六硝基六氮杂异伍兹烷中杂质的结构表征及热分解研究

分别以四乙酰基二苄基六氮杂异伍兹烷( TADBIW)为硝解基质通过亚硝解／硝解一锅法和四乙酰基二甲酰基六氮杂异伍兹烷( TADFIW)为硝解基质通过硝硫混酸法制备六硝基六氮杂异伍兹烷(HNIW)．用柱色谱对HNIW的主要杂质进行分离,以FTIR、1H NMR、MS、元素分析确定主要杂质为五硝基一乙酰基六氮杂异伍兹烷( PNMAIW)和五硝基一甲酰基六氮杂异伍兹烷(PNMFIW)．PNMFIW与PNMAIW的DSC分析和动力学参数计算表明,前者的初始分解温度和分解峰温均比后者的高,且前者的分解表观活化能约为后者的2倍,这可能是因为,对于一取代基的五硝基六氮杂异伍兹烷六元环上的甲酰基比五元环上的乙酰基有助于笼型结构的稳定。     

四乙酰基ニ甲酰基六氮杂异伍兹烷的硝解杂质与硝解机理

研究四乙酰基二甲酰基六氮杂异伍兹烷在浓硝酸和硝硫混酸介质中的硝解反应，两种介质体系中的主要硝解产物均为六硝基六氮杂异伍兹烷。采用柱色谱分离从两种硝解产物中得到了两种完全不同的杂质：前者为五硝基一乙酰基六氮杂异伍兹烷；后者为五硝基一甲酰基六氮杂异伍兹烷。硝解产物中存在不同杂质说明，四乙酰基二甲酰基六氮杂异伍兹烷在两种不同的硝解剂中发生的硝解反应遵循不同的硝解机理。     

降低由四乙酰基二苄基六氮杂异伍兹烷制备的六硝基六氮杂异伍兹烷中杂质含量研究

由四乙酰基二苄基六氮杂异伍兹烷(TADBIW)制备六硝基六氮杂异伍兹烷(HNIW),产品为纯γ晶型,得率达90%,纯度达98%以上.其中2%杂质主要为五硝基-乙酰基六氮杂异伍兹烷(PNMAIW).根据薄层色谱(TLC)和高效液相色谱(HPLC)分析结果,研究了HNIW得率及其中PNMAIW含量与硝解条件的关系.     

六硝基六氮杂异伍兹烷中硝解不完全产物的分离和鉴定

本文采用薄层色谱(TLC)及柱色谱方法,分离出了由三种不同硝解基质合成的六硝基六氮杂异伍兹烷(HNIW)中所含的主要硝解不完全产物.并用FTIR、1HNMR、MS(CI)及元素分析等对它们进行了鉴定,确证其为一乙酰基五硝基六氮杂异伍兹烷、二乙酰基四硝基六氮杂异伍兹烷.由四乙酰基二苄基六氮杂异伍兹烷(TADBIW)经亚硝解脱苄再硝解制得的HNIW(试样Ⅰ)中的主要杂质为一乙酰基五硝基六氮杂异伍兹烷,含量在1%左右(高效液相色谱(HPLC)归一化法测定).由TADBIW经氧化硝解制得的HNIW(试样Ⅱ)中的主要杂质也是一乙酰基五硝基六氮杂异伍兹烷,含量在5%左右.由六乙酰基六氮杂异伍兹烷(HAIW)制得的HNIW(试样Ⅲ)中的杂质为一乙酰基五硝基六氮杂异伍兹烷和二乙酰基四硝基六氮杂异伍兹烷.     

六硝基六氮杂异伍兹烷中硝解不完全产物的分离和鉴定

本文采用薄层色谱（TLC）及柱色谱方法,分离出了由三种不同硝解基质合成的六硝基六氮杂异伍兹烷（HNIW）中所含的主要硝解不完全产物。并用FTIR,^1HNMR,MS(CI)及元素分析等对它们进行了鉴定,确证其为一乙酰基五硝基六氮杂异伍兹烷,二乙酰基四硝基六氮杂异伍兹烷,由四乙酰基二苄基六氮杂异伍兹烷（TADBIW）经亚硝解脱苄再硝解制得的HNIW（试样Ⅰ）中的主要杂质为一乙酰基五硝基六氮杂异伍兹烷,含量在1％左或（高效液相色谱（HPLC）归一化法测定）。由TADBIW经氧化硝解制得的HNIW（试样Ⅱ）中的主要杂质也是一乙酰基五硝基六氮杂异伍兹烷,含量在5％左右,由六乙酰基六氮杂异伍兹烷（HAIW）制得的HNIW（试样Ⅲ）中的杂质为一乙酰基五硝基六氮杂异伍兹烷和二乙酰基四硝基六氮杂异伍兹烷。     

