4-氨基-5-硝基-1,2,3-三唑(ANTZ)合成与表征

以丙二酸单乙酯为原料,经脱羧氧化硝化得到二硝基乙酸乙酯,二硝基乙酸乙酯、叠氮化钠、乙醛缩合环化获得关键中间体4-甲基-5-硝基-1,2,3-三唑,再经氧化、酯化、酰化、霍夫曼重排得到目标产物4-氨基-5-硝基-1,2,3-三唑(ANTZ).利用元素分析、核磁共振、红外光谱等鉴定中间体及最终产物的结构;初步探讨了缩合环化反应历程,研究了影响关环反应的主要条件,确定了氧化反应的最佳反应条件为反应时间90 min,反应温度100 ℃,K2CO3和4-甲基-5-硝基-1,2,3-三唑的最佳物料比为1:2.     

1-甲基-3,5-二硝基-1,2,4-三唑的合成及表征

以双氰胺、二盐酸肼为起始原料,经缩合环化、重氮化硝化、甲基化等三步反应合成1-甲基-3,5-二硝基-1,2,4-三唑(MDNT),总收率为16.75％.精制后,熔点95 ～96℃,纯度大于99％,用核磁氢谱(1 H NMR)、红外光谱(IR)、元素分析对其结构进行了表征.同时,改善了3,5-二氨基-1,2,4-三唑( ...     

1-甲基-3-氨基-5-硝基-1,2,4-三唑的合成新工艺

以甲基肼为原料,与盐酸反应得到盐酸甲基肼,再与二氰二胺在50℃进行缩合环化反应,调节溶液pH值,经重氮化反应合成含能化合物1-甲基-3-氨基-5-硝基-1,2,4-三唑(DNMT),总收率62.3%,纯度99.4%,并用红外光谱、核磁共振、质谱、元素分析等方法表征了其结构。探讨了缩合环化反应工艺条件,确定适宜的反应条件为:溶剂为乙醇,n(C2H3N4)∶n(NH2NHCH3.2HCl)=1∶1.1,pH=8~9,成盐组分是盐酸,重结晶溶剂为丙酮。     

5-硝基-3-三硝甲基-1H-1,2,4-三唑和5,5'-双(三硝甲基)-3,3'-偶氮-1H-1,2,4-三唑的合成与理论研究

以氨基胍碳酸氢盐与丙二酸为原料,经缩合-环化反应、重氮化-取代反应、氧化偶联反应和硝化反应分别合成出5-硝基-3-三硝甲基-1H-1,2,4-三唑(TNNT)和5,5'-双(三硝甲基)-3,3'-偶氮-1H-1,2,4-三唑(BTNAT)。用红外光谱、核磁共振、元素分析表征了它们的结构。进行了B3LYP/6-31G(d,p)基组水平下它们的全结构优化和自然键轨道(NBO)分析。用DSC测定了它们的分解温度。结果表明,10℃·min~(-1)升温速率,氮气气氛条件下,TNNT和BTNAT的分解温度分别为135℃和146℃。     

1-氨基-3-甲基-1,2,3-三唑硝酸盐的合成与表征

以乙二醛和水合肼为起始原料,经加成-消除、环化甲基化、置换反应得到1-氨基-3-甲基-1,2,3-三唑硝酸盐(1-AMTN),总收率71.8%(以乙二醛计),采用核磁(NMR)、红外(IR)、质谱(MS)和元素分析对产物进行了表征。预测了1-AMTN的性能:密度为1.63 g.cm-3,生成焓84 kJ.mol-1,爆速8115 m.s-1。研究了溶剂、温度、物料比对产物得率的影响,确定了环化甲基化的最佳反应条件:溶剂为乙腈,反应温度20℃,乙二腙与碘甲烷的物料比1∶5,环化甲基化收率为86.7%。对活性二氧化锰进行了回收利用并对其机理进行了探讨。     

