CHINESE JOURNAL OF ENERGETIC MATERIALS
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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
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南京理工大学化工学院,江苏 南京 210094

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国家自然科学基金资助( 21676147,21875110)


Crystal Structure and Detonation Performance of 5,5′-Diamino-4,4′-dinitroamino-3,3′-bi-1,2,4-triazole Triaminoguanidinium Salt (TAGAT)
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School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

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    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P21/c,晶胞参数为a=11.4979(5) Å,b=6.3468(2) Å,c=14.0945(5) Å,β=101.7910(10)°,V=1006.84(6) Å3Z=2,µ=0.136 mm-1F(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Gaussian 09程序,计算TAGAT的标准生成焓为1218.5 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。

    Abstract:

    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) Å, b=6.3468(2) Å, c=14.0945(5) Å, β=101.7910(10)°, V=1006.84(6) Å3, Z=2, µ=0.136 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.

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薛钰冰,程广斌,杨红伟.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[J].含能材料, 2020, 28(7):638-643. DOI:10.11943/CJEM2019304.
XUE Yu-bing, CHENG Guang-bin, YANG Hong-wei. Crystal Structure and Detonation Performance of 5,5′-Diamino-4,4′-dinitroamino-3,3′-bi-1,2,4-triazole Triaminoguanidinium Salt (TAGAT)[J]. Chinese Journal of Energetic Materials, 2020, 28(7):638-643. DOI:10.11943/CJEM2019304.

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  • 收稿日期: 2019-12-02
  • 最后修改日期: 2020-01-30
  • 录用日期: 2020-01-02
  • 在线发布日期: 2020-01-16
  • 出版日期: 2020-07-25