CN115784240B - Preparation method of non-spherical silica sol - Google Patents
Preparation method of non-spherical silica sol Download PDFInfo
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- CN115784240B CN115784240B CN202211657222.1A CN202211657222A CN115784240B CN 115784240 B CN115784240 B CN 115784240B CN 202211657222 A CN202211657222 A CN 202211657222A CN 115784240 B CN115784240 B CN 115784240B
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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 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000013078 crystal Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 70
- 239000000413 hydrolysate Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012452 mother liquor Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 26
- -1 amine compound Chemical class 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229920002125 Sokalan® Polymers 0.000 claims description 16
- 239000004584 polyacrylic acid Substances 0.000 claims description 16
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 6
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- NQOFYFRKWDXGJP-UHFFFAOYSA-N 1,1,2-trimethylguanidine Chemical compound CN=C(N)N(C)C NQOFYFRKWDXGJP-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 4
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 37
- 235000012431 wafers Nutrition 0.000 abstract description 9
- 238000005498 polishing Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003321 amplification Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 11
- 230000002572 peristaltic effect Effects 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000011163 secondary particle Substances 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- 241001089723 Metaphycus omega Species 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 241001553178 Arachis glabrata Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Abstract
The invention relates to a preparation method of non-spherical silica sol, which comprises the following steps: (1) Mixing siloxane with water, and hydrolyzing to obtain hydrolysate; (2) Mixing the hydrolysate with the mother liquor, adding an anionic polymer into the system in the mixing process, and maintaining the pH value of the system to be more than or equal to 6 to obtain seed crystals; (3) And mixing the seed crystal with the hydrolysate to complete seed crystal growth and obtain the non-spherical silica sol. The preparation method successfully synthesizes the nonspherical silica sol with peanut-shaped particles, wherein the silica mass content is high, the metal ion content is low, the nonspherical silica sol can be used for polishing large semiconductor silicon wafers or wafers, the preparation method is not limited to small-scale preparation in a laboratory, the particle size and the association degree are only slightly changed after the process is amplified, the amplification effect is small, and the nonspherical silica sol is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of silica sol, in particular to a preparation method of non-spherical silica sol.
Background
Silica sol is a colloidal substance obtained by dispersing silica particles in water or other solvents, and is widely used in the industries of papermaking, catalysts, casting, paints, and the like. With the high integration and high functionality of semiconductor integrated circuits, in order to prevent the problem that the roughness (height difference) of the layer surface exceeds the depth of focus of photolithography and a sufficient resolution cannot be obtained in the manufacture of semiconductor integrated circuit devices, a Chemical Mechanical Polishing (CMP) method (CHEMICAL MECHANICAL Polishing: hereinafter) is used to planarize interlayer insulating films, buried wirings, and the like.
CN102390838a discloses a preparation method of non-spherical silica sol, comprising the following steps: (1) Preparing non-spherical silica sol crystal seed mother solution with the particle diameter of 20-50 nm; (2) preparing a water-soluble silica sol having less than 5wt% alcohol. The silica sol with non-spherical structure is prepared directly by adopting a sol-gel method and controlling the process of the charging proportion, the material concentration, the pH value of the reaction solution and the reaction temperature in the reaction process. The method has the advantages of less side reaction, short growth period, simple process, no need of adding additives, inorganic salts or carrying out surface modification and the like. The prepared silica sol can be applied to grinding and polishing in the rough polishing process of the CMP technology or used as a carrier required in the modification process of other particles, the proportion of spherical particles in the non-spherical silica sol is lower than 5%, the particle size of the colloid is controllable at 20-100 nm, and the content of SiO 2 in the water-soluble silica sol is controlled to be 5-50wt% by an evaporation and water removal process.
CN103896287a discloses an aspherical silica sol and a method for preparing the same. The disclosed non-spherical silica sol comprises a liquid medium and sol particles, wherein the sol particles are formed by gathering 2-10 silica colloid particles.
In the prior art, high-purity silica sol is widely used in polishing of silicon wafers and CMP steps of semiconductor devices, and if metal impurities exist in the CMP polishing process, the metal impurities can be diffused into the silicon wafers or electronic devices to cause short circuits, so that the content of the metal impurities in the silica sol is strictly required.
In view of the above, it is important to develop a method for preparing a non-spherical silica sol having a low content of metal impurities, which overcomes the above drawbacks.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of non-spherical silica sol, which is used for successfully synthesizing the non-spherical silica sol with peanut-shaped particles, wherein the silicon dioxide mass content is high, the metal ion content is low, the preparation method can be used for polishing large semiconductor silicon wafers or wafers, the preparation method is not limited to small-scale preparation in a laboratory, the particle size and the association degree are only slightly changed after the process amplification, the amplification effect is small, and the preparation method is suitable for large-scale production.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of non-spherical silica sol, which comprises the following steps:
(1) Mixing siloxane with water, and hydrolyzing to obtain hydrolysate;
(2) Mixing the hydrolysate with a mother liquor, adding an anionic polymer into the system in the mixing process, and maintaining the pH of the system to be more than or equal to 6 (for example, 6.5, 7, 7.5, 8 and the like, and more preferably 7-8.5) to obtain seed crystals;
(3) And mixing the seed crystal with the hydrolysate to complete seed crystal growth and obtain the non-spherical silica sol.
