碳硼烷活性基团的调控及其在丁羟推进剂中迁移的抑制作用

Design and synthesis of burning-rate catalysts to improve the performance of HTPB has an important meaning. However, development of carborane-based burning-rate catalyst has been restricted by its migration. Traditional methods need harsh reaction conditions and introduce functional groups on carbon. We proposed a method which can achieve regioselective dialkylation including functional groups of o-carboranes by direct cage B-H activation to reduce its migration in HTPB. The desired products have both high combustion heat and interaction force with HTPB. This project includes design, synthesis and analysis of carboranes to improve their abilities in HTPB. The combustion heat can be measured by oxygen bomb burning and DSC to understand the relationship between molecular structure andcombustion heat. After that, molecular dynamic simulation and experimental studys can explain relationship between functional groups and migration. This project has a significant meaning for synthesizing high-performance solid propellant.

碳硼烷等新型高效燃速催化剂的设计和合成，对提高丁羟推进剂的燃速具有重要意义，而且应用前景广阔。但是，易迁移一直是制约碳硼烷类燃速催化剂应用的关键。传统的改善方法基于碳原子的衍生化，难以对结构进行准确调控。本项目提出利用硼原子反应位点多以及对整体结构影响较小的优势，在硼原子上选择性引入双烷基活性基团，与丁羟推进剂产生分子间氢键，实现碳硼烷与丁羟推进剂的协调匹配和调控；拟采用烷基化手段，开展碳硼烷衍生物设计、合成，达到同时提高燃烧热值和增加燃速催化剂与丁羟推进剂有效结合的目的；揭示活性基团对迁移性的影响规律，获得分子结构与燃烧热值的关系；采用色谱分析与分子模拟相结合的手段，研究碳硼烷在丁羟推进剂中的扩散机理，揭示活性基团与丁羟推进剂的混合作用机制。本项目的成功实施，对合成高性能固体推进剂具有重要的理论意义和应用价值。

碳硼烷作为燃速催化剂使用时需要降低其在丁羟推进剂的迁移性。本项目通过利用羧基导向的作用，铑催化区域选择性的合成数十种双烷基取代碳硼烷，提出了其反应机理；另外通过钯催化区域选择性的合成数十种双烯基取代碳硼烷，提出了其反应机理。为合成新型碳硼烷衍生物提供了两种高效的合成方法。项目后续对改性后的碳硼烷进行分子动力学模拟，模拟计算碳硼烷在其中的分子动力学，分析其在丁羟推进剂中的迁移性，计算碳硼烷与HTPB的相互作用力，发现活性基团可以降低碳硼烷在丁羟推进剂中的迁移性。.项目负责人以第一或通讯作者在Organic letters，Organic & Biomolecular Chemistry发表标注项目号（21905223）的SCI论文2篇，授权发明专利1项。