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 PDF

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CN117342569A
CN117342569A CN202310297507.7A CN202310297507A CN117342569A CN 117342569 A CN117342569 A CN 117342569A CN 202310297507 A CN202310297507 A CN 202310297507A CN 117342569 A CN117342569 A CN 117342569A
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submicron
hollow
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stirring
sio
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高林
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
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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

Submicron high purity SiO 2 Controllable preparation method of hollow microsphere and product thereof
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.
CN202310297507.7A 2023-03-24 2023-03-24 Submicron high purity SiO2Controllable preparation method of hollow microsphere and product thereof Active CN117342569B (en)

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