel microspheres.
FIG. 3 is a polarizing microscope photograph showing that the average particle diameter was 3.1 μm and C was measured by a polarizing microscopevWas 0.0282.
Example 3
The preparation method of the core-shell micron-sized monodisperse silica gel microspheres provided by the embodiment of the invention comprises the following steps:
(1) preparing polystyrene microspheres according to the method of the patent CN111019028A, obtaining the polystyrene microspheres with the average particle size of 2.2 mu m through particle size distribution detection, centrifuging, ultrasonically dispersing in deionized water, and preparing 5 wt% polystyrene microsphere dispersion liquid; adding 100g of the polystyrene microsphere dispersion, 4g of methacrylic acid and 1g of acrylic acid into a reactor provided with a stirrer device, a nitrogen protection device and a temperature control device, blowing nitrogen for 30min to remove oxygen, and swelling for 3.5h at 25 ℃ under the stirring of 300RPM in the nitrogen atmosphere; adding K2S2O8 0.012g、NaHSO3 0.0045g、FeCl3·6H20.0033mg of O, and reacting for 20 hours at 25 ℃ under the stirring of 300 RPM; after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence, and air-drying at room temperature;
(2) hydrolyzing 0.95g of tetraethoxysilane and 9.05g of deionized water for 3 hours in advance at 50 ℃ under vigorous stirring to prepare hydrolysate of tetraethoxysilane; simultaneously dispersing 0.1g of carboxylated polystyrene microspheres in 35g of 0.1 wt% aqueous solution of polyether Pluronic P123 to prepare a carboxylated polystyrene microsphere dispersion, and heating to 50 ℃; then mixing the carboxylated polystyrene microsphere dispersion liquid with the prehydrolysis liquid of tetraethoxysilane, stirring at the speed of 35RPM, and reacting at the constant temperature of 50 ℃ for 160 hours; and after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence and drying to obtain the core-shell type micron-sized monodisperse silica gel microspheres.
FIG. 4 is a polarizing microscope photograph showing that the average particle diameter measured by a polarizing microscope is 3.3. mu.m, CvIs 0.0186.
Example 4
The preparation method of the core-shell micron-sized monodisperse silica gel microspheres provided by the embodiment of the invention comprises the following steps:
(1) preparing polystyrene microspheres according to the method of the patent CN111019028A, obtaining the polystyrene microspheres with the average particle size of 2.2 mu m through particle size distribution detection, centrifuging, ultrasonically dispersing in deionized water, and preparing 3 wt% polystyrene microsphere dispersion liquid; adding 100g of the polystyrene microsphere dispersion and 2g of acrylic acid into a reactor provided with a stirrer device, a nitrogen protection device and a temperature control device, blowing nitrogen for 30min to remove oxygen, and swelling for 3h at 25 ℃ under the stirring of 150RPM in the nitrogen atmosphere; adding K2S2O8 0.012g、NaHSO3 0.0045g、FeCl3·6H2O0.0033 mg, and reacting for 24 hours at 25 ℃ under the stirring of 150 RPM; after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence, and air-drying at room temperature;
(2) hydrolyzing tetraethoxysilane 0.91g and deionized water 9.09g in advance for 3h at 50 ℃ under vigorous stirring to prepare hydrolysate of tetraethoxysilane; simultaneously dispersing 1.0g of carboxylated polystyrene microspheres in 35g of 0.1 wt% aqueous solution of polyether Pluronic P123 to prepare a carboxylated polystyrene microsphere dispersion, and heating to 50 ℃; then mixing the carboxylated polystyrene microsphere dispersion liquid with the prehydrolysis liquid of tetraethoxysilane, stirring at the speed of 15RPM, and reacting for 80 hours at the constant temperature of 50 ℃; and after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence and drying to obtain the core-shell type micron-sized monodisperse silica gel microspheres.
FIG. 5 is a polarizing microscope photograph showing that the average particle diameter was 2.7 μm and C was measured by a polarizing microscopevIs 0.0415.
