CN117342569A - Submicron high purity SiO 2 Controllable preparation method of hollow microsphere and product thereof - Google Patents
Submicron high purity SiO 2 Controllable preparation method of hollow microsphere and product thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 22
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- HJQCAEDIUJXGCQ-UHFFFAOYSA-N 6-bromo-2-chloro-8-cyclopentyl-5-methylpyrido[2,3-d]pyrimidin-7-one Chemical compound C12=NC(Cl)=NC=C2C(C)=C(Br)C(=O)N1C1CCCC1 HJQCAEDIUJXGCQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910021426 porous silicon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- 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
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
-
- 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
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/12—Surface area
-
- 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)
- Silicon Compounds (AREA)
Abstract
The invention provides submicron-level high-purity SiO 2 A controllable preparation method of hollow microspheres and products thereof. The purpose of controlling the morphology and the particle size of the silicon dioxide formed by regulating and controlling a dispersion system by pH is achieved by modifying the surfactant. The structural formula I of the modified surfactant is shown in the specification. The invention achieves the aim of submicron SiO by preparing the modified surfactant 2 Controllable preparation of particle size of hollow microsphere to obtain SiO 2 The hollow microsphere has high purity and narrow particle size distribution, and the lowest particle size is only 842nm. Meanwhile, the preparation method provided by the invention is simple and economic, does not need high-temperature calcination and heating, and can controllably prepare the SiO with the required particle size by adjusting the pH 2 The hollow microsphere has wide application prospect.
Description
Technical Field
The invention relates to the technical field of inorganic materials, in particular to submicron high-purity SiO 2 A controllable preparation method of hollow microspheres and products thereof.
Background
The hollow silica sphere has the characteristics of low density, large specific surface area, high surface activity, strong surface permeability and the like, and has important commercial value and wide application prospect in the fields of nano microreactors, sensors, controllable transportation and release of medicines, solar cells, lithium ion batteries, high-selectivity catalysts, catalyst carriers and the like. Hollow SiO 2 Has the advantages of no toxicity, good biocompatibility and the like, so that SiO 2 The hollow ball has good development prospect.
The hollow silica spheres are mainly composed of white carbon black, silica gel and aerogel. At present, the preparation method mainly comprises the following steps: (1) Silica produced by using sulfuric acid, hydrochloric acid or carbon dioxide and water glass as basic raw materials, although the method has simple process, the operation period is longer, and the used acid raw materials are easy to become pollution sources; (2) The porous silicon dioxide is prepared by adopting a supergravity technology, a sol-gel method, a chemical crystal method, a secondary crystallization method or a reverse micelle microemulsion method and the like, and the process flow is relatively complex and the steps are relatively complicated; (3) The porous silicon dioxide is prepared by using chlorosilane through oxyhydrogen flame high-temperature hydrolysis, and the porous silicon dioxide prepared by the process has high energy consumption and high production cost although the porous silicon dioxide has excellent performance. Therefore, the hollow silica sphere material cannot be quickly and conveniently prepared by the method.
Meanwhile, various properties of the nano material are closely related to the size, particle size distribution, morphology, composition and the like of nano grains, such as hedgehog-shaped SiO prepared by a patent CN101804990A 2 The hollow microsphere has wide application value in the fields of controllable transportation and release of catalysts, medicines and the like; for example, patent CN112194147a provides a macroporous high adsorption silica with large pore size and good adsorption performance. The preparation method of the hollow silica spheres cannot accurately prepare the high-strength molten product in a submicron level in a controllable way, so that the preparation method has the important significance in the fields of material synthesis chemistry and practical production application by simply, environmentally-friendly and economically regulating and controlling the hollow silica sphere material with specific structure, morphology and size.
Disclosure of Invention
The invention aims to: the invention aims to overcome the problems of the prior art for preparing hollow silica sphere materials, and provides a controllable preparation method of high-purity silica hollow microspheres with submicron particle size, which can prepare high-strength SiO in submicron order in a controllable manner 2 Hollow microsphere to meet the requirement of small particle size and high purity hollow silica microsphere in available communication market.
