Preparation And Physicochemical Properties Of Energetic Supramolecular Compounds

It is a hot spot to explore a new generation of energetic compound with high energy, good safety and environmental friendly in the field of energetic materials. Cocrystallization technology is a method to modify the physicochemical properties of energetic materials. According to the supramolecular strategy, seven energetic compounds were prepared. The structures and the physicochemical properties were studied. The main research content is summarized as follows:Firstly, the compounds with energy group, such as triazole, tetrazole, triazine, amino and nitro were employed as the energy souces. Based on supramolecular chemistry, target compounds were prepared by Host-Guest energy souces interactions. Structure analysis showed that seven compounds exhibit stabilized structures due to the existence of abundance hydrogen bonding and π-π interactions.3D structure of 1、2、5、6 and 7,2D structure of 3, 1D structure of 4 are formed based on supramolecular interaction.Secondly, the thermal decomposition behavior of seven compounds was investigated by TG and DSC. Compound 5 exhibits an outstanding decomposition temperature up to 280 ℃. The non-isothermal thermokinetics parameters (The apparent activation energy E and the pre-exponential factor A) were also obtained by Kissinger’s and Ozawa’s methods.Thirdly, the DFT-B3LYP/6-31+G(d) method in Gaussian 03 package was used to optimize the structure of the compounds and compute their frequencies. Molecular total energies, frontier orbit energies and charge densities of 4-7 were obtained by theoretical method.Finally, the constant-volume combustion energies of the compounds were determined with a rotating-oxygen bomb calorimeter. The standard molar enthalpies of formation were calculated from the constant-volume combustion energies. Detonation performances [detonation velocity (D), detonation pressure (P) and heats of detonation (△Hdet)] of 1-7 are discussed, the range of D and P are 8121.94-9300.42 m s-1 and 28.21-37.60 GPa, respectively. The calculated P and D of compounds 2 and 3 are larger to those of TNT, and slightly larger than RDX. In addition, the impact and friction sensitivities of the compounds were measured. It is worth noting that the values of impact sensitivity are measured to be 30,>40,38, and >40 J for 4-7, respectively, which well corresponds to the order of nitro group charge (QNitro) calculated by density functional theory. The results would provide theoretical guidance for the design and synthesis of energetic materials.