CN109985584B - Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres - Google Patents
Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres Download PDFInfo
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Abstract
The invention relates to a preparation method of adjustable strawberry-shaped silicon dioxide-organic hybrid composite microspheres. The method comprises the following steps: mixing silicon dioxide nano particles, an organic solvent and deionized water, and then carrying out ultrasonic dispersion to obtain a mixed solution; dropwise adding the monomer into the reaction system, heating to 50-80 ℃, and dropwise adding an initiator aqueous solution into the reaction system; and naturally cooling the system to 20-30 ℃ after the reaction, and washing the reaction product by using absolute ethyl alcohol to obtain the strawberry-shaped hybrid composite microspheres. The invention expands the method for preparing the strawberry-shaped particles, obtains the strawberry-shaped hybrid composite microspheres with inorganic particle silicon dioxide as a core and organic polymer as surface convex particles, does not need to carry out surface modification on the silicon dioxide core particles, and has simple and easy preparation method.
Description
Technical Field
The technical scheme of the invention relates to the field of inorganic, organic and high polymer materials, in particular to a preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres.
Background
Anisotropic particles (asymmetric or anistropic particles, or Janus particles) refer to particles that are asymmetric in shape/chemical composition and are not uniformly distributed. With the development and deep research of science and technology, people successfully prepare acorn-shaped, strawberry-shaped, snowman-shaped, pudding-shaped and other hybrid composite microspheres. Wherein the strawberry-Like hybrid composite microspheres are classified into strawberry-Like organic-inorganic hybrid composite microspheres (Wang R K, Liu H R, Wang F W. facility Preparation of strawberry-Like Superhydrophilic Polystyrene Particles: selected Dispersion Polymerization [ J ]. Langmuir,2013,29(36): 11440. 11448.), strawberry-Like organic-organic hybrid composite microspheres (Wang L, Pan M, Song S, et al. internal Morphology Polymerization from Non-crosslinked polymer (tert-butyl acrylate) selected phase Polymerization with particulate filtration Polymerization group, slurry Polymerization with inorganic microspheres [ J ]. Langmuir, St. synthetic microspheres (2016, 7832, 2016. 7831. hybrid microspheres, S, of strawberry-inorganic hybrid microspheres (of strawberry-inorganic hybrid microspheres of strawberry synthesis resin: S. J.), 2002,14(5): 2354-. The Strawberry-Like Hybrid composite microspheres have excellent properties of large specific surface area, high surface roughness, good light scattering property and phase-separated structure, and are used in Catalysis (Kim M, Heo E, Kim A, et al. Synthesis of Pd/SiO2Nanobeads for Use in Suzuki Coupling Reactions by Reverse Micelle Sol-gel Processes [ J ]. Catalysis Letters,2012,142(5):588-593.), templates (Qia Y, Xiao M, Katja L. purification of Nano-Sized Hybrid ceramics, Particles of library-library Composites [ J ]. Macromolecular Chemistry and Chemistry, 2018:1800267), Self-Assembly (Hong Chemistry, J. random fiber-library of molecular Chemistry, Journal of Chemistry [ W ]. 19940, Journal of molecular Chemistry [ J ]. 76, Journal of molecular Chemistry, Journal of chemical Chemistry, and chemical Chemistry [ 76, Journal of molecular Chemistry, Journal of chemical Chemistry, Journal of molecular Chemistry, Journal of chemical analysis [ J ] (76, Journal of molecular analysis, Journal of chemical analysis [ 10, Journal of chemical analysis, H, Journal of chemical analysis, molecular analysis, and analysis [ 10, Journal of chemical analysis, Journal of chemical, S, S., The coating (Keonyun H, Young dust Glass Coated with Fluorinated-Silica Nanoparticles [ J ]. Materials Letters,2018,229:213-216.) and other fields have wide application.
The current preparation method of the strawberry-shaped hybrid composite particles comprises the following steps: polymerization (Xiao T Z, Yang Y S, Yi J M, et al. controllable Synthesis of Raspberry-Like PS-SiO)2Nanocomposite Particles via Pickering Emulsion Polymerization[J]RSC Advances,2018,8(7):3910-].ACS Applied Materials&Interfaces,2014,6(4):2629-r@Silica Hybrid Colloidal Particles through Biphasic Sol-gel Process[J]Gels and Surfaces A: physical and Engineering assays, 2018,553:230-]Colloid and Polymer Science,2016,294(7): 1117-1128), and the like. Although the above method can synthesize strawberry-like particles, the synthesis method is complicated and the steps are complicated.
