CN1317488A - Process and equipment for preparing chloromethyl chlorosilane by gas-phase chlorination - Google Patents
Process and equipment for preparing chloromethyl chlorosilane by gas-phase chlorination Download PDFInfo
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- CN1317488A CN1317488A CN 01105690 CN01105690A CN1317488A CN 1317488 A CN1317488 A CN 1317488A CN 01105690 CN01105690 CN 01105690 CN 01105690 A CN01105690 A CN 01105690A CN 1317488 A CN1317488 A CN 1317488A
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Abstract
A process and equipment for preparing chloromethyl chlorosilane by gas-phase chlorination features that the methylchlorosilane as raw material takes part in gas-phase chlorinating reaction without any special ultraviolet light source to obtain said product with high output rate.
Description
The present invention relates to the preparation method of organosilicon reagent, specifically, it is to be CH with the molecular formula
3Si (CH
3)
mCl
3-m, the methyl chlorosilane of m=0-2 is a raw material, under special ultraviolet source condition, and the gas phase chlorination reaction that only relies on indoor general radiation of visible light to carry out, thus the molecular formula that obtains higher yields is ClCH
2Si (CH
3) mCl
3-m, the method and apparatus of many chloromethyls chlorosilane of m=0-2 belongs to the organic synthesis category.
Chloromethyl silane (ClCH
2Si (CH
3) pCl
3-p, P=0-3) be a series of very important organosilicon reagents, extensively be used in fields such as agricultural chemicals, medicine and organic synthesis.
Relevant chloromethyl chlorosilane (ClCH
2Si (CH
3)
mCl
3-m, preparation m=0-2) is by people such as Gilliam " W.F.Gilliam, H.A.Liebhafsky and A.F.Winslow, J.A.C.S., 1941,63,801 the earliest; W.F.Gilliam and R.O.Sauer, ibid., 1944,66,1793 " by (Si (CH of methyl chlorosilane under the UV-irradiation
3)
pCl
4-p, liquid phase chlorination prepared in reaction P=1-3), but the result is not ideal, and many chloro-products are more; Nineteen forty-six, people such as Whitmore " referring to: Whitmore; Sommer; Am.Soc.68 p481-4831946 " once attempted with reference to aforesaid method, be that solvent, tetramethylsilane are raw material first with the tetracol phenixin, and in the presence of phosphorus pentachloride, prepared chloromethyl trimethyl silane, but more many chloro-products have been obtained equally by illumination reaction.Nineteen forty-seven, and people such as Whitmore " referring to: Whitmore, Sommer; Am.Soc., 69,1976,1947 " utilize again dimethyl chloride methyl chlorosilane and monobromethane magnesium Grignard reagent in ether prepared in reaction chloromethyl trimethyl silane.Equally, Rodel is " referring to Vgl.Roedel; Am.Soc., 71,271,1949 " also prepared chloromethyl trimethyl silane with above-mentioned Grignard reagent method with 1949 annual interests.During the 1954-1989, although reported in literature is also arranged " referring to Ponomarenko, V.A.Et al., Dokl.Akad.Nauk SSSR, Ser.Khim., 1954,94,485; Seyferth, D.Et al., J.A.C.S., 1955,77,907; Inorg.Synth., 1960,6., 37; Pola, J.Et al., Coll.Czech.Chem.Comm., 1973,38,1522; Wojnowski, W.Et al., Przem.Chem., 1989,68,409 " utilize the gas phase optical chlorinating reaction to prepare chloromethylmethyldichlorsilane and chloromethyl trichlorosilane, must under UV-irradiation, carry out but all point out to react; and the danger of catching fire is arranged, and also obtained more many chloros by product; 1985, and people such as M.Bordeau " referring to: M.Bordeau, S.M.Djamei, R.Calas, J.Dunogues; J.Organomet.Chem., 1985,288, N2,131-138 " utilize dimethyl chloride methyl chlorosilane and tetramethylsilane in the presence of aluminum chloride, to prepare chloromethyl trimethyl silane.1988, and people such as V.D.Sheludyakov " referring to: V.D.Sheludyakov, V.I.Zhun, M.I.Shumilim, V.N.Bochkarev, T.F.Slyusarenko; Zh.Obshch.Ximii, 58, N7,1583-1588,1988 " be raw material with the chloromethyl trichlorosilane again, prepared chloromethyl trimethyl silane by methyl iodide magnesium grignard reaction.1989, and people such as Mottsarev G.V. " referring to: Mostarev G.V., Inshakova