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  

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[1] 张聪[1] 严彪[1] 郭兆琦 高红旭[2] 马海霞[1] CHEN Xiang;ZHANG Cong;YAN Biao;GUO Zhao qi;GAO Hong xu;MA Hai xia(College of Chemical Engineering, Northwest University, Xi′an 710069, China;Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

机构地区：[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

出　　处：《火炸药学报》2017年第6期43-48,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21673179;No.21373161;No.21504067)

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(ΔcHm)和标准摩尔生成焓(ΔfHm)。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、ΔcHm值和ΔfHm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。3,6Dihydrazine-1,2,4,5-tetrazine-3,5-dinitrosalicylic acid salt dihydrate(DHT·2DNS·2H2O)was synthesized using-3,6dihydrazine-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(ΔcHm)and the standard molar enthalpy of formation(ΔfHm)were estimated via theΔcU.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 ofΔcU,ΔcHm andΔfHm of DHT·2DNS are(-11938.17±25.33)J/g,(-7119.77±15.16)kJ/mol and(-1177.2±11.14)kJ/mol,respectively.

关 键 词：3 6-二肼基四嗪 3 5-二硝基水杨酸 差示扫描量热法 热重-红外联用 热分解行为 四嗪类化合物 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]