六硝基六氮杂异伍兹烷的制备工艺及性能研究

研究了以四乙酰基二甲酰基六氮杂异伍兹烷(TADFIW)和四乙酰基二苄基六氮杂异伍兹烷(TADB IW)为硝解基质,经过硝解和转晶得到-εHNIW的热分解动力学参量和撞击感度,用电子扫描显微镜拍摄了ε-HNIW的晶体外貌。结果表明,两种-εHNIW的晶体外形相近,热分解动力学参量和撞击感度相同。这说明,两种-εHNIW样品的化学物理性质相同,虽然两种样品所含杂质不同,但对-εHNIW的热分解和撞击感度没有影响。     

六苯甲酰基六氮杂异伍兹烷的硝解

为探索六硝基六氮杂异伍兹烷制备的新方法 ,研究了六苯甲酰基六氮杂异伍兹烷在多种条件下的硝解反应。采用未见文献报道的稀硝酸 /硝酸盐为硝解剂 ,首次实现了苯甲酰胺的硝解 ,以六苯甲酰基六氮杂异伍兹烷为底物 ,得到四硝基二苯甲酰基六氮杂异伍兹烷 ,得率不低于 60 %     

四硝基-二(3,5-二硝基-4-氯苯甲酰基)六氮杂异伍兹烷的合成

介绍了六氮杂异伍兹烷(HNIW)衍生物———四硝基-二(3,5-二硝基-4-氯苯甲酰基)六氮杂异伍兹烷的合成:在钯催化下将四乙酰基二苄基六氮杂异伍兹烷(TADB IW)氢解为四乙酰基六氮杂异伍兹烷(TAIW),再与对氯苯甲酰氯反应,得中间产物四乙酰基-二(对氯苯甲酰基)六氮杂异伍兹烷(TAB IW),90℃下TAB IW经发烟硫酸(w(SO3)=20%)与发烟硝酸(w(HNO3)=98%)硝化4 h,即得到目标化合物四乙酰基-二(3,5-二硝基-4-氯苯甲酰基)六氮杂异伍兹烷TNB IW,其熔点242~244℃,总收率57.2%;通过红外光谱、核磁共振、质谱及元素分析表征了目标产物、TAB IW、TAIW的结构。     

3,5,9,11-四乙酰基-14-氧杂-1,3,5,7,9,11-六氮杂五环［5.5.3.02,6.04,10.08,12］十五烷的硝解反应研究

对3,5,9,11-四乙酰基-14-氧杂-1,3,5,7,9,11-六氮杂五环[5.5.3.02,6.04,10.08,12]十五烷(Ⅰ)的硝解反应进行了详细研究.以硝酸-乙酸酐为硝化剂可选择性硝化Ⅰ得到: 4-硝基氧甲基-2,6,8,12-四乙酰基-10-硝基-2,4,6,8,10,12-六氮杂异伍兹烷(Ⅱ).以硝硫混酸为硝化剂直接在80 ℃下与Ⅰ反应得到CL-20,而先低温反应再提高反应温度的两段法则得到4-硝基氧甲基-2,6,8,10,12-五硝基-2,4,6,8,10,12-六氮杂异伍兹烷(Ⅲ).硝硫混酸硝化Ⅱ可得到Ⅲ.Ⅱ和Ⅲ是新型的六氮杂异伍兹烷衍生物,用元素分析、FTIR、MS和NMR等手段对其进行了结构表征.     

转晶对降低六硝基六氮杂异伍兹烷中主要杂质五硝基一乙酰基六氮杂异伍兹烷含量的研究

制备了六硝基六氮杂异伍兹烷(HNIW),对其主要杂质五硝基一乙酰基六氮杂异伍兹烷(PNMAIW)进行了分离鉴定。以乙酸乙酯/氯仿溶剂体系对所得HNIW进行了转晶。结果表明,转晶操作可降低HNIW中PNMAIW的含量,但降幅不大于1%,且转晶完成时间受PNMAIW含量的影响。     

Open Rule-setting System Applied to Conceptual Design of Engines

Open rule-setting method advanced in this paper concentrates on providing designers of engines with a convenient way to express their design innovations and develop the expected prototypes in the early CAD stage, and constitute effective models for the following analysis process of CAE and CAPP. The problems arisen in the process of conceptual design with the traditional experience-based development method are analyzed. Based on those analyses, open rule-setting method is presented and some associated technical problems are discussed. The functional framework of open rule-setting system was built as software engineering methods. The speciality of the engine product as a kind of complex product and the requirement of the engine product based on its structural particularity to rule-setting system are considered carefully. A demonstration is supplied to illustrate how the open rule-setting method enhances the efficiency and quality of the engine conceptual design.     

Research on Linux Network Device Driver

By analyzing the working principle of Linux network device driver, discussing the Linux network driver structure and its key technologies, the general network driver structure and its design methodologies in Linux system are summarized. Through modifying the network device driver of Linux device driver 3rd version snull, c and improving the COW technology, the Zero-Copy technology in Linux （kernel version 2.6.11 ） is implemented. In the end, the success test tells us that the thorough analysis of network device driver is the foundation of many applications, and it also provides a certain improvement to a lot of real applications, even to military application development.     

