CN100445289C - Process for preparing chloromethylmethyldichlorsilane - Google Patents
Process for preparing chloromethylmethyldichlorsilane Download PDFInfo
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- CN100445289C CN100445289C CNB2006101185513A CN200610118551A CN100445289C CN 100445289 C CN100445289 C CN 100445289C CN B2006101185513 A CNB2006101185513 A CN B2006101185513A CN 200610118551 A CN200610118551 A CN 200610118551A CN 100445289 C CN100445289 C CN 100445289C
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- dimethyldichlorosilane
- chloromethylmethyldichlorsilane
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Abstract
The invention discloses a preparing method of is characterized by the following: irradiating dimethyldichlorosilane and chloride under fluorescent lamp; making the receiving rate at 32-41%; decompressing; rectifying; obtaining the product within short time safely.
Description
Technical field
The present invention relates to the preparation method of silicoorganic compound, specifically is the preparation method about chloromethylmethyldichlorsilane.
Background technology
Chloromethylmethyldichlorsilane is a kind of very useful organosilicon product, is widely used in fields such as agricultural chemicals, medicine and organic synthesis.
Prior art is reported, mainly contains the preparation method of following several chloromethylmethyldichlorsilanes.
During 1954～1989, reported in literature is 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, the danger of catching fire is arranged, and also have more many chloros by product.
In April, 2004 Granted publication U.S. Pat 6720440B2 (equating patent: EP1310502B1, DE10154943C1, JP2003183288A), reported a kind of chlorination method of methyl-monosilane, the synthesis technique of wherein introducing chloromethylmethyldichlorsilane is: liquid chlorine, dimethyldichlorosilane(DMCS) (30～33 ℃), gaseous hydrogen chloride are added VA steel pipe type reactor respectively, and reactor has the mercury vapor lamp of a power 4kw, wavelength 366nm; The gas/liquid mixture that leaves reactor (57 ℃) separates in cyclone separator, and hydrogenchloride separates with gaseous state through the top, and liquid head product obtains different components through continuous still battery.Contain 8.6% chloromethylmethyldichlorsilane in the head product that obtains.In continuous still battery, unreacted dimethyldichlorosilane(DMCS) is gone out from the distillation tower top, turns back to tubular reactor.In reactor, stop to drop into hydrogen chloride gas, the recycle dimethyldichlorosilane(DMCS), the new dimethyldichlorosilane(DMCS) of restock makes dimethyldichlorosilane(DMCS) reach 4m
3/ h.The distillation tower head temperature is 69 ℃, and the bottom steady temperature is 130 ℃.Component after the rectifying: finished product 91.6%, dimethyldichlorosilane(DMCS) 0.1%, dichloromethyl dichlorosilane 7.1%, other high boiling material 1.2%.Just finished product is through rectification and purification for product, and purity is greater than 99.0%.The chloromethylmethyldichlorsilane content of its single step reaction is low, has only 8.6%, and concerning suitability for industrialized production, distillation, rectifying device require high, and investment is big.
October 17 calendar year 2001 disclosed Shanghai Organic Chemistry Institute, Chinese Academy of Sciences Chinese patent CN1317488A, reported a kind of method and apparatus of the chloromethyl chlorosilane by the gas phase chlorination prepared in reaction.This method is raw material with the methyl chlorosilane, and under special ultraviolet source condition, the gas phase chlorination that only depends on indoor general radiation of visible light to carry out is reacted, thereby obtains the method for the chloromethyl chlorosilane of higher yields.But, their long reaction time, atmospheric distillation GC analysed preparation purity only is 97.8%.
Summary of the invention
The invention provides a kind of preparation method of chloromethylmethyldichlorsilane, this method is dimethyldichlorosilane(DMCS), chlorine to be fed pipeline reactor carry out optical chlorinating reaction under luminescent lamp catalysis irradiation, and single step reaction synthesizes chloromethylmethyldichlorsilane.
Reaction formula is expressed as follows:
(CH
3)
2SiCl
2+Cl
2→ClCH
2CH
3SiCl
2+HCl
Preparation method's step of the present invention: dimethyldichlorosilane(DMCS) is dropped in the reactor, be preheated between 28～35 ℃.With 0.15～0.25 liter/minute speed dimethyldichlorosilane(DMCS) is imported the bottom of a silica glass pipeline reactor with infusion pump, open luminescent lamp simultaneously and illuminate the entire reaction pipe, after treating that dimethyldichlorosilane(DMCS) has been full of whole pipe, open the chlorine intake valve of bottom, chlorine flowrate is controlled at 0.1～0.15 liter/minute, temperature of reaction rises to 45～65 ℃ gradually, and reaction kept 1～3.5 hour.The reaction product that generates overflows to one from silica glass pipeline reactor head and accepts the pot, analyze through GC, single step reaction product dimethyldichlorosilane(DMCS) content 40～75%, chloromethylmethyldichlorsilane content 21～36%, methyl dichloro dimethyl dichlorosilane (DMCS) content 3.3～20.5%, other foreign matter contents 0.65%～3.5%.
