CN115924924A - Hollow spherical silicon dioxide with adjustable specific surface area and preparation method and application thereof - Google Patents
Hollow spherical silicon dioxide with adjustable specific surface area and preparation method and application thereof Download PDFInfo
- Publication number
- CN115924924A CN115924924A CN202211011039.4A CN202211011039A CN115924924A CN 115924924 A CN115924924 A CN 115924924A CN 202211011039 A CN202211011039 A CN 202211011039A CN 115924924 A CN115924924 A CN 115924924A
- Authority
- CN
- China
- Prior art keywords
- hollow spherical
- specific surface
- surface area
- silicon dioxide
- spherical silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 75
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000002002 slurry Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000012720 thermal barrier coating Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 30
- 239000011248 coating agent Substances 0.000 abstract description 29
- 239000000945 filler Substances 0.000 abstract description 9
- 238000002834 transmittance Methods 0.000 abstract description 5
- 239000011521 glass Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 18
- 238000009413 insulation Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 2
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention provides a preparation method of hollow spherical silicon dioxide with adjustable specific surface area, which comprises the following steps: 1) Synthesizing hollow spherical silicon dioxide with different particle sizes by a soft template method; 2) The specific surface area of the hollow spherical silica is regulated and controlled by controlling the calcination temperature. The prepared hollow spherical silicon dioxide with different specific surface areas has lower heat conductivity coefficient and excellent visible light transmittance, is a filler of an ideal transparent heat-insulating coating, and can be applied to the fields of buildings, automobiles, trains, airplane glass and the like. The method has the advantages of simple process, low cost, extremely high application value and wide market prospect.
Description
Technical Field
The invention belongs to the technical field of transparent heat insulation material production, and particularly relates to hollow spherical silicon dioxide with an adjustable specific surface area, and a preparation method and application thereof.
Background
Some spaces (such as houses and vehicles) of human life need to have two functions of heat preservation and lighting. Although the transparency of common glass is good, the barrier property to infrared rays and ultraviolet rays is poor, so that the development of the transparent heat-insulating coating has important significance.
The research on the transparent heat insulation coating has been carried out earlier in the countries of the united states, the japanese and the korean, and the research is mainly focused on the metal oxide nano material, such as ITO (indium tin oxide), ATO (antimony tin oxide), and the like. The prepared nano metal oxide is firstly blended into stable dispersed water-based or oil-based slurry, and then the slurry is applied to the coating to prepare the multifunctional transparent coating with heat insulation, ultraviolet ray and infrared ray resistance and the like. The filler has the main defects that the hardness is high, and the preparation of the slurry can obtain the slurry with proper fineness only by complex process flows such as ball milling, sand milling and the like; the preparation period is long and the cost is expensive. Therefore, a novel functional filler is urgently needed to be developed, which not only has a good transparent heat insulation effect, but also can realize simple and efficient large-scale preparation.
Disclosure of Invention
The invention aims to overcome and solve the problems and defects in the prior art, and provides the hollow spherical silicon dioxide with adjustable specific surface area, which has simple preparation process, easily controlled reaction conditions and lower cost and is suitable for industrial production; the prepared hollow spherical silica is used as the filler of the coating, can obtain the transparent heat-insulating coating with higher ultraviolet and infrared blocking rate, is expected to replace metal oxide in the coating filler, and becomes a new generation of transparent heat-insulating coating.
The invention also provides a preparation method and application of the hollow spherical silicon dioxide.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of hollow spherical silicon dioxide with adjustable specific area comprises two steps of synthesizing the hollow spherical silicon dioxide by a soft template method and regulating the specific area by high-temperature calcination, and specifically comprises the following steps:
1) Synthesizing hollow spherical silicon dioxide with different particle sizes by a soft template method: carrying out hydrolytic condensation reaction on a surfactant (serving as a spherical soft template), a silane coupling agent (serving as a surface modifier), tetraethyl orthosilicate (TEOS) and an ethanol aqueous solution under an alkaline condition to obtain mesoporous spherical silica slurry; then carrying out high-temperature hydrothermal reaction to obtain hollow spherical silicon dioxide slurry;
2) And washing, drying, crushing and calcining the hollow spherical silica slurry to obtain the hollow spherical silica with the adjustable specific area.
