离子液体对乌洛托品硝解反应的影响

摘要

Direct nitrolysis of hexamethylenetetramine(HA) catalyzed by ionic liquids (ILs) was studied. The effects of dosage of IL and different ILs on the n itrolysis were investigated in the systems of 95 ％H NO3 and N2 O5/H N O3. In the system of 95 ％ H NO3, [ Hmim ] NO3 shows the best catalytic activity in all of ILs we screened. The optimal reaction condition is 1.5mol％ IL loading,12: 1 of quality ratio of 95％ HNO3 to HA and 90 min of reaction time at -5 ～0 ℃. RDX can be obtained in yield of 75.9％ using IL as catalyst under optimized condition,while RDX can be generated in lower yield of 68.3％ without adding 1L. In the　system of N2O5/HNO3 ,[ Bmim] BF4 shows the best catalytic activity. The optimal reaction conditions are 5mol％ 1L loading,9: 1 of mass ratio of 100％ HNO3 to HA,2: 1 of quality ratio of 100％ HA to N2O5 and 60 min of reaction time at -5 ～0 ℃.Under optimized conditions,77.6％ yield of RDX can be obtained without adding IL, while yield of RDX can be improved to　85.4％ using IL as catalyst. It indicates that ILs have observably catalytic activity on the direct nitrolysis of HA.%以离子液体为催化剂,分别在95%HNO3和N2O5/HNO3体系下,直接硝解乌洛托品(HA)制备黑索今(RDX).考察了离子液体用量和种类对硝解反应的影响.结果表明:在95%HNO3体系下,[Hmim]NO3具有最好的催化效果,离子液体用量与HA物质的量之比为1.5%,硝酸与HA的质量比为12:1,在-5～0℃下反应90 min,RDX的收率为75.9%,而在不加离子液体的条件下黑索今的收率为68.3%;在N2O5/HNO3体系下,[Bmim]BF4的催化效果最好,离子液体用量与HA的物质的量之比为5%,硝酸与HA的质量比为9:1,HA与N 2O5的质量比为2:1,在-5～0℃下反应60 min,RDX收率可达到85.4%,而在不加离子液体的条件下黑索今的收率为77.6%.可见离子液体对HA硝解生成RDX反应有明显的催化作用.