In the invention, in the process of preparing seed crystals, anionic polymers are added, molecules have larger space structures, after the anionic polymers are added into a reaction system, repulsive force among silica sol particles is improved on one hand, collision and contact among the silica sol particles are hindered through a steric hindrance effect on the other hand, and finally, non-spherical silica sol particles with a certain association degree are obtained and are in peanut shapes. In addition, the pH of the system is maintained during seed preparation because an increase in pH will tend to cause the particles to grow into spheres and a decrease in pH will tend to cause the particles to aggregate and even gel.
In the invention, the hydrolysate prepared in the step (1) is used in the step (2) and the step (3), the ratio of the hydrolysate siloxane to water in the step (2) and the step (3) can be the same or different, and the preparation of the hydrolysate in the step (1) is adjusted according to the requirements of the step (2) and the step (3).
In the present invention, the seed crystal used in the step (3) may be all or part of the seed crystal prepared in the step (2), and may be prepared as required.
In the present invention, the water concerned is preferably ultrapure water.
Further, the resistivity of the ultrapure water is not less than 10 M.OMEGA.cm, for example, 12 M.OMEGA.cm, 14 M.OMEGA.cm, 16 M.OMEGA.cm, 18 M.OMEGA.cm, etc., and more preferably not less than 18.2 M.OMEGA.cm.
Preferably, in step (1), the siloxane comprises any one or a combination of at least two of tetramethoxysilane, tetraethoxysilane or tetrapropoxysilane, wherein typical but non-limiting combinations include: a combination of tetramethoxysilane and tetraethoxysilane, a combination of tetraethoxysilane and tetrapropoxysilane, a combination of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane, and the like, and tetramethoxysilane is further preferable.
Preferably, the temperature of the hydrolysis is 2 to 30 ℃, for example 5 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, etc., further preferably 5 to 20 ℃.
Preferably, in step (2), the mother liquor comprises water, optionally the mother liquor further comprises a pH adjuster.
Preferably, the pH adjuster comprises a basic catalyst.
Preferably, the basic catalyst comprises any one or a combination of at least two of an alkali metal hydroxide, ammonia, an organic amine compound, or a guanidine compound, wherein a typical but non-limiting combination comprises: a combination of an alkali metal hydroxide and aqueous ammonia, a combination of aqueous ammonia, an organic amine compound and a guanidine compound, a combination of an alkali metal hydroxide, aqueous ammonia, an organic amine compound and a guanidine compound, and the like.
Preferably, the alkali metal hydroxide comprises potassium hydroxide and/or sodium hydroxide.
Preferably, the organic amine compound comprises any one or a combination of at least two of ethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, diethanolamine, triethanolamine or tetramethylammonium hydroxide, wherein typical but non-limiting combinations include: combinations of ethylenediamine and diethylenetriamine, combinations of triethylenetetramine, ethanolamine, diethanolamine and triethanolamine, combinations of diethylenetriamine, triethylenetetramine, ethanolamine, diethanolamine, triethanolamine and tetramethylammonium hydroxide, and the like.
Preferably, the guanidine compound includes any one or a combination of at least two of tetramethylguanidine, trimethylguanidine, or guanidine carbonate, wherein typical but non-limiting combinations include: a combination of tetramethylguanidine and trimethylguanidine, a combination of trimethylguanidine and guanidine carbonate, a combination of tetramethylguanidine, trimethylguanidine and guanidine carbonate, and the like.
Preferably, in the step (2), the mass ratio of the hydrolysis liquid to the mother liquid is 1: (0.2-0.8), wherein 0.2-0.8 may be 0.3, 0.4, 0.5, 0.6, 0.7, etc., further preferably 1: (0.3-0.7).
Preferably, in the step (2), the mass ratio of siloxane to water in the hydrolysate is (5-26): 100, wherein 5-26 may be 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, etc.
Preferably, the means of mixing the hydrolysate with the mother liquor comprises adding the hydrolysate to the mother liquor.
Preferably, the flow rate of the hydrolysate added to the mother liquor is 0.5-10mL/min, such as 0.6mL/min, 0.7mL/min, 0.8mL/min, 0.6mL/min, 1mL/min, 1.2mL/min, 1.4mL/min, 2mL/min, 4mL/min, 6mL/min, 8mL/min, etc.
