【作者】 陈俊显；

【导师】 傅相锴；

【作者基本信息】 西南大学 ， 有机化学， 2009， 硕士

【摘要】 多相手性催化是目前催化领域重要的研究方向,多相手性催化环氧化是最为活跃的研究课题之一。聚（苯乙烯基-异丙烯膦酸）-磷酸氢锆（ZPS-IPPA）是本课题组在新型催化剂载体领域开发出来的一类新型复合催化剂载体材料。在性能上表现出较高的热稳定性和较好的耐酸碱性能,在结构上具有聚苯乙烯有机链段的可设计、可修饰性及层状结构,是集有机、无机载体的优点为一体的新型载体。本文首先对ZPS-IPPA中的苯环进行氯甲基修饰,进而进行胺化修饰,分别接枝不同链长的二胺（乙二胺、1,4-丁二胺,1,6-己二胺,对苯胺,联苯胺及4,4’-二胺基二苯醚）和多胺（二乙烯三胺、三乙烯四胺及四乙烯五胺）,再利用二胺或多胺端基氮原子与均相手性Salen Mn（Ⅲ）配合物中心的Mn原子进行轴向配位固载,实现了手性均相催化剂的多相化。运用FT-IR、DRUV-Vis、AAS、XPS、N₂吸附、SEM、TEM和TG等测试技术对同载型手性Salen Mn（Ⅲ）催化剂进行了表征。分别以次氯酸钠和间氯过氧苯甲酸为氧源考察了固载手性Salen Mn（Ⅲ）催化剂催化苯乙烯、α-甲基苯乙烯及茚的不对称环氧化反应的性能。研究了助催化剂、反应时间、反应温度、轴向接枝链长及催化剂用量对烯烃环氧化反应的影响。结果表明,同载手性Salen Mn（Ⅲ）催化剂表现出与均相手性Salen Mn（Ⅲ）值相当或更高的催化活性和对映选择性,尤其在对α-甲基苯乙烯的不对称环氧化反应时,转化率达68%,ee值达99%。固载催化剂有优良的重复使用性,重复使用8次后,催化性能无明显降低。更多还原

【Abstract】 In recent years,the heterogeneous asymmetric catalysis has received more and more attention.Among all the reactions,the heterogeneous asymmetric epoxidation is the most impressive.In this paper,Zirconium poly（styrene-isopropenyl phosphonate）-phosphate （ZPS-IPPA）,was synthesized.There are many caves,channels and pores with different shapes and sizes in the ZPS-IPPA particles.This kind of organic-inorganic hybrid materials has high thermal stability,acid and base stabilities, which can be used as a new kind of support material posessing advantages of organic-inorganic supports.In this work,it is pursued our research in the untapped area and diamine or ployamines modified ZPS-IPPA was prepared by the reaction of ZCMPS-IPPA with diamines or ployamines and then homogeneous chiral Salen Mn（Ⅲ） was immobilized onto the diamine or ployamines modified ZPS-IPPA by axial coordination thus a new type of heterogeneous chiral Salen Mn（Ⅲ） catalysts was obtained.All the heterogeneous chiral Salen Mn（Ⅲ） catalysts prepared were characterized by FT-IR, diffusion reflection UV-Vis,AAS,N₂ volumetric adsorption,SEM,TEM and TG..The NaClO and m-CPBA were used as oxidant for asymmetric epoxidation of styrene,α-methylstyrene and indene respectively.The factors,such as amount of catalyst, co-catalyst,the reaction time,the reaction temperature solvent and axial length were investigated for asymmetric epoxidation ofα-methylstyrene.The results confirmed that the catalysts exhibit comparable or even higher activity and enantioselectivity for asymmetric epoxidation of various unfunctionalized alkenes than those of homogeneous Jacobsen’s catalyst. Especially,in the epoxidation of a-methylstyrene,the conversion and enantiometric excess（ee） of 68%and 99%were obtained respectively.The catalysts were easily recovered by filtration and could be reused at least eight times with little loss of activity and enantioselectivity.更多还原