Specifically, in the step 1), the surfactant is one or more of cetyl trimethyl ammonium bromide, dodecyl ammonium chloride, sodium dodecyl sulfate, cetyl trimethyl ammonium chloride, and the like.
Further, in the step 1), the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, hexamethyldisilazane and the like.
Specifically, in the ethanol aqueous solution in the step 1), the molar ratio of ethanol to water is 1: (10-30); the ethanol is industrial alcohol with the concentration of 95 percent. One or more of organic bases such as triethanolamine, diethanolamine, triethylamine, diethylamine and the like are selected to adjust the pH value to be alkaline (pH =9 to 12).
Further, in the step 1), the temperature of the hydrolysis condensation reaction (mainly used for the hydrolysis condensation and the surface modification of TEOS) is 30-60 ℃, and the reaction time is 1-5h.
Further, in the step 1), the mass ratio of the surfactant to the tetraethyl orthosilicate is 1: (5-30), wherein the molar ratio of the silane coupling agent to the tetraethyl orthosilicate is 1: (2-20).
Specifically, in the step 1), the hydrothermal reaction temperature is 110-180 ℃, and the reaction time is 6-16h.
Specifically, in the step 2), the calcining temperature of the specific surface area, the pore volume and the pore diameter of the hollow spherical silica is regulated to be 500-1100 ℃, and the calcining time is 2-12h.
The invention provides the hollow spherical silicon dioxide with adjustable specific surface area prepared by the method. The hollow spherical silica with different specific surface areas: particle outer diameter: 50-500nm, wall thickness: 2-60nm, specific surface area: 20-600m 2 (ii) in terms of/g. The prepared hollow spherical silicon dioxide has complete shell, good sphericity and uniform particle size distribution.
The invention also provides application of the hollow spherical silicon dioxide with the adjustable specific surface area in transparent heat-insulating coating.
The preparation process provided by the invention is simple, the reaction conditions are easy to control, the cost is lower, and the preparation method is suitable for industrial production. The prepared hollow spherical silica is used as the filler of the coating, can obtain the transparent heat-insulating coating with higher ultraviolet and infrared blocking rates, is expected to replace metal oxide in the coating filler, and becomes a new-generation transparent heat-insulating coating. Compared with the prior art, the invention has the following beneficial effects:
1) The hollow spherical silica particles with adjustable specific surface area prepared by the invention have relatively low hardness, and can be used as a filler in a thermal insulation coating to obtain slurry with required fineness only by high-speed stirring through a dispersion machine. The whole preparation period of the transparent heat-insulating coating is short, and the preparation can be completed in 1 hour;
2) The hollow spherical silica with the adjustable specific surface area prepared by the invention is used as a filler to prepare the transparent heat-insulating coating, under the condition of keeping 70% of transmittance for visible light, the blocking rates for ultraviolet rays and infrared rays can respectively reach 89% and 90%, and the heat-insulating temperature difference reaches 9 ℃;
3) The preparation method provided by the invention has the characteristics of simple process and low cost, and is suitable for large-scale production.
Drawings
FIG. 1 is an SEM image (a) and a TEM image (b) of 50nm hollow spherical silica in example 1, respectively, under calcination conditions at 500 ℃; it can be seen in the figure that: the 50nm hollow spherical silicon dioxide still keeps complete shell and sphericity after being calcined at 500 ℃;
FIG. 2 is TEM images of 100nm hollow spherical silica in examples 2 (a), 3 (b), 4 (c) and 5 (d) at calcination conditions of 500 ℃, 700 ℃, 900 ℃ and 1000 ℃, respectively; it can be seen in the figure that: after calcination at different temperatures, the 100nm hollow spherical silica still keeps complete shell and sphericity and has more densified surface;
FIG. 3 is a TEM image (a) of 200nm hollow spherical silica in example 6 under 500 ℃ calcination conditions and a TEM image (b) of 300nm hollow spherical silica in example 7 under 500 ℃ calcination conditions; it can be seen in the figures that: the hollow spherical silicon dioxide of 200nm and 300nm still keeps complete shell and sphericity after being calcined at 500 ℃;
FIG. 4 is data of the thermal insulation performance of 50nm hollow spherical silica calcined at 500 ℃ in different amounts of the coating.
