Reaction mechanism and kinetics of Criegee intermediate and hydroperoxymethyl formate

摘要

The reaction mechanism and kinetics of the simplest Criegee intermediate CH_(2)OO reaction with hydroperoxymethyl formate(HPMF)was investigated at high-level quantum chemistry calculations.HPMF has two reactive functional groups,-C(O)OH and-OOH.The calculated results of thermodynamic data and rate constants indicated that the insertion reactions of CH_(2) OO with-OOH group of HPMF were more favorable than the reactions of CH_(2)OO with-C(O)OH group.The calculated overall rate constant was 2.33×10^(−13) cm^(3)/(moleculesec)at 298 K and the rate constants decreased as the temperature increased from 200 to 480 K.In addition,we also proved the polymerization reaction mechanism between CH_(2)OO and-OOH of HPMF.This theoretical study interpreted the previous experimental results,and supplied the structures of the intermediate products that couldn’t be detected during the experiment.