多磺酸官能化杂多酸离子杂化体的合成与催化性能研究

Synthesis of Multi-SO_3H Functionalized Multi-heteropolyanion-based Ionic Hybrids and Catalytic Performance

以四甲基乙二胺、五甲基二乙烯三胺、1,3-丙烷磺内酯、Keggin型杂多酸磷钨酸、硅钨酸为原料,经季铵化、酸化两步原子经济反应,合成了两种多磺酸基、多杂多酸阴离子官能化杂多酸离子杂化体8S3Si IH和6S2PIH。8S3Si IH、6S2PIH作为非均相催化剂,研究了柠檬酸与正丁醇的Fischer酯化反应,确定了最佳反应条件:n(酸)∶n(醇)∶n(杂化体)=1∶4∶0.001 5,无溶剂回流分水反应4 h,柠檬酸三丁酯产率分别为97.8%和95.7%。杂化体经过滤、乙醚洗涤、真空干燥即可再生循环使用,循环使用5次的催化活性保持不变。

Two novel multi-SO_3H functionalized multi-heteroplyanion-based ionic hybrids was synthesized using N,N,N＇,N＇-tetramethylethylene diamine,N,N,N＇,N″,N″-pentamethyldiethylenetriamine,1,3-propanesultone and Keggin type heteropolyacidas starting materials via two step atom economic reaction. It acted as catalyst in the synthesis of tributyl citrate under solvent-free conditions. Under optimum conditions of n（ acid） ∶ n（ butanol） ∶ n（ hybrids） = 1 ∶ 4 ∶ 0. 001 5,the yield of esters are 97. 8% and95. 7%,respectively. Two ionic hybrids can reused five times after simple work-up and without significant loss in catalytic activity.