CN1763052A - Triphenylacetylene silane novle synthesis method - Google Patents
Triphenylacetylene silane novle synthesis method Download PDFInfo
- Publication number
- CN1763052A CN1763052A CN 200510110132 CN200510110132A CN1763052A CN 1763052 A CN1763052 A CN 1763052A CN 200510110132 CN200510110132 CN 200510110132 CN 200510110132 A CN200510110132 A CN 200510110132A CN 1763052 A CN1763052 A CN 1763052A
- Authority
- CN
- China
- Prior art keywords
- silane
- reaction
- phenylacetylene
- acetenyl
- phenylacetylene base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention is new type of triphenyl acetenyl silane synthesizing process. By using phenyl acetylene, organic lithium reagent and methyl trichlorosilane as material and anhydrous tetrahydrofuran as solvent, the present invention synthesizes methyl triphenyl acetenyl silane monomer through two-step reaction under the protection of inert gas. Phenyl acetylene and butyl lithium first react to produce phenyl acetenyl lithium, and phenyl acetenyl lithium and trichlorosilane 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 triphenyl 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 three phenylacetylene base silane.
Background technology
Organosilicon polymer is the speciality polymer material, has unique physical and chemical performance, has and application widely at aerospace field.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.
The organosilane monomer that contains C ≡ C and Si-H functional group in the molecule, reaction forms polymkeric substance under the effect of high temperature or catalyzer, has general polymerization thing good processing properties, and at the bismaleimides and the polyimide resin that are better than aspect heat-resisting and the dielectric properties using at present, have and application widely at aerospace field, become the research focus of high-performance polymer material.This compounds generally has two kinds of synthetic methods.First method is the Grignard reagent method, and another kind of method is the organolithium method.
Chinese patent CN1421446A " phenylacetylene base silane and preparation method thereof " 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 benzene 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%.
The reaction of organolithium reagent is similar to Grignard reagent, but compares with Grignard reagent, and the reactive behavior of organolithium is much better than.For sterically hindered bigger substituting group, be difficult to finish with Grignard reagent.
The Chungkyun Kim of Korea S etc. has reported that the synthetic three phenylacetylene base silane of organolithium method are used for preparing branch-shape polymer, but technological process for this reaction, do not describe in detail on the document, it adopts anhydrous tetrahydro furan as solvent, the mol ratio of phenylacetylene base lithium and METHYL TRICHLORO SILANE is 3.5: 1, under refluxad reacted 3 hours, the yield of final product has only 79%.By column chromatography product is purified, therefore almost do not have the possibility of scale production.
Summary of the invention
The objective of the invention is in order to overcome the existing shortcoming of aforesaid method, the technology of carrying out the reaction of phenylacetylene base lithium and METHYL TRICHLORO SILANE in anhydrous tetrahydrofuran solution is improved, proportioning to reactant, temperature of reaction and time are optimized, and need not to carry out complicated aftertreatment purifies, improve the yield and the purity of product, made the technical process of synthetic phenylacetylene base silane simple, be beneficial to suitability for industrialized production.
The present invention wants the molecular formula of synthetic compound three phenylacetylene base silane to be:
Wherein R is: hydrogen, alkyl or aryl.
The present invention is with phenylacetylene, and organolithium reagent and METHYL TRICHLORO SILANE are raw material, and anhydrous tetrahydro furan (THF) is made solvent, reacts synthesizing methyl three phenylacetylene base silane monomers in two steps.
Concrete reaction process 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 methyl triphen dialkoxy silane:
The mol ratio of phenylacetylene lithium and trichlorosilane is (2～5): 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 reagent is added drop-wise in the phenylacetylene, 10～50 minutes dropping time, dropwises back (30 ℃)～60 ℃ reaction 1～5 hour.Then METHYL TRICHLORO SILANE is added drop-wise in the phenylacetylene base lithium solution, 15～60 minutes dropping time, dropwises back (40 ℃)～70 ℃ reaction 1～6 hour.Reaction adds saturated ammonium chloride solution in the reaction solution after finishing, 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 methyl three phenylacetylene base silane.
