CN102532187A - Method for preparing octaphenyl polyhedral oligomeric silsesquioxane - Google Patents
Method for preparing octaphenyl polyhedral oligomeric silsesquioxane Download PDFInfo
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- CN102532187A CN102532187A CN2011104194290A CN201110419429A CN102532187A CN 102532187 A CN102532187 A CN 102532187A CN 2011104194290 A CN2011104194290 A CN 2011104194290A CN 201110419429 A CN201110419429 A CN 201110419429A CN 102532187 A CN102532187 A CN 102532187A
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Abstract
The invention relates to a method for preparing octaphenyl polyhedral oligomeric silsesquioxane (OPS), belonging to the technical field of organic-inorganic hybrid materials. The method comprises the steps of: adding phenyl trichlorosilane and solvent in a reactor equipped with an ice water circulating device, stirring, controlling the temperature of the reaction system in a range of 0-5 DEG C, adding deionized water in the reactor, hydrolyzing the phenyl trichlorosilane for 1-3h at a temperature of 0-10 DEG C, stirring for 10-20min, obtaining organic phase and aqueous phase through liquid separation, adding catalyst in the organic phase, stirring for 18-20h, filtering and drying in vacuum and obtaining solid powder products. The method disclosed by the invention is high in yield, small in particle diameter of OPS and short in synthesis time, 50L of synthesis enlargement of the OPS can be realized, so that enough raw material condition is provided for anti-flaming engineering plastic research of the OPS.
Description
Technical field
The present invention relates to the preparation method of octaphenyl clathrasil sesquioxyalkane, belong to the hybrid inorganic-organic materials technical field.
Background technology
Cage type oligomer silasesquioxanes (polyhedral oligomeric silsesquioxanes; Be called for short POSS); Be a kind of novel hybrid inorganic-organic materials, it is good to have consistency when adding in the macromolecular material, is prone to disperse; Can when keeping the base material excellent machinability, improve thermal property, mechanical property and the flame retardant properties of material greatly.Extensive studies and application have been obtained at aspects such as biomedicine, aerospace, electronic apparatus, energy and materials.
Octaphenyl clathrasil sesquioxyalkane (octaphenyl polyhedral oligomeric silsesquioxanes is called for short OPS) is that a kind of organic group is the full reduced hexahedron body structure that gathers of phenyl.
Consuming time is the subject matter place of synthetic OPS, and successful solution problem consuming time will make the cost of synthetic OPS be minimized, and the product that obtains industrially scalable will become possibility.
Summary of the invention
The objective of the invention is in order to propose the preparation method of octaphenyl clathrasil sesquioxyalkane.
The objective of the invention is to realize through following technical scheme.
The preparation method of octaphenyl clathrasil sesquioxyalkane of the present invention, concrete steps are:
1) in the reactor drum that the ice water circulation device is housed, add phenyl-trichloro-silicane and solvent, stir, it is 0～5 ℃ that control makes the temperature of reaction system;
2) in the reactor drum of step 1), add deionized water, phenyl-trichloro-silicane generation hydrolysis; Hydrolysis temperature is 0～10 ℃, and behind hydrolysis 1～3h, restir 10～20min leaves standstill separatory; Obtain organic phase and water;
3) with step 2) add catalyzer in the organic phase that obtains, carry out polycondensation, control reaction temperature is 70～100 ℃, stirs 18～20h, vacuum filtration, drying obtain the solid powdery product then; Drying temperature is 80～100 ℃, and be 2～3h time of drying.
TM, tap funnel and reflux exchanger are housed in the device above-mentioned steps 1);
Above-mentioned steps 1) solvent is benzene, toluene or its mixture in; The mass ratio of phenyl-trichloro-silicane and solvent is 1: 4～9;
The mol ratio of the phenyl-trichloro-silicane that adds in deionized water that adds above-mentioned steps 2) and the step 1) is 3～10: 1;
Above-mentioned steps 3) catalyzer that adds in is a kind of or its mixture in Pottasium Hydroxide, sodium hydroxide, TMAH, tetraethyl ammonium hydroxide, TBAH, the benzyltrimethylammonium hydroxide; The mol ratio of the phenyl-trichloro-silicane that adds in catalyzer that adds and the step 1) is 0.02～0.05: 1.
Beneficial effect
Method productive rate of the present invention is high, the particle diameter of OPS is little, generated time short, and realizes synthetic amplification of 50L of OPS, for OPS provides enough material conditions in fire-resistant engineering plastics research.
