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

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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, 34(8): 928-935
YANG Jin, LIU Qing, REN Yinghui, et al. A New Energetic Material-Tetrazine Cobalt Salt: Synthesis, Thermal Decomposition Kinetics and Thermal Safety[J]. Chinese Journal of Applied Chemistry, 34(8): 928-935 复制到剪切板

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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

杨瑾^a, 刘晴^a, 任莹辉^a,^*, 张鲜波^a, 马海霞^a, 徐抗震^a, 赵凤起^b, 胡荣祖^b

^a西北大学化工学院西安 710069

^b西安近代化学研究所,燃烧与爆炸技术重点实验室西安 710065

通讯联系人:任莹辉,副教授; Tel:29-88307755; Fax:029-88302223; E-mail:nwuryh@163.com; 研究方向:含能材料的制备及性能

收稿日期:2016-11-17 修回日期:2017-01-31 接受日期:2017-04-11

基金:武器装备预研基金资助项目(No.***3401);

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

中图分类号:O622 文献标志码:A 文章编号:1000-0518(2017)08-0928-08

A New Energetic Material-Tetrazine Cobalt Salt: Synthesis, Thermal Decomposition Kinetics and Thermal Safety

YANG Jin^a, LIU Qing^a, REN Yinghui^a, ZHANG Xianbo^a, MA Haixia^a, XU Kangzhen^a, ZHAO Fengqi^b, HU Rongzu^b

^aSchool of Chemical Engineering Northwest University,Xi'an 710069,China

^b Science and Technology on Combustion and Explosion Laboratory,Xi'an Modern Chemistry Research Institute,Xi'an 710065,China

Corresponding author:REN Yinghui, associate professor; Tel:029-88307755; Fax:029-88302223; E-mail:nwuryh@163.com; Research interests:synthesis and property of the energetic materials

Received:2016-11-17 Revised:2017-01-31 Accepted:2017-04-11

Fund:Supported by the National Defense Pre-Research Foundation of China(No.***3401)

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.

Keyword: s-tetrazine; cobalt salt; thermal decomposition mechanism; thermal safety

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四嗪类化合物是近年来国内外研究较多的一类高氮化合物,其能量主要来源于其正生成焓,且大多不含硝基基团,感度较低,热稳定性较好;同时分子结构中的高氮、低碳氢含量不仅使其成气量大、燃烧产物少烟或者无烟,且易达到氧平衡。该类化合物被广泛应用于低特征信号推进剂、气体发生剂、无烟焰火技术等各个领域^[1]。

作为四嗪类化合物之一的3,6-双(1-氢-1,2,3,4四唑-5-氨基)-1,2,4,5-四嗪(BTATz)是分子中同时包含四嗪和四唑环的高氮含能化合物,最初由美国Los Alamos国家实验室的Hiskey等合成^[2,3]。因其具有含氮量高(79.02%)、密度高(1.76 g/cm³)及拥有正的生成焓(+883 kJ/mol)等优势引起了国内外研究者的广泛关注^{[2,3,4,5,6,7,8]}。此后众多的研究者对BTATz进行了进一步的研究,内容涉及到合成工艺的优化和量子化学^[3]、燃烧性能^[9]、溶解热^[10]、BTATz衍生物的合成及性能^{[11,12,13,14,15,16]}、甚至是将其部分替代黑索今(RDX)用于改性双基推进剂(CMDB)中^[17]以及形成的BTATz-HNIW-CMDB(HNIW:六硝基六氮杂异伍兹烷)体系的热分解反应动力学机理及热安全性研究等方面^[18]。

本文在前期研究^{[11,12,13,14]}基础上,以BTATz钾盐为原料合成了其钴盐,并对其进行了结构表征。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热分解反应动力学,并对自加速分解温度( 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)进行计算研究,为其在推进剂中的应用提供必要的理论基础。

1 实验部分

1.1 试剂和仪器

BTATz钾盐的制备按照文献[19]方法进行。其余试剂药品均为分析纯,购自天津市科密欧化学试剂有限公司,使用前未经进一步精制。

X-5型显微熔点测定仪(控温型)(北京泰克仪器公司);VarioELⅢ型元素分析仪(德国艾乐曼公司);EQUINOX-55型傅里叶变换红外光谱仪(KBr压片,400~4000 cm^-1)(德国布鲁克公司);Agilent 7700X型电感耦合等离子体质谱仪(美国Agilent公司);比热容测定采用法国(SETARAM)Micro-DSCⅢ型微量量热仪中的连续比热容测定模式进行,测定原理及仪器校正同文献^[20];DSC曲线测定选用NETZSCH DSC204型热分析仪,TG/DTG曲线测定选用的SDT Q600型热分析仪(美国TA公司)。

1.2 实验方法

将0.3684 g BTATz钾盐溶于30 mL水中,过滤,滤液于圆底烧瓶中。逐渐滴加40 mL含有0.5820 g Co(NO₃)₂·6H₂O的水溶液,室温下搅拌。随着滴加的进行,溶液中出现黑色的沉淀,继续反应1 h后沉淀变为红棕色。滴加完毕后继续反应6 h后抽滤,滤饼多次水洗后于50 ℃下真空干燥,得到红棕色粉末,产率67%。反应历程如Scheme 1所示。

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	Scheme 1 Reaction of the title compound

