N_2O_5/HNO_3/有机溶剂混合体系硝解DPT制备HMX

为了提高以N_2O_5为硝化剂的硝化体系硝解3,7-二硝基-1,3,5,7-四氮杂双环[3,3,1]壬烷(DPT)制备HMX的收率,考察了在N_2O_5/HNO_3/有机溶剂混合体系中,乙酸酐、乙腈、硝基甲烷、二氯甲烷4种有机溶剂与HNO_3在不同体积比下对DPT的硝解,测定了体系的H+浓度和N_2O_5的电导率,并分析了其对HMX收率的影响。结果表明,与4种N_2O_5/有机溶剂体系相比,N_2O_5/HNO_3/有机溶剂混合体系中产品收率明显提高;体系的酸度和硝化能力是影响HMX收率的两个重要因素,低酸度且硝化能力介于乙酰硝酸酯和NO2+之间时,有利于HMX生成;N_2O_5/HNO_3/乙酸酐混合体系为最适宜的硝解体系,当HNO_3与乙酸酐的体积比为3∶2时制备的HMX收率最高,为87.9%。     

Molecular Dynamic Simulation for HMX/NTO Supramolecular Explosive

Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramolecular explosive was investigated by the molecular dynamic (MD) method. Interaction between oxygen atoms in HMX and hydrogen atoms in NTO or between hydrogen atoms in HMX and oxygen atoms in NTO were studied by the radial distribution function (RDF). It shows that there are strong hydrogen bonds and Van Der Waals forces between HMX and NTO, in which the hydrogen bonds between oxygen atoms in the NTO and hydrogen atoms in HMX are the main host-guest interactions. The distributions of bond length, bond angle and dihedral angle were simulated by MD. It shows that the structure of HMX is seriously distorted. The binding energies and X-ray powder diffraction (XRD) patterns were calculated on the basis of the final HMX/NTO supramolecular structures. The results show that the binding energies of six supramolecular models are E binding (1 1 1-) >E binding (1 0 0)>E binding (0 2 0)>E binding (random)>E binding (1 0 2-)>Ebinding (0 1 1), and the XRD patterns of six supramolecular models are quite different from pure HMX or NTO. Based on the investigation for growth morphology, binding energies and RDF, the model of HMX supercell substituted by NTO along the (1 1 1-) surface of HMX is easier to form.     

The Nitrolysis Mechanism of 3,7‐Dinitro‐1,3,5,7‐tetraazabicyclo[3,3,1]nonane

Two intermediates, 1,5‐dinitroso‐3,7‐dinitro‐1,3,5,7‐tetraazacyclooctane (DNDS) and 1‐nitroso‐3,5,7‐trinitro‐1,3,5,7‐tetraazacyclooctane (MNX), were isolated and characterized in the synthesis of 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) from the nitrolysis of 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3,3,1]nonane (DPT) for the first time. When the nitrolysis of DPT was slowed down, two intermediates were detected with HPLC. It was proposed that electrophilic NO₂⁺ and NO⁺ from HNO₃ and N₂O₄ might attack nitrogen atoms at positions 3 and 7 of DPT to form the cations of the intermediates, then nucleophilic H₂O attacked the bridge carbon atoms of DPT to produce the intermediates, which were oxidized to form HMX.     

回收HMX基炸药制备民用耐热炸药性能研究

利用回收HMX基炸药制备民用炸药H781A,对该炸药药粉在产品组成、热安定性、机械感度等性能和装药的高温安全性、使用性能以及穿深性能进行试验。药粉试验结果表明,该产品符合民用炸药产品验收规范;装药试验结果表明,H781A与民用炸药H781性能相当。因此,由废旧HMX基炸药回收制备的耐热炸药H781A,可安全、有效地装填射孔弹进行高温射孔作业。     

TATB原位包覆HMX的研究

为提高TATB对HMX的钝化效果,利用声化学合成方法,在HMX颗粒表面原位生成了TATB,制备了HMX/TATB复合物。并与混合法制备的样品进行了比较。SEM观察表明,原位包覆法TATB对HMX的包覆效果比混合法的包覆效果更好。DSC分析表明,原位包覆法样品中HMX的热分解温度更高。机械感度测试结果表明,在TATB含量相当的情况下,原位包覆法样品具有更低的机械感度,在TATB含量为10%时,撞击感度为24%,摩擦感度为0%。     

