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 (Delta G(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-tetranitro1,3,5,7-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.