摘要
以五甲基二乙烯三胺、1,4-丁烷磺内酯为起始原料经季铵化反应生成N,N,N＇,N＇＇,N＇＇-五甲基-N,N＇＇-双（4-磺丁基）二乙烯基三铵,其再分别与磷钨酸、硅钨酸经酸化反应,合成了两种直链多磺酸基官能团Keggin型杂多酸离子杂化体HPAILs-1、HPAILs-2。目标杂化体的结构经红外光谱、核磁共振波谱、XRD等得到确认。以HPAILs-1、HPAILs-2为非均相催化剂、35%（质量分数）H2O2为氧化剂,在无溶剂条件下进行环己酮的Baeyer-Villiger氧化反应,结果表明,当n（HPAILs-1或HPAILs-2）∶n（环己酮）∶n（过氧化氢）=0.05∶1∶2.5,反应温度50℃,反应时间3 h时,ε-己内酯产率分别为75%、70%。HPAILs-1、HPAILs-2经过滤、水洗、乙醚洗涤、真空干燥即可循环使用,循环使用5次催化活性仅下降1%-2%。
Two straight chain multi-SO3 H functionalized Keggin-type heteropolyacid ionic hybrids（ HPAILs- 1,HPAILs- 2） were synthesized by using aliphatic polyamines,1,4-butane sultone and Keggin type heteropolyacid as the source chemicals via a two-step reaction of quaternarization and acidification. Their structures were confirmed by FTIR,1HNMR and XRD. The oxidation of cyclohexanones using 35% H2O2 as oxidant under solvent-free conditions,in which HPAILs- 1 and HPAILs- 2 acted as heterogeneous catalysts,was studied. Under the optimized conditions,when the mole ratio of HPAILs- 1 or HPAILs- 2 / cyclohexanone / H2O2= 0. 05 ∶ 1 ∶ 2. 5,the reaction could be completed at 50 ℃ within 3 hours and gave ε-caprolactone in the isolated yields of 75% and 70%.HPAILs- 1 and HPAILs- 2 could be easily recovered after filtration,being washed with water and diethyl ether and vacuum drying and exhibited only a 1% ~ 2% loss in their catalytic activity after being reused for five times.
出处
《精细化工》
EI
CAS
CSCD
北大核心
2015年第3期348-352,共5页
Fine Chemicals
基金
福建省自然科学基金项目(2013J01053)
福建省教育厅科研项目(JA13252)
福州市科研项目(2012-G-138)
福建省大学生创新项目(201310395061)~~