Preferably, the hydrolysis solution is added to the mother liquor for a period of 4 to 50 hours, for example, 5 hours, 10 hours, 20 hours, 30 hours, 40 hours, etc.
Preferably, the temperature of the system during the mixing is 50 to 100 ℃, for example 60 ℃, 70 ℃,80 ℃, 90 ℃, etc., more preferably 60 to 95 ℃.
Preferably, the anionic polymer comprises any one or a combination of at least two of polyacrylic acid, poly (4-styrenesulfonic acid) or acrylic acid maleic acid copolymers, wherein typical but non-limiting combinations include: the combination of polyacrylic acid, poly (4-styrenesulfonic acid), acrylic acid-maleic acid copolymer is more preferably polyacrylic acid and/or acrylic acid-maleic acid copolymer.
In the present invention, the anionic polymer is preferably polyacrylic acid and/or acrylic acid-maleic acid copolymer because: polyacrylic acid and acrylic acid maleic acid copolymers have a higher molecular weight than other anionic polymers and produce anionic macromolecules upon dissolution in water.
Preferably, the anionic polymer has a number average molecular weight of 2000-80000g/mol, e.g. 2000g/mol, 4000g/mol, 6000g/mol, 8000g/mol, 10000g/mol, 20000g/mol, 60000g/mol, 80000g/mol etc.
In the present invention, the reason why the number average molecular weight of the anionic polymer is controlled in the above range is that: can maintain a certain steric hindrance; higher number average molecular weights can lead to the formation of spherical particles; lower number average molecular weights can result in increased particle aggregation and even gel formation.
Preferably, the anionic polymer is added in an amount of 50 to 1000ppm, for example, 100ppm, 200ppm, 400ppm, 600ppm, 800ppm, etc., based on 100% of the total mass of the siloxane used to prepare the hydrolysate.
In the present invention, the reason for controlling the addition amount of the anionic polymer in the above range is as follows: the method has good steric hindrance and electrostatic repulsion, and can well control the association degree of particles; too low an amount can result in a higher degree of particle aggregation and even gel formation; too high an amount may result in the formation of spherical particles.
Preferably, the anionic polymer is added to the system for a period of time ranging from 0 to 6 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, etc., where the hydrolysis solution and the mother liquor begin to mix.
Preferably, the system pH is from 6 to 8.5, e.g., 6.5, 7, 7.5, 8, etc., more preferably from 7 to 8.5, and even more preferably from 6 to 8.5, during the mixing process.
In the invention, in the mixing process, the pH of the system is 6-8.5, because in the reaction system with the pH of 6-8.5, electrostatic repulsive force among silica sol particles is low, the particles tend to be aggregated together, and the phenomenon that the particles are adhered together is caused, so that the non-spherical silica sol is formed.
Preferably, the pH adjuster employed to maintain the pH of the system comprises a basic catalyst.
Preferably, in the step (3), the mass ratio of the hydrolysate to the seed crystal is 1: (0.125-0.875), wherein 0.125-0.875 may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, etc., further preferably 1: (0.15-0.7).
Preferably, in the step (3), the mass ratio of siloxane to water in the hydrolysate is (11-44): 100, wherein 11-44 can be 15, 20, 25, 30, 35, 40, etc.
Preferably, the mixing mode comprises: the hydrolysate is added to a seed crystal, which is optionally mixed with water first.
Preferably, when the seed crystal is mixed with water first, the mass ratio of the seed crystal to the water is 1: (1-3), wherein 1-3 may be 1.5, 2, 2.5, etc.
Preferably, the flow rate of the hydrolysate added to the seed crystal is 0.5-10mL/min, such as 0.6mL/min, 0.7mL/min, 0.8mL/min, 0.6mL/min, 1mL/min, 1.2mL/min, 1.4mL/min, 2mL/min, 4mL/min, 6mL/min, 8mL/min, etc.
Preferably, the time taken for seeding the hydrolysate is 4-50 hours, e.g. 5 hours, 10 hours, 20 hours, 30 hours, 40 hours, etc.
Preferably, the temperature of the system during the mixing is 50 to 100 ℃, for example 60 ℃, 70 ℃,80 ℃, 90 ℃, etc., more preferably 60 to 95 ℃.
Preferably, during the mixing, the system pH is maintained.
Preferably, the system pH is maintained to be the same as the system pH in step (2).
Preferably, after the seed crystal growth, the obtained non-spherical silica sol is used as a seed crystal, and the seed crystal growth is continued.
Preferably, in step (3), after the completion of seed crystal growth, concentration and solvent replacement are further included.
Preferably, the concentrating means comprises vacuum heating.
Preferably, after the solvent replacement, the content of the organic solvent in the system is less than or equal to 200ppm, for example, 180ppm, 160ppm, 140ppm, etc.
In the present invention, the reason for the solvent substitution is to remove a solvent such as methanol generated during the hydrolysis of the siloxane.
