3-乙氧基-2,4,6-三硝基苯胺的合成、晶体结构及性能  

Synthesis,Crystal Structure and Properties of the 3-Ethoxy-2,4,6-Trinitroaniline

作　　者：梁义 蒋雨荷 吴金婷 谌思嘉 黄明[2] 张勇[2] 李鸿波[1] LIANG Yi;JIANG Yuhe;WU Jinting;SHEN Sijia;HUANG Ming;ZHANG Yong;LI Hongbo(School of Materials Science and Engineering,Southwest University of Science and Technology,Mianyang 621010,Sichuan,China;Institute of Chemical Materials,China Academy of Engineering Physics,Mianyang 621900,Sichuan,China)

机构地区：[1]西南科技大学材料科学与工程学院,四川绵阳621010 [2]中国工程物理研究院化工材料研究所,四川绵阳621999

出　　处：《西南科技大学学报》2021年第2期1-6,共6页Journal of Southwest University of Science and Technology

基　　金：国家自然科学基金(22075260);爆炸科学与技术国家重点实验室开放基金(北京理工大学)(KFJJ20-03M)。

摘　　要：以苦味酸和原甲酸三乙酯为原料合成中间体2,4,6-三硝基苯乙醚,再经4-氨基-1,2,4-三唑(ATA)胺化制得3-乙氧基-2,4,6-三硝基苯胺,总收率为75.2%。中间体和产物经FT-IR,1H NMR,13 C NMR,MS确证结构。成功培养出3-乙氧基-2,4,6-三硝基苯胺单晶,单晶测试其为正交晶系,空间群为Pna 21,晶体学参数为:a=1.4028(2)nm,b=0.58767(10)nm,c=2.6458(5)nm,V=2.1811(6)nm 3,Z=8,D=1.658 g/cm 3。研究了胺化反应原料投料比、反应温度及时间对收率的影响,得到适宜工艺条件为:n 2,4,6-三硝基苯乙醚∶n ATA∶n乙醇钠=1.0∶3.0∶4.5(反应物摩尔比),反应温度50~55℃,反应时间6 h。通过DSC-TG研究了产物的热分解过程,其吸热熔化峰温为108.3℃,放热峰温为245.9℃,在193.1℃时,质量损失4.9%。基于密度泛函理论对产物理论爆轰性能进行了计算,其理论爆速为6.86 km/s,理论爆压为19.61 GPa。研究表明:3-乙氧基-2,4,6-三硝基苯胺熔点较低(108.3℃)且具有较好的热稳定性,爆轰性能与2,4,6-三硝基甲苯(TNT)相当,撞击感度(h 50=267 cm)远低于TNT(h 50=98 cm),有作为熔铸炸药液相载体的潜力。The intermediate 2,4,6-trinitrophenetole was synthesized from picric acid and triethyl orthoformate,and then 2,4,6-trinitrophenetole was aminated with 4-amino-1,2,4-triazole(ATA),with a total yield of 75.2%.The structure of the intermediate and product were confirmed by FT-IR,1H NMR,13 C NMR and MS.The single crystal of 3-ethoxy-2,4,6-trinitroaniline was successfully cultured,and the single crystal tested it to be an orthorhombic crystal system,the space group was Pna 21,and the crystallographic parameters were:a=1.4028(2)nm,b=0.58767(10)nm,c=2.6458(5)nm,V=2.1811(6)nm 3,Z=8,D=1.658 g/cm 3.The effects of raw material ratio,reaction temperature and reaction time on the yield of amination reaction were examined.The suitable process conditions were obtained:n 2,4,6-trinitrophenetole∶n ATA∶n sodium ethylate=1.0∶3.0∶4.5,reaction temperature was 50~55℃,reaction time was 6 h.The thermal decomposition process of the product was studied by DSC-TG.Its endothermic melting peak temperature was 108.3℃and the exothermic peak temperature was 245.9℃.At 193.1℃,the mass loss was 4.9%.The theoretical detonation performance of the product was calculated based on density functional theory.The theoretical detonation velocity is 6.86 km/s and the theoretical detonation pressure was 19.61 GPa.The results show that 3-ethoxy-2,4,6-trinitroaniline has a low melting point(108.3℃)and good thermal stability,detonation performance is similar to 2,4,6-trinitrotoluene(TNT),and impact sensitivity(h 50=267 cm)is much lower than TNT(h 50=98 cm),and it has the potential to be used as liquid carrier for molten cast explosives.

关 键 词：3-乙氧基-2 4 6-三硝基苯胺 合成 单晶 热分解 熔铸炸药 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]