CN117887073A - Preparation method of low-water-content polymethylsilsesquioxane microsphere - Google Patents
Preparation method of low-water-content polymethylsilsesquioxane microsphere Download PDFInfo
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- CN117887073A CN117887073A CN202311647275.XA CN202311647275A CN117887073A CN 117887073 A CN117887073 A CN 117887073A CN 202311647275 A CN202311647275 A CN 202311647275A CN 117887073 A CN117887073 A CN 117887073A
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- polymethylsilsesquioxane
- microsphere
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- methyltrimethoxysilane
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- 239000004005 microsphere Substances 0.000 title claims abstract description 31
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- 125000005375 organosiloxane group Chemical group 0.000 claims description 10
- -1 carboxylic acid sodium salt Chemical class 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 4
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000002245 particle Substances 0.000 abstract description 26
- 239000008367 deionised water Substances 0.000 abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 230000002431 foraging effect Effects 0.000 abstract 1
- 238000007789 sealing Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention discloses a preparation method of a low-water-content polymethylsilsesquioxane microsphere. Hydrolyzing methyltrialkoxysilane under the condition of hydrochloric acid at room temperature, adding a surfactant under the condition of alkalinity for polycondensation to obtain suspension, adding organic siloxane into the suspension for modification, heating for aging after reacting for a period of time, filtering the suspension, washing with deionized water, drying and crushing to obtain the polymethylsilsesquioxane microsphere. The microspheres obtained by the invention have good dispersibility, good sphericity and narrow particle size distribution range, and more particularly provide polyalkylsilsesquioxane particles with moisture content lower than 1.0%, high water resistance and low storage hygroscopicity.
Description
Technical Field
The invention belongs to the technical field of organic silicon, and particularly relates to a preparation method of a low-water-content polymethylsilsesquioxane microsphere.
Background
Polymethylsilsesquioxane has excellent heat resistance, hydrophobicity, light transmittance, dispersibility and other properties due to its organic-inorganic structure, and has been receiving more and more attention in the fields of biomedicine, chemical analysis, optoelectronics, environmental science and the like. The micron-sized polymethylsilsesquioxane microsphere has excellent light transmittance and light diffusivity, and is widely used as a light diffusion additive of light diffusion plastic at present. Therefore, polymethylsilsesquioxane microspheres need to have low moisture content, avoiding the problem of high storage hygroscopicity when mixed with various rubbers or plastics and used.
Chinese patent CN114181395 discloses a polyorganosilsesquioxane microsphere and a preparation method thereof, wherein the polyorganosilsesquioxane microsphere is prepared by ultrasonic instead of mechanical stirring, and the polyorganosilsesquioxane microsphere with uniform particle size distribution is obtained. However, it cannot solve the problems of low water content and high storage hygroscopicity of the polysilsesquioxane microspheres.
Disclosure of Invention
The invention provides a preparation method of a low-water-content polymethylsilsesquioxane microsphere, and the obtained polymethylsilsesquioxane microsphere has low water content and low hygroscopicity.
In order to achieve the above object, the present invention adopts the following technical scheme: the preparation method of the low-water-content polymethylsilsesquioxane microsphere comprises the following steps:
s1, mixing methyltrimethoxysilane, water and hydrochloric acid for hydrolysis;
s2, adding a surfactant and ammonia water into the hydrolysate, mixing to obtain a suspension, adding organosiloxane for modification treatment, and then heating and ageing;
and S3, filtering the aged material, washing and drying a filter cake, and crushing to obtain the polymethylsilsesquioxane microsphere.
Further, the hydrolysis condition in S1 is room temperature, the mixing speed is 200-300r/min during hydrolysis, and the time is 0.5-1h.
Further, the mass ratio of the methyltrimethoxysilane to the water in the S1 is 1:7-10; the mass fraction of the hydrochloric acid is 1.2-1.5%, and the addition amount is 0.1-0.15% of the mass of the methyltrimethoxysilane.
Further, the surfactant in S2 is an anionic nonionic surfactant, and the addition amount is 0.5-1% of the mass of the methyltrimethoxysilane.
Further, the surfactant is at least one of fatty acid methyl ester ethoxylate sulfonate, aromatic long-chain polyether carboxylic acid sodium salt and alkylphenol polyoxyethylene ammonium salt.
Further, the concentration of ammonia water in S2 is 2.2-2.5%, and the addition amount is 5.5-6.5% of the mass of methyltrimethoxysilane.
Further, the organosiloxane is added after the suspension is formed for 10-20 min; the addition amount is 0.5-1% of the mass of the methyltrimethoxysilane.
Further, the organosiloxane is at least one of dimethyl dimethoxy silane, trimethyl methoxy silane and dimethyl diethoxy silane.