2 结果与讨论

2.1 Co(C₄H₂N₁₄)·4H₂O的表征

元素分析和ICP-MS分析测定值(计算值)/%:C 12.90(12.74),H 2.54(2.67),N 52.20(51.99),Co 13.00(15.63)。推测该化合物的化学式为Co(C₄H₂N₁₄)·4H₂O。 IR(KBr), σ/cm^-1:3519(O—H),3464,3244(N—H),2986,2756,1617(N=N),1530,1471(N—N),1060(C—N),995。

2.2 Co(C₄H₂N₁₄)·4H₂O的热分解行为及热分解动力学

图1为Co(C₄H₂N₁₄)·4H₂O在5、10、15和20 K/min升温速率下的DSC曲线,图2为10 K/min下的TG/DTG曲线。

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	图1 Co(C₄H₂N₁₄)·4H₂O在不同升温速率下的DSC曲线Fig.1 DSC curves of Co(C₄H₂N₁₄)·4H₂O at different heating rates

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	图2 Co(C₄H₂N₁₄)·4H₂O在10 K/min的TG/DTG曲线Fig.2 TG/DTG curves of Co(C₄H₂N₁₄)·4H₂O at the heating rate of 10 K/min

从图1曲线 b可知,Co(C₄H₂N₁₄)·4H₂O的热分解由一个吸热过程和一个放热过程组成,且吸热和放热是连续的。吸热阶段始于401.23 K,终于492.36 K,峰温为463.78 K。放热阶段始于吸热分解的终点,终于672.33 K,放热量为1152 J/g,该阶段对应TG/DTG曲线(图2)上第2个失重阶段。

TG/DTG图上存在两个失重阶段,第1个失重阶段出现在350~450 K温度范围内,失重率为18%,推测该阶段为失去4分子水的过程(计算值19.1%)。第2个失重阶段出现在450~800 K,最后剩余残渣45%应为形成的高熔点聚合物。

本文计算热分解动力学参数值的方法主要有Kissinger法^[21]、Flynn-Wall-Ozawa法^[22]和积分方程法^[23]。通过常用的41种机理函数计算化合物的热分解反应动力学参数。按照文献[24-25]进行合理地选择计算方法及物质分解反应的动力学参数和机理函数。

表1为在升温速率为5、10、15和20 K/min下由DSC曲线所获得的基本参数值( T_e、 T_p值和Δ H)。采用Kissinger和Ozawa两种方法求得表观活化能( E_a)、指前因子( A)和线性相关系数( r)分别列于表3中。

表1 由不同升温速率下的DSC曲线得到的参数值 Table 1 The parameters determined by DSC curves at different heating rates

表2 不同升温速率下由DSC曲线得到的热分解数据 Table 2 Thermal decomposition data determined by DSC curves at different heating rates

表2是在上述4个升温速率( β)下,放热分解过程任意反应分数( α_i)所对应的分解温度( T_i)。将不同 β对应的 T_i值代入Ozawa方程,计算出各升温速率下的等转化活化能 E_a,并作出对应的 E_a~ α曲线(图3)。由图3可知,将反应分数 α在0.2~0.8之间时对应的活化能求算数平均值(平均值为150.90 kJ/mol),同时与以 T_e, T_p值利用Ozawa和Kissinger所算出的数值相比发现它们较为接近(表3),并且不同方法算出的 A值也接近, r值均大于0.98,表明计算所得结果可信。

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'>	图3 不同 β时由Ozawa法得到的 E_a- α曲线Fig.3 E_a- α curve by the Ozawa's method at different heating rates

表3 主要热分解阶段的动力学参数计算值 Table 3 Calculated values of the main stage of thermal decomposition kinetic parameters

该化合物的主要热分解反应对应37号机理函数,其最可积机理函数的积分式是 f( α) =(1 -α)²,微分式是 G( α) =(1 -α) ^-¹ -1。将 f( α) =(1 -α)², E=150.90 kJ/mol, A =10^11.88 s^-1代入方程d α/d t= Af( α) e^-E/RT中,得到Co(C₄H₂N₁₄)·4H₂O的热分解反应的动力学方程为:d a/d t=10^11.88×(1- α)²×exp(-1.51×10⁵/ RT)。

2.3 Co(C₄H₂N₁₄)·4H₂O的热力学函数

采用Micro-DSCⅢ微量量热仪测得Co(C₄H₂N₁₄)·4H₂O的比热容方程为:

$\begin{matrix} C_{p} = 11.36 - 0.10 T + 3.72 \times 10^{- 4} T^{2} - 4.11 \times 10^{- 7} T^{3} (1) \end{matrix}$

计算得到298.15 K下的标准摩尔比热容为415.45 J/(mol·K)。根据方程(1)及热力学函数与比热容的关系式(2)~(4),采用MATLAB^[26]软件计算得到Co(C₄H₂N₁₄)·4H₂O基于298.15 K在283~353 K范围内的焓、熵和吉布斯自由能函数值。所得结果分别列于表4中。

$H_{T} - H_{298.15} = \int_{298.15}^{T} C_{p} dT (2)$

$S_{T} - S_{298.15} = \int_{298.15}^{T} C_{p} \cdot T^{- 1} dT (3)$

$G_{T} - G_{298.15} = \int_{298.15}^{T} C_{p} dT - T \int_{298.15}^{T} C_{p} \cdot T^{- 1} dT (4)$

表4 Co(C₄H₂N₁₄)·4H₂O的热力学函数 Table 4 Themodynamic functions of Co(C₄H₂N₁₄)·4H₂O

2.4 Co(C₄H₂N₁₄) 4H₂O的热安全性

2.4.1 自加速分解温度( T_SADT) 自加速分解温度( T_SADT)是^[23,27]将不同升温速率下所的到的 T_e, T_p值代入到式(5)中,计算 β→0时的峰温 T_e0和 T_p0:

$\begin{matrix} T_{(0, e or p) i} = T_{(00, e 0 or p 0)} + n β_{i} + m β_{i}^{2} i = 1 ~ 4 (5) \end{matrix}$

式中, n和 m为常数。根据 T_SADT= T_e0,可以得到 T_SADT和 T_p0。最后得出 T_SADT=509.69 K, T_p0=539.45 K。

2.4.2 热爆炸临界温度( T_b)和热点火温度( T_TIT) T_b和 T_TIT由式(6)计算得到^[23,27]:

$\begin{matrix} T_{be 0 (or bp 0)} = \frac{E_{o} - \sqrt[]{E_{o}^{2} - 4 E_{o} R T_{e 0 (or p 0)}}}{2 R} (6) \end{matrix}$

式中,当 E_o取 E_p0, T取 T_p0时计算得到热爆炸临界温度 T_b;当 E_o取 E_e0, T取 T_e0时即可得到热点火温度 T_TIT。

将上述由Ozawa法得到的 E_e0、 E_p0和 T_e0、 T_p0代入方程(6)中,计算得到BTATz钴盐的 T_b和 T_TIT分别为556.31和524.93 K。

2.4.3 绝热至爆时间( t_TIAD) 绝热至爆时间是评价含能物质热稳定性和热安全性的重要参数指标^[28,29],其值可根据热分析方法所计算得到的热动力学参数值及比热容方程进行估算。计算原理如式(7)~(9)所示。

$C_{p} \frac{dT}{dt} = QAexp (- E / RT) f (α) (7)$

$t = \int_{0}^{t} d t = \int_{T_{0}}^{T} \frac{C_{p} \exp (E / RT)}{QAf (α)} dT (8)$

$α = \int_{T_{0}}^{T} \frac{C_{p}}{Q} dT (9)$

将 C_p=11.36-0.10 T+3.72×10^-4 T²-4.11×10^-7 T³, E=E_K=151.12×10³ J/mol, A=A_K=10^11.95 s^-1, Q=Δ H_d=1134.50 J/g, T=T_b=556.31 K, T₀ =T_e0=509.69 K, f( α) =(1 -α)²代入以上公式,求得绝热至爆时间 t_TIAD=88.40 s。

3 结论

合成了一种新的 s-四嗪含能金属盐——BTATz的钴盐Co(C₄H₂N₁₄)·4H₂O。采用DSC和TG/DTG方法对其进行了热分解行为和热分解动力学研究。结果表明,该含能金属盐的热分解过程包含一个吸热阶段和一个放热阶段,采用非等温法获得了放热阶段的热分解反应机理方程为d α/d t=10^11.88×(1- α)²exp(-1.51×10⁵/ RT)。计算了自加速分解温度、热爆炸临界温度、热点火温度及绝热至爆时间分别为509.69 K、556.31 K、524.93 K和88.40 s。从绝热至爆时间的大小可知,BTATz的钴盐的热安全性优于相应的Ca盐(52.98 s)^[30]、Mg盐(45.42 s)^[11]和Sr盐(71.93 s)^[12]。从放热量来说,该钴盐在4个升温速率下放热量的平均值为1134.50 J/g(表1)略高于其配体BTATz(1101 J/g)。而BTATz作为燃烧催化剂已用于双基/改性双基推进剂中,并且显示了良好的催化性能^[17]。由此推断标题化合物有望成为良好的燃烧催化剂。

