CN112938990A - High-purity silica sol and preparation method thereof - Google Patents
High-purity silica sol and preparation method thereof Download PDFInfo
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000002270 dispersing agent Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000005416 organic matter Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 6
- 239000000413 hydrolysate Substances 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 238000005498 polishing Methods 0.000 description 13
- 229910052814 silicon oxide Inorganic materials 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- -1 silicate ester Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940090948 ammonium benzoate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
Abstract
The invention discloses a preparation method of high-purity silica sol, belonging to the technical field of silica sol. Which comprises the following steps: 1) preparation of high-purity silica sol reaction liquid and 2) addition of a dispersing agent. In addition, the invention also provides high-purity silica sol. According to the high-purity silica sol provided by the invention, firstly, a micro-channel method is adopted to carry out hydrolytic condensation treatment on silicon-containing organic matters, the particle size of the silica sol is controlled by controlling the dosage of a catalyst and the dropping speed, so that a silica sol hydrolysate with the particle size of 20-30 nm is obtained, and then a dispersing agent is added into the silica sol hydrolysate, so that the uniformly dispersed high-purity silica sol with the particle size of 20-30 nm can be formed due to the high compatibility of the dispersing agent and the silica sol hydrolysate. The whole operation process is simple and convenient, the process is easy to control, the reaction is stable, and the obtained high-purity silica sol is found to have uniform size and uniform dispersion of silica particles and can be stably stored.
Description
Technical Field
The invention belongs to the technical field of silica sol, and particularly relates to high-purity silica sol and a preparation method thereof.
Background
Chemical Mechanical Polishing (CMP) techniques are most widely used in the polishing of silicon wafers, the base material, in Integrated Circuits (ICs) and ultra large scale integrated circuits (ULSI). Currently, it is internationally accepted that global planarization is necessary to ensure lithographic image delivery accuracy and resolution when device feature sizes are smaller than 0.35 μm, and CMP is the only technology that can meet the global planarization requirement. CMP technology is a technology that combines chemical etching and mechanical abrasion, and utilizes the principle of "soft and hard" in abrasion, i.e., abrading a hard polishing workpiece with a softer material. By applying a pressure to the polishing slurry to cause the polishing workpiece to reciprocate relative to the polishing pad, a higher quality finish is formed on the surface of the workpiece being polished by the combination of the abrasive action of the nanoparticles and the corrosive action of the oxidizing agent. Thereby avoiding the defects of low polishing speed, uneven surface, poor polishing consistency, surface damage caused by pure mechanical polishing and the like easily caused by single-purification chemical polishing.
At present, the polishing solution adopting the CMP technology in the domestic integrated circuit high-end market is mainly from foreign enterprises, and the polishing solution has an absolute dominant position in the market and shows a monopolized pattern. Because the CMP polishing solution for semiconductors has high technical barrier and extremely high market concentration, high-end products in the Chinese market are mainly monopolized by the Japanese and American enterprises. From the technical analysis, one of the main factors determining the CMP quality is a high-purity and high-stability silica sol abrasive, so that the high-purity and high-stability silica sol must be independently developed in the integrated circuit industry in China to get rid of the monopoly abroad, which is an urgent need for the rapid development of large-scale integrated circuits in China.
At present, the most advanced method for preparing silica sol is a silicate hydrolysis method, which is a method for preparing high-purity silica sol by taking silicate as a raw material and hydrolyzing, dispersing and concentrating the silicate.
