离子液体中易位环化聚合及共轭聚乙炔离聚物结构和导电性研究

In light of the fact that the international and domestic academic research of metathesis cyclopolymerization (MCP) in ionic liquid has just started and a disputed contention, and the exploration of MCP catalyzed by the vanadium carbene catalyst has not yet been carried out, we propose this project focused on the fundamental studies about the MCP methodology and multifunctional polymers. The research involves four aspects, including synthesis of hyperbranched triazolium as side group and the macromonomer of 1,6-heptadiyne derivatives, evaluation of the reaction behavior and kinetics of MCP catalyzed by the ruthenium carbene catalysts in different reaction media, investigation of the essential characteristics of MCP initiated by the vanadium carbene catalysts, and elucidation of the relationship between the microstructure and functionality of conjugated polyacetylene ionomers. The research will master the efficient synthetic approach of hyperbranched ionic diyne macromonomer, discriminate the difference of the general rule and stereoselectivity control of MCP in both organic solvent and ionic liquid, and reveal the reaction mechanism of MCP under the vanadium carbene catalytic system. The main objective of this research is not only to obtain a novel class of hyperbranched and conjugated polyacetylene ionomers with high moleculer weight, good solubility and film-forming properties, well-defined microstructure, and unique ionic/electronic conductivity, but also to know the matched information between the conjugated chain length, the density and type of ion on the side chain, microstructure and functionality, and finally to provide full and accurate evidence for further optimizing the structure and functionality of polymers. The study is expected to improve and perfect the generally adaptability of MCP method in ionic liquid, which would be a valuable strategy for establishing a novel family of conjugated polyacetylene ionomers with hyperbranched ionic side chain. It has the high academic value and strongly applied prospect for enriching and developing the researched new field in metathesis polymerization and multifunctional conjugated polymers.

基于离子液体中易位环化聚合（MCP）研究少且存有争议、钒卡宾催化剂尚未用于MCP研究的现状，拟开展关于MCP方法学和多功能聚合物的基础研究。通过超支化三氮唑离子侧基和二炔烃单体的合成、不同介质中钌卡宾催化剂引发MCP反应的行为和动力学、钒卡宾催化剂的MCP反应特征和聚乙炔离聚物微结构与功能性的研究，掌握合成超支化离子二炔烃大分子单体的有效方法，甑别有机溶剂和离子液体中MCP反应的规律和可控性差异，揭示钒卡宾催化剂的MCP反应机理。研制出一类分子量高、溶解性和成膜性好、导电性强的多功能离子/电子导电的超支化聚乙炔离聚物，获得关于共轭主链长度、离子密度和种类、聚合物微结构与功能性相互关系的信息，为进一步优化聚合物结构和光电性能提供翔实的依据。本项研究旨在建立普通离子液体中MCP反应的普适性方法，丰富多功能共轭聚合物的内涵，这无论是对高分子化学还是新材料科学的研究与发展，都具有重要的科学意义。

易位环化聚合（MCP）受到的关注比开环易位聚合（RMP）和非环二烯烃易位（ADMET）聚合少，尤其是普通咪唑离子液体（IL）中的MCP研究更少；而MCP反应能形成溶解性好的聚乙炔（PA）衍生物，是制备共轭聚合物的有效手段。基于此，我们开展了该领域的基础研究，完成了三方面的研究计划和预期目标，已发表论文19篇，授权发明专利3件。（1）MCP方法学的建立与新型结构聚合物的形貌和功能性评价。对于IL中的MCP反应，优化聚合条件，并利用1H NMR原位监测了MCP反应进程，为IL中MCP反应的成功实施提供了第一例直观的证据，回答了IL中MCP反应能否进行这个困扰该领域的争论性问题，揭示了离子化二炔烃在IL中的MCP反应规律，体现了重要的学术价值。利用MCP反应合成了苝酰亚胺桥联的首例梯形PA，可组装成规整的条带织构，具有优异的光物理性能。创建了串联式MCP-ADMET聚合新方法，合成出桥形结构的聚合物。利用串联式ROMP-MCP方法，合成了有规立构的聚烯烃-PA嵌段共聚物，能自组装形成以导电PA为核、绝缘聚烯烃为壳的胶束、空心球或超分子螺旋管纳米形貌，丰富和拓展了易位聚合方法学的研究内容。（2）超支化聚三唑的合成、表征和导电性考察。利用点击化学反应，制备了高分子量的超支化聚三唑离子，表现出较高的室温离子导电率（σi为7.70×10-6 S/cm）；合成了超支化三唑离子/季铵盐离子杂化聚合物，σi提高为1.9×10-5 S/cm，体现了杂化离子对增强导电性的贡献。（3）支化/树形三唑离子化聚乙炔（iPA）的合成、微结构表征与离子/电子双重导电性调控。有效地解决了低分子量支化三唑的合成难题，合成了一系列含支化或树形三唑离子侧基的iPA，具有较低的玻璃化转变温度（Tg低于 -20 oC），σi为2.1×10-5-7.3×10-5 S/cm；掺杂LiTFSI后，σi上升为4.3×10-5-5.2×10-4 S/cm；用LiTFSI和I2掺杂后，表现出离子/电子双重导电性，σi提高至7.1×10-5-7.1×10-4 S/cm，σe为4.5×10-6-1.3×10-5 S/cm。总之，本项研究建立了IL中MCP反应的普适性方法，创新了易位聚合的研究手段，丰富了导电聚合物的内涵，为推动我国易位聚合的发展做出了应有的贡献。