Disclosure of Invention
The invention aims to provide a preparation method of novel strawberry-shaped silicon dioxide-organic hybrid composite microspheres aiming at the defects in the prior art. According to the method, the proportion of the organic solvent to the deionized water and the proportion of the silicon dioxide seed particles to the organic monomers are proper, so that the organic monomers are prevented from being stabilized by using an emulsifier, the step of performing surface modification on the silicon dioxide particles in advance is omitted, and the strawberry-shaped silicon dioxide-organic matter hybrid composite microspheres with complete coatings are finally prepared. The invention expands the method for preparing the strawberry-shaped particles, obtains the strawberry-shaped hybrid composite microspheres with inorganic particle silicon dioxide as a core and organic polymer as surface convex particles, does not need to carry out surface modification on the silicon dioxide core particles, and has simple and easy preparation method.
The technical scheme of the invention is as follows:
a preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres comprises the following steps:
(1) mixing the silicon dioxide nano particles, the organic solvent and the deionized water, and then carrying out ultrasonic dispersion to obtain a mixed solution; wherein the mass ratio of the silica nanoparticles: organic solvent: deionized water is 1: 35-90: 110-180;
(2) introducing inert gas while stirring the mixed solution, and keeping for 30-60 minutes; then dropwise adding the monomer into the reaction system within 1-10 min, and heating to 50-80 ℃, wherein the mass ratio of the silicon dioxide nanoparticles: monomer 10: 12 to 49;
(3) dropwise adding an initiator aqueous solution into the reaction system within 2-10 min, and keeping for 2-8 hours, wherein the mass of the initiator is 0.1-10% of that of the polymerized monomer; the concentration of the initiator aqueous solution is 0.5 to 3 percent;
(4) naturally cooling the reaction system to 20-30 ℃, and washing the reaction product by using absolute ethyl alcohol to obtain the strawberry-shaped hybrid composite microspheres.
The inert gas in the step (2) is argon or nitrogen.
The particle size range of the silicon dioxide nano particles is 80-1200 nm.
The organic solvent is one of methanol, ethanol, n-propanol, isopropanol, glycerol, 1, 4-butanediol, ethylene glycol and polyethylene glycol 200.
The ultrasonic power of the ultrasonic treatment in the step (1) is 100W, and the ultrasonic treatment time is 30-60 minutes.
The monomer is one of styrene, 4-fluorostyrene, aminostyrene, p-chloromethyl styrene or p-hydroxystyrene.
The initiator is at least one of potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, sodium sulfite, sodium bisulfite and ferrous sulfate.
The invention has the substantive characteristics that:
the polymerization method of the invention is seed soap-free emulsion polymerization, does not need an emulsifier to stabilize organic monomers, and omits the step of surface modification of silicon dioxide particles in advance. Compared with the prior subject group patent 'strawberry-shaped organic/inorganic hybrid microspheres and application thereof' (CN106433406A), the invention takes inorganic particles as core particles, and organic polymers are coated on the inorganic particles. Compared with articles and patents published by other people, the strawberry-shaped hybrid composite microspheres which take inorganic silicon dioxide as core particles and organic matter coats the inorganic silicon dioxide are prepared, an emulsifier is not needed in the whole preparation process, the surface modification of the silicon dioxide particles is not needed in advance, the mixed solution of an organic solvent and deionized water is used as the solvent instead of the deionized water used as the solvent in the traditional method, and the preparation method is simple.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of an adjustable strawberry-shaped silicon dioxide-organic hybrid composite microsphere, which takes inorganic silicon dioxide nano particles as core particles, and grows organic polymers on the silicon dioxide particles by a seed soap-free emulsion polymerization method to finally obtain the strawberry-shaped silicon dioxide-organic hybrid composite microsphere. Compared with the traditional method for preparing the strawberry-shaped silicon dioxide-organic hybrid composite microspheres, the method has the advantages that the surface treatment of the silicon dioxide nanoparticles in advance is not needed in the whole preparation process, and the preparation method is simple.
(2) The preparation method provided by the invention has large compatibility with the types of organic polymers, and is suitable for various organic polymer monomers, such as the strawberry-shaped silica-polystyrene hybrid composite microspheres prepared by using the styrene organic monomers in example 2, and the strawberry-shaped silica-poly 4-fluorophenylene hybrid composite microspheres prepared by using the 4-fluorophenylene organic monomers in example 3.