Description of drawings
Fig. 1 is the scanning electron microscope figure of the octaphenyl clathrasil sesquioxyalkane of embodiment 1 preparation;
Fig. 2 is the scanning electron microscope figure of the octaphenyl clathrasil sesquioxyalkane of embodiment 2 preparations;
Fig. 3 is ground substance assistant laser desorption ionization flight time mass spectrum (MALDI-TOF-MS) figure of the octaphenyl clathrasil sesquioxyalkane of embodiment 2 preparations;
Fig. 4 is the granularity graph of the octaphenyl clathrasil sesquioxyalkane of embodiment 2 preparations.
Embodiment
Embodiment 1
The preparation method of octaphenyl clathrasil sesquioxyalkane, concrete steps are:
1) in the reactor drum that TM, tap funnel, reflux exchanger and ice water circulation device are housed, add 529g phenyl-trichloro-silicane and 2500mL benzene, stir, it is 0～5 ℃ that control makes the temperature of reaction system;
2) in the reactor drum of step 1), add deionized water, phenyl-trichloro-silicane generation hydrolysis; Hydrolysis temperature is 0～5 ℃, behind the hydrolysis 2.5h, continues to stir 10min and makes system even, leaves standstill separatory; Obtain organic phase and water;
3) with adding 6.2g catalyzer TMAH in the organic phase, polycondensation is carried out in heating then, and Heating temperature is 80 ℃, stirs 20h, and vacuum filtration, drying obtain octaphenyl clathrasil sesquioxyalkane then; Drying temperature is 100 ℃, and be 3h time of drying.The ground substance assistant laser desorption ionization flight time mass spectrum (MALDI-TOF-MS) of the octaphenyl clathrasil sesquioxyalkane that obtains is as shown in Figure 1; The instrument that ground substance assistant laser desorption ionization flight time mass spectrum (MALDI-TOF-MS) test is adopted is: Bruker BIFLEX III type MALDI-TOF mass spectrograph; Nitrogen laser; Optical maser wavelength is 337nm, adopts ion to postpone the mode of operation of drawing and reflecting, and positive ion detects.Adopt the alpha-cyano styracin as matrix, for impelling the formation of molion, in matrix, add an amount of sodium salt, methylene dichloride is as solvent; The granularity graph of the octaphenyl clathrasil sesquioxyalkane that the new handkerchief Tyke dry method laser particle analyzer HELOS/RODOS test of Germany obtains is as shown in Figure 2, and test specification is 0.1～3500 micron, and data processing adopts Fraunhofer or Mie theory.
Embodiment 2
The preparation method of octaphenyl clathrasil sesquioxyalkane, concrete steps are:
1) in the reactor drum that TM, tap funnel, reflux exchanger and ice water circulation device are housed, add 17.6kg phenyl-trichloro-silicane and 20L benzene, stir, it is 0～5 ℃ that control makes the temperature of reaction system;
2) in the reactor drum of step 1), add deionized water, phenyl-trichloro-silicane generation hydrolysis; Hydrolysis temperature is 0～5 ℃, behind the hydrolysis 2.5h, continues to stir 20min, leaves standstill separatory; Obtain organic phase and water;
3) with adding 49.6g catalyzer TMAH in the organic phase, polycondensation is carried out in heating then, and Heating temperature is 80 ℃, stirs 20h, and vacuum filtration, drying obtain octaphenyl clathrasil sesquioxyalkane 2.5kg then; Drying temperature is 100 ℃, and be 2.5h time of drying.The ground substance assistant laser desorption ionization flight time mass spectrum (MALDI-TOF-MS) of the octaphenyl clathrasil sesquioxyalkane that obtains is as shown in Figure 3; The instrument that ground substance assistant laser desorption ionization flight time mass spectrum (MALDI-TOF-MS) test is adopted is: BrukerBIFLEX III type MALDI-TOF mass spectrograph; Nitrogen laser; Optical maser wavelength is 337nm, adopts ion to postpone the mode of operation of drawing and reflecting, and positive ion detects.Adopt the alpha-cyano styracin as matrix, for impelling the formation of molion, in matrix, add an amount of sodium salt, methylene dichloride is as solvent; The granularity graph of the octaphenyl clathrasil sesquioxyalkane that the new handkerchief Tyke dry method laser particle analyzer HELOS/RODOS test of Germany obtains is as shown in Figure 4, and test specification is 0.1～3500 micron, and data processing adopts Fraunhofer or Mie theory.
Claims (8)
1. the preparation method of octaphenyl clathrasil sesquioxyalkane is characterized in that concrete steps are:
1) in the reactor drum that the ice water circulation device is housed, add phenyl-trichloro-silicane and solvent, stir, it is 0～5 ℃ that control makes the temperature of reaction system;
2) in the reactor drum of step 1), add deionized water, phenyl-trichloro-silicane generation hydrolysis; Hydrolysis temperature is 0～10 ℃, and behind hydrolysis 1～3h, restir 10～20min leaves standstill separatory; Obtain organic phase and water;
3) with step 2) add catalyzer in the organic phase that obtains, carry out polycondensation, control reaction temperature is 70～100 ℃, stirs 18～20h, vacuum filtration, drying obtain the solid powdery product then.