In order to suppress methyl dichloro dimethyl dichlorosilane (DMCS) and other high boiling point by-products produced formation, the temperature of optical chlorinating reaction is controlled in necessary strictness, and control reaction temperature is 45～65 ℃, and optimum temps is 55 ℃～60 ℃.Reaction temperature is spent low, and by product is less, and still, the also corresponding reduction of the growing amount of principal product influences response capacity; Temperature of reaction is too high, will produce a large amount of by products, and the yield of influence reaction increases production cost.
In reaction process, must regulate the proportionlity between chlorine flowrate and the dimethyldichlorosilane(DMCS) flow, the volume flow ratio of reaction is controlled between 1: 1～2.5, is the best with 1: 1.67.
The preparation method of chloromethylmethyldichlorsilane of the present invention is that dimethyldichlorosilane(DMCS) and chlorine are carried out optical chlorinating reaction under luminescent lamp catalysis irradiation, and single step reaction makes chloromethylmethyldichlorsilane.Owing to adopted the luminescent lamp catalysis irradiation of low pressure 115V, the suitable chlorine and the flow of dimethyldichlorosilane(DMCS) be suitable reaction temperature and time when, make the growing amount of single step reaction principal product chloromethylmethyldichlorsilane of short period of time reach best, the yield of single step reaction can reach about 32-41%, by rectification under vacuum, can obtain content and reach high purity chloromethylmethyldichlorsilane product more than 99%.As everyone knows, have only highly purified chloromethylmethyldichlorsilane more than 99%, could satisfy the ingredient requirement of agricultural chemicals, medicine and other fields,, otherwise can cause impurity to increase with the quality of assurance agricultural chemicals and medical.Because suitable process conditions also is difficult in the production process deflagration phenomenon takes place, and produces safer.Reaction times lacks again, and production unit is simple, and easily-controlled operation is a kind of preparation method who is suitable for suitability for industrialized production.
Embodiment
The present invention is further elaborated by the following examples, but does not limit the scope of the invention.
Embodiment 1
The oxygen in the armamentarium in the logical nitrogen replacement reaction process before going into operation.In 50 liters of glassed steel reaction vessels, drop into 98%30 kilograms of dimethyldichlorosilane(DMCS)s, be preheated between 30 ℃～32 ℃.With 0.25 liter/minute speed dimethyldichlorosilane(DMCS) is imported 200 millimeters of diameters with infusion pump, the bottom of long 2 meters silica glass pipeline formula reactor, pipe external application 115V operating voltage, the luminescent lamp of 5800Im optical throughput is made the catalysis illumination lamp, open luminescent lamp simultaneously and illuminate the entire reaction pipe, after treating that dimethyldichlorosilane(DMCS) has been full of whole pipe, open the chlorine intake valve of bottom, chlorine flowrate is controlled at 0.15 liter/minute, temperature of reaction rises to 55 ℃～60 ℃ gradually, and reaction kept 3.1 hours.The reaction product that generates overflows to the acceptance pot of one 50 liter from silica glass pipeline reactor head, analyze through GC, single step reaction product dimethyldichlorosilane(DMCS) content 59.12%, chloromethylmethyldichlorsilane content 33.35%, methyl dichloro dimethyl dichlorosilane (DMCS) content 6.54%, other foreign matter contents 0.99%.
31.8 kilograms of above-mentioned single step reaction products are moved in the glass-lined kettle, the external reflux fractional column is housed on the still, carry out underpressure distillation, control of reflux ratio was at 1: 1, collect the cut of 83 ℃ (under 5mmHg posts), obtain 6.1 kilograms of chloromethylmethyldichlorsilane products, reclaim 19 kilograms of dimethyldichlorosilane(DMCS)s (content 93.4%), analyze through GC, chloromethylmethyldichlorsilane content 99.3%, dimethyldichlorosilane(DMCS) content 0.23%, methyl dichloro dimethyl dichlorosilane (DMCS) 0.08%, other total impurities 0.39% (each impurity thing is less than 0.1%), yield (in dimethyldichlorosilane(DMCS)) is 41.03%.
The spectroscopic analysis of product chloromethylmethyldichlorsilane is as follows:
Infrared absorption spectrum characteristic frequency (cm
-1): 2,935 1,380 1,270 1,105 740
Each functional group's absorption peak and standard spectrogram in this infrared spectrogram (Aldrich29,150-1) consistent;
The mass spectroscopy of product chloromethylmethyldichlorsilane:
Mass-to-charge ratio (m/z) 113 28 63 99 49 149 164
Specific absorption (%RA) 100 58.23 35.44 6.33 5.71 5.70 2.53
This mass spectrum and standard diagram (Library Searched, C: MSDCHEM 1 5973N KY0094.D) consistent,
Embodiment 2
The oxygen in the armamentarium in the logical nitrogen replacement reaction process before going into operation.In 50 liters of glassed steel reaction vessels, drop into 98%30 kilograms of dimethyldichlorosilane(DMCS)s, be preheated between 28 ℃～30 ℃, with 0.2 liter/minute speed dimethyldichlorosilane(DMCS) is imported 200 millimeters of diameters with infusion pump, the bottom of long 2 meters silica glass pipeline formula reactor, pipe external application 115V operating voltage, the luminescent lamp of 5800Im optical throughput is made the catalysis illumination lamp, open luminescent lamp simultaneously and illuminate the entire reaction pipe, after treating that dimethyldichlorosilane(DMCS) has been full of whole pipe, open the chlorine intake valve of bottom, chlorine flowrate is controlled at 0.15 liter/minute, and temperature of reaction rises to 45 ℃～50 ℃ gradually, and reaction kept 2.3 hours.The reaction product that generates overflows to the acceptance pot of one 50 liter from silica glass pipeline reactor head, analyze through GC, single step reaction product dimethyldichlorosilane(DMCS) content 74.84%, chloromethylmethyldichlorsilane content 21.13%, methyl dichloro dimethyl dichlorosilane (DMCS) content 3.38%, other foreign matter contents 0.65%.