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[10]	Li N, Zhao F Q, Luo Y, et al. Dissolution Properties of 3, 6-Bis(1H-1, 2, 3, 4-tetrazol-5-ylamino)-1, 2, 4, 5-tetrazine in N-Methyl Pyrrolidone and Dimethyl Sulfoxide[J]. J Solution Chem, 2014, 43(7): 1250-1258. [本文引用:1]
[11]	Zhang X B, Ren Y H, Li W, et al. A Novel Magnesium Salt Based on BTATz: Crystal Structure, Thermal Behavior and Thermal Safety[J]. Chem Res Chinese Univ, 2013, 29(4): 627-631. [本文引用:3]
[12]	Zhang X B, Ren Y H, Li W, et al. 3, 6-Bis(1H-1, 2, 3, 4-tetrazol-5-yl-amino)-1, 2, 4, 5-Tetrazine-Based Energetic Strontium(Ⅱ) Complexes: Synthesis, Crystal Structure and Thermal Properties[J]. J Coord Chem, 2013, 66(12): 2051-2064. [本文引用:1]
[13]	REN Yinghui, ZHAO Fengqi, YI Jianhua, et al. Energetic Metal Complexes of BTATz and Its Method of Preparation: CN, 201110149420. 2[P], 2011(in Chinese). 任莹辉, 赵凤起, 仪建华, 等. BTATz含能金属配合物及其制备方法: 中国, 201110149420. 2[P], 2011. [本文引用:1]
[14]	LI Wen, REN Yinghui, ZHAO Fengqi, et al. Nitrogen-rich Energetic Zinc Salt on BTATz: Syntheses and Thermodynamic[J]. J Funct Mater, 2003, 44(22): 3326-3329(in Chinese). 李文, 任莹辉, 赵凤起, 等. 高氮含能化合物BTATz(BTATz=3, 6-双(1-氢-1, 2, 3, 4-四唑-5-氨基)-1, 2, 4, 5-四嗪)锌盐的合成及热分解特性[J]. 功能材料, 2013, 44(22): 3326-3329. [本文引用:1]
[15]	LI Wen, REN Yinghui, ZHAO Fengqi, et al. Effects of Lead Complex-Based BTATz on Thermal Behaviors, Non-Isothermal Reaction Kinetics and Combustion Properties of DB/RDX-CMDB Propellants[J]. Acta Phys Chim Sin, 2013, 29(10): 2087-2094(in Chinese). 李文, 任莹辉, 赵凤起, 等. BTATz-Pb复合物对双基和RDX-改性双基推进剂的热行为、非等温动力学及燃烧性能的影响[J]. 物理化学学报, 2013, 29(10): 2087-2094. [本文引用:1]
[16]	REN Yinghui, LI Wen, ZHANG Xianbo, et al. Nonisothermal Decomposition Kinetics and Thermal Safety of Ag₂(BTATz)·2H₂O(BTATz=3, 6-Bis(1-H-1, 2, 3, 4-Tetrazole-5-Amino)-1, 2, 4, 5-Tetrazine)[J]. Chinese J Appl Chem, 2013, 30(9): 1036-1041(in Chinese). 任莹辉, 李文, 张鲜波, 等. 3, 6-双(1-氢-1, 2, 3, 4-四唑-5-氨基)-1, 2, 4, 5-四嗪银盐的热分解反应动力学及热安全性[J]. 应用化学, 2013, 30(9): 1036-1041. [本文引用:1]
[17]	Yi J H, Zhang F Q, Wang B Z, et al. Thermal Behaviors, Non-isothermal Decomposition Reaction Kinetics, Thermal Safety and Burning Rates of BTATz-CMDB Propellant[J]. J Hazard Mater, 2010, 181(3): 432-439. [本文引用:2]
[18]	Yi J H, Zhao F Q, Wang B Z, et al. BTATz-HNIW-CMDB Propellants Decomposition Reaction Kinetics and Thermal Safety[J]. J Therm Anal Calorim, 2014, 115(2): 1227-1234. [本文引用:1]
[19]	ZHANG Chao. Study on New High Burning Rate Component-Derivatives of BTATz: Synthesis, Characterization and Properties[D]. Xi'an: School of Chemical Engineering, Northwest University 2012(in Chinese). 张超. 新型高燃速组分BTATz衍生物的合成、表征及特性研究[D]. 西安: 西北大学化工学院, 2012. [本文引用:1]
[20]	XU Kangzhen, SONG Jirong, ZHAO Fengqi, et al. Special Heat Capacity, Thermodynamic Properties and Adiabatic Time-to-Explosion of 1, 1-Diamino-2, 2-dinitroethylene[J]. Acta Chim Sin, 2007, 65(25): 2827-2831(in Chinese). 徐抗震, 宋纪蓉, 赵凤起, 等. 1, 1-二氨基-2, 2-二硝基乙烯的比热容、热力学性质及绝热至爆时间研究[J]. 化学学报, 2007, 65(25): 2827-2831. [本文引用:1]
[21]	Kissinger H E. Reaction Kinetics in Differential Thermal Analysis[J]. Anal Chem, 1957, 29(11): 1702-1706. [本文引用:1]
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[23]	HU Rongzu, SHI Qizhen. Thermal Analysis Kinetics[M]. Beijing: SciencePress, 2001(in Chinese). 胡荣祖, 史启祯. 热分析动力学[M]. 北京: 科学出版社, 2001. [本文引用:3]
[24]	LI Dan. High Nitrogen Organic Metal Complexes and Energetic Ionic Compounds: Synthesis, Structure, Thermodynamic Properties and Theoretical Calculation[D]. Xi'an: School of Chemical Engineering, Northwest University, 2010(in Chinese). 李丹. 高氮有机金属配合物和含能离子化合物的合成、结构、热力学性质及量子化学研究[D]. 西安: 西北大学化工学院, 2010. [本文引用:1]
[25]	Ren Y H, Yi J H, Zhao F Q, et al. Synthesis, Decomposition Reaction Kinetics and Thermal Safety of Bismuth Complex of Picric Acid[J]. Chinese J Explos Propellants, 2011, 33(5): 19-24. [本文引用:1]
[26]	HUANG Huajiang. Practical Computer Simulation of Chemical Processes-MATLAB's Application in Chemical Engineering[M]. Beijing: Chemical Industry Press, 2004(in Chinese). 黄华江. 实用化工计算机模拟-MATLAB在化学工程中的应用[M]. 北京: 化学工业出版社, 2004. [本文引用:1]
[27]	Hu R Z, Gao H X, Zhao F Q, et al. Estimation of Critical Temperature of Thermal Explosion for Some Furazano-fused Cyclic Compouds Using Non-isothermal DSC[J]. Chinese J Energ Mater, 2009, 17(6): 635-642. [本文引用:2]
[28]	WANG Yun, FENG Changgen, ZHENG Rao. Prediction of Thermal Safety of Energetic Materials[J]. Chinese J Energy Mater, 2000, 8(3): 119-121(in Chinese). 王耘, 冯长根, 郑娆. 含能材料热安全性的预测方法[J]. 含能材料, 2000, 8(3): 119-121. [本文引用:1]
[29]	HU Rongzu, GAO Hongxu, ZHAO Fengqi, et al. Thermal Safety of 1, 1'-Dimethyl -5, 5'-azotetrazole and 2, 2'-Dimethyl-5, 5'-azotetrazole[J]. Chinese J Energy Mater, 2011, 19(2): 126-131(in Chinese). 胡荣祖, 高红旭, 赵凤起, 等. 1, 1'-二甲基-5, 5'-偶氮四唑-水合物和2, 2'-二甲基-5, 5'-偶氮四唑的热安全性[J]. 含能材料, 2011, 19(2): 126-131. [本文引用:1]
[30]	ZHANG Xianbo. Synthesis, Crystal Structure, Thermal Properties and Performance of High Nitrogen Tetrazine BTATz Metal Salts/Complexes[D]. Xi'an: School of Chemical Engineering, Northwest University, 2013(in Chinese). 张鲜波. 高氮四嗪BTATz金属盐/配合物的合成、晶体结构、热分解特性及性能研究[D]. 西安: 西北大学化工学院, 2013. [本文引用:1]