Preferably, after the solvent replacement, the mass percent of silica in the silica sol in the system is more than or equal to 20%, such as 25%, 30%, 35%, 40% and the like.
Preferably, the solvent displacement is followed by filtration.
Preferably, the filter core material used for filtering comprises polytetrafluoroethylene.
Preferably, the accuracy of the filtration is 0.2-5 μm, e.g. 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Mixing siloxane with water, and hydrolyzing at 2-30deg.C to obtain hydrolysate;
Water is used as a mother solution, and optionally, the mother solution also comprises a pH regulator;
(2) Continuously adding the hydrolysate into the mother liquor at a flow rate of 0.5-1.5mL/min, mixing for 4-50h, adding the anionic polymer into the system at the time of 0-6h of adding the hydrolysate, maintaining the pH of the system to 6-8.5 and the temperature of 50-100 ℃, and controlling the mass ratio of the hydrolysate to the mother liquor to be 1: (0.2-0.8) to obtain seed crystal;
(3) Continuously adding the hydrolysate into the seed crystal according to the flow rate of 0.5-1.5mL/min, mixing for 4-50h, maintaining the pH of the system to 6-8.5 and the temperature of 50-100 ℃, and controlling the mass ratio of the hydrolysate to the seed crystal to be 1: (0.125-0.875), completing the growth of seed crystal to obtain the non-spherical silica sol initial material;
Optionally, mixing seed crystals with water to form a seed crystal solution before adding seed crystals to the hydrolysate;
(4) Concentrating and replacing the initial material of the non-spherical silica sol obtained in the step (3) by a solvent until the content of the organic solvent in the system is less than or equal to 200ppm, and optionally filtering the initial material of the non-spherical silica sol until the mass percentage of silicon dioxide in the silica sol is more than or equal to 20 percent to obtain the non-spherical silica sol.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method successfully synthesizes the nonspherical silica sol with peanut-shaped particles, wherein the silica mass content is high, the metal ion content is low, the nonspherical silica sol can be used for polishing large semiconductor silicon wafers or wafers, the preparation method is not limited to small-scale preparation in a laboratory, the particle size and the association degree are only slightly changed after the process is amplified, the amplification effect is small, and the nonspherical silica sol is suitable for large-scale production.
(2) The seed crystal obtained by the preparation method has the primary particle size of 15.7-18.8nm, the secondary particle size of 29.3-35nm and the association degree of 1.8-1.92; the primary particle size of the non-spherical silica sol obtained by the preparation method is between 41.4 and 66.6nm, the secondary particle size is between 77.9 and 130nm, and the association degree is between 1.76 and 1.98; the mass fraction of silicon dioxide in the non-spherical silica sol obtained by the preparation method is more than 20%.
(3) The total content of metal ions in the non-spherical silica sol obtained by the preparation method is less than 1ppm, for example, the content of sodium ions is less than 99ppb, the content of potassium ions is less than 87ppb, the content of chromium ions is less than 13ppb, the content of copper ions is less than 11ppb, the content of iron ions is less than 30ppb, the content of nickel ions is less than 28ppb, and the content of titanium ions is less than 11 ppb.
Drawings
FIG. 1 is a transmission electron microscope image of the seed crystal described in example 1;
FIG. 2 is a transmission electron microscope image of the non-spherical silica sol described in example 1;
FIG. 3 is a transmission electron microscope image of the seed crystal described in example 6;
FIG. 4 is a transmission electron micrograph of the non-spherical silica sol described in comparative example 1.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the present invention, the purchase information of a part of raw materials according to each embodiment is as follows:
polyacrylic acid: the number average molecular weight was 2300g/mol, purchased from Dow chemical company;
Acrylic maleic acid copolymer: the number average molecular weight was 3000g/mol, CAS number 29132-58-9, available from Shanghai Ala Di Biochemical technologies Co., ltd.