The technical scheme of the invention is as follows:
submicron high purity SiO 2 The controllable preparation method of the hollow microsphere comprises the following steps:
step 1: preparing sodium silicate solution, and putting the sodium silicate solution into a reactor;
step 2: adding the modified surfactant into the reactor while stirring, and continuing stirring;
step 3: adding dilute sulfuric acid into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 5-8 to obtain a pre-product;
step 4: and (3) spray drying and dispersing to obtain the high-purity silica hollow microspheres with submicron particle sizes.
Wherein, the structural formula of the modified surfactant is shown in formula I:
in some embodiments, the sodium silicate solution of step 1 has a molar concentration of 0.40 to 0.70mol/L.
In some embodiments, the method of preparing the modified surfactant comprises:
mixing hexamethyldisilazane with toluene under nitrogen atmosphere, and adding into a reactor; slurrying 6-bromo-2-chloro-8-cyclopentyl-5-methylpyrido [2,3-d ] pyrimidin-7 (8H) -one in toluene, then adding to the reactor, mixing and stirring; quenching and filtering the mixture by adopting sodium bicarbonate, washing and drying a filter cake, and filtering to obtain the modified surfactant.
In some embodiments, the molar ratio of hexamethyldisilazane to 6-bromo-2-chloro-8-cyclopentyl-5-methylpyrido [2,3-d ] pyrimidin-7 (8H) -one is 10 to 14:5-7.
In some embodiments, the reaction temperature of the mixing and stirring is 0-15 ℃ and the reaction time is 0.5-2h.
In some embodiments, the molar ratio of sodium bicarbonate to hexamethyldisilazane is from 2 to 3:1.
in some embodiments, the washing is washing with a mixed solution of toluene, acetone, water; the drying is at 50-75deg.C.
In some embodiments, the modifying surfactant of step 2 comprises 0.3 to 0.7% by mass of sodium silicate.
In some embodiments, the stirring temperature in step 2 is 80-90℃and the stirring time is 20-30min.
In some embodiments, the dilute sulfuric acid in step 3 has a molar concentration of 0.7 to 1.5mol/L.
In some embodiments, the spray drying process parameters of step 4 are: the slurry conveying speed is 4-20ml/min, the compressed air pressure is 0.1-0.4Mpa, and the temperature at the nozzle is 80-150 ℃.
In another aspect, the present application provides the above submicron-grade high purity SiO 2 Submicron SiO prepared by controllable preparation method of hollow microsphere 2 Hollow microspheres of submicron order SiO 2 The particle size of the hollow microsphere is 843nm-10 mu m; preferably, the submicron order SiO 2 The particle size of the hollow microsphere is 843nm-2 μm.
The beneficial effects are that:
1. the invention achieves the aim of submicron SiO by preparing the modified surfactant 2 Controllable preparation of particle size of hollow microsphere to obtain SiO 2 The hollow microsphere has high purity and narrow particle size distribution, and the lowest particle size is only 842nm.
2. The preparation method provided by the invention is simple and economic, does not need high-temperature calcination and heating, and can controllably prepare the SiO with the required particle size by adjusting the pH 2 The hollow microsphere has wide application prospect.
Description of the drawings:
FIG. 1 is a SEM schematic of 500 μm of a product 1 prepared according to example 1 of the present application;
FIG. 2 is a SEM schematic of the product 2 prepared in example 2 of the present application at 20 μm;
FIG. 3 is a SEM schematic of 100 μm of the product 4 prepared in example 4 of the present application;
FIG. 4 is a SEM schematic of 10 μm of the product 2 prepared in example 2 of the present application.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
The 6-bromo-2-chloro-8-cyclopentyl-5-methylpyrido [2,3-d ] pyrimidin-7 (8H) -one used in the examples was purchased from Hubei corporation of Shandong Kokai; other reagents were all of the general commercial analytical purity unless specified.
