高等学校化学学报

高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (09): 1984.doi: 10.3969/j.issn.0251-0790.2012.09.019

• 有机化学 • 上一篇    下一篇

新型层状晶态聚(苯乙烯-苯乙烯基膦酸)-磷酸锌铵有机聚合物-无机杂化材料的合成与表征

苗强1, 傅相锴1,2, 黄静1, 李超1, 陈国栋1, 王国明1   

  1. 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
  • 收稿日期:2012-01-09 出版日期:2012-09-10 发布日期:2012-08-14
  • 通讯作者: 傅相锴,男,教授,博士生导师,主要从事精细化工、功能材料及不对称催化研究.E-mail:fxk@swu.edu.cn E-mail:fxk@swu.edu.cn
  • 基金资助:

    国家科技部科技中小型企业技术创新基金资助项目(批准号: 09C26215112399)和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资助.

Synthesis and Characterization of Novel Layered Crystalline Organic Polymer-inorganic Hybrid Materials Zinc Poly(styrene-phenylvinyl phosphonate)-phosphate Ammonium

MIAO Qiang1, FU Xiang-Kai1,2, HUANG Jing1, LI Chao1, CHEN Guo-Dong1, WANG Guo-Ming1   

  1. 1. College of Chemistry and Chemical Engineering, Research Institute of Applied Chemistry, Key Laboratory of Applied Chemistry of Chongqing Municipality, Chongqing 400715, China;
    2. Key Laboratory of the Three Gorges Reservoir Regions Eco-Environment, Ministry of Education, Southwest University, Chongqing 400715, China
  • Received:2012-01-09 Online:2012-09-10 Published:2012-08-14

PDF (PC)

被引次数

7

摘要：

将苯乙烯-苯乙烯基膦酸共聚物、 二水合醋酸锌和磷酸二氢铵在温和的条件下反应, 通过调节无机磷酸盐和有机膦酸的比例, 合成了一系列有机聚合物-无机杂化材料聚(苯乙烯-苯乙烯基膦酸)-磷酸锌铵. 通过FTIR, TG, XRD, SEM和TEM等手段对其进行表征并测试了其催化性能. 结果表明, 聚(苯乙烯-苯乙烯基膦酸)-磷酸锌铵是一种新型层状晶态的有机聚合物-无机杂化材料, 具有较高的热稳定性和特殊的多孔结构. 将其作为催化剂载体, 以芳香二胺作为连接基团, 轴向固载手性Salen Mn(Ⅲ)制备了多相催化剂, 并用于非功能化烯烃的不对称环氧化反应. 催化实验结果表明, 该催化剂在以m-CPBA/NMO为氧化体系催化α-甲基苯乙烯和茚的反应中显示出优良的催化性能, 如催化茚的e.e.值可达99%, 并且可以回收利用, 循环使用8次仍具有较好的催化活性, 具有潜在的工业应用价值.

关键词: 苯乙烯-苯乙烯基膦酸共聚物, 聚(苯乙烯-苯乙烯基膦酸)-磷酸锌铵, 层状晶态, 特殊多孔结构, 催化剂载体

Abstract:

A series of organic polymer-inorganic hybrid materials, zinc poly(styrene-phenylvinyl phosphonate)-phosphate ammonium(ZnPS-PVPPA), was prepared with mild and facile conditions from the copolymer of styrene-phenylvinyl phosphonic acid with zinc acetate dihydrate and ammonium dihydrogen phosphate treated with different ratios of inorganic phosphate to organic phosphonate. The structures of ZnPS-PVPPA were characterized by FTIR, TG, XRD, SEM and TEM and their catalytic abilities were also tested. It could be deduced that the compounds were novel types of layered crystalline organic polymer-inorganic hybrid materials and possessed high thermal stability and porous structure. The heterogeneous catalysts were synthesized to catalyze the asymmetric epoxidation of unfunctional olefins via ZnPS-PVPPA as supports, aryldiamines as linkers and axial coordinating with Salen Mn(Ⅲ). The catalytic results indicated that the superior catalytic abilities were obtained in the asymmetric epoxidation of α-methylstyrene and indene with m-CPBA/NMO as oxidant, such as up to 99% e.e. according to indene. Meanwhile, the supported catalysts could be reused and still display fine catalytic abilities after recycled 8 times and have potential applications for industry.

Key words: Copolymer of styrene-phenylvinyl phosphonic acid, Zinc poly(styrene-phenylvinyl phosphonate)-phosphate ammonium, Layered crystalline, Porous structure, Catalyst support

中图分类号: 

TrendMD: