高热稳定性多硝基芳烃的研究（英）

1 IntroductionAnumber of high-energy heterocyclic and carbocyclicsubstances have been prepared and characterized[1,2]aspotential substitutes for 1,3,5,7-tetranitro-1,3,5,7-tet-razocane(HMX),2,4,6-triamino-1,3,5-trinitrobenzene(TATB)and 2,2′,4,4′,6,6′-hexanitrostilbene(HNS)inweapon systems[1,2]and downhole well[3-5]applications.2,4,6,4′,6′,2″,4″,6″-Octanitro[1,1′,3′,1″]-terphenyl(ONT)[6,7]and 2,2′,2″,4,4′,4″,6,6′,6″-nonanitro[1,1′,3′,1″]-terphenyl(NONA)[8,9].belong amo…     

新耐热炸药

美国海军道康斯合成了两个新热安定和放射安定的炸药,即3,3″-二氨基-2,2″,4,4″,6,6′6″-八硝基间联三苯和3,3″-二氨基-2,2″,4,4″,5′,6,6″-七硝基间联三苯,这两个化合物熔点分别为345℃(分解)     

A New Aspect of Relationships between Electric Spark Sensitivity and Thermal Stability of Some Polynitro Arenes（英）

An ESZ KTTV instrument of a new,relatively simple construction has been applied to determination of electric spark sensitivity of 29 polynitro arenes,expressed as spark energy,EES,required for 50-percent initiation probability.The thermal stability thresholds,Tmax,were calculated from the published Arrhenius parameters of monomolecular thermal decomposition of the studied compounds,predominantly obtained under the conditions of the Russian manometric method.An approximate relationship has been found between the ln EES values and threshold Tmax values.In the sense of this relationship,the compounds studied fall into several sub-groups.The reason of the said diversification lies in the decomposition reaction rate at the temperature of onset of their thermal decomposition.It has been found that in each sub-group increasing thermal stability of polynitro arenes is accompanied by increasing electric spark sensitivity of these substances.This fact must be taken into account if we deal with the problem of electric spark energy transfer into the reaction centre of the molecule.     

Comparison with Molecular Surface Electrostatic Potential and Thermal Reactivity of Nitramines（英）

Molecular surface electrostatic potentials V_S(r) ( ESP) of seventeen nitramines have been calculated. As a criterion of the imbalance between the maximum positive,V_(S,max) and minimum negative,V_(S,min),values of molecular surface electrostatic potentials their sum was derived and used as a new simple characteristic for ESPs-V_(S,Σ). These V_(S,Σ) values have close relationships with the Arrhenius parameters,activation energy E_a and preexponent log A,of thermal decomposition of the nitramines studied. The correlation between the V_(S,Σ) values and heats of fusion of the nitramines studied is described. These findings suggested analyzing the physico-chemical behavior of the nitramine crystals during this decomposition; in this connection an investigation was carried out using isothermal thermogravimetry and scanning electron microscopy of thermally exposed crystals of cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole( sintering of its crystal surfaces),of β-1,3,5,7-tetranitro-1,3,5,7-tetrazocane( cracking of its crystals during β !δ transition) and of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane. The results suggest a need to study the pre-decomposition states on thermal decomposition of the nitramines' molecule's crystals.     

Flame Retardant and Pyrolytic Behaviors of Polyamide 6/Montmorillonite Nanocomposite

Na -montmorillonite(Na -MMT) was converted to organic montmorillonite(OMMT) using modifier which was synthesized at authors‘ laboratory. PA6/OMMT nanocomposite was prepared via in situ intercalative polymerization. The limiting oxygen index (LOI), UL 94V flame retardancy and thermal stability of PA6/OMMT using thermal gravity analysis (TGA) were measured. The Fourier transform infrared (FTIR) technique was used to analyze the pyrolytic residuum and the cone calorimeter (CONE) was applied to determine a number of combustion parameters which were closely related to fire safety, including heat release rate, mass loss rate, effective combustion heat, total heat release, specific extinction area and the time of ignition. In addition, the elemental composition of the surface pyrolytic residuum and the corresponding X-ray photoelectron spectroscopy (XPS) data were obtained, and the morphology of the residuum from CONE measurement was examined by scanning electron microscope (SEM).     

