CN111302347B - Preparation method of high-purity large-particle-size silica sol - Google Patents
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Abstract
The invention discloses a preparation method of high-purity large-particle size silica sol, belonging to the technical field of silica sol preparation. The preparation method comprises mixing acidic silica sol solution with pH of 2-3 with polyethylene glycol 2000-10000, adjusting pH to 8-9.5, heating and boiling to obtain sol crystal; adding acid to activate resin, washing the resin until the pH value is 3.0-4.5, adding an aluminum salt modifier and water glass, and carrying out ion exchange reaction on the water glass to prepare aluminum modified silicic acid; adding aluminum modified silicic acid into the sol crystal grains, adding an alkali solution to adjust the pH value to 9.5-10.5, carrying out ultrafiltration and synthesis, and heating to synthesize the high-purity large-particle-size silica sol. According to the invention, the acidic silica sol is subjected to hydroxylation reaction to enable the acidic silica sol to be aggregated to form a large-particle silica sol matrix, the water glass is used as a raw material, the aluminum modified active silicic acid is prepared by adopting an ion exchange method, and the active silicic acid is synthesized while being subjected to ultrafiltration, so that the particle size is increased quickly, the energy consumption is low, the synthesis period is short, the production efficiency is improved, and the polishing requirement of novel devices in the electronic industry can be met.
Description
Technical Field
The invention belongs to the technical field of silica sol preparation, and particularly relates to a preparation method of high-purity large-particle size silica sol.
Background
Silica sol is a colloidal solution of amorphous silica particles dispersed in water, is an important inorganic material, and is widely applied to the fields of petroleum catalysis, precision casting, spinning, papermaking, refractory materials, coatings, electronics and the like. The solution can be divided into acid silica sol and alkaline silica sol according to the pH value range of the solution, and the alkaline silica sol is a stable system. According to the colloid theory, the size of the silica sol is divided into 5-100 nm. However, due to the development and progress of silica sol technology, silica sol has broken the traditional 100nm boundary and tends to be larger in particle size and stable in existing silica sol systems.
The preparation method of the silica sol mainly comprises the following steps: the simple substance silicon hydrolysis method, the ion exchange method and the sol-gel method are widely adopted in industry at present. The sol-gel method has a complex process, so that some enterprises adopt the process.
The silica sol synthesized by the simple substance silicon hydrolysis method generally has the grain diameter of about 20-150nm and the concentration of 30-40 percent, but the product is difficult to meet the requirements of certain special industries on the grain diameter and the concentration of the silica sol. Patent CN101597066A discloses a method for preparing silica sol seed crystal by a hydrothermal method, wherein the reaction time is 2-48 hours. The ion exchange method disclosed in patent CN 102432027a is used to prepare monodisperse, large-particle-size, high-stability acidic silica sol and the preparation method thereof, the particle size of the prepared silica sol can reach 100nm at most, but the particle size of the obtained silica sol is distributed between 1-100nm, which cannot meet the requirements of modern integrated circuit manufacturing.
The particle size of the silica sol synthesized by the ion exchange method at present is 50-100nm, the concentration is 40-50%, and the requirement of many special industries on the particle size of the silica sol, such as polishing of alumina and aluminum nitride ceramics, curing of building coatings and the like, cannot be realized. Patent 106044786.B discloses a polydisperse silica sol with large particle size prepared by ion exchange method, which is prepared by taking silica sol with 20-30nm as seed crystal, and then dripping 20-30 silica sol and silicic acid at a certain flow rate to obtain polydisperse silica sol with 20-95 nm.
Generally, the use of uniform silica sol particles with large particle size and high uniformity for chemical mechanical polishing can increase the material removal rate while maintaining good surface flatness, while the high concentration of silica sol means that the number of silica particles per unit volume is large, which is not only beneficial to increase of the polishing rate but also beneficial to the canning and transportation cost of the silica sol. Due to the appearance of 300nm alumina sol, the polishing speed is higher, so that higher requirements are put forward for taking silica sol as a polishing component, and the silica sol with super-large particle size needs to be developed to meet the polishing requirements of novel devices in the electronic industry.
Disclosure of Invention
Aiming at the problems of small silica sol particle size, difficult particle size control, large dispersion degree and poor stability in the prior art, the invention provides the preparation method of the high-purity large-particle size silica sol, which can synthesize the silica sol with larger particle size, higher concentration and more uniform particle size distribution and meet the polishing requirements of novel devices in the electronic industry.
