CN111099597B - Active nano silicon dioxide microsphere, solution, preparation method and application thereof - Google Patents

Active nano silicon dioxide microsphere, solution, preparation method and application thereof Download PDF

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CN111099597B
CN111099597B CN201811248743.5A CN201811248743A CN111099597B CN 111099597 B CN111099597 B CN 111099597B CN 201811248743 A CN201811248743 A CN 201811248743A CN 111099597 B CN111099597 B CN 111099597B
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silicon dioxide
silica
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CN111099597A (en
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翟晓东
李应成
苏智青
沙鸥
沈之芹
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
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    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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Abstract

The invention relates to an active nano silicon dioxide microsphere, a solution, a preparation method and application thereof, and mainly aims to solve the problem of using
Figure DDA0001841146710000011
The nano silicon dioxide microspheres prepared by the method can not directly react with the modified glass, ceramics and silicon surface, so that the problem of difficulty in preparing the coating with the micro-nano characteristic structure is solved. The invention better solves the problem by adopting the technical scheme that the active nano-silica microspheres comprise nano-silica microspheres and an active layer on the surfaces of the nano-silica microspheres, and the active layer contains condensable siloxane, and can be used for preparing coatings with micron or nano structure characteristics on the surfaces of glass, ceramics and silicon.

Description

Active nano silicon dioxide microsphere, solution, preparation method and application thereof
Technical Field
The invention relates to a solution of nano silicon dioxide microspheres capable of directly carrying out chemical reaction with glass, ceramic or silicon surfaces so as to prepare coatings with micron and nano structural characteristics on the solid surfaces, and a preparation method and application thereof.
Background
The molecular structure, the nano-structure and the micro-structure of the material jointly determine the function of the material. The nano structure is a mesoscopic system which is constructed or built according to a certain rule based on a material unit with a micron and nano scale and comprises a one-dimensional structure, a two-dimensional structure and a three-dimensional structure. Since the nano-structure may give the material a quantum size effect, a small size effect, a surface effect, a quantum coupling effect, a synergistic effect and the like, the construction of the material with the micro-and nano-sized features by various methods is one of the hot spots of the research of the materials science in recent years.
Micro-and nanostructures can impart very rich properties and functionalities to materials. Natural biomaterials such as shells, bones, teeth, etc. have excellent overall properties and functions because they have a complex and elaborate multi-scale hierarchical structure. In the hierarchical structure of these natural biomaterials, small inorganic particles play a very important role. For example, in mollusk shells 95% of calcium carbonate ceramic disks are stacked on top of each other like coins, with a very thin layer of biopolymer between each layer of ceramic disks to bind them together. And each ceramic disk platelet has its own complex nanostructure. Furthermore, the nanostructure system can easily control the performance thereof by an external field. Due to the special role played by nano-inorganic particles on natural biomaterials as well as other materials. The use of inorganic nanoparticles to prepare a wide variety of materials with nano-micro structures has attracted a great deal of attention from scientists.
Wetting is one of the most common phenomena in nature. The phenomenon of infiltration plays an extremely important role both in the daily life of people and in industrial and agricultural production. The physicochemical structure of the surface interface determines the solid surface wettability. Many scientists at home and abroad find that the micro-and nano-structures on the surfaces of animals and plants endow organisms with peculiar wetting behaviors, such as the self-cleaning effect of lotus leaves, by researching the relationship between the wetting properties of various animals and plants in nature and peculiar structures of the surfaces. Many researchers have found that the surface of lotus leaves has specific micron and nanometer size waxy protrusions. Due to the unique micro-nano structure, the lotus leaf surface has super-hydrophobicity. If water drops fall on the lotus leaf surface, the water drops roll off quickly and cannot wet the lotus leaf surface, and meanwhile dust falling on the lotus leaf surface is adhered away, so that the lotus leaf has self-cleaning performance, and people often see that the lotus leaf surface in summer is very clean and rarely stained with dust and water.
In order to realize the peculiar properties of the biosurfaces/interfaces on the material surface, many scientists use various methods to prepare structures with micron and nanometer sizes on the material surface. For example, the Jiangre research group of the chemical research institute of Chinese academy of sciences proposes a simple and effective method for self-assembling a one-dimensional array carbon nanotube into a three-dimensional micrometer-scale patterned surface. The national laboratory Liujun research group in the North of the Taiping American utilizes a wet chemical method to build a complex multi-scale hierarchical ordered nanostructure through the distribution sequential nucleation and growth of crystals.
