CN116119674A - Method for preparing silicon dioxide hollow microspheres by hard template method - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000004005 microsphere Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 46
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000000725 suspension Substances 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000006124 Pilkington process Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000004793 Polystyrene Substances 0.000 claims description 22
- 229920002223 polystyrene Polymers 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 9
- 238000005199 ultracentrifugation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- UJGIYHXRNBCGRE-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)[Na] Chemical compound C(CCCCCCCCCCCCCCC)[Na] UJGIYHXRNBCGRE-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to the technical field of inorganic nonmetallic materials, in particular to a method for preparing silicon dioxide hollow microspheres by adopting a hard template method; mixing the hollow silica microsphere with mesoporous surface with surfactant in solvent and dispersing to obtain suspension, adding ammonia water, stirring to react for 0.1-1 hr, adding silicon source, stirring to react continuously until suspension is obtained, separating, drying, sintering the obtained product at 800-1200 deg.c by flame float process to obtain hollow silica microsphere without mesoporous; the hollow silica microsphere prepared by the method has no mesoporous, compact structure and high strength.
Description
Technical Field
The invention relates to the technical field of inorganic nonmetallic materials, in particular to a method for preparing silica hollow microspheres by adopting a hard template method.
Background
The hollow silica microsphere is a novel inorganic material, has the size between nanometer and micrometer, has a hollow cavity, large specific surface area, narrow particle size distribution range, good dispersibility, good stability and high melting point, has special physical properties such as mechanics, light, electricity and the like, and has wide development prospect in the directions of biochemical industry, medicine, optics, catalysis, composite materials and the like.
The hard template method is the most effective method for synthesizing the silica hollow microsphere with stable size and morphology at present, and has the advantages of simple required equipment, simple and convenient process and controllable various process parameters. However, in the existing hard template method, in the process of preparing the silica hollow microspheres, a plurality of tiny mesopores are easily formed on the walls of the microspheres, so that the hollow silica particles are not compact, the surface strength is insufficient, the whole structure is unstable, and the application of the silica hollow microspheres in a plurality of high-end precision equipment is limited. For example, in a semiconductor electronic packaging system such as a PCB carrying electronic components, a packaging substrate, an underfill, etc., it is difficult for mesoporous silica hollow microspheres to meet the low dielectric constant and low loss requirements required by the material.
Disclosure of Invention
The invention aims to provide a method for preparing a silicon dioxide hollow microsphere by adopting a hard template method, and the prepared silicon dioxide hollow microsphere has no mesoporous, compact structure and high strength.
The technical scheme adopted by the invention is as follows: a process for preparing hollow silicon dioxide microballoons by hard template method includes such steps as mixing the hollow silicon dioxide microballoons with mesoporous surface with surfactant in solvent, dispersing to obtain suspension, adding ammonia water, stirring for 0.1-1 hr, adding Si source, stirring for reacting until obtain suspension, separating, drying, and sintering at 800-1000 deg.C by flame float method.
Preferably, the method for obtaining the hollow silica microspheres with mesoporous surfaces comprises the following steps:
(1) Adding a mixed solution of azodiisobutyronitrile and styrene into an absolute ethanol solution containing polyvinylpyrrolidone in a nitrogen atmosphere at 60-80 ℃, continuously stirring and reacting for 20-30h, centrifuging, repeatedly cleaning a sediment at the lower layer by using absolute ethanol, and drying to obtain submicron-sized polystyrene microspheres;
(2) Mixing polystyrene microsphere and surfactant in solvent and dispersing to obtain suspension, adding ammonia water, stirring to react for 0.1-1 hr, adding ethyl orthosilicate, stirring to react continuously until suspension is obtained, separating, drying, heating to remove polystyrene, and obtaining mesoporous silica hollow microsphere.
Preferably, the surfactant is one of hexadecyl trimethyl ammonium bromide, hexadecyl sodium sulfonate, hexadecyl trimethyl ammonium chloride, sodium stearate, sodium oleate, sodium p-dodecyl benzene sulfonate, laureth and dodecyl ammonium chloride.
