新型含能基团偕叠氮硝基熔铸炸药载体AzDNAZ的合成及性能

A Melt-cast Explosive 3-Azido-1,3-dinitroazetidine(AzDNAZ)with Gem-azidonitro of Novel Energetic Group:Synthesis and Performance

以1-叔丁基-3-硝基-3-羟甲基氮杂环丁烷盐酸盐为原料,经氧化-叠氮化、成盐、硝化等反应合成了具有偕叠氮硝基的熔铸炸药3-叠氮基-1,3-二硝基氮杂环丁烷(AzDNAZ),总收率达到58.8%,采用红外光谱、^1H NMR、^13C NMR及元素分析等对中间体及最终产物进行了结构表征;培养了新的中间体1-叔丁基-3-叠氮基-3-硝基氮杂环丁烷硝酸盐的单晶,X射线单晶衍射分析表明:1-叔丁基-3-叠氮基-3-硝基氮杂环丁烷硝酸盐晶体结构属单斜晶系,空间群为P2(1)/n,a=0.8281(314)nm,b=0.8607(2)nm,c=1.7195(2)nm,α=90°,β=95(2)°,γ=90°,V=1.2210(6)nm^3,Z=4,Mr=262,Dc=1.427 g·cm^-3,μ=0.174 mm^-1,F(000)=552,R=0.0418,wR2=0.1168。利用DSC-TG方法分析了热性能,结果表明:AzDNAZ的熔点为78.2℃,分解点为180.7℃。采用Gaussian 09程序和Kamlet-Jacobs方程预估了AzDNAZ的性能,结果表明:AzDNAZ的密度为1.75 g·cm^-3,生成焓为331.73 kJ-mol^-1,爆速8460 m·s^-1爆压31.83 GPa。表明AzDNAZ可以作为熔铸炸药和含能增塑剂的候选含能材料。

Starting from(1-tert-butyl-3-nitroazetidin-3-yl)methanol,a melt-cast explosive of 3-azido-1,3-dinitroazetidine(AzDNAZ)with novel gem-azidonitro energetic group was obtained through an improved azidation-salinization-nitration strategy with a total yield of 58.8%.Structu res of the intermediates and AzDNAZ were characterized by^1H NMR,^13C NMR,IR and element analysis.One of the intermediates,1-t-butyl-3-azido-3-nitro-azetidinium nitrate(compound 2),was obtained for the first time with the single crystal determined by X-ray single crystal diffraction,which reveals that it crystallizes in monoclinic,space group P2(1)/n with a=0.8281(314)nm,b=0.8607(2)nm,c=1.7195(2)nm,α=90°,β=94.983(2)°,γ=90°,V=1.2210(6)nm3,Z=4,Mr=262,Dc=1.427 g·cm^-3,μ=0.174 mm^-1,F(000)=552,R=0.0418 andωR=0.1168.Meanwhile,thermal behaviors of AzDNAZ were studied by subsequently differential scanning calorimetry(DSC)and thermal gravimetric analyzer(TG)methods.Based on the measured values of density and heat of formation,the detonation parameters were calculated by Gaussian 09 program and Kamlet-Jacobs equations.Results show that the melting point,decomposition point,density,heat of formation,detonation velocity and detonation pressu re are 78.2℃,180.7℃,1.75 g·cm^-3,331.73 kJ·mol^-1,8460 m·s^-1 and 31.83 GPa,respectively,indicating AzDNAZ can be applied as a promising melt-cast explosive or an energetic plasticizer with satisfactory performances.