CN105198913A - Method for preparing chloromethyl trichlorosilane - Google Patents
Method for preparing chloromethyl trichlorosilane Download PDFInfo
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- CN105198913A CN105198913A CN201510659849.4A CN201510659849A CN105198913A CN 105198913 A CN105198913 A CN 105198913A CN 201510659849 A CN201510659849 A CN 201510659849A CN 105198913 A CN105198913 A CN 105198913A
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- reaction
- sicl
- evaporating kettle
- zone
- heating
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- 238000000034 method Methods 0.000 title claims abstract description 24
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000000460 chlorine Substances 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000011344 liquid material Substances 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 abstract description 26
- 239000005055 methyl trichlorosilane Substances 0.000 abstract description 25
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 4
- 239000000047 product Substances 0.000 description 29
- 238000005660 chlorination reaction Methods 0.000 description 27
- 239000012071 phase Substances 0.000 description 12
- 125000001309 chloro group Chemical group Cl* 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000003556 assay Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 208000006278 hypochromic anemia Diseases 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000009466 transformation Effects 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
- 230000008569 process Effects 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 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
- 238000005286 illumination Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 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
- 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
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 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
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- 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 temperature of the materials 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 to (B); thereby improving the conversion rate of the chloromethyl trichlorosilane.
Description
Technical field
The present invention relates to a kind of method preparing chloromethyl trichlorosilane, belong to technical field of organic synthesis.
Background technology
Chloromethyl trichlorosilane is the most important raw material of preparation α-functional silane coupling agent, compared with (traditional) γ-functional silane coupling agent, α-functional silane coupling agent has the advantages such as raw material is easy to get, character is active, thermotolerance is better, has and apply widely.
Scholars synthesizes ClCH to chlorination process
2siCl
3travel the trial of multiple method, mainly contain liquid phase method chlorination, vapor phase process Light chlorimation, gas phase thermal chlorination etc.
When adopting Diisopropyl azodicarboxylate to be the liquid phase method of initiator, product C lCH
2siCl
3, Cl
2cHSiCl
3chlorination speed compare CH
3siCl
3hurry up, therefore will expect the object product C lCH that purity is higher
2siCl
3, the ClCH of generation must be isolated in time
2siCl
3, or at CH
3siCl
3carry out under greatly excessive condition.At first, the people such as Gilliam is by the methyl chlorosilane (Si (CH under ultra violet lamp
3)
ncl
4-n, n=1 ~ 3) liquid phase chlorination reaction preparation corresponding chloromethyl chlorosilane, because the many chloro-products obtained are more, result is not ideal.For liquid phase chlorination reaction, due to certain temperature must be kept in reaction unit, and the initiator that this reaction needed is a large amount of, expensive, and the selectivity of reaction is low, and speed of reaction is considerably slower than vapor phase process, and therefore, its application is restricted.
The people such as nearest Jin Jun report (publication No.: CN104558003A) is using benzoyl peroxide and iron chloride mixture as catalyzer, take METHYL TRICHLORO SILANE as raw material, evenly chlorine is passed into it, when being 1:0.6-0.9 by controlling the amount of METHYL TRICHLORO SILANE and chlorine, the transformation efficiency of METHYL TRICHLORO SILANE can be made to reach 70-80%, it is reported, the selectivity of chloromethyl trichlorine significantly improves 95%, the total content <5% of many Chloromethyltrichlorosilanes, but according to the experiment that we repeat, transformation efficiency is 50%, the content of Chloromethyltrichlorosilane is also no more than 48%, reason of searching to the bottom is the ClCH generated
2siCl
3the speed of reaction that continuation chloro occurs, with the chloro speed of the ratio of the order of magnitude far above METHYL TRICHLORO SILANE, directly causes Cl in product
3siCl
3what account for is larger, and according to M, the report of G.Voronkov, iron(ic) chloride only has positive effect to the chloro of arylchlorosilane, little on the chlorination impact of METHYL TRICHLORO SILANE, in sum, take liquid phase method methyl chloride chlorosilane, a chlorine product yield is lower, and the possibility continuing chloro is higher, finally obtain more polychloride, be therefore difficult to occur high yield and selectivity.
