关键词: 交联聚苯乙烯, 苯基卟啉, 合成, 固载, 环己烷羟基化

By adopting Kornblum reaction, the chloromethyl groups of chloromethylated crosslinked polystyrene (CMCPS) microspheres were first oxidated as aldehyde groups, resulting in aldehyde group (AL)-modified microspheres ALCPS. Subsequently, synchronistic synthesis and immobilization of porphyrins on CPS microspheres were realized successfully by using benzaldehyde (or substituted benzaldehyde), pyrrole and the microspheres ALCPS as the co-reactants and via the Adler reaction between solid and liquid phases, obtaining three kinds of functional microspheres, on which phenyl porphyrin (PP), p-chlophenyl porphyrin (CPP) and p-nitrophenyl porphyrin (NPP) were immobilized, respectively. Finally, three immobilized cobalt porphyrins were prepared through the complex reaction between these functional microspheres and cobalt salt. This study focused on two aspects: (1) the effects of the main factors on the synchronistic synthesis and immobilization process of porphyrins were examined|(2) the catalytic characters of the immobilized metalloporphyrins in the cyclohexane hydroxylation with molecular oxygen were investigated. The experimental results show that the synchronistic synthesis and immobilization of porphyrin on CPS microspheres can be carried out smoothly by using ALCPS microspheres, benzaldehyde (or substituted benzaldehyde) and pyrrole in solution as co-reactants via the Adler reaction between solid and liquid phases. The substituent structure of benzaldehyde derivatives, the acidity of the catalysts and the properties of the solvents affect the synchronistic synthesis and immobilization of porphyrin greatly. The prepared immobilized metalloporphyrins have very high catalytic activity (a maximum cyclohexane conversion of about 40%) and excellent selectivity (selectivity of more than 90% for cyclohexanol), and this is attributed to their special chemical structure.

Key words: crosslinked polystyrene, phenyl porphyrin, synthesis, immobilization, cyclohexane hydroxylation