Detailed Description
The patent is described below in connection with specific examples, but the scope of protection of the patent is not limited thereto.
In the following examples, all the raw materials are common commercial products which can be directly purchased in the field. The ethanol is industrial alcohol with the concentration of 95 percent.
Example 1
A preparation method of hollow spherical silicon dioxide with adjustable specific surface area comprises the following steps:
1) Weighing 22.5g of hexadecyl trimethyl ammonium chloride, 180g of triethanolamine, 225g of ethanol, 1950g of pure water and 75g (0.38 mol) of gamma-mercaptopropyl trimethoxy silane into a 5L high-pressure reaction kettle (the pH value of a mixed solution is 10), adding 450g (2.16 mol) of TEOS under stirring at 60 ℃, and reacting for 3 hours at constant temperature to obtain mesoporous spherical silicon dioxide slurry;
2) Heating on the basis of the step 1), and carrying out hydrothermal reaction at 160 ℃ for 10h to obtain hollow spherical silicon dioxide slurry;
3) Respectively pumping and washing the slurry obtained in the step 2) for 3 times by using ethanol and pure water, drying and crushing the obtained filter cake, calcining the processed white powder in a muffle furnace at 500 ℃ for 11h, and finally obtaining the product with complete shell storage, 50nm of outer diameter, 6nm of wall thickness and 550.7m of specific surface area 2/ g. Pore volume is 1.6cm 3 (ii) hollow spherical silica having a pore diameter of 20.9nm in a volume of/g (see FIG. 1 for SEM and TEM images).
Example 2:
a preparation method of hollow spherical silicon dioxide with adjustable specific surface area comprises the following steps:
1) Weighing 30g of hexadecyl trimethyl ammonium bromide, 375g of triethanolamine, 270g of ethanol, 1800g of pure water and 120g (0.54 mol) of gamma-aminopropyl triethoxysilane, adding into a 5L high-pressure reaction kettle (the pH value of a mixed solution is 9), adding 600g (2.88 mol) of TEOS under stirring at 30 ℃, and reacting for 1 hour at constant temperature to obtain mesoporous spherical silica slurry;
2) Heating on the basis of the step 1), and carrying out hydrothermal reaction at 110 ℃ for 16h to obtain hollow spherical silicon dioxide slurry;
3) Respectively pumping and washing the slurry obtained in the step 2) for 3 times by using ethanol and pure water, drying and crushing the obtained filter cake, calcining the processed white powder in a muffle furnace at 500 ℃ for 11h, and finally obtaining the product with complete shell storage, 100nm of outer diameter, 17nm of wall thickness and 542.5m of specific surface area 2/ g. Pore volume of 1.7cm 3 (ii) hollow spherical silica having a pore diameter of 30.2 nm.
Example 3
A preparation method of hollow spherical silicon dioxide with adjustable specific surface area comprises the following steps:
1) Weighing 27g of hexadecyl trimethyl ammonium chloride, 375g of triethanolamine, 270g of ethanol, 1800g of pure water and 90g (0.38 mol) of gamma-glycidyl ether oxypropyl trimethoxysilane into a 5L high-pressure reaction kettle (the pH of a mixed solution is 10), adding 600g (2.88 mol) of TEOS under stirring at 30 ℃, and reacting for 1 hour at constant temperature to obtain mesoporous spherical silica slurry;
2) Heating on the basis of the step 1), and carrying out hydrothermal reaction at 120 ℃ for 15h to obtain hollow spherical silicon dioxide slurry;
3) Respectively pumping and washing the slurry obtained in the step 2) for 3 times by using ethanol and pure water, drying and crushing the obtained filter cake, calcining the processed white powder in a muffle furnace at 700 ℃ for 8 hours, and finally obtaining the product with complete shell preservation, outer diameter of 100nm, wall thickness of 18nm and specific surface area of 391.3m 2/ g. Pore volume of 1.1cm 3 (ii) hollow spherical silica having a pore diameter of 19.1 nm.
