六苄基六氮杂异伍兹烷氧化产物的亚硝化

采用硝酸（65％）／亚硝酸钠体系对六苄基六氮杂异伍兹烷氧化物－乙酰基三苯甲酰基二苄基六氮杂异伍兹烷（3）、二乙酰基二苯甲酰基二苄基六氮杂异伍兹烷（4）和三乙酰基一苯甲酰基二苄基六氮杂异伍兹烷（5）进行亚硝解，成功脱去了上述三种化合物上剩余的两个苄基，将苄基转换为亚硝基，得到了一乙酰基三苯甲酰基二亚硝基六氮杂异伍兹烷（6）、二乙酰基二苯甲基二亚硝基六氮杂异伍兹烷（7）和三乙基酰基一苯甲酰基二亚硝基六氮杂异伍兹烷（8）。     

氧化法合成六硝基六氮杂异伍兹烷

研究了用氧化方法合成六硝基六氮杂异伍兹烷的无氢解合成路线。采用70％的HNO3／AN体系水解硝化六苄基六氮杂异伍兹烷的中间氧化产物，以21％的收率得到六硝基六氮杂异伍兹烷，讨论了六氮杂异伍兹烷母体环上苯甲酰基的硝解机理。     

四乙酰基二硝基六氮杂异伍兹烷的硝解研究

研究了ＴＡＤＮ在１００％ＨＮＯ３、Ｐ２Ｏ５／ＨＮＯ３、Ｎ２Ｏ５／ＨＮＯ３、Ｎ２Ｏ５／ＨＣＣｌ３、Ｎ２Ｏ５／ＣＨ３ＮＯ２、ＨＮＯ３／ＰＰＡ以及ＨＮＯ３／ＨＣｌＯ４等７种硝化剂中的硝解,结果表明这７种硝化剂均不适合用来硝解四乙酰基二硝基六氮杂异伍兹烷（ＴＡＤＮ）制备六硝基六氮杂异伍兹烷（ＨＮＩＷ）,同时发现在有硝酸的硝化剂硝解ＴＡＤＮ的过程中均出现了水溶性中间体。     

制备六硝基六氮杂异伍兹烷的硝解工艺近期进展

六硝基六氮杂异伍兹烷(HN研)是当今已工业化生产的能量水平最高的炸药，HNIW的制备包括基本母体的合成、母体的氢解、氢解产物(硝解底物)的硝解(即生成HN研)及HNIW的转晶4步。综述了近几年来制备HNIW的硝解工艺的进展(包括作者的若干研究成果)，详细报道了硝解3种底物([四乙酰基二苄基六氮杂异伍兹烷(TADBIW)、四乙酰基二甲酰基六氮杂杂异伍兹烷(TADFIW)及四乙酰基六氮杂异伍兹烷(TAIW]）以制备HNIW的工艺条件，并评价了各自的优、缺点。     

六苄基六氮杂异伍兹烷氧化产物的亚硝解反应

采用65％硝酸／亚硝酸钠体系对六苄基六氮杂异伍兹烷氧化产物四苯甲酰基二苄基六氮杂异伍兹烷(1)和五苯甲酰基-苄基六氮杂异伍兹烷(2)进行亚硝解，脱去了剩余的苄基，将苄基转换为亚硝基，得到了四苯甲酰基二亚硝基六氮杂异伍兹烷(3)和五苯甲酰基-亚硝基六氮杂异伍兹烷(4)。     

六乙酰基六氮杂异伍兹烷的合成

从苄胺和乙二醛出发 ,通过缩合、氢解脱苄等反应合成了高张力高密度笼形化合物——六乙酰基六氮杂异伍兹烷 ( HAIW) ,并经 FTIR、1H NMR、MS( CI)及元素分析等证实该化合物的结构。HAIW是合成六硝基六氮杂异伍兹烷 ( HNIW)的一种极佳中间体 ,而 HNIW是迄今为止密度和能量水平很高的高能量密度化合物。     

六氮杂异伍兹烷衍生物的氧化反应

研究了以过硫酸铵作为氧化剂，乙酸酐作为反应介质，在硝酸饰铵(Ⅳ)催化下四乙酞基二苄基六氮杂异伍兹烷的氧化脱苄反应，并将这种方法应用到六苄基六氮杂异伍兹烷的脱苄上，成功地通过氧化法合成出四乙酞基二苄基六氮杂异伍兹烷。     

二乙酰基四苄基六氮杂异伍兹烷的合成及表征

研究了HBIW的氧化脱苄乙酰化反应,采用单电子氧化剂硝酸铈铵（Ⅳ）对六苄基六氮杂异伍兹烷（HBIW）进行氧化,制备出二乙酰基四苄基六氮杂异伍兹烷（DATBIW）.用FT-IR、MS、1HNMR对其结构进行了鉴定.推测了对HBIW的氧化-脱苄化作用过程机理.     