V.T., Raskina, A.D.; Zh.Obshch.Khim., 1989,59 (11), 2628 (Russ) " think: no matter be the thermal chlorination by tetramethylsilane or the light chlorination by tetramethylsilane all can not get chloromethyl trimethyl silane; reason is because the initiation of the lower boiling of tetramethylsilane AIBN when having influenced thermal chlorination; and the light chlorination initial stage has the danger of catching fire, and therefore chlorination reaction can't be carried out; Japan three is total to company and once utilized the mode of logical chlorine in batches recently, prepare CMDMCS chloromethyl dimethyl chlorosilane under UV-irradiation, but operation is very loaded down with trivial details, and the result is also undesirable;
In sum, the difficult control of chloride solution, and also many chloros by product is more; Grignard condition harshness, more difficult industrialization, and also cost is also higher.People such as Jiang Biao have reported " a kind of method and apparatus for preparing chloromethyl trimethyl silane by the gas phase optical chlorinating reaction " (CN00119457.1), obtain comparatively satisfied result.
Purpose of the present invention just provides a kind of simple and easy to do, easy industrialization, cost is lower and by product is less, the method and apparatus of a series of chloromethyl chlorosilanes of preparation that transformation efficiency is higher.
Reaction in the method for the present invention is to carry out under the illumination of visible light or fluorescent lamp, and raw materials used is that molecular formula is CH
3Si (CH
3)
mCl
3-m, the methyl chlorosilane of m=0-2 is as tetramethylsilane, trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE etc.;
The used chloridating gas of the present invention can be that pure chlorine also can be the mixed gas of a kind of chlorine and rare gas element, and described rare gas element can be nitrogen, helium, argon gas etc., and wherein the content of rare gas element is 0-80% in the mixed gas, is preferably 20-50%.
The gas phase chlorination reaction that the present invention adopts, the mol ratio of unstripped gas and chlorine is 1: 0.1-0.75 is preferably 1: 0.15-0.43, the flow of unstripped gas can be controlled by the rate of heating of raw material in the reactor or the amount of input raw material usually.
Temperature of reaction is 50-80 ℃ among the present invention.Reaction times is relevant with the size and the raw material in the reactor of reactor.Usually the reaction times is 1-24h, but with 3-10h for well.
The used gas phase chlorination reaction unit of the present invention is a kind of special reactor, is made up of raw material still or reactor, Gas-phase reactor, Gas-phase reactor, reflux exchanger, filler and heating unit.As shown in Figure 1.1-raw material still or reactor among the figure, 2-Gas-phase reactor, 3-reflux exchanger, 4-filled column, 5-heating unit, T1-reactor liquid thermometer, T2-gas phase temperature meter.When reaction, the amount of vaporization of raw material can be by the heating and temperature control of heating unit 5 in the reactor 1; Need be furnished with filled column 4 between reactor 1 and the Gas-phase reactor 2, to guarantee fully separating of raw material and product; The material of Gas-phase reactor 2 can be general glass, also can be silica glass, pottery or enamel.For different raw materials, Gas-phase reactor need be furnished with different heat-eliminating mediums, and heat-eliminating medium can be a water-cooled, also fan can be installed around reactor; Gas-phase reactor does not need to be equipped with special ultraviolet source, and usually indoor visible light or fluorescent lamp can guarantee that chlorination carries out; Can also be equipped with 1-5 Gas-phase reactor according to the reactor size in addition, to increase speed of response.
By the inventive method, can obtain products such as chloromethyl trimethyl silane, CMDMCS chloromethyl dimethyl chlorosilane, methyl chloride dimethyl dichlorosilane (DMCS) or chloromethyl trichlorosilane respectively, its operational condition and physical parameter are as shown in table 1.