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 need not complicated aftertreatment purification, and productive rate reaches 90%, and purity reaches more than 98%, and suitable extension is produced.The prepared three phenylacetylene base silane of the present invention are white solid, and 130 ℃ of fusing points 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:
Embodiment 1: the phenylacetylene of 172mmol is dissolved in the 45ml tetrahydrofuran (THF), with the butyllithium reagent of constant pressure funnel dropping 144mmol, 40 minutes dropping time, dropwises-10 ℃ of reactions 4 hours.Then the METHYL TRICHLORO SILANE of 32mmol is dissolved in the 20ml tetrahydrofuran (THF) and is added drop-wise in the phenylacetylene base lithium reagent, dropwised back flow reaction 6 hours.After reaction finishes the 50ml saturated ammonium chloride solution is added in the reaction solution, fully stir, separatory, get upper oil phase again with the washing of 30ml saturated ammonium chloride solution, until pH value neutrality, the water of twice gained adds extracted with diethyl ether, separatory, collect the resulting oil phase of merging, underpressure distillation removes and desolvates, and obtains product methyl three phenylacetylene base silane.
Embodiment 2: the phenylacetylene of 88mmol is dissolved in the 40ml tetrahydrofuran (THF), with the butyllithium reagent of constant pressure funnel dropping 80mmol, 40 minutes dropping time, dropwises-20 ℃ of reactions 3 hours.Then the METHYL TRICHLORO SILANE of 20mmol is dissolved in the 15ml tetrahydrofuran (THF) and is added drop-wise in the phenylacetylene base lithium reagent, dropwised back flow reaction 6 hours.After reaction finishes the 30ml saturated ammonium chloride solution is added in the reaction solution, fully stir, separatory, get upper oil phase again with the washing of 30ml saturated ammonium chloride solution once, until pH value neutrality, the water of twice gained adds the diethyl ether solution extraction, separatory, collect the resulting oil phase of merging, underpressure distillation removes and desolvates, and obtains product methyl three phenylacetylene base silane.
Embodiment 3: the phenylacetylene of 60mmol is dissolved in the 30ml tetrahydrofuran (THF), with the butyllithium reagent of constant pressure funnel dropping 60mmol, 30 minutes dropping time, dropwises-20 ℃ of reactions 4 hours.Then the METHYL TRICHLORO SILANE of 15mmol is dissolved in the 10ml tetrahydrofuran (THF) and is added drop-wise in the phenylacetylene base lithium reagent, dropwised normal-temperature reaction 6 hours.After reaction finishes the 30ml saturated ammonium chloride solution is added in the reaction solution, fully stir, separatory, get upper oil phase again with the washing of 30ml saturated ammonium chloride solution once, until pH value neutrality, the water of twice gained adds the diethyl ether solution extraction, separatory, collect the resulting oil phase of merging, underpressure distillation removes and desolvates, and obtains product methyl three phenylacetylene base silane.
Claims (7)
1. organosilane monomer, described organosilane monomer is the phenylacetylene base substituted silane, it is characterized in that: described compound has following structural formula:
Wherein: R is alkyl, aryl or hydrogen atom.
2. prepare the method for the described compound of claim 1, it is characterized in that, the key step of described method is: butyllithium reagent is added drop-wise at first that reaction generates the phenylacetylene base lithium in the phenylacetylene under protection of inert gas; Then METHYL TRICHLORO SILANE is added drop-wise in the phenylacetylene base lithium solution, reaction generates methyl triphen dialkoxy silane.
3. according to the technology of claim 2, it is characterized in that raw material is selected for use has the phenylacetylene base substituted silane that structural unit is R (R is alkyl, aryl or hydrogen atom).
4. according to the technology of claim 2, it is characterized in that the mass ratio of phenylacetylene and organolithium reagent is (1～1.2): 1.
