CN1045299C - Process for recovering and preparing trialkyl chlorosilane - Google Patents
Process for recovering and preparing trialkyl chlorosilane Download PDFInfo
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- CN1045299C CN1045299C CN95112224A CN95112224A CN1045299C CN 1045299 C CN1045299 C CN 1045299C CN 95112224 A CN95112224 A CN 95112224A CN 95112224 A CN95112224 A CN 95112224A CN 1045299 C CN1045299 C CN 1045299C
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- Prior art keywords
- pcl
- catalyzer
- compound
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- present
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The present invention relates to a process for recovering and preparing trialkyl chlorosilane whose reaction formula is disclosed in the specification, wherein R is a straight chain of C1 to C4 or branched alkyl. Metal halide is used as catalysts, and PCl3 or PCl5 is used as chlorinating agents; the metal halide and the PCl3 or the PCl5 react with a compound (i), which generates a compound (ii). The present invention has the characteristics that by-products are common chemical raw materials of POCl or POCl3 which are easily processed; the catalysts can be circularly used, and the activity of the catalysts is not changed; the yield is high (more than 90%), and the highest yield can reach more than 95%. The present invention is a method which is suitable for industrial production.
Description
The invention belongs to the preparation technology of organic compound.Particularly relate to from the reaction mother liquor that contains hexamethyldisilane, reclaim the technology of trimethylchlorosilane.
Trimethylchlorosilane is as the protection reagent of some reactive group in the organic synthesis; in reaction at the end; be hydrolyzed into the form of hexamethyldisilane; be present in the reaction solution in a large number; and trimethylchlorosilane is owing to be subjected to the restriction of synthetic method; annual production is limited, causes valuable product, source of goods anxiety.Therefore, the hexamethyldisilane in the reaction solution is recycled, both can have been reached greatly and reduce production costs, can alleviate the situation of raw material anxiety again.
The recovery method for transformation of present existing trimethylchlorosilane has: (1) sulfur oxychloride chlorination process (U.S. Pat 2,500,761), the shortcoming of this technology is that reaction generates a large amount of sulfurous gas, " three wastes " are seriously polluted, and the big yield of sulfur oxychloride consumption is low, and difficulty is applicable to suitability for industrialized production.(2) vitriol oil and ammonium chloride method (J.Am.Chem.Soc.70,433-4,1948).The shortcoming of this technology is to need the excessive vitriol oil, with hydrogenchloride and the hexamethyldisiloxane reaction that reaction generates, equipment requirements condition height, yield low (85%).(3) aluminum chloride chlorination process (" report of Soviet Union academy of sciences " Doklady Akad.NaukS.S.S.R 84,959-61,1952), this process byproducts is AlOCl, is difficult to handle, and the equipment requirements height, yield is low, and is the highest by 81%.(4) logical hydrogen chloride.A. low temperature (17～25 ℃) (JP 8,092,392)
Perhaps this process energy consumption of B. high pressure (Ger.0ffen 3,013,920) is big, the equipment requirements height.(5) dimethyldichlorosilane(DMCS) conversion method (JP 78,147,030), this technological reaction generates hydrogenchloride and silicone oil, and " three wastes " are big and be difficult to handle; Yield is influenced greatly by silicon oil viscosity, only between 70～90%, and industrial this technology of general employing now.
The objective of the invention is to propose a kind of recovery preparation technology of trialkylchlorosilane, particularly from the reaction mother liquor that contains hexamethyldisiloxane, reclaim the technology of trimethylchlorosilane, have the yield height, do not have " three wastes ", characteristics such as the processing requirement condition is low.
The present invention uses PCl
3Or PCl
5Make chlorizating agent, make catalyzer, handle with metal halide, reaction formula promptly:
Catalyzer
(i) (ii)
Wherein: the straight or branched alkyl of R=C1-C4.
Processing condition are:
PCl
3Or PCl
5: compound (i)=1: 0.5～2 (mol ratios)
Compound (i): catalyzer=1: 0.1%～5% (weight ratio)
The used catalyzer of the present invention can be AlCl
3, FeCl
3, ZnCl
2, TiCl
4, preferably select AlCl for use
3Or FeCl
3
Reaction can be carried out under normal temperature and pressure, can adopt the rectifying mode after the reaction, collects product.
The invention will be further described below in conjunction with some embodiment, is not confined among these embodiment certainly.
Embodiment 1
PCl
3: hexamethyldisiloxane=1: 0.6 (mol ratio)
Hexamethyldisiloxane: catalyzer=1: 1% (weight ratio)
PCl
3, catalyzer adds in the retort, stir and drip hexamethyldisiloxane down, slowly be warming up to backflow then, 70～75 ℃ of reflux temperatures, 2 hours, the cut of 57～59 ℃/0.1MPa was collected in rectifying, promptly get trimethylchlorosilane, content 98% (gas phase bag spectrometry), yield 95%, residue are solid POCl.