Preparation of modified surfactants
16.1g hexamethyldisilazane was mixed with 25ml toluene under nitrogen atmosphere and added to the reactor; 23.9g of 6-bromo-2-chloro-8-cyclopentyl-5-methylpyrido [2,3-d ] pyrimidin-7 (8H) -one was slurried in 50ml of toluene and then added to the above reactor, followed by mixing and stirring at 15℃for 2 hours; the mixture was quenched with 200ml of 1m sodium bicarbonate and filtered using toluene, acetone, water in a volume ratio of 1:2: and 1, washing a filter cake by the mixed solution, and drying at 50 ℃ to obtain the modified surfactant.
Mass spectrum data of the modified surfactant: the resulting product was analyzed by LC-MS and m/z was 466.12 (76.9%), 467.87 (100.0%), 468.86 (33.5%), 469.95 (10.6%), 470.98 (2.0%); it was confirmed that the modified surfactant of the structure of formula I was successfully obtained.
Example 1
Step 1: preparing 0.5mol/L sodium silicate solution, and adding 100ml into a reactor;
step 2: adding 4.4g of the modified surfactant into a reactor while stirring at the temperature of 80 ℃ and the frequency of 40Hz, and stirring for 30min;
step 3: adding dilute sulfuric acid with the concentration of 1M into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 5 to obtain a pre-product;
step 4: the slurry conveying speed is 10ml/min, the compressed air pressure is 0.1Mpa, the temperature at the nozzle is 90 ℃ for spray drying, cooling and dispersing are carried out, and the high-purity silicon dioxide hollow microsphere-1 with submicron particle size is obtained and is marked as a product-1.
Example 2
Step 1: preparing 0.5mol/L sodium silicate solution, and adding 100ml into a reactor;
step 2: adding 4.4g of the modified surfactant into a reactor while stirring at the temperature of 80 ℃ and the frequency of 40Hz, and stirring for 30min;
step 3: adding dilute sulfuric acid with the concentration of 1M into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 6 to obtain a pre-product;
step 4: the slurry conveying speed is 10ml/min, the compressed air pressure is 0.1Mpa, the temperature at the nozzle is 90 ℃ for spray drying, cooling and dispersing are carried out, and the high-purity silicon dioxide hollow microsphere-2 with submicron particle size is obtained and is marked as a product-2.
Example 3
Step 1: preparing 0.5mol/L sodium silicate solution, and adding 100ml into a reactor;
step 2: adding 4.4g of the modified surfactant into a reactor while stirring at the temperature of 80 ℃ and the frequency of 40Hz, and stirring for 30min;
step 3: adding dilute sulfuric acid with the concentration of 1M into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 7 to obtain a pre-product;
step 4: the slurry conveying speed is 10ml/min, the compressed air pressure is 0.1Mpa, the temperature at the nozzle is 90 ℃ for spray drying, cooling and dispersing are carried out, and the high-purity silicon dioxide hollow microsphere-3 with submicron particle size is obtained and is marked as a product-3.
Example 4
Step 1: preparing 0.5mol/L sodium silicate solution, and adding 100ml into a reactor;
step 2: adding 4.4g of the modified surfactant into a reactor while stirring at the temperature of 80 ℃ and the frequency of 40Hz, and stirring for 30min;
step 3: adding dilute sulfuric acid with the concentration of 1M into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 8 to obtain a pre-product;
step 4: the slurry conveying speed is 10ml/min, the compressed air pressure is 0.1Mpa, the temperature at the nozzle is 90 ℃ for spray drying, cooling and dispersing are carried out, and the high-purity silicon dioxide hollow microsphere-4 with submicron particle size is obtained and is marked as a product-4.
