Borate and MAO Free Activating Supports for Metallocene Complexes

Fluorinated activating supports (AS) for metallocene complexes were prepared via treatment of silica with AlEt 3 or AlEt 2 F followed by pyrolysis and combustion steps, and a subsequent fluorination step when AlEt 3 was used. This new family of activators appears to be universal for metallocene complexes leading to catalysts displaying high activities in ethylene polymerization without the addition of MAO. A productivity of 3200 g g AS –1 was obtained in 1 h with the catalyst rac -Et(Ind) 2 ZrCl 2 /AS 8 /Al( i Bu) 3 at 80 °C under 10 bar of ethylene. An isotactic polypropylene with a melting transition at 145 °C was prepared using rac -Me 2 Si(2-Me-benz(e)Ind) 2 ZrCl 2 activated by AS9 and Al( i Bu) 3 . The spherical particle morphology of polyolefins was particularly adapted to slurry processes employed in industry.