二甲基一氯硅烷和三氯氢硅的热氯化反应及机理研究

doi:10.19964/j.issn.1006-4990.2023-0059

Abstract

Abstract:

Removal of carbon impurities from trichlorosilane（SiHCl₃） can improve the purity of polysilicon.However，the points of chlorodimethylsilane［（CH₃）₂SiHCl］ and SiHCl₃ are very close，and azeotrope is easily formed in the distillation process.Therefore，（CH₃）₂SiHCl in SiHCl₃ is difficult to remove.It was proposed to use Cl₂ as the chlorine source to convert（CH₃）₂SiHCl into high boiling methyl chlorosilane through thermal chlorination reaction to increase the relative volatility and facilitate the distillation.However，SiHCl₃ and（CH₃）₂SiHCl were chlorinated at same time.Therefore，the change of the conversion of the two with temperature was investigated.The results showed that the conversions of（CH₃）₂SiHCl and SiHCl₃ were 53.1% and 14.3% at 60 ℃ and 120 min，and the selectivity of（CH₃）₂SiHCl was the best.Finally，the reaction path was calculated and analyzed by density functional theory，and the reaction mechanism was determined.The difference between the reactions of SiHCl₃ and（CH₃）₂SiHCl resulted from the different energy barriers for the reactions of the SiCl₃· and（CH₃）₂SiCl· radicals with Cl₂.The energy barrier of the reaction of SiCl₃· with Cl₂ was 60.4 kJ/mol higher than that of the reaction of（CH₃）₂SiCl·.

Key words: chlorodimethylsilane, thermal chlorination, trichlorosilane, chlorine gas, density functional theory

CLC Number:

TQ127.2

DUAN Rui, JIA Zhaohang, XU Maolan, MA Tianyue, PENG Wencai, ZHANG Jianshu. Study on thermal chlorination and mechanism of chlorodimethylsilane and trichlorosilane[J]. Inorganic Chemicals Industry, 2023, 55(12): 82-87.

Figures/Tables 13

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化合物	化学键	DE/（kJ·mol^-1）
SiHCl₃	H—Si	333.3
SiHCl₃	Si—Cl	379.6
Cl方正汇总行₂	Cl—Cl	193.6

自由基、原子	DE/（kJ·mol^-1）
·Cl与·Cl	193.6
·Cl与·SiCl₃	366.8
·SiCl₃与·SiCl₃	216.4

化合物	化学键	DE/（kJ·mol^-1）
（CH₃）₂SiHCl	H—Si	343.5
	H—C	378.4
	Si—Cl	411.9

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Inorganic Acid-Base-Salt Committee of CIESC

Study on thermal chlorination and mechanism of chlorodimethylsilane and trichlorosilane

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