Example 5
The preparation method of the core-shell micron-sized monodisperse silica gel microspheres provided by the embodiment of the invention comprises the following steps:
(1) preparing polystyrene microspheres according to the method of the patent CN111019028A, obtaining the polystyrene microspheres with the average particle size of 2.2 mu m through particle size distribution detection, centrifuging, ultrasonically dispersing in deionized water, and preparing 5 wt% polystyrene microsphere dispersion liquid; adding 100g of the polystyrene microsphere dispersion and 2g of acrylic acid into a reactor provided with a stirrer device, a nitrogen protection device and a temperature control device, blowing nitrogen for 30min to remove oxygen, and swelling for 3h at 25 ℃ under the stirring of 150RPM in the nitrogen atmosphere; adding K2S2O8 0.012g、NaHSO3 0.0045g、FeCl3·6H2O0.0033 mg, and reacting for 24 hours at 25 ℃ under the stirring of 150 RPM; after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence, and air-drying at room temperature;
(2) hydrolyzing 0.99g of tetraethoxysilane and 9.01g of deionized water for 3 hours in advance at 50 ℃ under vigorous stirring to prepare hydrolysate of tetraethoxysilane; simultaneously dispersing 0.35g of carboxylated polystyrene microspheres in 35g of 0.3 wt% aqueous solution of polyether Pluronic P123 to prepare a carboxylated polystyrene microsphere dispersion, and heating to 50 ℃; then mixing the carboxylated polystyrene microsphere dispersion liquid with the prehydrolysis liquid of tetraethoxysilane, stirring at the speed of 30RPM, and reacting at the constant temperature of 55 ℃ for 100 hours; and after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence and drying to obtain the core-shell type micron-sized monodisperse silica gel microspheres.
FIG. 6 is a polarizing microscope photograph showing that the average particle diameter was 4.0. mu.m, C, as measured by a polarizing microscopevIs 0.0199.
Comparative example 1
The preparation method of the core-shell micron-sized monodisperse silica gel microspheres as the comparative example of the invention comprises the following steps:
(1) preparing polystyrene microspheres according to the method of the patent CN111019028A, detecting the particle size distribution to obtain the polystyrene microspheres with the average particle size of 2.2 mu m, centrifuging and drying in vacuum;
(2) hydrolyzing 0.95g of tetraethoxysilane and 9.05g of deionized water for 3 hours in advance at 50 ℃ under vigorous stirring to prepare hydrolysate of tetraethoxysilane; simultaneously dispersing 0.1g of polystyrene microspheres in 35g of 0.1 wt% aqueous solution of polyether Pluronic P123 to prepare a polystyrene microsphere dispersion, and heating to 50 ℃; then mixing the polystyrene microsphere dispersion liquid with the prehydrolysis liquid of tetraethoxysilane, stirring at the speed of 35RPM, and reacting at the constant temperature of 50 ℃ for 160 hours; and after the reaction is finished, centrifugally washing the product by using ethanol and deionized water in sequence and drying to obtain the product.
FIG. 7 is a polarizing microscope photograph showing that the average particle diameter was 2.0. mu.m, C, as measured by a polarizing microscopevIs 0.1542. The particle size of the product is slightly smaller than that of the core polystyrene used, which is illustrated by comparison with the examples, as a result of the unhydrolyzed tetraethoxysilane being able to dissolve the polystyrene which has not been surface-modified. In addition, the product is in the form of polydisperse irregular spherical particles and simultaneously contains a large amount of agglomerates, because no carboxyl group is grafted on the polystyrene microsphere, tetraethoxysilane added into a reaction system is directly hydrolyzed and polymerized in a liquid phase, and a part of hydrolyzed polymerization product is adhered to the polystyrene microsphere, so that the microsphere is irregular in shape, and meanwhile, a large amount of amorphous silica gel is separated out from the liquid phase. The invention adopts carboxylated polystyrene as a core, and tetraethoxysilane can carry out in-situ hydrolytic polymerization on the surface of the core, so that the uniformity of silica gel coated on the surface of the microsphere is improved, and the probability of separating out the silica gel in a liquid phase is reduced, thereby improving the performance of the product.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of core-shell micron-sized monodisperse silica gel microspheres is characterized by comprising the following steps:
(1) mixing the polystyrene microsphere dispersion liquid with an acrylic monomer, swelling at 20-30 ℃ under an anaerobic condition, and reacting under initiation of a redox initiator; washing, air-drying and collecting the product carboxylated polystyrene microspheres; the particle size of the polystyrene microspheres in the polystyrene microsphere dispersion liquid is 2.0-2.5 microns;
(2) dispersing the carboxylated polystyrene microspheres in an aqueous solution containing a polyether nonionic dispersing agent to obtain a carboxylated polystyrene microsphere dispersion, mixing tetraethoxysilane hydrolysate with the carboxylated polystyrene microsphere dispersion, and reacting at 50-60 ℃ for 80-160 hours; washing and drying to obtain the core-shell type micron-sized monodisperse silica gel microspheres; the weight ratio of the tetraethoxysilane to the carboxylated polystyrene microspheres is 1: (0.1 to 1).