Patent CN100586851C relates to a preparation method of alkali-resistant ultra-pure silica sol. The method comprises the following four steps: (1) dissolving organosilane in inorganic acid or organic acid to prepare acid silicic acid sol; (2) dissolving organosilane in inorganic base or organic base water solution to prepare alkaline silicon-containing solution; (3) reacting the acidic silicon solution with the alkaline silicon solution at 105 ℃ to prepare silica sol; (4) heating the silica sol to boiling to remove by-products such as methanol and the like to obtain the high-purity silica sol. The obtained silica sol has a particle size of about 70nm and high solid content. Patent CN107445172B relates to a high-solid content high-purity silica sol and a preparation method thereof. The method comprises the following four steps: (1) heating and stirring ultrapure water, low-molecular alcohol and a pH regulator to obtain a solution A; (2) adding partial silicate ester, heating and stirring to obtain a solution B; (3) mixing the solution A and the solution B, performing ion exchange, distillation and water supplement treatment, and performing temperature rise reaction to obtain a solution D; (4) and (3) repeating the steps (2) and (3) twice, and performing step-by-step hydrolysis and ion exchange to obtain the high-solid-content high-purity silica sol. The silica sol thus obtained has a high solid content. Patent US10239758B2 relates to a process for preparing silica sols by dispersion followed by concentration. Firstly, TEOS is added into a mixed solution composed of pure water and ammonia water and having the temperature of 80 ℃, then the temperature of 80 ℃ is maintained for 1h, then the mixed solution is heated to 90 ℃ and stirred for 1h to obtain silicon dioxide dispersion liquid, finally, diisopropylamine is added, and the silicon dioxide sol is prepared by rotary evaporation and concentration. The obtained silica sol has low viscosity, high solid content and small particle size. Patent US20090143490a1 relates to a novel process for preparing high purity, high concentration silica sol by adding a dispersant and performing ultrapure water substitution. Firstly, silicate ester is hydrolyzed and condensed to obtain silica sol, and then ammonium benzoate dispersant is added and concentrated to obtain silica concentrated solution. Then, the concentrated solution is subjected to solvent replacement by ultrapure water and a dispersant is added to obtain a high-purity silica sol. The above preparation method also has the problems of high content of metal impurity ions caused by adopting unpurified raw materials or dispersing agents, poor dispersion stability of the sol caused by improper selection of the dispersing agents, incomplete hydrolysis reaction caused by using a traditional reactor, uneven size of sol particles and the like.
Disclosure of Invention
Aiming at the industrial problems of high content of metal impurity ions, poor stability, difficult control of the shape and the particle size of the sol and the like existing in the existing silica sol, the invention realizes the successful preparation of the high-purity silica sol by adopting key technologies such as a micro-channel reactor, high purification of silicon-containing organic matters, synthesis of the high-purity silica sol with controllable particle size, screening of a super dispersant without metal ions and the like.
One of the purposes of the invention is to provide a method for preparing high-purity silica sol with the particle size of 20-30 nm by adopting a micro-channel process technology.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of high-purity silica sol comprises the following steps:
1) preparing a high-purity silica sol reaction solution: the raw materials of the following components are prepared according to the weight percentage:
and (2) component A:
5 to 40 percent of silicon-containing organic matter,
60-95% of alcohol solvent;
and (B) component:
35 to 74.99 percent of alcohol solvent,
0.01 to 2 percent of catalyst,
25-64.99% of water;
carrying out synthetic reaction on the component A and the component B to obtain high-purity silica sol reaction solution;
2) addition of a dispersant: the raw materials of the following components are prepared according to the weight percentage:
80-99.99% of the high-purity silica sol reaction solution obtained in the step 1),
0.01 to 20 percent of dispersant;
and mixing the high-purity silica sol reaction solution with a dispersing agent, and dispersing at a high speed to obtain the high-purity silica sol.
In the step 1), the synthesis reaction is carried out in a micro-channel reactor, and the component A and the component B are introduced into the micro-channel reactor in a parallel flow manner to carry out a coprecipitation reaction, so as to obtain a synthesis reaction product; wherein the component A and the component B are respectively introduced into two feed pipes of the micro-channel reactor. The inner diameter of the feeding pipe of the micro-channel reactor is 0.5-1.5 mm. The reaction flow rate is controlled to be 2-20 mL/min at normal temperature, and the reaction time is 15-60 min. The micro-channel reactor synthesizes the nano-particles by using continuous flow, has the advantages of repeatability, narrow particle size distribution and easiness in large-scale production, and overcomes the limitation of the traditional batch preparation method. The continuous flow microchannel reactor synthesis method is advantageous in obtaining a relatively narrow particle size distribution and a small particle size compared to the conventional method. The micro flow channel reactor described above is commercially available, for example from the 24290 series of SYRRIS, UK.
In the step 1), the silicon-containing organic matter in the component A is rectified and purified silicon-containing organic matter, wherein the purity of the silicon-containing organic matter is more than 99% by mass; the catalyst in the component B is any one of glacial acetic acid, hydrochloric acid and ammonia water.
Wherein, in the step 1), the alcohol solvents in the component A and the component B are the same and are any one or more of methanol, ethanol, isopropanol and n-butanol;
wherein, in the step 2), the high-speed dispersion is carried out in a high-speed dispersion machine, the rotating speed is set to be 800-1600 revolutions per minute, and the dispersion time is 30-90 minutes.
