高分子负载金属卟啉化合物催化氧化异丙苯的动力学研究

Study on kinetics of Cumene Oxidation Catalyzed by Polymer-Bonded Metallo-Porphyrins

高分子负载的金属卟啉化合物，对异丙苯催化氧化效果显著。产物有过氧化氢异丙苯、二甲基苄醇、甲基苯乙烯、苯乙酮等。在８０℃、１０１．３ｋＰａ的氧压下，催化剂还可催化分解过氧化氢异丙苯。在异丙苯转化率小于４０％时，过氧化氢异丙苯和二甲基苄醇的总收率大于９５％。研究了高分子负载铜卟啉化合物在异丙苯氧化中的动力学，发现催化氧化的初速率对异丙苯和氧气均为一级，即ｒ０＝ｋＣｃｕｍｅｎｅＰｏ２；活化能为５１．６９ｋＪ／ｍｏｌ；提出了包括氧活化的可能机理。

The polymer-bonded metalloporphyrins efficiently catalyzed the oxidation of cumene to cumyl hydroperoxide, cumyl alcohol,α-methylstyrene acetophenone etc. At 80℃ under 101.3KPa pressure of O2, the catalysts also catalyzed the decomposition of cumyl hydroperoxide. The overall recovery of cumyl hydroperoxide and cumyl alcohol is higher than 95% as the conversion of cumene is less than 40%.The kinetics of polymer-bonded copper-porphyrin in the oxidation of cumene was studied. The initial rate of the catalyzed oxidation was found to be of first order with respect to cumene and first order to oxygen,r0 = kCcumenePo2; The activity energy of oxidation of cumene was determined to be of 51.69 kJ/mol. A possible mechanism involving activation of dioxygen was proposed.