Structural Characteristics and Decomposition Mechanism of 2,2′-Dimethyl-5,5′-Azotetrazole

The geometry and the potential curve of thermal decomposition for 2,2′dimethyl-5,5′-azotetraol (2-DMAT) are calculated by ab initio quantum chemistry method. The structural characteristics and decomposition mechanism are carefully studied. It is found that the terrazzo ring satisfies 4n+2 rule and it is a conjugated π-systems for 2-DMAT. The azotetrazol has aromaic characteristic and its thermal decomposition can proceed in two steps: ring opening and N2 separation. The activation energies of the two steps are 152.3kJ/mol and 44.67kJ/mol respectively. The ring opening is the rate-controlling step.     

Structural Characteristics and Decomposition Mechanism of 1, 1′-Dimethyl-5,5′-Azotetrazole

The geometry and the potential curve of thermal decomposition for 1,1′dimethyl-5,5′-azotetraol (1-DMAT) are calculated by ab initio quantum chemistry method. The structural characteristics and decomposition mechanism are carefully studied. It is found that the terrazzo ring satisfies 4n+2 rule and it is a conjugated π-system for 1-DMAT. The azotetrazol has aromatic characteristic and its thermal decomposition can proceed in two steps: ring opening and separation N2. The activation energies of the two steps are 243.5kJ/mol and 64.01kJ/mol, respectively. The ring opening is the rate-controlling step.     

Friction Sensitivity of Nitramines. Part Ⅲ: Comparison with Detonation Performance（英）

The friction sensitivities (FS) of five linear and eight cyclic nitramines have been determined.These FS values were compared with the respective detonation velocities,D,and with the dimensionless ratio created by relating the heat of explosion,Qreal,to the activation energy,Ea,of non-autocatalyzed thermal decomposition of the explosives concerned.For the nitramaines studied,these comparisons show a general trend of FS decreasing with increasing energy content.     

Mg-Al／PTEE烟火药爆炸性能的研究（英）

The object of the research are explosive properties of the pyrotechnic composite consist of fine grade magnesium-aluminium powder(PAM)and highly dispersed polytetrafluorethylene(PTFE).The composite reveals high resistance to all mechanical and thermal impulses and is extremely sensitive to hot sparks and open fire.The burning rate of the composition changes from 1 cm·s-1 to 100 m·s-1 along with decreasing its density.Charges of the composition with density below 1 g·cm-3 burn so violently,that the phenomena is similar to explosion.Charges with density above 1.1 g·cm-3 burn relatively rapidly and stably.The main part of the paper concerns the pressure impulses in the air generated during high-rate burning of the composition of bulk density.The nature of the generated pressure impulse is not that of a typical shock wave.A rise of pressure over the distance from the point of explosion to the maximum value lasts 50-100 milliseconds,while for shock waves this factor is less than a microsecond for equivalent charges.The methods of initiation of the composition influence the shape and parameters of the pressure impulse.The explanation of the nature of great changes of the composition burning rate has been proposed.The effect described in the paper was used for evaluation of explosive pressure resistance of industrial doors and windows.     

Construction and Properties of Structure- and Size-controlled Micro/Nano-energetic Materials

The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development of the construction strategies for achieving zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) micro/nanostructures from energetic molecules is introduced. Also, an overview of the unique properties induced by micro/nanostructures and size effects is provided. Special emphasis is focused on the size-dependent properties that are different from those of the conventional micro-sized energetic materials, such as thermal decomposition, sensitivity, combustion and detonation, and compaction behaviors. A conclusion and our view of the future development of micro/nano-energetic materials and devices are given.     

