1-氨基-1-肼基-2,2-二硝基乙烯(AHDNE)的合成、 晶体结构和理论计算

利用1,1-二氨基-2,2-二硝基乙烯(FOX-7)和水合肼在水体系中合成了1-氨基-1-肼基-2,2-二硝基乙烯(AHDNE), 并在甲醇溶液中培养出可用于X射线衍射的单晶. 晶体属正交晶系, 空间群为Pnma, 晶胞参数为: a＝0.6283(4) nm, b＝0.7713(5) nm, c＝1.2280(8) nm, a＝b＝g＝90°, V＝0.5950(7) nm3, Dc＝1.821 g/cm3, μ＝0.171 mm－1, F(000)＝336, Z＝4, R1＝0.0489, wR2＝0.1456. 选取标题化合物的一个结构单元作为初始模型, 运用Gaussian 03程序, 在6-311＋G(d)的基组水平上, 用HF, MP2以及B3LYP三种计算方法对标题化合物进行了几何全优化, 并对其成键情况及自然键轨道(NBO)进行了分析.     

1,1-二氨基-2,2-二硝基乙烯的合成研究进展

1,1-二氨基-2,2-二硝基乙烯（FOX-7）是一种低感度高能量的新型含能材料.现有的1,1-二氨基-2,2-二硝基乙烯的合成包括以2-甲基咪唑、盐酸乙脒与乙二酸二乙酯、2-甲基-4,6-二羟基嘧啶为前体的三条合成路线.使用硫酸/硝酸体系硝化2-甲基-4,6-二羟基嘧啶可得到2-二硝基亚甲基-5,5-二硝基嘧啶-4,6-二酮,然后水解可得到FOX-7,正相硅胶薄层色谱可对该反应进行监测.使用曲拉通X-100/正己烷体系的反相微乳法可制备FOX-7球形纳米晶;FOX-7球形纳米晶具有良好的应用前景,对其合成工艺与路线进行探索和研究具有一定的意义.     

新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基- 2-氧)苯的合成及热分解动力学研究

以新戊二醇、三氯氧磷及1,3,5-三羟基苯等为原料, 经过两步反应合成新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基-2-氧)苯, 采用元素分析、FT-IR、MS及1H NMR等技术确定了标题化合物的分子结构. 以TG-DTG为手段, 研究该新型磷系阻燃剂在氮气气氛中的热分解动力学; 利用Kissinger法、Flynn-Wall-Ozawa (FWO)法对其进行热分解动力学研究, 求出该阻燃剂的热分解动力学参数; 利用Coast-Redfern法研究该阻燃剂的热分解机理. 结果表明, Kissinger法所求得的表观活化能为171.72 kJ•mol－1, 指前因子ln A为37.57; Flynn-Wall-Ozawa法所求得的表观活化能为172.05 kJ•mol－1. 标题化合物的热分解动力学方程g(α)＝α1/4, 反应级数n＝1/4.     

2,6-二氨基-3,5-二硝基吡嗪-1-氧化物(LLM-105)晶体结构、安全性及密度泛函理论研究

利用DMSO和水的混合溶剂培养出2,6-二氨基-3,5-二硝基吡嗪-1-氧化物(LLM-105)的单晶,晶体属单斜晶系,空间群为Pna2(1)。运用Dmol3中的密度泛函理论计算了LLM-105的晶体性质,态密度计算表明C-N 为该物质的热解引发键。通过设计等键反应预测得到LLM-105的生成热(HOF),结合HOF与晶体密度利用 Kamlet-Jacobs公式得到该物质的爆速、爆压;键断裂能的计算结果表明 C-NO2为热解引发键。运用微热量仪对其进行比热容测定,由比热容与温度的关系式及LLM-105的热分解参数得到了该化合物从开始分解到爆炸所需的时间即绝热至爆时间。     

1,4-二氢-5H-(二硝基亚甲基)-四唑(DNMT)的合成、晶体结构和热行为研究

利用1-氨基-1-肼基-2,2-二硝基乙烯(AHDNE)和亚硝酸钾在酸性水溶液中合成出了高能富氮化合物1,4-二氢- 5H-(二硝基亚甲基)-四唑(DNMT), 并在水溶液中培养出DNMT•2H2O单晶. 该晶体属正交晶系, 空间群为Pnma, 晶胞参数为: a＝10.392(2) Å, b＝15.809(4) Å, c＝5.0640(11) Å, V＝832.0(3) Å3, Dc＝1.629 g•cm－3, μ＝0.163 mm－1, F(000)＝432, Z＝4, R1＝0.0311, wR2＝0.0885. 运用Gaussian 03程序, 在6-311＋＋G**基组水平上, 用HF和B3LYP两种方法对DNMT分子进行了几何全优化和相应的电荷、轨道能量分析. 理论计算和热分析结果表明DNMT呈现较差的热稳定性.     