Example 1
The embodiment provides an aspheric silica sol, and the preparation method of the aspheric silica sol comprises the following steps:
(1) Weighing 524g of water in a beaker, adding 76g of tetramethoxysilane into the beaker after the water temperature is controlled to 12 ℃, and stirring the mixture for 1.5 hours to obtain a first hydrolysate with the pH of about 4.3;
463.2g of water is weighed in a beaker, 136.8g of tetramethoxysilane is added into the beaker after the water temperature is controlled to 12 ℃, and the mixture is stirred for 2 hours to obtain a second hydrolysate;
350g of water was added to a 1L-sized flask with thermometer and condenser tube and heated to 80℃to give a mother liquor;
(2) At 80 ℃, adding the first hydrolysate into the mother liquor by a peristaltic pump at a feeding speed of 1.1mL/min, maintaining the pH of the system at 8.0 by adding ethanolamine (10 mmol/L) in the early stage of feeding, adding 10mg of polyacrylic acid after feeding for 1h, and controlling the mass ratio of the hydrolysate to the mother liquor to be 1 by adding ethanolamine to maintain the pH of the system at 8.0 in the feeding process after that: 0.58, obtaining seed crystal;
(3) Selecting 350g of seed crystal obtained in the step (2), adding the seed crystal into a 1L-specification flask with a thermometer and a condenser tube, adding a second hydrolysate into the seed crystal by a peristaltic pump, maintaining the pH of the system at 8.0 by adding ethanolamine in the feeding process, and controlling the mass ratio of the hydrolysate to the seed crystal to be 1:0.58, after the feeding is finished, obtaining a non-spherical silica sol primary material;
(4) Heating and concentrating the initial material of the non-spherical silica sol under reduced pressure at 10kPa and 100 ℃ until the content of silica is 20 percent, thus obtaining concentrated silica sol; then adding ultrapure water, evaporating until the content of organic solvent in the silica sol is reduced to below 100ppm, and obtaining the non-spherical silica sol.
Example 2
The embodiment provides an aspheric silica sol, and the preparation method of the aspheric silica sol comprises the following steps:
(1) Weighing 524g of water in a beaker, adding 76g of tetramethoxysilane into the beaker after the water temperature is controlled to 12 ℃, and stirring the mixture for 1.5 hours to obtain a first hydrolysate with the pH of about 4.3;
463.2g of water is weighed in a beaker, 136.8g of tetramethoxysilane is added into the beaker after the water temperature is controlled to 12 ℃, and the mixture is stirred for 2 hours to obtain a second hydrolysate;
350g of water was added to a 1L-sized flask with thermometer and condenser tube and heated to 80℃to give a mother liquor;
(2) At 80 ℃, adding the first hydrolysate into the mother liquor by a peristaltic pump, wherein the feeding speed is 1.1mL/min, the pH of the system is maintained to be 8.0 by adding ammonia water (10 mmol/L) in the early feeding stage, 10mg of polyacrylic acid is added after feeding for 1h, and in the feeding process, the pH of the system is maintained to be 8.0 by adding ammonia water, and the mass ratio of the hydrolysate to the mother liquor is controlled to be 1:0.58, obtaining seed crystal;
(3) Selecting 350g of seed crystal obtained in the step (2), adding the seed crystal into a 1L-specification flask with a thermometer and a condenser tube, adding a second hydrolysate into the seed crystal by a peristaltic pump, maintaining the pH of the system at 8.0 by adding ammonia water in the feeding process, and controlling the mass ratio of the hydrolysate to the seed crystal to be 1:0.58, after the feeding is finished, obtaining a non-spherical silica sol primary material;
(4) Heating and concentrating the initial material of the non-spherical silica sol under reduced pressure at 10kPa and 100 ℃ until the concentration is 20%, thus obtaining concentrated silica sol; then adding ultrapure water, evaporating until the content of organic solvent in the silica sol is reduced to below 100ppm, and obtaining the non-spherical silica sol.
Example 3
The embodiment provides an aspheric silica sol, and the preparation method of the aspheric silica sol comprises the following steps:
(1) 1389.6g of water is weighed in a beaker, 410.4g of tetramethoxysilane is added into the beaker after the water temperature is controlled to 12 ℃, and the hydrolysis liquid is obtained after stirring for 2 hours;
(2) Using the initial material of the non-spherical silica sol prepared in the step (3) of example 2 as seed crystal of this example, specifically, 350g of the initial material of the non-spherical silica sol was added into a 2L-sized flask having a thermometer and a condenser tube, and heated to 80℃as seed crystal;
(3) Adding the hydrolysate into the seed crystal by a peristaltic pump at the temperature of 80 ℃ at the feeding speed of 1.1mL/min, maintaining the pH of the system at 8.0 by adding ammonia water (10 mmol/L) in the feeding process, and controlling the mass ratio of the hydrolysate to the seed crystal to be 1:0.19, after the feeding is finished, obtaining a non-spherical silica sol primary material;
(4) Heating and concentrating the initial material of the non-spherical silica sol under reduced pressure at 10kPa and 100 ℃ until the concentration is 20%, thus obtaining concentrated silica sol; then adding ultrapure water, evaporating until the content of organic solvent in the silica sol is reduced to below 100ppm, and obtaining the non-spherical silica sol.