磁铁矿(Fe3O4)纳米粒子与常用爆炸物的热相容性研究(英)

利用氧化-沉淀法成功制备出了磁铁矿纳米粒子,经过XRD技术表征,磁铁矿纳米粒子的平均直径约为50 nm,粒径分布狭窄.使用DSC技术研究了平均直径为50 nm的磁铁矿纳米粒子与常用的爆炸物高氯酸钾（PP）,六硝基芪、 （HNS）,奥克托今（HMX）和二苦氨基二硝基吡啶（PYX）的热相容性,得到有意义的结论.实验表明,50 nm左右的磁铁矿纳米粒子与PP及PYX热相容,与HNS不相容,与HMX严重不相容.     

两种多硝基偶氮苯类含能化合物的合成及其性能

为了研制新型耐热含能材料,合成了2,2′,4,4′,6,6′六氯3,3′,5,5′四硝基偶氮苯(HCTNAB)和4,4′二氯2,2′,3,3′,5,5′六硝基6,6′二甲氧基偶氮苯(DCHNDOCAB)两种新型的多硝偶氮苯化合物,通过元素分析、FTIR、X射线单晶衍射等表征了合成产物结构,应用DSC和TG DTG研究了其热稳定性,其中HCTNAB分解温度为266.8℃,DCHNDOCAB分解温度为269℃。基于Gaussian09程序、在6311++G^**基组水平上用B3LYP法对DCHNDOCAB分子结构进行优化和性能预估。研究发现:HCTNAB的是一种重要的含氯含能中间体;计算得DCHNDOCAB的爆速达到7117m s^-1,爆压为21.0GPa,有望成为一种新型的偶氮类耐热炸药。     

1,3,5,7,7-五硝基-1,3,5-三氮杂环辛烷合成方法的改进

改进了１，３，５，７，７五硝基１，３，５三氮杂环辛烷及其中间体３，７，７三硝基１，３，５三氮杂双环［３．３．１］壬烷的合成方法。对中间体成环机理进行了探讨     

2,2′,5,5′-四氯-1,1′-偶氮-1,3,4-三唑的合成与晶体结构（英）

4-氨基-1,2,4-三唑与二氯异氰脲酸钠反应合成了2,2′,5,5′-四氯-1,1′-偶氮-1,3,4-三唑,利用X射线衍射分析方法测定了它的晶体结构. 该化合物的晶体结构属三斜晶系,空间群P-1,a=6.2824(13)(A),b=7.7173(15) (A),c=10.443(2)(A),α=89.16(3)°,β=88.20(3)°,γ=89.10(3)°,V=505.94(18)(A)3,Z=2,Mr=301.92,DC=1.982 mg·m-3,F(000) = 296 和μ(MoKα)=1.152 mm-1,最终偏离因子R=0.0498,wR=0.1139,结构分析表明在三唑环和四氮烯键中有强的π电子共轭作用.     

新型光学检测靶标静态指向误差修正

为检验新研制的光学检测靶标空间静态指向精度是否满足±5′设计指标要求,分析了引起指向误差的各项误差源,利用齐次坐标变换法建立了检测靶标机构的指向误差模型。通过高精度Leica全站仪标定出检测靶标的方位角误差和俯仰角误差,进一步合成检测靶标指向误差。结果显示：在标定域内最大空间静态指向误差θ_max=275″、均值θ=165.9″,均方根值σ_θ=71.5″,满足设计指标但富余量较小。为进一步提升检测靶标指向精度,利用误差模型及标定出的数据样本,采用最小二乘法曲面拟合出误差模型中的各系数,并作为方位角误差与俯仰角误差修正模型。指向误差经模型修正后,检测靶标机构在标定点和特定轨道处的总指向误差均值分别为21.1″和20.9″、均方根值分别为10.6″和7.2″,表明经误差修正后,可很大程度上减小检测靶标的空间静态指向误差。     

1-氯-1,1-二硝基-2-(N-氯脒基)乙烷的合成、表征和晶体结构

采用高锰酸钾/盐酸体系氧化氨基的方法获得了1-氯-1,1-二硝基-2-(N-氯脒基)乙烷,收率为70%,用核磁、红外、质谱、元素分析等方法对该产物进行了结构表征.以二氯甲烷为溶剂制备出了其单晶,用X射线单晶衍射仪测定了晶体结构.结果表明,该化合物的分子式为C2H2Cl2N4O4,相对分子质量为216.98,该晶体为正交...     

