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

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.