CN105198913B - Method for preparing chloromethyl trichlorosilane - Google Patents
Method for preparing chloromethyl trichlorosilane Download PDFInfo
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- CN105198913B CN105198913B CN201510659849.4A CN201510659849A CN105198913B CN 105198913 B CN105198913 B CN 105198913B CN 201510659849 A CN201510659849 A CN 201510659849A CN 105198913 B CN105198913 B CN 105198913B
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- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000460 chlorine Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 36
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000005055 methyl trichlorosilane Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 230000036632 reaction speed Effects 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims 1
- 239000011344 liquid material Substances 0.000 abstract description 7
- 238000009835 boiling Methods 0.000 abstract description 5
- 238000010992 reflux Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 4
- 239000007789 gas Substances 0.000 description 21
- 125000001309 chloro group Chemical group Cl* 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000003556 assay Methods 0.000 description 5
- 239000002826 coolant Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- BWROMPNXPAWQEP-UHFFFAOYSA-N chloro(chloromethyl)silane Chemical compound ClC[SiH2]Cl BWROMPNXPAWQEP-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- UYQUWIXWVDVROU-UHFFFAOYSA-N chloromethane chlorosilane Chemical compound ClC.Cl[SiH3] UYQUWIXWVDVROU-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention relates to a method for preparing chloromethyl trichlorosilane, belonging to the technical field of organic synthesis. The preparation method of the invention is to evaporate CH in the kettle3SiCl3Direction CH when the back flow is stable3SiCl3Introducing chlorine below the liquid level; heating the mixed gas from the evaporation kettle, and then leading the mixed gas to enter a reaction zone; white light or ultraviolet light is irradiated on the reaction area; condensing the material from the reaction zone, and refluxing the high boiling point liquid material to the heating zone; stopping the reaction when the material temperature in the evaporation kettle reaches 100-108 ℃; after the reaction is finished, closing a valve above the packed tower, directly rectifying the materials in the evaporation kettle at normal pressure, and collecting the fraction at 117-118.5 ℃ to obtain the chloromethyl trichlorosilane. In the preparation method of the invention, chlorine is introduced into CH in the evaporation kettle3SiCl3Can ensure that the chlorine and the methyltrichlorosilane are fully mixed to form uniformly mixed gas below the liquid level; at the same time, effectively control Cl2And CH3SiCl3The molar ratio of (A) to (B); thereby improving the conversion rate of the chloromethyl trichlorosilane.
Description
Technical field
The present invention relates to a kind of method for preparing chloromethyl trichlorosilane, belong to technical field of organic synthesis.
Background technology
Chloromethyl trichlorosilane is the most important raw material for preparing α-functional silane coupling agent, with（Traditional）γ-official
Energy silane coupler is compared, and α-functional silane coupling agent has the advantages that raw material is easy to get, property is active, heat resistance is preferable, has
Widely application.
Scholars synthesize ClCH to chloridising2SiCl3The trial of a variety of methods is travelled, mainly there is liquid phase method chlorination, gas
Phase method Light chlorimation, gas phase thermal chlorination etc..
When using azodiisobutyronitrile as the liquid phase method of initiator, product ClCH2SiCl3、Cl2CHSiCl3Chlorination speed
Compare CH3SiCl3It hurry up, therefore to expect the higher purpose product ClCH of purity2SiCl3, it is necessary to isolate generation in time
ClCH2SiCl3, or in CH3SiCl3Carried out under the conditions of large excess of.Initially, Gilliam et al. passes through ultra violet lamp
Under methylchlorosilane (Si (CH3)nCl4-n, n=1 ~ 3) liquid phase chlorination reaction prepares corresponding chloromethyl chlorosilane, due to must
The more chloro-products arrived are more, as a result not ideal.Reacted for liquid phase chlorination, due to that must keep certain in reaction unit
Temperature, and the reaction need a large amount of, expensive initiators, and the selectivity reacted is low, and reaction rate is considerably slower than gas phase
Method, therefore, its application are restricted.
