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Polymerization of methylsilylenes into polymethylsilanes or polycarbosilanes after dechlorination of dichloromethylsilanes?
Tian, Yuelong1,2; Zhang, Weigang1; Ge, Min1; Yu, Shouquan1; Lv, Xiaoxu1,2; Zhang, Tingting1,2
2016
Source PublicationRSC ADVANCES
ISSN2046-2069
Volume6Issue:25Pages:21048-21055
Abstract

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.

KeywordSilicon-carbide Fiber High-tensile Strength Preceramic Polymer Pyrolysis
SubtypeArticle
Subject AreaChemistry, Multidisciplinary ; Chemistry
WOS HeadingsScience & Technology ; Physical Sciences
DOI10.1039/c5ra27889a
URL查看原文
Indexed BySCI
Language英语
WOS KeywordSilicon-carbide Fiber ; High-tensile Strength ; Preceramic Polymer ; Pyrolysis
WOS Research AreaChemistry
WOS SubjectChemistry, Multidisciplinary
Funding OrganizationChinese Academy of Sciences, National Natural Science Foundation of China(51472243) ; National High-tech R&D Program (MOST)
WOS IDWOS:000371019000073
Citation statistics
Document Type期刊论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/20710
Collection研究所(批量导入)
Corresponding AuthorZhang, Weigang
Affiliation1.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
Recommended Citation
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.
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