D3h对称性导向聚酰亚胺分子设计及超分子聚集体可调控构筑

Symmetry is a strong and powerful framework to perceive and predict the physical world,triptycene has very special symmetry D3h with high internal molecular free volume in organic compounds.The research objective of this proposal is to develop the efficient chemistry for the molecular design and modular construction of polyimides with novel supramolecular architectures derived from D3h symmetry of triptycene.We plan to prepare a series of the novel triptycene-based dianhydride with varying number of 2D planar π-extended benzene rings and the shape-persistent core and periphery of different size and dimensionality.we will develop the simple and effective approach for preparation and investigate the structural characteristic and polymerization chemistry of the novel triptycene-based dianhydrides so as to synthesize new linear polyimides with high molecular weight.Using the modular strategy and through careful control and optimization of polymerization,we will construct new poly(arylene triptycene imide)s with different nanoscale supramolecular topological architectures derived from varying number of 2D planar π-extended benzene rings and the shape-persistent core and periphery of different size and dimensionality,in order to gain insight into the effect of the supramolecular hierarchical architectures across different length scales under both field-free and diverse gradient fields such as mechanics,electricity and temperature on the properties,we intend to explore the formation mechanism and evolving law of the novel poly(arylene triptycene imide)s and the relationship between structure and property from the supramolecular chemistry point of view.It is anticipated that this research will not only create new compounds and macromolcules to advance and enhance our understanding in triptycene chemistry and polymer science but also generate advanced functional materials to foster high-tech innovations.

对称性是认识物质世界的强有力结构特征，三蝶烯在有机化合物中有非常独特对称性D3h。我们提出基于三蝶烯结构基元D3h对称性导向聚酰亚胺分子设计及其超分子聚集体可调控构筑研究。基于三蝶烯结构D3h对称性设计合成可以逐渐调节变化二维平面刚性伸展的苯环的数量和三维结构的新型系列二酐单体，研究该类新型单体的简便有效合成方法、结构特征和聚合反应化学，探索高分子量线型聚酰亚胺的聚合反应体系和方法。通过逐渐调节二酐单体结构中的二维平面刚性伸展的苯环数量和三维结构来调控聚酰亚胺大分子链间相互作用，进而调控聚酰亚胺超分子聚集体凝聚态拓扑结构，研究该类聚合物分别在无场存在与在力学场、 电场和温度场等梯度场中不同层次不同尺度超分子结构的形成机制和演进规律，从超分子化学角度揭示新型聚酰亚胺超分子聚集体的多尺度结构及其结构与性能关系。本研究不仅对三蝶烯化学具有重要意义，而且为聚酰亚胺类先进功能材料研究应用提供新思路。

聚酰亚胺是一类重要的芳杂环高技术材料， 由于具有突出的综合性能和在合成上多种途径，以先进结构材料或功能材料广泛应用于航空航天、电子电器以及环境能源等与国家安全和高新技术发展密切相关的领域。基于反合成化学，目前绝大多数聚酰亚胺是二酐和二胺通过缩合聚合共聚制备的。为何聚酰亚胺没有像聚烯烃那样普及？成本过高是目前聚酰亚胺面临的主要问题，其中单体二酐是导致高成本的源头，芳香二酐不仅价格昂贵，可选择数量非常有限，只有区区数个，而且相关研究也极具特殊性和挑战性。对称性是物质世界强有力的结构特征，溶剂热反应可多层次多尺度调控无机材料结构与性质，将对称性与溶剂热反应组合,协同对有机高分子进行多层次多尺度可调控构筑研究鲜见.本项目开展了D3h对称性导向聚酰亚胺分子精准设计、溶剂热合成及其超分子聚集体多层次多尺度可调控构筑研究.通过精确调控二酐分子结构中的二维平面伸展苯环的数量,精确设计合成了新型系列功能单体，研究了该类单体的绿色合成化学、结构特征和溶剂热聚合反应.探索了系列新型聚酰亚胺溶剂热合成化学，从而多层次多尺度构筑了具有全新堆积组装拓扑结构的高分子超分子聚集体，研究了新型聚酰亚胺超分子聚集体结构和大分子链间非共价相互作用,探究了该类聚酰亚胺超分子聚集体在力场、电场和温度场以及溶剂场等梯度场中聚酰亚胺超分子结构的构筑形成机制和演进变化规律。基于单晶结构分析和理论模拟计算,全面认识和充分揭示了新型PI超分子聚集体多尺度不同层次结构及结构与性能关系。本研究不仅对高分子科学和超分子科学具有重要意义，而且对聚酰亚胺材料的研究开发应用提供新途径。