Nearest Jin Jun et al. report (publication No.s：CN104558003 A) made with benzoyl peroxide and iron chloride mixture
For catalyst, using methyl trichlorosilane as raw material, chlorine uniformly is passed through to it, by the amount for controlling methyl trichlorosilane and chlorine
For 1:During 0.6-0.9, it may be such that the conversion ratio of methyl trichlorosilane up to 70-80%, it was reported that the selectivity of chloromethyl trichlorine
Significantly improve to 95%, the total content of more Chloromethyltrichlorosilanes<5%, but the experiment repeated according to us, conversion ratio 50%,
The content of Chloromethyltrichlorosilane is also no more than 48%, and reason of searching to the bottom is the ClCH of generation2SiCl3Occur to continue the anti-of chloro
Answer speed to be far above the chloro speed of methyl trichlorosilane with the ratio of the order of magnitude, directly contribute Cl in product3SiCl3The ratio accounted for
It is larger, and according to M, G. Voronkov report, iron chloride only has positive effect to the chloro of arylchlorosilane, to methyl
The chlorination of trichlorosilane influences little, in summary, takes liquid phase method methyl chloride chlorosilane, a chlorine product yield compared with
It is low, continue that the possibility of chloro is higher, finally give more polychloride, therefore be difficult high yield and selectivity occur.
The research of many decades shows that gas phase thermal chlorination has broad application prospects, and is to realize large-scale industry metaplasia
The best mode of production.Gas phase thermal chlorination is the radical reaction carried out at high temperature, is generated in free radical chain reaction of propagation
Chloromethyl, dichloromethyl, the reaction constant of trichloromethyl silane and activation energy be more or less the same, therefore preparing
ClCH2SiCl3When, it is necessary to use excessive CH3SiCl3.In addition, it is also necessary to isolate the one of generation from reaction zone in time
Chloromethane based products are to improve the yield of reaction.
M. G. Voronkov in 2001 et al. [M. G. Voronkov, V. K. Stankevich, B. F.
Kukharev,K. A. Abzaeva. Zhurnal Prikladnoi Khimii, 2001, 74:778-780.] in loop body
Thermal chlorination is utilized in system, is 300 ~ 400 DEG C in gas phase temperature, it is n (CH to control reaction ratio3SiCl3):n(Cl2) = (25
~ 100):In the case of 1, the higher Chloromethyltrichlorosilane of yield is obtained using chlorinated with chlorine gas phase reaction.But in this report
Thermal chlorination needs methyl trichlorosilane significantly excessive, easily causes the wasting of resources.Meanwhile reaction temperature is to the selectivity of product
Have a great influence, requirement of the high temperature to equipment is also higher.
CH3SiCl3Interval optical chlorinating reaction under light illumination is the method being widely studied, and the light source of use has ultraviolet
Light, general visible ray and various rays.1986, Russian scholar Iueva, G. Y used laser as light trigger.In gas phase
Middle chlorination CH3SiCl3, obtain the ClCH that yield is 70%2SiCl3, 1987, M. G. Voronkov et al. were anti-using hedgerow formula
Device is answered, in gas phase reaction system, obtains 65.7% chloro-product.The main function of wherein hedgerow formula reactor is by original
Material separates with product.
2001, Jiang Biao, Xie Deliang et al. were reported " method and apparatus of preparing chloromethyl chlorosilane by gas-phase chlorination "（It is public
The number of opening：CN 1317488A）, there is provided a kind of preparation method of chloromethyl chlorosilane：It is CH by molecular formula3Si(CH3)mCl3-m's
Methylchlorosilane is raw material, by Cl2Reaction zone is passed directly into, is mixed with the unstrpped gas after gasification, only by indoor general visible
Light irradiation carries out gas phase chlorination reaction, so as to obtain the chloromethyl chlorosilane of higher yields, according to report, unstrpped gas and chlorine
Mol ratio be 1：0.1 ~ 0.75, reaction temperature is 50 ~ 80 DEG C, and the reaction time is 1 ~ 24h, but the method and equipment still face
Many problems：Chlorine is directly entered reaction zone, and the amount of reactant is difficult to control；Described according to patent, a chloro-product and more chlorine
There is no distinction for product, only pursue total conversion ratio of chlorination；Reaction time is long；Necessary periodic cleaning reactor
Generated polymer is removed on surface；Reactant spontaneous combustion or blast etc. are likely to occur in some cases；After reaction terminates,
Product needs to move kettle again and does the larger rectifying separation of difficulty.
The content of the invention
The present invention provide it is a kind of it is easy to operate, accessory substance is few, cost is low and high income prepares chloromethyl trichlorosilane
Method.
