1-硅烯的茂金属催化插入聚合制备聚碳硅烷

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes.

作者信息

Tian Yuelong, Ge Min, Zhang Weigang, Lv Xiaoxu, Yu Shouquan

机构信息

State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China.

University of Chinese Academy of Sciences, Beijing, 100049, China.

出版信息

Sci Rep. 2015 Nov 6;5:16274. doi: 10.1038/srep16274.

DOI:10.1038/srep16274

PMID:26541636

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4635340/

Abstract

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

摘要

锆茂用作催化剂，在二氯二甲基硅烷与钠脱氯过程中，使1-甲基硅烯直接插入到陶瓷前驱体聚锆茂碳硅烷（PZCS）中进行插入聚合反应，该催化剂具有很高的催化效率，聚碳硅烷的最大转化率高达91%。合成聚合物的平均分子量小于1400，且多分散性都很窄。催化聚合反应的机理被认为类似于锆茂对1-烯烃的配位插入聚合反应。所得到的PZCS具有很高的陶瓷产率，形成了ZrC-SiC复合陶瓷，它们是超高温陶瓷（UHTC）纤维和复合材料的新型聚合物前驱体。