Reaction characteristics and process intensification of tert ‐butyl peroxy(2‐ethylhexanoate) synthesis in a microreactor

Abstract

tert ‐Butyl peroxy(2‐ethylhexanoate) (TBPEH) is an important initiator widely used in polymerization processes. To address the low reaction efficiency and poor process safety of the conventional semi‐batch process, a continuous‐flow microreaction platform was developed for TBPEH synthesis, and an apparent kinetic model was established for process optimization. KOH was selected as the base, and the stable operating window of the tert ‐butyl hydroperoxide (TBHP) alkali metal salt system was determined. Kinetic modeling revealed that both the KOH/TBHP equivalence ratio ( φ _KOH ) and the TBHP/EHCl equivalence ratio ( φ _TBHP ) significantly affected reaction performance, while φ _TBHP was a more dominant parameter. Under the optimized conditions ( φ _KOH  = 1.01, φ _TBHP  = 1.25, 45°C, and 140 s residence time), 99.71% EHCl conversion, 95.05% TBPEH selectivity, and 94.77% TBPEH yield were achieved. This work provides a methodology for the continuous‐flow synthesis and process optimization of TBPEH, providing guidance for the development of continuous processes for related peroxyesters.