双磺酸基Br鴑sted酸性离子液体/[bmim]Br介导的山梨醇类成核透明剂的均相合成研究

Synthesis of Sorbitol Nucleating Agent in Double SO3H-FunctionalizedBr鴑sted Acidic Ionic Liquids/[bmim]Br under Homogeneous Conditions

摘要:

摘要：以脂肪多胺四甲基乙二胺、五甲基二乙烯三胺、1，4-丁烷磺内酯为起始原料，经季铵化、酸化二步反应，合成了阳离子结构中具有双磺酸基官能团的Br鴑sted酸功能化离子液（BAIL-1-2），离子液体的结构经红外光谱、核磁共振得到确认，以4-硝酸苯胺为指示剂测定离子液体的Hammett 酸函数，二种离子液体酸强度均高于无机强酸硫酸。以合成的离子液体与1-丁基-3-甲基咪唑溴化物构成的二元离子液体体系为反应体系，应用于山梨醇与苯甲醛、对甲基苯甲醛、3，4-二甲基苯甲醛的缩合反应中，结果表明，当离子液体的用量为 15mol%（以山梨醇计），山梨醇/醛=1：2.05（摩尔比），于70℃下反应4h时，反应即可在无溶剂均相反应条件下顺利完成，体系中加入水，目标化合物即可析出，分离产率77.6～84.8%，产物熔距≤5℃，水相中的二元离子液体经旋蒸除水、乙醚洗涤、真空干燥后可循环使用，循环使用三次催化活性基本保持不变。

Abstract:

Abstract：Two double SO3H-functionlized Br鴑sted acidic ionic liquids (BAILs-1-2) were synthesized by using commericial available aliphatic polyamine tetramethylethylene diamaine, pentamethyldiethylenetriamine and 1,4-propanesultone as the sources chemicals via quaternarization and acidification two step reaction, their structure were confirmed by FT-IR and 1H NMP, their Hammett acidic functions were determinated using 4-nitroanilins as indicator by UV spectrum, two kind ionic liquids all showed stronger acidity than H2SO4 BAILs1-2 acted as catalyst and medium together with [bmim]Br for synthesis of sorbitol transparent nucleating agent was studied, the results indicate that the reaction could carried out smoothly under homogeneous conditions. Upon the optimized conditions，the amount ofBAILs1or 2 was 15mol%(based on aldehyde), the mass ratio of sorbitol/[bmim]Br was 4:1, the reaction could completed at 60℃ within two hour in isolated yields of 67～75%with high purity(melting range ≤5℃) .Ionic liquids could be recovered after removal of water in vacuum and washed with diether and reused three times without significant loss in their catalytic activity.