(3) The solvent used in the preparation method provided by the invention is a mixed solution of an organic solvent and deionized water, and the strawberry-shaped hybrid composite microspheres are prepared according to the proper proportion of the organic solvent and the deionized water, for example, the strawberry-shaped silica-polystyrene hybrid composite microspheres are prepared from the mixed solution of absolute ethyl alcohol and deionized water in the embodiment 2, wherein the proportion of the absolute ethyl alcohol to the deionized water is 3: 7; in example 4, a mixed solvent of absolute methanol and deionized water is used to prepare a strawberry-shaped silica-polystyrene hybrid composite microsphere, wherein the ratio of the absolute methanol to the deionized water is 2: 8. Compared with the traditional preparation method which mostly uses deionized water as a solvent and needs to add an emulsifier to stabilize the organic monomer, the preparation method provided by the invention is novel and feasible.
Description of the drawings:
FIG. 1: a preparation flow chart of the strawberry-shaped silicon dioxide-organic matter hybrid composite microspheres;
FIG. 2: SEM photograph of silica nanoparticles having a particle size of 400nm in example 1;
FIG. 3: in example 1, an SEM photograph of silica-polystyrene was prepared using absolute ethanol and deionized water as solvents, and 200 μ l of organic monomer styrene was used;
FIG. 4: in example 2, an SEM photograph of silica-polystyrene was prepared using absolute ethanol and deionized water as solvents, and an organic monomer styrene at 400 μ l;
FIG. 5: in example 3, an SEM photograph of silica-poly-4-fluorostyrene was prepared using anhydrous ethanol and deionized water as solvents and 400 μ l of organic monomer 4-fluorostyrene;
FIG. 6: in example 4, an SEM photograph of silica-polystyrene was prepared using anhydrous methanol and deionized water as solvents and an organic monomer styrene at 400 μ l;
detailed description of the preferred embodiments
The flow chart of the method of the invention is shown in the attached figure 1. Selecting silicon dioxide as core particles, dispersing the silicon dioxide in a mixed solution of an organic solvent and deionized water, adding different reaction monomers and initiators, and directly obtaining the strawberry-shaped silicon dioxide-organic hybrid composite microspheres through seed soap-free emulsion polymerization. The technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiment of the present invention.
The silicon dioxide nano particles related to the invention are all known materials, and one of the following methods is adopted according to the requirements:
the method comprises the following steps: preparing the silicon dioxide nano particles with the average particle size range of 80-600 nm:
according to patent CN101691426A
the-Fink-Hohn synthesis method comprises the steps of sequentially adding absolute ethyl alcohol, ammonia water and distilled water into a three-neck flask, uniformly stirring, and quickly adding ethyl orthosilicate, wherein the mass ratio of the absolute ethyl alcohol to the ammonia water is as follows: anhydrous ethanol: distilled water: reacting ethyl orthosilicate at the ratio of 1: 1-60: 1-5: 0.2-10 at room temperature for 8 hours, transferring the obtained suspension into a beaker, and naturally volatilizing the solvent completely to obtain the final productAnd grinding the silicon dioxide colloid crystal template with the average particle size of 80-600 nm by using a mortar to obtain the silicon dioxide nano particles.
The second method comprises the following steps: preparing the silicon dioxide nano particles with the average particle size range of 600-1200 nm:
according to patent CN101691426A, in a reaction system for preparing silica nanoparticles with an average particle size within a range of 80-600 nm, after ethyl orthosilicate is completely hydrolyzed, adding ammonia water, absolute ethyl alcohol, distilled water and ethyl orthosilicate in the same mass ratio again, repeating for 1-4 times, after ethyl orthosilicate is completely hydrolyzed, removing turbid liquid and standing, after a solvent is completely naturally volatilized, obtaining a silica colloid crystal template with an average particle size within a range of 600-1200 nm, and grinding the template by using a mortar to obtain the silica nanoparticles.
Example 1: strawberry-shaped silicon dioxide-polystyrene hybrid composite microspheres with absolute ethyl alcohol and deionized water as solvents
(1) Preparation of 400nm silica particles
According to patent CN101691426A
the-Fink-Hohn synthesis method comprises the steps of sequentially adding 140g of absolute ethyl alcohol, 30g of ammonia water with the mass fraction of 25% and 30.5g of distilled water into a 500mL three-necked flask with electric stirring at room temperature, rapidly adding 20.6g of ethyl orthosilicate into the three-necked flask after uniformly stirring, and reacting for 8 hours at room temperature. And transferring the obtained suspension into a beaker, obtaining a silica colloid crystal template with the average particle size of 400nm after the solvent is completely volatilized naturally, and grinding the template in a mortar to obtain the silica nano particles.