The invention is realized by the following technical scheme:
a preparation method of high-purity large-particle size silica sol comprises the following steps:
(1) preparing sol crystal grains: mixing the acidic silica sol solution with the pH value of 2-3 with polyethylene glycol 2000-10000, adjusting the pH value to 8-9.5, and heating and boiling to obtain sol grains;
(2) preparation of aluminum modified silicic acid: adding acid activated resin at 60 ℃, washing the resin until the pH value is 3.0-4.5, adding an aluminum salt modifier and water glass, and carrying out ion exchange reaction on the water glass to prepare aluminum modified silicic acid;
(3) preparing large-particle size silica sol: adding the aluminum modified silicic acid obtained in the step (2) into the sol crystal grains obtained in the step (1), adding an alkali solution to adjust the pH value to 9.5-10.5, carrying out ultrafiltration and synthesis, and heating to synthesize the high-purity large-particle-size silica sol.
Preferably, the mass percentage of the silicon dioxide in the acidic silica sol solution in the step (1) is 30%, and the average particle size is 20 nm;
preferably, the mass of the polyethylene glycol in the step (1) is 0.5-5% of the mass of the acidic silica sol solution.
Preferably, the aluminum salt modifier in step (2) is one or more of sodium metaaluminate, aluminum nitrate, aluminum sulfate and polyaluminum chloride.
Preferably, the aluminum salt modifier in step (2) is used in an amount of 0.1 to 1% by weight based on the weight of the water glass.
Preferably, the flow rate of the active silicic acid in the step (3) is 5-12 mL/min; the flow rate of the alkali solution is 0.5-1.5 mL/min.
Preferably, the alkali solution in step (3) is one or more of sodium hydroxide, ethylamine, ethanolamine, trimethylamine, tetrahydroxy ammonium, and tetrapropyl ammonium hydroxide.
Preferably, the reaction temperature in the step (3) is 100 ℃, the synthesis is carried out while ultrafiltration is carried out, and the reaction time is 4-8 hours.
Preferably, the volume ratio of the sol crystal grains, the silicic acid and the alkali solution in the step (3) is 8-15: 84.8-91.8: 0.2, more preferably, the volume ratio of the sol crystal grains, the silicic acid and the alkali solution in the step (3) is 15: 84.8: 0.2.
in the invention, the acidic silica sol is subjected to hydroxylation reaction to lead the gel to be aggregated to form a large-particle silica sol matrix. The method comprises the following steps of preparing aluminum modified active silicic acid by taking water glass as a raw material by adopting an ion exchange method, adding an aluminum salt modifier to prepare silicic acid, obtaining silicic acid with larger particles and better stability, quickly enriching the silicic acid on substrate particles when synthesizing silica sol with super-large particle size, and preparing large-particle size and monodisperse silica sol by dropwise adding active silicic acid into a seed solution; the method of simultaneous ultrafiltration and synthesis is adopted, the particle size is increased quickly in the synthesis process, the energy consumption is low compared with that of a constant liquid level evaporation method, the synthesis period is short, and the production efficiency is greatly improved. Therefore, the invention can synthesize the silica sol with larger grain diameter, higher concentration and more uniform grain size distribution to meet the polishing requirement of novel devices in the electronic industry.
Advantageous effects
(1) The invention makes the acid silica sol undergo hydroxylation reaction to make it gather to gel, so as to form large-grain silica sol crystal grain.
(2) The aluminum modified silicic acid with larger particles and better stability can be obtained by performing aluminum modification on the silicic acid, and can be quickly enriched on matrix particles when the silica sol with super-large particle size is synthesized, so that the silica sol with larger particle size, higher concentration and more uniform particle size distribution can be synthesized by the method, and the polishing requirement of novel devices in the electronic industry is met.
(3) The method can obtain the silica sol with the average particle size of 120-400 nm; compared with the existing method for preparing the silica sol with large particle size, the method has the advantages of larger particle size, uniform particles, low viscosity, good stability, simple preparation steps, shorter production period and process flow, and reduced production energy consumption and cost.
Detailed Description
The method for producing a large-particle-size silica sol according to the present invention will be described in further detail below with reference to specific examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
The techniques used in the following examples, including ion exchange reactions and the like, are conventional techniques known to those skilled in the art unless otherwise specified; the instruments and equipment used, unless otherwise noted in this specification, are commonly available to those of ordinary skill in the art.
The acidic silica sol solution in the following examples is: the silicon dioxide is a commercial product with the mass fraction of 30 percent and the pH value of 2-4 and the average grain diameter of 20 nm.
The water glass is commercial high-grade water glass.
The water used in the examples of the invention was high purity water with a conductivity of >18 megaohms.
