新型碳化硅陶瓷前驱体聚（甲基硅烷-碳硅烷）的合成与表征

Synthesis and characterization of a new poly(methylsilane-carbosilane) for SiC precursor

摘要

碳化硅陶瓷基复合材料（SiC-CMC）是一种轻质高强的耐高温热结构材料，已广泛应用于航空航天等高新技术领域。碳化硅陶瓷前驱体是采用前驱体浸渍裂解工艺制备这类复合材料的基础原材料，但高昂成本限制了其商业化批量应用，发展新型的低成本碳化硅陶瓷前驱体对SiC-CMC的发展和规模应用具有重要意义。本工作以二氯甲基甲基硅烷（Cl₂CHSiMeH₂）为单体、氯甲基甲基硅烷（ClCH₂SiMeH₂）为封端剂，通过Wurtz偶联反应合成新型碳化硅陶瓷前驱体聚合物（PMSCS）。由于单体中部分Si―H键在聚合过程中也参与反应，PMSCS是一种分子结构主链由C―C和Si―C键组成的支化结构聚合物，其储存稳定性和溶解性良好，1000 ℃陶瓷产率达74%（质量分数）。与目前应用最广的Yajima法聚碳硅烷相比，PMSCS的合成更为简便，无需高温重排步骤，熔点更低且陶瓷产率更高；与超支化液态聚碳硅烷的制备相比，PMSCS不涉及使用昂贵的还原剂氢化铝锂，因此，其作为低成本碳化硅陶瓷前驱体具有良好的应用前景。

Abstract

Silicon carbide ceramic matrix composites (SiC-CMC) are lightweight，high-strength and high-temperature resistant thermal structural materials，which have been widely applied in high-tech fields such as aerospace. Preceramic polymers are key materials for the fabrication of such composites via the process of precursor infiltration and pyrolysis. However，the high cost of the materials has prevented their widespread use. Developing new silicon carbide ceramic precursors and reducing their preparation costs are of great significance for the advancement and application of SiC-CMC. In this work，a new silicon carbide ceramic precursor polymer，PMSCS，was synthesized via the Wurtz coupling reaction using dichloromethylmethylsilane (Cl₂CHSiMeH₂) and chloromethylmethylsilane (ClCH₂SiMeH₂) as the monomer and end-capping agent，respectively. Owing to the participation of reactive Si―H bonds in the monomer during polymerization，PMSCS is a branched polymer with a main chain consists of C―C bonds along with Si―C bonds，which exhibits good solubility and storage stability，with a ceramic yield of 74% (mass fraction) upon pyrolysis at 1000 ℃ under inert atmosphere. Compared with the most widely used Yajima method polycarbosilane，PMSCS offers a higher ceramic yield，and its synthesis is simpler，eliminating the need for a high-temperature rearrangement step. Additionally，the synthesis of PMSCS does not require expensive lithium aluminum hydride as a reducing agent，which is essential for the preparation of hyperbranched liquid polycarbosilane. Therefore，PMSCS shows promising potential as a cost effective silicon carbide ceramic precursor.

关键词

碳化硅陶瓷 / 聚合物前驱体 / 改性聚甲基硅烷

Key words

SiC ceramic / polymer precursor / modified polymethylsilane

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