Continuous flow synthesis of di‐tert‐butyl peroxide in microreactors and kinetic study

Di‐tert‐butyl peroxide (DTBP) is a widely used organic peroxide. Its synthesis using tert‐butyl alcohol (TBA) and H₂O₂ via traditional batch processes has suffered from low space–time yield, uncontrollable product distribution, and safety issues. An efficient continuous‐flow microreaction system was proposed to enhance DTBP synthesis. Optimal reaction conditions were determined: a molar ratio of 1.5 (H₂SO₄/TBA) and 0.5 (H₂O₂/TBA), a reaction temperature of 50°C, and concentrations of 75 wt% H₂SO₄, 85 wt% TBA, and 50 wt% H₂O₂. A kinetic model was established, indicating that reducing local H₂O₂ concentration is key to increasing space‐time yield. Consequently, a novel two‐stage H₂O₂ feeding strategy was proposed, which improved the DTBP selectivity from 94.7% to 97.6% compared to the single‐stage feeding process. The maximum TBA conversion reached upto 98.7% within only 410 s, with a DTBP yield of 96.3%. With proper design and optimization, this microreaction system could be further applied to continuously synthesize other dialkyl peroxides.