Example 4
The embodiment provides an aspheric silica sol, and the preparation method of the aspheric silica sol comprises the following steps:
(1) 2620g of water is weighed in a beaker, 380g of tetramethoxysilane is added into the beaker after the water temperature is controlled to 12 ℃, and after stirring is carried out for 1.5h, the pH is about 4.3, so as to obtain a first hydrolysate;
2316g of water is weighed in a beaker, 684g of tetramethoxysilane is added into the beaker after the water temperature is controlled to 12 ℃, and the mixture is stirred for 2 hours to obtain a second hydrolysate;
1650g of water was added to a 5L-sized flask having a thermometer and a condenser tube, and heated to 80℃to obtain a mother liquor;
(2) At 80 ℃, adding the first hydrolysate into the mother liquor by a peristaltic pump, wherein the feeding speed is 5.5mL/min, the pH of the system is maintained to be 8.0 by adding ethanolamine (10 mmol/L) in the early feeding period, 50mg of polyacrylic acid is added after feeding for 1h, and the pH of the system is maintained to be 8.0 by adding ethanolamine in the feeding process, wherein the mass ratio of the hydrolysate to the mother liquor is controlled to be 1:0.58, obtaining seed crystal;
(3) Selecting 1650g of the seed crystal obtained in the step (2), adding the seed crystal into a 5L-specification flask with a thermometer and a condenser, adding a second hydrolysate into the seed crystal by a peristaltic pump, maintaining the pH of the system at 8.0 by adding ethanolamine in the feeding process, and controlling the mass ratio of the hydrolysate to the seed crystal to be 1:0.58, after the feeding is finished, obtaining a non-spherical silica sol primary material;
(4) Heating and concentrating the initial material of the non-spherical silica sol under reduced pressure at 10kPa and 100 ℃ until the concentration is 20%, thus obtaining concentrated silica sol; then adding ultrapure water, evaporating until the content of organic solvent in the silica sol is reduced to below 100ppm, and obtaining the non-spherical silica sol.
Example 5
The embodiment provides an aspheric silica sol, and the preparation method of the aspheric silica sol comprises the following steps:
(1) Weighing 524g of water in a beaker, adding 76g of tetramethoxysilane into the beaker after the water temperature is controlled to 12 ℃, and stirring the mixture for 1.5 hours to obtain a first hydrolysate with the pH of about 4.3;
463.2g of water is weighed in a beaker, 132.8g of tetramethoxysilane is added into the beaker after the water temperature is controlled to 12 ℃, and the mixture is stirred for 2 hours to obtain a second hydrolysate;
350g of water and 3g of ethanolamine (10 mmol/L) were added to a 1L-sized flask having a thermometer and a condenser, and heated to 80℃to obtain a mother liquor;
(2) The first hydrolysate was added to the mother liquor with peristaltic pump at a feed rate of 1.8mL/min, the pH of the system was maintained at 8.0 by the addition of ethanolamine in the early stage of the feed, 10mg of polyacrylic acid was added after 1h of the feed, the pH of the system was maintained at 8.0 by the addition of aqueous ammonia during the feed thereafter, and the temperature of the system was 80 ℃, and the mass ratio of the hydrolysate to the mother liquor was controlled at 1:0.58, obtaining seed crystal;
(3) Selecting 350g of seed crystal obtained in the step (2), adding the seed crystal into a 1L-specification flask with a thermometer and a condenser tube, adding a second hydrolysate into the seed crystal by a peristaltic pump, maintaining the pH of the system at 8.0 by adding ethanolamine in the feeding process, and controlling the mass ratio of the hydrolysate to the seed crystal to be 1:0.58, after the feeding is finished, obtaining a non-spherical silica sol primary material;
(4) Heating and concentrating the initial material of the non-spherical silica sol under reduced pressure at 10kPa and 100 ℃ until the concentration is 20%, thus obtaining concentrated silica sol; then adding ultrapure water, evaporating until the content of organic solvent in the silica sol is reduced to below 100ppm, and obtaining the non-spherical silica sol.
Example 6
This comparative example was different from example 1 in that the amount of polyacrylic acid added at the time of seed crystal preparation was 100mg, and the rest was the same as example 1.
Example 7
This example differs from example 1 in that polyacrylic acid was replaced with an acrylic maleic acid copolymer of equal mass, the remainder being the same as example 1.
Comparative example 1
This comparative example differs from example 1 in that no polyacrylic acid was added at the time of seed preparation, and the remainder was the same as example 1.
Comparative example 2
This comparative example differs from example 1 in that the pH of the system was not maintained after the addition of polyacrylic acid at the time of seed preparation, and the rest was the same as example 1, and the reaction system gelled during the feeding.
Performance testing
The seed crystals and the non-spherical silica sol obtained by the preparation methods described in examples 1 to 7 and comparative example 1 (the reaction system in comparative example 2 was gelled during the feeding, and the results were not shown) were subjected to the following tests:
(1) Morphology characterization: and observing the morphology of the seed crystal and the non-spherical silica sol by adopting a transmission electron microscope.
(2) Primary particle diameter and secondary particle diameter:
The secondary particle size of the silica sol colloidal particles is measured by a Markov particle size analyzer Zetasizer Nano ZS, the primary particle size is measured by a BET specific surface area measurement method to obtain a specific surface area S bet, and the primary particle size is 2727/S bet. The degree of association is the ratio of the secondary particle size to the primary particle size.
