Elucidation and Control of the Reaction Network for Efficient Synthesis of Di- tert -amyl Peroxide in Microreactor

Abstract Di-tert-amyl peroxide (DTAP) is a class of dialkyl peroxide initiators with high polymerization efficiency. However, its traditional batch synthesis suffers from multiple side reactions with unclear mechanisms, poor interphase mass transfer, and intense heat release, ultimately leading to a low product quality. To address these challenges, a novel synthesis strategy coupled with mechanistic investigation is required to guide the DTAP production. In this work, microreactor technology was employed to elucidate and control the reaction network for the efficient synthesis of DTAP. The complex reaction network of peroxidation was systematically deciphered, leading to the identification of three major classes of impurities, including 2-methyl-2-butene (MB), tert-amyl ethyl ether (TAEE), and the previously unreported compound 2,2-bis(tert-amyloxy)propane (BTAOP). On the basis of these mechanistic insights, advanced control strategies including ex situ temporal extension and in situ feedstock modulation were proposed to further improve the DTAP purity to exceed 96% by precise network steering. The proposed reaction network was further validated by density functional theory (DFT) calculations. The superiority of this paradigm was demonstrated through a systematic comparison with conventional and alternative advanced approaches. Beyond delivering a high-purity product, this work establishes a mechanistically guided process intensification paradigm, offering a transferable framework for organic peroxide synthesis.