The research of many decades shows, gas phase thermal chlorination has broad application prospects, and is the best mode realizing large-scale industrial production.Gas phase thermal chlorination is the free radical reaction of at high temperature carrying out, and reaction constant and the activation energy of the chloromethyl generated in free radical chain reaction of propagation, dichloromethyl, trichloromethyl silane are more or less the same, therefore at preparation ClCH
2siCl
3time, excessive CH must be used
3siCl
3.In addition, also need the chloromethyl product isolating generation in time from reaction zone to improve the yield of reaction.
People [the M.G.Voronkov such as calendar year 2001 M.G.Voronkov, V.K.Stankevich, B.F.Kukharev, K.A.Abzaeva.ZhurnalPrikladnoiKhimii, 2001,74:778-780.] in circulating system, utilize thermal chlorination, being 300 ~ 400 DEG C at gas phase temperature, controlling reaction than being n (CH
3siCl
3): n (Cl
2)=(25 ~ 100): when 1, adopt chlorinated with chlorine gas-phase reaction to obtain the higher Chloromethyltrichlorosilane of productive rate.But in this report, thermal chlorination needs METHYL TRICHLORO SILANE greatly excessive, easily causes the wasting of resources.Meanwhile, the selectivity impact of temperature of reaction on product is comparatively large, and high temperature is also higher to the requirement of equipment.
CH
3siCl
3intermittent light chlorination reaction is under light illumination the method be widely studied, and the light source of employing has UV-light, general visible ray and various ray.1986, Russian scholar Iueva, G.Y adopted laser to be light trigger.Chlorination CH in the gas phase
3siCl
3, obtain the ClCH that yield is 70%
2siCl
3, 1987, the people such as M.G.Voronkov adopted hedgerow formula reactor, in gas-phase reaction system, obtained a chloro-product of 65.7%.Wherein the Main Function of hedgerow formula reactor is by raw material and product separation.
Calendar year 2001, the people such as Jiang Biao, Xie Deliang report " method and apparatus of preparing chloromethyl chlorosilane by gas-phase chlorination " (publication number: CN1317488A), provide a kind of preparation method of chloromethyl chlorosilane: be CH by molecular formula
3si (CH
3)
mcl
3-mmethyl chlorosilane be raw material, by Cl
2directly pass into reaction zone, mix with the unstripped gas after gasification, only carry out gas phase chlorination reaction by indoor general radiation of visible light, thus obtain the chloromethyl chlorosilane of higher yields, according to report, the mol ratio of unstripped gas and chlorine is 1:0.1 ~ 0.75, temperature of reaction is 50 ~ 80 DEG C, reaction times is 1 ~ 24h, but this method and equipment are still faced with a lot of problem: chlorine directly enters reaction zone, and the amount of reactant is wayward; Describe according to patent, a chloro-product and many chloro-products do not have distinction, only pursue total transformation efficiency of chlorination; Reaction times is long; The surface of routine cleaning reactor must remove generated polymkeric substance; Likely reactants occur spontaneous combustion or blast etc. in some cases; After reaction terminates, product needs again to move still and does the larger rectifying separation of difficulty.
Summary of the invention
The invention provides a kind of easy and simple to handle, by product is few, cost is low and the method preparing chloromethyl trichlorosilane that yield is high.
