在聚合物微球GMA/MMA表面同步合成与固载卟啉及固载化金属卟啉的催化氧化性能

Synchronistic Synthesis and Immobilization of Porphyrins on Microspheres GMA/MMA and Catalytic Performance of Immobilized Metalloporphyrins

制备了甲基丙烯酸缩水甘油酯(GMA)与甲基丙烯酸甲酯(MMA)共聚微球GMA/MMA,并通过键合有对羟基苯甲醛(HBA)的改性微球HBA-GMA/MMA与苯甲醛(或取代苯甲醛)以及吡咯间的Adler反应,实现了卟啉在共聚微球GMA/MMA表面的同步合成与固载,制得了固载有苯基卟啉(PP)、对氯苯基卟啉(CPP)、对硝基苯基卟啉(NPP)的功能化微球PP-GMA/MMA,CPP-GMA/MMA和NPP-GMA/MMA.重点考察了影响卟啉同步合成与固载过程的因素.制备了固载有钴卟啉的催化剂,并以分子氧氧化乙苯为模型反应,考察了催化剂的活性.结果表明,苯甲醛取代基的结构、催化剂的酸性和溶剂的极性对卟啉的同步合成与固载都有较大的影响;钴卟啉催化剂对分子氧氧化乙苯反应具有较高的催化活性,且当钴卟啉外环上含有强吸电子基团硝基时,催化剂活性最高.

The suspension polymerization of glycidyl methacrylate （GMA） and methyl methacrylate （MMA） was conducted, resulting in polymeric microspheres GMAJMMA. Subsequently, p-hydroxybenzaldehyde （HBA） was bonded on GMA/MMA, obtaining modified microspheres HBA-GMA/MMA. Adler reaction was performed by using microspheres HBA-GMA/MMA, benzaldehyde derivatives, and pyrrole in solution, so that the synchronistic synthesis and immobilization of porphyrins on the microspheres GMA/MMA were realized successfully, resulting in three kinds of porphyrin-supported microspheres. The effects of main factors on the process of synchronistic synthesis and immobilization of porphyrin were studied. Via the coordination reaction between the functional microspheres and cobalt salt, polymer-supported cobalt porphyrin was prepared. The catalytic activity of the catalysts was tested in the oxidation reaction of ethyl benzene by oxygen molecules. The results showed that the substitute structure of benzaldehyde derivatives, the acidity of the catalysts, and the polarity of solvents affected the synchronistic synthesis and immobilization of porphyrin greatly. The porphyrin-supported catalysts had obvious catalytic activity for the oxidation reaction. The immobilized cobalt porphyrin with strong electron-withdrawing substitute on phenyl ring has higher catalytic activity.