Algorithm for Multi-laser-target Tracking Based on Clustering Fusion

Multi-laser-target tracking is an important subject in the field of signal processing of laser warners. A clustering method is applied to the measurement of laser warner, and the space-time fusion for measurements in the same cluster is accomplished. Real-time tracking of multi-laser-target and real-time picking of multi-laser-signal are introduced using data fusion of the measurements. A prototype device of the algorithm is built up. The results of experiments show that the algorithm is very effective.     

Influence of Installing Error on the Surface Shape Precision of the Axial Symmetry Aspheric Workpiece in Lapping

A method to calculate the surface shape error, which is caused by the installing error between the workpiece and the lapping tool in the process of form lapping, is proposed. The mathematical model which the installing translation error influences on the workpiece surface shape error is established. The changing rule of the error is simulated through the calculating example of the paraboloid workpiece. The results indicate that the surface shape error of the workpiece is increasing with the increase of the installing translation error, it is also increasing gradually along the center point of the curve surface to the edge, and the influence is severer to the curve surface with great curvature than that of the small curvature when the translation error is the same.     

Experimental Research on Output Performances of Giant Magnetostrictive Actuator

The paper introduces the performances of magnetostrictive actuators and its applications, discusses the design methods for the structure and internal magnetic circuit of a giant magnetostrictive actuator, and makes tests on the output displacement and force characteristics for an actuator using homemade magnetostrictive material. The experimental result shows that the actuator has satisfactory output precisions and ranges in transient and stable states, and can be used in lowfrequency vibration control system of precise equipment.     

Overview of Anti-tank Mines

First the different anti-tank mines laying possibilities are shortly summarized： hand emplaced, with mine layers, ground or helicopter relatively topographical well defined, and with cluster systems of projectiles, rockets and aircraft dispensers. Then examples of the three generations of anti-tank mines are presented：Ⅰ generation： detonating only beneath the track; Ⅱ generation： detonating beneath the track and belly; Ⅲ generation： mines with off-route actions. Weight and cost comparisons are strongly favoring the off-route Ⅲ-generation mines.     

A Finite Element Analysis on Static Strength of a Complex Section

A static finite element analysis （FEA） of an impulsive controller section is presented. The boundary condition and a part of the loads are applied. Considering the grades of the stress around the holes being large, the dense grids are adjusted accordingly. Four cases with different loads are compared, thus the influences of different loads on the section are analyzed. Numerical results show that the maximum stress of the section is lower than the strength limit of the material, and the section will not be broken with the static loads.     

Discussion on Mechanism of Breech-Blow Caused by Propellant Charge

From the view point of launch safety caused by fracture of propellant charge, this paper points out that the safety criterion of pressure wave is inadequate to evaluate the launch safety of propellant charge based on the initial negative differential pressure and sensitivity tests. Generally, the maximum barrel pressure does not depend upon the intensity of pressure wave correspondingly. The pressure wave intensity can not describe the fracture degree of propellant charge in chamber and reflect the mechanical environment of propellant charge fracturing exactly and wholly. The evaluation criterion for launch safety of propellant charge should be built on the basis of depicting the fracture degree of propellant bed.     

Experimental Studies of Toxicity on HNIW and Its Intermediates

The polycyclic nitramine hexanitrohexaazaisowurtane（HNIW） is a compound of high energy density. HNIW can replace 1, 3, 5-trinitro-1, 3, 5-triazacyclohexane（RDX） or HMX, hut its toxicity is unknown. In this paper, HNIW, hexabenzylhexaazaisowurtzitane （HBIW）, tetraacetyldibenzulhexaazaisowurtzitane （TADBIW）, tetraacetyldiformylhexaazaisowurtzitane（TADFIW） and tetraacetylhexaazaisowurtzitane（TAIW）, which are intermediates of the synthesis of the HNIW, were selected as the tested objects in acute toxicity test, acute eye stimulation test and skin irritation test according to the standards of ＂chemical product testing method-401 ： acute oral toxicity test＂, ＂chemical product testing means-405： acute eye irritation/corrosion test＂ and ＂chemical product testing means-404： acute dermal irritation/corrosion test＂ of National Circumstance Protect Bureau. The results show that all of the five objects have no toxicity, no stimulation to eye and skin under the tested conditions.     

Dynamic Simulation for Missile Erection System

In order to study the dynamic characteristics of the missile erection system, it can be considered as a rigid-flexible coupling multi-body system. Firstly, the actual system is abstracted as an equal and simplified one and then the forces applied to it are analyzed. Secondly, the rigid-flexible coupling dynamic simulation for erection system is accomplished by use of the system simulation software, for example Pro/E, ADAMS, ANSYS, MATLAB/Simulink, etc. Finally, having the aid of simulation results, the kinetic and dynamic characteristics of the flexible bodies in erection system are analyzed.The simulation considering the erection system as a rigid-flexible coupling system can provide valuable results to the research of its kinetic, dynamic and vibrational characteristics.