5,5′-二氨基-4,4′-二硝胺基-3,3′-联-1,2,4-三唑三氨基胍盐(TAGAT)的晶体结构及爆轰性能  

Crystal Structure and Detonation Performance of 5,5′-Diamino-4,4′-dinitroamino-3,3′-bi-1,2,4-triazole Triaminoguanidinium Salt(TAGAT)

作　　者：薛钰冰 程广斌[1] 杨红伟[1] XUE Yu-bing;CHENG Guang-bin;YANG Hong-wei(School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

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》2020年第7期638-643,I0006,共7页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(21676147,21875110)。

摘　　要：以1.3-二氨基胍盐酸盐和乙二酸为原料,经关环-硝化-成盐三步反应,得到高能钝感的5,5'-二氨基-4,4'-二硝胺基-3,3'-联-1,2,4-三唑三氨基胍盐(TAGAT)。采用降温法从水中得到了TAGAT的单晶,通过X-射线单晶衍射仪对TAGAT的单晶结构进行扫描,结果表明,TAGAT分子在170 K下晶体密度为1.631 g·cm^-3,属于单斜晶系,空间群为P2_1/c,晶胞参数为a=1 1.4979(5) A,b=6.3468(2) A,c=1 4.0945(5) A,β=1 01.7910(10)°,V=1 006.84(6) A^3,Z=2,μ=0.1 36 mm^-1,F(000)=516.0。用热重及差示扫量热仪(TG-DSC)对TAGAT的热性能进行分析,结果表明,其起始分解温度为211℃。采用定容燃烧实验对TAGAT的燃烧性能进行评估,结果表明,TAGAT的最大放气压力为6.38 MPa,平均放气速率为0.275 GPa·ms^-1。基于Born-Harber能量循环机理,利用Gaussian09程序,计算TAGAT的标准生成焓为1 21 8.5 kJ·mol^-1。采用EXPLO5(V6.02)程序预测其爆速为8795 m·s^-1、爆压为28.4 GPa、放气量为924.9 L·kg^-1。BAM感度测试仪对TAGAT感度的测试结果表明,TAGAT的撞击感度为32 J,摩擦感度大于360 N。With 1.3-diaminoguanidine hydrochloride and oxalic acid as starting materials,an insensitive energetic salt of 5,5’-diamino-4,4’-dinitroamino-3,3’-bi-1,2,4-triazole triaminoguanidinium salt(TAGAT)was synthesized by cyclization,nitration and salt formation reactions.The single crystal sample of TAGAT was obtained from water by cooling method and the detailed crystal structure was characterized by X-ray diffraction analysis.Results showed that TAGAT crystallizes in the monoclinic space group P21/c with cell parameters of a=11.4979(5)A,b=6.3468(2)A,c=14.0945(5)A,β=101.7910(10)°,V=1006.84(6)A^3,Z=2,μ=0.36 mm-1,F(000)=516.0 and its crystal density was 1.631 g·cm^-3 at 170 K.Thermal behaviors of TAGAT were investigated through TG-DSC method,indicating an onset decomposition temperature of 211℃.Constant-volume combustion experiment showed that the maximum gas-generating pressure of TAGAT was 6.38 MPa and the average pressure-up rates of TAGAT was 0.275 GPa·ms^-1.Based on Born-Harber Energy Cycle,the Gaussian 09 program was applied to calculate the standard generation enthalpy of TAGAT as 1218.5 kj·mol^-1.The detonation parameters of TAGAT were calculated with the EXPLO5(V6.02)program,leading to a calculated detonation velocity of 8795 m·s^-1,a calculated detonation pressure of 28.4 GPa and a calculated gas volume of 924.9 L·kg^-1.Sensitivities toward impact and friction were determined through BAM sensitivity testers,exhibiting that the impact sensitivity of TAGAT was 32 J and the friction sensitivity of TAGAT was greater than 360 N.

关 键 词：5 5'-二氨基-4 4'-二硝胺基-3 3'-联-1 2 4-三唑三氨基胍盐 晶体结构 热性能 定容燃烧实验 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]