Synchronous Synthesis and Immobilization of Metal Phthalocyanine for Aerobic Oxidation of Styrene

In this study,the precursor 4-(4-carboxy-phenoxy)phthalonitrile(CPPN)was first bonded onto the silica gel surface modified with poly(glycidyl methacrylate)(PGMA)(PGMA/SiO2)to prepare CPPN-PGMA/SiO2,and metal phthalocyanine(MPc;M=Co,Fe,Cu,Mn)was supported on the PGMA/SiO2 surface to prepare MPc-PGMA/SiO2 by synchronous synthesis and immobilization with phthalonitrile and metal salt in the solution.The chemical composition and surface morphology were characterized by the Fourier transform infrared(FTIR)spectroscopy,UV-Vis spectroscopy,scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),and thermogravimetry analysis(TGA).The catalytic performance of MPc-PGMA/SiO2 in epoxidation of styrene was also investigated with molecular oxygen acting as the oxidant.The results show that MPc-PGMA/SiO2 can efficiently and selectively catalyze molecular oxygen for oxidation of styrene to styrene oxide under mild conditions.However,the catalytic activity differs substantially depending on the central metal,and a highest catalytic activity is achieved by CoPc-PGMA/SiO2.The CoPc-PGMA/SiO2 amount and temperature can also affect the catalytic oxidation of styrene,and at normal atmospheric pressure,a maximum conversion rate of styrene(99%)and selectivity of styrene oxide(53%)are obtained using 0.1 g of CoPc-PGMA/SiO2(22.61μmol of CoPc)at 100℃ for 6 h.CoPc-PGMA/SiO2 also has excellent reusability,and the conversion rate of styrene is still over 90%after 5 cycles.