CN104892658A - Preparation method of diphenyl difluorosilane - Google Patents
Preparation method of diphenyl difluorosilane Download PDFInfo
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- CN104892658A CN104892658A CN201510321600.2A CN201510321600A CN104892658A CN 104892658 A CN104892658 A CN 104892658A CN 201510321600 A CN201510321600 A CN 201510321600A CN 104892658 A CN104892658 A CN 104892658A
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- phenylbenzene
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- silicon fluoride
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Abstract
The invention discloses a preparation method of diphenyl difluorosilane. The method comprises the following steps: taking sodium fluoride (or potassium fluoride), and diphenyl dichlorosilane as raw materials; carrying out a reaction under the action of a dilution solvent A and a phase transfer catalyst B; carrying out solid-liquid separation after the reaction is finished to obtain a filtrate; conducting rectification under reduced pressure on the filtrate, so as to obtain diphenyl difluorosilane. As the dilution solvent A and the phase transfer catalyst B are used in the preparation method, the synthetic efficiency of sodium fluoride (or potassium fluoride) and diphenyl dichlorosilane is greatly improved, the reaction time is shortened, and the production efficiency is improved.
Description
Technical field
The present invention relates to the preparation method of phenylbenzene two silicon fluoride.
Background technology
From new forms of energy development trend, the demand of lithium-ion battery electrolytes will increase rapidly in several years of future, and along with the introducing of some functional additives, the excellent properties of lithium-ion battery electrolytes in anti-overcharge, high-low temperature resistant etc. also will embody better.
Phenylbenzene two silicon fluoride can be used as the additive of lithium-ion battery electrolytes, makes electrolytic solution in resistance to elevated temperatures, have better lifting.The shortcoming of the preparation method of existing phenylbenzene two silicon fluoride is as follows: the combined coefficient of raw material is low, sluggish, and production efficiency is lower.
Summary of the invention
Technical problem to be solved by this invention is: will provide a kind of preparation method that can improve phenylbenzene two silicon fluoride of Material synthesis efficiency.
In order to solve the problem, the technical solution used in the present invention is: the preparation method of phenylbenzene two silicon fluoride, be characterized in: chemical compounds I and diphenyl dichlorosilane are under the effect of dilution solvent orange 2 A and phase-transfer catalyst B, and reaction generates phenylbenzene two silicon fluoride, wherein: chemical compounds I is Sodium Fluoride or Potassium monofluoride, dilution solvent orange 2 A is diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, methyl tertiary butyl ether, normal hexane, octane, acetone, methylethylketone, N, dinethylformamide, ethyl acetate, propyl propionate, methylcarbonate, diethyl carbonate, NSC 11801, at least one in tetrahydrofuran (THF), phase-transfer catalyst B is four butyl bromation amine, tetrabutyl phosphorus chloride, tetrabutyl ammonium sulfate, tetrabutyl iodate amine, tetraphenylphosphonichloride chloride phosphorus, tri-n-octyl methyl ammonium chloride, at least one in triphenyl ethyl phosphonium bromide phosphorus,
Preparation process is as follows:
(1) in reaction vessel, drop into chemical compounds I, then add dilution solvent orange 2 A and phase-transfer catalyst B;
(2) diphenyl dichlorosilane is dropped in there-necked flask;
(3) intensification is stirred, stirring reaction at the temperature of 10 ~ 150 DEG C;
(4) question response completely after, the temperature of reaction vessel is cooled to blowing after room temperature, then carries out solid-liquid separation, obtain filtrate;
(5), after filtrate carries out rectification under vacuum, phenylbenzene two silicon fluoride is obtained.
Further, the preparation method of aforesaid phenylbenzene two silicon fluoride, wherein: the quality that feeds intake of dilution solvent orange 2 A is 20% ~ 200% of the total mass of chemical compounds I and diphenyl dichlorosilane.
Further, the preparation method of aforesaid phenylbenzene two silicon fluoride, wherein: the quality that feeds intake of phase-transfer catalyst B is 0.2% ~ 2% of the total mass of chemical compounds I and diphenyl dichlorosilane.
Further, the preparation method of aforesaid phenylbenzene two silicon fluoride, wherein: diphenyl dichlorosilane feed intake quality needed for diphenyl dichlorosilane and chemical compounds I complete reaction Theoretical Mass 90% ~ 98%.
Further, the preparation method of aforesaid phenylbenzene two silicon fluoride, wherein: with the air in inert gas replacement reaction vessel before stirring reaction.