2011

0.0

XUE

Jinqiang

, SHANG

Bingkun

, WANG

Wei

, et al. Research Advances in Tetrazine-based High-nitrogen Molecular and Ionic Energetic Compounds[J]. Chem Propellants Polym Mater, 2011, 9(4): 91-99(in Chinese).

薛金强, 尚丙坤, 王伟, 等. 四嗪类高氮分子及离子含能化合物的研究进展[J]. 化学推进剂与高分子材料, 2011, 9(4): 91-99.

... 该类化合物被广泛应用于低特征信号推进剂、气体发生剂、无烟焰火技术等各个领域^[1] ...

2002

0.0

... 作为四嗪类化合物之一的3,6-双(1-氢-1,2,3,4四唑-5-氨基)-1,2,4,5-四嗪(BTATz)是分子中同时包含四嗪和四唑环的高氮含能化合物,最初由美国Los Alamos国家实验室的Hiskey等合成^[2-3] ...

... 76 g/cm³)及拥有正的生成焓(+883 kJ/mol)等优势引起了国内外研究者的广泛关注^[2-8] ...

2003

0.0

... 此后众多的研究者对BTATz进行了进一步的研究,内容涉及到合成工艺的优化和量子化学^[3]、燃烧性能^[9]、溶解热^[10]、BTATz衍生物的合成及性能^[11-16]、甚至是将其部分替代黑索今(RDX)用于改性双基推进剂(CMDB)中^[17]以及形成的BTATz-HNIW-CMDB(HNIW:六硝基六氮杂异伍兹烷)体系的热分解反应动力学机理及热安全性研究等方面^[18] ...

2004

0.0

2008

0.0

WANG

Bozhou

, LAI

Weipeng

, LIU

Qian

, et al. Synthesis, Characterization and Quantum Chemistry Study on 3, 6-Bis(1H-1, 2, 3, 4-tetrazol-5-yl-amino)-1, 2, 4, 5-tetrazine[J]. Chinese J Org Chem, 2008, 28(3): 422-428(in Chinese).

王伯周, 来蔚鹏, 刘愆, 等. 3, 6-双(1H-1, 2, 3, 4-四唑-5-氨基)-1, 2, 4, 5-四嗪的合成、表征及量子化学研究[J]. 有机化学, 2008, 28(3): 422-428.

3,6-Bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) was synthesized by triamino- guanidinium nitrate with 2,4-pentanedione of condensation, followed by oxidation and substitution reaction. The product was characterized by elemental analysis, IR, NMR and DSC. Instead of nitrogen dioxide/N-methylpyrrolidone, acetic acid/sodium nitrite was as oxidizer during the oxidation, thus the cost was reduced and the process was simplified. The theoretical properties of BTATz were estimated by a B3LYP method based on 6-31G(d,p) basis set. The stable geometric configuration and bond order were obtained. The vibrational frequencies, IR spectrum and thermodynamics properties under different temperatures were obtained from vibrational analysis, and the relationship between temperature and thermodynamics properties was deducted. Pyrolysis mechanism of BTATz was discussed, and the transition state and activation energy of ring opening reaction of the tetrazole were deducted.

(a Xi′an Modern Chemistry Research Institute, Xi′an 710065) (b College of Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024)

以三氨基胍硝酸盐、戊二酮为起始原料, 经缩合、氧化、取代等反应合成了3,6-双(1H-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz), 并通过元素分析、红外、核磁、差示扫描量热法(DSC)等分析手段对其进行了表征. 采用亚硝酸钠/乙酸代替了二氧化氮/N-甲基吡咯烷酮, 改进了氧化步骤, 降低了成本, 简化了合成工艺. 用B3LYP方法, 在6-31G(d,p)基组水平上对其性能进行了计算, 得到了其稳定的几何构型和键级; 在振动分析的基础上求得体系的振动频率、IR谱及不同温度下的热力学性质, 并得到了温度对热力学性能影响的关系式; 探讨了其热解机理, 推断出四唑环开环时的过渡态和活化能.

2009

0.0

2007

0.0

ZHANG

Xinggao

, ZHU

Hui

, YANG

Shiqing

, et al. Study on Thermal Decomposition Kinetics and Mechanism of Nitrogen-rich Compound BTATz[J]. J Propul Technol, 2007, 8(3): 322-326(in Chinese).

张兴高, 朱慧, 阳世清, 等. 富氮高能物质BTATz的热分解动力学和分解机理[J]. 推进技术, 2007, 8(3): 322-326.

2004

0.0

... 76 g/cm³)及拥有正的生成焓(+883 kJ/mol)等优势引起了国内外研究者的广泛关注^[2-8] ...

