Direct synthesis of silicon compounds from metallic silicon

由金属硅直接合成硅化合物

• 批准号: 11450304
• 负责人: SUZUKI Eiichi
• 金额: $ 1.66万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450304/
• 关键词: metallic silicon; direct synthesis; silicon compounds; silylene

Based on the reaction mechanism proposed by the head investigator and coworkers for the direct synthesis of trimethoxysilane from metallic silicon and methanol using copper (I) chloride as the catalyst, the reaction of metallic silicon with hydrogen chloride was carried out. When this reaction was conducted in the presence of propene, organosilicon compounds were formed. By examining the reaction factors such as amount of catalyst, reaction temperature, and molar ratio of propene to hydrogen chloride, optimum reaction conditions were obtained.For example, physical mixture of metallic silicon and copper (I) chloride powders (Cu= 5wt.%) was loaded in a fixed-bed flow reactor operating under the atmospheric pressure, and was heat-treated at 723 K for 10 min in a helium stream. Then, hydrogen chloride (10 mmol h^<-1>) and propene (5 mmol h^<-1>) were fed to the reactcr. The reaction for 5 h gave isopropyldichlorosilane and propyldichlorosilane with selectivity of 13 and 3%, respectively, the conversion of metallic silicon being 87%. Other silicon-containing compounds were trichlorosilane, dichlorosilane, and tetrachlorosilane.Just as same as the direct synthesis of trimethoxysilane from metallic silicon and methanol, the reaction proceeds via surface silylene formed on the silicon surface : silylene reacts with propene to finally form organosilicon ccmpounds

根据研究组长及其同事提出的以氯化铜(I)为催化剂，金属硅与甲醇直接合成三甲氧基硅烷的反应机理，进行了金属硅与氯化氢的反应。当这个反应在丙烯的存在下进行时，就形成了有机硅化合物。通过考察催化剂用量、反应温度、丙烯与氯化氢的摩尔比等因素，得到了最佳反应条件。例如，金属硅和氯化铜(I)粉末（Cu= 5wt）的物理混合物。在常压下的固定床流动反应器中装载，在723 K的氦气流中热处理10 min。然后，将氯化氢（10 mmol h^<-1>）和丙烯（5 mmol h^<-1>）送入反应器。反应5 h得到的异丙基二氯硅烷和丙基二氯硅烷的选择性分别为13%和3%，金属硅的转化率为87%。其它含硅化合物有三氯硅烷、二氯硅烷和四氯硅烷。与金属硅和甲醇直接合成三甲氧基硅烷一样，该反应是通过硅表面形成的表面硅烯进行的：硅烯与丙烯反应，最终生成有机硅化合物

项目成果

Masaki Okamoto: "Direct synthesis of Organodichlorosilanes by the reaction of metallic silicon. Hydrogen chloride and alkene/alkye"Journal of Chemical Society, Dalton Transaction. 71-78 (2001)

Masaki Okamoto：“通过金属硅反应直接合成有机二氯硅烷。氯化氢和烯烃/烷基”化学会杂志，道尔顿交易。

Masaki Okamoto: "Direct synthesis of alkyldialkoxysilanes by the reaction of silicon, alcohol and alkene using high-pressure reactor"Journal of Organometallic Chemistry. 619. 235-240 (2001)

Masaki Okamoto：“使用高压反应器通过硅、醇和烯烃的反应直接合成烷基二烷氧基硅烷”有机金属化学杂志。

M.Okamoto, S.Onodera, Y.Yamamoto, E.Suzuki, and Y.Ono: "Direct Synthesis of Organodichlorosilanes by the Reaction of Metallic Silicon, Hydrogen Chloride and Alkene/Alkyne and by the Reaction of Metallic Silicon and Alkyl Chloride"J.Chem.Soc.Dalton Trans..

M.Okamoto、S.Onodera、Y.Yamamoto、E.Suzuki 和 Y.Ono：“通过金属硅、氯化氢和烯烃/炔的反应以及通过金属硅和烷基氯的反应直接合成有机二氯硅烷”

M.Okamoto, J.Komai, M.Uematsu, E.Suzuki, Y.Ono: "Direct Synthesis of Alkyldialkoxysilanes by the Reaction of Silicon, Alcohol and Alkene Using a High-pressure Flow Reactor"J.Organomet.Chem.. 619. 235-240 (2001)

M.Okamoto、J.Komai、M.Uematsu、E.Suzuki、Y.Ono：“使用高压流动反应器通过硅、醇和烯烃的反应直接合成烷基二烷氧基硅烷”J.Organomet.Chem.. 619