Technical scheme
A kind of preparation method of chloromethyl trichlorosilane, including step are as follows：
By liquid CH3SiCl3Evaporating kettle is added, with nitrogen or inert gas by the gas displacement in reaction system；Evaporating kettle
It is heated to CH3SiCl3More than boiling point, to CH when system flows back stable3SiCl3Lead to chlorine below liquid level；To being come out from evaporating kettle
Mixed gas heated in heating zone, then make it into reaction zone, the temperature control of reaction zone is at 60-80 DEG C；To anti-
Area is answered to carry out white light or UV Light；The material come out from reaction zone is condensed, and higher boiling liquid material is back to heating zone；
Stop reaction when temperature of charge reaches 100-108 DEG C in evaporating kettle；After reaction terminates, the valve above closing packed tower, directly
Atmospheric distillation is carried out to the material in evaporating kettle, collects 117-118.5 DEG C of cut, as chloromethyl trichlorosilane；
Wherein, evaporating kettle and heating zone device are light tight, reaction zone printing opacity；
Cl used2With CH3SiCl3Mol ratio be 1:15~50
The preparation method of the present invention, the chlorine and CH come out from evaporating kettle3SiCl3Mixed gas heating zone only added
Heat, do not reacted under conditions of no illumination.Reaction zone is reached after gas is heated after mixing, is carried out under illumination condition
Reaction；The material of reaction zone includes unreacted CH3SiCl3, generation a chloro-product and hydrogen chloride.One chloro-product of generation
Boiling point be higher than 80 DEG C, be in a liquid state, it is most of to fall after rise to evaporating kettle；An a small amount of chloro-product, hydrogen chloride and unreacted
CH3SiCl3In gaseous state, into condensing unit；After condensed, not solidifying hydrogen chloride enters alkali adsorption tower, a chloro-product and not anti-
The CH answered3SiCl3Caloic occurs in packed tower upper end with the mixed gas of rising to exchange, a chloro thing is fallen after rise to heating zone,
CH3SiCl3Reaction zone is reentered in the form of a vapor.Chlorine is passed through to CH in evaporating kettle3SiCl3Liquid level below, can ensure that
Chlorine is sufficiently mixed with methyl trichlorosilane, forms well mixed mixed gas；It can effectively control Cl simultaneously2With CH3SiCl3
Mol ratio；So as to improve the conversion ratio of chloromethyl trichlorosilane.
Unreacted CH included in condensed fluid3SiCl3, when by heating zone, with the mixing come from evaporating kettle
Mass-and heat-transfer occurs for gas, reenters reaction zone reaction；And a small amount of chloro thing product in condensed fluid is by heating
Qu Shi, because the temperature of heating zone is well below its boiling point, still it can not be vaporized after carrying out heat exchange, but be back to evaporating kettle
In.Therefore, condensed fluid is when by heating zone, unreacted CH therein3SiCl3And one carried out between chloro thing product
Efficiently separate.If the heating stepses, condensed fluid are not directly entered evaporating kettle, wherein unreacted CH3SiCl3Can be with steaming
Azeotropic mixture is formed between a chloro thing product in hair kettle, the difficulty for continuing reaction is added, so as to cause the reaction time
Extend.In addition, the setting of heating stepses, can be effectively ensured the temperature control of reaction zone at 66 DEG C or so.
The above method, it is preferred that the device of heating zone is the outside rectifying column for being provided with zone of heating, and the number of plates of rectifying column is
9~15.The product of the present invention is extremely toxic substance, and is easily reacted with the water in air.In the prior art, reaction knot
Need to move kettle after beam, reenter separator；In this operating process, the careless slightly danger that toxic products leakage will occur
Danger.When heating zone device is changed into the rectifying column in the present invention, react after terminating, the valve that can be closed above rectifying column, directly
Connect and distillation operation is carried out to the material heating in evaporating kettle；So as to greatly reduce hazardous material situations danger occurrence probability,
So that operation is simpler, artificial, time cost is reduced.
The above method, it is preferred that reaction zone temperature is 66 DEG C.
Beneficial effect
1st, the high conversion rate of chlorination, the content of chloromethyl trichlorosilane is high in product；
2nd, the required reaction time is short；Reduce the dosage of chlorine；
3rd, simple to operate, dangerous reduction；
4th, production cost reduces.
