4,4′,5,5′-四硝基-2,2′-双(三硝甲基)-2H,2′H-3,3′-联吡唑(DNBP-10)的合成、热行为与能量性能  

4,4′,5,5′-Tetranitro-2,2′-bis(trinitromethyl)-2H,2′H-3,3′-bipyrazole(DNBP-10):Synthesis,Thermal Behavior and Energy Characteristics

作　　者：霍欢[1] 毕福强[1,2] 罗义芬 王民昌[1] 唐望[1] 王伯周[1,2] HUO Huan;BI Fu-qiang;LUO Yi-fen;WANG Min-chang;TANG Wang;WANG Bo-zhou(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China;State Key Laboratory of Fluorine&Nitrogen Chemicals,Xi′an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065

出　　处：《火炸药学报》2020年第6期597-601,607,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21805224)。

摘　　要：以4,4′,5,5′-四硝基-2H,2′H-3,3′-联吡唑(TNBP)和氯丙酮为原料,经取代、硝化反应得到一种高能氧化剂4,4′,5,5′-四硝基-2,2′-双(三硝甲基)-2H,2′H-3,3′-联吡唑(DNBP-10),总收率22.1%,并用红外光谱、13C NMR、15N NMR及元素分析等进行了结构表征;对取代反应进行了工艺优化;采用差示扫描量热和热重(DSC-TG)法研究了DNBP-10的热行为,并采用Kissinger方法计算了热分解参数;采用EXPLO5软件对比分析了RDX、HMX、CL-20与DNBP-10对熔铸混合炸药爆轰性能的影响。结果表明,氯丙酮和KBr作为取代试剂,在DMF中70℃反应2h得到取代产物,与文献反应时间72h对比,显著缩短了反应周期;DNBP-10的熔点和分解点分别为124.2和136.4℃;TNT/DNBP-10(30/70)和BOM/DNBP-10(30/70)的理论爆热分别为6156.7和6598.3J/g,比TNT/CL-20和BOM/CL-20分别高出511.2和790J/g,理论爆速分别达到9002.0和9250.8m/s,较TNT/CL-20提高225.8m/s,与BOM/CL-20相当,表明DNBP-10可大幅提高熔铸混合火炸药的能量性能。A high energetic oxidizer,4,4′,5,5′-tetranitro-2,2′-bis(trinitromethyl)-2H,2′H-3,3′-bipyrazole(DNBP-10),was synthesized via substitution and nitration reaction with an overall yield of 22.1%using 4,4′,5,5′-tetranitro-2H,2′H-3,3′-bipyrazole(TNBP)and chloroacetone as raw materials.Its structure was characterized by FT-IR spectra,13C NMR,15N NMR and elemental analysis.The reaction process of the substitution for the DNBP-10 was optimized.The thermal behaviors for DNBP-10 was studied by differential scanning calorimetry and thermogranvimetic(DSC-TG)techniques,and the thermal decomposition parameters were calculated by Kissinger method.The detonation parameters of TNT or BOM-based melt casting explosives with RDX,HMX,CL-20 and DNBP-10 as high energy phases were theoretically calculated by EXPLO5 software.The results show that the substitution condition is as follows:chloroacetone and KBr were regarded as the substitution regents,and the reaction time is 2h at 70℃in DMF.The peak temperature of melting point and the exothermic decomposition reaction are 124.2℃and 136.4℃,respectively.The theoretical heat of detonation of TNT/DNBP-10(30/70)and BOM/DNBP-10(30/70)are 6156.7 and 6598.3J/g,which are higher than those of TNT/CL-20(511.2J/g)and BOM/CL-20(790J/g),respectively.The theoretical detonation velocity for TNT/DNBP-10(30/70)and BOM/DNBP-10(30/70)are 9002.0 and 9250.8m/s,higher than TNT/CL-20(225.8m/s)and close to BOM/CL-20.Compared with RDX,HMX and CL-20,the energy is improved greatly with DNBP-10 as solid phase in melting and casting mixed explosives.

关 键 词：有机化学 高能氧化剂 4 4′ 5 5′-四硝基-2 2′-双(三硝甲基)-2H 2′H-3 3′-联吡唑 DNBP-10 能量特性 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]