调控高分子效应构筑纤维-铜配合物高效催化端炔偶联和串联反应

Polymer effects involve the essential questions on structure-activity relationship of polymer-supported metal catalysts, and tuning the polymer effects affords an important guiding significance to design and develop novel polymer-supported catalytic systems. However, the polymer effects have not yet put together a quite mature theory and be many influence factors, it will always be the emphases and difficulty in the research area of polymer-supported catalysis. Based on the polymer fiber-supported catalysis in our group, this project proposes to utilize the commercial available fibers involve polypropylene, polyacrylonitrile, polybenzimidazole, poly(p-phenylene benzobisoxazole), polyphenylene sulfide and poly(ether-ether-ketone) as the support to construct copper complexs, and tuning the polymer effects to orientedly acquire the moderate and controllable catalytic systems about the coupling and cascade reactions of terminal alkynes. By tuning the effects on polymer matrix, functional group and the synergistic effect on multi-functional groups, to construct the copper complexs in the surface layer of fiber, and studying the catalytic properties on terminal alkyne coupling and cascade reactions. Moreover, through adjusting the skeleton structures to inquiry the structure-activity relationship and the tuning mechanism of the fiber-supported copper complex, and then improving the manufacture to establish new green catalytic systems for terminal alkyne coupling and cascade reactions. Furthermore, to summarize the polymer effect rules of the fiber-supported copper complex catalysts, and providing a scientific basis for the development of new types polymer-supported catalysts, especially for the progress of fiber-supported metal catalytic systems.

高分子效应涉及高分子负载金属催化剂结构与性能关系的本质问题，通过高分子效应的调控，对设计和开发性能优异的高分子负载催化体系具有重要指导意义。然而高分子效应影响因素多，理论不成熟，仍将是该领域的研究重点和难点。本项目在课题组高分子纤维负载催化的基础上，提出了以商用纤维聚丙烯腈、聚丙烯、聚苯并咪唑、聚对苯撑苯并二噁唑、聚苯硫醚和聚醚醚酮等为载体，调控高分子效应，负载铜配合物，定向获取温和可控的端炔偶联和串联反应体系的研究。拟通过高分子基体效应、载体功能基效应和多功能协同效应的调控，在纤维表层构筑铜配合物，研究其在端炔偶联和串联反应中的催化性能，调节构筑方式，探究纤维-铜配合物的构效关系及其高分子效应调控机制，继而改进催化工艺，构建新型、绿色的端炔偶联和串联反应催化体系，并总结纤维负载铜配合物催化剂高分子效应的作用规律，为设计新型高分子负载催化剂，特别是纤维负载金属催化体系发展提供科学依据。

高分子负载催化体系中，高分子不只是催化剂的惰性载体，它可以对催化活性中心进行修饰或改变其特征结构，即存在着高分子效应从而影响催化剂的性能，并影响催化反应进程。本项目针对纤维负载铜配合物及其它金属配合物和小分子等，在端炔偶联和串联反应以及拓展催化体系中的高分子效应开展了系统调控，研究基本明确了：（1）纤维基体种类的调控能够影响反应溶剂的选择性，一些反应能特异性的在水中进行是由于高分子基体的疏水性且水促使反应底物在纤维表层富集导致的；（2）通过载体功能基的调控如调节配体链接长短以及引入辅助基团改变活性位周围的极性环境等，可显著影响纤维催化剂的活性，其中铜配合物以阴离子配位的负载模式可有效避免胺类配体易与卤代烃、酸等反应造成的铜流失来高效催化端炔偶联和串联反应；（3）纤维表层可同时构筑铜配合物和其它活性位，通过进一步调控二者的协同作用，能够显著提高一些反应的性能。项目执行期间在J. Catal.、Green Chem.、Chem. Commun.、Chem. Eng. J.等期刊发表研究论文9篇，化学工业出版社出版专著1部，发明专利2项，相关研究发现对更深层次地揭示纤维负载催化材料性能与结构的内在关系，推动高分子负载催化的进程以及绿色催化体系的设计和构建都具有积极意义，特别是对聚合物纤维负载催化“高分子效应”的系统认识提供一些科学的依据，并对纤维催化材料在工业催化中的应用提供了一些技术支持。