Preferably, the silicon source is one of tetraethoxysilane, metaethoxysilane and polyethylsilicate.
Preferably, the adding ratio of the silicon dioxide hollow microspheres to the surfactant to the ammonia water to the silicon source is 1-5:0.5-2:15-30:1-2 (wt/wt/vt/vt), preferably in a ratio of 3:1:20:1 (wt/wt/vt/vt).
Preferably, the concentration of the absolute ethanol solution containing polyvinylpyrrolidone in step (1) is 0.1 to 1wt%, preferably 0.1 to 0.2wt%, more preferably 0.17wt%.
Preferably, the concentration of the mixed solution of azobisisobutyronitrile and styrene in the step (1) is 15 to 30wt%, preferably 20wt%.
Preferably, in the step (2), the adding ratio of the polystyrene microsphere, the surfactant, the ammonia water and the tetraethoxysilane is 1-3:0.5-2:15-30:1-2 (wt/wt/vt/vt), preferably in a ratio of 1.5:1:20:1 (wt/wt/vt/vt).
Preferably, the solvent is 30-90vt% ethanol water solution.
The term "flame float process" is used herein as a forming process known in the art (hollow glass microspheres).
The invention has the beneficial effects that: the method for preparing the silicon dioxide hollow microsphere by adopting a hard template method is characterized in that submicron polystyrene spheres are used as templates, hexadecyl trimethyl ammonium bromide is used as a cationic surfactant, and tetraethoxysilane is used as a silicon source to synthesize the silicon dioxide hollow microsphere. The product has no mesoporous, submicron particle size, stable size, high compactness and low dielectric constant. In addition, the prepared silicon dioxide micro-hollow spheres have high compressive strength, and can keep complete morphology after processing technologies such as ultrasonic processing, stirring processing, ball milling processing and the like under the condition of being processed as composite material fillers, and the conditions such as crushing, cracking and the like can not occur.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of hollow silica microspheres prepared according to example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of hollow silica microspheres prepared according to example 2 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of hollow silica microspheres prepared according to example 3 of the invention.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
(1) 200ml of 0.17wt% absolute ethanol of polyvinylpyrrolidone was added to a three-necked flask, after mixing uniformly, nitrogen was introduced for 0.5h, the oxygen was evacuated, the temperature was raised to 70 ℃, and 15ml of a 20wt% mixed solution of azobisisobutyronitrile and styrene was slowly added. Continuously stirring for 24 hours under nitrogen atmosphere, putting the obtained reaction liquid into a centrifugal machine for ultracentrifugation, removing supernatant, washing lower sediment with absolute ethyl alcohol, repeating the centrifugation step for 5 times, and putting the obtained centrifugal product into a vacuum drying machine at 70 ℃ for 24 hours to obtain submicron-sized polystyrene microspheres;
(2) Weighing 0.15g of the submicron-sized polystyrene microsphere, adding the submicron-sized polystyrene microsphere and 0.1g of hexadecyl trimethyl ammonium bromide into a mixed solution of water (160 ml)/ethanol (80 ml), performing ultrasonic dispersion for 30min to obtain a uniformly dispersed suspension, adding 2ml of ammonia water, stirring for 30min, dropwise adding 0.1ml of tetraethoxysilane at a certain stirring speed, continuously stirring for reacting for 20h, putting the obtained reaction solution into a centrifuge for ultracentrifugation, removing supernatant, respectively cleaning three times by using high-purity water and ethanol, and drying for 12h at 120 ℃; placing the dried polystyrene and silicon dioxide core-shell structure sample into a box furnace, heating to 100 ℃, preserving heat for 4 hours, then heating to 500 ℃, preserving heat for 2 hours, and removing a polystyrene template to obtain the mesoporous silicon dioxide hollow microsphere;
(3) Weighing 0.15g of mesoporous silica hollow microspheres, adding 0.05g of hexadecyl trimethyl ammonium bromide into a mixed solution of water (160 ml)/ethanol (80 ml), performing ultrasonic dispersion for 30min to obtain a uniformly dispersed suspension, and adding 2ml of ammonia water and stirring for 30min; dropwise adding 0.1ml of ethyl orthosilicate at a stirring speed of 60r/min, continuously stirring for reacting for 20h, placing the obtained suspension into a centrifuge for ultracentrifugation, removing supernatant, respectively cleaning with high-purity water and ethanol for three times, and drying at 120 ℃ for 12h in an oven; carrying out secondary sintering reinforcement on the obtained dried product by a flame floatation method at 1150 ℃, wherein the sintering molding temperature by the flame floatation method is 1000 ℃, the feeding speed is 30g/min, the feeding wind speed is 4m/s, and the induced wind speed is 5m/s; obtaining the mesoporous-free silica hollow microsphere.
