CN1392151A - Process for preparing methyl silicane chloride - Google Patents
Process for preparing methyl silicane chloride Download PDFInfo
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- CN1392151A CN1392151A CN 01121551 CN01121551A CN1392151A CN 1392151 A CN1392151 A CN 1392151A CN 01121551 CN01121551 CN 01121551 CN 01121551 A CN01121551 A CN 01121551A CN 1392151 A CN1392151 A CN 1392151A
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- methylchlorodisilane
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Abstract
The present invention relates to the preparation process of methyl silicane chloride. methylchloro disilane mixture, as the side product of reaction between methane chloride with the general expression (CH3)nSi2Cl6-n and silicon powder to produce organic silicon monomer, is made to react with HCl to prepare silicane chloride with the general expression of (CH3)mSiCl4-m. The preparation process features the reaction carried under inert gas, organic amine as catalyst, reaction temperature of 80-200 deg.c and the molar ratio between methylchloro disilane and HCl is 2-4. The present invention has relatively low production cost.
Description
The invention relates to a method for preparing alkyl chlorosilane, in particular to a method for preparing alkyl chlorosilane by cracking alkyl chlorodisilane.
In the process of preparing the organic silicon monomer by gas-solid phase reaction of chloromethane and silicon powder by using copper powder as a catalyst, a byproduct, namely methyl chlorodisilane, is generated. The patent application publication of china 92111250.5 discloses a method for preparing monosilane by cracking disilane, wherein the reaction includes Si-Si bond breakage and Si-H and Si-Cl bond formation, and the method uses group VIII noble metals in the periodic table of elements, such as platinum and palladium, as catalysts, which has the disadvantage of high price of the used catalysts.
The invention aims to overcome the defects and provide a method for preparing methylchlorosilane with lower production cost.
The technical solution of the invention is to use the general formula (CH)3)nSi2Cl6-n(n is a positive integer of 2-6) and hydrogen chloride to prepare the compound with the general formula of (CH)3)mSiCl4-m(m is a positive integer of 1-3), wherein the reaction is carried out in the presence of an inert gas, organic amine is used as a catalyst, and the reaction temperature is 80-200 ℃.
The invention preferentially adopts the method that methyl chloride and silicon powder react to produce a byproduct methyl chlorodisilane mixture generated by an organic silicon monomer and react with hydrogen chloride to prepare methyl chlorosilane.
The mixture is a substance which is separated from an organic silicon mixed monomer and has a relatively high boiling point temperature, contains a plurality of impurities such as metal ions Fe and Cu, and fine silicon powder, and has poor effect on preparing methyl chlorosilane monomer by directly carrying out a cracking reaction with HCl gas, so that the mixture needs to be pretreated, distilled and separated before the cracking reaction, a section of fraction is cut out to serve as a reaction raw material, and generally the fraction at 120-180 ℃, preferably the fraction at 140-170 ℃ is taken.
The catalyst is preferably aliphatic or aromatic tertiary amine, quaternary ammonium salt compound.
The reaction of the present invention is carried out at ambient pressure, and may also be carried out at a pressure above or below ambient pressure.
The amount of hydrogen chloride used is 1 to 6 moles, preferably 2 to 4 moles, per mole of methylchlorodisilane used in the present invention.
The dosage (weight) of the catalyst is 0.5 to 3 percent of that of the methyl chlorodisilane, and the optimal dosage is 1 to 2 percent.
It is noted in the present invention that when the cracking reaction is carried out, if a small amount of a relatively low-boiling point substance such as MeHSiCl is mixed in the raw material of a relatively high-boiling point methylchlorodisilane mixture2、(CH3)4Si, etc. are very advantageous for the reaction: firstly, the reaction time can be shortened, and secondly, the selectivity of the dimethyldichlorosilane can be improved, and the economic benefit is increased. The presence includes the reaction: the selectivity of the dimethyldichlorosilane is improved, and the hydrogen-containing monomer (MeHSiCl)2) Acts as a promoter. Therefore, during the cleavage reaction, step a: absorbing part of uncondensed gaseous products by using a methyl chlorodisilane mixture, and adding the methyl chlorodisilane mixture after absorbing the gaseous products into a reaction system for cracking reaction; step b may also be performed: adding (CH) into the reaction system3)4Si and MHSiCl2Mixing; it is also possible to perform both step a and step b.