Example 4
A preparation method of hollow spherical silicon dioxide with adjustable specific surface area comprises the following steps:
1) Weighing 45g of hexadecyl trimethyl ammonium bromide, 375g of diethanolamine, 270g of ethanol, 2100g of pure water and 90g (0.46 mol) of gamma-mercaptopropyl trimethoxy silane, adding the mixture into a 5L high-pressure reaction kettle (the pH value of the mixed solution is 10), adding 600g (2.88 mol) of TEOS under stirring at 30 ℃, and reacting for 1 hour at constant temperature to obtain mesoporous spherical silica slurry;
2) Heating on the basis of the step 1), and carrying out hydrothermal reaction at 140 ℃ for 14h to obtain hollow spherical silicon dioxide slurry;
3) Respectively pumping and washing the slurry obtained in the step 2) for 3 times by using ethanol and pure water, drying and crushing the obtained filter cake, calcining the processed white powder in a muffle furnace at 900 ℃ for 4 hours, and finally obtaining the product with complete shell preservation, 100nm of outer diameter, 15nm of wall thickness and 163.2m of specific surface area 2/ g. Pore volume of 0.7cm 3 (ii) hollow spherical silica having a pore diameter of 9.8 nm.
Example 5
A preparation method of hollow spherical silicon dioxide with adjustable specific surface area comprises the following steps:
1) Weighing 30g of hexadecyl trimethyl ammonium chloride, 300g of triethanolamine, 270g of ethanol, 1650g of pure water and 75g (0.51 mol) of dimethyl diethoxy silane, adding the mixture into a 5L high-pressure reaction kettle (the pH value of the mixed solution is 10), adding 750g (3.60 mol) of TEOS under stirring at 50 ℃, and reacting for 2 hours at constant temperature to obtain mesoporous spherical silicon dioxide slurry;
2) Heating on the basis of the step 1), and carrying out hydrothermal reaction at 160 ℃ for 10h to obtain hollow spherical silicon dioxide slurry;
3) Respectively pumping and washing the slurry obtained in the step 2) for 3 times by using ethanol and pure water, drying and crushing the obtained filter cake, calcining the processed white powder in a muffle furnace at 1000 ℃ for 2 hours, and finally obtaining a product with a complete shell, an outer diameter of 100nm, a wall thickness of 16nm and a specific surface area of 70.1m 2/ g. Pore volume of 0.2cm 3 (ii) hollow spherical silica having a pore diameter of 8.4 nm.
BET data of the hollow spherical silicas obtained in the preparation of examples 2 to 5 at different calcination temperatures are shown in Table 1. The results in table 1 show that: by controlling the calcination temperature, hollow spherical silica with different specific surface areas, pore volumes and pore diameters can be obtained.
TABLE 1 BET test data for 100nm hollow spherical silica at different calcination temperatures
Example 6
A preparation method of hollow spherical silicon dioxide with adjustable specific surface area comprises the following steps:
1) Weighing 40g of hexadecyl trimethyl ammonium chloride, 180g of triethanolamine, 225g of ethanol, 1950g of pure water and 75g (0.38 mol) of gamma-mercaptopropyl trimethoxy silane, adding the mixture into a 5L high-pressure reaction kettle (the pH value of the mixed solution is 10), adding 450g (2.16 mol) of TEOS under stirring at 60 ℃, and reacting for 3 hours at constant temperature to obtain mesoporous spherical silicon dioxide slurry;
2) Heating on the basis of the step 1), and carrying out hydrothermal reaction at 160 ℃ for 10h to obtain hollow spherical silicon dioxide slurry;
3) Filtering and washing the slurry obtained in the step 2) with ethanol and pure water respectively for 3 times, drying and crushing the obtained filter cake, calcining the processed white powder in a muffle furnace at 500 ℃ for 11 hours, and finally obtaining the product with complete shell preservation, 200nm of outer diameter, 40nm of wall thickness and 500.7m of specific surface area 2/ g. Pore volume is 1.8cm 3 (ii) hollow spherical silica having a pore diameter of 20.9 nm.
