The role of certain morphological properties of different silica used as supports for metallocene catalysts was investigated in order to quantify their eventual influence on the kinetics of ethylene polymerisation in heptane slurry, as well as on the polymer properties. It was shown that there is no clear link between porosity and observed activity with some highly porous silica producing relatively inactive supported catalysts. It was further shown that within a batch of silica, the particle size had a significant impact on observed kinetics. While it appears that there is possibly some diffusion resistance encountered in the larger particles, it was also shown that prolonged contact between the support and the alkylating agent could increase reaction rates in the larger particles. magnified image

Fluorinated activating supports (AS) for metallocene complexes were prepared via treatment of silica with AlEt3 or AlEt2F followed by pyrolysis and combustion steps, and a subsequent fluorination step when AlEt3 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 gAS –1 was obtained in 1 h with the catalyst rac-Et(Ind)2ZrCl2/AS8/Al(iBu)3 at 80 °C under 10 bar of ethylene. An isotactic polypropylene with a melting transition at 145 °C was prepared using rac-Me2Si(2-Me-benz(e)Ind)2ZrCl2 activated by AS9 and Al(iBu)3. The spherical particle morphology of polyolefins was particularly adapted to slurry processes employed in industry.