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  

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

作　　者：苗强[1] 傅相锴[1,2] 黄静[1] 李超[1] 陈国栋[1] 王国明[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》2012年第9期1984-1990,共7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资助项目(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：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.A series of organic polymer-inorganic hybrid materials, zinc poly （styrene-phenylvinyl phosphohate）-phosphate ammonium（ZnPS-PVPPA） , was prepared with mild and facile conditions from the eopolymer 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 FFIR, 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 a-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.

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 

分 类 号：O621.251[理学—有机化学] O643.3[理学—化学]