1,1-二氨基-2,2-二硝基乙烯的比热容、热力学性质及绝热至爆时间研究

应用Micro-DSCⅢ微热量仪的两种连续比热容测定模式对1,1-二氨基-2,2-二硝基乙烯(FOX-7)比热容进行了测定. 得到298.15 K时FOX-7的标准摩尔比热容分别为176.56和176.02 J•mol^－1•K^－1, 相对偏差为0.31%. 运用Gaussian 03W程序的DFT-RB3LYP/6-311＋＋G**方法对FOX-7在283～353 K温度范围内进行了比热容理论计算, 结果为147.11～170.54 J•mol^－1•K^－1, 与Micro-DSCⅢ微热量仪测定值偏差在13.27%～15.46%之间. 用测得的比热容方程计算了298.15 K为基础的FOX-7的热力学函数并得到了绝热至爆时间.     

N,N'-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺的热分解动力学研究

以TG-DTG为手段, 研究了N,N'-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺(DPTDEDA)在氮气气氛中的热分解动力学, 利用 Kissinger法、Flynn-Wall-Ozawa(FWO)法对DPTDEDA进行了动力学分析, 求出了该物质的热分解动力学参数, 同时利用Satava-Sestak法研究了该物质的热分解机理. 结果表明, Kissinger法所求得的表观活化能为137.37 kJ•mol^－1, 指前因子ln A＝28.00; Flynn-Wall-Ozawa法所求得的活化能为139.83 kJ•mol^－1. DPTDEDA的热分解机理为相边界反应, 其动力学方程为G(α)＝1－(1－α)⁴, 反应级数n＝4.     

N,N′-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺在空气中的热分解动力学研究

以TG-DTG为手段, 研究了N,N′-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺(DPTDEDA)在空气中的热分解动力学,利用Friedman法、Flynn-Wall-Ozawa(FWO)法对DPTDEDA进行了动力学分析, 求出了该物质两个主要的热分解阶段的热分解动力学参数, 同时利用Coats-Redfern法、Achar法研究了该物质的热分解机理. 结果表明, 用Friedman法所求得的两个热分解阶段的表观活化能的平均值分别为128.03和92.59 kJ•mol^－1; 而Flynn-Wall-Ozawa法所求得的两个热分解阶段的表观活化能的平均值分别为138.75和106.78 kJ•mol^－1. 由Coats-Redfern法、Achar法得出DPTDEDA在空气中的热分解过程虽主要分为两段反应, 但经过推理其反应机理函数却是相同的, 为f(α)＝3/2(1－α)^4/3[(1－α)^－1/3－1]^－1.     

蝶形主体分子的设计、合成及其包结性能的研究

设计、合成了两种蝶形主体分子：2，5－二（三苯甲基）对苯二酚1，2，5－二（二苯甲基）对苯二酚2.1和2可与许多有机小分子形成配位包合物。用IR表征了主体分子1和2 的包结物， 用¹H NMR测定了主客体分子的摩尔比：1•DMF (1：2)，1•DMSO (1:2)，1 •吡啶 （1：2），1•环戊酮 （2：3）和2•DMF 1：2），2•DMSO （1：2），2 •THF （1：1），2•苯甲醛（1：2），2•苯乙酮 （1：2），2•2，5－己二酮 （1：1），2 •N－甲基－2－吡咯烷酮 （1：3）。单晶X-射线衍射分析了包结物2·苯甲醛的晶体结构，在分子间氢键的相互作用下晶体得以稳定。     

2-（2-喹啉偶氮）-1，5-二氨基苯固相萃取光度法测定痕量钯

根据2-（2-喹啉偶氮）-1,5-二氨基苯（QADAB）与钯的显色反应及MCI—GEL反相固相萃取小柱对显色络合物的固相萃取,建立了一种测定痕量钯的方法。在0．2～3.0mol·L^-1高氯酸介质中,溴化十六烷基三甲胺（CTMAB）存在下,QADAB与钯反应生成2：1稳定络合物,该络合物可被MCI—GEL反相固相萃取小柱萃取富集,富集的络合物用丙酮洗脱后用光度法测定,在丙酮介质中体系的最大吸收波长为600nm,表观摩尔吸光率为9．63×10^4L·mol^-1·cm^-1。钯质量浓度在0．01～1.5mg·L^-1内符合比耳定律,方法用于几种实样中痕量钯的测定,测得回收率在86％～96％间。     

