Mechanism of Acid-Catalyzed Decomposition of Dicumyl Peroxide in Dodecane: Intermediacy of Cumene Hydroperoxide

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• 作者：Mark L. Conley ; Fiaz S. Mohammed ; Charles Winslow ; Harris Eldridge ; Jeffrey M. Cogen ; Bharat I. Chaudhary ; Pamela Pollet ; Charles L. Liotta
• 刊名：Industrial & Engineering Chemistry Research
• 出版年：2016
• 出版时间：May 25, 2016
• 年：2016
• 卷：55
• 期：20
• 页码：5865-5873
• 全文大小：429K
• 年卷期：0
• ISSN：1520-5045

文摘

Acid-catalyzed decomposition of dicumyl peroxide in dodecane from 60 to 130 °C produces α-methylstyrene and phenol as the major products. Pseudo-first-order rate constants were determined as a function of the temperature for the reaction of DCP with dodecylbenzenesulfonic acid in dodecane and resulted in an Arrhenius plot exhibiting two distinct kinetic regimes with differing activation energies: 76.9 kJ/mol at low temperatures (measured from 60 to 90 °C) and 8.50 kJ/mol at higher temperatures (measured from 90 to 130 °C). With employment of a combination of kinetics, product analysis, and trapping experiments, evidence is presented to show the intermediacy of cumene hydroperoxide—a reactive intermediate absent from previous mechanistic descriptions of this process. The yield of cumene hydroperoxide production is discussed, and the mechanistic pathways for formation of the observed products are presented.