(3) Metal impurities: the metal impurities in the non-spherical silica sol were tested by agilent 7900 ICP-MS.
The test results are summarized in tables 1-2 and FIGS. 1-4.
TABLE 1
As can be seen from the analysis of the data in Table 1, taking examples 1-7 (except example 6), the seed crystal obtained by the preparation method of the invention has a primary particle size of 15.7-18.8nm, a secondary particle size of 29.3-35nm, and a degree of association of 1.8-1.92; the primary particle size of the non-spherical silica sol obtained by the preparation method is between 41.4 and 66.6nm, the secondary particle size is between 77.9 and 130nm, and the association degree is between 1.76 and 1.98; in addition, according to the implementation process, the mass fraction of the silicon dioxide of the non-spherical silica sol obtained by the preparation method is more than 20%; the preparation method successfully synthesizes the nonspherical silica sol with peanut-shaped particles, wherein the mass content of the silica is high, and the nonspherical silica sol can be used for polishing large semiconductor silicon chips or wafers.
Analysis of comparative example 1 and example 1 revealed that comparative example 1 did not add an anionic polymer during the reaction, the seed particles had a polydisperse, a multi-association morphology, severe interparticle blocking, failure to obtain silica sol particles having a uniform particle size distribution, broad particle size distribution of the obtained sample particles, and severe interparticle blocking.
Analysis of example 6 and example 1 shows that the amount of anionic polymer added in example 6 is high, and the obtained seed particles mostly have spherical shapes.
Fig. 1, 2, 3 and 4 show TEM images of seed crystals or silica sols obtained in example 1, example 6 and comparative example 1 of the present invention. As can be seen from the figure, the particles of example 1 are most associated with each other in pairs, and exhibit a peanut shape. Whereas the particles of example 6 mostly exhibited spherical shapes.
From example 4, it can be seen that the particle size and association degree of example 1 are only slightly changed after being amplified, and the amplification effect is small, so that the preparation method is not limited to laboratory small-scale preparation, the particle size and association degree of the amplified process are only slightly changed, and the amplification effect is small, and the preparation method is suitable for large-scale production. Therefore, the association degree of the silica sol prepared by the method is controllable, and the association of the prepared silica sol particles can be well controlled by adding polyacrylic acid.
TABLE 2
As can be seen from the analysis of the data in Table 2, the non-spherical silica sol obtained by the preparation method of the present invention has a low metal ion content, and the total metal ion content is less than 1ppm, for example, the sodium ion content is 99ppb or less, the potassium ion content is 87ppb or less, the chromium ion content is 13ppb or less, the copper ion content is 11ppb or less, the iron ion content is 30ppb or less, the nickel ion content is 28ppb or less, and the titanium ion content is 11ppb or less.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (38)
1. A method for preparing non-spherical silica sol, which is characterized by comprising the following steps:
(1) Mixing siloxane with water, and hydrolyzing to obtain hydrolysate;
(2) Mixing the hydrolysate with the mother liquor, adding an anionic polymer into the system in the mixing process, and maintaining the pH value of the system to be more than or equal to 6 to obtain seed crystals;
(3) Mixing the seed crystal with the hydrolysate to complete seed crystal growth and obtain the non-spherical silica sol;
The mode of mixing the hydrolysis liquid and the mother liquid comprises the steps of adding the hydrolysis liquid into the mother liquid;
the anionic polymer comprises any one or a combination of at least two of polyacrylic acid, poly (4-styrene sulfonic acid) or acrylic acid maleic acid copolymer;
the number average molecular weight of the anionic polymer is 2000-80000g/mol;
the addition amount of the anionic polymer is 50-1000ppm based on 100 percent of the total mass of siloxane adopted for preparing the hydrolysate;
in the step (3), the pH of the system is maintained to be 6-8.5 during the mixing process.
2. The method of claim 1, wherein in step (1), the siloxane comprises any one or a combination of at least two of tetramethoxysilane, tetraethoxysilane, or tetrapropoxysilane.
3. The method of claim 2, wherein in step (1), the siloxane is tetramethoxysilane.
4. The process according to claim 1, wherein in step (1), the hydrolysis temperature is 2-30 ℃.
5. The method of claim 1, wherein in step (2), the mother liquor comprises water.
6. The method according to claim 5, wherein in the step (2), the mother liquor further comprises a pH adjuster.
7. The method according to claim 6, wherein in the step (2), the pH adjuster comprises a basic catalyst.
8. The method according to claim 7, wherein in the step (2), the basic catalyst comprises any one or a combination of at least two of alkali metal hydroxide, aqueous ammonia, an organic amine compound, and a guanidine compound.
