新型晶态层状载体聚(苯乙烯-苯乙烯基膦酸)-磷酸锌轴向固载手性Salen Mn(Ⅲ)的合成及催化烯烃的环氧化性能  

Synthesis of Chiral Salen Mn(Ⅲ) Immobilized on Novel Layered Crysalline Hybrid Support Zinc Poly(styrene-phenylvinylphosphonate)-phosphate as Effective Catalysts and Asymmetric Epoxidation of Unfuntionalized Olefins

作　　者：胡小艳[1] 傅相锴[1,2] 刘志坚[1] 许江威[1] 罗云飞[1] 

机构地区：[1]西南大学化学化工学院 应用化学研究所 重庆市应用化学市级重点实验室,重庆400715 [2]三峡库区生态环境教育部重点实验室,重庆400715

出　　处：《高等学校化学学报》2011年第11期2605-2612,共8页Chemical Journal of Chinese Universities

基　　金：国家科技部科技中小型企业技术创新基金(批准号:09C26215112399);国家人力资源和社会保障部留学人员回国创业启动支持计划项目[批准号:人社厅发2009(143号)]资助

摘　　要：在温和条件合成了新型晶态层状有机聚合物-无机杂化载体材料聚(苯乙烯-苯乙烯基膦酸)-磷酸锌,结合实验数据提出了其可能的理想结构模型.对该载体进行氯甲基化和酚羟基化修饰后,轴向配位固载手性Salen Mn(Ⅲ),合成了一类新型的多相催化剂.以间氯过氧苯甲酸为氧源,考察了其对α-甲基苯乙烯及茚不对称环氧化反应的催化性能.结果表明,这类固载催化剂具有与均相Jacobsen催化剂相当或更高的催化活性和对映选择性,并具有优良的重复使用性.特别是在该氧化体系中,当无助催化剂N-甲基吗啉氮氧化物(NMO)参与时,固载催化剂获得更高的转化率及e.e.值,这为其扩大化生产增加了可能性.A new type of organic polymer-inorganic hybrid material zinc poly （styrene-phenylvinylphosphonate）-phosphate was designed and synthesized under mild conditions. The characterized results show that the new hybrid material is crystalline with regular layered structure, and the ideal structure model is proposed. A series of new heterogeneous eatalysts was obtained by grafting chemical modified on support and subsequently axial coordination with chiral salen Mn （ III ） complexes. The supported catalysts were applied to the enantiose- lective epoxidation of unfunctionalized olefins with m-CPBA as oxidants. The heterogeneous catalysts exhibited higher activity and enantioselectivity than in homogeneous catalyst system, and excellent reusability. It was surprised that the heterogeneous catalysts afforded remarkable increases of conversion and e. e. values in the absence of co-catalyst 4-methylmorpholine N-oxide （NMO）, which increases the possibility for industry applications.

关 键 词：层状聚(苯乙烯-苯乙烯基膦酸)-磷酸锌 酚羟基化 手性SalenMn(Ⅲ) 不对称环氧化 助催化剂 

分 类 号：O643.3[理学—物理化学] O621.251[理学—化学]