CN104004011A - Method for chlorination of diphenyl dichlorosilane - Google Patents
Method for chlorination of diphenyl dichlorosilane Download PDFInfo
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- CN104004011A CN104004011A CN201410205967.3A CN201410205967A CN104004011A CN 104004011 A CN104004011 A CN 104004011A CN 201410205967 A CN201410205967 A CN 201410205967A CN 104004011 A CN104004011 A CN 104004011A
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- chlorination
- diphenyl dichlorosilane
- reaction
- chlorine
- dichlorosilane
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Abstract
The invention relates to a method for chlorination of diphenyl dichlorosilane, particularly relates to diphenyl dichlorosilane chlorination with Cl2 as a chloridizing agent and under the catalysis of a catalyst, and belongs to the technical field of organosilicon materials. The method comprises: adding a catalyst of ZnCl2, SnCl4, a mixture of ZnCl2 and SbCl5 with a mole ratio of 1:1, a mixture of SnCl4 and SbCl5 with a mole ratio of 1:1, or a mixture of FeCl3 and SbCl5 with a mole ratio of 1:1 into diphenyl dichlorosilane, stirring for uniform dispersion; injecting chlorine, reacting at a certain chlorination reaction temperature for a certain time, condensing the tail gas, and removing HCl by absorption with a NaOH solution. The method is mild in reaction condition, wide in catalyst sources, low in catalyst using amount, simple and environment-friendly in reaction process, and suitable for industrialization.
Description
Technical field
A kind of method that the present invention relates to diphenyl dichlorosilane chlorination, specifically refers to use Cl
2for chlorizating agent, adopt the chlorination of catalyst diphenyl dichlorosilane, belong to organosilicon material technical field.
Background technology
Aerospace comprise rocket engine fuel, aircraft oil and aeronautic hydraulic oil with three large oil plants, belong to aircraft class functional materials; Gas fuel is for gas turbine engine, aircraft oil is for engine lubrication system, aeronautic hydraulic oil, for plane hydraulic system, holds water and selects these materials to ensureing the advance of aircraft overall design and the reliability important in inhibiting of aviation work.
Diphenyl dichlorosilane is a kind of machine silicon monomer that common are, and it is carried out, after chlorination, can generating multiple chloro-product; Take chlorophenyl dichlorosilane and other organochlorosilane monomer as the synthetic oil of raw material, fat use temperature scope wide, it is little that viscosity index changes, oilness, scale resistance and high and low temperature resistance are good, have good abrasion resistance; No matter whether this oil, fat add the additive agent modified aerospace engine that all can be used for, can be more excellent compared with synthesizing ester oiliness, be the organosilicon product of a class high added value.
Main purpose of the present invention is the novel process of a diphenyl dichlorosilane chloro of research and development, for research and development high-and low-temperature resistance aerospace engine lays the foundation with silicone oil, break China's high-and low-temperature resistance lubricating oil and research and develop situation backward in technique, there is good economic and social benefit.
Summary of the invention
On the basis of early-stage Study, the present invention adopts ZnCl
2, SnCl
4, ZnCl
2with SbCl
5mixture, SnCl
4with SbCl
5mixture or FeCl
3with SbCl
5the chlorination of mixture through catalytic diphenyl dichlorosilane prepare chlorophenyl dichlorosilane; The method reaction conditions is gentle, and catalyzer source is wide, consumption is few, and reaction process is simple, environmental protection, is easy to industrialization.
A method for diphenyl dichlorosilane chlorination, is characterized in that carrying out in the steps below:
In diphenyl dichlorosilane, add ZnCl
2, SnCl
4, ZnCl
2with SbCl
5be mixture, the SnCl of 1: 1 in molar ratio
4with SbCl
5be mixture or the FeCl of 1: 1 in molar ratio
3with SbCl
5be the mixture of 1: 1 in molar ratio, stir it is uniformly dispersed; Then pass into chlorine, under certain chlorination reaction temperature, react certain hour, tail gas condensing absorbs and removes HCl by NaOH solution.
Wherein said total catalyst levels is 0.1%～10% of diphenyl dichlorosilane mole number, wherein preferably 0.5%～5%.
Wherein said chlorine is through the dry chlorine of the vitriol oil, and chlorine flowrate is 10～25mL/min, wherein preferred 15～20mL/min.
Wherein chlorination reaction temperature is 20～100 ℃, wherein preferably 80～100 ℃.
The wherein said chlorination reaction time is 4h～18h, wherein preferred 10h～14h.
The invention has the advantages that:
1. the catalyzer source of using in the present invention is wide, cheap, consumption is few, is conducive to the industrial applications of this reaction.
2. the present invention adopts continuous gas-liquid catalytic reaction, and technical process is simple, be easy to control, reaction conditions is gentle.
3. diphenyl dichlorosilane chlorination method of the present invention is used cheap chlorine, and feed stock conversion is high, and chlorophenyl product yield is high.
4. the chlorophenyl dichlorosilane that prepared by the present invention can be prepared silicone oil high temperature resistant, that oilness is good together with other organosilane monomers, has a extensive future.
Embodiment
Be below preferred embodiment of the present invention, can understand better the present invention, but embodiments of the invention be not limited to this, shown in it, data do not represent the restriction to characteristic range of the present invention simultaneously.
Embodiment 1
In the four-hole boiling flask of 100mL, add 0.5mol diphenyl dichlorosilane, then add the anhydrous FeCl of 0.0125mol
3anhydrous SbCl with 0.0125mol
5, stir it be uniformly dispersed; Then in system, pass into through the dry chlorine of the vitriol oil, its flow is 20mL/min, at 80 ℃, reacts 14h, and tail gas condensing absorbs and removes HCl by NaOH solution; Product is by gas-mass spectrometer (Agilent GC (7890A)-MS (5975C)) qualitative analysis, gas-chromatography (GC7890, capillary column is SE-54) quantitative analysis.
Fixing total catalyst levels, changes the combination of catalyzer in chlorination reaction, and concrete data and experimental result are as shown in table 1:
The impact of table 1 composite catalyst on diphenyl dichlorosilane chlorination reaction
Experiment condition: dichloromethyl phenylsilane consumption: 0.5mol; Total catalyst consumption (accounting for material molar ratio): 5%; Chlorine flowrate: 20mL/min; Temperature of reaction: 80 ℃; Reaction times: 14h.
Table 1 has been shown with ZnCl
2, SnCl
4or FeCl
3with SbCl
5be the experimental result of this chlorination reaction of mixture through catalytic of 1: 1 in molar ratio, as can be seen from the table, in three kinds of combination catalysts, FeCl
3with SbCl
5compound catalyzer is beneficial to the carrying out of this reaction most, and the yield of chlorophenyl product can reach 79%.
Embodiment 2
In the four-hole boiling flask of 100mL, add 0.5mol diphenyl dichlorosilane, then add the anhydrous FeCl of 0.0125mol
3anhydrous SbCl with 0.0125mol
5, stir it be uniformly dispersed; Then in system, pass into through the dry chlorine of the vitriol oil, its flow is 20mL/min, at 80 ℃, react 14h, tail gas condensing absorbs and removes HCl by NaOH solution, product is by gas-mass spectrometer (Agilent GC (7890A)-MS (5975C)) qualitative analysis, gas-chromatography (GC7890, capillary column is SE-54) quantitative analysis.
Fixing FeCl in chlorination reaction catalyzer
3and SbCl
5ratio, total consumption of composite catalyst (accounting for dichloromethyl phenylsilane mole number) 5% is changed into 0.1%, 0.5% and 10%, experimental result is as shown in table 2:
The impact of table 2 catalyst levels on diphenyl dichlorosilane chlorination reaction
Experiment condition: dichloromethyl phenylsilane consumption: 0.5mol; Catalyzer is FeCl
3-SbCl
5; Chlorine flowrate: 20mL/min; Temperature of reaction: 80 ℃; Reaction times: 14h.
Along with the increase of catalyst levels, speed of reaction has the trend of increase, and the total recovery of chlorophenyl product first increases afterwards and reduces, and by product chlorobenzene class yield significantly increases.Wherein, when catalyst levels is 5%, the total recovery of chlorophenyl product can reach 79%.
Embodiment 3
In the four-hole boiling flask of 100mL, add 0.5mol diphenyl dichlorosilane, then add the anhydrous FeCl of 0.0125mol
3anhydrous AlCl with 0.0125mol
3, stir it be uniformly dispersed; Then in system, pass into through the dry chlorine of the vitriol oil, its flow is 10mL/min, at 80 ℃, react 14h, tail gas condensing absorbs and removes HCl by NaOH solution, product is by gas-mass spectrometer (Agilent GC (7890A)-MS (5975C)) qualitative analysis, gas-chromatography (GC7890, capillary column is SE-54) quantitative analysis.
The flow that changes chlorine in chlorination reaction is respectively 15mL/min, 20mL/min and 25mL/min, and experimental result is as shown in table 3:
The impact of table 3 chlorine flowrate on diphenyl dichlorosilane chlorination reaction
Experiment condition: dichloromethyl phenylsilane consumption: 0.5mol; Catalyzer: FeCl
3-SbCl
5; Total catalyst consumption (accounting for material molar ratio): 5%; ; Temperature of reaction: 80 ℃; Reaction times: 14h.
As can be seen from Table 3, chlorine flowrate has larger impact to the distribution of speed of reaction and reaction product, along with the increase of chlorine flowrate, speed of reaction increases, monochloro-benzene based products yield reduces, and dichloro-and trichloro-benzene based products yield increase, and by product chlorobenzene class yield significantly increases; Wherein, when chlorine flowrate is within the scope of 15～20mL/min, the yield of chlorophenyl product is all greater than 77%.
Embodiment 4
In the four-hole boiling flask of 100mL, add 0.5mol diphenyl dichlorosilane, then add the anhydrous FeCl of 0.0125mol
3anhydrous AlCl with 0.0125mol
3, stir it be uniformly dispersed; Then in system, pass into through the dry chlorine of the vitriol oil, its flow is 20mL/min, at 20 ℃, reacts 14h, and tail gas condensing absorbs and removes HCl by NaOH solution; Product is by gas-mass spectrometer (Agilent GC (7890A)-MS (5975C)) qualitative analysis, gas-chromatography (GC7890, capillary column is SE-54) quantitative analysis.
Change temperature in chlorination reaction and be respectively 60 ℃, 80 ℃ and 100 ℃, experimental result is as shown in table 4:
The impact of table 4 temperature of reaction on diphenyl dichlorosilane chlorination reaction
Experiment condition: dichloromethyl phenylsilane consumption: 0.5mol; Catalyzer: FeCl
3-SbCl
5; Total catalyst consumption (accounting for material molar ratio): 5%; Chlorine flowrate: 20mL/min; Reaction times: 14h.
As can be seen from Table 4, temperature of reaction has larger impact to the distribution of speed of reaction and reaction product, increase along with temperature of reaction, speed of reaction increases, one chloro and dichlorobenzene based products yield first increase rear reduction, and this is because this product more easily continues chlorination and generates many chloro-products and by product chlorobenzene under comparatively high temps; Therefore, trichloro-benzene based products and by product chlorobenzene class yield are all along with temperature of reaction increases and significantly increase.Wherein, when temperature of reaction is within the scope of 80～100 ℃, the total recovery of chlorophenyl product is all greater than 74%.
Embodiment 5
In the four-hole boiling flask of 100mL, add 0.5mol diphenyl dichlorosilane, then add the anhydrous FeCl of 0.0125mol
3anhydrous AlCl with 0.0125mol
3, stir it be uniformly dispersed; Then in system, pass into through the dry chlorine of the vitriol oil, its flow is 20mL/min, at 80 ℃, reacts 4h, and tail gas condensing absorbs and removes HCl by NaOH solution; Product is by gas-mass spectrometer (Agilent GC (7890A)-MS (5975C)) qualitative analysis, gas-chromatography (GC7890, capillary column is SE-54) quantitative analysis.
Change time of chlorinating in chlorination reaction and be respectively 10h, 14h and 18h, experimental result is as shown in table 5:
The impact of table 5 reaction times on diphenyl dichlorosilane chlorination reaction
Experiment condition: dichloromethyl phenylsilane consumption: 0.5mol; Catalyzer: FeCl
3-SbCl
5; Total catalyst consumption (accounting for material molar ratio): 5%; Chlorine flowrate: 20mL/min; Temperature of reaction: 80 ℃.
Increase along with the reaction times, feed stock conversion increases, one chloro and dichlorobenzene based products yield first increase rear reduction, this is to generate many chloro-products and by product chlorobenzene because this product continues chlorination, and trichloro-benzene based products and by product chlorobenzene class yield are all along with temperature of reaction increases and significantly increase.
Claims (14)
1. a method for diphenyl dichlorosilane chlorination, is characterized in that carrying out in the steps below: in diphenyl dichlorosilane, add ZnCl
2, SnCl
4, ZnCl
2with SbCl
5be mixture, the SnCl of 1:1 in molar ratio
4with SbCl
5be mixture or the FeCl of 1:1 in molar ratio
3with SbCl
5be in molar ratio the mixture of 1:1 as catalyzer, stir it be uniformly dispersed; Then pass into chlorine, under certain chlorination reaction temperature, react certain hour, tail gas condensing absorbs and removes HCl by NaOH solution.
2. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 1, is characterized in that: the consumption of described catalyzer is 0.1% ~ 10% of diphenyl dichlorosilane mole number.
3. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 2, is characterized in that: the consumption of described catalyzer is 0.5% ~ 5% of diphenyl dichlorosilane mole number.
4. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 3, is characterized in that: the consumption of described catalyzer is 5% of diphenyl dichlorosilane mole number.
5. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 1, is characterized in that: described chlorine is through the dry chlorine of the vitriol oil, and chlorine flowrate is 10 ~ 25 mL/min.
6. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 5, is characterized in that: the flow of described chlorine is 15 ~ 20 mL/min.
7. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 6, is characterized in that: the flow of described chlorine is 20 mL/min.
8. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 1, is characterized in that: the temperature of reaction of described chlorination is 20 ~ 100 ℃.
9. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 8, is characterized in that: the temperature of reaction of described chlorination is 80 ~ 100 ℃.
10. the method for a kind of diphenyl dichlorosilane chlorination as claimed in claim 9, is characterized in that: the temperature of reaction of described chlorination is 80 ℃.
The method of 11. a kind of diphenyl dichlorosilane chlorinations as claimed in claim 1, is characterized in that: the reaction times of described chlorination is 4 h ~ 18 h.
The method of 12. a kind of diphenyl dichlorosilane chlorinations as claimed in claim 11, is characterized in that: the reaction times of described chlorination is 10 h ~ 14 h.
The method of 13. a kind of diphenyl dichlorosilane chlorinations as claimed in claim 12, is characterized in that: the reaction times of described chlorination is 14 h.
The method of 14. a kind of diphenyl dichlorosilane chlorinations as claimed in claim 1, is characterized in that: described catalyzer is FeCl
3with SbCl
5be the mixture of 1:1 in molar ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410205967.3A CN104004011A (en) | 2014-05-16 | 2014-05-16 | Method for chlorination of diphenyl dichlorosilane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410205967.3A CN104004011A (en) | 2014-05-16 | 2014-05-16 | Method for chlorination of diphenyl dichlorosilane |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2803638A (en) * | 1954-08-18 | 1957-08-20 | Gen Electric | Method for preparing chlorophenylchlorosilanes |
| US2887503A (en) * | 1957-08-19 | 1959-05-19 | Gen Electric | Method for preparing chlorophenylchlorosilanes |
| CN102659828A (en) * | 2012-04-26 | 2012-09-12 | 江苏大学 | Method for chlorinating methyl phenyl dichloro-silane |
-
2014
- 2014-05-16 CN CN201410205967.3A patent/CN104004011A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2803638A (en) * | 1954-08-18 | 1957-08-20 | Gen Electric | Method for preparing chlorophenylchlorosilanes |
| US2887503A (en) * | 1957-08-19 | 1959-05-19 | Gen Electric | Method for preparing chlorophenylchlorosilanes |
| CN102659828A (en) * | 2012-04-26 | 2012-09-12 | 江苏大学 | Method for chlorinating methyl phenyl dichloro-silane |
Non-Patent Citations (2)
| Title |
|---|
| 管仲达: "多氯代苯基三氯硅烷的合成研究", 《浙江化工》, 31 December 2006 (2006-12-31), pages 4 - 6 * |
| 赵德明: "《有机合成工艺》", 30 June 2012, article "芳环上的取代氯化", pages: 158 * |
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Application publication date: 20140827 |