DNTF原位红外热分解动力学及机理  

Thermal Decomposition Kinetics and Mechanism of DNTF by in Situ Infrared Technology

作　　者：南海 潘清[2] 姜帆[2] 王煊军 金朋刚 张坤[2] NAN Hai;PAN Qing;JIANG Fan;WANG Xuan-jun;JIN Peng-gang;ZHANG Kun(Rocket Force University of Engineering,Xi'an 710025,China;Xi'an Modern Chemistry Research Institute,Xi'an 710065,China)

机构地区：[1]火箭军工程大学,陕西西安710025 [2]西安近代化学研究所,陕西西安710065

出　　处：《含能材料》2022年第6期604-610,共7页Chinese Journal of Energetic Materials

摘　　要：为了深入研究3,4⁃二硝基呋咱基氧化呋咱(DNTF)特征基团的热分解特性,采用差示扫描量热法(DSC)、快速扫描傅里叶变换红外光谱法(FTIR)分析了DNTF的凝聚相热分解特性;利用变温红外原位池技术在2.5,5.0,10.0℃·min^(-1)等三种升温速率下研究了DNTF的特征基团随时间(温度)的变化;采用Coats⁃Redfern法计算得到了DNTF的硝基、呋咱环、氧化呋咱环的热分解动力学参数;基于DNTF的特征基团热分解特性,推测了DNTF的热分解机理。结果表明:DNTF特征基团的热分解受三维扩散机理控制,DNTF分子内的基团反应活性为硝基>氧化呋咱环>呋咱环,随着加热速率提高,各基团的反应活性表现出增大的趋势。推测DNTF热分解过程为C─NO2先断裂,然后连接呋咱环和氧化呋咱环的C─C键断裂,最后氧化呋咱环和呋咱环中N─O键断裂,且氧化呋咱环比呋咱环更快发生分解。In order to study the thermal decomposition properties of the characteristic groups of 3,4⁃Dinitrofurazanylfuroxan(DNTF),differential scanning calorimetry(DSC)and fast scanning Fourier transform infrared spectroscopy(FTIR)were adopted to study the thermal decomposition properties of DNTF in condensed phase.The changes of characteristic groups of DNTF were studied by using FTIR technology at three different heating rates of 2.5,5.0,10℃·min^(-1).The thermal decomposition kinetic pa⁃rameters of C─NO_(2),furazan ring,and furoxan ring of DNTF were calculated by the Coats⁃Redfern method.The thermal decom⁃position mechanism of DNTF was inferred based on the thermal decomposition properties of the characteristic group of DNTF.The results show that the thermal decomposition of DNTF is controlled by the three⁃dimensional diffusion mechanism.The reac⁃tivity of groups in DNTF molecule is nitro>furoxan ring>furazan ring.With the increase of heating rate,the reactivity of each group shows an increasing trend.It is speculated that the thermal decomposition process is that C─NO_(2) breaks first,and then the C─C bond connecting furuzan and furoxan ring breaks,and finally the N─O bond in furazan ring and furoxan ring breaks.The furoxan ring decomposes faster than furazan ring.

关 键 词：3 4⁃二硝基呋咱基氧化呋咱(DNTF) 快速扫描傅里叶变换红外光谱法(FTIR) 热分解 分解机理 

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]