CN100506827C - Diphenylacetylene silane novle synthesis method - Google Patents
Diphenylacetylene silane novle synthesis method Download PDFInfo
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- CN100506827C CN100506827C CNB2005101101335A CN200510110133A CN100506827C CN 100506827 C CN100506827 C CN 100506827C CN B2005101101335 A CNB2005101101335 A CN B2005101101335A CN 200510110133 A CN200510110133 A CN 200510110133A CN 100506827 C CN100506827 C CN 100506827C
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- silane
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- acetenyl
- phenylacetylene
- lithium
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Abstract
The present invention is new type of diphenyl acetenyl silane synthesizing process. By using phenyl acetylene, organic lithium reagent and methyl dichlorosilane as material and anhydrous tetrahydrofuran as solvent, the present invention synthesizes methyl diphenyl acetenyl silane monomer through two-step reaction. Phenyl acetylene and butyl lithium first react to produce phenyl acetenyl lithium, and phenyl acetenyl lithium and hydrogen-containing dichlorosilane then react to produce phenyl acetenyl silane. The present invention has simple technological process, simple and feasible operation, short reaction time, controllable reaction condition, high product yield and purity and other advantages, and is suitable for industrial production. The prepared diphenyl acetenyl silane may be used in high performance composite material, ceramic precursor, heat resistant coating, etc.
Description
Technical field
The present invention relates to a kind of novel method for synthesizing of organosilane monomer, particularly a kind of novel method for synthesizing of tolane base silane.
Background technology
Organosilicon polymer is the speciality polymer material, has unique physical and chemical performance, has extremely widely at aerospace field and uses.In recent years, in molecular chain, contain si-h bond simultaneously and carbon carbon triple-linked organosilicon polymer constantly is in the news.These polymkeric substance produce crosslinking curing by the hydrosilylation addition reaction between carbon carbon triple bond and the si-h bond, thereby obtain having the material of good heat-resisting and ablation resistance.
Chinese patent ZL02151140.3 " improving one's methods of preparation phenylacetylene base silane " relates to employing Grignard reagent method and has synthesized a kind of novel silane containing hydrogen that contains two aryl ethane bases, this patent is a raw material with phenylacetylene and hydrogeneous dichlorosilane, anhydrous tetrahydro furan is a solvent, makes by Grignard reagent is synthetic.The mol ratio of phenylacetylene and hydrogeneous dichlorosilane is 2～2.2:1, and temperature of reaction is 60～70 ℃, and the reaction times is 4～8h.Technological line is as follows:
Adopt the Grignard reagent method to have following shortcomings:
(1), cause the entire reaction productive rate to descend because the utilization ratio of the first step reacting metal magnesium is not high.
(2) adopt toxic substance toluene to carry out extracting and separating.
(3) this method reaction process is long, and technology is loaded down with trivial details.
(4) productive rate is low has only about 80%, and purity also has only 82%.
Summary of the invention
The objective of the invention is in order to overcome the existing shortcoming of aforesaid method, in order to address the above problem, make the technical process of synthesizing diphenylacetylene base silane simple, the purity of product and productive rate improve, try hard to be beneficial to suitability for industrialized production from the different new synthetic methods of approach developing.
The present invention is with phenylacetylene, and butyllithium and dimethyl dichlorosilane (DMCS) are raw material, and tetrahydrofuran (THF) (THF) is made solvent, reacts synthesizing diphenylacetylene base silane monomer in two steps.
Technological line is as follows:
The first step reaction generates the phenylacetylene base lithium:
The mol ratio of phenylacetylene and butyllithium is 1～1.2:1; Temperature of reaction is-30 ℃～60 ℃; Reaction times is 1～5h.
The reaction of second step generates the tolane base silane:
The mol ratio of phenylacetylene base lithium and dimethyl dichlorosilane (DMCS) is 2～4:1; Temperature of reaction is-40 ℃～70 ℃; Reaction times is 1～6h.
Technical scheme of the present invention is: under protection of inert gas, butyllithium is added drop-wise in the phenylacetylene, 10～50 minutes dropping time, dropwises-30 ℃～60 ℃ reactions in back 1～5 hour.Then dimethyl dichlorosilane (DMCS) is added drop-wise in the phenylacetylene base lithium solution, 15～60 minutes dropping time, dropwises-40 ℃～70 ℃ reactions in back 1～6 hour.Reaction is poured saturated ammonium chloride solution into after finishing in reaction solution, fully stirs, and washing, separatory, until pH value neutrality, the water of gained adds extracted with diethyl ether.Collect and merge resultant 70 ℃ of reactions 1～6 hour.Reaction is poured saturated ammonium chloride solution into after finishing in reaction solution, fully stirs, and washing, separatory, until pH value neutrality, the water of gained adds extracted with diethyl ether.Collect the resulting ether phase of merging, underpressure distillation removes and desolvates, and obtains final product tolane base silane.
