CN103524744B - A kind of preparation method of ultra-low-oxygen narrow molecular weight distribution dimethylsilane - Google Patents
A kind of preparation method of ultra-low-oxygen narrow molecular weight distribution dimethylsilane Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of ultra-low-oxygen narrow molecular weight distribution dimethylsilane, adopt Wurtz synthesis, now required for reaction solvent is carried out drying, control dimethyldichlorosilane(DMCS) drop rate, the oxygen level of the polydimethylsiloxane produced is made to drop to 0.1%, regulate temperature of reaction, adopt compounded organic solvent dissolution precipitation again, improve productive rate, reduce the oxygen level of product polydimethylsiloxane, the follow-up obtained silicon carbide fiber performance of polydimethylsiloxane is high simultaneously, meets the requirement of various field to polydimethylsiloxane.
Description
Technical field
The present invention relates to a kind of preparation method of polydimethylsiloxane, especially a kind of preparation method of ultra-low-oxygen narrow molecular weight distribution dimethylsilane.
Background technology
Polydimethylsiloxane is the macromolecular material that a kind of main chain is made up of Siliciumatom.Due to Si low electronegativity and there is 3d unoccupied orbital, therefore, electronics can along the extensive delocalization of Si-Si main chain, it is also containing abundant Si-H key simultaneously, thus makes polydimethylsiloxane all have extraordinary application prospect in the preparation of photoconduction, photodiode, nonlinear optical material and SiC ceramic and functional materials.Polydimethylsiloxane is as a kind of new functional macromolecule material, no matter studying it is have important meaning in theory or in practice, polydimethylsiloxane chemistry has become a focus in field of organic silicon, very active to its research.Along with deepening continuously of research, polydimethylsiloxane is expected to obtain in a lot of fields applying more widely.
The synthetic method of current polydimethylsiloxane has Wurtz method, supersonic method etc.The wherein method of Wurtz coupling method synthesis polysilane to be a kind of be also the earliest the most frequently used synthesis polysilane, the polysilane stable performance synthesized, Wurtz2 has the advantages such as method is simple, workable simultaneously; But because the method reaction is violent, release a large amount of heat, wayward, therefore synthesize small, general each synthesis output only has 10g-15g, and yield only has about 50%, is not suitable for suitability for industrialized production.
Summary of the invention
The object of this invention is to provide a kind of preparation method of ultra-low-oxygen narrow molecular weight distribution dimethylsilane, adopt and now required for reaction solvent is carried out drying, control dimethyldichlorosilane(DMCS) drop rate, regulate temperature of reaction, adopt compounded organic solvent dissolution precipitation again, improve productive rate, reduce the oxygen level of product polydimethylsiloxane, the follow-up obtained silicon carbide fiber performance of polydimethylsiloxane is high simultaneously, meets the requirement of various field to polydimethylsiloxane.
A preparation method for ultra-low-oxygen narrow molecular weight distribution dimethylsilane, concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, make its water content be down to below 5ppm; Add the solvent xylene 900-1100kg after dewatering in the reactor, put into sodium Metal 99.5 270-330kg again, be first heated to 105 DEG C and keep 5 minutes, reheat 110 DEG C and keep 10 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; Refining dimethyldichlorosilane(DMCS) 810-990kg is added in protection of inert gas downhill reaction device, first add 90-110min by the speed of 2kg/min, 36-44min is added again by the speed of 10kg/min, finally add 54-66min by the speed of 5kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add ethanol 90-110kg and water 90-110kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally by 18-22kg tetrahydrofuran (THF), 18-22kg butanols, 18-22kg phenylcarbinol and 36-44kg dissolve with ethanol precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
Wherein reactor adopts enamel material, be about to glass containing high-purity silicon dioxide through high temperature sintering the matrix material that formed in the internal surface of Steel Vessel of adherence securely; Reactor inside diameter is 2180mm, be highly 1940mm, the stirring rake of reactor is frame type stirring, and adopt variable frequency control and the speed of adjustment stirring rake and direction, frame type agitating blade internal diameter becomes large, and height reduction increases reaction area, makes stirring more even, react more abundant thorough, take away the heat of generation in time.
Wherein refining dimethyldichlorosilane(DMCS) refers to and carries out secondary rectifying in advance to dimethyldichlorosilane(DMCS), and rectifying adopts separation column, improves the purity of dimethyldichlorosilane(DMCS) and reduces oxygen level.
Wherein the specific implementation of external multistage cooling recirculation system cooling is three grades of coolings, namely first in the recycle system, passes into thermal oil, by the heat fast transfer of reaction mass, the temperature in reactor is significantly reduced, complete one-level cooling; While thermal oil is to reaction mass cooling, adopt that recirculated water is reverse cools thermal oil, thermal oil can be made to recycle, play maximum utility, complete secondary cooling; Pass into recirculated water in last third stage water cooler, again reduce through the oil cooled reaction mass of heat conduction.Through three grades of coolings, control the heat produced in reaction, ensure that industrial safety is carried out smoothly; Wherein thermal oil is the middle river board thermal oil CD-350 that Jiangyin Zhong Jiang Industrial Co., Ltd. produces.
