Propylene Polymerization Catalyzed by Metallocene/Methylaluminoxane Systems on Rice Husk Ash

摘要

Silica generated from agricultural waste is more cost effective and environmentally friendly than silica from traditional commercial processes. In this study, spherical silica particles with a diameter of around 120 nm were fabricated from rice husk ash (RHA), and were used to support two bridged zirconcene complexes ((I) Me2Si(Ind)2ZrCl2 and (II) C2H4(Ind)2ZrCl2) for catalyzing propylene polymerization to produce polypropylene (PP) in a temperature range of 40–70 °C and in a solution methylaluminoxane (MAO) range of 0.1–0.6 wt%. Due to its small particle size, RHA-supported catalyst exhibited much higher activity than micro-sized commercial silica-supported catalyst. At the optimum polymerization temperature of 55 °C and with increasing MAO concentration, polymer yield increased proportionally with the increase of number average molecular weight. Compared to (I), (II) produced more polymer molecules but with much shorter chain length, ascribed to the differences of Zr loading and bridge structure. With increasing polymerization temperature, polymer molecular weight decreased rapidly and resulted in a significant change of PP assembly morphology (shape and size). At 55 °C, (I) produced uniform PP assemblies which had dumbbell-like structure with a smooth middle section and two fibrillar ends, while (II) produced spherical PP particles. The dumbbell middle part width was essentially identical to the Batchelor microscale proposed in turbulent mixing theory.