聚金属卟啉配合物膜催化氧化环己烯性能研究

Polymeric Metalloporphyrin Catalytic Oxidation of Cyclohexene with Molecular Oxygen

以聚卟啉金属配合物PMTPP(M=Co(Ⅱ)、Mn(Ⅱ)和Zn(Ⅱ))为催化剂催化分子氧氧化环己烯,氧化产物以2-环己烯-1-醇(1)、2-环己烯-1-酮(2)和7-氧杂二环[4.1.0]环己烷(3)为主。配合物PCo(Ⅱ)TPP具有最好的催化活性,对影响该配合物活性的因素研究发现,反应温度在70℃,反应时间为8 h时,环己烯的转化率可达到90%,且产物1的选择性可达54%,催化剂使用3次后活性没有明显下降。在此基础上,还探讨了配合物PCo(Ⅱ)TPP氧化环己烯的可能反应机理,初步认为氧化反应的过程是链式自由基反应。

The catalytic oxidation of cyclohexene with molecular oxygen by polymeric metalloporphyrin complexes PMTPP [ M = Co（ II ） , Mn（ II ） , Zn（ II ） ] as catalysts was studied. The obtained major products of the reaction were 2-cyclohexen-l-ol （ 1）, 2-cyclohexen-l-one （2） and epoxidation （3）. The experiments indicated that the PCo （ II ） TPP complex exhibited the higher catalytic activity, so it was selected to carry out reaction for investigating the influence factors on the oxidations. The results showed that the 90% conversion of cyclohexene and 54% selectivity of product 1 were achieved by reaction 8 h at 70℃. Moreover, it had been found that the catalytic activity had not been descended with the PCo（ II ）TPP after using three times. Further, the radical-chain mechanism had been proposed for the catalytic oxidation of cyclohexene.