In the step 2), the dispersant is any one or more of citric acid, ammonium citrate, polyacrylamide and ammonium polymethacrylate.
In addition, the invention also comprises the high-purity silica sol prepared by the method, and further, the high-purity silica sol has a particle size of 20-30 nm.
According to the high-purity silica sol provided by the invention, firstly, a micro-channel method is adopted to carry out hydrolytic condensation treatment on silicon-containing organic matters, the particle size of the silica sol is controlled by controlling the dosage of a catalyst and the dropping speed, so that a silica sol hydrolysate with the particle size of 20-30 nm is obtained, and then a dispersing agent is added into the silica sol hydrolysate, so that the uniformly dispersed high-purity silica sol with the particle size of 20-30 nm can be formed due to the high compatibility of the dispersing agent and the silica sol hydrolysate. The whole operation process is simple and convenient, the process is easy to control, the reaction is stable, and the obtained high-purity silica sol is found to have uniform size and uniform dispersion of silica particles and can be stably stored.
In connection with the mechanism of the present invention, the particle size of the silica particles in the silica sol is controlled by adjusting the amount of the catalyst used and the speed of the components passing through the micro flow channel. When the catalyst consumption is large and the micro-channel flow velocity is high, the hydrolysis reaction speed is high, the reaction is violent, so that a large amount of silicon oxide nano-particles can be generated in a short time, and because the surface activity of the newly generated particles is high, the energy and the high activity which are reached by collision and agglomeration are generated among the particles, the particle size of the particles is large; and with the reduction of the catalyst dosage and the slowing of the flow velocity of the micro-channel, the hydrolysis speed becomes slow, the rate of generating the nano silicon oxide particles is also reduced, at the moment, the particles are easy to obtain energy release in a solution with a larger volume to be balanced, the collision chance among the particles is less, and therefore the particle size of the particles is reduced. A dispersing agent is added into high-purity silica sol reaction liquid, a bilayer structure is formed on the surface of a silicon oxide particle through the addition of the dispersing agent, and the polar end of the outer-layer dispersing agent has strong affinity with water, so that the degree of wetting of the solid particle by the water is increased. The silicon oxide particles are separated from each other by electrostatic repulsion, and thus, the dispersion stability of the silica sol is greatly improved. The preparation method is simple to operate, environment-friendly and efficient, the prepared silica sol has uniform particle size of 20-30 nm, and the dispersion stability is greatly improved.
The high-purity silica sol prepared by the method has the advantages of simple and feasible preparation process, environmental protection, high efficiency, particle size of 20-30 nm, good uniformity and good dispersion stability.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a high purity silica sol according to the present invention.
Detailed Description
For a better understanding of the present invention, the following further illustrates the present invention with reference to the accompanying drawings and specific examples, but the present invention is not limited to the following examples.
Example 1:
as shown in fig. 1, the method for preparing a high purity silica sol according to this embodiment includes the following steps:
99.99 percent of high-purity silica sol reaction solution
0.01% of a dispersant;
the high-purity silica sol reaction solution is prepared from the following raw materials in percentage by weight:
and (2) component A:
40 percent of silicon-containing organic matter
Methanol 60 percent
And (B) component:
methanol 64 percent
0.8 percent of catalyst
35.2 percent of water
And (3) introducing the component A and the component B into a micro-channel reactor in a cocurrent manner, controlling the reaction flow rate to be 4mL/min at normal temperature, and carrying out coprecipitation reaction in the micro-channel for 50min to obtain a synthetic reaction product, namely a high-purity silica sol reaction solution.
The finished product of the high-purity silica sol with the particle size of 20-30 nm comprises the following components in percentage by weight: 5.2 percent of silicon oxide particles, 68.7 percent of alcohol solvent, 24.9 percent of water, 0.7 percent of catalyst and 0.5 percent of dispersant.
Example 2:
the preparation method of the high-purity silica sol with the particle size of 20-30 nm provided by the embodiment is basically the same as that of the embodiment 1, and is different in that the preparation method comprises the following components in percentage by weight:
99.95 percent of high-purity silica sol reaction solution
0.05% of a dispersant;
the high-purity silica sol reaction solution is prepared from the following raw materials in percentage by weight:
and (2) component A:
38 percent of silicon-containing organic matter
Methanol 62 percent
And (B) component:
66 percent of methanol
Catalyst 1%
33 percent of water
And (3) introducing the component A and the component B into a micro-channel reactor in a cocurrent manner, controlling the reaction flow rate to be 5mL/min at normal temperature, and carrying out coprecipitation reaction in the micro-channel for 40min to obtain a synthetic reaction product, namely a high-purity silica sol reaction solution.