2000

0.0

2014

0.0

2013

0.0

... 本文在前期研究^[11-14]基础上,以BTATz钾盐为原料合成了其钴盐,并对其进行了结构表征 ...

... 42 s)^[11]和Sr盐(71 ...

2013

0.0

... 93 s)^[12] ...

2011

0.0

2003

0.0

Wen

, REN

Yinghui

, ZHAO

Fengqi

, et al. Nitrogen-rich Energetic Zinc Salt on BTATz: Syntheses and Thermodynamic[J]. J Funct Mater, 2003, 44(22): 3326-3329(in Chinese).

李文, 任莹辉, 赵凤起, 等. 高氮含能化合物BTATz(BTATz=3, 6-双(1-氢-1, 2, 3, 4-四唑-5-氨基)-1, 2, 4, 5-四嗪)锌盐的合成及热分解特性[J]. 功能材料, 2013, 44(22): 3326-3329.

采用一锅煮的方法在二甲基甲酰胺(DMF)中利用3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)和醋酸锌,60℃下合成了BTATz的锌盐,并用元素分析、红外光谱分析和1H-NMR对其进行了结构表征。采用DSC和TG/DTG技术对标题化合物进行了热分解行为及热分解反应动力学研究,计算了热自加速分解温度(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),并以此来评价化合物的热安全性。

... 本文在前期研究^[11-14]基础上,以BTATz钾盐为原料合成了其钴盐,并对其进行了结构表征 ...

2013

0.0

Wen

, REN

Yinghui

, ZHAO

Fengqi

, et al. Effects of Lead Complex-Based BTATz on Thermal Behaviors, Non-Isothermal Reaction Kinetics and Combustion Properties of DB/RDX-CMDB Propellants[J]. Acta Phys Chim Sin, 2013, 29(10): 2087-2094(in Chinese).

李文, 任莹辉, 赵凤起, 等. BTATz-Pb复合物对双基和RDX-改性双基推进剂的热行为、非等温动力学及燃烧性能的影响[J]. 物理化学学报, 2013, 29(10): 2087-2094.

The composite double base (DB)/hexogen (RDX)-modified double base (CMDB) propellants (Nos. DB001 and CMDB100) were prepared with the lead complex of 3,6-bis(1H-1,2,3,4-tetrazol-5-ylamino)-1,2,4,5-tetrazine (LCBTATz), with and without the ballistic modifier. Their thermal behaviors and nonisothermal decomposition reaction kinetics were investigated by thermogravimetry, derivative thermogravimetry (TG-DTG), and differential scanning calorimetry (DSC). For the LCBTATz-DB propellant, there was one mass loss stage in the TG curve and one exothermic peak in the DSC curve over the temperature range 350-540 K. For LCBTATz-CMDB, there were two continuous exothermic stages in the TG curve, and only one corresponding exothermic peak in the DSC curve over the range 390-540 K. The exothermal decomposition reaction mechanisms of LCBTATz-DB and LCBTATz-CMDB follow the functions f(α)=α^-1/2 and f(α)=2(1-α)^3/2, respectively (α: conversion degree). The self-accelerating decomposition temperatures (T_SADT), thermal ignition temperatures (T_TITT), critical temperatures of thermal explosion (T_b), adiabatic timesto-explosion (t_Tlad), and thermodynamic parameters of activation reaction were calculated, and the thermal safety was evaluated. For DB001, T_SADT=444.50 K, T_TITT=453.96 K, T_b=471.84 K; t_Tlad=39.36 s. For CMDB100, T_SADT=442.38 K, T_TITT=452.89 K,T_b=464.13 K,t_Tlad=21.3 s. As a high-efficiency combustion catalyst, LCBTATz in double-base propellants increases the propulsion rate and reduces the pressure index for larger scale pressures. This makes the DB propellant appear to have a significant super burning effect at 2-8 MPa and a "mesa effect" at 8-12 MPa. Meanwhile, the pressure exponent of the CMDB propellant decreased to 0.18.

制备了含3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)铅复合物(LCBTATZ)的双基推进剂和改性双基推进剂. 采用热重-微商热重法(TG-DTG)及差示扫描量热法(DSC)研究了其热分解行为和非等温分解动力学并在此基础上评价了其热安全性. 结果表明, LCBTATz-DB复合物中在350-540 K之间只存在一个放热分解峰, LCBTATz-CMDB复合物中存在两个连续的放热分解峰在390-540 K温度范围内, 其机理方程分别为: f(α)=α^-1/2和f(α)=2(1-α)^3/2. 计算了热加速分解温度(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_Tlad),其值分别为: DB001复合物T_SADT=444.50 K, T_TITT=453.96 K, T_b=471.84 K; t_Tlad=39.36 s; CMDB100复合物, T_SADT=442.38 K, T_TITT=452.89 K,T_b=464.13 K,t_Tlad=21.3 s,并以此来评价化合物的热安全性. 考察了LCBTATz-DB以及LCBTATz-CMDB的燃烧性能, 结果表明LCBTATZ 是一种高效的双基燃烧催化剂, 在较大的压力范围内可以显著的提高燃速并且大幅度的降低压力指数. 对于双基推进剂在2-8 MPa压力范围内出现了明显的超燃速现象, 8-12 MPa出现了“麦撒”效应, 对于改性双基推进剂的压力指数降到0.18.