Brief description of the drawings
Fig. 1 is a kind of structural representation of device used in the method for the present invention；
In figure, 1, chlorine cylinder, 2, surge tank, 3, current meter, 4, evaporating kettle, 5, rectifying column, 6, reactor, 7, condensation
Device, 8, caustic wash tower, 9, finished pot, 10, heater.
Embodiment
Embodiment 1
Gas phase chlorination reaction unit is as shown in figure 1, the top of evaporating kettle 4 connection rectifying column 5（The number of plates is 9-15）, rectifying column
The reactor 6 of 5 top connection simple glass materials, the connection condensation of reactor 6 fill 7 and put, and the return duct of condensing unit 7 is connected to essence
Evaporate the top of tower 5；Wherein evaporating kettle 4, rectifying column 5 are covered with light-proof material.The outer surface of rectifying column 5 sets heater 10.
500 W incandescent lamp is irradiated to reactor 6.In advance by reflux condensate device 10, it is not necessary to cooling medium.Cl2With methyl
The mol ratio of trichlorosilane is 1:15（Cl2Refer to 5kg methyl trichlorosilanes and the chlorine being passed through with the mol ratio of methyl trichlorosilane
The mol ratio of the total amount of gas；Similarly hereinafter）.5kg methyl trichlorosilanes are added in evaporating kettle 4, electromagnetic agitation are opened, to evaporating kettle 4
Heated, while open the heater 10 of rectifying column 5；When system flows back stable, the chlorine of chlorine cylinder 1 is slowly opened
Valve, chlorine is set to be passed through by surge tank 2 below methyl trichlorosilane liquid level；The firing rate of evaporating kettle 4 is controlled, makes backflow moderate,
Current meter 3 is adjusted simultaneously and controls chlorine flowrate, reaction speed excessively acutely, is not controlled the firing rate of heater 10,
The temperature for making reactor 6 is 66 DEG C.The liquid material flowed out from condensing unit 7 flows into rectifying column 5, is come out from condensing unit 7
Gaseous materials enter caustic wash tower 8.With the progress of chlorination reaction, the temperature in evaporating kettle 4 can be raised constantly, in kettle 4 to be evaporated
Temperature is increased to stop reaction at 100 DEG C.Sampling analysis, ClCH in material in evaporating kettle 42SiCl3Amount product composition in account for
75.11%, ClCH2SiCl3Conversion ratio be 76.89%
Atmospheric distillation, less than 117 DEG C cut recoveries are carried out to the material in evaporating kettle 4；Collect 117-118.5 DEG C
Cut is that product chloromethyl trichlorosilane enters finished pot 9, and GC purity assays are 98.6%；More than 118.5 DEG C cuts are more
Chloro accessory substance.
Embodiment 2
Gas phase chlorination reaction unit is as shown in figure 1, connection rectifying column, rectifying column top connect simple glass above evaporating kettle
The reactor of material, reactor connection condensing unit, the return duct of condensing unit are connected to rectifier；Wherein evaporating kettle,
Rectifying column is covered with light-proof material.Rectifying column outer surface sets heating assembling device.500 W uviol lamp is carried out to reactor
Irradiation.The cooling system of returned cold coagulation zone is opened in advance, it is not necessary to cooling medium.Cl2With the mol ratio of methyl trichlorosilane
For 1:20.5kg methyl trichlorosilanes are added in evaporating kettle, electromagnetic agitation is opened, evaporating kettle is heated, while open essence
Evaporate the heater of tower；When system flows back stable, slowly open chlorine valve, make chlorine be passed through methyl trichlorosilane liquid level with
Under；Evaporating kettle firing rate is controlled, makes backflow moderate, while controls chlorine flowrate, makes reaction speed should not excessively acutely, control
The firing rate of heater, the temperature for making reactor are 66 DEG C.Rectifying column is flowed into from the liquid material of condensing unit outflow, from
The Gaseous materials that condensing unit comes out enter caustic wash tower.With the progress of chlorination reaction, the temperature in evaporating kettle can be raised constantly,
Stop reaction when temperature in the kettle is increased to 100 DEG C.Sampling analysis, ClCH in material in evaporating kettle2SiCl3Amount in product group
79.11%, ClCH is accounted in2SiCl3Conversion ratio be 80.11%.