5,5′-(2-三氟甲基)-咪唑-4,5-二(1H-四唑)及其含能离子盐的合成与表征

以二氨基马来腈为原料,经过与三氟乙酸酐缩合、环化,与叠氮化纳再次缩合,合成得到了新型含能化合物5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑),收率61.3%;基于该化合物的酸性,设计合成了2种含能离子盐5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑)的羟胺盐和胍盐。利用红外光谱、核磁共振和元素分析对中间体及产物结构进行了表征。探讨了生成5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑)过程中影响四唑环化反应的关键因素,确定的最佳反应条件为:反应介质为水,n(2-三氟甲基-4,5-二氰基咪唑)∶n(Na N3)=1∶2.4,反应温度98℃,反应时间4 h。收率最高达86.3%。通过DSC-TG研究了5,5'-(2-三氟甲基)-咪唑-4,5-二(1H-四唑)的热分解性能,热分解曲线表明化合物直到223.65℃才开始分解,整个分解过程经历了两个主要的放热分解阶段和热失重阶段,最大放热峰温度为285.78℃,说明该化合物结构比较稳定。     

3-硝基-1,2,4-三唑-5-酮(NTO)废酸的循环利用

针对3-硝基-1,2,4-三唑-5-酮(NTO)硝化过程中产生大量废酸导致“三废”综合治理成本高的问题,通过向废酸中补加少量工业浓硝酸制成质量分数为70%的硝酸溶液作为硝化剂,硝化1,2,4-三唑-5-酮(TO),循环合成目标化合物NTO。采用红外光谱、核磁共振光谱、元素分析对其进行了结构表征。考察了硝化剂用量、反应时间、反应温度对产品的影响,优化了硝化反应条件,确定硝化的最佳反应条件为: n(TO)n(HNO₃)=16,反应温度60~65 ℃,反应时间1 h,纯度可达99.9%。废酸循环利用10次以上,平均收率82%,硝酸用量减少了67.6%。      

2-甲基-6-硝基苯胺的合成工艺研究

研究了2-甲基-6-硝基苯胺的合成方法及工艺.以邻甲苯胺为原料,改进了原有乙酰化、硝化一锅煮的方法,采用乙酰化和硝化反应分步实施的路线进行合成.用红外、核磁、质谱等对2-甲基-6-硝基苯胺及其中间体2-甲基乙酰苯胺进行了结构表征.结果表明,改进方法工艺稳定,硝化反应温度容易控制,2-甲基-6-硝基苯胺产率最高为59.4%,纯度为99.68%.     

1-甲基-3,4,5-三硝基吡唑的一步法合成及热性能

以1-甲基吡唑为原料、硝酸与发烟硫酸为硝化剂,一步硝化得到了不敏感单质炸药1-甲基-3,4,5-三硝基吡唑(MTNP),采用熔点、红外光谱、核磁共振、元素分析及质谱对其进行了结构表征,优化了反应条件。结果表明,反应温度90℃、反应时间6h、摩尔比n(硝酸)∶n(发烟硫酸)=1∶8为最优反应条件,此时目标物MTNP收率为15.2%。采用差示扫描量热法(DSC)分析了热性能,分解温度为272.0℃,其热稳定性良好。     

1-羟基-1,2,3-三唑并[4,5-e]-5,7-二氧化-1,2,3,4-四嗪合成、晶体结构及性能

以3?氨基?4(?叔丁基?NNO?氧化偶氮基)呋咱(ABAo F)为原料,经重氮化开环、肟化、氧化、氨化和硝化环化五步反应得到目标化合物1?羟基?1,2,3?三唑并[4,5?e]?5,7?二氧化?1,2,3,4?四嗪(HTTDO),总收率24.1%,采用红外光谱、核磁共振、质谱及元素分析对中间体及产物的结构进行了表征;探讨了氨化及硝化环化的反应机理;培养了HTTDO·4.5H2O的单晶,X射线衍射分析表明,其为正斜方晶系,空间群为Pna2(1),晶体密度为1.659 g·cm~(-3);利用Gaussian 09程序和Kamlet?Jacobs方程计算HTTDO理论密度为1.88 g·cm~(-3),爆速为9393 m·s-1,爆压为41.9 GPa,爆热为8010 J·g~(-1);采用差示扫描量热(DSC)研究了HTTDO的热性能:其在热分解过程中,放热剧烈,峰温最高达194.5℃。     