六糠基六氮杂异伍兹烷的合成及其工艺的研究

通过用α-糠胺和乙二醛为原料合成了六糠基六氮杂异伍兹烷,对产物进行分离、提纯,目标产物的熔点为98.2～99.5℃。并通过正交实验法考察了温度、pH值、催化剂、时间等对产物收率的影响,确定了在温度为0～5℃、pH值为9～10、催化剂为高氯酸、时间为20h时产物的收率为42%。六糠基六氮杂异伍兹烷是一种新的具有六硝基六氮杂异伍兹烷(HNIW)构型的笼状前体,打破了过去只能用苄胺或取代苄胺来合成此前体的传统工艺,为两步法合成HNIW提供了有利的条件。即第一步HNIW笼状前体的合成,第二步前体的直接硝化合成HNIW。     

六硝基六氮杂异伍兹烷四种晶型的晶体结构

测定了六硝基六氮杂异伍兹烷四种晶型（α、β、γ及ε）的单晶结构,报道了它们的晶体学参数,给出了它们的分子构型,讨论了它们的结构,并与ＨＭＸ作了比较。     

A Novel Synthetic Route to Hexanitrohexaazaisowurtzitane

A new, non‐hydrogenolytic synthesis of hexanitrohexaazaisowurtzitane (HNIW, 1 ) has been investigated. The treatment of hexabenzylhexaazaisowurtzitane (HBIW, 2 ) with potassium permanganate in acetic anhydride resulted in oxidative debenzylation and acetylation to give tetraacetyldibenzylhexaazaisowurtzitane (TADB, 3a ) and other intermediates from the oxidation. Subsequent nitrosolysis and nitrolysis of these intermediates with 65% HNO₃/NaNO₂ and 70% HNO₃/AN produced HNIW in fair yield.     

高能量密度化合物HNIW的最新研究进展及其应用前景

介绍了HNIW（六硝基六氮杂异伍兹烷,又称CL-20）的几种常用合成方法,并分析比较了这些方法的优缺点以及需要进一步改进的工艺条件。详细综述了HNIW在固体推进剂及炸药中的应用现状,分析了该高能化合物在实际应用中的优势以及需要解决的关键技术问题。总结了HNIW在固体推进剂及炸药领域中面临的主要挑战及其应用前景。     

Study of Deactivation of Pd(OH)2/C Catalyst in Reductive Debenzylation of Hexabenzylhexaazaisowurtzitane

The conversion of hexabenzylhexaazaisowurtzitane (HBIW) to 2,6,8,12‐tetraacetyl‐4,10‐dibenzyl‐2,4,6,8,10,12‐hexaazaisowurtzitane (TADB) is the major challenge in the production of hexanitrohexaazaisowurtzitane (HNIW) which only proceeds over supported palladium catalyst in a reductive debenzylation reaction. The catalyst is quickly deactivated during the debenzylation reaction. In this study, the change in Pd content in the catalyst during the reaction was measured. It was demonstrated that a portion of the palladium particles in the catalyst was leached during the reaction. The H₂ chemisorption isotherm on the catalyst at 303 K showed that the volume of chemisorbed H₂ on spent catalyst was significantly less than that on fresh catalyst. The N₂ physisorption isotherm on the catalyst at 77 K revealed that the surface area of spent catalyst was less than that of fresh catalyst. Moreover, the FESEM‐EDS and TEM images and also wide‐angle XRD patterns demonstrated that the mean sizes of palladium crystallites and particles in spent catalyst were larger than those in the fresh catalyst. These results demonstrated that the leaching of palladium particles and the aggregation of palladium particles in catalyst play active roles in the deactivation of catalyst in the debenzylation of HBIW.     

六硝基六氮杂异伍兹烷在硝酸中的转晶

采用硝酸含水体系将α、γ-HNIW晶体转晶成-εHNIW晶体;用在线粒度仪实时监测HNIW晶体成核、生长的动力学过程;研究了降温、不溶溶剂水的加入、晶种的加入对ε-HNIW晶体析出的影响;用FTIR、SEM、激光粒度仪对转晶得到的样品进行了晶型、形貌及粒度分布的表征。结果表明:在温度低于64℃、有ε-HNIW晶种存在的条件下,通过降温和加入不溶溶剂水,可以转晶得到ε-HNIW晶体,得率98%。     

不同结晶体系中PNMAIW对HNIW转晶影响的理论研究

为了从理论上揭示五硝基-乙酰基六氮杂异伍兹烷(PNMAIW)对六硝基六氮杂异伍兹烷(HNIW)转晶的影响,采用分子模拟的方法,设计了PNMAIW的稳定构型,分别研究了硝酸-水体系、乙酸乙酯-正己烷体系和乙酸乙酯-三氯甲烷体系中PNMAIW对HNIW转晶的影响.结果表明,PNMAIW存在4种稳定构型;由于PNMAIW与HNIW各面的键合能远大于溶剂和非溶剂与HNIW各面的键合能,因此,如果转晶体系中存在杂质PNMAIW,PNMAIW更容易接近HNIW的晶面,从而阻碍HNIW在溶液中的转晶.     