2. the preparation method of octaphenyl clathrasil sesquioxyalkane according to claim 1 is characterized in that: drying temperature is 80～100 ℃ in the step 3), and be 2～3h time of drying.
3. the preparation method of octaphenyl clathrasil sesquioxyalkane according to claim 1 is characterized in that: TM, tap funnel and reflux exchanger are housed in the device in the step 1).
4. the preparation method of octaphenyl clathrasil sesquioxyalkane according to claim 1 is characterized in that: solvent is benzene, toluene or its mixture in the step 1).
5. the preparation method of octaphenyl clathrasil sesquioxyalkane according to claim 1 is characterized in that: the mass ratio of phenyl-trichloro-silicane and solvent is 1: 4～9 in the step 1).
6. the preparation method of octaphenyl clathrasil sesquioxyalkane according to claim 1 is characterized in that: step 2) in the mol ratio of the phenyl-trichloro-silicane that adds in the deionized water that adds and the step 1) be 3～10: 1.
7. the preparation method of octaphenyl clathrasil sesquioxyalkane according to claim 1 is characterized in that: the catalyzer that adds in the step 3) is a kind of or its mixture in Pottasium Hydroxide, sodium hydroxide, TMAH, tetraethyl ammonium hydroxide, TBAH, the benzyltrimethylammonium hydroxide.
8. the preparation method of octaphenyl clathrasil sesquioxyalkane according to claim 1 is characterized in that: the mol ratio of the phenyl-trichloro-silicane that adds in catalyzer that adds in the step 3) and the step 1) is 0.02～0.05: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111233A (en) * | 2015-08-28 | 2015-12-02 | 合肥会通新材料有限公司 | Preparation method of octaphenyl silsesquioxane |
| CN107961815A (en) * | 2017-12-12 | 2018-04-27 | 新沂市中诺新材料科技有限公司 | A kind of modified porous catalyst of preparing methane by synthetic gas |
| CN109880100A (en) * | 2019-03-28 | 2019-06-14 | 北京理工大学 | A kind of preparation method of octaphenyl silsesquioxane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB892985A (en) * | 1959-01-21 | 1962-04-04 | Gen Electric | Improvements relating to organopolysiloxanes |
| US3162614A (en) * | 1962-02-23 | 1964-12-22 | Gen Electric | Process for making benzene-soluble phenyl silsesquioxane |
| CN1432590A (en) * | 2002-01-10 | 2003-07-30 | 中国石油化工股份有限公司 | Prepn of phenyl sesquisiloxane prepolymer |
-
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- 2011-12-15 CN CN2011104194290A patent/CN102532187A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB892985A (en) * | 1959-01-21 | 1962-04-04 | Gen Electric | Improvements relating to organopolysiloxanes |
| US3162614A (en) * | 1962-02-23 | 1964-12-22 | Gen Electric | Process for making benzene-soluble phenyl silsesquioxane |
| CN1432590A (en) * | 2002-01-10 | 2003-07-30 | 中国石油化工股份有限公司 | Prepn of phenyl sesquisiloxane prepolymer |
Non-Patent Citations (4)
| Title |
|---|
| JUN-CHAO HUANG等,: "Polyimide/POSS nanocomposites: interfacial interaction, thermal properties and mechanical properties", 《POLYMER》, vol. 44, no. 16, 31 July 2003 (2003-07-31) * |
| MD. ASADUL HOQUE等,: "High performance holographic gratings formed with novel photopolymer films containing hyper-branched silsesquioxane", 《REACTIVE AND FUNCTIONAL POLYMERS》, vol. 67, no. 11, 24 July 2007 (2007-07-24) * |
| 何辉等,: "笼型倍半硅氧烷(POSS)的合成及应用进展", 《高分子材料科学与工程》, vol. 24, no. 4, 30 April 2008 (2008-04-30), pages 5 - 9 * |
| 杜建科等,: "笼形八苯基硅倍半氧烷的合成及表征", 《精细化工》, vol. 22, no. 6, 30 June 2005 (2005-06-30) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111233A (en) * | 2015-08-28 | 2015-12-02 | 合肥会通新材料有限公司 | Preparation method of octaphenyl silsesquioxane |
| CN107961815A (en) * | 2017-12-12 | 2018-04-27 | 新沂市中诺新材料科技有限公司 | A kind of modified porous catalyst of preparing methane by synthetic gas |
| CN109880100A (en) * | 2019-03-28 | 2019-06-14 | 北京理工大学 | A kind of preparation method of octaphenyl silsesquioxane |
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Application publication date: 20120704 |