CN115725081B - Preparation method of monodisperse organic silicon microsphere - Google Patents
Preparation method of monodisperse organic silicon microsphere Download PDFInfo
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- CN115725081B CN115725081B CN202211447443.6A CN202211447443A CN115725081B CN 115725081 B CN115725081 B CN 115725081B CN 202211447443 A CN202211447443 A CN 202211447443A CN 115725081 B CN115725081 B CN 115725081B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 69
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 30
- 239000010703 silicon Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000413 hydrolysate Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 108010009736 Protein Hydrolysates Proteins 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000003377 acid catalyst Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 20
- 230000001105 regulatory effect Effects 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 22
- 238000007664 blowing Methods 0.000 description 11
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 9
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 229920001558 organosilicon polymer Polymers 0.000 description 5
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention relates to the technical field of preparation of organic silicon microspheres, in particular to a preparation method of monodisperse organic silicon microspheres, which comprises the following steps: (1) Mixing an organosilicon end-capping agent and trialkoxysilane, uniformly stirring with water, adding an acid catalyst to adjust the pH to 4-6, and hydrolyzing to obtain an organosilicon hydrolysate; (2) Adding an alkaline aqueous solution into the organic silicon hydrolysate, and regulating the pH value of the solution to 7-9 to obtain a suspension; (3) Filtering, washing and drying the suspension to obtain the monodisperse organosilicon microspheres. The invention uses the organosilicon end-capping agent and the organosilicon monomer to carry out copolymerization, so that the end group of the organosilicon monomer is passivated, and the thermal stability of the polymer is increased, thereby effectively preventing the cross-linking among particles and realizing the preparation of the monodisperse microsphere by the high-concentration monomer. The method is environment-friendly and high in safety, simultaneously saves a large amount of solvents, remarkably reduces the amount of waste liquid, greatly reduces the volume of equipment, remarkably improves the production capacity of the equipment, greatly reduces the production cost and is more beneficial to large-scale production.
Description
Technical Field
The invention relates to the technical field of preparation of organic silicon microspheres, in particular to a preparation method of monodisperse organic silicon microspheres.
Background
The molecular structure of the organosilicon microsphere is mainly a three-dimensional network structure formed by alternately arranging silicon atoms and oxygen atoms, and meanwhile, various organic functional groups (such as alkyl, alkenyl, phenyl and the like) are usually connected to the silicon atoms, and the structure has both organic and inorganic characteristics. The special molecular structure endows the organosilicon microsphere with excellent lipophilicity, heat resistance, flame retardance, electrical insulation and the like, and can be widely applied to the fields of cosmetics, paint, printing ink, electronic packaging materials, light diffusion agents, rubber plastic products and the like. Therefore, in recent years, the organic silicon microsphere has become one of research hotspots in the fields of domestic and foreign industry and scientific research.
Methyltrialkoxysilane is a main raw material for preparing monodisperse organic silicon microspheres, and when the monomer concentration is too high, the microspheres are often crosslinked in the polymerization process, so that the monodisperse organic silicon microspheres are difficult to obtain, and the product performance is greatly reduced. Patent CN113881050a uses methyltrialkoxysilane to obtain monodisperse organosilicon microspheres by one-step polymerization under the action of base catalysis. The method provided by the invention is simple, but in order to ensure the monodispersity of the microspheres, the precursor concentration needs to be controlled not to be too high, so that a large amount of solvent is needed in the preparation process. The mass ratio (namely the feed-liquid ratio) of the monomer to the solvent water is controlled between 1:5 and 15. This results in large amounts of waste water produced during the production process, increasing production costs, and the high proportion of solvents necessitates large volume equipment, increasing equipment investment, and being unfavorable for industrial production.
In order to prevent crosslinking among microsphere particles, the patent CN102675643A uses chlorosilane for surface modification, thereby realizing the purpose of preparing the monodisperse organosilicon microspheres in a high-concentration precursor solution, the highest feed-liquid ratio can reach about 1:2, a large amount of solvents are saved, and the amount of waste liquid is obviously reduced. However, the introduction of chlorosilane can lead to the continuous release of hydrogen chloride in the reaction system, so that improper protection is caused, serious corrosion of equipment is easily caused, and even the personal safety of production personnel is threatened. In addition, ethanol or acetone is used as a precipitator in the microsphere production process, so that potential safety hazards in the production process and waste liquid treatment difficulty are increased.
