高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (10): 2319-2326.doi: 10.7503/cjcu20130012

• 有机化学 • 上一篇    下一篇

ZPS-IPPA杂化载体的合成及在非均相不对称环氧化中的应用

邹晓川1, 石开云1, 陈绍成1, 傅相锴2   

  1. 1. 重庆第二师范学院生物与化学工程系, 重庆 400067;
    2. 西南大学应用化学研究所, 重庆市应用化学重点实验室, 三峡库区生态环境教育部重点实验室, 重庆 400715
  • 收稿日期:2013-01-05 出版日期:2013-10-10 发布日期:2013-10-10
  • 作者简介:邹晓川,男,讲师,主要从事不对称催化及功能材料等方面的研究.E-mail:zxcvip2003@163.com
  • 基金资助:

    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)和2013年重庆高校创新团队建设计划项目(批准号:KJTD201325)资助.

Synthesis of Hybrid Supports ZPS-IPPA and Application for Heterogeneous Olefin Epoxidation

ZOU Xiao-Chuan1, SHI Kai-Yun1, CHEN Shao-Cheng1, FU Xiang-Kai2   

  1. 1. Department of Biological & Chemical Engineering, Chongqing University of Education, Chongqing 400067, China;
    2. Research Institute of Applied Chemistry, Key Laboratory of Applied Chemistry of Chongqing Municipality, Key Laboratory of Eco-environments in Three Gorges Reservoir Region, Ministry of Education, Southwest University, Chongqing 400715, China
  • Received:2013-01-05 Online:2013-10-10 Published:2013-10-10

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Mn(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.

关键词: 聚(苯乙烯-异丙烯基膦酸)-磷酸氢锆, 手性Mn(salen)催化剂, 不对称环氧化反应, 轴向助催化剂

Abstract:

In this work, a different kind of linker group modified ZPS-IPPA-supported chiral 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 conversion and enantioselectivity could maintain the same level when the template reaction was simultaneously magnified, which has a preliminary prospect in the application for industrial.

Key words: Zirconium poly(styrene-isopropenyl phosphonate)-phosphate, Chiral Mn(salen) catalyst, Asymmetric epoxidation, Axial co-catalyst

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