Table 1. raw material and product structure, physical parameter, and gas phase chlorination reaction table look-up
The gas phase chlorination method that the present invention adopts does not need special ultraviolet source, is raw material with a series of above-mentioned methyl chlorosilanes, by adding thermosetting gas, in Gas-phase reactor, converge, under indoor general visible light, carry out chlorination reaction, generate the chloromethyl chlorosilane with chlorine.The product chloromethyl chlorosilane that forms passes back into raw material still or reactor immediately, so circulation, as long as control rate of heating and chlorine flowrate well, can guarantee that the above methyl chlorosilane of 90-95% is chlorinated fully and be the chloromethyl chlorosilane, and have only few many chloros by product to produce.
Method of the present invention is not only a kind of simple and easy to do, cost is lower, by product is less, transformation efficiency is higher method, and is a kind of industrial method for preparing the chloromethyl chlorosilane
The further the present invention of understanding will be helped by following embodiment, but content of the present invention can not be limited.
Prepare the gas phase chlorination reaction unit as shown in Figure 1,500 milliliters of reactors with freezing brine refrigeration to the 0-5 degree, open the cooling system of Gas-phase reactor and reflux exchanger simultaneously, the Gas-phase reactor heat-eliminating medium adopts room temperature water usually, as 5-30 ℃ of room temperature water all can, reflux exchanger can adopt dry ice-Virahol acetone or superpower freezing brine media usually.The 400ml tetramethylsilane is injected above-mentioned reactor, logical high-purity N
2Oxygen in the replacement(metathesis)reaction system, open induction stirring then, heating, the system for the treatment of refluxes when stablizing, and this moment, reaction flask liquidus temperature T1 was 27-28 ℃, and gas phase temperature T2 is 28 ℃, slowly open the chlorine valve, this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas was acid.The control rate of heating makes backflow moderate, should control chlorine flowrate simultaneously, makes speed of response too violent.Along with the carrying out of chlorination reaction, temperature T 1 can constantly raise in the reaction flask, stopped reaction when treating that temperature in the kettle rises to 80 ℃.Sampling send GC to analyze, and each component content is as shown in table 1 in the reaction solution.
Atmospheric distillation is used less than 98 degree fraction recovery sets; Collecting 98-99 ℃ of fraction is the product chloromethyl trimethyl silane, and the GC purity assay is 98%; Greater than 99 degree fractions is many chloros by product.
Prepare the gas phase chlorination reaction unit as shown in Figure 1, in advance the cooling system of reflux exchanger is opened, reflux exchanger adopts freezing brine media to get final product, and Gas-phase reactor does not need heat-eliminating medium.The 400ml trimethylchlorosilane is injected above-mentioned reactor, logical high-purity N
2Oxygen in the replacement(metathesis)reaction system, open induction stirring then, heating, the system for the treatment of refluxes when stablizing, and this moment, reactor liquidus temperature T1 was 57-58 ℃, and gas phase temperature T2 is 58 ℃, slowly open the chlorine valve, this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas was acid.The control rate of heating makes backflow moderate, should control chlorine flowrate simultaneously, makes speed of response too violent.Along with the carrying out of chlorination reaction, temperature T 1 can constantly raise in the reaction flask, stopped reaction when treating that temperature in the kettle rises to 100 ℃.Sampling send GC to analyze, and each component content is as shown in table 1 in the reaction solution.
Atmospheric distillation is used less than 113 degree fraction recovery sets; Collecting 113-115 ℃ of fraction is the product CMDMCS chloromethyl dimethyl chlorosilane, and the GC purity assay is 98%; Greater than 115 degree fractions is many chloros by product.
