"Thermal escape" of MTNP: the phase separation of CL-20/MTNP cocrystals under long-term heating

High-energy, low-sensitivity energetic cocrystals are one successful application of the supramolecular strategy. The practical application of cocrystal explosives requires an in-depth understanding of the stability of their crystal phase structure under long-term heating, but relevant research is rare. In this study, the CL-20/MTNP (2, 4, 6, 8, 10, 12-hexanitrohexaazaisowurtzitane/1-methyl-3,4,5-trinitropyrazole) cocrystal was selected as a representative cocrystal explosive to investigate its crystal phase structure stability under long-term heating. The phase separation of the CL-20/MTNP cocrystal was observed for the first time. It was revealed that the MTNP molecules at crystal defects first underwent molecular rotation, which weakened interactions between CL-20 and MTNP molecules. Then, the MTNP molecules diffused along channels surrounded by CL-20 molecules to the crystal surface and escaped to generate γ-CL-20. We call this process the "thermal escape" of MTNP, whose effect on the safety performance of the CL-20/MTNP cocrystal was studied by comparing the mechanical sensitivity of samples with different degrees of thermal escape. The mechanical sensitivity of the CL-20/MTNP cocrystal did not greatly change during the induction period, but it increased upon the loss of MTNP. Moreover, the thermal escape kinetics for the two stages were obtained to prevent or control their thermal escape. The prediction of the kinetics confirmed the validity of the kinetic analysis. This study promotes the performance evaluation and application of CL-20/MTNP cocrystals and also provides a new perspective in the investigation of cocrystal explosives.