五氧化二氮/硝酸/乙酸酐体系的拉曼光谱  

Raman Spectroscopic of Dinitrogen Pentoxide / Nitric Acid / Acetic Anhydride Systems

作　　者：孙昱[1] 唐月娇[1] 吕早生[1] 吕春绪[2] SUN Yu TANG Yue-jiao LU Zao-sheng LU Chun-xu(School of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081 , China School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China)

机构地区：[1]武汉科技大学化学工程与技术学院,湖北武汉430081 [2]南京理工大学化工学院,江苏南京210094

出　　处：《含能材料》2016年第10期1000-1004,共5页Chinese Journal of Energetic Materials

摘　　要：研究了五氧化二氮/硝酸/乙酸酐体系溶剂体积比对硝解3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)合成环四亚甲基四硝胺(HMX)的影响。结果表明:在V硝酸∶V乙酸酐=3∶2时,HMX的最高收率为87.9%。拉曼光谱研究显示,随着乙酸酐比例的增加,体系中的硝酰阳离子浓度逐渐降低并出现硝酰阳离子振动频率的显著红移,呈现五氧化二氮离子对中弯曲变形的硝酰阳离子浓度呈先增加后降低的趋势。五氧化二氮处于一定的离子对及自由离子范围之间,并且溶剂体系具有一定的供电子效应,可能具有适宜的硝化能力和较高的反应性,有利于HMX的合成。The effect of solvent volume ratio of dinitrogen pentoxide/nitric acid/acetic anhydride system on the synthesis of cyclotetramethylenetetramine （HMX） via the nitration of 3,7-dinitro-1,3,5,7-tetrazabicyclo[3.3.1]nonane （DPT） was investigated. Results show that the highest yield of HMX is 87.9% when the volume ratio of nitric acid/acetic anhydride is 3∶2. Raman spectra reveals that, the concentration of nitronium ion in the system gradually decreases with increasing the ratio of acetic anhydride and the significant red-shift of the vibration frequency of nitronium ion occurs, revealing that the trend of the concentration of the nitronium ion with bending deformation in dinitrogen pentoxide ion pairs is increases first and then decreases. The dinitrogen pentoxide which is between the range of certain ion pairs and free ions, as well as certain electron donating effect for solvent system, may have appropriate nitrification ability and high reactiviy, and be conducive to the synthesis of HMX.

关 键 词：五氧化二氮 拉曼光谱 硝解 3 7-二硝基-1 3 5 7-四氮杂双环[3.3.1]壬烷(DPT) 环四亚甲基四硝胺(HMX) 

分 类 号：TQ560.1[化学工程—炸药化工] O657.37[理学—分析化学]