Above (CH)3)4Si and MHSiCl2The mixture, preferably taken as a by-product in the production of silicone monomer by reaction of methyl chloride with silicon powder.
The raw material high-boiling residue used in the invention contains methyl chloro disilane with the general formula: (CH)3)nSi2Cl6-n(n is a positive integer from 2 to 6) which includes moieties of the formula:
MeCl2SiSiCl2Me Me2ClSiSiCl2Me Me2ClSiSiClMe2
Me3SiSiCl2Me Me3SiSiClMe2Me3SiSiMe3wherein Me is methyl.
The preparation method of methyl chlorosilane has the general formula: (CH)3)mSiCl4-mWherein m is 1, 2, 3, which includes the products of the following formula:
MeSiCl3Me2SiCl2Me3SiCl MeHSiCl2wherein Me is methyl.
The reaction temperature of the method is 80-200 ℃, and preferably 100-180 ℃.
The catalyst used in the presentinvention may be a fatty or aromatic tertiary amine, a quaternary ammonium salt, preferably an aromatic tertiary amine.
The reaction of the present invention may be carried out in a batch, semi-continuous or fully continuous manner.
The invention adopts organic amine as catalyst, and the reaction is carried out under the environmental pressure, so the production cost is low, and the reaction is safer.
The embodiment of the present invention will be described in detail below, wherein the pretreatment of the raw material methylchlorodisilane mixture means that the mixture is distilled to cut a fraction at 120 to 180 ℃, preferably a fraction at 140 to 170 ℃.
Example 1:
100 g of the pretreated methylchlorodisilane mixture and 1 g of catalyst (C)4H9)3N was added under nitrogen atmosphere to a three-necked flask equipped with a flaskThe reaction product was separated from the three-necked flask by passing through a fractionating column and then condensed and received. After 5 hours of reaction, 71.4 g of fraction were obtained, which was analyzed by gas chromatography and nuclear magnetic resonance spectroscopy and had a composition (based on the total weight of the fraction) of:
methyltrichlorosilane (MeSiCl)3)42.54％
Dimethyldichlorosilane (Me)2SiCl2)21.76％
Hydrogen-containing monomers (MeHSiCl)2)28.14％
Chlorotrimethylsilane (Me)3SiCl)0.47％
Unconverted high boilers 7.06%.
Example 2:
100 g of the pretreated methylchlorodisilane mixture and 1 g of catalyst (C)4H9)4NCl was added to the reactor described in example 1 under a nitrogen atmosphere, the mixture was heated to 135 ℃ and hydrogen chloride was passed through the mixture at a rate of 5 liters per hour, and the reaction product was separated from the three-necked flask by means of a fractionating column and was received after condensation. After 5 hours of reaction, a 78.5 g fraction was obtained, which was analyzed by the method of example 1 and had a composition (based on the total weight of the fraction) of:
methyltrichlorosilane (MeSiCl)3)41.32％
Dimethyldichlorosilane (Me)2SiCl2)22.31％
Hydrogen-containing monomers (MeHSiCl)2)30.14％
Chlorotrimethylsilane (Me)3SiCl)0.63％
Unconverted high boilers 5.59%.
Example 3:
100 g of the pretreated methylchlorodisilane mixture and 1 g of the catalyst N, N-dimethylaniline were introduced under nitrogen into the reactor described in example 1, the mixture was heated to 135 ℃ and hydrogen chloride was introduced into the mixture at a flow rate of 5 liters per hour, and the reaction product was separated from the three-necked flask by means of a fractionating column and received after condensation. After 5 hours of reaction, a 78.5 g fraction was obtained, which was analyzed by the method of example 1 and had a composition (based on the total weight of the fraction) of:
methyltrichlorosilane (MeSiCl)3)28.76％
Dimethyldichlorosilane (Me)2SiCl2)23.74％
Hydrogen-containing monomers (MeHSiCl)2)31.62％
Chlorotrimethylsilane (Me)3SiCl)0.75％
Unconverted high boilers 5.12%.