Dissociation Mechanism of HNIW Ions Investigated by Chemical Ionization and Electron Impact Mass Spectroscopy

Chemical Ionization (CI) with Collision‐Induced Dissociation (CID) spectroscopy and Electron Impacting (EI) with metastable Mass analyzed Ion Kinetic Energy (MIKE) spectroscopy have been applied to study ionic dissociations of Hexanitrohexaazaisowurtzitane (HNIW). Similarities and differences between EI/MIKE and CI/CID mass spectra of HNIW were analyzed. In EI mass spectra, the ions [HNIW−n NO₂]⁺ (n=2–5), such as the ion at m/z 347, were less frequent (1–2% relative abundance), but in CI mass spectra, these ions were very abundant. For some ions of large molar mass from HNIW, their dissociations pathways from parent ions to daughter ions were built according to CID and MIKE spectra. Molecular ions of HNIW with a protonated nitro group at five‐member ring seem more stable than at six‐member ring. The HNIW ions losing five of six nitro groups are very stable based on CID spectra, which agrees with some research results for thermal decomposition of HNIW in literature.     

A Novel Cocrystal Explosive of HNIW with Good Comprehensive Properties

In order to improve the safety of the high explosive 2,4,6,8,10,12‐hexanitrohexaazaisowurtzitane (HNIW), we cocrystallized HNIW with the insensitive explosive DNB (1,3‐dinitrobenzene) in a molar ratio 1 : 1 to form a novel cocrystal explosive. Structure determination showed that it belongs to the orthorhombic system with space group Pbca. Therein, layers of DNB alternate with bilayers of HNIW. Analysis of interactions in the cocrystal indicated that the cocrystal is mainly formed by hydrogen bonds and nitro‐aromatic interactions. Moreover, the thermal behavior, sensitivity, and detonation properties of the cocrystal were evaluated. The results implied that the melting point of the cocrystal is 136.6 °C, which means an increase of 45 °C relative that of pure DNB. The predicted detonation velocity and detonation pressure of the cocrystal are 8434 m s⁻¹ and 34 GPa, respectively, which are similar to that of the reported HNIW/TNT cocrystal, but its reduced sensitivity (H₅₀=55 cm) makes it an attractive ingredient in HNIW propellant formulations.     

HBIW的纯度分析方法

研究了流动相、流速、柱温等因素对HBIW纯度分析的影响.建立了HBIW的高效液相色谱分析条件:反相色谱柱,紫外检测波长241nm,二元流动相四氢呋喃-水体积比90:10,流速1.000mL/min,柱温25℃.采用归一化法、外标法和内标法对HBIW进行了纯度分析.结果表明,3种方法标准偏差均小于1%,归一化法准确度受样...     

Preparation of ε‐HNIW by a One‐Pot Method in Concentrated Nitric Acid from Tetraacetyldiformylhexaazaisowurtzitane

ε‐HNIW was prepared by a one‐pot method in concentrated nitric acid from tetraacetyldiformylhexaazaisowurtzitane (TADFIW). γ‐HNIW was firstly obtained, then γ‐HNIW was directly transformed to ε‐HNIW in the solution in which nitration reaction occurred. The acid number of ε‐HNIW prepared by the method mentioned above is less than 0.2‰, yield of ε‐HNIW is up to 91%, and the purity of ε‐HNIW is up to 99.5%. Because steps of filtration and drying of γ‐HNIW were omitted, the process by which ε‐HNIW was prepared simplified greatly.     

笼形含能化合物HNIW的结构与性能研究

根据Ｘ射线单昌衍射测定六硝基六氮杂异伍北钾种晶型的结构数据,在ＲＨＦ水平上,分别应用ＡＭ１和ＰＭ３量子化学半经验分子轨方法,对这四种晶型进行行全参数优化,并从计算的生成热,偶极矩,ＨＯＭＯ和ＨＵＭＯ轨道能级之间的差值△Ｅ,预测ＨＮＩＷ的某些性能和电子结构。