30.6 kilograms of above-mentioned single step reaction products are moved in the glass-lined kettle, the external reflux fractional column is housed on the still, carry out underpressure distillation, control of reflux ratio was at 1: 1, collect the cut of 83 ℃ (under 5mmHg posts), obtain 5.4 kilograms of chloromethylmethyldichlorsilane products, reclaim 20 kilograms of dimethyldichlorosilane(DMCS)s (content 93.8%), analyze through GC, chloromethylmethyldichlorsilane content 99.1%, dimethyldichlorosilane(DMCS) content 0.49%, methyl dichloro dimethyl dichlorosilane (DMCS) 0.04%, other total impurities 0.37% (each impurity thing is less than 0.1%), yield (in dimethyldichlorosilane(DMCS)) is 39.7%.
Embodiment 3
The oxygen in the armamentarium in the logical nitrogen replacement reaction process before going into operation.In 50 liters of glassed steel reaction vessels, drop into 98%30 kilograms of dimethyldichlorosilane(DMCS)s, be preheated between 31 ℃～33 ℃.With 0.15 liter/minute speed dimethyldichlorosilane(DMCS) is imported 200 millimeters of diameters with infusion pump, the bottom of long 2 meters silica glass pipeline formula reactor, pipe external application 115V operating voltage, the luminescent lamp of 5800Im optical throughput is made the catalysis illumination lamp, opens luminescent lamp simultaneously and illuminates the entire reaction pipe, treat that dimethyldichlorosilane(DMCS) has been full of whole pipe after, open the chlorine intake valve of bottom, chlorine flowrate is controlled at 0.1 liter/minute, and temperature of reaction rises to 60 ℃～65 ℃ gradually, and reaction kept 2.3 hours.The reaction product that generates overflows to the acceptance pot of one 50 liter from silica glass pipeline reactor head, analyze through GC, single step reaction product dimethyldichlorosilane(DMCS) content 40.87%, chloromethylmethyldichlorsilane content 35.64%, methyl dichloro dimethyl dichlorosilane (DMCS) content 20.1%, other foreign matter contents 3.39%.
33.4 kilograms of above-mentioned single step reaction products are moved in the glass-lined kettle, the external reflux fractional column is housed on the still, carry out underpressure distillation, control of reflux ratio was at 1: 1, collect the cut of 83 ℃ (under 5mmHg posts), obtain 7.2 kilograms of chloromethylmethyldichlorsilane products, reclaim 12.8 kilograms of dimethyldichlorosilane(DMCS)s (content 93.2%), analyze through GC, chloromethylmethyldichlorsilane content 99.2%, dimethyldichlorosilane(DMCS) content 0.22%, methyl dichloro dimethyl dichlorosilane (DMCS) 0.09%, other total impurities 0.49% (each impurity thing is less than 0.1%), yield (in dimethyldichlorosilane(DMCS)) is 32.27%.
Claims (4)
1. the preparation method of a chloromethylmethyldichlorsilane, it is characterized in that it being under luminescent lamp catalysis irradiation, to carry out optical chlorinating reaction with liquid dimethyl base dichlorosilane and chlorine, single step reaction makes, temperature of reaction is 45～65 ℃, 1～3.5 hour reaction times, the volume flow ratio of chlorine and dimethyldichlorosilane(DMCS) is 1: 1～2.5, and before optical chlorinating reaction, the dimethyldichlorosilane(DMCS) preheating temperature is 28～35 ℃.
2. preparation method as claimed in claim 1 is characterized in that described temperature of reaction is 55～60 ℃.
3. preparation method as claimed in claim 1, the volume flow ratio that it is characterized in that described chlorine and dimethyldichlorosilane(DMCS) is 1: 1.67.
4. preparation method as claimed in claim 1 is characterized in that described chlorine flowrate is 0.1～0.15 liter/minute, and the dimethyldichlorosilane(DMCS) flow is 0.15～0.25 liter/minute.
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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 |
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Assignee: SHANGHAI SHISI CHEMICAL PRODUCT CO., LTD. Assignor: Shanghai Shishi Hewei Chemical Industry Co., Ltd. Contract record no.: 2011310000226 Denomination of invention: Process for preparing chloromethylmethyldichlorsilane Granted publication date: 20081224 License type: Exclusive License Open date: 20070516 Record date: 20111028 |