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

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.

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

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.