Further, the preparation method of aforesaid phenylbenzene two silicon fluoride, wherein: the moisture content of chemical compounds I is less than 5000ppm.
Further, the preparation method of aforesaid phenylbenzene two silicon fluoride, wherein: the stirring reaction time is 2 ~ 20h.
Advantage of the present invention is: in the preparation method of phenylbenzene two silicon fluoride of the present invention, employ dilution solvent orange 2 A and phase-transfer catalyst B, such combined coefficient of chemical compounds I and diphenyl dichlorosilane that can make improves greatly, decrease the reaction times, improve production efficiency.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
In the present embodiment, chemical compounds I is Sodium Fluoride, and dilution solvent orange 2 A is diethylene glycol dimethyl ether and TRIGLYME, and phase-transfer catalyst B is Tetrabutyl amonium bromide and tetraphenylphosphonichloride chloride phosphorus;
Preparation process is as follows:
(1) in there-necked flask, dried chemical compounds I 84g is dropped into, drop into 482g dilution solvent orange 2 A and 1.3g phase-transfer catalyst B again, wherein 482g dilution solvent orange 2 A is made up of 282g diethylene glycol dimethyl ether and 200g TRIGLYME, and 1.3g phase-transfer catalyst B is made up of 0.8g Tetrabutyl amonium bromide and 0.5g tetraphenylphosphonichloride chloride phosphorus;
(2) 241g diphenyl dichlorosilane is dropped in there-necked flask, and in there-necked flask, pass into the air in nitrogen replacement there-necked flask;
(3) intensification is stirred, stirring reaction 8 hours at 90 ~ 100 DEG C of temperature;
(4) after reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane residual quantity is 0.42%, can think and react completely, then reaction solution be poured in positive press filtration device, open nitrogen press filtration, filter to obtain filter residue 188g, filtrate 608g;
(5) filtrate is carried out rectification under vacuum, adopt low boil and front heat up in a steamer after, collect the cut of still temperature 110 ~ 140 DEG C time, obtain the phenylbenzene two silicon fluoride 181g of purity more than 99%, the molar yield of diphenyl dichlorosilane is 86.4%.
Embodiment 2
In the present embodiment, chemical compounds I is Sodium Fluoride, and dilution solvent orange 2 A is ethyl acetate, and phase-transfer catalyst B is tetrabutyl ammonium sulfate;
Preparation process is as follows:
(1) in there-necked flask, drop into dried chemical compounds I 84g, then drop into 420g dilution solvent orange 2 A and 1.0g phase-transfer catalyst B;
(2) 245g diphenyl dichlorosilane is dropped in there-necked flask, and in there-necked flask, pass into the air in nitrogen replacement there-necked flask;
(3) intensification is stirred, stirring reaction 16 hours at 35 ~ 45 DEG C of temperature;
(4) after reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane residual quantity is 0.23%, can think and react completely, then reaction solution be poured in positive press filtration device, open nitrogen press filtration, filter to obtain filter residue 209g, filtrate 531g;
(5) filtrate is carried out rectification under vacuum, adopt low boil and front heat up in a steamer after, collect the cut of still temperature 110 ~ 140 DEG C time, obtain the phenylbenzene two silicon fluoride 176g of purity more than 99%, the molar yield of diphenyl dichlorosilane is 82.6%.
Embodiment 3
In the present embodiment, chemical compounds I is Potassium monofluoride, and dilution solvent orange 2 A is tetraethyleneglycol dimethyl ether ester, and phase-transfer catalyst B is tri-n-octyl methyl ammonium chloride and tetrabutyl phosphorus chloride;
Preparation process is as follows:
(1) in there-necked flask, drop into dried chemical compounds I 116g, then drop into 300g dilution solvent orange 2 A and 1.5g phase-transfer catalyst B, wherein 1.5g phase-transfer catalyst B is made up of 1.0g tri-n-octyl methyl ammonium chloride and 0.5g tetrabutyl phosphorus chloride;
(2) 240g diphenyl dichlorosilane is dropped in there-necked flask, and in there-necked flask, pass into the air in nitrogen replacement there-necked flask;
(3) intensification is stirred, stirring reaction 6 hours at 130 ~ 140 DEG C of temperature;
(4) after reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane residual quantity is 0.33%, can think and react completely, then reaction solution be poured in positive press filtration device, open nitrogen press filtration, filter to obtain filter residue 170g, filtrate 484g;
(5) filtrate is carried out rectification under vacuum, adopt low boil and front heat up in a steamer after, collect the cut of still temperature 110 ~ 140 DEG C time, obtain the phenylbenzene two silicon fluoride 172g of purity more than 99%, the molar yield of diphenyl dichlorosilane is 82.4%.