Technical scheme
A preparation method for chloromethyl trichlorosilane, comprises step as follows:
By liquid CH
3siCl
3add evaporating kettle, with nitrogen or rare gas element by the gas displacement in reaction system; Evaporating kettle is heated to CH
3siCl
3more than boiling point, to CH when system reflux stabilizes
3siCl
3logical chlorine below liquid level; Heat in heating zone from evaporating kettle mixed gas out, then make it enter reaction zone, the temperature of reaction zone controls at 60-80 DEG C; White light or UV Light are carried out to reaction zone; From reaction zone, material is out through condensation, and high boiling point liquid material is back to heating zone; The stopped reaction when temperature of charge in evaporating kettle reaches 100-108 DEG C; After reaction terminates, close the valve above packing tower, directly atmospheric distillation is carried out to the material in evaporating kettle, collect 117-118.5 DEG C of cut, be chloromethyl trichlorosilane;
Wherein, evaporating kettle and heating zone device all light tight, reaction zone printing opacity;
Cl used
2with CH
3siCl
3mol ratio be 1:15 ~ 50
Preparation method of the present invention, from evaporating kettle chlorine out and CH
3siCl
3mixed gas only heated in heating zone, do not react under the condition not having illumination.After mixing, gas arrives reaction zone after heating, reacts under illumination condition; The material of reaction zone comprises unreacted CH
3siCl
3, generate a chloro-product and hydrogenchloride.The boiling point of the chloro-product generated, higher than 80 DEG C, is in a liquid state, and major part falls after rise in evaporating kettle; A small amount of a chloro-product, hydrogenchloride and unreacted CH
3siCl
3in gaseous state, enter condensing works; After condensation, not solidifying hydrogenchloride enters Alkali absorption tower, a chloro-product and unreacted CH
3siCl
3in packing tower upper end, caloic occurs with the mixed gas risen to exchange, a chloro thing falls after rise to heating zone, CH
3siCl
3reenter reaction zone in the form of a vapor.Chlorine passes into CH to evaporating kettle
3siCl
3liquid level below, can guarantee that chlorine fully mixes with METHYL TRICHLORO SILANE, form the mixed gas that mixes; Simultaneously can effective control Cl
2with CH
3siCl
3mol ratio; Thus improve the transformation efficiency of chloromethyl trichlorosilane.
The unreacted CH comprised in condensed fluid
3siCl
3, through heating zone, with the mixed gas generation mass-and heat-transfer come from evaporating kettle, reenter reaction zone reaction; And a small amount of chloro produce thing in condensed fluid is through heating zone, because the temperature of heating zone is well below its boiling point, still cannot vaporizes after carrying out heat exchange, but be back in evaporating kettle.Therefore, condensed fluid through heating zone, unreacted CH wherein
3siCl
3with one has carried out effective separation between chloro produce thing.If not this heating steps, condensed fluid directly enters evaporating kettle, wherein unreacted CH
3siCl
3form azeotropic mixture between a chloro produce thing in meeting and evaporating kettle, add the difficulty continuing reaction, thus cause the reaction times to extend.In addition, the setting of heating steps, effectively can ensure that the temperature of reaction zone controls at about 66 DEG C.
Aforesaid method, preferably, the device of heating zone is the rectifying tower that outside is provided with zone of heating, and the stage number of rectifying tower is 9 ~ 15.Product of the present invention is highly toxic substance, and very easily reacts with the water in air.In the prior art, reaction needs to move still, reenter tripping device after terminating; In this operating process, the careless slightly danger that toxic products will occur and leak.When becoming the rectifying tower in the present invention when heating zone device, after reaction terminates, the valve above rectifying tower can be closed, directly distillation operation is carried out to the heating material in evaporating kettle; Thus greatly reduce the dangerous occurrence probability of hazardous material situations, also make operation more simple, reduce artificial, time cost.
Aforesaid method, preferably, reaction zone temperature is 66 DEG C.
Beneficial effect
1, the transformation efficiency of chlorination is high, and in product, the content of chloromethyl trichlorosilane is high;
2, the required reaction times is short; Reduce the consumption of chlorine;
3, simple to operate, dangerous reduction;
4, production cost reduces.
Accompanying drawing explanation
Fig. 1 is the structural representation of method of the present invention a kind of device used;
In figure, 1, chlorine cylinder, 2, surge tank, 3, velocimeter, 4, evaporating kettle, 5, rectifying tower, 6, reactor, 7, condensing works, 8, soda-wash tower, 9, finished pot, 10, heating unit.
