CN108948073B - Preparation method of polyhydroxy silsesquioxane - Google Patents
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- CN108948073B CN108948073B CN201810929844.2A CN201810929844A CN108948073B CN 108948073 B CN108948073 B CN 108948073B CN 201810929844 A CN201810929844 A CN 201810929844A CN 108948073 B CN108948073 B CN 108948073B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000012086 standard solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 229910000077 silane Inorganic materials 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- -1 acryloxy Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
A preparation method of polyhydroxy sesqui-silane belongs to the technical field of POSS preparation. The method comprises the following steps: tetraethyl orthosilicate and tetramethyl ammonium hydroxide are weighed and dissolved in ethanol water solution, and then tetraethyl orthosilicate is dripped; placing the mixed solution at 25 ℃ for reaction for 24h, heating to 60 ℃ for reaction for 6h, and naturally cooling to room temperature after the reaction; performing rotary evaporation and concentration on the product, cooling, crystallizing, filtering, precipitating and drying to obtain octa-tetramethyl ammonium POSS ammonium salt; weighing octatetramethylammonium POSS ammonium salt and distilled water, mixing, and adjusting the pH to be = 1; and (3) carrying out rotary evaporation and concentration on the solution to obtain a transparent viscous liquid, drying, and washing a product to obtain the polyhydroxy silsesquioxane. The invention has the advantages that: the invention has short synthesis reaction time, easy operation and mild reaction conditions, and simultaneously, the active reaction groups of the material can be crosslinked with polymer molecular chains, thereby enhancing the compatibility of POSS and material matrix and enhancing the heat resistance and impact resistance of the polymer to a certain extent.
Description
Technical Field
The invention belongs to the technical field of POSS (polyhedral oligomeric silsesquioxane) preparation, and particularly relates to a preparation method of polyhydroxy silsesquioxane.
Background
Polyhedral oligomeric silsesquioxane (POSS for short) is a compound with a nanoscale cage-like structure, also called cubic silane, and has a molecular general formula of (RSiO)1.5)nThe basic structural unit is-Si-O-, the size of the whole molecule is between 1 and 3nm, and the silicon particle is the smallest. The molecule takes a silica framework as a core, organic substituent groups are connected at eight Si vertexes, the inorganic silica framework can endow the material with good heat resistance and mechanical properties, peripheral organic groups are designed into reactive groups such as alkylene, silanol, acryloxy and the like, and POSS and organic polymers can be subjected to surface bond, grafting, copolymerization and other reactions through the reactive groups, so that the POSS modified high polymer has good properties by combining a nano-size effect.
At present, the synthesis of multifunctional POSS (polyhedral oligomeric silsesquioxane) reported at home and abroad is mostly concentrated on TnIn the form of a trichloro (methoxy,ethoxy) organosilane is obtained by hydrolytic condensation under the condition of a solvent, the process has long period, low yield and efficiency, a large amount of byproducts and relatively difficult separation and purification. By using QxMyDocuments and patents of POSS synthesis in which octatetramethylammonium POSS ammonium salt is synthesized in a form, and then hydroxyl groups are directly connected to the vertex angle Si by one-step substitution are not reported so far.
Disclosure of Invention
The invention aims to solve the problems of low efficiency and difficult product purification process of the existing synthesis method of polyhydroxy POSS, and provides a preparation method of polyhydroxy silsesquioxane.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing polyhydroxy silsesquioxane comprises the following steps:
weighing tetraethyl orthosilicate and tetramethylammonium hydroxide according to a molar ratio of 1: 1, dissolving the tetramethylammonium hydroxide in an ethanol water solution to obtain a tetramethylammonium hydroxide solution of 0.08-0.2 g/m L, and dropwise adding the tetraethyl orthosilicate, wherein the volume ratio of ethanol to water in the ethanol water solution is 8: 1;
step two: under the condition of stirring, placing the mixed solution obtained in the step one at 25 ℃ for reaction for 24 hours, then heating to 60 ℃ for reaction for 6 hours, and naturally cooling to room temperature after the reaction is finished;
step three: concentrating the product obtained in the second step to the volume of the remaining one third by rotary evaporation, cooling, crystallizing and filtering at the room temperature of 25 ℃, precipitating with acetone, and drying the precipitate at the temperature of 45 ℃ for 1h to obtain octa-poly (tetramethylammonium) POSS ammonium salt;
step four, weighing octa-tetramethyl ammonium POSS ammonium salt and distilled water prepared in the step three according to the mass-volume ratio of 1: 20, dissolving the octa-tetramethyl ammonium POSS ammonium salt in the distilled water, and dropwise adding 1 mol/L HCl standard solution until the pH value of the solution is 1;
step five: and (3) carrying out rotary evaporation and concentration on the solution to obtain a transparent viscous liquid, drying the transparent viscous liquid in a 45 ℃ oven for 6 hours to obtain a product which is white powder, and washing the product with distilled water to obtain the polyhydroxy silsesquioxane.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts QxMyThe POSS containing the polyhydroxy group is synthesized in the form, the silsesquioxane POSS is taken as a core and is connected with a plurality of active hydroxyl groups, the synthesis reaction time is short, the operation is easy, the reaction condition is mild, meanwhile, the active reaction group of the material can be crosslinked with a polymer molecular chain, the compatibility of the POSS and a material matrix is enhanced, and the heat resistance and the impact resistance of the polymer are enhanced to a certain degree. The unique structural advantages of multifunctional reactive POSS in polymer modification make it potentially useful in applications.