Embodiment 3 is the method that raw material passes through gas phase chlorination prepared in reaction methyl chloride dimethyl dichlorosilane (DMCS) with the dimethyldichlorosilane(DMCS)
Prepare the gas phase chlorination reaction unit as shown in Figure 1, in advance the cooling system of reflux exchanger is opened, reflux exchanger adopts freezing brine media to get final product, and Gas-phase reactor does not need heat-eliminating medium.The 400ml trimethylchlorosilane is injected above-mentioned reactor (bottle), logical high-purity N
2Oxygen in the replacement(metathesis)reaction system, open induction stirring then, heating, the system for the treatment of refluxes when stablizing, and this moment, reaction flask liquidus temperature T1 was 70-72 ℃, and gas phase temperature T2 is 72 ℃, slowly open the chlorine valve, this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas was acid.The control rate of heating makes backflow moderate, should control chlorine flowrate simultaneously, makes speed of response too violent.Along with the carrying out of chlorination reaction, temperature T 1 can constantly raise in the reaction flask, stopped reaction when treating that temperature in the kettle rises to 110 ℃.Sampling send GC to analyze, and each component content is as shown in table 1 in the reaction solution.
Atmospheric distillation is used less than 120 degree fraction recovery sets; Collecting 120-121 ℃ of fraction is product methyl chloride methyl-monosilane, and the GC purity assay is 97.8%; Greater than 121 degree fractions is many chloros by product.
Embodiment 4 is the method that raw material passes through gas phase chlorination prepared in reaction chloromethyl trichlorosilane with the METHYL TRICHLORO SILANE
Prepare the gas phase chlorination reaction unit as shown in Figure 1, in advance the cooling system in reflux condensation mode district is opened, reflux exchanger adopts freezing brine media to get final product, and Gas-phase reactor does not need heat-eliminating medium.The 400ml trimethylchlorosilane is injected above-mentioned reactor (bottle), logical high-purity N
2Oxygen in the replacement(metathesis)reaction system, open induction stirring then, heating, the system for the treatment of refluxes when stablizing, and this moment, reaction flask liquidus temperature T1 was 66-68 ℃, and gas phase temperature T2 is 67 ℃, slowly open the chlorine valve, this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas was acid.The control rate of heating makes backflow moderate, should control chlorine flowrate simultaneously, makes speed of response too violent.Along with the carrying out of chlorination reaction, the temperature T 1 in the reactor can constantly raise, stopped reaction when treating that temperature in the kettle rises to 108 ℃.Sampling send GC to analyze, and each component content is as shown in table 1 in the reaction solution.
Air distillation is used less than 117 ℃ of fraction recovery sets; Collecting 117-118.5 ℃ of fraction is product chloromethyl trichlorosilane, and the GC purity assay is 97.2%; Greater than 118.5 ℃ of fractions is many chloros by product.
Claims (8)
1. the method for a gas phase chlorination prepared in reaction chloromethyl chlorosilane, it is characterized in that under visible light, be that chlorine in the mixed gas of raw material and chlorine and rare gas element directly carries out the gas phase chlorination reaction and makes with the methyl chlorosilane, the mol ratio of methyl chlorosilane and chlorine is 1: 0.1-0.75, at 50-80 ℃ of the reaction time 1-24h, described methyl chlorosilane molecular formula is CH
3Si (CH
3)
mCl
3-m, described chloromethyl chlorosilane molecular formula is ClCH
2Si (CH
3)
mCl
3-m, m=0-2 wherein, the content of rare gas element is 0-80% in the mixed gas.
2. the method for gas phase chlorination prepared in reaction chloromethyl chlorosilane according to claim 1 is characterized in that described methyl chlorosilane is tetramethylsilane, trimethylchlorosilane, dimethyldichlorosilane(DMCS) or METHYL TRICHLORO SILANE.
3. the method for gas phase chlorination prepared in reaction chloromethyl chlorosilane according to claim 1 is characterized in that described chloromethyl chlorosilane is chloromethyl trimethyl silane, CMDMCS chloromethyl dimethyl chlorosilane, methyl chloride dimethyl dichlorosilane (DMCS) or chloromethyl trichlorosilane.
4. the method for gas phase chlorination prepared in reaction chloromethyl chlorosilane according to claim 1, the mol ratio that it is characterized in that described methyl chlorosilane and chlorine is 1: 0.15-0.43.
