Preparation Of Supramolecular Energetic Compounds And Study On Their Insensitivity

It is one of the research and development focus on energetic materials to study insensitive explosive. Five new N-azo calixarene derivatives were synthesized and fifteen novel energetic supramolecule compounds were prepared and the new idea, i.e to depress the sensitive of the energetic material through supramolecule chemistry, was put forward for the first time in this thesis.p-Nitro-calix[8]arene was synthesized using p-t-butylphenol and formaldehyde as starting materials, the structural optimization and theoretical analysis of host, guest and supramolecule system were operated by quantum chemistry half-empirical AM1 and DFT-B3LYP/6-31G* methods. The result showed that the complex be obtained between p-nitro-calix[8]arene and RDX, HMX through a series of hydrogen bonds. The molar ratio between host and guest of the complex was determined via UV and Fluroscence spectrum. Results revealed that p-nitro-calix[8]arene can complex with RDX in DMF and HMX in CHCl3, and the molar ratio of host and guest is 1:1. The stability constant of these two complexes are 20803 and 3119.90, respectively. Two superamoleculs were prepared via solvent diffusion method and charactered by XRD.Two aza-bridged calix[2]arene[2]triazines were synthesized by using cyanuric chloride, m-phenylenediamine and p-phenylenediamine as starting materials, and four novel derivatives were prepared through azotization and amination reactions. Their structures were charactered. Interactions between tetraazacalix[2]arene[2]triazines and RDX, HMX were discussed through quatum chemistry. The result showed RDX can just be embedded by tetraaza-p-phenyldiaminecalix[2]arene-[2]-(6-azido)triazine to make a complex through a series of hydrogen bonds, whereas HMX can't. One superamolecule that tetraazacalix[2]arene[2]triazines as host and RDX as guest was prepared via solvent diffusion method and charactered by XRD.β-Cyclodextrin nitric esters(NCD) were synthesized by using HNO3 and mix acid, respectively. Five pure NCD with different nitration degree were obtained through column chromatography. Twelve superamolecule energetic compounds were prepared via co-deposition method using five NCD with different nitration degree as host and RDX, HMX as guest. Their structures were identified through XRD and IR. The molar ratio of host to guest is 1:1 which was determined by Job's method.Impact sensitivity of fifteen supramolecule energetic compounds prepared above were measured by using Kust drop hammer. Results showed that the impact sensitivity of RDX and HMX were decreased remarkably after they were embeded by p-nitro-calix[8]arene, tetraazacalix[2]arene[2]triazines, cyclodextrin, NCD-7, and NCD-9, respectively.