Thermal Behaviors of 2‐(Dinitromethylene)‐1,3‐diazacycloheptane (DNDH)

2‐(Dinitromethylene)‐1,3‐diazacycloheptane (DNDH) was prepared by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) with 1,4‐diaminoethane in NMP. Thermal decomposition behavior of DNDH was studied under the non‐isothermal conditions with DSC method, and presents only one intensely exothermic decomposition process. The kinetic equation of the decomposition reaction is dα/dT=10^33.88×3α^2/3exp(−3.353×10⁵/RT)/β. The critical temperature of thermal explosion is 215.97°C. Specific heat capacity of DNDH was studied with micro‐DSC method and theoretical calculation method, and the molar heat capacity is 215.40 J·mol⁻¹·K⁻¹ at 298.15 K. Adiabatic time‐to‐explosion was calculated to be 92.07 s. DNDH has same thermal stability to FOX‐7.     

Non‐Isothermal Decomposition Kinetics,Specific Heat Capacity and Adiabatic Time‐to‐explosion of a Novel High Energy Material: 1‐Amino‐1‐Methylamino‐2,2‐Dinitroethylene (AMFOX‐7)

A novel high energy material, 1‐amino‐1‐methylamino‐2,2‐dinitroethlyene (AMFOX‐7), was synthesized by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and methylamine aqueous solution in N‐methyl pyrrolidone at 80°C. The thermal behavior and non‐isothermal decomposition kinetics of AMFOX‐7 were studied with DSC and TG/DTG methods. The kinetic equation of thermal decomposition reaction can be expressed as: $ {\rm d\alpha /d}T = \frac{{10^{21.03}}}{{\rm \beta}}\frac{3}{2}\left({1 - {\rm \alpha}} \right)\left[{- 1{\rm n}\left({{\rm 1} - {\rm \alpha}} \right)} \right]^{\frac{1}{3}} \exp \left({- 2.292 \times 10^5 {\rm /}RT} \right) A novel high energy material, 1‐amino‐1‐methylamino‐2,2‐dinitroethlyene (AMFOX‐7), was synthesized by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and methylamine aqueous solution in N‐methyl pyrrolidone at 80°C. The thermal behavior and non‐isothermal decomposition kinetics of AMFOX‐7 were studied with DSC and TG/DTG methods. The kinetic equation of thermal decomposition reaction can be expressed as: $ {\rm d\alpha /d}T = \frac{{10^{21.03}}}{{\rm \beta}}\frac{3}{2}\left({1 - {\rm \alpha}} \right)\left[{- 1{\rm n}\left({{\rm 1} - {\rm \alpha}} \right)} \right]^{\frac{1}{3}} \exp \left({- 2.292 \times 10^5 {\rm /}RT} \right) $. The critical temperature of thermal explosion of AMFOX‐7 is 244.89°C. The specific heat capacity of AMFOX‐7 was determined with micro‐DSC method and theoretical calculation method, and the standard molar specific heat capacity is 199.39 J·mol^?1·K^?1 at 298.15 K. Adiabatic time‐to‐explosion of AMFOX‐7 was also calculated to be 215.41 s. AMFOX‐7 has higher thermal stability than FOX‐7.     

Thermal Behavior of 2‐(Dinitromethylene)‐1,3‐diazacyclopentane

A new compound, 2‐(dinitromethylene)‐1,3‐diazacyclopentane (DNDZ), was prepared by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) with 1,2‐diaminoethane in N‐methylpyrrolidone (NMP). Thermal decomposition of DNDZ was studied under non‐isothermal conditions by DSC, TG/DTG methods, and the enthalpy, apparent activation energy and pre‐exponential factor of the exothermic decomposition reaction were obtained as 317.13 kJ·mol^?1, 269.7 kJ·mol^?1 and 10^24.51 s^?1, respectively. The critical temperature of thermal explosion was 261.04°C. Specific heat capacity of DNDZ was determined with a micro‐DSC method and a theoretical calculation method, and the molar heat capacity was 205.41 J·mol^?1·K^?1 at 298.15 K. Adiabatic time‐to‐explosion was calculated to be a certain value between 263–289 s. DNDZ has higher thermal stability than FOX‐7.     

