CN104892658B - The preparation method of the silicon fluoride of diphenyl two - Google Patents
The preparation method of the silicon fluoride of diphenyl two Download PDFInfo
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- CN104892658B CN104892658B CN201510321600.2A CN201510321600A CN104892658B CN 104892658 B CN104892658 B CN 104892658B CN 201510321600 A CN201510321600 A CN 201510321600A CN 104892658 B CN104892658 B CN 104892658B
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Abstract
The invention discloses the preparation method of the silicon fluoride of diphenyl two.Preparation method is using sodium fluoride or potassium fluoride, diphenyl dichlorosilane as raw material, is reacted in the presence of dilution is with solvent orange 2 A and phase transfer catalyst B, question response carries out separation of solid and liquid afterwards completely, obtains filtrate；After filtrate carries out rectification under vacuum, the silicon fluoride of diphenyl two is obtained.Dilution solvent orange 2 A and phase transfer catalyst B have been used in preparation method of the present invention, so as to greatly improve the combined coefficient of sodium fluoride or potassium fluoride and diphenyl dichlorosilane, has reduced the reaction time, improves production efficiency.
Description
Technical field
The present invention relates to the preparation method of the silicon fluoride of diphenyl two.
Background technology
From the point of view of new energy development trend, the demand of lithium-ion battery electrolytes will increase rapidly in several years of future
It is long, and as the introducing of some functional additives, lithium-ion battery electrolytes are excellent anti-overcharge, high-low temperature resistant etc.
Performance also will be embodied preferably.
The silicon fluoride of diphenyl two can be such that electrolyte has in resistance to elevated temperatures as the additive of lithium-ion battery electrolytes
Preferably lifting.The shortcomings that preparation method of the existing silicon fluoride of diphenyl two, is as follows：The combined coefficient of raw material is low, and reaction is slow,
Production efficiency is relatively low.
The content of the invention
The technical problems to be solved by the invention are：A kind of diphenyl difluoro silicon that can improve Material synthesis efficiency will be provided
The preparation method of alkane.
In order to solve the above problems, the technical solution adopted by the present invention is：The preparation method of the silicon fluoride of diphenyl two, it is special
Putting is：Chemical compounds I and diphenyl dichlorosilane are in the presence of dilution solvent orange 2 A and phase transfer catalyst B, reaction generation hexichol
The silicon fluoride of base two；Wherein：Chemical compounds I is sodium fluoride or potassium fluoride, and dilution is diethylene glycol dimethyl ether, triethylene glycol with solvent orange 2 A
Dimethyl ether, tetraethyleneglycol dimethyl ether, methyl tertiary butyl ether(MTBE), n-hexane, normal octane, acetone, MEK, N, N- dimethyl formyls
At least one of amine, ethyl acetate, propyl propionate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, tetrahydrofuran, phase
Transfer catalyst B is four butyl bromation amine, tetrabutyl phosphorus chloride, tetrabutyl ammonium sulfate, tetrabutyl iodate amine, tetraphenylphosphonichloride chloride
At least one of phosphorus, tri-n-octyl methyl ammonium chloride, triphenyl ethyl phosphonium bromide phosphorus；
Preparation process is as follows：
（1）Chemical compounds I is put into three-necked flask, adds dilution solvent orange 2 A and phase transfer catalyst B；
（2）Diphenyl dichlorosilane is put into three-necked flask；
（3）Stirring heating, the stirring reaction at a temperature of 30 ~ 150 DEG C；
（4）After question response is complete, the temperature of reaction vessel is cooled to blowing after room temperature, separation of solid and liquid is then carried out, obtains
To filtrate；
（5）After filtrate carries out rectification under vacuum, the silicon fluoride of diphenyl two is obtained.
Further, the preparation method of the foregoing silicon fluoride of diphenyl two, wherein：Dilution is with the quality that feeds intake of solvent orange 2 A
The 20% ~ 200% of the gross mass of chemical compounds I and diphenyl dichlorosilane.
Further, the preparation method of the foregoing silicon fluoride of diphenyl two, wherein：The phase transfer catalyst B quality that feeds intake
For the 0.2% ~ 2% of chemical compounds I and the gross mass of diphenyl dichlorosilane.
Further, the preparation method of the foregoing silicon fluoride of diphenyl two, wherein：The quality that feeds intake of diphenyl dichlorosilane
For 90% ~ 98% of Theoretical Mass needed for diphenyl dichlorosilane and the complete reaction of chemical compounds I.
Further, the preparation method of the foregoing silicon fluoride of diphenyl two, wherein：Put before stirring reaction with inert gas
The air changed in reaction vessel.
Further, the preparation method of the foregoing silicon fluoride of diphenyl two, wherein：The moisture of chemical compounds I is less than
5000ppm。
Further, the preparation method of the foregoing silicon fluoride of diphenyl two, wherein：The stirring reaction time is 2~20h.
Advantages of the present invention is：Use and diluted with molten in the preparation method of the silicon fluoride of diphenyl two of the present invention
Agent A and phase transfer catalyst B, so can greatly improve the combined coefficient of chemical compounds I and diphenyl dichlorosilane, reduce anti-
Between seasonable, production efficiency is improved.
Embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
In the present embodiment, chemical compounds I is sodium fluoride, and dilution is diethylene glycol dimethyl ether and triethylene glycol two with solvent orange 2 A
Methyl ether, phase transfer catalyst B are TBAB and tetraphenylphosphonichloride chloride phosphorus；
Preparation process is as follows：
（1）Dried chemical compounds I 84g is put into three-necked flask, then puts into 482g dilutions solvent orange 2 A and 1.3g phases
Transfer catalyst B, wherein 482g dilutions are made up of with solvent orange 2 A 282g diethylene glycol dimethyl ethers and 200g TRIGLYMEs,
1.3g phase transfer catalysts B is made up of 0.8g TBABs and 0.5g tetraphenylphosphonichloride chloride phosphorus；
（2）241g diphenyl dichlorosilanes are put into three-necked flask, and nitrogen displacement three is passed through into three-necked flask
Air in mouth flask；
（3）Stirring heating, stirring reaction 8 hours at a temperature of 90 ~ 100 DEG C；
（4）After reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane is residual
Allowance is 0.42%, it is believed that reaction is complete, then pours into reaction solution in positive press filtration device, opens nitrogen press filtration, filters to obtain filter residue
188g, filtrate 608g；
（5）Filtrate is subjected to rectification under vacuum, after adopting low boiling and before evaporating, collects cut of the kettle temperature at 110 ~ 140 DEG C, i.e.,
Diphenyl two silicon fluoride 181g of the purity more than 99% is obtained, the molar yield of the silicon fluoride of diphenyl two is 86.4%.
Embodiment 2
In the present embodiment, chemical compounds I is sodium fluoride, and dilution is ethyl acetate with solvent orange 2 A, and phase transfer catalyst B is four
Butyl ammonium sulfate；
Preparation process is as follows：
（1）Dried chemical compounds I 84g is put into three-necked flask, then puts into 420g dilutions solvent orange 2 A and 1.0g phases
Transfer catalyst B；
（2）245g diphenyl dichlorosilanes are put into three-necked flask, and nitrogen displacement three is passed through into three-necked flask
Air in mouth flask；
（3）Stirring heating, stirring reaction 16 hours at a temperature of 35 ~ 45 DEG C；
（4）After reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane is residual
Allowance is 0.23%, it is believed that reaction is complete, then pours into reaction solution in positive press filtration device, opens nitrogen press filtration, filters to obtain filter residue
209g, filtrate 531g；
（5）Filtrate is subjected to rectification under vacuum, after adopting low boiling and before evaporating, collects cut of the kettle temperature at 110 ~ 140 DEG C, i.e.,
Diphenyl two silicon fluoride 176g of the purity more than 99% is obtained, the molar yield of the silicon fluoride of diphenyl two is 82.6%.
Embodiment 3
In the present embodiment, chemical compounds I is potassium fluoride, and dilution is tetraethyleneglycol dimethyl ether ester with solvent orange 2 A, phase transfer catalysis (PTC)
Agent B is tri-n-octyl methyl ammonium chloride and tetrabutyl phosphorus chloride；
Preparation process is as follows：
（1）Dried chemical compounds I 116g is put into three-necked flask, then puts into 300g dilutions solvent orange 2 A and 1.5g
Phase transfer catalyst B, wherein 1.5g phase transfer catalysts B are by 1.0g tri-n-octyl methyl ammonium chlorides and 0.5g tetrabutyl phosphorus chloride groups
Into；
（2）240g diphenyl dichlorosilanes are put into three-necked flask, and nitrogen displacement three is passed through into three-necked flask
Air in mouth flask；
（3）Stirring heating, stirring reaction 6 hours at a temperature of 130 ~ 140 DEG C；
（4）After reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane is residual
Allowance is 0.33%, it is believed that reaction is complete, then pours into reaction solution in positive press filtration device, opens nitrogen press filtration, filters to obtain filter residue
170g, filtrate 484g；
（5）Filtrate is subjected to rectification under vacuum, after adopting low boiling and before evaporating, collects cut of the kettle temperature at 110 ~ 140 DEG C, i.e.,
Diphenyl two silicon fluoride 172g of the purity more than 99% is obtained, the molar yield of the silicon fluoride of diphenyl two is 82.4%.
Embodiment 4
In the present embodiment, chemical compounds I is potassium fluoride, and dilution is tetrahydrofuran and acetone with solvent orange 2 A, phase transfer catalyst
B is triphenyl ethyl phosphonium bromide phosphorus；
Preparation process is as follows：
（1）Dried chemical compounds I 116g is put into three-necked flask, then puts into 480g dilutions solvent orange 2 A and 1.8g
Phase transfer catalyst B, wherein 480g dilutions are made up of with solvent orange 2 A 280g tetrahydrofurans and 200g acetone；
（2）243g diphenyl dichlorosilanes are put into three-necked flask, and nitrogen displacement three is passed through into three-necked flask
Air in mouth flask；
（3）Stirring heating, stirring reaction 18 hours at a temperature of 40 ~ 50 DEG C；
（4）After reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane is residual
Allowance is 0.38%, it is believed that reaction is complete, then pours into reaction solution in positive press filtration device, opens nitrogen press filtration, filters to obtain filter residue
188g, filtrate 635g；
（5）Filtrate is subjected to rectification under vacuum, after adopting low boiling and before evaporating, collects cut of the kettle temperature at 110 ~ 140 DEG C, i.e.,
Diphenyl two silicon fluoride 175g of the purity more than 99% is obtained, the molar yield of the silicon fluoride of diphenyl two is 82.8%.
Embodiment 5
In the present embodiment, chemical compounds I is potassium fluoride, and dilution is methyl tertiary butyl ether(MTBE) with solvent orange 2 A, phase transfer catalyst B
For tetrabutyl iodate amine；
Preparation process is as follows：
（1）Dried chemical compounds I 116g is put into three-necked flask, then puts into 200g dilutions solvent orange 2 A and 1.8g
Phase transfer catalyst B；
（2）243g diphenyl dichlorosilanes are put into three-necked flask, and nitrogen displacement three is passed through into three-necked flask
Air in mouth flask；
（3）Stirring heating, stirring reaction 18 hours at a temperature of 30 ~ 40 DEG C；
（4）After reaction to be mixed terminates, the temperature of reaction solution is cooled to room temperature, Chromatogram display diphenyl dichlorosilane is residual
Allowance is 0.38%, it is believed that reaction is complete, then pours into reaction solution in positive press filtration device, opens nitrogen press filtration, filters to obtain filter residue
191g, filtrate 355g；
（5）Filtrate is subjected to rectification under vacuum, after adopting low boiling and before evaporating, collects cut of the kettle temperature at 110 ~ 140 DEG C, i.e.,
Diphenyl two silicon fluoride 178g of the purity more than 99% is obtained, the molar yield of the silicon fluoride of diphenyl two is 84.2%.
Beneficial effects of the present invention are：The preparation method of the silicon fluoride of diphenyl two of the present invention makes during the course of the reaction
With dilution solvent orange 2 A and phase transfer catalyst B, the synthesis for so substantially increasing chemical compounds I and diphenyl dichlorosilane is imitated
Rate, reduce the reaction time, improve production efficiency.In preparation process, the quality that actually feeds intake of diphenyl dichlorosilane is
The 90% ~ 98% of Theoretical Mass, the quality that feeds intake of diphenyl dichlorosilane needed for diphenyl dichlorosilane and the complete reaction of chemical compounds I
So set is that the quality that actually feeds intake of diphenyl dichlorosilane is few because the price of diphenyl dichlorosilane is more expensive than chemical compounds I
In theoretical amount diphenyl dichlorosilane reaction can be made complete, so as to reach the purpose for not wasting diphenyl dichlorosilane.Stirring
It with the air in inert gas replacement reaction vessel is to prevent the water in air from participating in reaction to mix before reaction.Compound
I moisture is less than 5000ppm, the water content of chemical compounds I so set be in order to prevent excessive water from participating in reaction,
Excessive water participates in reaction and is also easy to produce a large amount of impurity.The stirring reaction time is 2 ~ 20h, the stirring reaction time in this way,
It is on the one hand to prevent that the reaction time is too short, causes reaction incomplete, is on the other hand the drop in order to prevent that the reaction time is long
Low production efficiency.
Claims (7)
1. the preparation method of the silicon fluoride of diphenyl two, it is characterised in that：Chemical compounds I and diphenyl dichlorosilane are in dilution solvent
In the presence of A and phase transfer catalyst B, the reaction generation silicon fluoride of diphenyl two；Wherein：Chemical compounds I is sodium fluoride or potassium fluoride,
Dilution with solvent orange 2 A be diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, methyl tertiary butyl ether(MTBE), just oneself
Alkane, normal octane, acetone, MEK, N,N-dimethylformamide, ethyl acetate, propyl propionate, dimethyl carbonate, carbonic acid diethyl
At least one of ester, ethylene carbonate, tetrahydrofuran, phase transfer catalyst B be four butyl bromation amine, tetrabutyl phosphorus chloride,
In tetrabutyl ammonium sulfate, tetrabutyl iodate amine, tetraphenylphosphonichloride chloride phosphorus, tri-n-octyl methyl ammonium chloride, triphenyl ethyl phosphonium bromide phosphorus
It is at least one；
Preparation process is as follows：
(1) chemical compounds I is put into three-necked flask, adds dilution solvent orange 2 A and phase transfer catalyst B；
(2) diphenyl dichlorosilane is put into three-necked flask；
(3) stirring heating, the stirring reaction at a temperature of 30 ~ 150 DEG C；
(4) after question response is complete, the temperature of reaction vessel is cooled to blowing after room temperature, separation of solid and liquid is then carried out, is filtered
Liquid；
(5) after filtrate carries out rectification under vacuum, the silicon fluoride of diphenyl two is obtained.
2. the preparation method of the silicon fluoride of diphenyl two according to claim 1, it is characterised in that：The throwing of dilution solvent orange 2 A
Expect the 20% ~ 200% of the gross mass that quality is chemical compounds I and diphenyl dichlorosilane.
3. the preparation method of the silicon fluoride of diphenyl two according to claim 1 or 2, it is characterised in that：Phase transfer catalyst B
The quality that feeds intake for the 0.2% ~ 2% of the gross mass of chemical compounds I and diphenyl dichlorosilane.
4. the preparation method of the silicon fluoride of diphenyl two according to claim 1 or 2, it is characterised in that：Diphenyl dichloro silicon
The quality that feeds intake of alkane is 90% ~ 98% of Theoretical Mass needed for diphenyl dichlorosilane and chemical compounds I react completely.
5. the preparation method of the silicon fluoride of diphenyl two according to claim 1 or 2, it is characterised in that：Before stirring reaction
With the air in inert gas replacement reaction vessel.
6. the preparation method of the silicon fluoride of diphenyl two according to claim 1 or 2, it is characterised in that：The moisture of chemical compounds I
Content is less than 5000ppm.
7. the preparation method of the silicon fluoride of diphenyl two according to claim 1 or 2, it is characterised in that：The stirring reaction time
For 2~20h.
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| DE102015222019A1 (en) * | 2015-11-09 | 2017-05-11 | Wacker Chemie Ag | Process for the preparation of cyanoalkylfluorosilanes |
| 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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Non-Patent Citations (5)
| Title |
|---|
| Alkali Metal Salts of Perfluorinated Complex Anions. Effective Reagents for Nucleophilic Fluorination;Omar Farooq et al.;《J.Org.Chem.》;19941231;第59卷;2122-2124 * |
| Nucleophilic fluorination of alkoxysilane with alkali metal salts of perfluorinated complex anions;Omar Farooq;《J.Chem.Soc.,Perkin Trans.》;19981231;661-665 * |
| Some New Ethyl and Phenyl Silicon Fluorides;H.J.Emeleus et al.;《J.Chem.Soc.》;19441231;454-456 * |
| Synthesis of Fluorosilanes from Chlorosilanes: The Use of Hexafluorosillcates;Robert Damrauer et al.;《Organometallics》;19881231;第7卷(第5期);1161-1164 * |
| The Use of Hydrogen Fluoride in Preparing Organo-silicon Fluorides;W.H.Pearlson et al.;《J.Am.Chem.Soc.》;19451231;第67卷;1769-1770 * |
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