The nano silicon dioxide microspheres are a commonly used unit for constructing a micro-nano structure. By using
Figure BDA0001841146690000021
The silicon dioxide microsphere synthesized by the method has the characteristics of uniform structure size, adjustable particle size, low refractive index and the like. Many researchers have attempted to build coatings with micro-and nano-features on the surface of materials using nano-silica microspheres. The preparation of SiO with different grain diameters by adopting a sol-gel method for the blue2The particles are obtained by surface modification of composite particles with different shapes, and the super-hydrophobic coating film with the lotus effect is prepared by utilizing the surface self-assembly function of fluorosilicone. The fluoroalkyl functionalized nano mesoporous silica particles are prepared by taking tetraethoxysilane and fluoroalkyl siloxane as silicon sources, such as Wubao tiger and the like, and the nano particle coating has good permeability-increasing performance on optical glass and is an optical anti-reflection material with excellent performance.
Although nanosilica has a number of advantages, it has a distinct disadvantage: the silica particles themselves cannot react directly with the glass, ceramic and silicon surfaces to be modified to form a bond of some strength. In order to fix silica microsphere coatings with certain micron nanostructures, which have been formed on modified surfaces, with chemical bonds, many researchers have tried many approaches. In order to fix the silicon dioxide microsphere structure with the micro-nano structure, such as Hawai of the university of Compound denier, the coating is soaked by tetrachlorosilane solution. Although the silica microspheres can be immobilized by such a method, tetrachlorosilane may block nano voids in the micro-nano structure.
The invention develops an alcoholic solution system of nano silicon dioxide microspheres with surface reactivity. The alcoholic solution can be directly coated on glass, ceramic and silicon surfaces, and a coating with a micro-nano structure is directly formed on the solid surfaces. The method can be used for preparing rough coatings with changed wettability and can also be used for preparing anti-reflecting coatings on the surfaces of lenses. In addition, the method is expected to be applied to the fields of catalysis, coating, biology and the like.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the nano-silica microspheres for constructing the surface micro-nano structure in the prior art can not directly react with the modified glass, ceramic and silicon surface, and the invention provides the active nano-silica microspheres which have surface activity and can be used for the modified glass, ceramic and silicon surface.
The second technical problem to be solved by the invention is that the nano-silica microspheres for constructing the surface micro-nano structure in the prior art can not directly react with the modified glass, ceramic and silicon surface, and provides an active nano-silica microsphere solution containing surface activity, which comprises active nano-silica microspheres, a surfactant, acid and alcohol.
The third technical problem to be solved by the present invention is to provide a method for preparing an active nano silica microsphere solution corresponding to the second technical problem.
The third technical problem to be solved by the present invention is to provide an application of the active nano-silica microsphere solution corresponding to the second technical problem.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: an active nano-silica microsphere comprises a nano-silica microsphere and an active layer on the surface of the nano-silica microsphere, wherein the active layer contains condensable siloxane.
In the above technical solution, the condensable siloxane is derived from or selected from siloxanes, and the molecular formula of the siloxane is preferably:
Figure BDA0001841146690000031
in the formula (I), R1And R2Is selected from C1-C10Alkoxy group of (a); r3And R4Selected from hydrogen, alkyl, C-alkenyl or C1-C10Alkoxy group of (2).
In order to solve the second technical problem, the invention adopts the following technical scheme: an active nano silicon dioxide microsphere solution comprises the following components in parts by weight:
(1) 0.01-20 parts of active nano silicon dioxide microspheres in one of the technical schemes for solving the technical problems;
(2) 0.001-1 part of a surfactant;
(3) 0.005-5 parts of acid.
In the above technical solution, in the active nano-silica microsphere solution, the active nano-silica microspheres are prepared by modifying the surfaces of the nano-silica microspheres with siloxane under alkaline or acidic conditions, and the siloxane has a molecular general formula:
Figure BDA0001841146690000032
in the formula (I), R1And R2Is selected from C1-C10Alkoxy of (3), preferably C1-C3Alkoxy group of (a); r2And R4Selected from hydrogen, alkyl, C-alkenyl or C1-C10Alkoxy of (3), preferably C1-C3Alkoxy group of (2).
In the technical scheme, the active nano silicon dioxide microspheres are more preferably 0.01-1 part.
In the technical scheme, the surfactant is preferably 0.01-0.1 part; the general molecular formula of the surfactant is preferably:
Figure BDA0001841146690000041
in the formula (II), R5Is selected from C10-18Alkyl or alkenyl of (a), 1 to 20 siloxy units or C8-18N is selected from 1 to 20, and m is selected from 0 to 20.
