1,4-Bis[1-(2-hydroxyethyl)-1H-tetrazol-5-yl]-1,4-dimethyl-2-tetrazene (12a), 1,4-bis[1-isopropoxycarbonylmethyl-1H-tetrazol-5-yl]-1,4-dimethyl-2-tetrazene (12b), and 1,4-bis[1-carboxymethyl-1H-tetrazol-5-yl]-1,4-dimethyl-2-tetrazene (13) have been synthesized as new nitrogen-rich compounds. The tetrazenes were obtained by oxidation of the corresponding tetrazolylhydrazines using bromine. Moreover, a new method to prepare tetrazolylhydrazines in high yield using 5-bromotetrazoles has been developed. 12a, 12b, and 13 were characterized using vibrational spectroscopy (IR, Raman), mass spectrometry, and multinuclear NMR spectroscopy. The crystal structures of 12a, 12b, and 13 were determined using single crystal X-ray diffraction. Furthermore, the energetic properties of 12a, 12b, and 13 have been investigated using DSC and bomb calorimetric measurements. The sensitivity data toward impact and friction has been determined using BAM methods.

A one‐dimensional coordination polymer based on copper(II) nitrate and 1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane as ligand was prepared. The thermal and physical stability was determined by differential scanning calorimetry and BAM methods. The polymer was investigated by vibrational spectroscopy and single X‐ray diffraction. Moreover, the ligand itself and the 1,2‐bis(1H‐tetrazolyl)ethane were characterized as energetic material by bomb calorimetric measurements along with calculations using the EXPLO5 software. Both compounds have moderate energetic properties along with a high thermal and physical stability. These findings render these compounds into promising environment friendly gas generating agents.

The general, high-yielding synthesis of extremely dangerous alkylated bis-5-azidotetrazoles is presented. The preparation using 5-bromotetrazoles for the generation of tetrazolyl hydrazines, which are then converted into the corresponding bis-5-azidotetrazoles, presents a safe, large-scale preparation of alkylated bis-5-azidotetrazoles. In this work, 1,2-bis(5-azido-1H-tetrazol-1-yl)ethane, 1,2-bis(5-azido-1H-tetrazol-1-yl)-1-methylethane, and 1,4-bis(5-azido-1H-tetrazol-1-yl)butane were synthesized and characterized by 1 H, 13 C, and 15 N

Nitrogen‐rich energetic polymers were synthesized by the polyaddition reaction of 1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane (1a), 1‐methyl‐1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane (1b), and 1,4‐bis(5‐mono‐methylhydrazinyl‐1H‐tetrazolyl)butane (1c) with hexamethylene diisocyanate. The experiments showed that neither a polymerization from solution or bulk was possible. Therefore, a new method for the polymerization of tetrazolyl hydrazines had to be developed. The formed polymers were characterized by vibrational spectroscopy (IR) and elemental analysis. The energetic properties were investigated by bomb calorimetric measurements along with calculations using the EXPLO5 software. The thermal stability was investigated by DSC measurements. The properties render the polymers into promising compounds regarding an application as energetic binder. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 122–127, 2010

Abstract:A new energetic glycidyl-based polymer containing nitramine groups (glycidyl nitramine polymer, GNAP) was synthesized using glycidyl azide polymer (GAP) as the starting material. The synthesis involved Staudinger azide-amine conversion, followed by carbamate protection of the amino group, nitration with nitric acid (100%) and trifluoroacetic anhydride and was concluded by deprotection with aqueous ammonia. The products obtained were characterized by elemental analysis and vibrational spectroscopy (IR). The energetic properties of GNAP were determined using bomb calorimetric measurements and calculated with the EXPLO5 V6.02 computer code, showing better values regarding the energy of explosion (∆EU = −4813 kJ kg −1 ), the detonation velocity (VDet = 7165 m·s −1 ), as well as the detonation pressure (pCJ = 176 kbar), than the comparable polymers GAP and polyGLYN. The explosion properties were tested by impact sensitivity (IS), friction sensitivity (FS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and electrostatic discharge (ESD) equipment. The results revealed GNAP to be insensitive towards friction and electrostatic discharge, less sensitive towards impact (40 J) and a decomposition temperature (170 °C) in the range of polyGLYN.