摘要
采用不同链接基团修饰的聚(苯乙烯-异丙烯基膦酸)-磷酸氢锆(ZPS-IPPA)为复合载体,通过轴向固载方式制得非均相手性MnⅢ(salen)催化剂,并将其应用于非功能烯烃的多相不对称环氧化反应.结果表明,在以间氯过氧苯甲酸(m-CPBA)为氧化剂的反应体系中,以二胺为链接手臂固载的催化剂需要有轴向助剂参与,其转化率和对映选择性才能有较大提高;而以二酚或者二醇为链接手臂固载的催化剂在不添加轴向助剂的情况下,转化率和对映选择性均比添加轴向助剂时有明显提高.此外,制备的非均相催化剂在重复使用5次后,催化活性和对映选择性均无明显降低.在对模板反应扩大化后,转化率及对映选择性均能维持在同一水平,说明制得的固载催化剂在工业化生产中具有初步的应用前景.
In this work, a different kind of linker group modified ZPS-IPPA-supported ehiral Mn （ salen ） were prepared and evaluated in the asymmetric epoxidation of unfunctionalized olefins with m-CPBA as an oxidant. The results demonstrated that the conversions and e. e. values increased in the presence of axial additive via diamine linkers for the immobilized Mn （salen） but sharply improved in the absence of axial additive via alkoxyl linkers or diphenoxyl. In addition, the heterogeneous catalyst could be reused at least five times without significant loss of activity and enantioselectivity. Furthermore, the could maintain the same level when the template reaction was simultaneously nary prospect in the application for industrial. conversion and enantioselectivity magnified, which has a preliminary prospect in the application for industrial.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2013年第10期2319-2326,共8页
Chemical Journal of Chinese Universities
基金
重庆市自然科学基金项目(批准号:cstc2011jjA50003)
重庆市教委科学技术研究项目(批准号:KJ131504)
重庆市基础与前沿研究计划项目(批准号:cstc2013jcyjA50013)
2013年重庆高校创新团队建设计划项目(批准号:KJTD201325)资助