Example 1
(1) Preparing sol crystal grains: adding 0.5 percent of polyethylene glycol 2000 with the mass being the silica sol solution into the acidic silica sol solution, adjusting the pH value to 9.7, heating to 100 ℃ to obtain sol crystal grains with the average grain diameter of 50 nm;
(2) preparation of aluminum modified silicic acid: adding acid to activate resin at 60 ℃, washing the resin until the pH value is 3.0, adding aluminum nitrate and water glass, and carrying out ion exchange reaction on the water glass to obtain the aluminum modified silicic acid with the average particle size of 9nm and good stability, wherein the adding amount of the aluminum nitrate is 0.3 percent of the weight of the water glass.
(3) Preparing large-particle size silica sol: heating the sol crystal grains in the step (1) to 100 ℃, adding the aluminum modified silicic acid prepared in the step (2), wherein the flow rate of the aluminum modified silicic acid is 14mL/min, simultaneously adding sodium hydroxide, adjusting the pH value to 9.6, carrying out ultrafiltration and synthesis, and carrying out heating reaction for 5 hours at 100 ℃ to synthesize silica sol with the average particle size of 128 nm;
wherein the volume ratio of the sol crystal grains, the aluminum modified silicic acid and the alkali solution is 12: 87.8: 0.2.
example 2
(1) Preparing sol crystal grains: adding 0.5 percent of polyethylene glycol 6000 with the mass being that of the silica sol solution into the acidic silica sol solution, adjusting the pH value to 9.7, heating to 100 ℃ to obtain sol crystal grains with the average grain diameter of 100 nm;
(2) preparation of aluminum modified silicic acid: adding acid activated resin at 60 ℃, washing the resin until the pH value is 3.0, adding sodium metaaluminate and water glass, and carrying out ion exchange reaction on the water glass to obtain the aluminum modified silicic acid with the average particle size of 8nm and good stability, wherein the addition amount of the sodium metaaluminate is 0.3 percent of the weight of the water glass.
(3) Preparing large-particle size silica sol: heating the sol crystal grains in the step (1) to 100 ℃, adding the aluminum modified silicic acid in the step (2), wherein the flow rate of the aluminum modified silicic acid is 12mL/min, simultaneously adding sodium hydroxide, adjusting the pH value to 9.5, carrying out ultrafiltration and synthesis, and carrying out heating reaction for 4 hours at 100 ℃ to synthesize silica sol with the average particle size of 200 nm;
wherein the volume ratio of the sol crystal grains, the aluminum modified silicic acid and the alkali solution is 15: 84.8: 0.2.
example 3
(1) Preparing sol crystal grains: adding polyethylene glycol 6000 with the mass being 1% of that of the silica sol solution into the acidic silica sol solution, adjusting the pH value to 9.5, and heating and boiling to obtain sol crystal grains with the average grain diameter of 150 nm;
(2) preparation of aluminum modified silicic acid: adding acid activated resin at 60 ℃, washing the resin until the pH value is 4.0, adding sodium metaaluminate and water glass, and carrying out ion exchange reaction on the water glass to obtain aluminum modified silicic acid with the average particle size of 10nm and good stability, wherein the addition amount of the sodium metaaluminate is 0.5 percent of the weight of the water glass;
(3) preparing large-particle size silica sol: boiling the sol matrix in the step (1), adding the aluminum modified silicic acid in the step (2), simultaneously adding sodium hydroxide, adjusting the pH value to 9.5, wherein the flow rate of the silicic acid is 10mL/min, carrying out ultrafiltration and synthesis, and heating and reacting for 5 hours at 100 ℃ to synthesize silica sol with the average particle size of 240 nm; wherein the volume ratio of the sol crystal grains, the aluminum modified silicic acid and the alkali solution is 12: 87.8: 0.2.
example 4
(1) Preparing sol crystal grains: adding polyethylene glycol 6000 with the mass being 1% of that of the silica sol solution into the acidic silica sol solution, adjusting the pH value to 8.8, and heating and boiling to obtain sol crystal grains with the average grain diameter of 180 nm;
(2) preparation of aluminum modified silicic acid: adding acid activated resin at 60 ℃, washing the resin until the pH value is 4.1, adding polyaluminium chloride and water glass, and carrying out ion exchange reaction on the water glass to obtain the aluminum modified silicic acid with the average particle size of 12nm and good stability, wherein the adding amount of the polyaluminium chloride is 0.6 percent of the weight of the water glass.
