杂多化合物配位水的数量对环己烯环氧化反应的影响  

The effect on selectivity of cyclohexene epoxidation by polyoxometalates containing different number of coordination water

作　　者：安文佳[1,2] 许林[1] 刘宇[1] 赵涛 邹小梅 

机构地区：[1]东北师范大学化学学院多酸化学研究所,吉林长春130024 [2]番禺出入境检验检疫局,广东番禺511400

出　　处：《东北师大学报（自然科学版）》2008年第4期67-71,共5页Journal of Northeast Normal University(Natural Science Edition)

基　　金：国家自然科学基金资助项目(20371010)

摘　　要：以30%H2O2溶液为氧化剂,以六配位水和三配位水的铋钨杂多酸四丁基铵盐([(C4H9)4N]10[(MⅡ(H2O)3)2(WO2)2(BiW9O33)2]和[(C4H9)4N]12[(MⅡ(H2O))3(BiW9O33)2](M=Ni,Mn,Co))为催化剂,催化了环己烯环氧化反应,探索了杂多酸催化剂中配位水的数量对催化剂性能的影响.结果表明:H2O2(30%)与环己烯的物质的量比为3∶1,反应温度为80℃,反应时间为6 h,六配位水的铋钨杂多酸四丁基铵盐具有更高的催化活性.底物环己烯的转化率为58.9%,产物环氧环己烷的选择性大于等于99%.同时还对杂多酸催化环氧化环己烯的机理做了初步的探讨.The tetra-n-butylammonium salts derivative of six coordination water of trivacant Keggin-type sandwich polyoxometalate [（M^Ⅱ （H2O）3）2 （WO2）2 （BiW9O33）2 ]^10- （M = Ni, Mn, Co） and three coordination water [（M^Ⅱ（H2O））3 （BiW9O33）2]^12- （M = Ni, Mn, Co）were used as catalysts for cyclohexene epoxidation using hydrogen peroxide as oxidant. The catalytic performance of these two catalysts was studied in the different reaction times. The catalytic activity of（[（C4H9）4N]10[（M^Ⅱ（H2O）3）2（WO2）2（BiW9O33）2]（M=Ni,Mn,Co）are superior to [（ C4H9）4N]12 [（M^Ⅱ（ H2O） ） 3 （ BiW9 O33）2]（ M = Ni, Mn, Co）. The best result was achieved with [（C4H9）4N]10[（M^Ⅱ（H2O）3）2（WO3）2（BiW9O33）2]. When the molar ratio of hydrogen peroxide to cyclohexene was 3, the conversion of cyclohexene was 58.9% and selectivity for cyclohexene oxide was 99.9% after 6 h of reaction at 80℃. Discussed the probable mechanisms of cyclohexene epoxidation to cyclohexene oxide catalyzed by heteropoly compounds.

关 键 词：配位水 环己烯 杂多酸 环氧化 

分 类 号：O61[理学—无机化学]