The finished product of the high-purity silica sol with the particle size of 20-30 nm comprises the following components in percentage by weight: 5.2 percent of silicon oxide particles, 68.7 percent of alcohol solvent, 24.9 percent of water, 0.7 percent of catalyst and 0.5 percent of dispersant.
Example 3:
the preparation method of the high-purity silica sol with the particle size of 20-30 nm provided by the embodiment is basically the same as that of the embodiments 1 and 2, and is different in that the preparation method comprises the following components in percentage by weight:
99.15 percent of high-purity silica sol reaction solution
0.85% of dispersing agent;
the high-purity silica sol reaction solution is prepared from the following raw materials in percentage by weight:
and (2) component A:
35 percent of silicon-containing organic matter
Isopropanol 65 percent
And (B) component:
70 percent of isopropanol
1.45 percent of catalyst
28.55 percent of water
And (3) introducing the component A and the component B into a micro-channel reactor in a cocurrent manner, controlling the reaction flow rate to be 8mL/min at normal temperature, and carrying out coprecipitation reaction in the micro-channel for 25min to obtain a synthetic reaction product, namely a high-purity silica sol reaction solution.
The finished product of the high-purity silica sol with the particle size of 20-30 nm comprises the following components in percentage by weight: 4.9 percent of silicon oxide particles, 67.1 percent of alcohol solvent, 26.2 percent of water, 0.9 percent of catalyst and 0.9 percent of dispersant.
Example 4:
the preparation method of the high-purity silica sol with the particle size of 20-30 nm provided by the embodiment is basically the same as that of the embodiments 1, 2 and 3, and is different in that the preparation method comprises the following components in percentage by weight:
98.85 percent of high-purity silica sol reaction solution
1.15% of a dispersant;
the high-purity silica sol reaction solution is prepared from the following raw materials in percentage by weight:
and (2) component A:
33 percent of silicon-containing organic matter
Isopropanol 67%
And (B) component:
71 percent of isopropanol
Catalyst 1.15%
27.85 percent of water
And (3) introducing the component A and the component B into a micro-channel reactor in a cocurrent manner, controlling the reaction flow rate to be 10mL/min at normal temperature, and carrying out coprecipitation reaction in the micro-channel for 20min to obtain a synthetic reaction product, namely a high-purity silica sol reaction solution.
The finished product of the high-purity silica sol with the particle size of 20-30 nm comprises the following components in percentage by weight: 4.7 percent of silicon oxide particles, 68.5 percent of alcohol solvent, 25.7 percent of water, 0.88 percent of catalyst and 0.22 percent of dispersant.
Example 5:
the preparation method of the high-purity silica sol with the particle size of 20-30 nm provided by the embodiment is basically the same as that of the embodiments 1, 2, 3 and 4, and is different in that the components in percentage by weight are as follows:
98.5 percent of high-purity silica sol reaction solution
1.5 percent of dispersant;
the high-purity silica sol reaction solution is prepared from the following raw materials in percentage by weight:
and (2) component A:
31 percent of silicon-containing organic matter
69 percent of ethanol
And (B) component:
ethanol 73 percent
1.8 percent of catalyst
25.2 percent of water
And (3) introducing the component A and the component B into a micro-channel reactor in parallel, controlling the reaction flow rate at the normal temperature to be 16mL/min, and performing coprecipitation reaction in the micro-channel for 12.5min to obtain a synthetic reaction product, namely a high-purity silica sol reaction solution.
The finished product of the high-purity silica sol with the particle size of 20-30 nm comprises the following components in percentage by weight: 4.6 percent of silicon oxide particles, 67.9 percent of alcohol solvent, 24.9 percent of water, 1.0 percent of catalyst and 1.6 percent of dispersant.
Example 6:
the preparation method of the high-purity silica sol with the particle size of 20-30 nm provided by the embodiment is basically the same as that of the embodiments 1, 2, 3, 4 and 5, and is different in that the components in percentage by weight are as follows:
98.1 percent of high-purity silica sol reaction solution
1.9 percent of dispersant;
the high-purity silica sol reaction solution is prepared from the following raw materials in percentage by weight:
and (2) component A:
30 percent of silicon-containing organic matter
70 percent of ethanol
And (B) component:
75 percent of ethanol
Catalyst 2%
27 percent of water
And (3) introducing the component A and the component B into a micro-channel reactor in a cocurrent manner, controlling the reaction flow rate to be 20mL/min at normal temperature, and carrying out coprecipitation reaction in the micro-channel for 10min to obtain a synthetic reaction product, namely a high-purity silica sol reaction solution.