Embodiment
embodiment 1
As shown in Figure 1, connect rectifying tower 5(stage number above evaporating kettle 4 is 9-15 to gas phase chlorination reaction unit), connect the reactor 6 of simple glass material above rectifying tower 5, reactor 6 connects condensation and fills 7 and put, and the return line of condensing works 7 is connected to rectifying tower 5 top; Wherein evaporating kettle 4, rectifying tower 5 all cover with light-proof material.Rectifying tower 5 outside surface arranges heating unit 10.The incandescent light of 500W irradiates reactor 6.In advance by reflux condensate device 10, do not need heat-eliminating medium.Cl
2be 1:15(Cl with the mol ratio of METHYL TRICHLORO SILANE
2the mol ratio of the total amount of chlorine referring to 5kg METHYL TRICHLORO SILANE with the mol ratio of METHYL TRICHLORO SILANE and pass into; Lower same).5kg METHYL TRICHLORO SILANE is added in evaporating kettle 4, open induction stirring, evaporating kettle 4 is heated, opens the heating unit 10 of rectifying tower 5 simultaneously; When system reflux stabilizes, slowly open the chlorine valve of chlorine cylinder 1, make chlorine pass into below METHYL TRICHLORO SILANE liquid level through surge tank 2; Control evaporating kettle 4 rate of heating, make backflow moderate, adjust velocimeter 3 simultaneously and control chlorine flowrate, make speed of response too inviolent, control the rate of heating of heating unit 10, make the temperature of reactor 6 be 66 DEG C.The liquid material flowed out from condensing works 7 flows into rectifying tower 5, enters soda-wash tower 8 from condensing works 7 Gaseous materials out.Along with the carrying out of chlorination reaction, temperature in evaporating kettle 4 can constantly raise, stopped reaction when temperature is increased to 100 DEG C in still 4 to be evaporated.Sampling analysis, ClCH in material in evaporating kettle 4
2siCl
3amount product composition in account for 75.11%, ClCH
2siCl
3transformation efficiency be 76.89%
Atmospheric distillation is carried out to the material in evaporating kettle 4, is less than 117 DEG C of cut recoveries; Collecting 117-118.5 DEG C of cut is that to enter finished pot 9, GC purity assay be 98.6% to product chloromethyl trichlorosilane; Being greater than 118.5 DEG C of cuts is many chloros by product.
embodiment 2
Gas phase chlorination reaction unit as shown in Figure 1, connects rectifying tower above evaporating kettle, connects the reactor of simple glass material above rectifying tower, and reactor connects condensing works, and the return line of condensing works is connected to rectifier; Wherein evaporating kettle, rectifying tower all cover with light-proof material.Rectifying tower outside surface arranges and adds hot charging device.The ultraviolet lamp of 500W irradiates reactor.In advance the cooling system of returned cold coagulation zone is opened, do not need heat-eliminating medium.Cl
2be 1:20 with the mol ratio of METHYL TRICHLORO SILANE.5kg METHYL TRICHLORO SILANE is added in evaporating kettle, opens induction stirring, evaporating kettle is heated, opens the heating unit of rectifying tower simultaneously; When system reflux stabilizes, slowly open chlorine valve, make chlorine pass into below METHYL TRICHLORO SILANE liquid level; Control evaporating kettle rate of heating, make backflow moderate, control chlorine flowrate simultaneously, make speed of response too inviolent, control the rate of heating of heating unit, make the temperature of reactor be 66 DEG C.The liquid material flowed out from condensing works flows into rectifying tower, enters soda-wash tower from condensing works Gaseous materials out.Along with the carrying out of chlorination reaction, temperature in evaporating kettle can constantly raise, stopped reaction when temperature in the kettle is increased to 100 DEG C.Sampling analysis, ClCH in material in evaporating kettle
2siCl
3amount product composition in account for 79.11%, ClCH
2siCl
3transformation efficiency be 80.11%.
