有机胺结构对氯代二硅烷催化裂解反应的影响研究  

Effect of Structure of Organic Amine on Catalytic Cracking of Chlorinated Disilane

作　　者：赵文龙 籍煜雯 彭文才 刘平[1] 张建树[1] 张金利[1,2] ZHAO Wenlong;JI Yuwen;PENG Wencai;LIU Ping;ZHANG Jianshu;ZHANG Jinli(School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering,Shihezi University,Shihezi 832003,Xinjiang;School of Chemical Engineering&Technology,Tianjin University,Tianjin 300072)

机构地区：[1]石河子大学化学化工学院,化工绿色过程省部共建国家重点实验室培育基地,新疆石河子832003 [2]天津大学化工学院,天津300072

出　　处：《有机硅材料》2023年第1期1-7,共7页Silicone Material

基　　金：兵团重大科技项目(2020AA004,2017AA007);八师重大科技项目(2020ZD02)。

摘　　要：采用气相色谱和核磁共振硅谱对多晶硅行业副产氯代二硅烷的成分进行了分析。研究了氯化氢、有机胺催化剂和反应温度对氯代二硅烷裂解反应的影响。结果表明,氯代二硅烷中主要含有Si_(2)Cl_(6)、Si_(2)HCl_(5)、Si_(2)OCl_(6)、SiCl_(4)和SiHCl_(3)。芳香胺作催化剂时,无裂解试剂氯化氢存在下Si_(2)Cl_(6)和Si_(2)HCl_(5)不发生裂解反应,通入氯化氢后Si_(2)Cl_(6)和Si_(2)HCl_(5)迅速发生裂解反应生成SiHCl_(3)和SiCl_(4);脂肪胺作催化剂时,无裂解试剂氯化氢存在下Si_(2)HCl_(5)可在30 min内完全裂解,通入氯化氢后Si_(2)Cl_(6)开始进行裂解反应;在有机硅胺存在下,氯代二硅烷中的Si_(2)OCl_(6)不发生裂解反应,Si_(2)HCl_(5)比Si_(2)Cl_(6)更容易发生裂解反应,氯化氢的加入有助于裂解反应的进行;氯代二硅烷裂解反应的催化剂优选N,N-二甲基苯胺,此时氯代二硅烷裂解率和氯代单硅烷收率均随着反应温度的升高而升高。The components of chlorinated disilane in polysilicon industry were analyzed by gas chromatography and nuclear magnetic resonance silicon spectroscopy. The effects of hydrogen chloride, organic amine and reaction temperature on the cracking reaction of chlorinated disilane were studied. The results show that the chlorinated disilane mainly contains Si_(2)Cl_(6), Si_(2)HCl_(5), Si_(2)OCl_(6), SiCl_(4) and SiHCl_(3). When aromatic amine was used as catalyst, Si_(2)Cl_(6) and Si2HCl5did not undergo cracking reaction in the absence of cracking reagent of hydrogen chloride. After the introduction of hydrogen chloride, Si2Cl6and Si2HCl5rapidly underwent cracking reaction to produce SiHCl_(3) and SiCl_(4). When aliphatic amine was used as catalyst, Si_(2)HCl_(5) could be completely decomposed within 30 min without the presence of cracking reagent hydrogen chloride, and Si2Cl6began cracking reaction after the introduction of hydrogen chloride. In the presence of organosilamine, the cleavage of Si_(2)OCl_(6) in chlorinated disilane did not occur, and the cracking of Si_(2)HCl_(5) was more likely than that of Si_(2)Cl_(6). The addition of hydrogen chloride helps the cracking reaction. N,N-dimethylaniline is preferred as the catalyst for the cracking reaction of chlorinated disilane. In this case, the cracking rate of chlorinated disilane and the yield of chlorinated monosilane increases with increasing temperature.

关 键 词：多晶硅 有机胺 氯代二硅烷 催化裂解 氯化氢 

分 类 号：TQ264.12[化学工程—有机化工]