In the technical scheme, the acid is preferably 0.01-0.1 part;
in the above technical scheme, R1And R2Preferably C1-C3Linear alkoxy groups of (1).
In the above technical scheme, R3And R4Preferably C1-C3Linear alkoxy groups of (1).
In the above technical solution, the acid is preferably an inorganic acid; more preferably at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
In the above technical scheme, the alcoholic solution of the active nano-silica microspheres preferably further comprises, in parts by weight: (4) 74-99.94 parts of alcohol; the alcohol may be methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and more preferably ethanol, propanol, isopropanol.
In the technical scheme, the nano active silica microsphere solution is a solution formed by uniformly mixing active nano silica microspheres, a surfactant, acid and alcohol.
In the above technical solution, the nano active silica microsphere solution preferably contains the following components: the weight percentage content of the active nano silicon dioxide microspheres is 0.01 to 20 percent by weight, the weight percentage content of the surface active agent is 0.001 to 1 percent by weight, the weight percentage content of the acid is 0.005 to 5 percent by weight, and the balance is alcohol
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a method for preparing the active nano-silica microsphere solution according to any one of the above two technical solutions, comprising the following steps:
(1) preparation of active nano silicon dioxide microsphere
a) Dissolving silicate ester with required amount in alcohol, reacting in the presence of a catalyst, and removing the catalyst to obtain nano silicon dioxide microsphere alcohol solution;
b) adding silicate ester, water and a catalyst into the nano-silica microsphere alcoholic solution obtained in the step a), and reacting for 2-20 hours to obtain the active nano-silica microspheres;
(2) preparation of active nano silicon dioxide microsphere solution
Uniformly mixing the active nano silicon dioxide microspheres, the surfactant, the acid and the solvent in required amount; obtaining the active nano silicon dioxide microsphere solution.
In the above technical solution, the catalyst is preferably selected from a basic catalyst or an acidic catalyst, and more preferably at least one of ammonia water, sodium hydroxide, hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid; for example, the catalyst in step a) is preferably aqueous ammonia; the catalyst in step b) is preferably at least one of sodium hydroxide, hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid.
In order to solve the fourth technical problem, the technical scheme adopted by the invention is as follows: an application method of the active nano-silica microsphere solution according to any one of the above two technical solutions.
In the above technical solution, the application method is not particularly limited, and for example, but not limited to, the method is directly applied to modifying glass, ceramic and silicon surface; for example, the active nano-silica microsphere solution can be used for forming a coating on the surface of the modified solid material by adopting a method such as soaking, spraying or spin coating. And then curing the coating by heating in a hot air, an oven, a hot plate, and the like. The temperature of the application is preferably from 15 ℃ to 100 ℃.
In the above technical scheme, the concentration of the active nano-silica microspheres in the active nano-silica microsphere solution is preferably 0.5 wt% to 5 wt% based on the weight of the active nano-silica microspheres.
In the above technical scheme, the active nano silica microspheres are not sensitive to alcohol, and may be alcohol known by those skilled in the art, such as methanol, ethanol, propanol, isopropanol, and the like.
The active nano silicon dioxide microspheres prepared by the invention have good structural regularity and good reaction activity performance, and can construct a coating with a regular structure, and the prepared coating has a regular structure and does not contain organic components, so that the ageing resistance is good. The alcoholic solution of the active nano silicon dioxide microspheres can construct a regular coating with a micro-nano characteristic structure and certain strength on the surfaces of various materials. The active nano silicon dioxide microspheres have the advantages of easily obtained raw materials, economic synthetic route, lower final product cost and the like.
The alcohol solution containing 5 wt% of active nano silicon dioxide microspheres prepared by the invention can form a coating with a regular structure and certain strength on glass and silicon surfaces at 65 ℃, and a better technical effect is achieved.
Drawings
FIG. 1 is a scanning electron microscope (410nm) image of the nano-silica microspheres synthesized in example 1.
FIG. 2 shows active nano-silica microspheres (550nm) prepared on the basis of nano-silica microspheres
The present invention will be further illustrated by the following specific examples.
Detailed Description
[ example 1 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano-silica microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of the nano-silica microspheres to be 410nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. After 5 drops of reaction liquid are diluted by ethanol, the average diameter of the active nano-silica microsphere particles is 550nm by a Malvern particle sizer.
[ example 2 ]
Adding 8ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 70 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 70 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 230nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. 5 drops of the reaction solution were diluted with ethanol and the silica particles were measured for diameter of 400nm using a Malvern particle sizer.