Air distillation is carried out to the material in evaporating kettle, is less than 117 DEG C of cut recoveries; Collecting 117-118.5 DEG C of cut is product Chloromethyltrichlorosilane, and GC purity assay is 97.8%; Being greater than 118.5 DEG C of cuts is many chloros by product.
embodiment 3
Gas phase chlorination reaction unit as shown in Figure 1, connects rectifying tower above evaporating kettle, connects the reactor of simple glass material above rectifying tower, and reactor connects condensing works, and the return line of condensing works is connected to rectifier; Wherein evaporating kettle, rectifying tower all cover with light-proof material.Rectifying tower outside surface arranges and adds hot charging device.The incandescent light of 500W irradiates reactor.In advance the cooling system of returned cold coagulation zone is opened, do not need heat-eliminating medium.Cl
2be 1:25 with the mol ratio of METHYL TRICHLORO SILANE.5kg METHYL TRICHLORO SILANE is added in evaporating kettle, opens induction stirring, evaporating kettle is heated, opens the heating unit of rectifying tower simultaneously; When system reflux stabilizes, slowly open chlorine valve, make chlorine pass into below METHYL TRICHLORO SILANE liquid level; Control evaporating kettle rate of heating, make backflow moderate, control chlorine flowrate simultaneously, make speed of response too inviolent, control the rate of heating of heating unit, make the temperature of reactor be 66 DEG C.The liquid material flowed out from condensing works flows into rectifying tower, enters soda-wash tower from condensing works Gaseous materials out.Along with the carrying out of chlorination reaction, temperature in evaporating kettle can constantly raise, stopped reaction when temperature in the kettle is increased to 100 DEG C.Sampling analysis, ClCH in material in evaporating kettle
2siCl
3amount product composition in account for 77.11%, ClCH
2siCl
3transformation efficiency be 79.55%.
Air distillation is carried out to the material in evaporating kettle, is less than 117 DEG C of cut recoveries; Collecting 117-118.5 DEG C of cut is product Chloromethyltrichlorosilane, and GC purity assay is 97.8%; Being greater than 118.5 DEG C of cuts is many chloros by product.
embodiment 4
Gas phase chlorination reaction unit as shown in Figure 1, connects rectifying tower above evaporating kettle, connects the reactor of simple glass material above rectifying tower, and reactor connects condensing works, and the return line of condensing works is connected to rectifier; Wherein evaporating kettle, rectifying tower all cover with light-proof material.Rectifying tower outside surface arranges and adds hot charging device.The ultraviolet lamp of 500W irradiates reactor.In advance the cooling system of returned cold coagulation zone is opened, do not need heat-eliminating medium.Cl
2be 1:50 with the mol ratio of METHYL TRICHLORO SILANE, 5kg METHYL TRICHLORO SILANE is added in evaporating kettle, open induction stirring, evaporating kettle is heated, opens the heating unit of rectifying tower simultaneously; When system reflux stabilizes, slowly open chlorine valve, make chlorine pass into below METHYL TRICHLORO SILANE liquid level; Control evaporating kettle rate of heating, make backflow moderate, control chlorine flowrate simultaneously, make speed of response too inviolent, control the rate of heating of heating unit, make the temperature of reactor be 66 DEG C.The liquid material flowed out from condensing works flows into rectifying tower, enters soda-wash tower from condensing works Gaseous materials out.Along with the carrying out of chlorination reaction, temperature in evaporating kettle can constantly raise, stopped reaction when temperature in the kettle is increased to 100 DEG C.Sampling analysis, ClCH in material in evaporating kettle
2siCl
3amount product composition in account for 82.11%, ClCH
2siCl
3transformation efficiency be 80.36%.
Air distillation is carried out to the material in evaporating kettle, is less than 117 DEG C of cut recoveries; Collecting 117-118.5 DEG C of cut is product Chloromethyltrichlorosilane, and GC purity assay is 97.8%; Being greater than 118.5 DEG C of cuts is many chloros by product.
