金刚烷基（超）静定有机框架材料的设计、制备与构效关系研究

With the increasingly strengthening of the concept of energy-saving, environmental protection and sustainable development, it turns into the long-term pursuit that partially replacing metal or alloy materials with high-strength and low-density organic polymer material so as to realize lightweight in the industry field of aerospace, automotive, shipbuilding and so on. Up to date, the known high-strength and low-density polymers can only display high-strength in a certain direction, which is difficult to meet the developing need of modern industry. In this project, with the goal of obtaining isotropic polymeric materials of high-strength, high-stability and low-density, we use the principle of macro- static (over-) determined structural engineering and the concept of"reticular chemistry"to construct a kind of covalent bonds orientated 3D organic framework materials based on rigid molecular "knot" and "rod" structural units, in hope that these static (over-) determined framework polymers possess isotropic characteristics of high-strength, high-stability and low-density. The controllable preparation of the target polymers is to be realized through molecular design, structure simulation and the polymerizing process optimization. The structure - performance relationship and regulation mechanism can be revealed and obtained from the systematic research on structure characterization and property measurements. The research of this project will contribute to expand the design idea and reseach method of organic framework materials, and provide theoretical guidance and technical reference for the future development of isotropic polymers with light weight, high strength and high stability.

随着节能、环保和可持续发展理念的日益加强，采用高强度、低密度的有机高分子材料部分替代金属或合金材料，实现机身的轻量化，已成为航空航天、汽车、造船等工业领域长期致力追求的目标。迄今已知的高强度、低密度材料大多只能在特定方向才显示高强度，难以满足现代工业的发展需要。本项目以具有各向同性特征的高强度、低密度聚合物为目标，运用宏观结构工程中的(超)静定框架结构原理和"框架化学"的基本理念，采用刚性分子"结"、"杆"为基本结构单元，构建一种基于刚性结构单元和共价键导向的三维有机框架材料，以期制备具有各向同性特点的高强度、高稳定性、低密度聚合物。通过分子设计、结构模拟以及聚合反应过程的化工基础研究，实现目标材料的可控制备，并揭示其构-效关系和结构性能的调控机制。本项目的研究有助于拓展有机框架材料的设计思路，并为在任意方向都具有高强度、高稳定性和低密度材料的研制提供理论指导和技术借鉴。

随着节能、环保和可持续发展的理念深入人心，新型轻质稳定型有机框架材料在各领域的应用日益加强。本项目基于（超）静定结构原理和框架化学的设计理念，以金刚烷为核心设计了系列有机框架聚合物，并利用计算机技术对其结构进行了模拟预测设计。通过偶联反应合成了系列高物理化学稳定性、低密度的三维有机框架聚合物，优化了其合成的反应条件并获得了高效、定向、可控的合成方法。测试表征了系列有机框架聚合物的分子结构、微观形貌、密度、孔性质，研究分析了该材料的物理化学稳定性。研究探索了它在环境处理领域的应用情况和前景（如能源气体及有机蒸汽的吸附应用、油水混合物分离应用），揭示了该材料的部分构-效关系，本课题的开展实施为制备同类型高稳定性、轻质的框架聚合物提供了理论指导和实践依据。项目执行期间，相关研究成果先后发表学术论文27篇（SCI收录26篇，EI收录1篇），申请发明专利3件，授权专利2件。此外，在项目的资助下，已培养了博士后3名，博士研究生2名，硕士研究生5名。