摘要
为了寻求新型耐热炸药,以TNT为原料,通过氧化、氯化、缩合、环化4步法合成了5,5′-双(2,4,6-三硝基苯基)-2,2′-二(1,3,4-恶二唑)(TKX-55);通过薄层色谱、傅里叶红外光谱(FTIR)、质谱、元素分析对其4步产物进行了表征,利用差示扫描量热法(DSC)对中间体及TKX-55的热安定性进行了分析。结果表明,氧化反应较佳反应条件为:TNT与氯酸钠(NaClO_3)的摩尔比为1∶4,反应时间为4h,反应温度为90℃,与文献[2]相比,使2,4,6-三硝基苯甲酸(TNBA)的收率提高了4%;缩合反应较佳反应条件为:选取四氢呋喃(THF)为溶剂,N,N-二甲基甲酰胺(DMF)为缚酸剂,2,4,6-三硝基苯甲酸(TNBC)与草酰二肼的摩尔比为2∶1,反应温度为5℃,反应时间为36h,与文献[2]相比,使双(2,4,6-三硝基苯甲酰基)草酰肼的收率提高了7%;环化反应较佳反应条件为:以发烟硫酸(质量分数20%)为脱水剂,反应温度为15℃,反应时间为24h,TKX-55的收率为93%;TKX-55的分解温度为365.5℃,表明TKX-55是一种热安定性良好的耐热炸药。
To seek the novel heat-resistant explosive,5,5′-bis(2,4,6-trinitrophenyl)-2,2′-bi(1,3,4-oxadiazole)(TKX-55)was synthesized via four steps of oxidation,chloridization,condensation and cyclization using 2,4,6-trinitrotoluene(TNT)as raw material.Four products were characterized by thin-layer chromatography,Fourier transform infrared spectrometer(FTIR),mass spectrometry(MS),elemental analysis and different scanning calorimetry(DSC).The results show that the optimal reaction conditions for the oxidation reaction are as follows:the molar ratio of TNT to sodium chlorate(NaClO3)is 1∶4,the reaction time is 4h,and the reaction temperature is 90℃to make the yield of 2,4,6-trinitrobenzoic acid(TNBA)increases by 4%.The optimal reaction conditions for the condensation reaction are:taking tetrahydrofuran(THF)as solvent,N,N-dimethylformamide(DMF)as deacid reagent,the molar ratio of 2,4,6-trinitrobenzoic acid(TNBC)to oxalyl dihydrazide as 2∶1,the reaction temperature as 5℃,and the reaction time as 36h to make the yield of bis(2,4,6-trinitrobenzoyl)oxalohydrazide increase by 7%.The optimal reaction conditions for cyclization reaction are as follows:the most suitable dehydrating agent is fuming sulfuric acid(mass fraction of 20%),the reaction temperature is 15℃,the reaction time is 24 h,and the yield of TKX-55 is 93%.The decomposition temperature of TKX-55 is 365.5℃,indicating that TKX-55 is a heat-resistant explosive with good thermal stability.
作者
柴笑笑
李永祥
曹端林
王建龙
郭昊琪
CHAI Xiao-xiao;LI Yong-xiang;CAO Duan-lin;WANG Jian-long;GUO Hao-qi(School of Environment and Safety Engineering,North University of China,Taiyuan 030051,China;School of Chemical Engineering and Technology,North University of China,Taiyuan 030051,China)
出处
《火炸药学报》
EI
CAS
CSCD
北大核心
2019年第2期135-140,I0002,共7页
Chinese Journal of Explosives & Propellants
关键词
有机化学
5
5′-双(2
4
6-三硝基苯基)-2
2′-二(1
3
4-恶二唑)(TKX-55)
2
4
6-三硝基甲苯(TNT)
双(2
4
6-三硝基苯甲酰基)草酰肼
耐热炸药
organic chemistry
5,5′-bis(2,4,6-trinitrophenyl)-2,2′-bi(1,3,4-oxadiazole)(TKX-55)
2,4,6-trinitrotoluene(TNT)
bis(2,4,6-trinitrobenzoyl)oxalohydrazide
heat-resistant explosive
