Chemical modification of silica-based supports is an alternative route for modulating the active sites of metallocene catalysts, presenting the potential to obtain polyethylenes with improved properties. Therefore, this work investigates the effect of octadecylsilane content in silica support on the behavior of resulting supported metallocene catalysts on ethylene polymerization. For this propose, a series of octadecyl-modified silicas whit different amounts of octadecyl (ODS) groups were synthesized by a modified Stöber sol-gel method and then applied as supports for a metallocene catalyst. The supported metallocene catalysts were evaluated in ethylene polymerization and ethylene/1-hexene copolymerization reactions. Besides, studies of the growth kinetics of polyethylene particles in a gas phase reactor were performed using videomicroscopy. The octadecylsilane content in the supports was in the range of 0.2 to 1.4 mmol g −1. DRIFTS and 13 C CP/MAS NMR results showed a predominance of an all-trans octadecyl chain conformation. SEM images showed spherical particle morphology for silicas having octadecylsilane content up to 0.6 mmol g −1. The supported catalysts presented activity in ethylene polymerization in the range of 1100-1900 kg PE molZr −1 h −1 bar −1. The surface polarity of the catalyst influenced the molar mass of the resulting polyethylene. The increase of the ODS content on the silica surface led to a supported catalyst with slower kinetic behavior in the gas phase, which might be attributed to the diffusive effects of the octadecyl layer on the catalyst surface.
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