多组分聚合反应制备新型含9,9-二苯基呫吨结构聚醚和聚酰胺及其性能研究

Aromatic polyethers and polyamides are all classified as high performance engineering thermoplastics because of their combination of excellent thermal and thermooxidative stabilites, outstanding mechanical and electrical properties, and are widely used in aerospace, electronics and other high technology fields. However, conventional methodologies for its preparation possess disadvantages including pre-activation, harsh reaction conditions, tedious protection-deprotection procedures, and toxic byproducts. Therefore, development of new methodologies for the synthesis of these polymers with novel structures and unique properties is a fundamental important area in macromolecular science. Multi-component reactions (MCRs) with advantages such as simple operation and high atom economy, have be recognized as a very powerful technique for rapid synthesis of structurally diverse organic compounds. Based on our own previous study results, and inspired the recent developments in MCRs, two series of novel aromatic polyethers and polyamides containing 9,9-diphenylxanthene moieties will be developed through 1,3-dipolar cycloaddition and coupling reactions, and by one-pot, multi-component polycondensation reaction based on monomers such as terminal diynes and terminal diazides bearing 9,9-diphenylxanthene units in this study, respectively. The reaction conditions for the preparation of monomers and one-pot, multi-component polycondensation reaction for the corresponding polymers will be investigated. The influences of 9,9-diphenylxanthene, 1,2,3-triazol and propargyl moieties on the properties such as the solubility, processability, thermal stability, and mechanical property as well as optical and dielectric behaviors of these new polymers will also be study. We hope to develop several novel kinds of these polymers with a combination of excellent properties, and provide theoretical and experimental foundation for their potential application of these resulting polymers as high performance engineering thermoplastics and functional materials.

芳香族聚醚和聚酰胺均属高性能工程塑料，它们以其优异的热、电和机械性能广泛应用于宇航、电子、电器等高新技术领域中，但传统的聚合方法，存在不少缺点，因而探索制备这类聚合物的新方法是高分子科学领域重要的研究课题之一。多组分反应具有操作简单，原子经济性好等优点，是一种高效、快速合成结构多样性化合物的技术。本项目拟在前期工作和近年来多组分反应研究的基础上，设计合成含9,9-二苯基呫吨结构的端二炔和二叠氮等新单体，通过1,3-偶极环加成和偶联等反应，探索其参与"一锅法、多组分"制备含9,9-二苯基呫吨结构单元的新型聚醚和聚酰胺的聚合方法。拟优化单体制备和多组分聚合反应条件，研究9,9-二苯基呫吨、三唑和炔丙基等结构单元对相应聚合物的溶解性、加工性以及热、电、光、力学等性能的影响，期望获得易制备且综合性能优异的聚醚和聚酰胺新品种，为其作为高性能工程塑料和功能材料的潜在应用提供一定的理论基础和实验依据。

传统的聚合方法和工艺，存在单体不易获得，或聚合条件苛刻，或多步反应后处理烦琐等缺点。发展快速高效、操作简单、原子经济性好的聚合方法以制备结构和性能独特的聚芳醚和聚芳酰胺等高性能聚合物和功能性大分子具有重要的学术意义和潜在的工业应用价值。多组分/串联聚合反应继承了有机小分子多组分反应的优点，是一种高效、快速合成结构可控和多样化先进聚合物材料的技术。. 本项目设计并合成了含9,9-二苯基呫吨结构的端二炔和二溴等新单体，通过1,3-偶极环加成和偶联等反应，探索了其参与“多组分、一锅法” 聚合反应、“多组分、串联”聚合反应制备含9,9-二苯基呫吨结构单元的新型聚酰胺、聚酯酰胺、聚三唑甲基芳基醚、聚烯胺酮、聚吡唑和聚异噁唑等一系列聚合物的聚合方法，并对其结构和性能进行了表征，研究了三氟甲基、呫吨、三苯胺和吡啶等基团对聚合物性能的影响，获得了一些易制备和加工，热、电、光、力学等综合性能优良的功能聚合物新品种，为其潜在应用提供了一定的实验依据和理论基础。