CN112479215B - Preparation method of narrow-dispersion large-particle-size silica sol - Google Patents
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Abstract
A preparation method of narrow-dispersion large-particle-size silica sol comprises the following steps: (1) Mixing low molecular alcohol and pure water, heating in oil bath at constant temperature of 80 deg.C, and mechanically stirring for 30min; (2) adding an alkali catalyst into the obtained solution; (3) Dropwise adding a silicon source precursor solution and a surface modifier solution into the solution, and continuously mechanically stirring at a constant temperature of 80 ℃; (4) Concentrating to the required solid content, thereby obtaining the silica sol product with narrow dispersion and large particle size. Compared with the traditional silica sol, the silica sol prepared by the invention has the advantages of large particle size, concentrated particle size distribution, high sphericity, good stability and the like, and can be better applied to the technical fields of optical film coating liquid and the like.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a preparation method of silica sol.
Background
In recent years, colloidal silica (silica sol) has played an important role in nano-and fine-particle research. Silica sols are colloidal dispersions of amorphous silica particles dispersed in water (or an organic solvent), usually colorless or milky transparent (translucent) liquids, mostly stable alkaline, and few acidic. The specific surface area of the silica sol particles is 50-400m 2 In the per gram range, the particle size is generally in the range from 5 to 100nm, i.e.on the nanoscale. Silica sol has many excellent properties, such as large specific surface area, high adsorbability, high dispersity, high fire resistance, heat insulation, oxidation resistance and the like, and has simple production process and wide raw material sources, so that the silica sol becomes an important inorganic polymer raw material and is widely applied to the fields of chemical industry, spinning, papermaking, precision casting, coatings, electronics and the like. However, with the continuous widening of the application range and the continuous improvement of the use requirement, the traditional silica sol can not be fully usedIn order to meet the needs of industrial development, silica sol with large particle size, narrow particle size distribution and good stability is in great demand in fine fields such as integrated circuit manufacturing and optical polyester films.
Currently, methods for preparing silica sol include elemental silicon hydrolysis, ion exchange, direct acid neutralization, electrolytic electrodialysis, peptization, and dispersion methods, and the like. The methods which can be applied in large quantities in industrial production are only elemental silicon hydrolysis and ion exchange. The simple substance silicon hydrolysis method is to hydrolyze simple substance silicon powder under the combined action of heating and catalyst to generate active silicic acid solution, and then generate SiO by continuous hydrolytic polymerization 2 Particles, and a silica sol is prepared by particle growth. The colloidal particle shape, particle size, density, purity and the like of the silicon dioxide in the silica sol prepared by the method can be controlled, the colloidal particle has round and uniform appearance, compact structure and better stability, but the prepared silica sol has the defects that the particle size is smaller and generally not more than 80nm, and the requirement of various fields on the silica sol with large particle size cannot be met. The silica sol prepared by the ion exchange method takes water glass as a raw material, and a silica sol product is prepared by the steps of ion exchange reaction, seed crystal preparation, particle growth reaction, concentration, purification and the like. Each step influences the quality of the final silica sol product, and physicochemical indexes of the silica sol product, such as size, uniformity, impurity content, stability and the like, of colloidal particles are determined by controlling various conditions in the preparation process. Although the cost of the method is low, the process is very complicated, the content of impurities generated in the production process is high, the particle size distribution range is wide, and the requirements of fine occasions such as modern integrated circuit manufacturing, optical polyester film production and the like cannot be met.
