超分子离子化二烯烃的易位聚合及聚合物结构与多重响应性

In light of the fact that the international academic research of polyrotaxanes via metathesis polymerization has just started, we propose this project focused on the fundamental studies about the acyclic diene metathesis (ADMET) polymerization methodology and multifunctional polyrotaxanes based on supramolecular monomers. The research involves four aspects, including synthesis of functional ionic dienes and supramolecular ionic diene monomers with cyclodextrin molecule, evaluation of the reaction behavior and kinetics of ADMET polymerization catalyzed by the ruthenium carbene catalysts, the topological structure of polyrotaxanes, and elucidation of multi-stimuli-responsive property. The research will master the efficient synthetic approach of supramolecular ionic diene monomers, discriminate the difference of the general rule and control of ADMET polymerization. The main objective of this research is not only to obtain a novel class of multifunctional polyrotaxanes with high molecular weight, good solubility property, high threading, unique environmental responsive property, and diversified structure, but also to know the matched information between the species of host molecule, the type of guest molecule, the structure and functionality of polyrotaxanes, and finally to provide full and accurate evidence for further optimizing the structure and functionality of polyrotaxanes. The study is expected to improve and perfect the generally adaptability of ADMET polymerization of supramolecular monomers, which would be a valuable strategy for establishing a novel family of multifunctional polyrotaxanes. It has the high academic value and strongly applied prospect for enriching and developing the researched new field in metathesis polymerization and supramolecular materials.

超分子单体易位合成聚轮烷的研究少，探索性强。基于此，本课题拟开展超分子单体的非环二烯烃易位（ADMET）聚合方法学和功能化聚轮烷多重响应性的基础研究。通过环糊精（CD）为主体分子的超分子离子化二烯烃的合成、钌卡宾催化剂引发ADMET聚合反应的行为和动力学、聚轮烷拓扑结构的构建与多重刺激响应性的研究，掌握合成超分子离子化二烯烃单体的有效方法，甑别不同反应介质中ADMET聚合反应的规律和差异。研制出一类分子量高、溶解性好、CDs覆盖率高、环境响应性强、结构多样化的多功能聚轮烷，获得关于主体分子种类、客体分子类型、聚轮烷结构与性能相互关系的信息，为进一步优化聚轮烷结构和刺激响应性能提供翔实的依据。本项研究旨在建立超分子二烯烃单体ADMET聚合的普适性方法，丰富多功能聚轮烷的内涵，这无论是对高分子化学还是超分子新材料科学的研究与发展，都具有重要的意义。

该项目基于偶氮苯与环糊精分子之间的主客体相互作用和离子化偶氮烯烃单体的易位聚合反应，进行探索和创新研究。设计合成了几种不同结构类型的、含偶氮苯功能基的离子化二（环）烯烃单体，对其在不同反应条件下的易位聚合反应进行系统研究，全面揭示反应条件、单体性质和烯烃种类等因素对聚合反应的影响、反应宏观动力学和微观特征等基本规律。经过积极探索，成功地实现了利用烯烃易位聚合反应制备离子化偶氮聚合物，研究聚合物的离子化效应及其他功能性基团与偶氮苯光响应行为之间的相互关系。进一步拓展偶氮聚合物的类型，在烯烃易位聚合的基础上通过与其他聚合方法联用，制备结构多样化的偶氮聚烯烃，探讨聚合物的拓扑结构与自组装形貌的关系及其对光响应性能的影响，获得关于结构、形貌和性能之间相互联系的信息。在此基础上利用“一锅法”制备了含金刚烷和环糊精的两亲性超分子嵌段和交替接枝共聚物，研究超分子结构的形态和性能。该项目完善了烯烃易位聚合方法，改善了易位聚合物的结构、形态和性能，丰富了易位聚合物的研究内容，开拓了易位聚合材料的应用领域。