离子液体对乌洛托品硝解反应的影响  

Nitrolysis of Hexamethylenetetramine in Presence of Ionic Liquids

作　　者：王鼐[1] 石煜[1] 杨红伟[1] 程广斌[1] 吕春绪[1] 

机构地区：[1]南京理工大学化工学院,江苏南京210094

出　　处：《含能材料》2011年第3期252-257,共6页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(10976014)

摘　　要：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N2O5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。Direct nitrolysis of hexamethylenetetramine（HA） catalyzed by ionic liquids（ILs） was studied.The effects of dosage of IL and different ILs on the nitrolysis were investigated in the systems of 95% HNO3 and N2O5/HNO3.In the system of 95%HNO3,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 IL.In the system of N2O5/HNO3,BF4 shows the best catalytic activity.The optimal reaction conditions are 5mol% IL 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.

关 键 词：有机化学 离子液体(IL) 乌洛托品(HA) 黑索今(RDX) 硝解反应 

分 类 号：TQ560.1[化学工程—炸药化工]