2013

0.0

REN

Yinghui

, LI

Wen

, ZHANG

Xianbo

, et al. Nonisothermal Decomposition Kinetics and Thermal Safety of Ag₂(BTATz)·2H₂O(BTATz=3, 6-Bis(1-H-1, 2, 3, 4-Tetrazole-5-Amino)-1, 2, 4, 5-Tetrazine)[J]. Chinese J Appl Chem, 2013, 30(9): 1036-1041(in Chinese).

任莹辉, 李文, 张鲜波, 等. 3, 6-双(1-氢-1, 2, 3, 4-四唑-5-氨基)-1, 2, 4, 5-四嗪银盐的热分解反应动力学及热安全性[J]. 应用化学, 2013, 30(9): 1036-1041.

The silver salt of 3,6-bis(1-H-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine(BTATz)(Ag2(BTATz)·2H2O) was synthesized by two steps, and its structure was characterized by elemental analysis, X-ray fluorescence diffraction and FT-IR spectra. The thermal behavior of the compound was studied under non-isothermal conditions using DSC and TGDTG methods, the result indicated that the thermal decomposition comprises of one endothermic and two exothermic stages, the nonisothermal decomposition reaction kinetics equation of the main exothermic stage can be expressed as:dα/dt=1014.29×{3(1-α)[-ln (1-α)]1/4/4}exp(-2.10×104/T). The values of the self-accelerating decomposition temperature(TSADT), critical temperatures of thermal explosion(Tb), thermal ignition temperature(TTIT) and the adiabatic time-to-explosion(tTIAD) for the compound were calculated as 517.10 K, 580.12 K, 531.00 K and 90.32 s, respectively. In addition, its thermal safety was evaluated.

(1.Science and Technology on Combustion and Explosion Laboratory,Xi′an Modern Chemistry Research Institute,Xi′an 710065,China; 2.School of Chemical Engineering,Shaanxi Key Laboratory of Physico-inorganic Chemistry,Northwest University,Xi′an ,710069,China; 3.Conservation Technology Department,The Palace Museum,Beijing 100009,China)

利用两步合成法，得到标题化合物3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)银盐（Ag2(BTATz)·2H2O），并用元素分析、X荧光和红外光谱分析对其进行了结构表征。采用DSC和TG-DTG技术对化合物进行热分解行为及非等温热分解动力学研究。结果表明，其热分解过程是由1个吸热阶段和2个放热阶段组成，主放热阶段的非等温热分解反应动力学方程为:dα/dt=1014.29×{3(1-α)[-ln(1-α)]1/4/4}exp(-2.10×104/T)。计算得到化合物的自加速分解温度(TSADT)、热爆炸临界温度(Tb)、热点火温度(TTIT)和绝热至爆时间（tTIAD）分别为517.10 K、580.12 K、531.00 K和90.32 s ，以此来评价其热安全性。

2010

0.0

... 而BTATz作为燃烧催化剂已用于双基/改性双基推进剂中,并且显示了良好的催化性能^[17] ...

2014

0.0

2012

0.0

2007

0.0

Kangzhen

, SONG

Jirong

, ZHAO

Fengqi

, et al. Special Heat Capacity, Thermodynamic Properties and Adiabatic Time-to-Explosion of 1, 1-Diamino-2, 2-dinitroethylene[J]. Acta Chim Sin, 2007, 65(25): 2827-2831(in Chinese).

徐抗震, 宋纪蓉, 赵凤起, 等. 1, 1-二氨基-2, 2-二硝基乙烯的比热容、热力学性质及绝热至爆时间研究[J]. 化学学报, 2007, 65(25): 2827-2831.

The standard molar special heat capacity of 1,1-diamino-2,2-dinitroethylene (FOX-7) was determined with two continuous C_p modes of a mircocalorimeter (Micro-DSCⅢ) to be 176.56 and 176.02 J•mol^－1•K^－1 at 298.15 K, respectively. The relative deviation between these two results is 0.31%. The special heat capacity of FOX-7 was also calculated by a DFT-RB3LYP/6-311＋＋G** method in Gaussian 03W package, and the relative deviation between theoretical calculation and experimental determination ranged from 13.27% to 15.46% within 283～353 K. Using the above determination results of special heat capacity, thermodynamic functions of FOX-7, relative to the standard temperature 298.15 K, were calculated through the thermodynamic relationship, and adiabatic time-to-explosion was also obtained.

应用Micro-DSCⅢ微热量仪的两种连续比热容测定模式对1,1-二氨基-2,2-二硝基乙烯(FOX-7)比热容进行了测定. 得到298.15 K时FOX-7的标准摩尔比热容分别为176.56和176.02 J•mol^－1•K^－1, 相对偏差为0.31%. 运用Gaussian 03W程序的DFT-RB3LYP/6-311＋＋G**方法对FOX-7在283～353 K温度范围内进行了比热容理论计算, 结果为147.11～170.54 J•mol^－1•K^－1, 与Micro-DSCⅢ微热量仪测定值偏差在13.27%～15.46%之间. 用测得的比热容方程计算了298.15 K为基础的FOX-7的热力学函数并得到了绝热至爆时间.

... 型微量量热仪中的连续比热容测定模式进行,测定原理及仪器校正同文献^[20] ...

1957

0.0

... 本文计算热分解动力学参数值的方法主要有Kissinger法^[21]、Flynn-Wall-Ozawa法^[22]和积分方程法^[23] ...

1965

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... 本文计算热分解动力学参数值的方法主要有Kissinger法^[21]、Flynn-Wall-Ozawa法^[22]和积分方程法^[23] ...