Advantage of the present invention: adopt and now required for reaction solvent is carried out drying, in advance secondary rectifying is carried out to dimethyldichlorosilane(DMCS) and improve its purity, make the oxygen level of the polydimethylsiloxane produced drop to 0.1%; Regulate temperature of reaction, control dimethyldichlorosilane(DMCS) drop rate, make the follow-up obtained silicon carbide fiber performance of polydimethylsiloxane produced high, then adopt compounded organic solvent dissolution precipitation, improve productive rate, meet the requirement of various field to polydimethylsiloxane simultaneously.
embodiment:
Embodiment 1:
A preparation method for ultra-low-oxygen narrow molecular weight distribution dimethylsilane, concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, make its water content be down to below 5ppm; Add the solvent xylene 900kg after dewatering in the reactor, then put into sodium Metal 99.5 270kg, be first heated to 105 DEG C and keep 5 minutes, reheat 110 DEG C and keep 10 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; Refining dimethyldichlorosilane(DMCS) 810kg is added in protection of inert gas downhill reaction device, first add 90min by the speed of 2kg/min, 36min is added again by the speed of 10kg/min, finally add 54min by the speed of 5kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add ethanol 90kg and water 90kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally by 18kg tetrahydrofuran (THF), 18kg butanols, 18kg phenylcarbinol and 36kg dissolve with ethanol precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
Wherein reactor adopts enamel material, be about to glass containing high-purity silicon dioxide through high temperature sintering the matrix material that formed in the internal surface of Steel Vessel of adherence securely; Reactor inside diameter is 2180mm, is highly 1940mm, and the stirring rake of reactor is frame type stirring, and adopts variable frequency control and the speed of adjustment stirring rake and direction.
Wherein refining dimethyldichlorosilane(DMCS) refers to and carries out secondary rectifying in advance to dimethyldichlorosilane(DMCS), and rectifying adopts separation column, improves the purity of dimethyldichlorosilane(DMCS) and reduces oxygen level.
Wherein the specific implementation of external multistage cooling recirculation system cooling is three grades of coolings, namely first in the recycle system, passes into thermal oil, by the heat fast transfer of reaction mass, the temperature in reactor is significantly reduced, complete one-level cooling; While thermal oil is to reaction mass cooling, adopt that recirculated water is reverse cools thermal oil, thermal oil can be made to recycle, play maximum utility, complete secondary cooling; Pass into recirculated water in last third stage water cooler, again reduce through the oil cooled reaction mass of heat conduction.Through three grades of coolings, control the heat produced in reaction, ensure that industrial safety is carried out smoothly; Wherein thermal oil is the middle river board thermal oil CD-350 that Jiangyin Zhong Jiang Industrial Co., Ltd. produces.
Embodiment 2:
A preparation method for ultra-low-oxygen narrow molecular weight distribution dimethylsilane, concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, make its water content be down to below 5ppm; Add the solvent xylene 1000kg after dewatering in the reactor, then put into sodium Metal 99.5 300kg, be first heated to 105 DEG C and keep 5 minutes, reheat 110 DEG C and keep 10 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; Refining dimethyldichlorosilane(DMCS) 900kg is added in protection of inert gas downhill reaction device, first add 100min by the speed of 2kg/min, 40min is added again by the speed of 10kg/min, finally add 60min by the speed of 5kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add ethanol 100kg and water 100kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally by 20kg tetrahydrofuran (THF), 20kg butanols, 20kg phenylcarbinol and 40kg dissolve with ethanol precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
All the other are with embodiment 1.
Embodiment 3:
A preparation method for ultra-low-oxygen narrow molecular weight distribution dimethylsilane, concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, make its water content be down to below 5ppm; Add the solvent xylene 1100kg after dewatering in the reactor, then put into sodium Metal 99.5 330kg, be first heated to 105 DEG C and keep 5 minutes, reheat 110 DEG C and keep 10 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; Refining dimethyldichlorosilane(DMCS) 990kg is added in protection of inert gas downhill reaction device, first add 110min by the speed of 2kg/min, 44min is added again by the speed of 10kg/min, finally add 66min by the speed of 5kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add ethanol 110kg and water 110kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally by 22kg tetrahydrofuran (THF), 22kg butanols, 22kg phenylcarbinol and 44kg dissolve with ethanol precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
All the other are with embodiment 1.
Embodiment 4:
A preparation method for ultra-low-oxygen narrow molecular weight distribution dimethylsilane, concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, make its water content be down to below 5ppm; Add the solvent xylene 950kg after dewatering in the reactor, then put into sodium Metal 99.5 280kg, be heated to 110 DEG C and keep 15 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; Refining dimethyldichlorosilane(DMCS) 810kg is added in protection of inert gas downhill reaction device, first add 90min by the speed of 2kg/min, 36min is added again by the speed of 10kg/min, finally add 54min by the speed of 5kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add alcohol 95 kg and water 95kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally by 19g tetrahydrofuran (THF), 19kg butanols, 19kg phenylcarbinol and 38kg dissolve with ethanol precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
All the other are with embodiment 1.