2. The method for preparing the core-shell micron-sized monodisperse silica gel microspheres according to claim 1, wherein in the step (1), the weight ratio of the polystyrene microspheres to the acrylic monomers is (2-5): 2.
3. The method for preparing the core-shell micron-sized monodisperse silica gel microsphere according to claim 2, wherein in the step (1), the mass concentration of the polystyrene microsphere in the polystyrene microsphere dispersion liquid is 3-5%; the redox initiator comprises the following components in parts by weight: 3.5-4.5 parts of K2S2O81-2 parts of NaHSO3And 0.0006 to 0.0007 part of FeCl3The weight ratio of the redox initiator to the polystyrene microsphere dispersion liquid is (0.0165-0.165): 100.
4. the method for preparing the core-shell type micron-sized monodisperse silica gel microspheres of claim 1, wherein the method for preparing the tetraethoxysilane hydrolysate comprises the following steps: mixing tetraethoxysilane and water according to a weight ratio of 1: (9-10) mixing, and hydrolyzing at 45-55 ℃ for 2.5-3.5 hours.
5. The method for preparing core-shell micron-sized monodisperse silica gel microspheres according to claim 1, wherein in the step (2), the mass concentration of the polyether dispersant in the carboxylated polystyrene microsphere dispersion is 0.25-0.35%, and the mass concentration of the carboxylated polystyrene microspheres in the carboxylated polystyrene microsphere dispersion is 0.25-3%.
6. The method for preparing core-shell micron-sized monodisperse silica gel microspheres according to claim 1, wherein in the step (1), the acrylic monomer is at least one of methacrylic acid and acrylic acid.
7. The method for preparing the core-shell micron-sized monodisperse silica gel microspheres according to claim 1, wherein in the step (1), the anaerobic condition is an inert gas atmosphere, and the core-shell micron-sized monodisperse silica gel microspheres are swelled under the stirring condition of 100-300 RPM, and the swelling time is 3-5 h; and adding a redox initiator after swelling, and reacting for 20-24 hours under the stirring condition of 100-300 RPM.
8. The method for preparing the core-shell type micron-sized monodisperse silica gel microsphere of claim 1, wherein in the step (1), the product is washed with ethanol and deionized water in sequence;
in the step (2), the product is washed by ethanol and deionized water in sequence.
9. The method for preparing core-shell micron-sized monodisperse silica gel microspheres according to claim 1, wherein in the step (2), the tetraethoxysilane hydrolysate and the carboxylated polystyrene microsphere dispersion are mixed, and the mixture is stirred and reacted at 50-60 ℃ for 140-160 hours, wherein the stirring speed is 15-60 RPM.
10. Core-shell micron monodisperse silica gel microspheres prepared by the method of any one of claims 1 to 9, wherein the core-shell micron monodisperse silica gel microspheres are prepared by the method of any one of claims 1 to 9The average particle size of the microspheres is 2.7-4.0 mu m, and the variation coefficient C of the core-shell type micron-sized monodisperse silica gel microspheresvIs 0.018-0.042.
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