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[1]陈湘,张聪,严彪,等.3,6-二肼基-1,2,4,5-四嗪二硝基水杨酸盐的合成、热分解及生成焓研究[J].火炸药学报,2017,40(6):43-48.[doi:10.14077/j.issn.1007-7812.2017.06.007]
 CHEN Xiang,ZHANG Cong,YAN Biao,et al.Study on Preparation, Thermal Behavior and Enthalpy of Formation of 3, 6-Dihydrazine-1, 2, 4, 5-tetrazine-3, 5-dinitrosalicylic Acid Salt[J].,2017,40(6):43-48.[doi:10.14077/j.issn.1007-7812.2017.06.007]
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3,6-二肼基-1,2,4,5-四嗪二硝基水杨酸盐的合成、热分解及生成焓研究()
     
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《火炸药学报》[ISSN:1007-7812/CN:61-1310/TJ]

卷:
40卷
期数:
2017年第6期
页码:
43-48
栏目:
出版日期:
2017-12-29

文章信息/Info

Title:
Study on Preparation, Thermal Behavior and Enthalpy of Formation of 3, 6-Dihydrazine-1, 2, 4, 5-tetrazine-3, 5-dinitrosalicylic Acid Salt
作者:
陈湘 张聪 严彪 郭兆琦 高红旭 马海霞
1. 西北大学化工学院, 陕西 西安 710069;
2. 西安近代化学研究所, 陕西 西安 710065
Author(s):
CHEN Xiang ZHANG Cong YAN Biao GUO Zhao-qi GAO Hong-xu MA Hai-xia
1. College of Chemical Engineering, Northwest University, Xi’an 710069, China;
2. Xi’an Modern Chemistry Research Institute, Xi’an 710065, China
关键词:
36-二肼基四嗪35-二硝基水杨酸差示扫描量热法热重-红外联用热分解行为四嗪类化合物
Keywords:
36-dihydrazine-1245-tetrazine35-dinitrosalicylic aciddifferential scanning calorimetryTG-FTIRthermal decomposition behaviortetrazine compound
分类号:
TJ55;O64
DOI:
10.14077/j.issn.1007-7812.2017.06.007
文献标志码:
-
摘要:
以3,6-二肼基四嗪(DHT)和3,5-二硝基水杨酸(DNS)为原料,合成了3,6-二肼基-1,2,4,5-四嗪二硝基水杨酸盐二水合物(DHT·2DNS·2H2O),采用核磁共振波谱、红外光谱、元素分析及热重法对其结构进行了表征。采用差示扫描量热法(DSC)并结合热重-红外联用(TG-FTIR)对无水DHT·2DNS的热行为及热分解产物进行了研究。利用氧弹量热仪测定了DHT·2DNS的恒容燃烧热(ΔcU),并通过ΔcU估算了标准摩尔燃烧焓(ΔcHmΘ)和标准摩尔生成焓(ΔfHmΘ)。结果表明,DHT·2DNS的热稳定性要高于DHT,其受热分解可分为4个阶段:首先DHT·2DNS的二硝基水杨酸离子脱去羟基和部分硝基、羧基,同时肼基发生分解;然后苯环上的基团与四嗪环发生解离;随后苯环发生裂解;最后苯环残余物继续发生分解。DHT·2DNS的ΔcU值、ΔcHmΘ值和ΔfHmΘ值分别为(-11 938.17±25.33) J/g、(-7 119.77±15.16) kJ/mol和(-1 177.2±11.14) kJ/mol。
Abstract:
3,6-Dihydrazine-1,2,4,5-tetrazine-3,5-dinitrosalicylic acid salt dihydrate (DHT·2DNS·2H2O) was synthesized using 3,6-dihydrazine-1,2,4,5-tetrazine (DHT) and 3,5-dinitrosalicylic acid (DNS) as raw materials and its structure was characterized by nuclear magnetic resonance spectroscopy, infrared spectroscopy, element analysis and thermogravimetry. The thermal behavior and thermal decomposition products of anhydrous DHT·2DNS were studied by differential scanning calorimetry (DSC) and thermogravimetry combined with Fourier transform infrared analysis (TG-FTIR). The constant-volume combustion heat (ΔcU) was determined by an oxygen bomb calorimeter and the standard molar enthalpy of combustion (ΔcHmΘ) and the standard molar enthalpy of formation (ΔfHmΘ) were estimated via the ΔcU. The results show that the thermal stability of DHT·2DNS is higher than DHT and its thermal decomposition process can be divided into four stages. Firstly, part of hydroxyl, nitro and carboxyl in DNS ion of DHT·2DNS were removed and hydrazine was decomposed; then, the tetrazine ring and groups on the benzene ring was dissociated, thirdly, benzene ring was broken; finally, the benzene residues kept decomposing. The values of ΔcU, ΔcHmΘ and ΔfHmΘ of DHT·2DNS are (-11 938.17±25.33) J/g,(-7 119.77±15.16) kJ/mol and (-1 177.2±11.14) kJ/mol, respectively.

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备注/Memo

备注/Memo:
收稿日期:2017-09-14;改回日期:2017-10-02。
基金项目:国家自然科学基金(No.21673179;No.21373161;No.21504067)
作者简介:陈湘(1991-),男,硕士研究生,从事含能材料合成及性质研究。E-mail:cxistayreal@163.com
通讯作者:马海霞(1974-),女,教授,从事新型功能材料的设计及开发、热化学、量子化学研究。E-mail:mahx@nwu.edu.cn
更新日期/Last Update: 1900-01-01