PDF (3342K)
摘要
以乙酸甲酯为溶剂,采用溶剂挥发法制得六硝基六氮杂异伍兹烷(CL-20)/2,4-二硝基-2,4-二氮杂戊烷(DNDAP)共晶含能材料。利用扫描电子显微镜和单晶X射线衍射仪对其形貌和结构进行表征,采用差示扫描量热法测试其热性能,并研究了该材料的机械感度和爆轰性能。结果表明,CL-20/DNDAP晶体属于单斜晶系,P21/c空间群,晶胞参数a=1.3022(2)nm,b=2.2619(4)nm,c=1.2962(2)nm,α=90°,β=104.648(3)°,γ=90°(a,b,c均为晶胞长度;α,β,γ均为空间角)。CL-20/DNDAP共晶含能材料在210～260℃集中放热分解,熔点明显高于DNDAP;共晶含能材料特性落高值为33.1cm,摩擦感度为48%,摩擦感度较CL-20大幅降低;应用Kamlet-Jacobs方程预测得到共晶含能材料的理论爆速为8870m/s,理论爆压为36.40GPa,具有较高的能量。
Abstract
The cocrystal of 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20) and 2,4-dinitro-2,4-diazapentane (DNDAP) was prepared through slow evaporation method.The morphology of cocrystal was characterized by scanning electron microscopy (SEM) and its structure was determined by single crystal X-ray diffraction.The thermal decomposition behavior,sensitivity and calculated detonation properties of CL-20/DNDAP were also investigated.Results showed that the crystal was monoclinic,space group P2/1c with crystal parameters of a=1.3022(2)nm,b=2.2619(4)nm,c=1.2962(2)nm,α=90°,β=104.648(3)°,γ=90°.DSC analysis showed that the exothermic decomposition of CL-20/DNDAP occured in the temperature range of 210～260℃ and the melting point of CL-20/DNDAP was higher than that of DNDAP.Results revealed that the mechanical sensitivity of cocrystal decreased obviously compared to that of CL-20 with H50=33.1 cm and P=48%.Furthermore,the detonation velocity and pressure of cocrystal were also calculated to be 8870m/s and 36.40GPa by Kamlet-Jacobs equation,respectively.It proved that CL-20/DNDAP cocrystal had a good detonation performance.
关键词
CL-20/DNDAP共晶含能材料
/
制备
/
晶体结构
/
性能
Key words
CL-20/DNDAP cocrystal energetic material
/
preparation
/
crystal structure
/
performance
CL-20/DNDAP共晶含能材料的晶体结构与性能研究[J].
化工新型材料, 2018, 46(11): 84-87 DOI:
[1] 欧育湘,刘进全.高能量密度化合物[M].北京:国防工业出版社,2005.
[2] 舒远杰,武宗凯,刘宁,等.晶形控制及形成共晶:含能材料改性研究的重要途径[J].火炸药学报,2015,38(5):1-9.
[3] Zhang Jiaheng,Shreeve J M.Time for pairing:cocrystals as advanced energetic materials[J].Cryst Eng Comm,2016,18:6124.
[4] 吴欣欣,吴晓青,邢会存,等.共晶技术在含能材料领域的研究进展[J].化工中间体,2014(6):10.
[5] 宋小兰,王毅,宋朝阳,等.CL-20/DNT共晶含能材料的制备及其性能研究[J].火炸药学报,2016,39(1):24.
[6] Gao Hongfei,Zhang Shuhai,Ren Fude,et al.Theoretical insight into the co-crystal explosive of 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane(CL-20)/1,1-diamino-2,2-dinitroethylene (FOX-7)[J].Computational Materials Science,2015(5):33.
[7] Yana Kholod,Sergiy,Okovytyy,et al.An analysis of stable forms of CL-20:A DFT study of conformational transitions,infrared and Raman spectra[J].Journal of Molecular Structure,2007,843(1/2/3):14-25.
[8] Tartakovsky V A,Ermakov A S,Sigai N V,et al.Synthesis of N,N′-dialkylmethylenebis (nitramines) from N-alkylsulfa-mates[J].Russian Chemical Bulletin,2000,49(6):1079-1081.
[9] 肖继军,朱卫华,朱伟,等.高能材料分子动力学[M].北京:科学出版社,2012:10-34.
[10] Goncharov T K,Aliev Z G,Aldoshin S M,et al.Preparation,structure,and main properties of bimolecular crystals CL-20-DNP and CL-20-DNG[J].Russian Chemical Bulletin,2015(2):367.
[11] 陶俊,王晓峰,赵省向,等.CL-20/HMX无规作用及共晶作用的理论计算[J].火炸药学报,2017,40(4):50-54.
[12] Yang Zongwei,Li Hongzhen,Huang Hui.Preparation and performance of a HNIW/TNT cocrystal explosive[J].Propellants,Explosives,Pyrotechnics,2013,38:495-501.
[13] Wang Yuping,Yang Zongwei,Li Hongzhen,et al.A novel cocrystal explosive of HNIW with good comprehensive properties[J].Propellants,Explosives,Pyrotechnics,2014,39:590-596.
[14] Bolton O,Simke L R,Pagoria P F,et al.High power explo-sive with good sensitivity:A 2:1 cocrystal of CL-20:HMX[J].Crystal Growth & Design,2012,12:4311-4314.
[15] Bushuyev O S,Brown P,Maiti A,et al.Ionic polymers as a new structural motif for high-energy-density materials[J].Journal of the American Chemical Society,2012,134(3):1422-1425.
基金资助
国家自然科学青年基金资助(21703168)
