大位阻IPr配体在磁性聚合物微球上的负载过程及其对Suzuki反应的催化-材料加工工程专业论文.docx

摘要 摘要 I I 摘要 Suzuki 反应自铃木章先生发现以来，已成为构建联芳烃结构的有力工具， 在过去几十年对于均相钯催化剂的发展和研究取得了巨大进步，目前应用最广 的是主要以含膦配体的钯催化剂为主，而这一类催化剂储存和使用稳定性较差， 且均相体系难以回收利用。采用细乳液技术我们制备了一种具有高磁含量的苯 乙烯复合微球作为载体，对其制备工艺进行优化，并在其表面修饰功能基团， 同时合成了具有大位阻基团的 IPr 配体及其碘代结构，探究了采用常规负载方法 中采用傅克反应所使用的催化剂 AlCl3 的对 Pd 与 IPr 配体络合的影响。创造性的 利用了钯催化剂对 Buchwald-Hartwig 偶联反应的催化作用，将催化剂与载体构 建 C-N 偶联底物条件，使催化剂通过自身催化实现负载的过程。同时对自催化 负载方案中氨基封端与苯基封端对催化剂性能的影响做了研究，并对最佳条件 作了研究，发现对于溴苯底物在采用乙醇水溶剂条件下，K2CO3 作为碱，70 oC 反应 4 h 即可达到反应完全，氨基封端磁性催化剂和苯基封端的催化剂对于溴苯 底物具有较高的催化效率，可以在 ppm 级的钯用量下催化溴苯的 Suzuki 反应的 发生，但遗憾的是由于位阻取代基电子效应的影响，对于氯苯却并无良好效果。 同时对比两种催化剂，发现吸电子基团封端的催化剂其性能要优于供电子基团 封端的催化剂，表明位阻基团上的取代基不仅仅起到了调节位阻的作用，其供 电性能的不同更是对催化剂的催化活性有不同的作用。 关键词：细乳液聚合 磁性苯乙烯纳米微球 Suzuki 偶联反应 自催化 负载 II II Ab Abstract -III- -III- Abstract Since the Suzuki reaction was first discovered by Suzuki, it has become a powerful tool to form biaryl compouds. It has made big progress on the homogeneous palladium catalyst research in the past few decades. Phosphines has always been used as ligands for Palladium catalysts in Suzuki reactions, which has low stability and also hard to separate and recovery. In this work, magnetic polystyrene microspheres with high magnetic content was prepared by miniemulsion polymerization and also the preparation process has been optimized optimized. Then, the surface was modified with functional groups. We also synthesized the bulky IPr ligand and its iodine substituted structure. The usage of AlCl3 in Fredel-Crafts to realize the loading process has affect the coordination between IPr and palladium. We have developed a new way to immobilize the catalyst by using its catalytic property in Buchwald-Hartwig coupling reaction to modify the IPr and carrier with correspond groups. We have investigated the catalytic activity of the supported catalysts with different capping groups in Suzuki reaction and the optimum reaction conditions. It was found that the optimum conditions were obtained as follows: the mixture of ethanol and water as solvent, K2CO3 at the temperatur