The finished product of the high-purity silica sol with the particle size of 20-30 nm comprises the following components in percentage by weight: 4.5% of silicon oxide particles, 68.1% of alcohol solvent, 24.7% of water, 1.2% of catalyst and 1.5% of dispersing agent.
The high purity silica sols obtained in examples 1 to 6 of the present invention were used to measure pH, particle size, viscosity and stability, respectively. The results of the performance tests are shown in table 1.
TABLE 1 results of the performance test on the highly pure silica sols obtained in examples 1 to 6
As can be seen from the performance indexes in Table 1, when the dispersing agent is added into the high-purity silica sol reaction solution, the dispersing agent has good compatibility with the high-purity silica sol reaction solution, and the dispersion stability of the silica sol is further improved.
The high-purity silica sol prepared by the method has the advantages of simple and feasible preparation process, environmental protection, high efficiency, particle size of 20-30 nm, good uniformity and good dispersion stability. Therefore, the obtained silica sol has good application prospect.
The above examples of the present invention are not exhaustive of all the components and ratios, and the components and ratios in examples 2-6 are only preferred embodiments.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of high-purity silica sol is characterized by comprising the following steps:
1) preparing a high-purity silica sol reaction solution: the raw materials of the following components are prepared according to the weight percentage:
and (2) component A:
5 to 40 percent of silicon-containing organic matter,
60-95% of alcohol solvent;
and (B) component:
35 to 74.99 percent of alcohol solvent,
0.01 to 2 percent of catalyst,
25-64.99% of water;
carrying out synthetic reaction on the component A and the component B to obtain high-purity silica sol reaction liquid;
2) addition of a dispersant: the raw materials of the following components are prepared according to the weight percentage:
80-99.99% of the high-purity silica sol reaction solution obtained in the step 1),
0.01 to 20 percent of dispersant;
and mixing the high-purity silica sol reaction solution with a dispersing agent, and dispersing at a high speed to obtain the high-purity silica sol.
2. The method for producing a high purity silica sol according to claim 1, characterized in that: in step 1), the synthesis reaction is carried out in a microchannel reactor, and the component a and the component B are co-currently passed into two feed tubes of the microchannel reactor.
3. The method for producing a high purity silica sol according to claim 2, characterized in that: the temperature of the synthesis reaction is normal temperature, the flow rate is 2-20 mL/min, and the reaction time is 15-60 min.
4. The method for producing a high purity silica sol according to claim 2, characterized in that: the inner diameters of the two feeding pipes are 0.5-1.5 mm.
5. The method for producing a high purity silica sol according to claim 1, characterized in that: in the step 1), the silicon-containing organic matter is a product obtained after rectification and purification, wherein the purity of the silicon-containing organic matter is more than 99% by mass fraction; the catalyst is any one of glacial acetic acid, hydrochloric acid and ammonia water.
6. The method for producing a high purity silica sol according to claim 1, characterized in that: in the step 1), the alcoholic solvents in the component A and the component B are the same and are any one or more of methanol, ethanol, isopropanol and n-butanol.
7. The method for producing a high purity silica sol according to any one of claims 1 to 5, characterized in that: in step 2), the dispersant is any one or more of citric acid, ammonium citrate, polyacrylamide and ammonium polymethacrylate.
8. The method for producing a high purity silica sol according to any one of claims 1 to 5, characterized in that: in the step 2), the high-speed dispersion is carried out in a high-speed dispersion machine, the rotating speed is 800-1600 revolutions per minute, and the dispersion time is 30-90 minutes.
9. A high purity silica sol according to any one of claims 1 to 8, which is produced by the method for producing a high purity silica sol.
10. The high purity silica sol according to claim 9, wherein the high purity silica sol has a particle size of 20 to 30 nm.
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| CN114591684A (en) * | 2022-02-18 | 2022-06-07 | 浙江开化元通硅业有限公司 | Environment-friendly chemical mechanical polishing solution based on high-purity spherical silica sol, and preparation method and polishing method thereof |
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| CN108147417A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of micron of spherical silica |
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Application publication date: 20210611 |