Guided synthesis of ketone-based energetic plasticizers for theoretical prediction and verification

Energetic plasticizers play an important role in improving the performance of solid propellants. Currently, research on the structure-activity relationships of energetic plasticizers remains limited, and the cost associated with trial-and-error-based research and development is relatively high. This situation hinders the establishment of a comprehensive energetic plasticizer database and the realization of intelligent design. To address this issue, we propose a novel research framework that integrates quantum chemistry methods to predict and screen candidate compounds for plasticizer design, with computational results guiding the experimental synthesis process. This approach minimizes reliance on empirical experimentation and facilitates the accumulation of structure-activity relationship data. In this study, using ketone nitro-based plasticizers as a case example, five novel energetic plasticizers (named as NEP1 to NEP5) are designed. Analyses of their surface electrostatic potential, initial step of thermal decompositon, atomic forces, volume-specific volume curves and solubility parameters are conducted, and preliminary performance predictions are made. Subsequently, during the experimental validation phase, the five target compounds were successfully synthesized and characterized. Encouragingly, the experimental results were largely consistent with the theoretical predictions, confirming the validity of the proposed design strategy. This work may serve as a valuable reference for future research and development of energetic plasticizers.