[ example 3 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 40 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 40 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 508nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was measured to be 610nm by a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 4 ]
Adding 15ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 450nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was measured to be 650nm by a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 5 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 230nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was measured to be 400 using a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 6 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 430nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 0.05 g of sodium hydroxide, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing for 5 hours at 50 ℃ to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was measured to be 400 using a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 7 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 230nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 0.05 g of sodium hydroxide, 5ml of dimethoxydimethylsilane and 0.05 g of water, and continuing for 5 hours at the temperature of 50 ℃ to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was 430 by using a malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 8 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 230nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 0.05 g of sodium hydroxide, 5ml of trimethoxy methyl silane and 0.05 g of water, and continuing for 5 hours at the temperature of 50 ℃ to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was 450 by using a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 9 ]
The nanospheres and the active nanospheres synthesized in example 1 were observed by scanning electron microscopy. The microspheres in fig. 1 are nanosilica microspheres synthesized in example 1, and the microspheres have an average diameter of about 410nm and a relatively smooth surface. The microspheres in fig. 2 are the active nano-silica microspheres obtained in example 1. It can be seen from the electron microscope photograph that the outer diameter of the active nano-silica microspheres is slightly larger than that of the nano-silica microspheres, the condensation degree between the hydrolyzed silanes of the active layer part is lower, and the surface is not compact and is rough. The nano-micron pore structure between the active nano-silica microspheres is very clear.
Example 10 construction of micro-nano coating by active nano-silica microspheres
Diluting the active nano silicon dioxide microsphere reaction solution to 1 wt% by using ethanol, adding 0.1 wt% of surfactant OFX5211, and then adjusting the pH of the solution to be equal to 3 by using hydrochloric acid. Dropping the active nanometer silicon dioxide microsphere alcohol solution on a glass slide, spreading the solution, and respectively standing overnight at room temperature, 65 ℃, 90 ℃, 150 ℃ and 300 ℃. It was found that a translucent coating having a certain strength could be formed at 65 c and 90 c, while a coating having a certain strength could not be formed at room temperature, 150 c and 300 c. The nano silica microspheres prepared in comparative example 1 could not form a coating having a certain strength at various temperatures. The treated slides were rinsed with ethanol and then blown dry with compressed air. Treated slides were tested for appearance and contact angle. Where contact angle 1 is measured with water at room temperature and contact angle 2 is measured with hot water at 70 deg.c.
Table 1 contact angle test of micro-nano coating constructed on glass surface by silicon dioxide microsphere
Alcoholic solution of active microspheres Contact angle 1 Contact angle 2
Example 1 68 37
Example 2 65 34
Example 3 70 36
Example 4 63 32
Example 5 66 31
Example 6 61 29
Example 7 65 38
Example 8 62 32
Glass slide 34 32
As can be seen from table 1, the composition of the present invention can effectively form a coating layer having a micro-nano structure with a certain strength on the glass surface. The contact angle of the coating is tested, and the contact angle of the surface of the glass slide with the nano silicon dioxide microsphere coating is obviously higher than that of the glass surface. When the contact angle is measured with hot water, the value of the contact angle is substantially the same as the untreated glass surface. This phenomenon is consistent with the Wenzel and Cassie models. The nano silicon dioxide microspheres are used for processing the surface of the glass to form a micro-nano structure.
Example 11 construction of micro-nano coating by active nano-silica microspheres
Diluting the active nano silicon dioxide microsphere reaction solution to 1 wt% by using ethanol, adding 0.1 wt% of surfactant OFX5211, and then adjusting the pH of the solution to be equal to 3 by using hydrochloric acid. Dripping the active nano silicon dioxide microsphere alcohol solution on a silicon wafer, spreading the solution, and respectively standing overnight at room temperature, 65 ℃, 90 ℃, 150 ℃ and 300 ℃. The treated silicon wafer was rinsed with ethanol and then blown dry with compressed air. Treated slides were tested for appearance and contact angle. Where contact angle 1 is measured with water at room temperature and contact angle 2 is measured with hot water at 70 deg.c.