FIG. 1 is a Scanning Electron Microscope (SEM) image of hollow silica microspheres prepared according to example 1 of the present invention. As can be seen from FIG. 1, the hollow silica microspheres have a uniform particle size and an average density of 0.62g/cm 3 。
Other performance tests were performed on the product with the following results: the dielectric constant is 1.69 (tested at 10 GHz), and the volume breakage rate is less than or equal to 5% under 170 MPa.
Example 2
(1) 200ml of 0.17wt% absolute ethanol of polyvinylpyrrolidone was added to a three-necked flask, after mixing uniformly, nitrogen was introduced for 0.5h, the oxygen was evacuated, the temperature was raised to 70 ℃, and 15ml of a 20wt% mixed solution of azobisisobutyronitrile and styrene was slowly added. Continuously stirring for 24 hours under nitrogen atmosphere, putting the obtained reaction liquid into a centrifugal machine for ultracentrifugation, removing supernatant, washing lower sediment with absolute ethyl alcohol, repeating the centrifugation step for 5 times, and putting the obtained centrifugal product into a vacuum drying machine at 70 ℃ for 24 hours to obtain submicron-sized polystyrene microspheres;
(2) Weighing 0.15g of the submicron-sized polystyrene microsphere, adding the submicron-sized polystyrene microsphere and 0.15g of hexadecyl trimethyl ammonium bromide into a mixed solution of water (160 ml)/ethanol (80 ml), performing ultrasonic dispersion for 30min to obtain a uniformly dispersed suspension, adding 4ml of ammonia water, stirring for 30min, dropwise adding 0.15ml of tetraethoxysilane at a certain stirring speed, continuously stirring for reacting for 20h, putting the obtained reaction solution into a centrifuge for ultracentrifugation, removing supernatant, respectively cleaning three times by using high-purity water and ethanol, and drying for 12h at 120 ℃; performing secondary sintering reinforcement on the obtained dried product by a flame floatation method at 900 ℃ to obtain mesoporous silica hollow microspheres;
(3) Weighing 0.15g of mesoporous silica hollow microspheres, adding 0.05g of hexadecyl trimethyl ammonium bromide into a mixed solution of water (160 ml)/ethanol (80 ml), performing ultrasonic dispersion for 30min to obtain a uniformly dispersed suspension, and adding 2ml of ammonia water and stirring for 30min; dropwise adding 0.1ml of ethyl orthosilicate at a stirring speed of 60r/min, continuously stirring for reacting for 20h, placing the obtained suspension into a centrifuge for ultracentrifugation, removing supernatant, respectively cleaning with high-purity water and ethanol for three times, and drying at 120 ℃ for 12h in an oven; and (3) carrying out secondary sintering strengthening on the obtained dried product by a flame floatation method at 1150 ℃, wherein the molding temperature of the sintering by the flame floatation method is 1150 ℃, the feeding speed is 30g/min, the feeding speed is 4m/s, and the induced air speed is 5m/s, so as to obtain the mesoporous-free silica hollow microsphere.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the hollow silica microspheres prepared according to example 2 of the present invention. As can be seen from FIG. 2, the hollow silica microspheres have a uniform particle size and an average density of 0.68g/cm 3 。
Other performance tests were performed on the product with the following results: the dielectric constant is 1.76 (tested at 10 GHz), and the volume breakage rate is less than or equal to 5% under 190 MPa.
