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[1]张聪,陈湘,白杨,等.6-(3,5-二甲基-1H-吡唑)-1,2,4,5-四嗪-3-酮(DPTzO)及其胍盐的晶体结构和热分解行为[J].火炸药学报,2019,42(5):432-437,444.[doi:10.14077/j.issn.1007-7812.2019.05.002]
 ZHANG Cong,CHEN Xiang,BAI Yang,et al.Crystal Structure and Thermal Decomposition Behaviors of 6-(3,5-Dimethyl-1H-pyrazole)-1,2,4,5-tetrazin-3-one (DPTzO) and Its Guanidine Salt[J].,2019,42(5):432-437,444.[doi:10.14077/j.issn.1007-7812.2019.05.002]
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6-(3,5-二甲基-1H-吡唑)-1,2,4,5-四嗪-3-酮(DPTzO)及其胍盐的晶体结构和热分解行为()
     
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《火炸药学报》[ISSN:1007-7812/CN:61-1310/TJ]

卷:
42卷
期数:
2019年第5期
页码:
432-437,444
栏目:
出版日期:
2019-10-31

文章信息/Info

Title:
Crystal Structure and Thermal Decomposition Behaviors of 6-(3,5-Dimethyl-1H-pyrazole)-1,2,4,5-tetrazin-3-one (DPTzO) and Its Guanidine Salt
作者:
张聪 陈湘 白杨 郭兆琦 马海霞
西北大学化工学院, 陕西 西安 710069
Author(s):
ZHANG Cong CHEN Xiang BAI Yang GUO Zhao-qi MA Hai-xia
School of Chemical Engineering, Northwest University, Xi’an 710069, China
关键词:
物理化学1245-四嗪晶体结构热行为四嗪衍生物DPTzO高氮杂环化合物
Keywords:
physical chemistry1245-tetrazinecrystal structurethermal behaviortetrazine derivativeDPTzOhigh-nitrogen heterocyclic compound
分类号:
TJ55;O64
DOI:
10.14077/j.issn.1007-7812.2019.05.002
文献标志码:
-
摘要:
合成了两种四嗪衍生物6-(3,5-二甲基-1H-吡唑)-1,2,4,5-四嗪-3-酮(DPTzO)及其胍盐(G·DPTzO),采用红外光谱(FT-IR)、元素分析(EA)、核磁共振(NMR)和X-射线单晶衍射对结构进行表征;利用差示扫描量热法(DSC)和热重法(TG-DTG)分析两种化合物的热分解行为;根据不同升温速率下的DSC曲线用Kissinger和Ozawa法计算热分解动力学参数。结果表明,DPTzO晶体属于正交晶系,Pna21空间群,晶胞参数为:a=1.224 7(2)nm,b=1.310 9(3)nm,c=0.529 88(10)nm,α=90°,β=90°,γ=90°,V=0.850 7(3)nm,Z=4;G·DPTzO晶体属于单斜晶系,P21/c空间群,晶胞参数为a=0.754 30(13)nm,b=0.923 52(17)nm,c=1.763 7(3)nm,α=90°,β=100.754(3)°,γ=90°,V=1.207(4)nm3Z=4;G·DPTzO中G+与DPTzO-上N、O原子形成大量氢键构成二维结构。DPTzO与G·DPTzO的活化能(E)和指前因子(A)分别为210.60和237.77 kJ/mol、1021.2和1021.0s-1;自加速分解温度(TSADT)、热点火温度(Tbe)和热爆炸临界温度(Tbp)分别为204.49和268.57℃、202.99和260.21℃、205.80和264.35℃,分子间氢键的存在提高了胍盐的热安定性。
Abstract:
6-(3,5-Dimethyl-1H-pyrazole)-1,2,4,5-tetrazin-3-one (DPTzO) and its guanidine salt (G·DPTzO) were synthesized and characterized by Fourier-transform infrared spectroscopy (FT-IR), elemental analysis (EA),nuclear magnetic resonance(NMR) and single crystal X-ray diffraction. The thermal decomposition behaviors of the two compounds were analyzed by thermogravimetry (TG-DTG) and differential scanning calorimetry (DSC) under non-isothermal conditions and then the thermal decomposition kinetic parameters were calculated by the Kissinger and Ozawa’s methods. The crystal parameters are determined as follows:DPTzO, orthorhombic, space group Pna21, a=1.224 7(2) nm, b=1.310 9(3) nm, c=0.529 88(10) nm, α=90°, β=90°, γ=90°,V=0.850 7(3) nm, Z=4; G·DPTzO, monoclinic, space group P21/c, a=0.754 30(13) nm, b=0.923 52(17) nm, c=1.763 7(3) nm, α=90°, β=100.754(3)°, γ=90°, V=1.207(4) nm3,Z=4. In G·DPTzO, hydrogen bonds between G+ and the N, O atoms on the DPTzO- group connect the molecules into a two-dimentional structure. The apparent activation energy (E) and pre-exponential constant (A) of the thermal decomposition were determined as 210.60 kJ/mol and 1021.2 s-1 for DPTzO and 237.77 kJ/mol and 1021.0 s-1 for G·DPTzO, respectively. The self-accelerating decomposition temperature (TSADT), the thermal ignition temperature (Tbe) and the critical thermal explosion temperature (Tbp) are 204.49 and 268.57℃, 202.99 and 260.21℃, 205.80 and 264.35℃, respectively. The intermolecular hydrogen bonds are helpful for enhancing the thermal stability of guanidine salt.

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备注/Memo

备注/Memo:
收稿日期:2019-03-14;改回日期:2019-04-17。
基金项目:国家自然科学基金(No.21673179,No.21504067);陕西省自然科学基金(No.2018JM2057)
作者简介:张聪(1993-),女,硕士,从事含能材料合成研究。E-mail:ZhangCong6389@163.com
通讯作者:马海霞(1974-),女,教授,博导,从事含能材料的合成、热力学性能及其量子化学研究。E-mail:mahx@nwu.edu.cn
更新日期/Last Update: 1900-01-01