Chinese patent CN105883824A and Chinese patent CN108002394A provide a preparation method of silica sol with large particle size, but the requirement of narrow particle size distribution can not be met; the method for rapidly preparing the silica sol with large particle size provided by the Chinese patent CN104495857A has relatively narrow particle size distribution, but the distribution of chain bead strings of the particles can be obviously seen from an electron microscope image of the method, and the chain bead string particles can not be applied to numerous fine fields; the preparation method of the monodisperse large-particle size silica sol provided by the Chinese patent CN1974385A has large particle size and narrow distribution range of the silica sol, and because more metal ions are added in the preparation process, the large amount of metal ions can generate negative effects on the application of the silica sol in the industries of precision casting, optical films and the like. In order to shorten the production period and improve the production efficiency by analyzing the prior art of silica sol preparation, a method capable of quickly and effectively preparing silica sol with good stability, high sphericity and narrow dispersion and large particle size is required at the present stage.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of narrow-dispersion large-particle-size silica sol, which has the advantages of simple process, high preparation speed and good physical and chemical properties of products.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of narrow-dispersion large-particle-size silica sol comprises the following steps:
(1) Mixing low molecular alcohol and a proper amount of pure water, adding into a three-neck flask, heating in an oil bath kettle at a constant temperature of 80 ℃, and mechanically stirring for 30min;
(2) Adding an alkali catalyst into the solution obtained in the step (1), and continuously mechanically stirring at the constant temperature of 80 ℃ for 10min;
(3) Quickly dropwise adding a silicon source precursor solution and a surface modifier solution into the solution obtained in the step (2), and continuously mechanically stirring at the constant temperature of 80 ℃ for 2-5 hours after dropwise adding is finished; the rapid dropwise addition is completed within 15 s;
(4) And (4) pouring the solution obtained in the step (3) into a beaker, stirring for 2 hours at room temperature by an open magnetic force, and concentrating to obtain the required solid content, thereby obtaining the narrow-dispersion large-particle-size silica sol product.
In the preparation method of the narrow-dispersion large-particle-size silica sol, the low molecular alcohol is at least one of methanol, ethanol, propanol or isopropanol, and the using amount is 100 volume units.
According to the preparation method of the narrow-dispersion large-particle-size silica sol, the precursor of the silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate, and the using amount of the precursor is (7-15) volume units.
In the preparation method of the narrow-dispersion large-particle-size silica sol, in the step (3), the surface modifier is gamma-methacryloxypropyltrimethoxysilane kh-570, and the using amount is (1-2) volume units.
In the preparation method of the narrow-dispersion large-particle-size silica sol, the using amount of the pure water is (0.5-7) volume unit. In the present invention, the main solvent is low molecular alcohol, pure water is used as reactant, and the addition amount is not suitable for excess, otherwise the particle size of the particles can be greatly changed, so the lower addition amount is selected.
According to the preparation method of the narrow-dispersion large-particle-size silica sol, the alkali catalyst is ammonia water, the concentration of the ammonia water is 25% -28%, and the using amount is 7 volume units.
In the preparation method of the narrow-dispersion large-particle-size silica sol, the stirring speed of the mechanical stirrer in the steps (1), (2) and (3) is 200-800rpm.
In the preparation method of the narrow-dispersion large-particle-size silica sol, the magnetic stirring speed in the step (4) is 200rpm. In the steps (1), (2) and (3), a mechanical stirring device is adopted to complete the synthesis process, and the higher rotating speed is used for controlling the preparation of the particle size; and the step (4) adopts a magnetic stirring device for the concentration process, and the concentration process needs a proper rotating speed to assist the concentration process.
Advantageous effects
Compared with the traditional silica sol, the silica sol prepared by the invention has the advantages of large particle size (the particle size is more than 65 nm), concentrated particle size distribution (the particle dispersion index is less than 0.065), high sphericity (no irregular particles exist), good stability (the stable period exceeds three months) and the like, and can be better applied to the application fields of optical film coating liquid and the like.
Drawings
FIG. 1 is a transmission electron micrograph of silica sol with a particle size of 80 nm;
FIG. 2 is a graph showing a distribution of the particle size of 100nm silica sol. In the figure, the median particle diameter is 100nm, the average (standard) particle diameter is 101nm, and the particle dispersion index is 0.061.
Detailed Description
The present invention is described in further detail below with reference to specific examples.
Example 1
The specific preparation method of the silica sol with the particle size of 80nm mainly comprises the following operation steps:
(1) Mixing 100mL of ethanol and 0.5mL of pure water, adding into a three-neck flask, heating in an oil bath kettle at a constant temperature of 80 ℃, and mechanically stirring for 30min;
(2) Adding 7mL of ammonia water into the solution obtained in the step (1), and continuing to mechanically stir at the constant temperature of 80 ℃ for 10min after the addition is finished;
(3) Quickly dropwise adding 7mL of ethyl orthosilicate solution and 1mL of gamma-methacryloxypropyl trimethoxysilane into the solution obtained in the step (2), and continuously mechanically stirring at the constant temperature of 80 ℃ for 2 hours after dropwise adding is finished;
(4) And (4) pouring the solution obtained in the step (3) into a beaker, carrying out open magnetic stirring for 2 hours at room temperature, and concentrating to obtain the required solid content, thus obtaining the narrow-dispersion large-particle-size silica sol with the average particle size of 80 nm.