Drawings
FIG. 1 is an infrared spectrum of octatetramethylammonium POSS ammonium salt of example 1;
FIG. 2 is an infrared spectrum of a polyhydroxy POSS from example 1;
FIG. 3 is a representation of the polyhydroxy POSS of example 129A Si nuclear magnetic spectrum;
FIG. 4 is a representation of the polyhydroxy POSS of example 11H nuclear magnetic spectrum.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
The first embodiment is as follows: the embodiment describes a preparation method of polyhydroxy silsesquioxane, which comprises the following steps:
weighing tetraethyl orthosilicate and tetramethylammonium hydroxide according to a molar ratio of 1: 1, dissolving the tetramethylammonium hydroxide in an ethanol water solution to obtain a tetramethylammonium hydroxide solution of 0.08-0.2 g/m L, and dropwise adding the tetraethyl orthosilicate, wherein the volume ratio of ethanol to water in the ethanol water solution is 8: 1;
step two: under the condition of stirring, placing the mixed solution obtained in the step one at 25 ℃ for reaction for 24 hours, then heating to 60 ℃ for reaction for 6 hours, and naturally cooling to room temperature after the reaction is finished;
step three: concentrating the product obtained in the second step to the volume of the remaining one third by rotary evaporation, cooling, crystallizing and filtering at the room temperature of 25 ℃, precipitating with acetone, and drying the precipitate at the temperature of 45 ℃ for 1h to obtain octa-poly (tetramethylammonium) POSS ammonium salt;
step four, weighing octa-tetramethyl ammonium POSS ammonium salt and distilled water prepared in the step three according to the mass-volume ratio of 1: 20, dissolving the octa-tetramethyl ammonium POSS ammonium salt in the distilled water, and dropwise adding 1 mol/L HCl standard solution until the pH value of the solution is 1;
step five: and (3) carrying out rotary evaporation and concentration on the solution to obtain a transparent viscous liquid, drying the transparent viscous liquid in a 45 ℃ oven for 6 hours to obtain a product which is white powder, and washing the product with distilled water to obtain the polyhydroxy silsesquioxane.
Example 1:
the preparation of octa-tetramethyl ammonium POSS ammonium salt is carried out according to the following steps:
firstly, 11.215g of tetramethylammonium hydroxide pentahydrate, 48m of L ethanol and 6m of L water are uniformly mixed, and 13.8m of L tetraethyl orthosilicate is dropwise added;
secondly, stirring the mixed system for 24 hours at 25 ℃, then quickly heating to 60 ℃ for reaction for 6 hours, and naturally cooling to room temperature after the reaction is finished;
and thirdly, concentrating the reaction product to one third of the volume of the solution through rotary evaporation, cooling, crystallizing and filtering, precipitating the product by using acetone, and drying the precipitate for 1h at the temperature of 45 ℃ to obtain octa-poly (tetramethylammonium) POSS ammonium salt, wherein the infrared spectrogram of the octa-poly (tetramethylammonium) POSS ammonium salt is shown in figure 1. The characteristic absorption peak of the octa-tetramethylammonium POSS ammonium salt can be obviously seen, 3500cm-1The nearby broad absorption peak is the hydroxyl vibration belonging to water; 2940cm-1Two peaks nearby belong to Me4N+C-H vibration of (2); the absorption peak of the MeNO group is 1650cm-1、1489cm-1、1400cm-1At least one of (1) and (b); the characteristic absorption peak of the Si-O-Si bond with the cage structure is 1035cm-1At the position of the air compressor, the air compressor is started,sharp peak shape and amorphous SiO2The broad peak shapes are clearly different.