Disclosure of Invention
Aiming at the technical problems that a large amount of solvents are needed to be used or corrosive gases such as hydrogen chloride are generated in the existing preparation method of the monodisperse organosilicon microspheres, and the environmental protection property and the safety are poor, the invention provides the preparation method of the monodisperse organosilicon microspheres, which comprises the following steps:
(1) Mixing an organosilicon end-capping agent and trialkoxysilane, uniformly stirring with water, adding an acid catalyst to adjust the pH to 4-6, and hydrolyzing to obtain an organosilicon hydrolysate;
(2) Adding an alkaline aqueous solution into the organic silicon hydrolysate, and regulating the pH value of the solution to 7-9 to obtain a suspension;
(3) Filtering, washing and drying the suspension to obtain the monodisperse organosilicon microspheres.
The end group of the organic silicon monomer is passivated by utilizing the copolymerization of the organic silicon end capping agent and the organic silicon monomer, and the thermal stability of the polymer is improved, so that the cross-linking among particles is effectively prevented, and the problem of preparing the monodisperse microsphere by the high-concentration monomer is solved.
Further, the organosilicon capping agent is trimethylsiloxane or a hydrolysate thereof.
Further, the mass ratio of the organosilicon end-capping agent to the trialkoxysilane is 1:20-50.
The amounts of organosilicon capping agent and trialkoxysilane affect the synthesis of the organosilicon microspheres. When only trialkoxysilane is used, significant multiparticulate crosslinking of the silicone microspheres occurs; when the mass ratio of the organosilicon end-capping agent to the trialkoxysilane is greater than 1:20, it is difficult to obtain a spherical organosilicon polymer; when the mass ratio of the organosilicon end-capping agent to the trialkoxysilane is less than 1:50, the organosilicon microspheres are gradually crosslinked; the mass ratio of the organosilicon end-capping agent to the trialkoxysilane is controlled to be 1:20-50, and the prepared organosilicon microsphere has good dispersing effect.
Further, the mass ratio of the total mass of the organosilicon end-capping agent and the trialkoxysilane to water is 1:1.2-2.
Further, the acid catalyst in the step (1) is one or more of hydrochloric acid, acetic acid and citric acid.
Further, the hydrolysis temperature in the step (1) is 35 ℃, and the hydrolysis time is 30-180 min.
Further, in the step (2), the added alkaline aqueous solution is one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water.
Further, the reaction temperature in the step (2) is 35 ℃ and the reaction time is 300min.
Further, the washing agent used in the step (3) is deionized water.
In the step (3), the drying mode is 160 ℃ oven drying for 3 hours.
The invention has the beneficial effects that:
according to the preparation method of the monodisperse organic silicon microsphere, provided by the invention, the organic silicon end capping agent is added to carry out copolymerization with the organic silicon monomer, so that the end group of the organic silicon monomer is passivated, and the thermal stability of the polymer is increased, thereby effectively preventing cross-linking among particles and successfully solving the problem of particle adhesion in the process of preparing the microsphere by using a high-concentration monomer solution. Meanwhile, the preparation method adopts water as the only solvent, the highest feed-liquid ratio can be controlled at 1:1.2, the technology is green and environment-friendly, the safety is good, a large amount of solvents are saved, and the amount of waste liquid is obviously reduced. In addition, the technology can greatly reduce the volume of equipment, remarkably improve the production capacity of the equipment, reduce the equipment investment and be more beneficial to large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a scanning electron microscope image of the silicone microsphere prepared in example 1.
FIG. 2 is a scanning electron microscope image of the silicone microspheres prepared in example 2.
FIG. 3 is a scanning electron microscope image of the silicone microsphere prepared in example 3.
FIG. 4 is a scanning electron microscope image of the silicone microsphere prepared in comparative example 1.
FIG. 5 is a scanning electron microscope image of the silicone microsphere prepared in comparative example 2.
FIG. 6 is a scanning electron microscope image of the silicone microspheres prepared in comparative example 3
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
(1) Mixing trimethylmethoxysilane and methyltriethoxysilane according to a mass ratio of 1:20, adding 56g of the mixture into 112g of deionized water, controlling the system temperature to be 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 2mol/L hydrochloric acid, adjusting the pH of the solution to 6, and hydrolyzing for 60min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 2mol/L sodium hydroxide solution into the organic silicon hydrolysate, regulating the pH value of the solution to be 7, carrying out reaction, controlling the reaction temperature to be 35 ℃, and the reaction time to be 300min, thus obtaining suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the monodisperse organosilicon microspheres.