Example 2
The specific preparation method of 100 nm-particle-size silica sol mainly comprises the following operation steps of:
(1) Mixing 100mL of ethanol and 5mL of pure water, adding into a three-neck flask, heating in an oil bath kettle at a constant temperature of 80 ℃, and mechanically stirring for 30min;
(2) Adding 7mL of ammonia water into the solution obtained in the step (1), and continuing to mechanically stir at the constant temperature of 80 ℃ for 10min after the addition is finished;
(3) Quickly dropwise adding 11mL of methyl orthosilicate solution and 1.5mL of gamma-methacryloxypropyltrimethoxysilane into the solution obtained in the step (2), and continuously mechanically stirring at the constant temperature of 80 ℃ for 3 hours after dropwise adding is finished;
(4) And (4) pouring the solution obtained in the step (3) into a beaker, carrying out open magnetic stirring for 2 hours at room temperature, and concentrating to obtain the required solid content, thus obtaining the narrow-dispersion large-particle-size silica sol with the average particle size of 80 nm.
Example 3
The specific preparation method of the silica sol with the particle size of 150nm mainly comprises the following operation steps:
(1) Mixing 100mL of ethanol and 7mL of pure water, adding the mixture into a three-neck flask, heating the mixture in an oil bath kettle at a constant temperature of 80 ℃, and mechanically stirring the mixture for 30min;
(2) Adding 7mL of ammonia water into the solution obtained in the step (1), and continuing to mechanically stir at the constant temperature of 80 ℃ for 10min after the addition is finished;
(3) Quickly dropwise adding 15mL of silicon source precursor solution and 2mL of gamma-methacryloxypropyltrimethoxysilane into the solution obtained in the step (2), and continuously mechanically stirring at the constant temperature of 80 ℃ for 5 hours after dropwise adding is finished;
(4) And (4) pouring the solution obtained in the step (3) into a beaker, magnetically stirring the solution for 2 hours at room temperature in an open manner, and concentrating the solution to the required solid content to obtain the narrow-dispersion large-particle-size silica sol with the average particle size of 150 nm.
Table 1: measurement results of silica Sol Performance data prepared in examples
Claims (5)
1. A preparation method of narrow-dispersion large-particle-size silica sol is characterized in that the particle size of the silica sol is more than 65nm, the particle dispersion index is less than 0.065, the sphericity is high, irregular particles do not exist, and the stabilization period exceeds three months;
the preparation method comprises the following steps:
(1) Mixing low molecular alcohol and appropriate amount of pure water, adding into three-neck flask, heating in oil bath at constant temperature of 80 deg.C, and mechanically stirring for 30min;
(2) Adding an alkali catalyst into the solution obtained in the step (1), and continuously mechanically stirring at the constant temperature of 80 ℃ for 10min;
(3) Quickly dropwise adding a silicon source precursor solution and a surface modifier solution into the solution obtained in the step (2), and continuously mechanically stirring at the constant temperature of 80 ℃ for 2-5 hours after dropwise adding is finished; the rapid dripping is completed within 15 s;
(4) Pouring the solution obtained in the step (3) into a beaker, carrying out open magnetic stirring for 2 hours at room temperature, and concentrating to obtain a required solid content, thereby obtaining a narrow-dispersion large-particle-size silica sol product;
the low molecular alcohol is at least one of methanol, ethanol, propanol or isopropanol, and the dosage is 100 volume units;
the silicon source precursor is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or butyl orthosilicate, and the using amount is (7-15) volume unit;
the surface modifier in the step (3) is gamma-methacryloxypropyltrimethoxysilane kh-570, and the using amount is (1-2) volume units.
2. The method for producing a narrow-dispersion large-particle-size silica sol according to claim 1, wherein the amount of pure water is (0.5 to 7) volume unit.
3. The method for preparing a narrow-dispersion large-particle-size silica sol according to claim 1, wherein the alkali catalyst is ammonia water having a concentration of 25 to 28% and an amount of 7 volume units.
4. The method for preparing a narrow-dispersion large-particle-size silica sol according to claim 1, wherein the stirring speed of the mechanical stirrer in the steps (1), (2) and (3) is 200 to 800rpm.
5. The method for preparing a narrowly dispersed large-particle-size silica sol according to claim 1, wherein the magnetic stirring speed in the step (4) is 200rpm.
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