embodiment 5
Gas phase chlorination reaction unit as shown in Figure 1, connects rectifying tower above evaporating kettle, connects the reactor of simple glass material above rectifying tower, and reactor connects condensing works, and the return line of condensing works is connected to rectifier; Wherein evaporating kettle, rectifying tower all cover with light-proof material.Rectifying tower outside surface arranges and adds hot charging device.The ultraviolet lamp of 500W irradiates reactor.In advance the cooling system of returned cold coagulation zone is opened, do not need heat-eliminating medium.Cl
2be 1:20 with the mol ratio of METHYL TRICHLORO SILANE.5kg METHYL TRICHLORO SILANE is added in evaporating kettle, opens induction stirring, evaporating kettle is heated, opens the heating unit of rectifying tower simultaneously; When system reflux stabilizes, slowly open chlorine valve, make chlorine pass into below METHYL TRICHLORO SILANE liquid level; Control evaporating kettle rate of heating, make backflow moderate, control chlorine flowrate simultaneously, make speed of response too inviolent, control the rate of heating of heating unit, make the temperature of reactor be 66 DEG C.The liquid material flowed out from condensing works flows into rectifying tower, enters soda-wash tower from condensing works Gaseous materials out.Along with the carrying out of chlorination reaction, temperature in evaporating kettle can constantly raise, stopped reaction when temperature in the kettle is increased to 108 DEG C.Sampling analysis, ClCH in material in evaporating kettle
2siCl
3amount product composition in account for 82.5%, ClCH
2siCl
3transformation efficiency be 84.3%.
Air distillation is carried out to the material in evaporating kettle, is less than 117 DEG C of cut recoveries; Collecting 117-118.5 DEG C of cut is product Chloromethyltrichlorosilane, and GC purity assay is 97.8%; Being greater than 118.5 DEG C of cuts is many chloros by product.
Claims (6)
1. a preparation method for chloromethyl trichlorosilane, is characterized in that, comprises step as follows:
By liquid CH
3siCl
3add evaporating kettle, with nitrogen or rare gas element by the gas displacement in reaction system; Evaporating kettle is heated to CH
3siCl
3more than boiling point, to CH when system reflux stabilizes
3siCl
3logical chlorine below liquid level; Heat in heating zone from evaporating kettle mixed gas out, then make it enter reaction zone, the temperature of reaction zone controls at 60-80 DEG C; White light or UV Light are carried out to reaction zone; From reaction zone, material is out through condensation, and liquid material is back to heating zone; The stopped reaction when temperature of charge in evaporating kettle reaches 100-108 DEG C; After reaction terminates, collect 117-118.5 DEG C of cut, be chloromethyl trichlorosilane;
Wherein, evaporating kettle and heating zone device all light tight, reaction zone printing opacity;
Cl used
2with CH
3siCl
3mol ratio be 1:15 ~ 50.
2. method according to claim 1, is characterized in that, the device of heating zone is the rectifying tower that outside is provided with zone of heating.
3. method according to claim 2, is characterized in that, the stage number of rectifying tower is 9 ~ 15.
4. method according to claim 1, is characterized in that, Cl used
2with CH
3siCl
3mol ratio be: 1:20 or 1:25.
5. the method according to claim 1,2,3 or 4, is characterized in that, reaction zone temperature is 66 DEG C.
6. method according to claim 5, is characterized in that, the stopped reaction when temperature of charge in evaporating kettle reaches 100 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957330A (en) * | 2016-01-08 | 2017-07-18 | 溧阳市智行新材料有限公司 | A kind of method that chlorination rectification process prepares chloromethyl trichlorosilane |
| CN109678194A (en) * | 2019-01-09 | 2019-04-26 | 中国原子能科学研究院 | A kind of ceria chloridizing unit |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-10-14 CN CN201510659849.4A patent/CN105198913B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| 王明成: "光氯化合成ClCH2SiCl3的研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957330A (en) * | 2016-01-08 | 2017-07-18 | 溧阳市智行新材料有限公司 | A kind of method that chlorination rectification process prepares chloromethyl trichlorosilane |
| CN106957330B (en) * | 2016-01-08 | 2019-01-22 | 溧阳市智行新材料有限公司 | A kind of method that chlorination rectification process prepares chloromethyl trichlorosilane |
| CN109678194A (en) * | 2019-01-09 | 2019-04-26 | 中国原子能科学研究院 | A kind of ceria chloridizing unit |
| CN109678194B (en) * | 2019-01-09 | 2024-02-23 | 中国原子能科学研究院 | Cerium dioxide chlorination device |
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|---|---|
| CN105198913B (en) | 2018-03-06 |
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