Polymerization of methylsilylenes into polymethylsilanes or polycarbosilanes after dechlorination of dichloromethylsilanes?

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	Polymerization of methylsilylenes into polymethylsilanes or polycarbosilanes after dechlorination of dichloromethylsilanes?
	Tian, Yuelong 1,2; Zhang, Weigang 1; Ge, Min 1; Yu, Shouquan 1; Lv, Xiaoxu 1,2; Zhang, Tingting 1,2
刊名	RSC ADVANCES
	2016
卷号	6 期号:25 页码:21048-21055
关键词	SILICON-CARBIDE FIBER HIGH-TENSILE STRENGTH PRECERAMIC POLYMER PYROLYSIS
ISSN号	2046-2069
通讯作者	Zhang, WG (reprint author), Chinese Acad Sci, Inst Proc Engn, State Key Lab Multiphase Complex Syst, Beijing 100190, Peoples R China.
英文摘要	Competition between two different polymerization pathways to polymethylsilanes (PMS) and polycarbosilanes (PCS) was studied. This occurs in a Wurtz reduction-coupling reaction system during dechlorination of several dichloromethylsilanes via sodium in toluene. These two reactions do not carry on pari-passu, i.e., PMS is exclusively formed. However, PCS can be formed dominantly when some zirconocenes are introduced. This competition was introduced as a result of a tautomeric transformation from methylsilylene (MeRSi:) into 1-silene (CH2=SiRH). These are formed simultaneously as two intermediates but are influenced by the substitution of methyl, ethyl, phenyl or vinyl groups on silicon in the dichloromethylsilanes. Polymerization of methylsilylenes into PMS can be inhibited by deactivation of the sodium surface via chemical adsorption of zirconocene dichloride. Hence, the catalytic insertion polymerization of 1-silene intermediates into PCS occurs at the active sites of zirconocenes-this leads to the formation of PCS conversion ratios of 82% to 93% from dichloromethylsilanes with methyl, ethyl and phenyl as substituents. However, catalytic polymerization does not happen from dichloromethylvinylsilane. The mechanisms of insertion polymerization as well as the thermal dynamic barrier from polymethylvinylsilane (PMVS) to polyvinylcarbosilane (PVCS) are discussed in detail.
学科主题	Chemistry, Multidisciplinary ; Chemistry
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Multidisciplinary
研究领域[WOS]	Chemistry
关键词[WOS]	SILICON-CARBIDE FIBER ; HIGH-TENSILE STRENGTH ; PRECERAMIC POLYMER ; PYROLYSIS
收录类别	SCI
原文出处	ROYAL SOC CHEMISTRY
语种	英语
WOS记录号	WOS:000371019000073
内容类型	期刊论文
源URL	[http://ir.ipe.ac.cn/handle/122111/20710]
专题	过程工程研究所_研究所（批量导入）
作者单位	1.Chinese Acad Sci, Inst Proc Engn, State Key Lab Multiphase Complex Syst, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Tian, Yuelong,Zhang, Weigang,Ge, Min,et al. Polymerization of methylsilylenes into polymethylsilanes or polycarbosilanes after dechlorination of dichloromethylsilanes?[J]. RSC ADVANCES,2016,6(25):21048-21055.
APA	Tian, Yuelong,Zhang, Weigang,Ge, Min,Yu, Shouquan,Lv, Xiaoxu,&Zhang, Tingting.(2016).Polymerization of methylsilylenes into polymethylsilanes or polycarbosilanes after dechlorination of dichloromethylsilanes?.RSC ADVANCES,6(25),21048-21055.
MLA	Tian, Yuelong,et al."Polymerization of methylsilylenes into polymethylsilanes or polycarbosilanes after dechlorination of dichloromethylsilanes?".RSC ADVANCES 6.25(2016):21048-21055.