一种新型含能材料s-四嗪钴盐的合成、热分解动力学及热安全性

doi:10.11944/j.issn.1000-0518.2017.08.160466

摘要/Abstract

摘要：

四嗪类含能化合物因其高能、钝感、高燃速、低压力指数、良好的热安定性等特点被广泛应用于含能材料领域。然而却存在低密度、低热稳定性的问题,为提高四嗪类化合物的这一性能,制备的一系列金属衍生物得到了广泛关注。 3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)作为四嗪类高氮含能化合物一种,具有良好的催化性能及应用前景。本文以BTATz钾与硝酸钴在水溶液中反应合成了1,2,4,5-四嗪(s-四嗪)的钴盐。采用元素分析(EA)、傅里叶变换红外光谱分析(FTIR)及电感耦合等离子体质谱(ICP-MS)对其进行了结构表征,推测其化学式为Co(C₄H₂N₁₄)·4H₂O。采用差示扫描量热仪(DSC)和热重分析仪(TG/DTG)研究了其热分解行为及主放热反应的动力学方程。计算了自加速分解温度(T_SADT)、热爆炸临界温度(T_b)、热点火温度(T_TIT)和绝热至爆时间(t_TIAD),其值分别为509.69 K、556.31 K、524.93 K和88.40 s,并以此来评价化合物的热安全性。该金属盐的绝热至爆时间大于相应的Ca盐、Mg盐和Sr盐,放热量高于配体BTATz,有望成为良好的燃烧催化剂。

关键词: s-四嗪, 钴盐, 热分解机理, 热安全性

Abstract:

Tetrazine compounds have great applications in energetic materials field, which is attributed to its high energy, insensitivity, high burning rate, low pressure and good thermal stability properties. However, they have disadvantages of low density and thermal stability. To enhance the low properties of tetrazine compounds, a series of the tetrazine derivatives have attracted considerable attention. 3,6-Bis(1-H-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine(BTATz), as a high-nitrogen energetic material, has good catalytic performance and application prospect. Therefore, we synthesized 1,2,4,5-tetrazine (s-tetrazine) cobalt salt with potassium salt of BTATz and cobalt nitrate in an aqueous solution. Its structure was characterized with elemental analysis, Fourier transform infrared spectrometer(FTIR) and inductively coupled plasma mass spectrometry(ICP-MS). Its chemical formula is Co(C₄H₂N₁₄)·4H₂O. The thermal behavior and thermal decomposition reaction kinetics were also investigated with differential scanning calorimetric(DSC) and thermal gravimetric-differential thermal gravimetric(TG-DTG) methods. The self-accelerating decomposition temperature(T_SADT), thermal ignition temperature(T_TIT), critical temperature of thermal explosion(T_b) and the adiabatic time-to-explosion(t_TIAD) were calculated as the important parameters to estimate the thermal safety, and the value were 509.69 K, 556.31 K, 524.93 K and 88.40 s, respectively. The adiabatic time-to-explosion is longer than those of Ca salt, Mg salt and Sr salt and the exothermic capacity is higher than that of its ligand BTATz. Therefore, it is expected to be a good combustion catalyst.

Key words: s-tetrazine, cobalt salt, thermal decomposition mechanism, thermal safety

杨瑾, 刘晴, 任莹辉, 张鲜波, 马海霞, 徐抗震, 赵凤起, 胡荣祖. 一种新型含能材料s-四嗪钴盐的合成、热分解动力学及热安全性[J]. 应用化学, 2017, 34(8): 928-935.

YANG Jin, LIU Qing, REN Yinghui, ZHANG Xianbo, MA Haixia, XU Kangzhen, ZHAO Fengqi, HU Rongzu. A New Energetic Material-Tetrazine Cobalt Salt: Synthesis, Thermal Decomposition Kinetics and Thermal Safety[J]. Chinese Journal of Applied Chemistry, 2017, 34(8): 928-935.

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