Comparative example 1
Step 1: preparing 0.5mol/L sodium silicate solution, and adding 100ml into a reactor;
step 2: adding 4.4g of hexamethyldisilazane into a reactor while stirring at a frequency of 40Hz at a temperature of 80 ℃ for 30min;
step 3: adding dilute sulfuric acid with the concentration of 1M into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 5 to obtain a pre-product;
step 4: the slurry is conveyed at the speed of 10ml/min, the pressure of compressed air is 0.1Mpa, the temperature at the nozzle is 90 ℃ for spray drying, and the silica microsphere-4 is obtained after cooling and dispersing.
Comparative example 2
Step 1: preparing 0.5mol/L sodium silicate solution, and adding 100ml into a reactor;
step 2: adding 4.4g of hexamethyldisilazane into a reactor while stirring at a frequency of 40Hz at a temperature of 80 ℃ for 30min;
step 3: adding dilute sulfuric acid with the concentration of 1M into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 6 to obtain a pre-product;
step 4: the slurry conveying speed is 10ml/min, the compressed air pressure is 0.1Mpa, the temperature at the nozzle is 90 ℃ for spray drying, and the silica microsphere-2 is obtained after cooling and dispersing.
Comparative example 3
Step 1: preparing 0.5mol/L sodium silicate solution, and adding 100ml into a reactor;
step 2: adding 4.4g of hexamethyldisilazane into a reactor while stirring at a frequency of 40Hz at a temperature of 80 ℃ for 30min;
step 3: adding dilute sulfuric acid with the concentration of 1M into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 7 to obtain a pre-product;
step 4: the slurry is conveyed at the speed of 10ml/min, the pressure of compressed air is 0.1Mpa, the temperature at the nozzle is 90 ℃ for spray drying, and the silica microsphere-3 is obtained after cooling and dispersing.
Comparative example 4
Step 1: preparing 0.5mol/L sodium silicate solution, and adding 100ml into a reactor;
step 2: adding 4.4g of hexamethyldisilazane into a reactor while stirring at a frequency of 40Hz at a temperature of 80 ℃ for 30min;
step 3: adding dilute sulfuric acid with the concentration of 1M into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 8 to obtain a pre-product;
step 4: the slurry is conveyed at the speed of 10ml/min, the pressure of compressed air is 0.1Mpa, the temperature at the nozzle is 90 ℃ for spray drying, and the silica microsphere-4 is obtained after cooling and dispersing.
Experiment 1: and (5) topography testing. And carrying out scanning electron microscopy on the products 1-4 and the silicon dioxide hollow microsphere-1-4 test sample, and measuring the average particle size and the specific surface area. The test results are shown in Table 1 and FIGS. 1-3; wherein FIG. 1 is a SEM schematic of product 1 at 500 μm; FIG. 2 is a SEM schematic of product 2 at 20 μm; FIG. 3 is a schematic of SEM product at 100 μm for product 4.
Experiment 2: silica additive stability performance test. Placing the product 1-4 and a silicon dioxide microsphere-1-4 test sample at 50 ℃ for 48 hours, and observing whether the test sample changes color and has caking; detecting the fluidity of a test sample by adopting a Lesion flow rate cup; the test results are shown in Table 2.
Table 1 test results of experiment 1
Average particle diameter (μm) | Specific surface area (m) 2 /g) | |
Product-1 | 8.37 | 430 |
Product-2 | 1.84 | 550 |
Product-3 | 3.45 | 500 |
Product-4 | 6.99 | 480 |
Silica microsphere-1 | 44.36 | 350 |
Silica microsphere-2 | 62.71 | 380 |
Silica microsphere-3 | 54.03 | 420 |
Silica microsphere-4 | 71.22 | 370 |
Table 2 test results of experiment 2
As can be seen from the drawings, the invention successfully prepares SiO with the thickness of 10 μm to 1 μm 2 Hollow microspheres. In particular, as can be seen from examples 1 to 4, the modified surface dispersant provided by the invention has a plurality of hydrophobic groups and hydrophilic groups, and has more active sites in the dispersion system, so that silicon dioxide can be gradually formed on the surface of the modified surfactant, and the morphology of the silicon dioxide particles is controlled by controlling the pH value of the reaction system, thereby being beneficial to controlling the particle size of the silicon dioxide.