Embodiment 2
PCl
3: hexamethyldisiloxane=1: 0.9 (mol ratio)
Hexamethyldisiloxane: catalyzer=1: 0.2% (weight ratio)
PCl
3, catalyzer adds in the retort, stirs down that logical chlorine drips hexamethyldisiloxane to saturated, slowly is warming up to backflow then, 70～75 ℃ of reflux temperatures, 2 hours, the cut of 57～59 ℃/0.1MPa was collected in rectifying, promptly get trimethylchlorosilane, content 98% (vapor-phase chromatography), yield 95%; Collect the cut of 106～108 ℃/0.1MPa, obtain content and be 99% phosphorus oxychloride, yield can reach more than 95%, residue can be used as following batch repeated use of catalyst supply and activity constant.
Embodiment 3
PCl
3: hexamethyldisiloxane=1: 1.2 (mol ratio)
Hexamethyldisiloxane: catalyzer=1: 2% (weight ratio)
Other presses embodiment 2 operations, yield 93%.
Embodiment 4
PCl
5: hexamethyldisiloxane=1: 1.5 (mol ratio)
Hexamethyldisiloxane: catalyzer=1: 4% (weight ratio)
PCl
5, catalyzer adds in the retort, stirs to add hexamethyldisiloxane down, temperature slowly is increased to backflow, 70～75 ℃ of reflux temperatures, 2 hours, the cut of 57～59 ℃/0.1MPa was collected in rectifying, is the trimethylchlorosilane of content 98%, yield can reach 90%; Collect the cut of 106～108 ℃/0.1MPa, obtain the phosphorus oxychloride of content 99%, yield can reach 95%, and residue can be used as catalyzer, for following batch of repeated use.
Embodiment 5
PCl
5: hexamethyldisiloxane 1: 1.1 (mol ratio)
Hexamethyldisiloxane: catalyzer=1: 5% (weight ratio)
Other operation reaches 97% by embodiment 4 yields.
Embodiment 6
PCl
5: (Et
3Si)
2O=1: 1.2 (mol ratios)
(Et
3Si)
2O: catalyzer=1: 0.5% (weight ratio)
PCl
5, (Et
3Si)
2O adds in the retort, stirs to add (Et down
3Si)
2O, temperature slowly is increased to backflow, and reflux temperature is 125～130 ℃, and 2 hours, the cut that 106～108 ℃/0.1MPa is collected in rectifying was POCl
3, the cut of 145～147 ℃/0.1MPa is a chlorotriethyl silane, yield is 92%.
Technology of the present invention is suitable for equally and reclaims corresponding trialkylchlorosilane from other six alkyl, two silicon ether.
Advantage of the present invention:
The present invention is low for equipment requirements, and energy consumption is low, and accessory substance is easy to handle POCl or POCl3, reaction yield is high, can reach more than 90%, and high energy reaches more than 95%, and catalyst can be reused, and is active constant, and production cost is low, more is applicable to suitability for industrialized production.
Claims (7)
1, a kind of recovery preparation method of trialkylchlorosilane is characterized in that: use PCl
3Or PCl
5Make chlorizating agent, make catalyzer, undertaken by following reaction formula with metal halide:
Catalyzer
(i) (ii)
Wherein: the straight or branched alkyl of R=C1-C4.
2, method according to claim 1, when it is characterized in that reacting:
PCl
3(or PCl
5): compound (i)=1: 0.5～2 (mol ratios)
Compound (i): catalyzer=1: 0.1%～5% (weight ratio)
3, method according to claim 1 and 2 is characterized in that used catalyzer is AlCl
3, FeCl
3, ZnCl
2, TiCl
4
4, method according to claim 3 is characterised in that catalyst system therefor is AlCl
3Or FeCl
3
5, method according to claim 1 is characterised in that wherein R is-CH
3
6, method according to claim 1 is characterised in that to react under the normal temperature and pressure and carries out, and R is-CH in the compound (i)
3, the reaction reflux temperature is 70～75 ℃.
7, method according to claim 1 is characterised in that reacted product carries out rectifying, and R is-CH
3, collect the cut under 57～59 ℃/0.1MPa, be trimethylchlorosilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112224A CN1045299C (en) | 1995-11-16 | 1995-11-16 | Process for recovering and preparing trialkyl chlorosilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112224A CN1045299C (en) | 1995-11-16 | 1995-11-16 | Process for recovering and preparing trialkyl chlorosilane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1188113A CN1188113A (en) | 1998-07-22 |
| CN1045299C true CN1045299C (en) | 1999-09-29 |
Family
ID=5079415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95112224A Expired - Fee Related CN1045299C (en) | 1995-11-16 | 1995-11-16 | Process for recovering and preparing trialkyl chlorosilane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1045299C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1733435A1 (en) * | 1989-08-25 | 1992-05-15 | Государственный научно-исследовательский институт химии и технологии элементоорганических соединений | Method of methylchlorosilanes synthesis |
| SU1766924A1 (en) * | 1990-01-30 | 1992-10-07 | Государственный научно-исследовательский институт химии и технологии элементоорганических соединений | Method of trimethylchlorosilane synthesis |
-
1995
- 1995-11-16 CN CN95112224A patent/CN1045299C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1733435A1 (en) * | 1989-08-25 | 1992-05-15 | Государственный научно-исследовательский институт химии и технологии элементоорганических соединений | Method of methylchlorosilanes synthesis |
| SU1766924A1 (en) * | 1990-01-30 | 1992-10-07 | Государственный научно-исследовательский институт химии и технологии элементоорганических соединений | Method of trimethylchlorosilane synthesis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1188113A (en) | 1998-07-22 |
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