Example 7
A preparation method of hollow spherical silicon dioxide with adjustable specific surface area comprises the following steps:
1) Weighing 50g of sodium dodecyl sulfate, 375g of triethanolamine, 270g of ethanol, 1800g of pure water and 105g (0.42 mol) of gamma-methacryloxypropyltrimethoxysilane into a 5L high-pressure reaction kettle (the pH value of the mixed solution is 10), adding 600g (2.88 mol) of TEOS under stirring at 30 ℃, and reacting for 1 hour at constant temperature to obtain mesoporous spherical silica slurry;
2) Heating the base of the step 1), and carrying out hydrothermal reaction at 130 ℃ for 15h to obtain hollow spherical silicon dioxide slurry;
3) Respectively carrying out suction filtration and washing on the slurry obtained in the step 2) for 3 times by using ethanol and pure water, drying and crushing the obtained filter cake, calcining the treated white powder in a muffle furnace at 500 ℃ for 11h, and finally obtaining a shellComplete preservation, 300nm of outer diameter, 50nm of wall thickness and 438.7m of specific surface area 2/ g. Pore volume is 1.9cm 3 (ii) hollow spherical silica having a pore diameter of 21.2 nm.
Application test
The preparation method of the transparent heat-insulating hollow spherical silicon dioxide/water-based polyacrylate composite coating and the film comprises the following steps:
1) The hollow sphere-shaped silicon dioxide powder obtained in example 1 is put in pure water again, and is stirred for 30min at a high speed by a dispersion machine, so that slurry with required fineness (the concentration is 20%) is obtained;
2) Adding the slurry obtained in the step 1) into a mixed solution consisting of an aqueous polyacrylate emulsion, a wetting agent (CF-10), a dispersing agent (DN 01), a defoaming agent (BYK 022) and a leveling agent (RM 2020) (the mass ratio is 100;
3) Coating the composite coating obtained in the step 2) on a glass substrate through a coating device, airing at room temperature, and obtaining the transparent heat-insulating hollow spherical silicon dioxide/water-based polyacrylate composite film, wherein the coating thickness is 75 micrometers.
TABLE 2 optical property data of hollow spherical silicas calcined at 500 ℃ (50 nm) in coatings with different addition amounts (based on polyacrylate in proportion)
The optical performance test standard of the transparent heat-insulating coating is carried out according to GBT 2680-2021 (the index requires that the visible light transmittance is not less than 60%, the ultraviolet light blocking rate is not less than 60%, and the infrared light blocking rate is not less than 70%), and the result is shown in Table 2. The results in table 2 show that: the transparent heat-insulating coating prepared by the invention (taking 50nm hollow spherical silicon dioxide as an example, the addition amount is 15% -25%) has higher ultraviolet and infrared blocking rate on the premise of ensuring good visible light transmittance, the ultraviolet blocking rate is more than 78%, and the infrared blocking rate is more than 70%.
The thermal insulation performance test standard of the transparent thermal insulation coating is carried out according to GBT 2680-2021. Figure 4 shows the thermal insulation performance data for different amounts of hollow sphere silica added to the coating. The results of fig. 4 show that: when the addition amount of the hollow spherical silicon dioxide is 25%, the maximum heat insulation temperature difference reaches 9 ℃, which shows that the transparent heat insulation coating prepared by the invention has good heat insulation performance.