5. according to the technology of claim 2, it is characterized in that, phenylacetylene and organolithium reagent temperature of reaction (30 ℃)～60 ℃, the reaction times is 1～5 hour.
6. according to the technology of claim 2, it is characterized in that the mass ratio of phenylacetylene base lithium and trichlorosilane is (2～5): 1.
7. according to the technology of claim 2, it is characterized in that, phenylacetylene base lithium and trichlorosilane temperature of reaction be-(40 ℃)～70 ℃, the reaction times is 1～6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101101320A CN100506826C (en) | 2005-11-09 | 2005-11-09 | Triphenylacetylene silane novle synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101101320A CN100506826C (en) | 2005-11-09 | 2005-11-09 | Triphenylacetylene silane novle synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1763052A true CN1763052A (en) | 2006-04-26 |
| CN100506826C CN100506826C (en) | 2009-07-01 |
Family
ID=36747395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101101320A Expired - Fee Related CN100506826C (en) | 2005-11-09 | 2005-11-09 | Triphenylacetylene silane novle synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100506826C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864076A (en) * | 2010-05-14 | 2010-10-20 | 华东理工大学 | Cyanate resin modified by phenylacetylene base silane 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 |
-
2005
- 2005-11-09 CN CNB2005101101320A patent/CN100506826C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864076A (en) * | 2010-05-14 | 2010-10-20 | 华东理工大学 | Cyanate resin modified by phenylacetylene base silane 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100506826C (en) | 2009-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3390410B1 (en) | Methods of making high purity trisilylamine | |
| Iwahara et al. | Synthesis and properties of ethynylene-disilanylene copolymers | |
| CN1884343A (en) | Novel carborane- (siloxane or silane)- ethinyl high temperature resistant polymer and its preparation method | |
| CN102532186B (en) | Method for preparing hydroxyimino organosilicon compounds | |
| CN101058585A (en) | Safe separation method for increasing yield of methyl phenyl dialkoxy silicane | |
| CN1763053A (en) | Diphenylacetylene silane novle synthesis method | |
| CN100506826C (en) | Triphenylacetylene silane novle synthesis method | |
| CN104017017A (en) | Method for synthesizing phenyl-containing organosilicon monomers | |
| CN103342715B (en) | Preparation method of aminopropyl-containing organic oximido-silicon compound | |
| CN101031576A (en) | Method for producing trimethylsilyl azide | |
| CN104496929B (en) | Chiral zinc complex crystal containing chloroform crystal and application thereof | |
| CN108084219B (en) | Synthesis method of bis (diethylamino) silane | |
| Cypryk et al. | Ring‐opening polymerization of strained cyclotetrasilanes as a new route towards well defined polysilylenes | |
| CN103113400B (en) | The method of synthesis of phenyl methyl dioxane TMOS | |
| CN101077878A (en) | Alkyl cyclohexyl dialkoxy silane prepared by sodium condensation method | |
| CN109305985B (en) | Synthesis method of dimethylvinylchlorosilane | |
| JP7322762B2 (en) | Method for producing organosilicon compound having ketimine structure | |
| CN1880361A (en) | Method for preparing organic polysilane | |
| CN102875416B (en) | Chiral compound | |
| CN113461695A (en) | Method for synthesizing freehand painting and freehand painting aromatic hydrocarbon based on microreactor | |
| JP2023022908A (en) | Method for producing organic silicon compound having ketimine structure | |
| CN102010510A (en) | Novel high-temperature resistant phenylacetylene terminated poly (acetenyl-silane) and preparation method thereof | |
| CN105218473A (en) | A kind of chiral zinc nitrogen complexes containing methanol crystallization | |
| CN101845055B (en) | Method for purifying dichloromethyl phenylsilane by chemical coordination effect | |
| JP2793008B2 (en) | Method for producing hexamethylcyclotrisilazane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090701 Termination date: 20141109 |
|
| EXPY | Termination of patent right or utility model |