The particle size of the monodisperse organosilicon microspheres obtained in the embodiment is between 1 and 10 mu m, and the scanning electron microscope is shown as figure 1, so that the organosilicon microspheres have good dispersibility.
Example 2
(1) Mixing trimethylmethoxysilane and methyltriethoxysilane according to a mass ratio of 1:30, adding 68g of the mixture into 102g of deionized water, controlling the system temperature to be 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 2mol/L acetic acid, adjusting the pH of the solution to 5, and hydrolyzing for 100min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 1mol/L ammonia water into the organic silicon hydrolysate, regulating the pH value of the solution to be 8, carrying out reaction, controlling the reaction temperature to be 35 ℃, and the reaction time to be 300min, so as to obtain suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the monodisperse organosilicon microspheres.
The particle size of the monodisperse organosilicon microspheres obtained in the embodiment is between 1 and 10 mu m, and the scanning electron microscope is shown as figure 2, so that the organosilicon microspheres have good dispersibility.
Example 3
(1) Mixing trimethylethoxysilane and methyltriethoxysilane according to a mass ratio of 1:40, adding 76g of the mixture into 91.2g of deionized water, controlling the system temperature at 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 2mol/L hydrochloric acid, adjusting the pH of the solution to 4, and hydrolyzing 180 to obtain an organosilicon hydrolysate;
(2) Dropwise adding 2mol/L potassium hydroxide solution into the organic silicon hydrolysate, regulating the pH value of the solution to be 8, carrying out reaction, controlling the reaction temperature to be 35 ℃, and the reaction time to be 300min, thus obtaining suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the monodisperse organosilicon microspheres.
The particle size of the monodisperse organosilicon microspheres obtained in the embodiment is between 1 and 10 mu m, and the scanning electron microscope is shown as figure 3, so that the organosilicon microspheres have good dispersibility.
Comparative example 1
(1) Adding 68g of methyltriethoxysilane into 102g of deionized water, controlling the system temperature at 35 ℃, mechanically stirring uniformly at the rotating speed of 600rpm, adding 2mol/L acetic acid, adjusting the pH of the solution to 5, and hydrolyzing for 100min to obtain organosilicon hydrolysate;
(2) Dropwise adding 1mol/L ammonia water into the organic silicon hydrolysate, regulating the pH value of the solution to be 8, carrying out reaction, controlling the reaction temperature to be 35 ℃, and the reaction time to be 300min, so as to obtain suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the organosilicon microspheres.
The particle size of the organosilicon microsphere obtained in the comparative example is between 1 and 10 mu m, a scanning electron microscope image is shown in figure 4, the cross-linking phenomenon of multiple particles exists among particles, even part of particles show irregular morphology, and the dispersibility of the organosilicon microsphere is poor.
Comparative example 2
(1) Mixing trimethylmethoxysilane and methyltriethoxysilane according to a mass ratio of 1:60, adding 68g of the mixture into 102g of deionized water, controlling the system temperature to be 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 2mol/L acetic acid, adjusting the pH of the solution to 5, and hydrolyzing for 100min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 1mol/L ammonia water into the organic silicon hydrolysate, regulating the pH value of the solution to be 8, carrying out reaction, controlling the reaction temperature to be 35 ℃, and the reaction time to be 300min, so as to obtain suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the organosilicon microspheres.
The particle size of the organosilicon microspheres obtained in the comparative example is between 1 and 10 mu m, a scanning electron microscope image is shown in figure 5, the conditions of crosslinking between particles are provided, and the dispersibility of the organosilicon microspheres is affected to a certain extent.
Comparative example 3
(1) Mixing trimethylmethoxysilane and methyltriethoxysilane according to a mass ratio of 1:10, adding 68g of the mixture into 102g of deionized water, controlling the system temperature to be 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 2mol/L acetic acid, adjusting the pH of the solution to 5, and hydrolyzing for 100min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 1mol/L ammonia water into the organic silicon hydrolysate, regulating the pH value of the solution to be 8, carrying out reaction, controlling the reaction temperature to be 35 ℃ and the reaction time to be 300min, and obtaining a semitransparent organic silicon polymer after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the organosilicon polymer.