FIG. 2 is a photograph obtained by scanning 400nm silica particles with a FEI Nano SEM 450 electron scanning microscope, and it can be seen that the prepared silica particles are uniform in size.
(2) Synthesis of strawberry-like hybrid composite microspheres
Taking 0.15g of the dried silica nanoparticles obtained in the step (1), adding 10.2mL of absolute ethyl alcohol and 23.8mL of deionized water into a four-mouth bottle, placing the four-mouth bottle into an ultrasonic cleaning instrument, carrying out ultrasonic treatment for 1h under the power of 100W, transferring a reaction system into an oil bath kettle with mechanical stirring, stirring at the rotating speed of 300rpm, introducing argon for 30min, adding 200 microliter (0.1818 g) of styrene monomer (St) at the speed of one drop per 3 seconds, heating to 70 ℃, adding 2mL of potassium persulfate (KPS) aqueous solution with the mass fraction of 1% at the speed of one drop per 3 seconds, reacting for 7h, naturally cooling to 20-30 ℃ after the reaction is stopped, centrifuging at 6000rpm, and washing for 2 times by using absolute ethyl alcohol to obtain the strawberry-shaped silica-polystyrene hybrid composite microspheres.
FIG. 3 is a photograph obtained by scanning a strawberry-shaped silica-polystyrene hybrid composite microsphere by using an electron scanning electron microscope with a model number of FEI Nano SEM 450, and it can be seen that the uniformly coated strawberry-shaped silica-polystyrene hybrid composite microsphere is obtained.
Example 2: strawberry-shaped silicon dioxide-polystyrene hybrid composite microspheres with absolute ethyl alcohol and deionized water as solvents
(1) The preparation of 400nm silica nanoparticles was performed as in step (1) of example one;
(2) taking 0.15g of dried silicon dioxide nano particles obtained in the step (1), adding 10.2mL of absolute ethyl alcohol and 23.8mL of deionized water into a four-mouth bottle, placing the four-mouth bottle into an ultrasonic cleaning instrument, carrying out ultrasonic treatment for 1h under the power of 100W, transferring a reaction system into an oil bath kettle with mechanical stirring, stirring at the rotating speed of 300rpm, introducing argon for 30min, adding 400 microliter (0.3636 g) of styrene monomer at the speed of one drop per 3 seconds, heating to 70 ℃, adding 2mL of potassium persulfate (KPS) aqueous solution with the mass fraction of 1% at the speed of one drop per 3 seconds, reacting for 7h, naturally cooling to 20-30 ℃ after the reaction is stopped, centrifuging at 6000rpm, and washing for 2 times by using absolute ethyl alcohol to obtain the strawberry-shaped silicon dioxide-polystyrene hybrid composite microspheres.
Fig. 4 is a photograph obtained by scanning a strawberry-shaped silica-polystyrene hybrid composite microsphere by using an electronic scanning electron microscope with a type FEI Nano SEM 450, and it can be seen from the figure that the completely coated strawberry-shaped silica-polystyrene hybrid composite microsphere is obtained.
Example 3: preparing strawberry-shaped silicon dioxide-poly 4-fluorostyrene hybrid composite microspheres (1) by using absolute ethyl alcohol and deionized water as solvents, wherein the preparation of 400nm silicon dioxide nano particles is the same as the step (1) in the first embodiment;
(2) taking 0.15g of the dried silica nanoparticles obtained in the step (1), adding 10.2mL of absolute ethyl alcohol and 23.8mL of deionized water into a four-mouth bottle, placing the four-mouth bottle into an ultrasonic cleaning instrument, carrying out ultrasonic treatment for 1h under the power of 100W, transferring a reaction system into an oil bath kettle with mechanical stirring, stirring at the rotating speed of 300rpm, introducing argon for 30min, adding 400 microliter (namely 0.4096g) of 4-fluorostyrene monomer at the speed of one drop per 3 seconds, heating to 70 ℃, adding 2mL of potassium persulfate (KPS) aqueous solution with the mass fraction of 1% at the speed of one drop per 3 seconds for reaction for 7h, naturally cooling to 20-30 ℃ after the reaction is stopped, centrifuging at 6000rpm, and washing for 2 times by using absolute ethyl alcohol to obtain the strawberry-shaped silica-poly 4-fluorostyrene hybrid composite microspheres.
Fig. 5 is a photograph obtained by scanning a strawberry-shaped silica-poly-4-fluorostyrene hybrid composite microsphere by using an electronic scanning electron microscope with a type FEI Nano SEM 450, and it can be seen from the figure that the completely coated strawberry-shaped hybrid composite microsphere is obtained.
