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CN-121991114-A - Continuous flow synthesis method of electronic grade methylsilane

CN121991114ACN 121991114 ACN121991114 ACN 121991114ACN-121991114-A

Abstract

The invention relates to the technical field of electronic chemical preparation, and provides a continuous flow synthesis method of electronic grade methylsilane, using magnesium scraps, halohydrocarbon and chlorosilane as raw materials, and continuously producing electronic grade methylsilane by using a Grignard reactor and a tubular reactor. The preparation method is simple to operate, the purity of the product is high, and the intrinsic safety of the process is improved. The Grignard reagent is directly subjected to alkylation reaction after the reaction, so that the danger of separation, transportation and feeding processes of the Grignard reagent is avoided, and meanwhile, the tubular reactor is adopted in the alkylation reaction, so that the reaction safety is improved, and the reaction selectivity is improved.

Inventors

  • LI REN
  • LIU JIE
  • ZHOU LEI
  • PAN QIJUN

Assignees

  • 安徽亚格盛电子新材料股份有限公司

Dates

Publication Date
20260508
Application Date
20260113

Claims (9)

  1. 1. A continuous flow synthesis method of electronic grade methylsilane, which is characterized by comprising the following steps: Firstly, adding magnesium scraps into a Grignard reactor, and introducing an organic solvent and halogenated hydrocarbon by using a plunger pump to obtain a methyl magnesium chloride solution; Step two, introducing methyl magnesium chloride solution and chlorosilane solution into a tubular reactor by using a plunger pump, and obtaining a reaction product methyl silane solution; And step three, distilling and rectifying the obtained methylsilane solution to obtain electronic-grade methylsilane with the purity of 6N, wherein the general chemical formula of the methylsilane is Si (CH 3) x H 4-x , and X=1-4.
  2. 2. The method for continuous flow synthesis of electronic grade methylsilane according to claim 1, wherein the monohalogenated hydrocarbon is one of chloromethane, bromomethane and iodomethane.
  3. 3. The continuous flow synthesis method of electronic grade methylsilane according to claim 1, wherein the step one organic solvent is an ether solvent, and the ether solvent is one of tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and diethylene glycol dimethyl ether.
  4. 4. The continuous flow synthesis method of electronic grade methylsilane according to claim 3, wherein the ether solvent is 2-methyltetrahydrofuran or ethylene glycol dimethyl ether.
  5. 5. The continuous flow synthesis method of electronic grade methylsilane according to claim 1, wherein the reaction temperature of the first grignard reaction in the step is-20-60 ℃, the molar ratio of magnesium chips to halogenated hydrocarbon is 100:1-10:1, the mass ratio of halogenated hydrocarbon to organic solvent is 1:5-1:20, the concentration of the obtained methylmagnesium chloride is 1-3M, and the liquid holding time is 10-120 minutes.
  6. 6. The continuous flow synthesis method of electronic grade methylsilane according to claim 1, wherein the reaction temperature of the tubular reaction in the step two is-20-60 ℃, the molar ratio of methylmagnesium chloride to chlorosilane is 5:1-1:1, and the liquid holding time is 10-120 minutes.
  7. 7. The continuous flow synthesis method of electronic grade methylsilane according to claim 6, wherein the step dichlorosilane is of general formula Si (CH 3) m Cl n H 4-n-m , wherein m = 0-3, n = 1-4, and m+n = 1-4.
  8. 8. The method for continuous flow synthesis of electronic grade methylsilane according to claim 7, wherein the chlorosilane is one of trimethylchlorosilane, dimethylchlorosilane, trichlorosilane and tetrachlorosilane.
  9. 9. The continuous flow synthesis of electronic grade methylsilane according to claim 1, wherein the synthesis is performed at room temperature under nitrogen protection.