Embodiment 4
In the present embodiment, chemical compounds I is Potassium monofluoride, and dilution solvent orange 2 A is tetrahydrofuran (THF) and acetone, and phase-transfer catalyst B is triphenyl ethyl phosphonium bromide phosphorus;
Preparation process is as follows:
(1) in there-necked flask, drop into dried chemical compounds I 116g, then drop into 480g dilution solvent orange 2 A and 1.8g phase-transfer catalyst B, wherein 480g dilution solvent orange 2 A is made up of 280g tetrahydrofuran (THF) and 200g acetone;
(2) 243g diphenyl dichlorosilane is dropped in there-necked flask, and in there-necked flask, pass into the air in nitrogen replacement there-necked flask;
(3) intensification is stirred, stirring reaction 18 hours at 40 ~ 50 DEG C of temperature;
(4) after reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane residual quantity is 0.38%, can think and react completely, then reaction solution be poured in positive press filtration device, open nitrogen press filtration, filter to obtain filter residue 188g, filtrate 635g;
(5) filtrate is carried out rectification under vacuum, adopt low boil and front heat up in a steamer after, collect the cut of still temperature 110 ~ 140 DEG C time, obtain the phenylbenzene two silicon fluoride 175g of purity more than 99%, the molar yield of diphenyl dichlorosilane is 82.8%.
Embodiment 5
In the present embodiment, chemical compounds I is Potassium monofluoride, and dilution solvent orange 2 A is methyl tertiary butyl ether, and phase-transfer catalyst B is tetrabutyl iodate amine;
Preparation process is as follows:
(1) in there-necked flask, drop into dried chemical compounds I 116g, then drop into 200g dilution solvent orange 2 A and 1.8g phase-transfer catalyst B;
(2) 243g diphenyl dichlorosilane is dropped in there-necked flask, and in there-necked flask, pass into the air in nitrogen replacement there-necked flask;
(3) intensification is stirred, stirring reaction 18 hours at 30 ~ 40 DEG C of temperature;
(4) after reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane residual quantity is 0.38%, can think and react completely, then reaction solution be poured in positive press filtration device, open nitrogen press filtration, filter to obtain filter residue 191g, filtrate 355g;
(5) filtrate is carried out rectification under vacuum, adopt low boil and front heat up in a steamer after, collect the cut of still temperature 110 ~ 140 DEG C time, obtain the phenylbenzene two silicon fluoride 178g of purity more than 99%, the molar yield of diphenyl dichlorosilane is 84.2%.
Beneficial effect of the present invention is: the preparation method of phenylbenzene two silicon fluoride of the present invention employs dilution solvent orange 2 A and phase-transfer catalyst B in reaction process, substantially increase the combined coefficient of chemical compounds I and diphenyl dichlorosilane like this, decrease the reaction times, improve production efficiency.In preparation process, diphenyl dichlorosilane actual feed intake quality needed for diphenyl dichlorosilane and chemical compounds I complete reaction Theoretical Mass 90% ~ 98%, it is because the cost ratio chemical compounds I of diphenyl dichlorosilane is expensive that the quality that feeds intake of diphenyl dichlorosilane is arranged like this, the actual quality that feeds intake of diphenyl dichlorosilane is less than theoretical amount can make diphenyl dichlorosilane react completely, thus reaches the object of not wasting diphenyl dichlorosilane.To prevent the water in air from participating in reaction with the air in inert gas replacement reaction vessel before stirring reaction.The moisture content of chemical compounds I is less than 5000ppm, and it is to prevent too much water from participating in reaction that the water-content of chemical compounds I is arranged like this, and too much water participates in reaction and easily produces a large amount of impurity.The stirring reaction time is 2 ~ 20h, and the stirring reaction time is arranged like this, is to prevent the reaction times too short on the one hand, and causing reaction not exclusively, is to prevent the reaction times long on the other hand, reduces production efficiency.