(3) Preparing silica sol with super large particle size: boiling the sol matrix in the step (1), adding the aluminum modified silicic acid in the step (2), adding potassium hydroxide at the same time, adjusting the pH value to 9.3, wherein the flow rate of the silicic acid is 8mL/min, carrying out ultrafiltration and synthesis, and heating and reacting for 6 hours at 100 ℃ to synthesize silica sol with the average particle size of 320 nm; wherein the volume ratio of the sol crystal grains, the aluminum modified silicic acid and the alkali solution is 10: 89.8: 0.2.
example 5
(1) Preparing sol crystal grains: adding 12000 polyethylene glycol with the mass being 1% of that of the silica sol solution into the acidic silica sol solution, adjusting the pH value to 8, and heating and boiling to obtain sol crystal grains with the average grain diameter of 220 nm;
(2) preparing Al modified silicic acid: adding acid activated resin at 60 ℃, washing the resin until the pH value is 4.5, adding polyaluminium chloride and water glass, and carrying out ion exchange reaction on the water glass to obtain aluminum modified silicic acid with the average particle size of 20nm and good stability, wherein the adding amount of the polyaluminium chloride is 1 percent of the weight of the water glass;
(3) preparing large-particle size silica sol: adding the aluminum modified silicic acid obtained in the step (2) into the sol matrix obtained in the step (1), adding a potassium hydroxide solution and a tetrapropyl ammonium hydroxide solution, adjusting the pH value to 9.5, wherein the flow rate of the silicic acid is 5mL/min, carrying out ultrafiltration and synthesis, and carrying out heating reaction at 100 ℃ for 8 hours to synthesize silica sol with the average particle size of 400 nm;
wherein the volume ratio of the sol crystal grains, the aluminum modified silicic acid and the alkali solution is 15: 84.8: 0.2.
comparative example 1
(1) Preparing sol crystal grains: adding 12000 polyethylene glycol with the mass being 1% of that of the silica sol solution into the acidic silica sol solution, adjusting the pH value to be 8, and heating and boiling to obtain a sol matrix with the average particle size of 220 nm;
(2) preparation of silicic acid: the resin is not activated, water glass is used as a raw material, and active silicic acid with the pH value of 4.2 and the average particle size of 20nm is prepared through ion exchange reaction.
(3) Preparing large-particle size silica sol: adding the active silicic acid obtained in the step (2) into the sol matrix obtained in the step (1), adding potassium hydroxide, adjusting the pH value to 9.5, wherein the flow rate of the silicic acid is 5mL/min, carrying out ultrafiltration and synthesis, and carrying out heating reaction at 100 ℃ for 8 hours to synthesize silica sol with the average particle size of 280 nm;
wherein the volume ratio of the sol crystal grains to the active silicic acid to the alkali solution is 8: 91.8: 0.2.
the properties of the silica sols described in examples 1 to 4 were compared with other commercially available silica sols, see Table 1
TABLE 1 Properties of the silica sols described in examples 1 to 4 and commercially available silica sols
(1) The average particle size of the silica sol obtained by the method of the embodiment 2-4 is between 200 and 400nm, the speed of synthesizing crystal grains in one step is high, the colloidal particles are stable, the silicic acid is modified by aluminum salt, the particle size of the silicic acid is rapidly increased from 5nm to 20nm, and the aluminum modified silicic acid manufacturing process is superior to the traditional silicic acid manufacturing process.
(2) The silica sol catalytically synthesized by using inorganic base and organic base has high purity and high stability.
(3) The lower the viscosity of the silica sol, the more uniform the particles and the better the stability. The low viscosity of examples 3-4, especially the very low viscosity of example 4, indicates that the silica sol particles obtained by the method of example 4 have good uniformity and good stability.
(4) The invention adopts a method of simultaneous ultrafiltration and synthesis, and has the advantages of fast particle size growth, relatively low energy consumption of a constant liquid level evaporation method, short synthesis period and greatly improved production efficiency in the synthesis process.
Claims (10)
1. A preparation method of high-purity large-particle size silica sol is characterized by comprising the following steps:
preparing sol crystal grains: mixing the acidic silica sol solution with the pH value of 2-3 with polyethylene glycol 2000-10000, adjusting the pH value to 8-9.5, and heating and boiling to obtain sol grains;
preparation of aluminum modified silicic acid: adding acid activated resin at 60 ℃, washing the resin until the pH value is 3.0-4.5, adding an aluminum salt modifier and water glass, and carrying out ion exchange reaction on the water glass to prepare aluminum modified silicic acid;
preparing large-particle size silica sol: adding the aluminum modified silicic acid obtained in the step (2) into the sol crystal grains obtained in the step (1), adding an alkali solution to adjust the pH value to 9.5-10.5, carrying out ultrafiltration and synthesis, and heating to synthesize high-purity large-particle-size silica sol;
the average particle size of the high-purity large-particle size silica sol prepared in the step (3) is 120-400 nm.