Example 4: strawberry-shaped silicon dioxide-polystyrene hybrid composite microspheres with anhydrous methanol and deionized water as solvents
(1) The preparation of 400nm silica nanoparticles was performed as in step (1) of example one;
(2) taking 0.15g of the dried silica nanoparticles obtained in the step (1) into a four-mouth bottle, adding 6.8mL of anhydrous methanol and 27.2mL of deionized water, placing the four-mouth bottle in an ultrasonic cleaning instrument, ultrasonic treatment is carried out for 1h under the power of 100W, the reaction system is transferred into an oil bath pot with mechanical stirring to be stirred, the rotating speed is 300rpm, argon is introduced for 30min, 400. mu.L (0.3636 g) of styrene monomer was added at a rate of one drop per 3 seconds and 1mL of an aqueous solution of potassium persulfate (KPS) having a mass fraction of 2% was added at a rate of one drop per 3 seconds, and after the temperature was raised to 50 ℃, adding 1mL of sodium bisulfite aqueous solution with the mass fraction of 1% at the speed of one drop per 3 seconds for reaction for 7 hours, naturally cooling to 20-30 ℃ after the reaction is stopped, centrifuging at 6000rpm and washing with absolute ethanol for 2 times to obtain the strawberry-shaped silicon dioxide-polystyrene hybrid composite microspheres.
FIG. 6 is a photograph obtained by scanning strawberry-shaped silica-polystyrene hybrid composite microspheres by using an electron scanning electron microscope with a model number of FEI Nano SEM 450, and it can be seen that the completely coated strawberry-shaped hybrid composite microspheres are obtained.
The invention is not the best known technology.
Claims (6)
1. A preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres is characterized by comprising the following steps:
(1) mixing the silicon dioxide nano particles, the organic solvent and the deionized water, and then carrying out ultrasonic dispersion to obtain a mixed solution; wherein the mass ratio of the silica nanoparticles: organic solvent: deionized water is 1: 35-90: 110-180;
(2) introducing inert gas while stirring the mixed solution, and keeping for 30-60 minutes; then dropwise adding the monomer into the reaction system within 1-10 min, and heating to 50-80 ℃, wherein the mass ratio of the silicon dioxide nanoparticles: monomer 10: 12 to 49;
(3) dropwise adding an initiator aqueous solution into the reaction system within 2-10 min, and keeping for 2-8 hours, wherein the mass of the initiator is 0.1-10% of that of the polymerized monomer; the concentration of the initiator aqueous solution is 0.5 to 3 percent;
(4) naturally cooling the reaction system to 20-30 ℃, and washing the reaction product by using absolute ethyl alcohol to obtain the strawberry-shaped hybrid composite microspheres;
the organic solvent is one of methanol, ethanol, n-propanol, isopropanol, glycerol, 1, 4-butanediol, ethylene glycol and polyethylene glycol 200.
2. The method for preparing controllable strawberry-shaped silica-organic hybrid composite microspheres according to claim 1, wherein the inert gas in the step (2) is argon or nitrogen.
3. The method for preparing adjustable strawberry-shaped silica-organic hybrid composite microspheres according to claim 1, wherein the particle size of the silica nanoparticles is 80-1200 nm.
4. The method for preparing adjustable strawberry-shaped silica-organic hybrid composite microspheres according to claim 1, wherein the ultrasonic power of the ultrasonic treatment in the step (1) is 100W, and the ultrasonic treatment time is 30-60 minutes.
5. The method of claim 1, wherein the monomer is one of styrene, 4-fluoro styrene, aminostyrene, p-chlorostyrene, and p-hydroxystyrene.
6. The method of claim 1, wherein the initiator is at least one of potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, sodium sulfite, sodium bisulfite and ferrous sulfate.
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| CN111850722B (en) * | 2020-07-16 | 2021-08-13 | 浙江理工大学 | Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber |
| CN113633779A (en) * | 2021-08-13 | 2021-11-12 | 吉纳迪(青岛)生物有限公司 | Gene delivery vector based on surface burr structure nano particle and preparation method thereof |
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| "Preparation of Colloid Microspheres of SiO2/Polystyrene without a Coupling Agent via Soapfree Emulsion Polymerization";Jin-qing CHEN et al.;《2011 International Conference on Consumer Electronics, Communications and Networks》;20111231;第5126页右栏倒数第2段-第5127页左栏第2段，第5127页右栏倒数第1段，图3 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023055991A1 (en) * | 2021-10-01 | 2023-04-06 | Pnp Research Llc | Optical background suppression in binding assays that employ polymeric microspheres |
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