Nitrosation and Nitration of Tetraacetyldibenzylhexaazaisowurtzitane

Tetraacetyldibenzylhitane (TADBIW) was subjected to debenzylation by nitrosating with inorganic materials available commercially to synthesize tetraacetyldinitrosohexaazaisowurtzitane (TADNSIW). TADNSIW was purified, and its structure was determined by FTIR, 1H NMR, MS and element analysis. The debenzylation reaction of TADBIW gave quantitative benzaldehyde as a by-product. This indicates that the reaction produces an imine cation as an intermediate. Hexanitrohexaazaisowurtzitane (HNIW) was prepared from unpurified TADNSIW with the yield over 96.0 % and the purity more than 98.0 %. And the mechanism of the reaction from TADNSIW to HNIW is proposed to be oxidation of nitroso and nitration of acetyl on the molecule of TADNSIW, This reaction system involved is simple, and the reaction can complete within a short time and under mild conditions. The product can be easily to separate and the waste disposed readily.     

A Robust Algorithm for Watermarking 2D Vector Maps with Low Shape-Distortions

The technique of watermarking has been introduced into 2D vector maps for many potential applications such as protecting the copyright of important GIS （geographical information system） data and tracing the data source of military maps. In most previous works, although the validity of the map data could be preserved during the embedding procedure, the shape-distortions of the map elements are usually neglected which would tend to degrade the invisibility of the watermarking schemes. A shape-preserving algorithm for watermarking 2D vector maps is presented in this paper. A 1D distance sequence extracted from the original map is adopted as the cover data instead of 2D coordinates. A watermark bit is represented by changing the distributions of the cover data. The embedding procedure induces lower shape-distortions than in former works. Experimental results indicate better invisibility of the proposed scheme, as well as its robustness to certain attacks such as map simplification, interpolation, additive noise and most geometric transforms.     

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.     

Improvement and Experiment of the Reamer in Vibra Cutter Against Wave Edge of Titanium Sheet Alloy Parts

By analyzing the influencing factors of part quality making of sheet alloy of titanium by vibra cutter, the shape of upper reamer is set as cylinder and wedge-shaped form, and the lower reamer as plain and hemicycle form, and its main structural parameters are defined as well. Then it is validated further that such improved vibra cutter reamer can be used to process curve-edged parts of titanium alloy sheet. The experimental result shows that the titanium alloy sheet parts processed by above equipment have no sharpen angles for convex parts and evident crevasse of concave-edged part. In summary, such improvement can eliminate the free-waved edge and improve the manufacture quality of titanium alloy sheet parts greatly.     

Experimental Study on the Small Flyer Initiating Behavior of Fine-grained Explosives

The initiating behavior of fine-grained explosives by small flyer is studied. The diameter of small flyer in this device is 1 ram. The test results indicate that the granularity of explosives has great effect on its flyer initiating sensitivity.The flyer initiating sensitivity of the fine-grained explosives is higher and the critical initiating energy is lower than that of common explosives. For common explosive, the flyer initiating sensitivity increases as the density is reduced. But for the fine-grained explosive, the test results are exactly opposite.     

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.     

Robust Graded Sliding Mode Tracking Control for Low Speed Spinning Ballistic Missiles

The nonlinear dynamic model of spinning ballistic missiles is established during the first boosting phase of the missile. Based on the conventional backstepping sliding mode control and the assumption of a two time-scale separation of missile dynamics, a graded sliding mode controller is designed with two sub-sliding surfaces which have invariability to external disturbances and parameter perturbations, and a matrix which comprises three first order low pass filters is introduced to prevent ＂explosion of terms＂. Owing to the upper bounds of the uncertainties are difficult to obtain in advance, adaptive laws are introduced to estimate the values of the uncertainties in real-time. Eventually, the numerical simulation results given to show the proposed controller can ensure the steady flight of missiles.