Structural Characterization and Thermal Behavior of 1-Amino-1-methylamino-2,2-dinitroethylene

A novel high energetic material, 1‐amino‐1‐methylamino‐2,2‐dinitroethylene (AMFOX‐7), was synthesized through 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) reacting with methylamine in N‐methyl pyrrolidone (NMP) at 80.0°C, and its structure was determined by single crystal X‐ray diffraction. The crystal is monoclinic, space group P2₁/m with crystal parameters of a=6.361(3) Å, b=7.462(4) Å, c=6.788(3) Å, β=107.367(9)°, V=307.5(3) ų, Z=2, µ=0.160 mm^?1, F(000)=168, D_c=1.751 g·cm^?3, R₁=0.0463 and wR₂=0.1102. Thermal decomposition of AMFOX‐7 was studied, and the enthalpy, apparent activation energy and pre‐exponential constant of the exothermic decomposition reaction are 303.0 kJ·mol^?1, 230.7 kJ·mol^?1 and 10^21.03 s^?1, respectively. The critical temperature of thermal explosion is 245.3°C. AMFOX‐7 has higher thermal stability than FOX‐7.     

Synthesis,Crystal Structure and Thermal Behavior of 4,5‐Diacetoxyl‐2‐(dinitromethylene)‐imidazolidine

A new energetic material, 4,5‐diacetoxyl‐2‐(dinitromethylene)‐imidazolidine (DADNI), was synthesized by the reaction of 4,5‐dihydroxyl‐2‐(dinitromethylene)‐imidazolidine (DDNI) and acetic anhydride, and characterized by single crystal X‐ray diffraction. Crystal data for DADNI are monoclinic, space group C2/c, a=15.9167(3) Å, b=8.6816(4) Å, c=8.5209(3) Å, β=103.294(9)°, V=1145.9(3) ų, Z=4, µ=0.150 mm⁻¹, F(000)=600, D_c=1.682 g·cm⁻³, R₁=0.0565 and wR₂=0.1649. Thermal decomposition behavior of DADNI was studied and an intensely exothermic process was observed. The kinetic equation of the decomposition reaction is: dα/dT=(10^16.64/β)×4α^3/4exp(−1.582×10⁵/RT). The critical temperature of thermal explosion is 163.76°C. The specific heat capacity of DADNI was studied with micro‐DSC method and theoretical calculation method. The molar heat capacity is 343.30 J·mol⁻¹·K⁻¹ at 298.15 K. The adiabatic time‐to‐explosion of DADNI was calculated to be 87.7 s.     

Non-isothermal Decomposition Kinetics, Specific Heat Capac-ity and Adiabatic Time-to-explosion of a High Energy Material: 4,6-Bis(5-amino-3-nitro-1,2,4-triazol-1-yl)-5-nitropyrimidine

The thermal behavior of 4,6‐bis‐(5‐amino‐3‐nitro‐1,2,4‐triazol‐1‐yl)‐5‐nitropyrimidine (BANTNP) was studied under a non‐isothermal condition by DSC, PDSC and TG/DTG methods. The kinetic parameters (E_a and A) of the exothermic decomposition reaction are 304.52 kJ·mol^?1 and 10^24.47 s^?1 at 0.1 MPa, 272.52 kJ·mol^?1 and 10^21.76 s^?1 at 5.0 MPa, respectively. The kinetic equation at 0.1 MPa can be expressed as: dα/dT=10^25.3(1?α)^3/4exp(?3.8044×10⁴/T)/β The critical temperature of thermal explosion is 588.28 K. The specific heat capacity of BANTNP was determined with a Micro‐DSC method, and the standard molar specific heat capacity is 397.54 J·mol^?1·K^?1 at 298.15 K. The adiabatic time‐to‐explosion of BANTNP was calculated to be 11.75 s.     

Theoretical Study on the Intermolecular Interactions between 1,1‐Diamino‐2,2‐Dinitroethylene and H2O

