Rapid Cocrystallization by Exploiting Differential Solubility: An Efficient and Scalable Process toward Easily Fabricating Energetic Cocrystals

A new energetic cocrystal (1), composed of 1,3,5-trinitrobenzene (TNB) and 1-methyl-2,4-dinitroimidazole (2,4-MDNI), was synthesized for the first time via rapid cocrystallization by exploiting differential solubility. Further, this method was extended to scale-up of the high-performance of CL-20 (2,4,6,8,10,12-hexanitrohexaazaisowurt-zitane)/MTNP (1-methyl-3,4,5-trinitropyrazole) energetic cocrystal (2) on the 100 g scale in a fast and simple way, which is another larger preparation scale in energetic cocrystal fields. The investigations of thermodynamics and kinetics for coprecipitation crystallization indicate that the solubility ratios of a cocrystal to pure components (R) associated with the Gibbs free energy (ΔG_form) offer valuable insights into the selection of suitable components for further cocrystal design and synthesis by the proposed method. Additionally, cocrystal 2 exhibited good experimental comprehensive performances, making it a potential candidate instead of HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane) in the future. Hence, rapid cocrystallization opens up an efficient, simple, and scalable method to manufacture energetic cocrystals on a high industrial production scale for future practical applications.