在交联聚苯乙烯微球表面同步合成与固载吡啶基卟啉及固载化钴卟啉的催化氧化性能

Synchronous Synthesis and Immobilization of Pyridyl Porphyrins on Crosslinked Polystyrene Microspheres and Catalytic Oxidation Performance of Immobilized Cationic Co-Porphyrins

先通过季铵化反应将吡啶甲醛(PyAL)基团键合于交联聚苯乙烯微球(CPS)表面,制得改性微球PyAL-CPS,再通过Adler反应,成功地实现了吡啶基卟啉(PyP)在CPS微球表面的同步合成与固载,制得功能微球PyP-CPS,它再与碘甲烷发生季铵化反应制成N-甲基吡啶基卟啉(MPyP)季铵盐,从而制得固载有阳离子卟啉的微球MPyP-CPS;最后通过与钴盐的配合反应,制备了固载有阳离子钴卟啉的固体催化剂CoMPyP-CPS.考察了影响吡啶基卟啉在CPS微球表面同步合成与固载的因素,固载化阳离子钴卟啉催化剂CoMPyP-CPS催化分子氧氧化乙苯的反应性能,也考察了CoMPyP-CPS(C)与磷钨杂多阴离子(PW)的复合催化剂CPW的催化性能.结果表明,以改性微球PyAL-CPS与溶液中的吡咯及4-吡啶甲醛为共反应物,通过固-液Adler反应,可以顺利地实现吡啶基卟啉在微球CPS表面的同步合成与固载,所制备的固体催化剂CoMPyP-CPS具有较好的催化分子氧氧化乙苯反应活性,而CPW催化剂的催化活性更高.

Pyridylaldehyde （PyAL） groups were bound onto the surface of crosslinked polystyrene （CPS） microspheres via quatemization between 4-pyridylaldehyde and chloromethyl groups of chloromethylated crosslinked polystyrene （CMCPS） microspheres, obtaining the modified microspheres PyAL-CPS. Subsequently, synchronous synthesis and immobilization of pyridylporphyrin on CPS microspheres were successfully realized using 4-pyridylaldehyde, pyrrole and the modified microspheres PyAL-CPS as the co-reactants via the Adler reaction between solid-liquid phases, resulting in functional microspheres PyP-CPS, on which pyridylporphyrin （PyP） was immobilized. The microspheres PyP-CPS were then allowed to react with methyl iodide, and PyP was transformed to N-methyl pyfidyl porphyrin （MPyP） iodide, leading to the formation of MPyP-CPS microspheres, on which cationic porphyrin was immobilized. Finally, the solid catalyst CoMPyP-CPS, on which cationic cobalt porphyrin was immobilized, was prepared through the coordination reaction between MPyP-CPS micro- spheres and cobalt salt. The effects of the main factors on the synchronous synthesis and immobilization of pyridylporphyrin on CPS microspheres were examined, and the catalytic performance of the solid catalyst CoMPyP-CPS in the oxidation of ethylbenzene by molecular oxygen was investigated mainly. Besides, the catalytic character of the composite catalyst CPW, which was prepared by association of CoMPyP-CPS （C） and phospho-tungstic（PW）heteropoly acid, was also investigated. The results show that the synchronous synthesis and immobilization of pyridylporphyrin on CPS microspheres can be favorably carried out using PyAL-CPS microspheres, 4-pyridylaldehyde, and pyrrole in the solution as co-reactants via the Adler reaction between solid-liquid phases. The immobilized cationic cobalt porphyrin catalyst CoMPyP-CPS has excellent catalytic performance in the oxidation of ethylbenzene by molecular oxygen, and the composite catalyst CPW possesses much higher catalytic activity.