Prospective Symbiosis of Green Chemistry and Energetic Materials

A global increase in environmental pollution demands the development of new “cleaner” chemical processes. Among urgent improvements, the replacement of traditional hydrocarbon‐derived toxic organic solvents with neoteric solvents less harmful for the environment is one of the most vital issues. As a result of the favorable combination of their unique properties, ionic liquids (ILs), dense gases, and supercritical fluids (SCFs) have gained considerable attention as suitable green chemistry media for the preparation and modification of important chemical compounds and materials. In particular, they have a significant potential in a specific and very important area of research associated with the manufacture and processing of high‐energy materials (HEMs). These large‐scale manufacturing processes, in which hazardous chemicals and extreme conditions are used, produce a huge amount of hard‐to‐dispose‐of waste. Furthermore, they are risky to staff, and any improvements that would reduce the fire and explosion risks of the corresponding processes are highly desirable. In this Review, useful applications of almost nonflammable ILs, dense gases, and SCFs (first of all, CO₂) for nitration and other reactions used for manufacturing HEMs are considered. Recent advances in the field of energetic (oxygen‐balanced and hypergolic) ILs are summarized. Significant attention is paid to the SCF‐based micronization techniques, which improve the energetic performance of HEMs through an efficient control of the morphology and particle size distribution of the HEM fine particles, and to useful applications of SCFs in HEM processing that makes them less hazardous.