Example 4:
100 g of the pretreated methylchlorodisilane mixture and 1 g of the catalyst N, N-dimethylaniline were introduced under nitrogen into the reactor described in example 1, the mixture was heated to 90 ℃ and hydrogen chloride was introduced into the mixture at a flow rate of 5 liters per hour, and the reaction product was separated from the three-necked flask by means of a fractionating column and received after condensation. After 6 hours of reaction, 80 g of a fraction were obtained, which, analyzed by the method of example 1, had a composition (based on the total weight of the fraction) of:
methyltrichlorosilane (MeSiCl)3)35.74％
Dimethyldichlorosilane (Me)2SiCl2)20.25％
Hydrogen-containing monomers (MeHSiCl)2)32.12％
Chlorotrimethylsilane (Me)3SiCl)0.32％
Unconverted high boilers 11.56%.
Example 5:
100 g of the pretreated methylchlorodisilane mixture and 1 g of the catalyst N, N-dimethylaniline were introduced under nitrogen into the reactor described in example 1, the mixture was heated to 190 ℃ and hydrogen chloride was introduced into the mixture at a flow rate of 5 liters per hour, and the reaction product was separated from the three-necked flask by means of a fractionating column and received after condensation. After 3 hours of reaction, a 85 g fraction was obtained, which was analyzed by the method of example 1 and had a composition (based on the total weight of the fraction) of:
methyltrichlorosilane (MeSiCl)3)30.25％
Dimethyldichlorosilane (Me)2SiCl2)21.33％
Hydrogen-containing monomers (MeHSiCl)2)27.30％
Chlorotrimethylsilane (Me)3SiCl)0.79％
Unconverted high boilers 20.32%.
Example 6:
100 g of the pretreated methylchlorodisilane mixture (21.3 g of low boilers) and 1 g of catalyst N, N-dimethylaniline were introduced under a nitrogen atmosphere into the reactor described in example 1, the mixture was heated to 135 ℃ and hydrogen chloride was introduced into the mixture at a flow rate of 5 liters per hour, and the reaction product was separated from the three-necked flask by means of a fractionating column and received after condensation. After 4 hours of reaction, 81.5 g of a fraction were obtained, which, analyzed by the method of example 1, had a composition (based on the weight of the total fraction) of:
methyltrichlorosilane (MeSiCl)3)32.73％
Dimethyldichlorosilane (Me)2SiCl2)31.84％
Hydrogen-containing monomers (MeHSiCl)2)25.75％
Chlorotrimethylsilane (Me)3SiCl)0.88％
Unconverted high boilers 8.79%.
Claims (10)
1. A process for preparing methylchlorosilanes of the general formula (CH)3)nSi2Cl6-n(n is a positive integer of 2-6) and hydrogen chloride to prepare the compound with the general formula of (CH)3)mSiCl4-m(m is a positive integer of 1-3), and is characterized in that the reaction is carried out in the presence of inert gas, organic amine is used as a catalyst in the reaction, and the reaction temperature is 80-200 ℃.
2. The process according to claim 1, wherein the methylchlorodisilane mixture is a byproduct of the reaction of methyl chloride with silicon powder to produce the organosilicon monomer.
3. The process according to claim 2, wherein the by-product is a methylchlorodisilane mixture having a boiling point of 120 to 180 ℃.
4. The process for preparing methylchlorosilanes according to claim 1, 2 or 3, wherein said catalyst is a tertiary aliphatic or aromatic amine, a quaternary ammonium compound.
5. Process for the preparation of methylchlorosilanes according to claim 4, characterized in that the reaction is carried out at ambient pressure.
6. The process according to claim 5, wherein 1 to 6 moles of hydrogen chloride are used per mole of methylchlorodisilane.
7. The process according to claim 5, wherein the amount of hydrogen chloride used is 2 to 4 mol per mol of methylchlorodisilane.