The density functional method was applied to the study of 1,1‐diamino‐2,2‐dinitroethylene (Fox‐7)/H₂O dimer. All the possible dimers ( 1, 2 and 3 ), as well as the monomers, were fully optimized with the DFT method at the B3LYP/6‐311++G^** level. The basis set superposition errors (BSSE) are 4.62, 4.07 and 3.45 kJ/mol, and the zero point energy (ZPE) corrections for the interaction energies are 7.94, 5.66 and 6.40 kJ/mol for 1, 2 and 3 , respectively. Dimer 1 is the most stable, judged by binding energy. After BSSE and ZPE corrections, the greatest corrected intermolecular interaction energy of dimer 1 was predicted to be ?29.36 kJ/mol. The charge redistribution mainly occurs on the adjacent N–H··· O atoms and N–O··· H atoms between submolecules. The oxygen in the nitro group acts as a moderate hydrogen acceptor as compared to water oxygen. Based on the statistical thermodynamic method, the standard thermodynamic functions, heat capacities (C⁰_P), entropies (S⁰_T) and thermal corrections to enthalpy (H⁰_T), and the changes of thermodynamic properties on going from monomer to dimer over the temperature range 200.00‐700.00 K were predicted. It is energetically or thermodynamically favorable for Fox‐7 to bind with H₂O and to form dimer 1 at room temperature.     

Synthesis and thermal behavior of a new high-energy organic potassium salt

A new high-energy organic potassium salt, 1-amino-1-hydrazino-2,2-dinitroethylene potassium salt [K(AHDNE)], was synthesized by reacting of 1-amino-1-hydrazino-2,2-dinitroethylene (AHDNE) and potassium hydroxide in methanol aqueous solution. The thermal behavior of K(AHDNE) was studied using DSC and TG/DTG methods and can be divided into three obvious exothermic decomposition processes. The decomposition enthalpy, apparent activation energy and pre-exponential factor of the first decomposition process were ?2662.5?J?g^?1, 185.2?kJ?mol^?1 and 10^19.63 s^?1, respectively. The critical temperature of thermal explosion of K(AHDNE) is 171.38?°C. The specific heat capacity of K(AHDNE) was determined using a micro-DSC method, and the molar heat capacity is 208.57?J?mol^?1 K^?1 at 298.15?K. Adiabatic time-to-explosion of K(AHDNE) was also calculated. K(AHDNE) presents higher thermal stability than AHDNE.     

Thermal Decomposition Behavior and Non-isothermal Decomposition Reaction of Copper（ll） Salt of 4-Hydroxy-3,5-dinitropyridine Oxide and Its Application in Solid Rocket Propellant

The thermal decomposition behavior and kinetic parameters of the exothermic decomposition reactions of the title compound in a temperature‐programmed mode have been investigated by means of DSC, TG‐DTG and lower rate Thermolysis/FTIR. The possible reaction mechanism was proposed. The critical temperature of thermal explosion was calculated. The influence of the title compound on the combustion characteristic of composite modified double base propellant containing RDX has been explored with the strand burner. The results show that the kinetic model function in differential form, apparent activation energy E_a and pre‐exponential factor A of the major exothermic decomposition reaction are 1‐a,207.98 kJ*mol^?1 and 10^15.64 s^?1, respectively. The critical temperature of thermal explosion of the compound is 312.87 C. The kinetic equation of the major exothermic decomposition process of the title compound at 0.1 MPa could be expressed as: dα/dT=10^16.42 (1–α)e‐2.502×10⁴/T As an auxiliary catalyst, the title compound can help the main catalyst lead salt of 4‐hydroxy‐3,5dinitropyridine oxide to enhance the burning rate and reduce the pressure exponent of RDX‐CMDB propellant.     

1，1－二氨基2，2－二硝基乙烯（DADE）的热化学性质、热行为和热分解机理

The constant-volume combustion energy, △cU （DADE, s, 298.15 K）, the thermal behavior, and kinetics and mechanism of the exothermic decomposition reaction of 1,1-diamino-2,2-dinitroethylene （DADE） have been investigated by a precise rotating bomb calorimeter, TG-DTG, DSC, rapid-scan fourier transform infrared （RSFT-IR） spectroscopy and T-jump/FTIR, respectively. The value of △cHm （DADE, s, 298.15 K） was determined as （-8518.09±4.59） j·g^-1. Its standard enthalpy of combustion, △cU （DADE, s, 298.15 K）, and standard enthalpy of formation, △fHm （DADE, s, 298.15 K） were calculated to be （-1254.00±0.68） and （- 103.98±0.73） kJ·mol^-1, respectively The kinetic parameters （the apparent activation energy Ea and pre-exponential factor A） of the first exothermic decomposition reaction in a temperature-programmed mode obtained by Kissinger＇s method and Ozawa＇s method, were Ek=344.35 kJ·mol^-1, AR= 1034.50 S^-1 and Eo=335.32 kJ·mol^-1, respectively. The critical temperatures of thermal explosion of DADE were 206.98 and 207.08 ℃ by different methods. Information was obtained on its thermolysis detected by RSFT-IR and T-jump/FTIR.