Description

Continuous flow synthesis method of electronic grade methylsilane Technical Field The invention relates to the technical field of electronic chemical preparation, in particular to a continuous flow synthesis method of electronic grade methylsilane. Background Methylsilane is an important organic silicon material and has wide application in the fields of medicine, aerospace construction, mechanical materials and the like. Ultra-high purity methylsilanes are useful as precursors for Chemical Vapor Deposition (CVD), such as Plasma Enhanced Chemical Vapor Deposition (PECVD) and Atomic Layer Deposition (ALD), in the semiconductor and integrated circuit industries for the preparation of high quality thin films and for the preparation of Low dielectric constant (Low-k) materials. In the aspect of the current electronic grade methylsilane market, the main required products are tetramethylsilane (4 MS), trimethylsilane (3 MS) and the like. At present, the synthesis of 4MS and 3MS is produced based on an alkylation kettle type process of Grignard reagent, and the risks of separating, transporting, feeding and the like of the Grignard reagent exist. Meanwhile, alkylation is used as a dangerous process with eighteen important supervision, and has high requirements on reaction conditions, reaction equipment and reaction process control. Microreactors are widely used in various organic reactions, especially highly exothermic and highly dangerous reactions, due to their strong heat and mass transfer properties. The method can accurately control the reaction temperature, shorten the reaction time, improve the reaction selectivity, reduce the volume of the reaction kettle under the condition of not reducing the yield, and simultaneously, the intrinsic safety of the process is improved because the volume of the holding liquid in the reactor in unit time is far smaller than that of a conventional reaction kettle. There is therefore a need for a continuous flow synthesis method for synthesizing electronic grade methylsilanes. Disclosure of Invention In view of the above, the present invention aims to provide a continuous flow synthesis method of electronic grade methylsilane, which solves the problems in the background art. Based on the above object, the present invention provides a continuous flow synthesis method of electronic grade methylsilane, comprising the following steps: Firstly, adding magnesium scraps into a Grignard reactor, and introducing an organic solvent and halogenated hydrocarbon by using a plunger pump to obtain a methyl magnesium chloride solution; Step two, introducing methyl magnesium chloride solution and chlorosilane solution into a tubular reactor by using a plunger pump, and obtaining a reaction product methyl silane solution; And step three, distilling and rectifying the obtained methylsilane solution to obtain electronic-grade methylsilane with the purity of 6N, wherein the general chemical formula of the methylsilane is Si (CH 3) xH4-x, and X=1-4. Preferably, the monohalogenated hydrocarbon is one of chloromethane, bromomethane and iodomethane. Preferably, the organic solvent in the first step is an ether solvent, and the ether solvent is one of tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and diethylene glycol dimethyl ether. Preferably, the ether solvent is 2-methyltetrahydrofuran or ethylene glycol dimethyl ether. Preferably, the reaction temperature of the step one Grignard reaction is-20-60 ℃, the molar ratio of magnesium chips to halogenated hydrocarbon is 100:1-10:1, the mass ratio of halogenated hydrocarbon to organic solvent is 1:5-1:20, the concentration of the obtained methyl magnesium chloride is 1-3M, and the liquid holding time is 10-120 minutes. Preferably, the reaction temperature of the tubular reaction in the step II is-20-60 ℃, the molar ratio of the methyl magnesium chloride to the chlorosilane is 5:1-1:1, and the liquid holding time is 10-120 minutes. Preferably, the step dichlorosilane is of general formula Si (CH 3) mClnH4-n-m, where m=0-3, n=1-4, m+n=1-4. Preferably, the method comprises the steps of, the chlorosilane is trimethylchlorosilane, dimethyl-chlorosilane one of trichlorosilane and tetrachlorosilane. Preferably, the synthesis process is carried out at room temperature under nitrogen protection. The continuous flow synthesis method has the beneficial effects that the continuous flow synthesis method is used for continuously producing the electronic grade methylsilane by taking magnesium chips, halogenated hydrocarbon and chlorosilane as raw materials and utilizing a Grignard reactor and a tubular reactor. The preparation method is simple to operate, the purity of the product is high, and the intrinsic safety of the process is improved. The Grignard reagent is directly subjected to alkylation reaction after the reaction, so that the danger of separation, transportation and feed