Embodiment 5:
A preparation method for ultra-low-oxygen narrow molecular weight distribution dimethylsilane, concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, make its water content be down to below 5ppm; Add the solvent xylene 1050kg after dewatering in the reactor, then put into sodium Metal 99.5 320kg, be first heated to 105 DEG C and keep 5 minutes, reheat 110 DEG C and keep 10 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; In protection of inert gas downhill reaction device, add refining dimethyldichlorosilane(DMCS) 900kg, add 90min by the speed of 10kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add ethanol 105kg and water 105kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally by 21kg tetrahydrofuran (THF), 21kg butanols, 21kg phenylcarbinol and 42kg dissolve with ethanol precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
All the other are with embodiment 1.
Embodiment 6:
A preparation method for ultra-low-oxygen narrow molecular weight distribution dimethylsilane, concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, make its water content be down to below 5ppm; Add the solvent xylene 1000kg after dewatering in the reactor, then put into sodium Metal 99.5 300kg, be first heated to 105 DEG C and keep 5 minutes, reheat 110 DEG C and keep 10 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; Refining dimethyldichlorosilane(DMCS) 900kg is added in protection of inert gas downhill reaction device, first add 100min by the speed of 2kg/min, 40min is added again by the speed of 10kg/min, finally add 60min by the speed of 5kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add ethanol 100kg and water 100kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally use 50kg tetrahydrofuran (THF) and 50kg butanols dissolution precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
All the other are with embodiment 1.
The oxygen level of the polydimethylsiloxane that each embodiment obtains, productive rate and follow-up obtained silicon carbide fiber performance are as shown in the table:
As can be seen from upper table data, the oxygen level, productive rate and the follow-up obtained silicon carbide fiber performance that adopt the embodiment 1-3 of present invention process to obtain obviously are better than other embodiment 4-5, wherein with embodiment 2 best results, the oxygen level of the embodiment 4 regulating temperature of reaction and the embodiment 5 not controlling dimethyldichlorosilane(DMCS) drop rate and follow-up obtained silicon carbide fiber performance are obviously not as good as oxygen level and the follow-up obtained silicon carbide fiber performance of embodiment 1-3, do not adopt the productive rate of productive rate not as good as embodiment 1-3 of the embodiment 6 of compounded organic solvent dissolution precipitation, visible excellent results of the present invention is that required for reaction solvent is being carried out drying, in advance secondary rectifying is carried out to dimethyldichlorosilane(DMCS) and improve its purity, regulate temperature of reaction, control dimethyldichlorosilane(DMCS) drop rate, adopt the techniques such as compounded organic solvent dissolution precipitation to act on down to complete simultaneously, meet the requirement of various field to polydimethylsiloxane.
Claims (2)
1. a preparation method for ultra-low-oxygen narrow molecular weight distribution dimethylsilane, is characterized in that: concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, makes its water content be down to below 5ppm; Add the solvent xylene 900-1100kg after dewatering in the reactor, put into sodium Metal 99.5 270-330kg again, be first heated to 105 DEG C and keep 5 minutes, reheat 110 DEG C and keep 10 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; Refining dimethyldichlorosilane(DMCS) 810-990kg is added in protection of inert gas downhill reaction device, first add 90-110min by the speed of 2kg/min, 36-44min is added again by the speed of 10kg/min, finally add 54-66min by the speed of 5kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add ethanol 90-110kg and water 90-110kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally by 18-22kg tetrahydrofuran (THF), 18-22kg butanols, 18-22kg phenylcarbinol and 36-44kg dissolve with ethanol precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
2. the preparation method of a kind of ultra-low-oxygen narrow molecular weight distribution dimethylsilane as claimed in claim 1, is characterized in that: concrete steps are as follows: solvent xylene is first dewatered with Calcium Chloride Powder Anhydrous, makes its water content be down to below 5ppm; Add the solvent xylene 1000kg after dewatering in the reactor, then put into sodium Metal 99.5 300kg, be first heated to 105 DEG C and keep 5 minutes, reheat 110 DEG C and keep 10 minutes, after sodium fusion, start high-speed stirring oar stir, reflux and within 24 hours, make solvent fully dry; Refining dimethyldichlorosilane(DMCS) 900kg is added in protection of inert gas downhill reaction device, first add 100min by the speed of 2kg/min, 40min is added again by the speed of 10kg/min, finally add 60min by the speed of 5kg/min, and open external multistage cooling recirculation system simultaneously, react 24 hours, be cooled to room temperature; Add ethanol 100kg and water 100kg stopped reaction, stratification, transfers to organic layer in reactor, washes with water to neutrality, centrifugal removing insolubles; Finally by 20kg tetrahydrofuran (THF), 20kg butanols, 20kg phenylcarbinol and 40kg dissolve with ethanol precipitation, filter, steaming desolventizes, and obtains product polydimethylsiloxane.
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