As shown in FIG. 6, the scanning electron microscope image of the organosilicon polymer obtained in the comparative example shows that the organosilicon polymer has an irregular morphology and contains only a small amount of particles with spherical morphology.
Example 4
(1) Mixing trimethylmethoxysilane and methyltriethoxysilane according to a mass ratio of 1:50, adding 68g of the mixture into 102g of deionized water, controlling the system temperature at 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 2mol/L hydrochloric acid to adjust the pH of the solution to 4, and hydrolyzing for 80min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 1mol/L ammonia water into the organic silicon hydrolysate, regulating the pH value of the solution to be 7, carrying out reaction, controlling the reaction temperature to be 35 ℃ and the reaction time to be 300min, and obtaining suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the monodisperse organosilicon microspheres.
The monodisperse organosilicon microsphere obtained in the embodiment has particle size of 1-10 μm and good dispersibility.
Example 5
(1) Mixing trimethylmethoxysilane and methyltriethoxysilane according to a mass ratio of 1:50, adding 56g of the mixture into 112g of deionized water, controlling the system temperature to be 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 2mol/L acetic acid, adjusting the pH value of the solution to 4, and hydrolyzing for 30min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 2mol/L sodium hydroxide solution into the organic silicon hydrolysate, regulating the pH value of the solution to be 9, carrying out reaction, controlling the reaction temperature to be 35 ℃, and reacting for 300min to obtain suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the monodisperse organosilicon microspheres.
The monodisperse organosilicon microsphere obtained in the embodiment has particle size of 1-10 μm and good dispersibility.
Example 6
(1) Mixing trimethylethoxysilane and methyltriethoxysilane according to a mass ratio of 1:30, adding 56g of the mixture into 112g of deionized water, controlling the system temperature to be 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 1mol/L citric acid, adjusting the pH of the solution to 4, and hydrolyzing for 30min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 2mol/L sodium hydroxide solution into the organic silicon hydrolysate, regulating the pH value of the solution to be 9, carrying out reaction, controlling the reaction temperature to be 35 ℃, and reacting for 300min to obtain suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the monodisperse organosilicon microspheres.
The monodisperse organosilicon microsphere obtained in the embodiment has particle size of 1-10 μm and good dispersibility.
Example 7
(1) Mixing trimethylmethoxysilane and methyltriethoxysilane according to a mass ratio of 1:30, adding 76g of the mixture into 91.2g of deionized water, controlling the system temperature at 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 2mol/L acetic acid, adjusting the pH of the solution to 4, and hydrolyzing for 150min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 2mol/L sodium hydroxide solution into the organic silicon hydrolysate, regulating the pH value of the solution to be 9, carrying out reaction, controlling the reaction temperature to be 35 ℃, and reacting for 300min to obtain suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the monodisperse organosilicon microspheres.
The monodisperse organosilicon microsphere obtained in the embodiment has particle size of 1-10 μm and good dispersibility.
Example 8
(1) Mixing trimethylethoxysilane and methyltriethoxysilane according to a mass ratio of 1:40, adding 68g of the mixture into 102g of deionized water, controlling the system temperature to be 35 ℃, mechanically stirring uniformly at a rotating speed of 600rpm, adding 1mol/L citric acid, adjusting the pH of the solution to 5, and hydrolyzing for 90min to obtain an organosilicon hydrolysate;
(2) Dropwise adding 1mol/L ammonia water into the organic silicon hydrolysate, regulating the pH value of the solution to be 8, carrying out reaction, controlling the reaction temperature to be 35 ℃, and the reaction time to be 300min, so as to obtain suspension after the reaction;
(3) Filtering the suspension, washing filter residues with deionized water, and then drying by blowing at 160 ℃ for 3 hours to obtain the monodisperse organosilicon microspheres.
The monodisperse organosilicon microsphere obtained in the embodiment has particle size of 1-10 μm and good dispersibility.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.
Claims (8)
1. The preparation method of the monodisperse organosilicon microsphere is characterized by comprising the following steps:
(1) Mixing an organosilicon end-capping agent and trialkoxysilane, wherein the mass ratio of the organosilicon end-capping agent to the trialkoxysilane is 1:20-50, uniformly stirring with water, the mass ratio of the total mass of the organosilicon end-capping agent and the trialkoxysilane to the water is 1:1.2-2, adding an acid catalyst to adjust the pH to 4-6, and hydrolyzing to obtain an organosilicon hydrolysate;
(2) Adding an alkaline aqueous solution into the organic silicon hydrolysate, and adjusting the pH value of the solution to 7-9 to obtain a suspension;
(3) Filtering, washing and drying the suspension to obtain the monodisperse organosilicon microspheres.