Air-distillation, less than 117 DEG C cut recoveries are carried out to the material in evaporating kettle；Collect 117-118.5 DEG C
Cut is product Chloromethyltrichlorosilane, and GC purity assays are 97.8%；More than 118.5 DEG C cuts are more chloro accessory substances.
Embodiment 3
Gas phase chlorination reaction unit is as shown in figure 1, connection rectifying column, rectifying column top connect simple glass above evaporating kettle
The reactor of material, reactor connection condensing unit, the return duct of condensing unit are connected to rectifier；Wherein evaporating kettle,
Rectifying column is covered with light-proof material.Rectifying column outer surface sets heating assembling device.500 W incandescent lamp is carried out to reactor
Irradiation.The cooling system of returned cold coagulation zone is opened in advance, it is not necessary to cooling medium.Cl2With the mol ratio of methyl trichlorosilane
For 1:25.5kg methyl trichlorosilanes are added in evaporating kettle, electromagnetic agitation is opened, evaporating kettle is heated, while open essence
Evaporate the heater of tower；When system flows back stable, slowly open chlorine valve, make chlorine be passed through methyl trichlorosilane liquid level with
Under；Evaporating kettle firing rate is controlled, makes backflow moderate, while controls chlorine flowrate, makes reaction speed should not excessively acutely, control
The firing rate of heater, the temperature for making reactor are 66 DEG C.Rectifying column is flowed into from the liquid material of condensing unit outflow, from
The Gaseous materials that condensing unit comes out enter caustic wash tower.With the progress of chlorination reaction, the temperature in evaporating kettle can be raised constantly,
Stop reaction when temperature in the kettle is increased to 100 DEG C.Sampling analysis, ClCH in material in evaporating kettle2SiCl3Amount in product group
77.11%, ClCH is accounted in2SiCl3Conversion ratio be 79.55%.
Air-distillation, less than 117 DEG C cut recoveries are carried out to the material in evaporating kettle；Collect 117-118.5 DEG C
Cut is product Chloromethyltrichlorosilane, and GC purity assays are 97.8%；More than 118.5 DEG C cuts are more chloro accessory substances.
Embodiment 4
Gas phase chlorination reaction unit is as shown in figure 1, connection rectifying column, rectifying column top connect simple glass above evaporating kettle
The reactor of material, reactor connection condensing unit, the return duct of condensing unit are connected to rectifier；Wherein evaporating kettle,
Rectifying column is covered with light-proof material.Rectifying column outer surface sets heating assembling device.500 W uviol lamp is carried out to reactor
Irradiation.The cooling system of returned cold coagulation zone is opened in advance, it is not necessary to cooling medium.Cl2With the mol ratio of methyl trichlorosilane
For 1:50,5kg methyl trichlorosilanes are added in evaporating kettle, electromagnetic agitation is opened, evaporating kettle is heated, while open essence
Evaporate the heater of tower；When system flows back stable, slowly open chlorine valve, make chlorine be passed through methyl trichlorosilane liquid level with
Under；Evaporating kettle firing rate is controlled, makes backflow moderate, while controls chlorine flowrate, makes reaction speed should not excessively acutely, control
The firing rate of heater, the temperature for making reactor are 66 DEG C.Rectifying column is flowed into from the liquid material of condensing unit outflow, from
The Gaseous materials that condensing unit comes out enter caustic wash tower.With the progress of chlorination reaction, the temperature in evaporating kettle can be raised constantly,
Stop reaction when temperature in the kettle is increased to 100 DEG C.Sampling analysis, ClCH in material in evaporating kettle2SiCl3Amount in product group
82.11%, ClCH is accounted in2SiCl3Conversion ratio be 80.36%.
Air-distillation, less than 117 DEG C cut recoveries are carried out to the material in evaporating kettle；Collect 117-118.5 DEG C
Cut is product Chloromethyltrichlorosilane, and GC purity assays are 97.8%；More than 118.5 DEG C cuts are more chloro accessory substances.