掺杂空穴传输层的有机电致发光器件性能研究

以F4-TCNQ为p型掺杂剂,掺入m-MTDATA作为空穴传输层,ITO导电玻璃作为阳极,Alq3作为发光层,Bphen作为电子传输层,LiF和Al分别用作电子注入层和阴极,制备有机电致发光器件。相比于未掺杂器件,电压及功率效率获得提高。这归功于p型掺杂使阳极与空穴传输层界面产生欧姆接触,及空穴传输层传导率的提高,而随着掺杂的引入及掺杂浓度的增加,注入的空穴变得过剩,使载流子不平衡变得越发严重,导致器件电流效率及亮度降低。因此,应该加强电子的注入及传输,以达到载流子平衡,同时达到降低器件电压、提高功率效率、电流效率及亮度的目的。     

4,4',5,5'-四硝基-2,2'-联咪唑及其含能离子盐的合成及热性能

以乙酸铵和乙二醛为原料,经环化、硝化等反应合成了4,4',5,5'-四硝基-2,2'-联咪唑(TNBI),然后TNBI与有机胺反应,获得了TNBI的二氨基呋咱盐(DAFTNBI)、草酰肼盐(ODTNBI)、二肼基四嗪盐(HTTNBI)、缩二胍盐(DBGTNBI)、脒基脲盐(DGUTNBI)、4-氨基-1,2,4-三唑盐(DATTNBI)、尿素盐(DUTNBI)等七种有机胺含能离子盐,采用红外光谱、核磁、元素分析等手段表征了化合物的结构;培养了TNBI·H2O单晶,结构分析表明,TNBI·H_2O为单斜晶系,空间群为P2(1)/n,晶体学参数为:a=0.5051(17)nm,b=0.8528(3)nm,c=1.5270(5)nm,β=96.948(6)°,V=0.6529(4)nm~3,Z=4,Dc=1.781 g·cm~(-3);利用差示扫描量热(DSC)、热重(TG)等热分析方法研究了七种含能离子盐的热性能,结果表明,含能离子盐的热分解峰温分别为199.23,204.52,230.13,266.96,240.63,187.98,260.19℃,热稳定性较好。     

3位氨基或硝基取代5-硝基-1,2,4三唑衍生物的合成与表征

以3-氨基-5-硝基-1,2,4三唑(ANTA)、3,5-二硝基-1,2,4三唑的铵盐(ADNT)及2,4,6-三硝基氯苯为原料,设计、合成了1-苦基-3-氨基-5-硝基-1,2,4三唑,4-苦基-3,5-二硝基-1,2,4三唑2种未见文献报道的硝基三唑衍生物,其熔点分别为251～252℃,156～157℃,同时改进了2,4,6-三(3-氨基-5-硝基-1,2,4三唑)-1,3,5-均三嗪合成方法,并采用红外光谱、核磁共振光谱、元素分析等对目标化合物进行了结构表征。探讨了3-氨基-5-硝基-1,2,4三唑与2,4,6-三硝基氯苯缩合反应机理,并研究了反应介质、催化剂等关键因素对缩合反应的影响。确定适宜的反应条件为:DMF作为介质,温度70℃,时间8h。     

N-甲基-2-(2,4,6-三硝基苯基)吡咯烷[3′,4′:1,2][60]富勒烯的合成及热稳定性

以2,4,6-三硝基甲苯(TNT)为起始物,四丁基氯化铵为催化剂,在碱性条件下经高锰酸钾氧化合成得到了2,4,6-三硝基苯甲醛(TNBD),TNBD再与C60,N-甲基甘氨酸经1,3-偶极环加成反应制得目标物N-甲基-2-(2,4,6-三硝基苯基)吡咯烷[3,′4:′1,2][60]富勒烯(MTNPF),产率74.3%(以消耗的C60计);经紫外可见光谱、红外光谱、质谱、核磁共振谱等检测手段对MTNPF结构进行了表征,用STA 449C型综合热分析仪对MTNPF热稳定性进行了测试,结果表明,MTNPF具有良好的热稳定性,在空气中分解温度超过250℃。