Example 3
(1) 200ml of 0.17wt% absolute ethanol of polyvinylpyrrolidone was added to a three-necked flask, after mixing uniformly, nitrogen was introduced for 0.5h, the oxygen was evacuated, the temperature was raised to 70 ℃, and 15ml of a 20wt% mixed solution of azobisisobutyronitrile and styrene was slowly added. Continuously stirring for 24 hours under nitrogen atmosphere, putting the obtained reaction liquid into a centrifugal machine for ultracentrifugation, removing supernatant, washing lower sediment with absolute ethyl alcohol, repeating the centrifugation step for 5 times, and putting the obtained centrifugal product into a vacuum drying machine at 70 ℃ for 24 hours to obtain submicron-sized polystyrene microspheres;
(2) Weighing 0.15g of submicron-sized polystyrene microspheres, adding the submicron-sized polystyrene microspheres and 0.2g of hexadecyl trimethyl ammonium bromide into a mixed solution of water (160 ml)/ethanol (80 ml), performing ultrasonic dispersion for 30min to obtain a uniformly dispersed suspension, adding 2ml of ammonia water, stirring for 30min, dropwise adding 0.2ml of tetraethoxysilane at a certain stirring speed, continuously stirring for reacting for 20h, putting the obtained reaction solution into a centrifuge for ultracentrifugation, removing supernatant, respectively cleaning three times by using high-purity water and ethanol, and drying for 12h at 120 ℃; placing the dried polystyrene and silicon dioxide core-shell structure sample into a box furnace, heating to 100 ℃, preserving heat for 4 hours, then heating to 500 ℃, preserving heat for 2 hours, and removing a polystyrene template to obtain the mesoporous silicon dioxide hollow microsphere;
(3) Weighing 0.15g of mesoporous silica hollow microspheres, adding the mesoporous silica hollow microspheres and 0.15g of hexadecyl trimethyl ammonium bromide into a mixed solution of water (160 ml)/ethanol (80 ml), performing ultrasonic dispersion for 30min to obtain a uniformly dispersed suspension, and adding 5ml of ammonia water and stirring for 30min; dropwise adding 0.2ml of ethyl orthosilicate at a stirring speed of 60r/min, continuously stirring for reacting for 20h, putting the obtained suspension into a centrifuge for ultracentrifugation, removing supernatant, respectively cleaning with high-purity water and ethanol for three times, and drying in an oven at 120 ℃ for 12h; and (3) carrying out secondary sintering strengthening on the obtained dried product by a flame floatation method at 1150 ℃, wherein the molding temperature of the sintering by the flame floatation method is 1180 ℃, the feeding speed is 30g/min, the feeding speed is 4m/s, and the induced air speed is 5m/s, so as to obtain the mesoporous-free silica hollow microsphere.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the hollow silica microspheres prepared according to example 3 of the present invention. As can be seen from fig. 3The hollow silica microsphere has uniform particle size and average density of 0.72/cm 3 。
Other performance tests were performed on the product with the following results: the dielectric constant is 1.81 (tested at 10 GHz), and the volume breakage rate is less than or equal to 5% under the condition that the compressive strength is 210 MPa.
Claims (7)
1. A method for preparing silica hollow microspheres by adopting a hard template method is characterized in that: mixing the hollow silica microsphere with mesoporous surface with surfactant in solvent, dispersing to obtain suspension, adding ammonia water, stirring to react for 0.1-1 hr, adding silicon source, stirring to react until suspension is obtained, separating, drying, sintering at 800-1000 deg.c by flame float process to obtain hollow silica microsphere without mesoporous.
