Synthesis and Properties of Azide‐Functionalized Ionic Liquids as Attractive Hypergolic Fuels

Hypergolic ionic liquids (ILs) have shown a great promise as viable replacements for toxic and volatile hydrazine derivatives used as propellant fuels, and hence, have attracted increasing interest over the last decade. To take advantage of the reactivity and high energy density of the azido group, a family of low-cost and easily prepared azide-functionalized cation-based ILs, including fuel-rich anions, such as nitrate, dicyanamide, and nitrocyanamide anions, were synthesized and characterized. All the dicyanamide- and nitrocyanamide-based ILs exhibited spontaneous combustion upon contact with 100 % HNO3 . The densities of these hypergolic ILs varied in the range 1.11-1.29 g cm-3 , and the density-specific impulse, predicted based on Gaussian 09 calculations, was between 289.9 and 344.9 s g cm-3 . The values of these two key physical properties are much higher than those of unsymmetrical dimethylhydrazine (UDMH). Among the studied compounds, compound IL-3b, that is, 1-(2-azidoethyl)-1-methylpyrrolidin-1-ium dicyanamide, shows excellent integrated properties including the lowest viscosity (30.9 M Pa s), wide liquid operating range (-70 to 205 °C), shortest ignition-delay time (7 ms) with 100 % HNO3 , and superior density specific impulse (302.5 s g cm-3 ), suggesting promising applications with potential as bipropellant formulations.