摘要
以三硝基甲苯(TNT)为主要原料,通过氧化、氯代、取代、成环反应合成耐热炸药5,5'?双(2,4,6?三硝基苯基)?2,2'?双(1,3,4?噁二唑)(TKX?55),综合收率60.3%。采用红外光谱(FTIR)、核磁共振(NMR)对产物进行了表征,并对氯代反应、取代反应进行了优化。结果显示以SOCl_2为氯代试剂,产率最高(88.8%);以THF为溶剂、反应时间为24 h时,加入无机碱NaHCO_3,取代效果好于加入其它缚酸剂(NaOH、Et_3N、Na-2CO_3),TKX?55分解温度为335℃。用Gaussian软件在b3lyp/6?31++g(d,p)水平下对TKX?55进行分子优化,并通过Kamlet?Jacob公式计算得到爆速(D=8052 m·s~(-1))和爆压(p=28.6 GPa),均优于2,6?二苦胺基?3,5?硝基吡啶(PYX)(D=7590 m·s~(-1),p=26.2 GPa)和2,2',4,4',6,6'?六硝基二苯基乙烯(HNS)(D=7545 m·s~(-1),p=23.6 GPa)。
5,5'?Bis(2,4,6?trinitrophenyl)?2,2'?bi(1,3,4?oxadiazole)(TKX?55),a thermally stable explosive,was synthesized with a total yield of 60.3% from trinitrotoluene via oxidation,chlorination,substitution and cyclization reactions. The chemical structure of TKX?55 was characterized by infrared(IR)spectroscopy,nuclear magnetic resonance(NMR,~1H and~(13)C). Next,we optimized the chlorine and substitution reaction conditions.When SOCl_2 acted as chlorine reagent,the highest yield was up to88.8%. When THF was used as solvent and the reaction time was 24 h,NaHCO_3 was a better acid?binding agent compared with others(such as NaOH、Et_3 N and Na_2CO_3). The decomposition temperature of TKX?55 is 335 ℃. After optimizing the molecularstructure of TKX?55,its detonation velocity(D=8052 m·s~(-1))and detonation pressure(p=28.6 GPa)are calculated by Kamlet?Jacob formula,which are better than those of PYX(D=7590 m·s~(-1),p=26.2 GPa)and HNS(D=7545 m·s~(-1),p=23.6 GPa).
引文
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