2. The method for preparing the silica hollow microspheres by using a hard template method according to claim 1, wherein the method comprises the following steps: the method for obtaining the hollow silica microsphere with the mesoporous surface comprises the following steps:
(1) Adding a mixed solution of azodiisobutyronitrile and styrene into an absolute ethanol solution containing polyvinylpyrrolidone in a nitrogen atmosphere at 60-80 ℃, continuously stirring and reacting for 20-30h, centrifuging, repeatedly cleaning a sediment at the lower layer by using absolute ethanol, and drying to obtain submicron-sized polystyrene microspheres;
(2) Mixing polystyrene microsphere and surfactant in solvent and dispersing to obtain suspension, adding ammonia water, stirring to react for 0.1-1 hr, adding ethyl orthosilicate, stirring to react continuously until suspension is obtained, separating, drying, heating to remove polystyrene, and obtaining mesoporous silica hollow microsphere.
3. The method for preparing silica hollow microspheres by a hard template method according to claim 1 or 2, wherein: the surfactant is one of hexadecyl trimethyl ammonium bromide, sodium hexadecyl sulfonate, hexadecyl trimethyl ammonium chloride, sodium stearate, sodium oleate, sodium p-dodecyl benzene sulfonate, laureth and dodecyl ammonium chloride.
4. The method for preparing silica hollow microspheres by a hard template method according to claim 1 or 2, wherein: the silicon source is one of tetraethoxysilane, metasilicic acid ethyl ester and polysilicate ethyl ester.
5. The method for preparing the silica hollow microspheres by using a hard template method according to claim 1, wherein the method comprises the following steps: the adding proportion of the silicon dioxide hollow microsphere, the surfactant, the ammonia water and the silicon source is 1-5:0.5-2:15-30:1-2 (wt/wt/vt/vt).
6. The method for preparing the silica hollow microspheres by using the hard template method according to claim 2, wherein the method comprises the following steps: the adding ratio of the polystyrene microsphere, the surfactant, the ammonia water and the tetraethoxysilane in the step (2) is 1-3:0.5-2:15-30:1-2 (wt/wt/vt/vt).
7. The method for preparing silica hollow microspheres by a hard template method according to claim 1 or 2, wherein: the solvent is 30-90vt% ethanol water solution.
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Citations (6)
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| CN101862630A (en) * | 2010-06-29 | 2010-10-20 | 西安理工大学 | Preparation method of hydroxyapatite hollow microsphere in core/shell composite structure |
| KR20160127871A (en) * | 2015-04-27 | 2016-11-07 | 계명대학교 산학협력단 | Syntehtic method of core material for mesoporous hollow sillica spheres, and core meterial manufactured by it |
| KR101719988B1 (en) * | 2015-12-04 | 2017-03-27 | 계명대학교 산학협력단 | Manufacuring method of Mesoporous hollow silica spheres without thermal process |
| CN108033688A (en) * | 2017-12-26 | 2018-05-15 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of silica based super hydrophobic coating and preparation method thereof |
| CN113213489A (en) * | 2021-06-23 | 2021-08-06 | 武汉理工大学 | Hollow silicon dioxide microsphere and preparation method thereof |
| CN113428867A (en) * | 2021-07-15 | 2021-09-24 | 深圳先进技术研究院 | Hollow silicon dioxide spherical particle and preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862630A (en) * | 2010-06-29 | 2010-10-20 | 西安理工大学 | Preparation method of hydroxyapatite hollow microsphere in core/shell composite structure |
| KR20160127871A (en) * | 2015-04-27 | 2016-11-07 | 계명대학교 산학협력단 | Syntehtic method of core material for mesoporous hollow sillica spheres, and core meterial manufactured by it |
| KR101719988B1 (en) * | 2015-12-04 | 2017-03-27 | 계명대학교 산학협력단 | Manufacuring method of Mesoporous hollow silica spheres without thermal process |
| CN108033688A (en) * | 2017-12-26 | 2018-05-15 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of silica based super hydrophobic coating and preparation method thereof |
| CN113213489A (en) * | 2021-06-23 | 2021-08-06 | 武汉理工大学 | Hollow silicon dioxide microsphere and preparation method thereof |
| CN113428867A (en) * | 2021-07-15 | 2021-09-24 | 深圳先进技术研究院 | Hollow silicon dioxide spherical particle and preparation method and application thereof |
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