The organolithium method of introduction of the present invention has following advantage: technical process is simple, and operating procedure is simple, and the reaction times is short, and reaction conditions is easy to control, and productive rate reaches 98%, and purity also can reach more than 90%, and suitable extension is produced.The prepared tolane base silane of the present invention can be applicable to prepare multiple uses such as high performance composite, ceramic forerunner, high-temperaure coating.
Embodiment:
Further specify technical solution of the present invention in conjunction with the embodiments, but it does not limit protection scope of the present invention:
Embodiment
The phenylacetylene of 19mmol is dissolved in the 10ml tetrahydrofuran (THF),, dropwises the back in-20 ℃ of reactions 5 hours with the butyllithium reagent of constant pressure funnel dropping 16mmol, 40 minutes dropping time.Then the dimethyl dichlorosilane (DMCS) of 6mmol is dissolved in the 10ml tetrahydrofuran (THF) and is added drop-wise in the phenylacetylene base lithium reagent, dropwise 50 ℃ of reactions 6 hours.Reaction finishes the back and pours reaction solution into the saturated ammonium chloride solution of 30ml ice, fully stir, separatory is got upper oil phase, again with the washing of 30ml saturated ammonium chloride solution, until pH value neutrality, the water of gained adds extracted with diethyl ether, and separatory is collected the resulting oil phase of merging, underpressure distillation removes and desolvates, and obtains final product methyldiphenyl ethynyl silane.
Claims (5)
1. method for preparing the tolane base silane, the key step of described method is: organolithium reagent is added drop-wise at first that reaction generates the phenylacetylene base lithium in the phenylacetylene under protection of inert gas; Then dimethyl dichlorosilane (DMCS) is added drop-wise in the phenylacetylene base lithium solution, reaction generates the tolane base silane, and wherein said organolithium reagent is a butyllithium, and its reaction equation is as follows:
2. according to the technology of claim 1, it is characterized in that the mol ratio of phenylacetylene and butyllithium is 1～1.2:1.
3. according to the technology of claim 1, it is characterized in that, phenylacetylene and butyllithium temperature of reaction-30 ℃～60 ℃, the reaction times is 1～5 hour.
4. according to the technology of claim 1, it is characterized in that the mol ratio of phenylacetylene base lithium and hydrogeneous dichlorosilane is 2～4:1.
5. according to the technology of claim 1, it is characterized in that phenylacetylene base lithium and hydrogeneous dichlorosilane temperature of reaction are-40 ℃～70 ℃, the reaction times is 1～6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101101335A CN100506827C (en) | 2005-11-09 | 2005-11-09 | Diphenylacetylene silane novle synthesis method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101101335A CN100506827C (en) | 2005-11-09 | 2005-11-09 | Diphenylacetylene silane novle synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1763053A CN1763053A (en) | 2006-04-26 |
| CN100506827C true CN100506827C (en) | 2009-07-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005101101335A Expired - Fee Related CN100506827C (en) | 2005-11-09 | 2005-11-09 | Diphenylacetylene silane novle synthesis method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665506B (en) * | 2009-09-10 | 2012-01-04 | 华东理工大学 | Novel boron-and benzene-contained acetenyl oxosilane and preparation method thereof |
| CN102226000B (en) * | 2011-04-21 | 2012-11-14 | 华东理工大学 | Novel boron silicon alkyne hybrid high temperature resistant resin and preparation method thereof |
| CN102321110A (en) * | 2011-07-21 | 2012-01-18 | 凯莱英医药化学（阜新）技术有限公司 | Synthesis method of alkynylsilane derivatives |
| CN104530386A (en) * | 2014-12-24 | 2015-04-22 | 华东理工大学 | Phenylethynyl silane-modified epoxy resin and preparation method thereof |
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2005
- 2005-11-09 CN CNB2005101101335A patent/CN100506827C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| . CA no.113:59287. 1990 |
| . CA no.131:257904. 1999 |
| . CA no.141:140334. 2004 |
| . CA no.113:59287. 1990;. CA no.131:257904. 1999;. CA no.141:140334. 2004 * |
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| CN1763053A (en) | 2006-04-26 |
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