基于1,5-二硝胺基四唑高能材料的合成及性能

Synthesis and Properties of High Energy Materials Based on 1,5-Di(nitramino)tetrazole

以甲氧基甲酰肼与叠氮氰为原料,经成环、硝解、酸化、中和等反应合成高能材料1,5-二硝胺基四唑(DNAT)及其含能离子盐——钾盐(DKDNAT)、铵盐(DADNAT)、肼盐(DHDNAT)、羟胺盐(DHADNAT),采用红外光谱、1 H NMR、13 C NMR及元素分析对DNAT及其含能离子盐的结构进行了表征;优化了关键中间体1-甲氧基甲酰基-1,5-二氨基四唑(MCDAT)的合成工艺;探讨了一锅法合成MCDAT的反应机理;采用DSC方法对DNAT及其钾盐、铵盐、肼盐和羟胺盐的热性能进行了分析;对DNAT-CMDB、DHDNAT-CMDB、DHADNATCMDB推进剂的能量特性进行了理论研究。结果表明,叠氮氰与甲氧基甲酰肼的最佳摩尔比为1.2∶1.0,反应温度为25℃,MCDAT的收率由文献中的37.3%提高到79.3%;DNAT及其4种含能离子盐(钾盐、铵盐、肼盐和羟胺盐)的热分解峰温依次为94.1、259.1、192.1、142.8、146.7°C;3种推进剂的理论比冲分别为2 539.1、2 489.9、2 532.6N·s/kg,特征速度为1 571.6、1 570.1、1 580.6m/s。

High energy materials 1,5-di(nitramino)tetrazole(DNAT)and its energetic ion salts-potassium salt(DKDNAT),ammonium salt(DADNAT),hydrazine salt(DHDNAT)and hydroxylammonium salt(DHADNAT)were synthesized via cyclication,nitrification,acidification and neutralization reactions using methylcarbazate and cyanogen azide as raw materials.Their structures were characterized by IR spectra,1 HNMR,13 C NMR and elemental analyses. The synthetic technology of key-intermediate 1-methoxycarbonyl-1,5-diaminotetrazole(MCDAT)was optimized.The reaction mechanism of MCDAT synthesized with one pot method was discussed.The thermal properties of DNAT,DKDNAT,DADNAT,DHDNAT and DHADNAT were analyzed by DSC.The energy characteristics of DNAT-CMDB,DHDNAT-CMDB and DHADNAT-CMDB propellants were theoretically studied.The results show that the best molar ratio of cyanogen azide and methylcarbazate is 1.2∶1.0,the reaction temperature is 20~25℃,and the yield of MCDAT is improved from 37.3% in the literature to 79.3%.The thermal decomposition peak temperature of DNAT and its energetic ion salts are 94.1,259.1,192.1,142.8and146.7℃,respectively.The theoritical specific impulse of the propellants are 2 539.1,2 489.9and 2 532.6N·s/kg,respectively,and the characteristic velocities of the propellants are 1 571.6,1 570.1and 1 580.6m/s,respectively.