In particular, when the pH is 6, siO 2 The average particle size of the hollow microsphere is only 1.8 mu m, the lowest particle size is only 842nm, and the hollow microsphere reaches submicron level, and the purity is high, the particle size distribution is concentrated, and the hollow microsphere has very important significance in the field of material synthesis chemistry and practical production application as can be seen from the attached figures 1-4 of the specification.
The present invention is capable of other and further embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. Submicron high purity SiO 2 Hollow coreThe controllable preparation method of the microsphere is characterized by comprising the following steps:
step 1: preparing sodium silicate solution, and putting the sodium silicate solution into a reactor;
step 2: adding the modified surfactant into the reactor while stirring, and continuing stirring;
step 3: adding dilute sulfuric acid into the reaction liquid, adding water and stirring when an emulsification point appears in the reaction liquid system, and controlling the pH value to be 5-8 to obtain a pre-product;
step 4: spray drying, and dispersing to obtain the high-purity silica hollow microspheres with submicron particle size;
wherein, the structural formula of the modified surfactant is shown in formula I:
2. the submicron-level high-purity SiO according to claim 1 2 The controllable preparation method of the hollow microsphere is characterized by comprising the following steps of:
mixing hexamethyldisilazane with toluene under nitrogen atmosphere, and adding into a reactor; slurrying 6-bromo-2-chloro-8-cyclopentyl-5-methylpyrido [2,3-d ] pyrimidin-7 (8H) -one in toluene, then adding to the reactor, mixing and stirring; quenching and filtering the mixture by adopting sodium bicarbonate, washing and drying a filter cake, and filtering to obtain the modified surfactant.
3. Submicron-order high-purity SiO according to claim 2 2 The controllable preparation method of the hollow microsphere is characterized in that the hexamethyldisilazane and 6-bromo-2-chloro-8-cyclopentyl-5-methylpyrido [2,3-d ] are prepared]The molar ratio of the pyrimidine-7 (8H) -ketone is 10-14:5-7.
4. Submicron-order high-purity SiO according to claim 2 2 The controllable preparation method of the hollow microsphere is characterized in that the mixingThe reaction temperature is 0-15 ℃ and the reaction time is 0.5-2h.
5. Submicron-order high-purity SiO according to claim 2 2 The controllable preparation method of the hollow microsphere is characterized in that the molar ratio of sodium bicarbonate to hexamethyldisilazane is 2-3:1.
6. the submicron-level high-purity SiO according to claim 1 2 The controllable preparation method of the hollow microspheres is characterized in that in the step 2, the modified surfactant accounts for 0.3-0.7% of the mass of sodium silicate.
7. The submicron-level high-purity SiO according to claim 1 2 The controllable preparation method of the hollow microspheres is characterized in that in the step 2, the stirring temperature is 80-90 ℃ and the stirring time is 20-30min.
8. The submicron-level high-purity SiO according to claim 1 2 The controllable preparation method of the hollow microspheres is characterized in that in the step 3, the molar concentration of the dilute sulfuric acid is 0.7-1.5mol/L.
9. The submicron-level high-purity SiO according to claim 1 2 The controllable preparation method of the hollow microspheres is characterized in that in the step 4, the spray drying process parameters are as follows: the slurry conveying speed is 4-20ml/min, the compressed air pressure is 0.1-0.4Mpa, and the temperature at the nozzle is 80-150 ℃.
10. The submicron-level high-purity SiO as claimed in any one of claims 1 to 9 2 Submicron SiO prepared by controllable preparation method of hollow microsphere 2 Hollow microspheres of submicron order SiO 2 The particle size of the hollow microsphere is 843nm-10 mu m; preferably, the submicron order SiO 2 The particle size of the hollow microsphere is 843nm-2 μm.
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