Table 2 contact angle test of micro-nano coating constructed on silicon surface by silicon dioxide microsphere
Alcoholic solution of active microspheres Contact angle 1 Contact angle 2
Example 1 61 36
Example 2 63 32
Example 3 67 37
Example 4 59 30
Example 5 60 29
Example 6 62 33
Example 7 64 34
Example 8 68 30
As can be seen from table 2, the composition of the present invention can effectively form a coating layer having a micro-nano structure with a certain strength on the surface of a silicon wafer. The contact angle of the coating is tested to find that the contact angle of the surface of the silicon wafer is obviously higher than that of the surface of the silicon wafer after the nano silicon dioxide microsphere coating is constructed on the surface of the silicon wafer. When the contact angle is measured with hot water, the value of the contact angle is substantially the same as that of the surface of the untreated wafer. This phenomenon is consistent with the Wenzel and Cassie models. Shows that the glass surface treated by the nano silicon dioxide microspheres can form a micro-nano structure
Comparative example 1
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃, taking 5 drops of reaction liquid, diluting with ethanol, and testing the diameter of the silicon dioxide particles to be 350nm by using a Malverometer.
The silica microsphere reaction solution was diluted to 1% wt with ethanol, 0.1% wt surfactant OFX5211 was added, and the PH of the solution was adjusted to about 3 with hydrochloric acid. Dripping the nanometer silicon dioxide microsphere alcohol solution on a glass slide, spreading the solution, and standing overnight at room temperature, 65 deg.C, 90 deg.C, 150 deg.C, and 300 deg.C respectively. The treated slides were rinsed with ethanol and then blown dry with compressed air. The treated slides were tested for contact angle. Where contact angle 1 is measured with water at room temperature and contact angle 2 is measured with hot water at 70 deg.c.
TABLE 3 contact angle of glass surface treated with alcoholic solution of silica microspheres
Temperature of heating Contact angle 1 Contact angle 2
At room temperature 34 32
65℃ 35 33
90℃ 33 31
150℃ 36 32
300℃ 35 31
Untreated slides 34 32
As can be seen from table 3, the contact angle of the glass slides treated with the silica microsphere composition without the active layer was substantially the same as that of the untreated glass slides. Therefore, the silica microspheres without the active layer cannot form a coating with certain strength on the glass surface.

Claims (8)

1. An active nano silicon dioxide microsphere solution comprises the following components in parts by weight:
(1) 0.01-20 parts of active nano silicon dioxide microspheres;
(2) 0.001-1 part of a surfactant;
(3) 0.005-5 parts of acid;
the active nano-silica microspheres comprise nano-silica microspheres and an active layer on the surfaces of the nano-silica microspheres, wherein the active layer contains condensable siloxane;
the molecular general formula of the surfactant is as follows:
Figure 249829DEST_PATH_IMAGE001
formula (II);
in the formula (II), R5Is selected from C10-18Alkyl or alkenyl of (a), 1 to 20 siloxy units or C8-18N is selected from 1 to 20, and m is selected from 0 to 20.
2. The active nano-silica microsphere solution according to claim 1, wherein the active nano-silica microspheres are obtained by modifying nano-silica microspheres with siloxane represented by formula (I) under alkaline or acidic conditions:
Figure DEST_PATH_IMAGE002
formula (I);
in the formula (I), R1And R2Is selected from C1-C10Alkoxy group of (a); r3And R4Selected from hydrogen, alkyl, C-alkenyl or C1-C10Alkoxy group of (2).
3. The active nanosilica microsphere solution according to claim 1, characterized in that the acid is selected from inorganic acids or organic carboxylic acids.
4. The active nanosilica microsphere solution according to claim 3, characterized in that the acid is selected from hydrochloric acid, sulphuric acid, phosphoric acid or acetic acid.
5. The active nano-silica microsphere solution according to claim 1, wherein the active nano-silica microsphere solution further comprises, in parts by weight: (4) 74-99.94 parts of alcohol.
6. The active nanosilica microsphere solution of claim 5, wherein the alcohol is at least one or more mixed alcohols selected from ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, ethylene glycol, glycerol, 1, 2-propanediol, 1, 3-propanediol, and butanediol.
7. A method for preparing the active nano silicon dioxide microsphere solution of any one of claims 1 to 6, comprising the following steps:
(1) preparation of active nano silicon dioxide microsphere
a) Dissolving silicate ester with required amount in alcohol, reacting in the presence of a catalyst, and removing the catalyst to obtain nano silicon dioxide microsphere alcohol solution;
b) adding silicate ester, water and a catalyst into the nano-silica microsphere alcoholic solution obtained in the step a), and reacting for 2-20 hours to obtain the active nano-silica microspheres;
(2) preparation of active nano silicon dioxide microsphere solution
Uniformly mixing the active nano silicon dioxide microspheres, the surfactant, the acid and the solvent in required amount; obtaining the active nano silicon dioxide microsphere solution.
8. Use of the active nanosilica microsphere solution according to any of claims 1 to 6 for the preparation of coatings.
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