Claims (7)
1. the preparation method of phenylbenzene two silicon fluoride, is characterized in that: chemical compounds I and diphenyl dichlorosilane are under the effect of dilution solvent orange 2 A and phase-transfer catalyst B, and reaction generates phenylbenzene two silicon fluoride, wherein: chemical compounds I is Sodium Fluoride or Potassium monofluoride, dilution solvent orange 2 A is diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, methyl tertiary butyl ether, normal hexane, octane, acetone, methylethylketone, N, dinethylformamide, ethyl acetate, propyl propionate, methylcarbonate, diethyl carbonate, NSC 11801, at least one in tetrahydrofuran (THF), phase-transfer catalyst B is four butyl bromation amine, tetrabutyl phosphorus chloride, tetrabutyl ammonium sulfate, tetrabutyl iodate amine, tetraphenylphosphonichloride chloride phosphorus, tri-n-octyl methyl ammonium chloride, at least one in triphenyl ethyl phosphonium bromide phosphorus,
Preparation process is as follows:
(1) in reaction vessel, drop into chemical compounds I, then add dilution solvent orange 2 A and phase-transfer catalyst B;
(2) diphenyl dichlorosilane is dropped in there-necked flask;
(3) intensification is stirred, stirring reaction at the temperature of 10 ~ 150 DEG C;
(4) question response completely after, the temperature of reaction vessel is cooled to blowing after room temperature, then carries out solid-liquid separation, obtain filtrate;
(5), after filtrate carries out rectification under vacuum, phenylbenzene two silicon fluoride is obtained.
2. the preparation method of phenylbenzene two silicon fluoride according to claim 1, is characterized in that: the quality that feeds intake of dilution solvent orange 2 A is 20% ~ 200% of the total mass of chemical compounds I and diphenyl dichlorosilane.
3. the preparation method of phenylbenzene two silicon fluoride according to claim 1 and 2, is characterized in that: the quality that feeds intake of phase-transfer catalyst B is 0.2% ~ 2% of the total mass of chemical compounds I and diphenyl dichlorosilane.
4. the preparation method of phenylbenzene two silicon fluoride according to claim 1 and 2, is characterized in that: diphenyl dichlorosilane feed intake quality needed for diphenyl dichlorosilane and chemical compounds I complete reaction Theoretical Mass 90% ~ 98%.
5. the preparation method of phenylbenzene two silicon fluoride according to claim 1 and 2, is characterized in that: with the air in inert gas replacement reaction vessel before stirring reaction.
6. the preparation method of phenylbenzene two silicon fluoride according to claim 1 and 2, is characterized in that: the moisture content of chemical compounds I is less than 5000ppm.
7. the preparation method of phenylbenzene two silicon fluoride according to claim 1 and 2, is characterized in that: the stirring reaction time is 2 ~ 20h.
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| CN201510321600.2A CN104892658B (en) | 2015-06-12 | 2015-06-12 | The preparation method of the silicon fluoride of diphenyl two |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207541A (en) * | 2015-11-09 | 2017-09-26 | 瓦克化学股份公司 | Method for producing cyanoalkyl silicon fluoride |
| CN110835354A (en) * | 2018-08-15 | 2020-02-25 | 张家港市国泰华荣化工新材料有限公司 | Process for preparing alkyl phenyl fluorosilane |
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2015
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Non-Patent Citations (5)
| Title |
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| H.J.EMELEUS ET AL.: "Some New Ethyl and Phenyl Silicon Fluorides", 《J.CHEM.SOC.》 * |
| OMAR FAROOQ ET AL.: "Alkali Metal Salts of Perfluorinated Complex Anions. Effective Reagents for Nucleophilic Fluorination", 《J.ORG.CHEM.》 * |
| OMAR FAROOQ: "Nucleophilic fluorination of alkoxysilane with alkali metal salts of perfluorinated complex anions", 《J.CHEM.SOC.,PERKIN TRANS.》 * |
| ROBERT DAMRAUER ET AL.: "Synthesis of Fluorosilanes from Chlorosilanes: The Use of Hexafluorosillcates", 《ORGANOMETALLICS》 * |
| W.H.PEARLSON ET AL.: "The Use of Hydrogen Fluoride in Preparing Organo-silicon Fluorides", 《J.AM.CHEM.SOC.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207541A (en) * | 2015-11-09 | 2017-09-26 | 瓦克化学股份公司 | Method for producing cyanoalkyl silicon fluoride |
| CN110835354A (en) * | 2018-08-15 | 2020-02-25 | 张家港市国泰华荣化工新材料有限公司 | Process for preparing alkyl phenyl fluorosilane |
| CN110835354B (en) * | 2018-08-15 | 2022-10-04 | 张家港市国泰华荣化工新材料有限公司 | Process for preparing alkyl phenyl fluorosilane |
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Address after: 215600 No.35 Nanhai Road, Jiangsu Yangzijiang International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu Province Patentee after: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. Address before: 215633 No.9 Nanhai Road, Yangzijiang International Chemical Industrial Park, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee before: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. |