2. The method of preparing monodisperse organosilicon microspheres according to claim 1, wherein the organosilicon capping agent is trimethylsiloxane or a hydrolysate thereof.
3. The method for preparing monodisperse organosilicon microspheres according to claim 1, wherein the acidic catalyst in step (1) is one or more of hydrochloric acid, acetic acid and citric acid.
4. The method for preparing monodisperse organosilicon microspheres according to claim 1, wherein the hydrolysis temperature in step (1) is 35 ℃ and the hydrolysis time is 30-180 min.
5. The method for preparing monodisperse organosilicon microspheres according to claim 1, wherein in the step (2), the added alkaline aqueous solution is one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water.
6. The method for preparing monodisperse organosilicon microspheres according to claim 1, wherein the reaction temperature in step (2) is 35 ℃ and the reaction time is 300min.
7. The method of preparing monodisperse organosilicon microspheres according to claim 1, wherein the washing agent used in step (3) is deionized water.
8. The method for preparing monodisperse organosilicon microspheres according to claim 1, wherein in step (3), the drying mode is 160 ℃ oven drying for 3 hours.
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|---|---|---|---|
| CN202211447443.6A CN115725081B (en) | 2022-11-18 | 2022-11-18 | Preparation method of monodisperse organic silicon microsphere |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3452562B1 (en) * | 2002-05-29 | 2003-09-29 | 日興リカ株式会社 | Method for producing spherical polyorganosilsesquioxane fine particles |
| KR20090056901A (en) * | 2007-11-29 | 2009-06-03 | 주식회사 코오롱 | Polyalkylsilsesquioxane particulates and a preparation method thereof |
| CN103030752A (en) * | 2011-09-29 | 2013-04-10 | 比亚迪股份有限公司 | Polymer microsphere, preparation method and application of polymer microsphere, composition, light diffusion plate or light diffusion film, lamp and backlight module |
| CN103739847A (en) * | 2013-12-17 | 2014-04-23 | 韦兴祥 | Preparation method of organic siloxane microspheres with narrow particle size distribution and richly organized surfaces |
| CN107879348A (en) * | 2017-08-07 | 2018-04-06 | 山东师范大学 | A kind of preparation method of the monodisperse silica nanosphere of novel green |
| CN111620342A (en) * | 2020-06-03 | 2020-09-04 | 南京特粒材料科技有限公司 | Small-size monodisperse hollow silica microsphere and preparation method and application thereof |
| CN113881050A (en) * | 2021-10-27 | 2022-01-04 | 湖北兴瑞硅材料有限公司 | Preparation method of polymethylsilsesquioxane microspheres |
-
2022
- 2022-11-18 CN CN202211447443.6A patent/CN115725081B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3452562B1 (en) * | 2002-05-29 | 2003-09-29 | 日興リカ株式会社 | Method for producing spherical polyorganosilsesquioxane fine particles |
| KR20090056901A (en) * | 2007-11-29 | 2009-06-03 | 주식회사 코오롱 | Polyalkylsilsesquioxane particulates and a preparation method thereof |
| CN103030752A (en) * | 2011-09-29 | 2013-04-10 | 比亚迪股份有限公司 | Polymer microsphere, preparation method and application of polymer microsphere, composition, light diffusion plate or light diffusion film, lamp and backlight module |
| CN103739847A (en) * | 2013-12-17 | 2014-04-23 | 韦兴祥 | Preparation method of organic siloxane microspheres with narrow particle size distribution and richly organized surfaces |
| CN107879348A (en) * | 2017-08-07 | 2018-04-06 | 山东师范大学 | A kind of preparation method of the monodisperse silica nanosphere of novel green |
| CN111620342A (en) * | 2020-06-03 | 2020-09-04 | 南京特粒材料科技有限公司 | Small-size monodisperse hollow silica microsphere and preparation method and application thereof |
| CN113881050A (en) * | 2021-10-27 | 2022-01-04 | 湖北兴瑞硅材料有限公司 | Preparation method of polymethylsilsesquioxane microspheres |
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