Further, when the temperature is raised and aged, the temperature is raised to 60-80 ℃ and aged for 4-8 hours.
The invention also relates to the polymethylsilsesquioxane microsphere obtained by the preparation method.
The invention has the following beneficial effects:
1. the invention prepares the polymethylsilsesquioxane by a hydrolysis-condensation method, and has simple experimental conditions; by adding the anionic and nonionic surfactant in the polycondensation stage, the polymethylsilsesquioxane microsphere with uniform size, narrow particle size distribution and perfect sphericity can be obtained.
2. By adding organic siloxane for modification at the initial stage of polycondensation, a small amount of silanol groups on the surface of the polymethylsiloxane microsphere are blocked, so that the polymethylsilsesquioxane microsphere with low water content and low hygroscopicity is obtained.
3. Treating the suspension by a physical temperature-rising aging mode, and condensing the silanol groups exposed by the polymethylsiloxane microspheres under a high temperature condition to reduce the water content of the polymethylsiloxane microspheres; and the long-time aging can enable the residual micromolecules in the reaction system to continue to react, so that the yield is improved, the content of organic matters in the filtrate is reduced, and the recycling difficulty of the filtrate is reduced.
Drawings
FIG. 1 is an electron micrograph of the microspheres obtained in example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
(1) And (5) hydrolyzing. At room temperature, 10kg of methyltrimethoxysilane, 70kg of deionized water and 10g of hydrochloric acid (mass concentration: 1.5%) were uniformly mixed, and the hydrolysis was continued for 1 hour at a stirring rotation speed of 300 r/min.
(2) And (5) polycondensation. 50g of fatty acid methyl ester ethoxylate sulfonate and 550g of ammonia water (mass concentration: 2.5%) were added to the hydrolysate, and a suspension was obtained at 70 r/min.
(3) And (3) modifying the organic siloxane. After the suspension was formed for 10min, 50g of dimethyldimethoxysilane was added for modification, and the reaction was carried out at 70r/min for 2h.
(4) And (5) heating and ageing. The obtained suspension was heated to 60℃and aged for 4 hours.
(5) And (5) post-treatment. Filtering the suspension, washing with deionized water, drying and crushing to obtain the polymethylsilsesquioxane microsphere. Its particle diameter D 90 At 2.5 mu m, the particle size distribution is narrow, the distribution span is 0.71, and the sphericity is good; the water content (15 min at 120 ℃) was 0.712%, and the water content after one month of sealing and standing was 0.738%.
Example 2
The parameters of this example were substantially the same as those of example 1, except that the mass of deionized water was 100kg. The particle diameter D of the obtained product 90 At 3.2 mu m, the particle size distribution is narrow, the distribution span is 0.82, and the sphericity is good; the water content (15 min at 120 ℃) was 0.723%, and after one month of sealing and standing, the water content was 0.747%.
Example 3
The parameters of this example are substantially the same as those of example 1, except that the mass of hydrochloric acid is 15g. Its particle diameter D 90 At 2.8 mu m, the particle size distribution is narrow, the distribution span is 0.76, and the sphericity is good; the water content (15 min at 120 ℃) was 0.695%, and the water content after one month of sealing was 0.712%.
Example 4
The parameters of this example are essentially the same as those of example 1, except that the fatty acid methyl ester ethoxylate sulfonateThe amount was 100g. Its particle diameter D 90 At 2.5 mu m, the particle size distribution is narrow, the distribution span is 0.80, and the sphericity is good; the water content (15 min at 120 ℃) was 0.681%, and the water content after one month of sealing and standing was 0.712%.
Example 5
The parameters of this example are basically the same as those of example 1, except that the surfactant is alkylphenol ethoxylate ammonium sulfate. Its particle diameter D 90 At 2.5 mu m, the particle size distribution is narrow, the distribution span is 0.78, and the sphericity is good; the water content (15 min at 120 ℃) is 0.770 percent, and the water content after sealing and standing for one month is 0.802 percent.
Example 6
The parameters of this example are substantially the same as those of example 1, except that the mass of ammonia water is 650g. Its particle diameter D 90 At 2.0 mu m, the particle size distribution is narrow, the distribution span is 0.75, and the sphericity is good; the water content (15 min at 120 ℃) is 0.743 percent, and the water content after sealing and standing for one month is 0.792 percent.
Example 7
This example is substantially identical to example 1 with the exception that the dimethyldimethoxysilane has a mass of 100g. Its particle diameter D 90 At 2.5 mu m, the particle size distribution is narrow, the distribution span is 0.75, and the sphericity is good; the water content (15 min at 120 ℃) is 0.661 percent, and the water content after sealing and standing for one month is 0.698 percent.
