2,4-二硝基咪唑含能锂盐的热分解行为及其对AP热分解的催化作用  

Thermal decomposition behavior of energetic lithium salt of 2,4-dinitroimidazole and its catalytic effect on thermolysis of AP

作　　者：成健[1] 邵灏 李振明[1] 黄斌[1] 王睿[1] 孙莉[1] 赵凤起[2] 徐司雨[2] 郝尧刚 苏宏平 李京霖 CHENG Jian;SHAO Hao;LI Zhenming;HUANG Bin;WANG Rui;SUN Li;ZHAO Fengqi;XU Siyu;HAO Yaogang;SU Hongping;LI Jinglin(Department of safety science and engineering,Zhejiang University of Technology,Hangzhou 310014,China;Xi＇an Modem Chemistry Research Institute,Xi＇an 710065,China;Research Institute of Gansu Yinguang Chemical Industry Group,Baiyin 730900,China)

机构地区：[1]浙江工业大学安全科学与工程系,杭州310014 [2]西安近代化学研究所,西安710065 [3]甘肃银光化学工业集团有限公司,白银730900

出　　处：《固体火箭技术》2018年第4期483-489,共7页Journal of Solid Rocket Technology

基　　金：浙江省大学生科技创新项目(2017R403042);浙江省自然科学基金项目(LY14E030005和LQ16E040002);火炸药十二五预研项目(62201070102)

摘　　要：为寻求2,4-二硝基咪唑为配体的新型含能催化剂,以2,4-二硝基咪唑和碳酸锂为原料,丙酮为反应溶剂,合成了2,4-二硝基咪唑含能锂盐(Li-DNI)。采用元素分析,1HNMR,13CNMR和XPS表征其结构。采用TG-DTG和DSC分析了Li-DNI的热分解行为及Li-DNI与高氯酸铵(AP)热分解反应过程中的互为催化反应。用Kissinger公式和Ozawa公式计算了Li-DNI热分解反应的表观活化能及Li-DNI/AP混合物在低温分解阶段(LTD)和高温分解阶段(HTD)的非等温反应动力学参数。结果表明,Li-DNI分子式为Li C3HN4O4·H2O。Li-DNI热分解过程主要由一个吸热熔融峰和分解放热峰组成,相应峰温分别为84.5℃和310.7℃,放热分解反应表观活化能为153.3 k J/mol。Li-DNI与AP热分解反应过程中产生互为催化作用:Li-DNI可加快AP热分解,使AP在LTD和HTD阶段的峰温和表观活化能分别降低41.8℃和75.6℃,56.0 k J/mol和10.8 k J/mol,表观放热量增加432.3 J/g,显示Li-DNI对AP热分解具有较好的催化作用。AP也可加速Li-DNI热分解,可使Li-DNI剧烈分解阶段的峰温提前19.9℃。To explore new energetic catalysts using 2,4-dinitroimidazole as a ligand,energetic lithium salt of 2,4-dinitroimidazole（ Li-DNI） was synthesized using lithium carbonate as a Li＋source,acetone as reaction solvent.Its structure was characterized by elemental analysis,1 H NMR,13 C NMR and XPS.The thermal decomposition behavior of Li-DNI and catalytic effect of Li-DNI on decomposition of ammonium perchlorate（ AP） were analyzed by TG-DTG and DSC. The apparent activation energy of the thermal decomposition of Li-DNI and non-isothermal kinetic parameters in the low temperature and high（ LTD and HTD） stages of Li-DNI/AP mixture were calculated by Kissinger and Ozawa methods.The results show that the molecular formula of Li-DNI is Li C3 HO4 N4·H2 O.The decomposition of Li-DNI consists of one endothermic melting peak and one exothermic decomposition peak,and the corresponding peak temperatures are 84.5 ℃ and 310.7 ℃,respectively.The apparent activation energy of the exothermic decomposition reaction is 153.3 k J/mol.Both of the Li-DNI and AP has catalytic effects on each other during the thermal decomposition process.LiDNI can accelerate the thermal decomposition of AP,make the exothermic peak temperatures decreased by 41.8 ℃ and 75.6 ℃,whereas the activation energy values of LTD stage and HTD stage of AP by 56.0 k J/mol and 10.8 k J/mol,respectively.The decomposition heat of AP was increased by 432.3 J/g,revealing that Li-DNI has a great catalytic effect on the thermal decomposition of AP.AP can accelerate the thermal decomposition of Li-DNI as well,make the exothermic peak temperature for Li-DNI decreased by 19.9 ℃.

关 键 词：2 4-二硝基咪唑 含能锂盐 热分解行为 高氯酸铵 催化作用 

分 类 号：V512[航空宇航科学与技术—航空宇航推进理论与工程]