5. the method for gas phase chlorination prepared in reaction chloromethyl chlorosilane according to claim 1 is characterized in that described rare gas element can be nitrogen, helium or argon gas.
6. the method for gas phase chlorination prepared in reaction chloromethyl chlorosilane according to claim 1 is characterized in that the content of rare gas element in the mixed gas is 0-50%.
7. the gas phase chlorination device of the method for gas phase chlorination prepared in reaction chloromethyl chlorosilane according to claim 1 is characterized in that this device comprises reactor, a 1-5 Gas-phase reactor, reflux exchanger and heating unit.
8. according to the described gas phase chlorination reaction unit of claim 7, the material that it is characterized in that described Gas-phase reactor is glass, silica glass, pottery or enamel.
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| CNB011056908A CN1181079C (en) | 2001-03-16 | 2001-03-16 | Process and equipment for preparing chloromethyl chlorosilane by gas-phase chlorination |
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445289C (en) * | 2006-11-21 | 2008-12-24 | 上海试四赫维化工有限公司 | Process for preparing chloromethylmethyldichlorsilane |
| CN104558003A (en) * | 2015-01-27 | 2015-04-29 | 荆州市江汉精细化工有限公司 | Method for preparing chloromethyl trichlorosilane by using liquid-phase chlorination reaction |
| CN104804031A (en) * | 2015-04-08 | 2015-07-29 | 湖北晶星科技股份有限公司 | Method for preparing chloromethyl chlorosilane through light chlorination process |
| CN105198913A (en) * | 2015-10-14 | 2015-12-30 | 济南大学 | Method for preparing chloromethyl trichlorosilane |
| CN105198914A (en) * | 2015-10-14 | 2015-12-30 | 济南大学 | Device for preparing chloromethyl trichlorosilane |
| CN106543217A (en) * | 2016-06-28 | 2017-03-29 | 宁夏海诚电化信息科技有限公司 | A kind of CMDMCS chloromethyl dimethyl chlorosilane production technology |
| 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 |
| CN113234101A (en) * | 2021-06-23 | 2021-08-10 | 唐山三孚新材料有限公司 | Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyltrichlorosilane |
-
2001
- 2001-03-16 CN CNB011056908A patent/CN1181079C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445289C (en) * | 2006-11-21 | 2008-12-24 | 上海试四赫维化工有限公司 | Process for preparing chloromethylmethyldichlorsilane |
| CN104558003B (en) * | 2015-01-27 | 2017-08-29 | 荆州市江汉精细化工有限公司 | A kind of method that liquid phase chlorination reaction prepares Chloromethyltrichlorosilane |
| CN104558003A (en) * | 2015-01-27 | 2015-04-29 | 荆州市江汉精细化工有限公司 | Method for preparing chloromethyl trichlorosilane by using liquid-phase chlorination reaction |
| CN104804031A (en) * | 2015-04-08 | 2015-07-29 | 湖北晶星科技股份有限公司 | Method for preparing chloromethyl chlorosilane through light chlorination process |
| CN105198914B (en) * | 2015-10-14 | 2018-03-13 | 济南大学 | Device for preparing chloromethyl trichlorosilane |
| CN105198914A (en) * | 2015-10-14 | 2015-12-30 | 济南大学 | Device for preparing chloromethyl trichlorosilane |
| CN105198913B (en) * | 2015-10-14 | 2018-03-06 | 济南大学 | Method for preparing chloromethyl trichlorosilane |
| CN105198913A (en) * | 2015-10-14 | 2015-12-30 | 济南大学 | Method for preparing chloromethyl trichlorosilane |
| 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 |
| CN106543217A (en) * | 2016-06-28 | 2017-03-29 | 宁夏海诚电化信息科技有限公司 | A kind of CMDMCS chloromethyl dimethyl chlorosilane production technology |
| CN113234101A (en) * | 2021-06-23 | 2021-08-10 | 唐山三孚新材料有限公司 | Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyltrichlorosilane |
| CN113234101B (en) * | 2021-06-23 | 2023-08-22 | 唐山三孚新材料有限公司 | Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyl trichlorosilane |
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