Different carboxylic acid derivatives of 2,2-dinitropropane-1,3-diol (DNPD) and 2,2-bis(azidomethyl)propane-1,3-diol (BAMP) were synthesized to investigate their suitability as energetic plasticizers. The syntheses were carried out using acyl chlorides of acetic, propionic, and butyric acid. The obtained products were characterized by elemental analysis, NMR, and IR spectroscopy. The energetic properties of the synthesized compounds were calculated on the basis of the computed heats of formation at the CBS-4M level of theory using the EXPLO5 version 6.02 computer code. Investigations of physical stabilities were carried out using BAM drop hammer and friction tester. Low and high temperature behavior was determined by differential scanning calorimetry (DSC). The energetic and physical properties of the synthesized compounds were compared to the literature known energetic plasticizers N-butyl nitratoethylnitramine (BuNENA) and diethylene glycol bis(azidoacetate) ester (DEGBAA)

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.

The tetrazole-5-carboxylate anion was investigated as ligand for earth alkali metal and transition metal complexes. Therefore, the strontium 4a (*3 H(2)O, *2.75 H(2)O, *2.5 H(2)O), barium 4b (*3 H(2)O), copper 4c (*3.5 H(2)O, *4 H(2)O), manganese 4d (*4 H(2)O, *5 H(2)O), and silver tetrazol-5-carboxylate 4e (*1.56 H(2)O) were synthesized and characterized by vibrational spectroscopy (IR), and the crystal structures of 4a (*2.75 H(2)O, *2.5 H(2)O), 4b*3 H(2)O, 4c*4 H(2)O, and 4d*5 H(2)O were determined using single crystal X-ray diffraction. The thermal stability was investigated by DSC-measurements, and the sensitivity toward impact and friction was determined by BAM-standards. The copper, strontium, and barium tetrazole-5-carboxyate proved to be suitable thermal and physical stable colorants for pyrotechnic compositions. The crystal structure of the tetragonal modification of strontium tetrazole-5-carboxyate possesses channels along the c-axis, leading to a porous material.

Tris(2-(1H-tetrazol-1-yl)ethyl)amine (1) was synthesized as gas-generating agent and characterized by vibrational (IR) and NMR spectroscopy. The energetic properties were determined by bomb calorimetric measurements along with calculations using the EXPLO5 software. Tris(2-(1H-tetrazol-1-yl)ethyl)amine (1) was used for further reactions with copper(II) nitrate to form a three-dimensional coordination polymer 3. Both compounds were characterized by single crystal X-ray diffraction. The thermal stability was determined by DSC measurements and the physical stability by BAM standards. Tris(2-(1H-tetrazol-1-yl)ethyl)amine (1) proved to be suitable as gas-generating agent with sufficient physical and thermal stabilities. The low thermal stability of the copper complex 3 disqualifies it as potential colorant agent for pyrotechnical applications.

On the base of 2,2-bis(azidomethyl)propane-1,3-diol (BAMP) and 2,2-dinitropropane-1,3-diol (DNPD) four different polyurethanes were synthesized in a polyaddition reaction using hexamethylene diisocyanate (HMDI) and diisocyanato ethane (DIE). The obtained prepolymers were mainly characterized using vibrational spectroscopy (IR) and elemental analysis. For determination of low and high temperature behavior, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used. Investigations concerning friction and impact sensitivities were carried out using a BAM drop hammer and friction tester. The energetic properties of the polymers were determined using bomb calorimetric measurements and calculated with the EXPLO5 V6.02 computer code. The obtained values were compared with the glycidyl azide polymer (GAP). The compounds turned out to be insensitive toward friction (>360 N) and less sensitive toward impact (40 J)