RDX和HMX的大气压电喷雾电离质谱分析

用液相色谱-大气压电喷雾电离-质谱（LC-ESI-MS）联用技术分离检测RDX和HMX混合物。由反相高效液相色谱法在C18柱上分离了RDX和HMX,检测在225nm处进行,流动相为甲醇／水（V（甲醇）：V（水）=50：50）,流速为0．2mL／min。分析了影响结果的因素,研究了通过诱导碰撞裂解（CID）电压调节RDX和HMX特征碎片离子的毛细管出口（CapEx）电压、pH值、电离方式和干燥气体温度等对其质谱图的影响。结果表明,用负离子检测模式,当CapEx电压为-100V、pH值为8时,可以得到比较理想的质谱图,可观察到RDX和HMX分子离子峰[M-H]^-、加合离子[M-H＋H2O]、[M-H＋2H2O]^-、[M-H＋NO2]^-、[M-H＋62]^-和其他特征碎片离子。根据CID技术得到的RDX和HMX的分子离子,加合离子和特征碎片离子,易确定RDX和HMX的结构。     

超细钝感HMX小尺寸沟槽装药爆轰波传播临界特性研究

选用粒径为587.3 nm的HMX,以LZ12为基板材料设计不同沟槽尺寸,采用精密压装法装药,对超细化钝感HMX在小尺寸沟槽装药条件下的爆轰波传播临界特性进行了研究。结果表明,在设计装药密度为1.77 g.cm-3时,超细化钝感HMX沟槽装药直线传播的临界尺寸约为0.4 mm×0.4 mm,极限尺寸为1.2 mm×1.2 mm,拐直角传播的临界尺寸为0.5 mm×0.5 mm。     

亚微米HMX/FPM2602超细混合炸药的制备工艺研究

采用"超声波、助剂-溶液-水悬浮-蒸馏-成型"和超临界流体反溶剂(SAS)包覆技术研究了亚微米奥克托今(HMX)/氟橡胶(FPM2602)混合炸药造型粉的制造工艺,并用组分分析、扫描电镜(SEM)和傅立叶变换红外光谱(FT-IR)等方法进行了表征,对两种制备工艺得到的混合炸药的起爆性能进行了测试.结果表明,超声波、助剂-溶液-水悬浮-蒸馏-成型由于自身的一些缺点不适合制备超细混合炸药;而SAS包覆技术适合制备超细混合炸药,是一种绿色环保技术.     

几种多态含能材料构型转变的DFT研究

为了从分子层面上对含能材料不同分子构型间的转变情况有一个直观认识,借助Gaussian 09软件,运用密度泛函理论(DFT),采用TS算法搜寻β-RDX→α-RDX、γ-HMX→β-HMX、ε-CL-20→β-CL-20及β-FOX-7→α-FOX-7在分子构型转变过程中的过渡态结构,确定了它们的构型转变过程;并通过计算吉布斯自由能随构型转变路径的变化,比较多态含能材料分子构型转变的难易程度。结果表明,由亚稳晶型到稳定晶型的转变首先会越过过渡态,克服自由能能垒转变为亚稳态结构,实现β-RDX→α-RDX、γ-HMX→β-HMX、ε-CL-20→β-CL-20及β-FOX-7→α-FOX-7分子构型转变分别需要克服的自由能能垒分别为5.25、22.21、9.69和10.24kJ/mol。因此,常温常压下β-RDX→α-RDX、γ-HMX→β-HMX、ε-CL-20→β-CL-20及β-FOX-7→α-FOX-7构型转变的难度大小排序为:HMX>>FOX-7>CL-20>RDX。     

纯度标准物质HMX的制备及均匀性检验

以工业特级品HMX为基体,研究了HMX的纯化工艺,制备出军用纯度标准物质HMX.考察了用不同溶剂重结晶对HMX纯度的影响,选择用两种重结晶方法、分三步操作纯化HMX:首先用二甲基亚砜作溶剂,80℃溶解HMX,趁热过滤除去无机杂质和机械杂质后,用溶剂-非溶剂沉淀技术使HMX结晶析出;第二步以乙腈为溶剂重结晶纯化HMX,HMX的纯度达到99.60%以上;最后用MOS级无水乙醇煮洗,进一步去除有机杂质和溶剂残留.液相色谱分析、X射线粉末衍射分析和均匀性研究结果表明,所制备的纯度标准物质HMX纯度不小于99.70%,晶型为β型并且均匀性良好.