9. The method according to claim 8, wherein in the step (2), the alkali metal hydroxide comprises potassium hydroxide and/or sodium hydroxide.
10. The method according to claim 8, wherein in the step (2), the organic amine compound comprises any one or a combination of at least two of ethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, diethanolamine, triethanolamine, and tetramethylammonium hydroxide.
11. The method according to claim 8, wherein in the step (2), the guanidine compound includes any one or a combination of at least two of tetramethylguanidine, trimethylguanidine, and guanidine carbonate.
12. The method according to claim 1, wherein in the step (2), the mass ratio of the hydrolysate to the mother liquor is 1: (0.2-0.8).
13. The method according to claim 1, wherein in the step (2), the mass ratio of siloxane to water in the hydrolysate is (5-26): 100.
14. The method according to claim 1, wherein in the step (2), the flow rate of the hydrolysis liquid added to the mother liquor is 0.5 to 10mL/min.
15. The method according to claim 1, wherein in the step (2), the hydrolysis liquid is added to the mother liquor for 4 to 50 hours.
16. The process of claim 1, wherein the temperature of the system during the mixing in step (2) is 50-100 ℃.
17. The method according to claim 1, wherein the anionic polymer is added to the system for a period of 0 to 6 hours from the start of mixing the hydrolysis liquid and the mother liquor.
18. The method according to claim 1, wherein in the step (2), the system pH is 6 to 8.5 during the mixing.
19. The method of claim 1, wherein the pH adjuster used to maintain the pH of the system comprises a basic catalyst.
20. The method according to claim 1, wherein in the step (3), the mass ratio of the hydrolysate to the seed crystal is 1: (0.125-0.875).
21. The method according to claim 1, wherein in the step (3), the mass ratio of siloxane to water in the hydrolysate is (11-44): 100.
22. The method according to claim 1, wherein in the step (3), the mixing means comprises: the hydrolysate was added to the seed crystals.
23. The method of claim 22, wherein in step (3), the seed crystal is first mixed with water.
24. The method according to claim 23, wherein in the step (3), when the seed crystal is mixed with water, the mass ratio of the seed crystal to water is 1: (1-3).
25. The method according to claim 22, wherein in the step (3), the flow rate of the hydrolysate added to the seed crystal is 0.5 to 10mL/min.
26. The process of claim 22, wherein in step (3), the time taken for seeding the hydrolysate is 4-50 hours.
27. The method according to claim 1, wherein in the step (3), the temperature of the system is 50 to 100 ℃ during the mixing.
28. The method according to claim 1, wherein after the seed crystal growth, the obtained non-spherical silica sol is used as a seed crystal, and the seed crystal growth is continued.
29. The method of claim 1, wherein in step (3), the seed crystal growth is completed and further comprising concentration and solvent displacement.
30. The method of claim 29, wherein the concentrating comprises vacuum heating.
31. The process of claim 29, wherein the organic solvent is present in the system at a level of less than or equal to 200ppm after the solvent displacement.
32. The method according to claim 29, wherein the mass percentage of silica in the silica sol in the system after the solvent substitution is not less than 20%.
33. The method of claim 29, wherein in step (3), the solvent is further filtered after the solvent is replaced.
34. The method of claim 33, wherein the filter element material used for the filtration comprises polytetrafluoroethylene.
35. The method of claim 33, wherein the filtration is performed with a precision of 0.2-5 μm.
36. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Mixing siloxane with water, hydrolyzing at 2-30deg.C to obtain hydrolysate, and using water as mother liquor;
(2) Continuously adding the hydrolysate into the mother liquor at a flow rate of 0.5-1.5mL/min, mixing for 4-50h, adding the anionic polymer into the system at the time of 0-6h of adding the hydrolysate, maintaining the pH of the system to 6-8.5 and the temperature of 50-100 ℃, and controlling the mass ratio of the hydrolysate to the mother liquor to be 1: (0.2-0.8) to obtain seed crystal;
(3) Continuously adding the hydrolysate into the seed crystal according to the flow rate of 0.5-1.5mL/min, mixing for 4-50h, maintaining the pH of the system to 6-8.5 and the temperature of 50-100 ℃, and controlling the mass ratio of the hydrolysate to the seed crystal to be 1: (0.125-0.875), completing the growth of seed crystal to obtain the non-spherical silica sol initial material;
(4) Concentrating and replacing the initial material of the non-spherical silica sol obtained in the step (3) by a solvent until the content of the organic solvent in the system is less than or equal to 200ppm, wherein the mass percentage of silicon dioxide in the silica sol is more than or equal to 20%, and filtering to obtain the non-spherical silica sol.
37. The process of claim 36, wherein the mother liquor of step (1) further comprises a pH adjuster.
38. The method of claim 36, wherein the seed crystals are mixed with water to form a seed crystal solution prior to adding the hydrolysate to the seed crystals in step (3).
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