Dissolving 5g of octatetramethylammonium POSS ammonium salt in 100m L distilled water, and dropwise adding a 1 mol/L HCl standard solution until the pH value of the solution is 1;
fifthly, the solution is concentrated by rotary evaporation to obtain transparent viscous liquid, the transparent viscous liquid is placed in a baking oven at 45 ℃ for drying for 6 hours, the product is changed into white powder, the product is washed by distilled water to obtain polyhydroxy POSS, the infrared spectrogram of the polyhydroxy POSS is shown in figure 2, and the polyhydroxy POSS is obtained29The nuclear magnetic spectrum of Si is shown in FIG. 3, which shows1The H nuclear magnetic spectrum is shown in FIG. 4.
From the infrared spectrogram, at 3500cm-1A strong hydroxyl characteristic absorption peak appears nearby, which proves that hydroxyl is generated in the reaction product, and the Si-O-Si bond with a cage structure is 1035cm-1A sharp characteristic absorption peak still appears, which indicates that the cage-type structure is not damaged.29In a Si nuclear magnetic spectrum, a peak appearing at a chemical shift of-100.544 is Si on the cage-type POSS, and because a functional group is not completely converted, sharp peaks exist at two positions of-90.754 and-110.122.1In the H nuclear magnetic spectrum, the peak at the chemical shift of 4.49 is determined to be the generated hydroxyl group H, considering that the hydroxyl group H in water is about 5, and the sample is dried. The peak at 2.75 is H in the tetramethylammonium ion still present in the reaction.
Claims (1)
1. A preparation method of polyhydroxy silsesquioxane is characterized in that: the method comprises the following steps:
weighing tetraethyl orthosilicate and tetramethylammonium hydroxide according to a molar ratio of 1: 1, dissolving the tetramethylammonium hydroxide in an ethanol water solution to obtain a tetramethylammonium hydroxide solution of 0.08-0.2 g/m L, and dropwise adding the tetraethyl orthosilicate, wherein the volume ratio of ethanol to water in the ethanol water solution is 8: 1;
step two: under the condition of stirring, placing the mixed solution obtained in the step one at 25 ℃ for reaction for 24 hours, then heating to 60 ℃ for reaction for 6 hours, and naturally cooling to room temperature after the reaction is finished;
step three: concentrating the product obtained in the second step to the volume of the remaining one third by rotary evaporation, cooling, crystallizing and filtering at the room temperature of 25 ℃, precipitating with acetone, and drying the precipitate at the temperature of 45 ℃ for 1h to obtain octa-poly (tetramethylammonium) POSS ammonium salt;
step four, weighing octa-tetramethyl ammonium POSS ammonium salt and distilled water prepared in the step three according to the mass-volume ratio of 1: 20, dissolving the octa-tetramethyl ammonium POSS ammonium salt in the distilled water, and dropwise adding 1 mol/L HCl standard solution until the pH value of the solution is 1;
step five: and (3) carrying out rotary evaporation and concentration on the solution to obtain a transparent viscous liquid, drying the transparent viscous liquid in a 45 ℃ oven for 6 hours to obtain a product which is white powder, and washing the product with distilled water to obtain the polyhydroxy silsesquioxane.
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| CN111423586A (en) * | 2020-05-12 | 2020-07-17 | 哈尔滨工业大学 | Synthesis method of polyhedral oligomeric silsesquioxane with silicon-hydrogen functional groups |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6660823B1 (en) * | 1998-03-03 | 2003-12-09 | The United States Of America As Represented By The Secretary Of The Air Force | Modifying POSS compounds |
| CN1513858A (en) * | 2003-08-20 | 2004-07-21 | 胡立江 | Preparation method of multihydroxy sesqui siloxane |
| CN101503420A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-epoxy cage type sesquialter siloxane and preparation thereof |
| CN101967230A (en) * | 2010-09-21 | 2011-02-09 | 苏州大学 | Cage silsesquioxane structure-based organic/inorganic microporous silicon and preparation method |
| CN101974225A (en) * | 2010-09-21 | 2011-02-16 | 苏州大学 | Microporous silicon/bismaleimide-triazine resin composite material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6660823B1 (en) * | 1998-03-03 | 2003-12-09 | The United States Of America As Represented By The Secretary Of The Air Force | Modifying POSS compounds |
| CN1513858A (en) * | 2003-08-20 | 2004-07-21 | 胡立江 | Preparation method of multihydroxy sesqui siloxane |
| CN101503420A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-epoxy cage type sesquialter siloxane and preparation thereof |
| CN101967230A (en) * | 2010-09-21 | 2011-02-09 | 苏州大学 | Cage silsesquioxane structure-based organic/inorganic microporous silicon and preparation method |
| CN101974225A (en) * | 2010-09-21 | 2011-02-16 | 苏州大学 | Microporous silicon/bismaleimide-triazine resin composite material and preparation method thereof |
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