碳硼烷聚合物分子设计及耐高温性能的构效关系研究

Carborane polymer is a good high-temperature stable polymer materials, widely used in the aerospace industry. The research on carborane polymers has become an important field for organic boron chemistry. This research project focuses on aspects of molecular design and quantitative structure-properties relationship of resistance to high temperature in carborane polymers. This project is divided into four parts: (a) computation and simulation of molecular structures and spectroscopy properties of carborane polymers; (b) research on the substituent effect in the process of molecular design of carborane polymers; (c) computation and analysis in carborane polymer synthesis; (d) research on molecular design and the mechanism of resistance to high temperature in carborane polymers. The high level quantum chemistry method and molecular modeling technique will be used to study this project. According to the scientific scheme designed, we will solve some key problems such as performance testing, reasonably constructing the network structures of carborane polymers, and model establishment of quantitative structure-performance relationship. This project is featured with a combined experimental and theoretical study the relationship between thermostablity and molecular structures of carborane polymers, which relies on the hardware and software platforms of Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences. This project aims at molecular design and exploration for the mechanism of resistance to high temperature in carborane polymers. The theoretical results will provide support to the modification and design of carborane polymers as well as its application in aviation and aerospace fields. The applicant has a good working basis and working conditions, which can ensure that this project will be systematically carried out with reliable scheme, feasible technology and verifiable objectives over three years.

碳硼烷聚合物是很好的耐高温有机高分子材料，在航空、航天工业中广泛使用。研究碳硼烷聚合物分子设计及耐高温性能的构效关系已成为有机硼化学的重要研究领域。项目共分为四部分研究内容：计算模拟碳硼烷聚合物的分子结构光谱性质；碳硼烷聚合物分子设计中的取代效应；碳硼烷聚合物合成中的计算分析；碳硼烷聚合物分子设计及其耐高温性能研究。通过高水平量化计算和分子模拟方法，按着合理的技术路线，重点解决碳硼烷聚合物本征性能和耐高温性能参数的测试，合理动力学模型的构建以及耐高温“结构—性能”关系的建立。以深入的理论研究和实验相结合为特色，依靠中科院上海有机所优良的软硬件平台，开展碳硼烷聚合物分子设计和耐高温构效关系研究，为碳硼烷聚合物的改性设计及其在航空、航天材料中的应用提供理论支持。申请人有着很好的工作基础和工作条件，确保申请课题是方案科学、技术可行、成果可考的。整个课题分三年有计划有步骤地开展。

碳硼烷是一种具有特殊化学稳定性和耐高温特性的化合物，将其引入到聚合物结构中，可以改善聚合物的耐热性质，具有很好的应用前景和潜在的应用价值。比如，将碳硼烷基团引入到具有π电子共轭结构的分子中（如吡咯、噻吩），形成具有耐高温的导电功能性的碳硼烷聚合物。.通过理论计算方法，对含有不同取代基结构的碳硼烷聚合物单体进行了性能预测，并对其聚合物进行了分子设计。优化了吡咯烷基碳硼烷、噻吩羧酸及吡咯羧酸碳硼烷甲酯的分子结构，计算了它们的11B核磁化学位移和1H核磁化学位移，比较了的理论和实验值，验证了理论计算的可靠性。计算比较了不同碳硼烷衍生物分子的LBO键级、HOMO/LUMO能隙、二聚体的能带等性质，探讨了吡咯烷基碳硼烷的耐高温和导电性的取代效应，分析了不同碳硼烷分子取代基对耐高温和导电性的“结构-性能”关系。发现了噻吩羧酸碳硼烷甲酯单体具有更小的HOMO/LUMO能隙，能够展现出更好的导电能力和耐高温性。探索合成了单吡咯-3-羧酸碳硼烷甲酯，并对其中间体进行了表征和理论计算，计算的11B NMR与实验结果基本一致。