8. The process for preparing methylchlorosilanes according to claim 5, wherein said catalyst is present in an amount of from 0.5% to 3% by weight based on the amount of methylchlorodisilane.
9. The process for preparing methylchlorosilanes according to claim 5, wherein said catalyst is present in an amount of from 1% to 2% by weight of the amount of methylchlorodisilane.
10.Process for the preparation of methylchlorosilanes according to claim 5, characterized in that said reaction comprises the following steps a and/or b:
a: absorbing a part of uncondensed products by a methyl chlorodisilane mixture when the reaction products are condensed and collected, and adding the methyl chlorodisilane mixture after absorbing the products into the reaction system for cracking reaction;
b: adding (CH) into the reaction system3)4Si and MeHSiCl2And (3) mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011215518A CN1168731C (en) | 2001-06-19 | 2001-06-19 | Process for preparing methyl silicane chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011215518A CN1168731C (en) | 2001-06-19 | 2001-06-19 | Process for preparing methyl silicane chloride |
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| CN1392151A true CN1392151A (en) | 2003-01-22 |
| CN1168731C CN1168731C (en) | 2004-09-29 |
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| CNB011215518A Expired - Lifetime CN1168731C (en) | 2001-06-19 | 2001-06-19 | Process for preparing methyl silicane chloride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301258C (en) * | 2004-02-19 | 2007-02-21 | 吉林市凇泰化工有限责任公司 | Improved producing process of methyl chlorosilane |
| CN1309725C (en) * | 2003-09-04 | 2007-04-11 | 中国石油天然气股份有限公司 | Method for preparing dimethyldichlorosilane by using organic silicon high-boiling residues |
| CN100400570C (en) * | 2006-06-01 | 2008-07-09 | 浙江新安化工集团股份有限公司 | Pugging type silicon rubber structured control agent |
| CN109384233A (en) * | 2018-12-13 | 2019-02-26 | 江苏中能硅业科技发展有限公司 | A method of for handling silicon polymer |
| CN109503646A (en) * | 2018-12-13 | 2019-03-22 | 江苏中能硅业科技发展有限公司 | A method of for handling polysilicon and organosilicon by-product higher boiling polymer |
| CN114573629A (en) * | 2020-11-30 | 2022-06-03 | 新疆硅基新材料创新中心有限公司 | Organic silicon monomer preparation method and system and polycrystalline silicon system |
-
2001
- 2001-06-19 CN CNB011215518A patent/CN1168731C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309725C (en) * | 2003-09-04 | 2007-04-11 | 中国石油天然气股份有限公司 | Method for preparing dimethyldichlorosilane by using organic silicon high-boiling residues |
| CN1301258C (en) * | 2004-02-19 | 2007-02-21 | 吉林市凇泰化工有限责任公司 | Improved producing process of methyl chlorosilane |
| CN100400570C (en) * | 2006-06-01 | 2008-07-09 | 浙江新安化工集团股份有限公司 | Pugging type silicon rubber structured control agent |
| CN109384233A (en) * | 2018-12-13 | 2019-02-26 | 江苏中能硅业科技发展有限公司 | A method of for handling silicon polymer |
| CN109503646A (en) * | 2018-12-13 | 2019-03-22 | 江苏中能硅业科技发展有限公司 | A method of for handling polysilicon and organosilicon by-product higher boiling polymer |
| CN109384233B (en) * | 2018-12-13 | 2023-10-20 | 江苏中能硅业科技发展有限公司 | Method for treating silicon polymers |
| CN109503646B (en) * | 2018-12-13 | 2023-11-10 | 江苏中能硅业科技发展有限公司 | Method for treating high-boiling point polymer as byproduct of polysilicon and organic silicon |
| CN114573629A (en) * | 2020-11-30 | 2022-06-03 | 新疆硅基新材料创新中心有限公司 | Organic silicon monomer preparation method and system and polycrystalline silicon system |
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| CN1168731C (en) | 2004-09-29 |
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Granted publication date: 20040929 |