Example 8
This example has substantially the same parameters as example 1, except that the organosiloxane is trimethylmethoxysilane. Its particle diameter D 90 At 2.5 mu m, the particle size distribution is narrow, the distribution span is 0.74, and the sphericity is good; the water content (15 min at 120 ℃) was 0.722%, and the water content after one month of sealing and standing was 0.748%.
Example 9
The parameters of this example were substantially the same as those of example 1, except that the modification was carried out by adding the organosiloxane after forming the suspension for 20 minutes. Its particle diameter D 90 At 2.4 mu m, the particle size distribution is narrow, the distribution span is 0.73, and the sphericity is good; the water content (15 min at 120deg.C) is 0.722%, and the water content after sealing and standing for one month0.778%.
Example 10
The parameters of this example are substantially the same as those of example 1, except that the aging temperature of the suspension is 80 ℃. Its particle diameter D 90 At 2.5 mu m, the particle size distribution is narrow, the distribution span is 0.80, and the sphericity is good; the water content (15 min at 120 ℃) was 0.692%, and the water content after one month of sealing and standing was 0.715%.
Example 11
The parameters of this example are substantially the same as those of example 1, except that the aging time of the suspension is 8 hours. Its particle diameter D 90 At 2.5 mu m, the particle size distribution is narrow, the distribution span is 0.78, and the sphericity is good; the water content (15 min at 120 ℃) was 0.676, and after one month of sealing and standing, the water content was 0.705%.
Comparative experiments
In order to compare the low water content effect of the polymethylsilsesquioxane microsphere of the present invention, a comparison experiment was set. The comparative example is substantially the same as example 1 except that no organosiloxane modification or elevated temperature aging is employed. The specific conditions are shown in table 1 below.
TABLE 1
As can be seen from the data in the table, the water content of the polymethylsilsesquioxane microsphere obtained by performing the organosiloxane modification or the physical temperature-increasing aging alone is higher than 1.0%, and the water content of the polymethylsilsesquioxane microsphere obtained by performing the organosiloxane modification and the physical temperature-increasing aging alone is higher than 1.8%, so that the polymethylsilsesquioxane microsphere with low water content and low hygroscopicity cannot be obtained.
The above examples describe preferred embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the low-water-content polymethylsilsesquioxane microsphere is characterized by comprising the following steps of:
s1, mixing methyltrimethoxysilane, water and hydrochloric acid for hydrolysis;
s2, adding a surfactant and ammonia water into the hydrolysate, mixing to obtain a suspension, adding organosiloxane for modification treatment, and then heating and ageing;
and S3, filtering the aged material, washing and drying a filter cake, and crushing to obtain the polymethylsilsesquioxane microsphere.
2. The method of manufacturing according to claim 1, characterized in that: the hydrolysis condition in S1 is room temperature, the mixing speed is 200-300r/min during hydrolysis, and the time is 0.5-1h.
3. The preparation method according to claim 2, characterized in that: the mass ratio of the methyltrimethoxysilane to the water in the S1 is 1:7-10; the mass fraction of the hydrochloric acid is 1.2-1.5%, and the addition amount is 0.1-0.15% of the mass of the methyltrimethoxysilane.
4. The method of manufacturing according to claim 1, characterized in that: the surfactant in S2 is anionic and nonionic surfactant, and the addition amount is 0.5-1% of the mass of methyltrimethoxysilane.
5. The method of claim 4, wherein: the surfactant is at least one of fatty acid methyl ester ethoxylate sulfonate, aromatic long-chain polyether carboxylic acid sodium salt and alkylphenol polyoxyethylene ammonium sulfate.
6. The method of manufacturing according to claim 1, characterized in that: the concentration of ammonia water in S2 is 2.2-2.5%, and the addition amount is 5.5-6.5% of the mass of methyltrimethoxysilane.
7. The preparation method according to any one of claims 1 to 6, characterized in that: the organosiloxane is added after the suspension is formed for 10-20 min; the addition amount is 0.5-1% of the mass of the methyltrimethoxysilane.
8. The preparation method according to any one of claims 1 to 6, characterized in that: the organic siloxane is at least one of dimethyl dimethoxy silane, trimethyl methoxy silane and dimethyl diethoxy silane.
9. The preparation method according to any one of claims 1 to 6, characterized in that: and (3) heating to 60-80 ℃ for ageing for 4-8 hours.
10. The polymethylsilsesquioxane microsphere obtained by the preparation method according to any one of claims 1 to 9.
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| CN202311647275.XA CN117887073A (en) | 2023-12-04 | 2023-12-04 | Preparation method of low-water-content polymethylsilsesquioxane microsphere |
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| CN202311647275.XA CN117887073A (en) | 2023-12-04 | 2023-12-04 | Preparation method of low-water-content polymethylsilsesquioxane microsphere |
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