4-氯-1-硝氨基-2,3,5,6-四硝基苯的合成及热性能分析  

Synthesis and Thermal Properties Analysis of 4-Chloro-1-nitroamino-2,3,5,6-tetranitrobenzene

作　　者：曹彩 闫宇民 廉鹏豹 王建龙[2] CAO Cai;YAN Yu-min;LIAN Peng-bao;WANG Jian-long(Shanxi North Xingan Chemical Industry Co.Ltd.,Taiyuan 030008,China;School of Chemistry and Chemical Engineering,North University of China,Taiyuan 030051,China)

机构地区：[1]山西北方兴安化学工业有限公司,山西太原030008 [2]中北大学化学与化工学院,山西太原030051

出　　处：《火炸药学报》2023年第10期911-919,I0010,共10页Chinese Journal of Explosives & Propellants

摘　　要：为了探索多硝基含能化合物的合成及其热分解性能,以4-氯-3,5-二硝基苯胺为原料,在乙酸酐溶液中加入4-氯-3,5-二硝基苯胺,乙酰化反应生成4-氯-3,5-二硝基乙酰苯胺(化合物Ⅰ),收率为91.7%;化合物Ⅰ在室温下硝化2h,制得4-氯-1-硝氨基-2,3,5,6-四硝基苯(化合物Ⅱ),收率为69.1%;采用傅里叶变换红外光谱(FT-IR)、核磁共振光谱(NMR)和元素分析(EA)对两种物质的结构进行了表征;培养了两种化合物的单晶,通过X-射线单晶衍射(SC-XRD)测定化合物的晶体结构;采用氮当量公式(NE)和修正氮当量公式(MNE)计算了化合物Ⅱ的爆轰性能,采用DSC和TG测试了化合物Ⅱ的热分解过程,并根据Kissinger法和FWO法计算了化合物Ⅱ的表观活化能(E)和指前因子(A),计算了放热分解过程的初始分解温度(Tp0)、自由活化能(ΔG≠)、活化焓(ΔH≠)、活化熵(ΔS≠),并估算了热爆炸临界温度(Tbp0)。结果表明,化合物Ⅰ的相对分子质量为259.61,空间群为C2,化合物Ⅱ的相对分子质量为352.5,空间群为C2/c,两种化合物的晶体结构均属单斜晶系;DSC显示,化合物Ⅱ在438.20K时达到最大放热峰,具有较好的热稳定性,爆轰参数表明该物质能量较高,有望成为极具前途的高能量高密度含能化合物。In order to explore the synthesis and thermal decomposition properties of polynitro energetic compounds,4-Chloro-3,5-dinitroacetaniline(compoundⅠ)was synthesized by acetylation of 4-chloro-3,5-dinitroaniline with the yield of 91.7%by using 4-chloro-3,5-dinitroaniline as raw material.4-Chloro-1-amino-2,3,5,6-tetranitrobenzene(compoundⅡ)was obtained by the nitrification of compound I for 2 h at room temperature with the yield of 69.1%.The structures of two compounds were characterized by Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance spectroscopy(NMR)and elemental analysis(EA).The single crystals of the two compounds were cultivated,and the crystal structure of two compounds were determined by single crystal X-ray diffraction(SC-XRD).The detonation performance of compoundⅡwas calculated by using nitrogen equivalent formula(NE)and modified nitrogen equivalent formula(MNE).The thermal decomposition process of compoundⅡwas studied by DSC and TG,and the apparent activation energy(E)and pre-exponential factor(A)of compoundⅡwere calculated by Kissinger method and FWO method.The initial decomposition temperature(T p0),free energy of activation(ΔG≠),activation enthalpy(ΔH≠),and activation entropy(ΔS≠)of the exothermic decomposition process were also calculated,and the critical temperature of thermal explosion(T bp0)was estimated.The results show that the molecular mass of compoundⅠis 259.61 with the space group of C 2,the molecular mass of compoundⅡis 352.5 with the space group of C 2/c,and the crystal structure of both compounds belong to the monoclinic system.DSC study shows that compoundⅡreaches the maximum exothermic peak at 438.20 K,implying its good thermal stability.The good detonation parameters indicate that it is expected to be a promising high energy density compound.

关 键 词：物理化学 4-氯-3 5-二硝基乙酰苯胺 4-氯-1-硝氨基-2 3 5 6-四硝基苯 乙酰化反应 硝化反应 多硝基含能化合物 

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]