Embodiment 5
Gas phase chlorination reaction unit is as shown in figure 1, connection rectifying column, rectifying column top connect simple glass above evaporating kettle
The reactor of material, reactor connection condensing unit, the return duct of condensing unit are connected to rectifier；Wherein evaporating kettle,
Rectifying column is covered with light-proof material.Rectifying column outer surface sets heating assembling device.500 W uviol lamp is carried out to reactor
Irradiation.The cooling system of returned cold coagulation zone is opened in advance, it is not necessary to cooling medium.Cl2With the mol ratio of methyl trichlorosilane
For 1:20.5kg methyl trichlorosilanes are added in evaporating kettle, electromagnetic agitation is opened, evaporating kettle is heated, while open essence
Evaporate the heater of tower；When system flows back stable, slowly open chlorine valve, make chlorine be passed through methyl trichlorosilane liquid level with
Under；Evaporating kettle firing rate is controlled, makes backflow moderate, while controls chlorine flowrate, makes reaction speed should not excessively acutely, control
The firing rate of heater, the temperature for making reactor are 66 DEG C.Rectifying column is flowed into from the liquid material of condensing unit outflow, from
The Gaseous materials that condensing unit comes out enter caustic wash tower.With the progress of chlorination reaction, the temperature in evaporating kettle can be raised constantly,
Stop reaction when temperature in the kettle is increased to 108 DEG C.Sampling analysis, ClCH in material in evaporating kettle2SiCl3Amount in product group
82.5%, ClCH is accounted in2SiCl3Conversion ratio be 84.3%.
Air-distillation, less than 117 DEG C cut recoveries are carried out to the material in evaporating kettle；Collect 117-118.5 DEG C
Cut is product Chloromethyltrichlorosilane, and GC purity assays are 97.8%；More than 118.5 DEG C cuts are more chloro accessory substances.
Claims (2)
- A kind of 1. preparation method of chloromethyl trichlorosilane, it is characterised in that evaporating kettle in gas phase chlorination reaction unit（4）On Side's connection rectifying column（5）, rectifying column（5）Top connects the reactor of simple glass material（6）, reactor（6）Connection condensation dress Put（7）, condensing unit（7）Return duct be connected to rectifying column（5）Top；Wherein evaporating kettle（4）, rectifying column（5）With impermeable Luminescent material covers；Rectifying column（5）Outer surface sets heater（10）, with incandescent lamp to reactor（6）It is irradiated；Cl2Mol ratio with methyl trichlorosilane is 1:15, methyl trichlorosilane is added into evaporating kettle（4）In, open electromagnetism and stir Mix, to evaporating kettle（4）Heated, while open rectifying column（5）Heater（10）；When system flows back stable, slowly Open chlorine cylinder（1）Chlorine valve, chlorine is passed through surge tank（2）It is passed through below methyl trichlorosilane liquid level；Control evaporating kettle （4）Firing rate, make backflow moderate, while adjust current meter（3）Chlorine flowrate is controlled, makes reaction speed excessively violent, Control heater（10）Firing rate, make reactor（6）Temperature be 66 DEG C；From condensing unit（7）The liquid object of outflow Stream enters rectifying column（5）, from condensing unit（7）Gaseous materials out enter caustic wash tower（8）；With the progress of chlorination reaction, Evaporating kettle（4）Interior temperature can be raised constantly, kettle to be evaporated（4）Interior temperature is increased to stop reaction at 100 DEG C；After reaction terminates, rectifying column is closed（5）The valve of top, directly to evaporating kettle（4）Interior material heating carries out rectifying behaviour Make；To evaporating kettle（4）Interior material carries out atmospheric distillation, less than 117 DEG C cut recoveries；Collect 117-118.5 DEG C Cut is that product chloromethyl trichlorosilane enters finished pot（9）.
- 2. according to the method for claim 1, it is characterised in that the number of plates of rectifying column is 9-15.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1317488A (en) * | 2001-03-16 | 2001-10-17 | 中国科学院上海有机化学研究所 | Process and equipment for preparing chloromethyl chlorosilane by gas-phase chlorination |
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| CN1317488A (en) * | 2001-03-16 | 2001-10-17 | 中国科学院上海有机化学研究所 | Process and equipment for preparing chloromethyl chlorosilane by gas-phase chlorination |
Non-Patent Citations (1)
| Title |
|---|
| 光氯化合成ClCH2SiCl3的研究;王明成;《中国优秀硕士学位论文全文数据库》;20050615;第17页3.4节，第16页图，第44-45页，第49页表20，第50页，第53页第2节 * |
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