Polymer derived ceramics have received lots of attention throughout the last few decades. Unfortunately, only a few precursor systems have been developed, focusing on silicon based polymers and ceramics, respectively. Herein, the synthesis of novel hafnium containing organometallic polymers by two different approaches is reported. Dialkenyl substituted hafnocene monomers were synthesized and subsequently polymerized via a free radical mechanism. Salt metathesis reactions of hafnocene dichloride with bifunctional linkers led to the formation of polymeric materials. NMR spectroscopic methods – in solution as well as in the solid state – were used to characterize the organometallic polymers. Ceramics were finally obtained after cross-linking and thermal treatment under argon (Tmax = 1800 °C). SEM investigations, elemental analyses, Raman spectroscopy and XRD investigations identified the pyrolyzed products as partially crystalline HfC/C mixed phases.
过去几十年来,聚合物衍生陶瓷受到了广泛关注。遗憾的是,目前仅开发出几种前驱体系统,分别侧重于
硅基聚合物和陶瓷。本文报告了通过两种不同方法合成新型含
铪有机
金属聚合物的情况。合成了
二苯乙烯取代的
铪单体,随后通过自由基机制进行聚合。二
氯化铪与双官能团连接体的盐偏合成反应导致了聚合物材料的形成。利用核磁共振光谱方法(溶液和固态)对有机
金属聚合物进行了表征。经过交联和
氩气热处理(Tmax = 1800 °C)后,最终获得了陶瓷。通过
SEM 研究、元素分析、拉曼光谱和 XRD 研究,确定热解产物为部分结晶的 HfC/C 混合相。