In conclusion, it can be seen that: the hollow spherical silica with different specific surface areas prepared by the invention has lower heat conductivity coefficient and excellent visible light transmittance, is a filler of an ideal transparent heat insulation coating, and can be applied to the fields of building, automobile, train, aircraft glass and the like; the method has the advantages of simple process, low cost, extremely high application value and wide market prospect.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above examples, and any other modifications without departing from the scope of the present invention should be replaced by equivalents, and all such modifications are included in the scope of the present invention.
Claims (10)
1. The preparation method of the hollow spherical silicon dioxide with the adjustable specific area is characterized by comprising the following steps:
1) Carrying out hydrolytic condensation reaction on a surfactant, a silane coupling agent, tetraethyl orthosilicate and an ethanol aqueous solution under an alkaline condition to obtain mesoporous spherical silica slurry; then carrying out hydrothermal reaction to obtain hollow spherical silicon dioxide slurry;
2) And washing, drying, crushing and calcining the hollow spherical silicon dioxide slurry to obtain the hollow spherical silicon dioxide with the adjustable specific area.
2. The method for preparing hollow spherical silica having adjustable specific area according to claim 1, wherein in step 1), the surfactant is one or more selected from cetyltrimethylammonium bromide, dodecylammonium chloride, sodium dodecylsulfate, and cetyltrimethylammonium chloride.
3. The method for preparing hollow spherical silica having a tunable specific surface area according to claim 1, wherein in step 1), the silane coupling agent is one or more selected from the group consisting of γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, and hexamethyldisilazane.
4. The method for preparing hollow spherical silica with adjustable specific surface area according to claim 1, wherein in the ethanol aqueous solution in the step 1), the molar ratio of ethanol to water is 1: (10-30); and adjusting the pH value to 9-12 by one or more of triethanolamine, diethanolamine, triethylamine and diethylamine.
5. The method for preparing hollow spherical silica with adjustable specific surface area according to claim 1, wherein in the step 1), the hydrolysis condensation reaction temperature is 30-60 ℃ and the reaction time is 1-5h.
6. The method for preparing the hollow spherical silica with the adjustable specific surface area according to claim 1, wherein in the step 1), the molar ratio of the silane coupling agent to the tetraethyl orthosilicate is 1: (2-20).
7. The method for preparing the hollow spherical silica with adjustable specific surface area according to claim 6, wherein in the step 1), the hydrothermal reaction temperature is 110-180 ℃ and the reaction time is 6-16h.
8. The method for preparing hollow spherical silica having an adjustable specific surface area according to claim 1, wherein in the step 2), the calcination temperature is 500 to 1100 ℃ and the calcination time is 2 to 12 hours.
