Safe and Scalable Synthesis of RDX/HMX Precursors: Bumping Risk Control in Batch and Microreactor for TRAT/TAT Production

ABSTRACT 1,3,5‐Triacetyl‐1,3,5‐triazinane (TRAT) and 1,3,5,7‐tetraacetyl‐1,3,5,7‐tetraazacyclic octane (TAT) serve as precursors for two crucial military explosives, namely 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX) and octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX), respectively. The small‐molecule synthesis method, which prepares TRAT/TAT from acetonitrile and 1,3,5‐trioxane, has proven to be more efficient and cost‐effective. However, it still suffers from the bumping risk during the process, which impedes its scalability. This study introduces optimized synthesis methods for TRAT/TAT, specifically aiming to tackle the bumping risks associated with conventional processes. In the batch process, heptane replacement achieves a 26.14% TAT mass fraction with >97.65% yield. Microreactor technology enables continuous production (383.15 K, 7 min residence) with 98.45% total yield and space‐time yields of 513.78 g·h −1 (TRAT) and 48.95 g·h −1 (TAT). Kinetic analysis reveals second‐order dependence on 1,3,5‐trioxane ( E a = 11.14 kJ·mol −1 ). Both approaches significantly improved safety and scalability while maintaining high efficiency, providing practical solutions for industrial energetic material production.