2001

0.0

... 本文计算热分解动力学参数值的方法主要有Kissinger法^[21]、Flynn-Wall-Ozawa法^[22]和积分方程法^[23] ...

... 1 自加速分解温度(T_SADT) 自加速分解温度(T_SADT)是^[23,27]将不同升温速率下所的到的T_e,T_p值代入到式(5)中,计算β ...

... 2 热爆炸临界温度(T_b)和热点火温度(T_TIT) T_b和T_TIT由式(6)计算得到^[23,27]: ...

2010

0.0

Dan.

High Nitrogen Organic Metal Complexes and Energetic Ionic Compounds: Synthesis, Structure, Thermodynamic Properties and Theoretical Calculation[D]. Xi'an: School of Chemical Engineering, Northwest University, 2010(in Chinese).

李丹. 高氮有机金属配合物和含能离子化合物的合成、结构、热力学性质及量子化学研究[D]. 西安: 西北大学化工学院, 2010.

1,2,4-三唑类化合物的五元杂环结构具有很高的能量,是一类重要的高能量密度材料,因此开展对1,2,4-三唑类化合物的研究具有十分重要的意义。本文合成了7种1,2,4-三唑类化合物的含能离子化合物和2种金属配合物,并通过元素分析、红外光谱等方法对其结构进行表征。采用溶剂缓慢挥发法在室温下培养出4-氨基-1,2,4-三唑的苦味酸盐(4ATz·PA)、3-氨基-1,2,4-三唑的3-硝基-1,2,4-三唑-5-酮盐(3ATz·NTO)、3,5-二氨基-1,2,4-三唑的苦味酸盐(DAT·PA)、3-硝基-1,2,4-三唑的乙二胺盐[3NTa·(CH2)2(NH2)2H2O]、咪唑的苦味酸盐(MZ·PA)、3,5-二硝基苯甲酸的二甲胺盐[DNBA-CH2(NH2)2]、4-氨基-1,2,4-三唑的乙酸锌配合物[Zn(4ATz)2(CH3COO)2]的单晶,并用X-射线衍射仪测定了单晶的结构,得到了结构数据。运用Gaussian 03程序对4ATz·PA、3ATz·NTO、DAT-PA、MZ·PA和DNBA·CH2(NH2)2进行几何优化和频率计算,且提供前线轨道能量和自然原子电荷。比较键长、键角的实验值和计算值,两者吻合较好。在非等温条件下,运用DSC-TG/DTG方法研究了这9种含能化合物的热行为。用Kissinger法、Ozawa法、一般积分法和微分法确定了Cu(4ATz)2Cl2H2O热分解过程的非等温反应动力学参数和热分解反应动力学机理函数,并得到了该化合物在峰温处的热分解反应活化焓(△H≠)、活化熵(△S≠)、活化自由能(△G≠)及临界热爆炸温度(Tb),对这些化合物的热稳定性进行分析比较。利用Micro-DSCⅢ微热量仪测定了这7种化合物的的连续比热容,并计算了各化合物以298.15 K为基准,283～353 K温区的热力学函数值(△H、△S和△G)。并运用Gaussian 03程序的优化结果对3ATz·NTO、DAT·PA、MZ·PA和DNBA·CH2(NH2)2在283～353 K的温度范围内进行比热容理论计算。

2011

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2004

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... 根据方程(1)及热力学函数与比热容的关系式(2)~(4),采用MATLAB^[26]软件计算得到Co(C₄H₂N₁₄)· ...

2009

0.0

... 1 自加速分解温度(T_SADT) 自加速分解温度(T_SADT)是^[23,27]将不同升温速率下所的到的T_e,T_p值代入到式(5)中,计算β ...

... 2 热爆炸临界温度(T_b)和热点火温度(T_TIT) T_b和T_TIT由式(6)计算得到^[23,27]: ...

2000

0.0

WANG

Yun

, FENG

Changgen

, ZHENG

Rao.

Prediction of Thermal Safety of Energetic Materials[J]. Chinese J Energy Mater, 2000, 8(3): 119-121(in Chinese).

王耘, 冯长根, 郑娆. 含能材料热安全性的预测方法[J]. 含能材料, 2000, 8(3): 119-121.

根据分解反应动力学分析了含能材料在绝热和近似绝热条件下的热分解反应.结果表明,在该条件下含能材料发生的热分解反应只与材料本身的特性相关,而与外界环境的影响无关,利用热分解反应的特征来评价含能材料本身的热安全特性,得出了含能材料开始发生热分解反应初始温度的计算公式.

... 3 绝热至爆时间(t_TIAD) 绝热至爆时间是评价含能物质热稳定性和热安全性的重要参数指标^[28-29],其值可根据热分析方法所计算得到的热动力学参数值及比热容方程进行估算 ...

2011

0.0

Rongzu

, GAO

Hongxu

, ZHAO

Fengqi

, et al. Thermal Safety of 1, 1'-Dimethyl -5, 5'-azotetrazole and 2, 2'-Dimethyl-5, 5'-azotetrazole[J]. Chinese J Energy Mater, 2011, 19(2): 126-131(in Chinese).

胡荣祖, 高红旭, 赵凤起, 等. 1, 1'-二甲基-5, 5'-偶氮四唑-水合物和2, 2'-二甲基-5, 5'-偶氮四唑的热安全性[J]. 含能材料, 2011, 19(2): 126-131.

2013

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... 98 s)^[30]、Mg盐(45 ...