2. The method according to claim 1, wherein the acidic silica sol solution in the step (1) contains 30% by mass of silica and has an average particle diameter of 20 nm.
3. The method according to claim 1, wherein the mass of the polyethylene glycol in the step (1) is 0.5 to 5% of the mass of the acidic silica sol solution.
4. The method according to claim 1, wherein the aluminum salt modifier in step (2) is one or more of sodium metaaluminate, aluminum nitrate, aluminum sulfate and polyaluminum chloride.
5. The method according to claim 1, wherein the aluminum salt modifier used in the step (2) is used in an amount of 0.1 to 1% by weight based on the weight of the water glass.
6. The method according to claim 1, wherein the flow rate of the aluminum-modified silicic acid in the step (3) is 5 to 12 mL/min; the flow rate of the alkali solution is 0.5-1.5 mL/min.
7. The method according to claim 1, wherein the alkali solution in step (3) is one or more selected from the group consisting of sodium hydroxide, ethylamine, ethanolamine, trimethylamine, and tetrapropylammonium hydroxide.
8. The process according to claim 1, wherein the reaction temperature in the step (3) is 100 ℃ and the synthesis is carried out while carrying out ultrafiltration, and the reaction time is 4 to 8 hours.
9. The method according to claim 1, wherein the volume ratio of the sol crystal grains, the silicic acid and the alkali solution in the step (3) is 8-15: 84.8-91.8: 0.2.
10. the method according to claim 9, wherein the volume ratio of the sol crystal grains, the silicic acid and the alkali solution in the step (3) is 15: 84.8: 0.2.
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| CN115626651A (en) * | 2022-09-08 | 2023-01-20 | 东营一鸣新材料有限公司 | Micron-sized high-purity spherical silica gel and preparation method thereof |
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| CN1029950C (en) * | 1990-11-09 | 1995-10-11 | 埃卡诺贝尔公司 | Silica sols, process for production of silica sols and use of sols |
| SE501214C2 (en) * | 1992-08-31 | 1994-12-12 | Eka Nobel Ab | Silica sol and process for making paper using the sun |
| JP4305627B2 (en) * | 2002-03-26 | 2009-07-29 | 日産化学工業株式会社 | Composite sol, method for producing the same, and inkjet recording medium |
| CN1295042C (en) * | 2003-11-19 | 2007-01-17 | 章浩龙 | Aluminum modified alkaline silicasol |
| CN1304288C (en) * | 2004-07-03 | 2007-03-14 | 河北工业大学 | Method for preparing silicasol with big grain diameter |
| CN101858043B (en) * | 2010-04-30 | 2012-07-04 | 湖北达雅化工技术发展有限公司 | Preparation method for stable borosilicate sol with high specific surface area |
| CN102432027B (en) * | 2011-08-31 | 2013-04-10 | 湖北大学 | Monodisperse large-grain-diameter and high-stability acid silica sol and preparation method thereof |
| JP6049368B2 (en) * | 2011-09-15 | 2016-12-21 | 日揮触媒化成株式会社 | Al-modified inorganic oxide fine particles, production method thereof, dispersion, and coating composition |
| CN108130801B (en) * | 2013-12-18 | 2020-11-24 | 艺康美国股份有限公司 | Method for producing activated colloidal silica for use in papermaking |
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| CN104556061B (en) * | 2014-12-31 | 2017-01-18 | 上海新安纳电子科技有限公司 | Preparation method for modified silicon dioxide colloid |
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| CN105586004A (en) * | 2015-12-31 | 2016-05-18 | 江苏天恒纳米科技股份有限公司 | Preparation method of aluminum-modified silica sol |
| CN105883824B (en) * | 2016-04-12 | 2018-06-29 | 广东惠和硅制品有限公司 | A kind of preparation method of big grain size Ludox |
| CN106044786B (en) * | 2016-06-01 | 2019-05-07 | 上海新安纳电子科技有限公司 | Big partial size silica solution of polydispersion and preparation method thereof |
| CN108083283B (en) * | 2017-12-07 | 2021-08-20 | 临汾博利士纳米材料有限公司 | Aluminum modified acidic silica sol and preparation method thereof |
| CN110482559B (en) * | 2019-09-16 | 2021-03-30 | 广东惠和硅制品有限公司 | Aluminum modified acidic silica sol and preparation method and application thereof |
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