Combination Multinitrogen with Good Oxygen Balance: Molecule and Synthesis Design of Polynitro-Substituted Tetrazolotriazine-Based Energetic Compounds

We investigated 5,8-dinitro-5,6,7,8-tetrahydrotetrazolo­[1,5-<i>b</i>]­[1,2,4]­triazine (short for DNTzTr (<b>1</b>)) using various ab initio quantum chemistry methods. We proposed an additional three novel polynitro-substituted tetrazolotriazine-based compounds with exceptional performance, including 5,8-dinitro-5,6-dioxotetrazolo­[1,5-<i>b</i>]­[1,2,4]­triazine, DNOTzTr (<b>2</b>), 4,5,9,10-tetranitro­[1,2,4,5]­tetrazolo­[3,4-<i>b</i>]­[1,2,4,5]­tetrazolo­[3′,4′:5,6]­triazino­[2,3-<i>e</i>]­triazine, TNTzTr (<b>3</b>), and 4,5,6,10,11,12-hexanitro-bis­[1,2,4,5]­tetrazolo­[3′,4′:5,6]­triazino­[2,3-<i>b</i>:2′,3′-<i>e</i>]­triazine, HNBTzTr (<b>4</b>). The optimized structure, electronic density, natural bond orbital (NBO) charges and HOMO–LUMO orbitals, electrostatic potential on surface of molecule, IR- and NMR-predicted spectra, as well as thermochemical parameters were calculated with the B3LYP/6-311+G­(2d) level of theory. Critical parameters such as density, enthalpy of formation (EOF), and detonation performance have also been predicted. Characters with positive EOF (1386.00 and 1625.31 kJ/mol), high density (over 2.00 g/cm³), outstanding detonation properties (<i>D</i> = 9.82 km/s, <i>P</i> = 45.45 GPa; <i>D</i> = 9.94 km/s, <i>P</i> = 47.30 GPa), the perfect oxygen balance set to zero, and acceptable impact sensitivity led novel compounds <b>3</b> and <b>4</b> to be very promising energetic materials. This work provides the theoretical molecule design and a reasonable synthesis path for further experimental synthesis and testing

The Mitigation Effect of Synthetic Polymers on Initiation Reactivity of CL-20: Physical Models and Chemical Pathways of Thermolysis

In this paper, the thermal decomposition physical models of different CL-20 polymorph crystals and their polymer bonded explosives (PBXs) bonded by polymeric matrices using polyisobutylene (PIB), acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), Viton A, and Fluorel binders are obtained and used to predict the temperature profiles of constant rate decomposition. The physical models are further supported by the detailed decomposition pathways simulated by a reactive molecular dynamics (ReaxFF-lg) code. It has been shown that both ε-CL-20 and α-CL-20 decompose in the form of γ-CL-20, resulting in close activation energy (169 kJ mol^–1) and physical model (first-order autoaccelerated model, AC1). Fluoropolymers could change the decomposition mechanism of ε-CL-20 from the “first-order autocatalytic” model to a “three-dimensional nucleation and growth” model (A3), while the polymer matrices of Formex P1, Semtex, and C4 could change ε-CL-20 decomposition from a single-step process to a multistep one with different activation energies and physical models. Compared to fluoropolymers, PIB, SBR and NBR may make ε-CL-20 undergo more complete N–NO₂ scission before collapse of the cage structure. This is likely the main reason why those polymer bases could greatly mitigate the decomposition process of ε-CL-20 from a single step to a multistep, resulting in lower impact sensitivity, whereas fluoropolymers have only a little effect on that. For ε-CL-20 and its PBXs, the impact sensitivity depends not only on the heat built-up period of their decomposition, but also on the probability of hotspot generation (defects in solid crystals and interfaces) especially when it decomposes in a solid state