9. Hollow spherical silica having a tunable specific surface area, prepared by the process of any one of claims 1 to 8.
10. Use of the hollow spherical silica with adjustable specific surface area according to claim 9 in a transparent thermal barrier coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211011039.4A CN115924924A (en) | 2022-08-23 | 2022-08-23 | Hollow spherical silicon dioxide with adjustable specific surface area and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211011039.4A CN115924924A (en) | 2022-08-23 | 2022-08-23 | Hollow spherical silicon dioxide with adjustable specific surface area and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115924924A true CN115924924A (en) | 2023-04-07 |
Family
ID=86549349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211011039.4A Pending CN115924924A (en) | 2022-08-23 | 2022-08-23 | Hollow spherical silicon dioxide with adjustable specific surface area and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115924924A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2409423C1 (en) * | 2009-11-02 | 2011-01-20 | Учреждение Российской академии наук Институт технической химии Уральского отделения РАН | Method of producing mesoporous silicon dioxide |
| CN102060300A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for synthesizing high-dispersibility high-specific surface area large-pore volume SiO2 hollow spheres |
| CN102491353A (en) * | 2011-12-10 | 2012-06-13 | 济南大学 | Method for preparing transparent porous silica microspheres |
| CN102718225A (en) * | 2012-07-18 | 2012-10-10 | 中国人民解放军南京军区南京总医院 | Preparation method of ordered mesoporous silica microspheres with hollow structures |
| CN102951648A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of nano silicon dioxide |
-
2022
- 2022-08-23 CN CN202211011039.4A patent/CN115924924A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2409423C1 (en) * | 2009-11-02 | 2011-01-20 | Учреждение Российской академии наук Институт технической химии Уральского отделения РАН | Method of producing mesoporous silicon dioxide |
| CN102060300A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for synthesizing high-dispersibility high-specific surface area large-pore volume SiO2 hollow spheres |
| CN102951648A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of nano silicon dioxide |
| CN102491353A (en) * | 2011-12-10 | 2012-06-13 | 济南大学 | Method for preparing transparent porous silica microspheres |
| CN102718225A (en) * | 2012-07-18 | 2012-10-10 | 中国人民解放军南京军区南京总医院 | Preparation method of ordered mesoporous silica microspheres with hollow structures |
Non-Patent Citations (2)
| Title |
|---|
| 宋方祥等: "不同方法脱除介孔氧化硅有机模板剂", 硅酸盐通报, vol. 37, no. 1, 31 January 2018 (2018-01-31), pages 333 * |
| 马雪慧等: "中空纳米二氧化硅微球的制备及表征", 无机化学学报, vol. 25, no. 6, 30 June 2009 (2009-06-30), pages 11 - 14 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107954429B (en) | Silicon dioxide hollow microsphere, preparation method thereof and application thereof in heat-insulating coating | |
| CN111303709B (en) | Radiation refrigeration coating and preparation method and application thereof | |
| CN111547730B (en) | Preparation method of ultrafine precipitated silica anticaking agent for powder coating | |
| CN107057549B (en) | A kind of preparation method of the insulating mold coating for high-transparent glass of superhydrophilic self-cleaning | |
| CN111498859A (en) | Preparation method of high-transparency high-dispersibility white carbon black | |
| CN111592805A (en) | Coating and preparation method and application thereof | |
| CN110526270A (en) | A kind of preparation method of low sodium ball shaped nano alpha-alumina powder | |
| CN114195158B (en) | Preparation method of high-purity monodisperse nano spherical silicon dioxide powder | |
| US5891565A (en) | Sol and fine powder of sodium magnesium fluoride and processes for their production | |
| CN113214740B (en) | Light-reflecting transparent heat-insulating coating, preparation method thereof and light-reflecting heat-insulating top coat | |
| CN115924924A (en) | Hollow spherical silicon dioxide with adjustable specific surface area and preparation method and application thereof | |
| CN102585557B (en) | Method for industrially preparing transparent filler nano calcium carbonate for agricultural polyethylene (PE) film | |
| CN112299425B (en) | Silica sol with convex colloid surface and preparation method and application thereof | |
| CN113683117A (en) | Nano tin oxide powder and preparation method thereof | |
| CN110980747B (en) | Low-viscosity high-transparency friction type silicon dioxide for toothpaste and preparation method thereof | |
| US20150315392A1 (en) | Coating liquid for forming alkali barrier layer, and article | |
| CN101302358A (en) | Waterless nano-znic antimonite sol and preparation thereof | |
| US5019146A (en) | Method for producing glass | |
| CN115010155B (en) | Method for modifying surface of carrier silicon dioxide | |
| CN110526586A (en) | A kind of preparation method of low-density hollow glass bead | |
| CN115785746A (en) | Water-based heat-insulating coating for metal surface and preparation method thereof | |
| CN100591728C (en) | Efficient flatting agent based on quartz powder and its preparation method and uses | |
| CN112500124A (en) | High-strength ceramic micro-bead and preparation method thereof | |
| CN111333412B (en) | Porous cordierite and preparation method and application thereof | |
| JP3286071B2 (en) | Production method of hydrophobic antimony-containing tin oxide fine particles, heat ray shielding coating liquid and its production method, and heat ray shielding glass and its production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |