The Role of Catalyst Support, Diluent and Co-Catalyst in Chromium-Mediated Heterogeneous Ethylene Trimerisation

Sequential treatment of a previously-calcined solid oxide support (i.e. SiO₂, γ-Al₂O₃, or mixed SiO₂-Al₂O₃) with solutions of Cr{N(SiMe₃)₂}₃ (0.71 wt% Cr) and a Lewis acidic alkyl aluminium-based co-catalyst (15 molar equivalents) affords initiator systems active for the oligomerisation and/or polymerisation of ethylene. The influence of the oxide support, calcination temperature, co-catalyst, and reaction diluent on both the productivity and selectivity of the immobilised chromium initiator systems have been investigated, with the best performing combination (SiO_2-600, modified methyl aluminoxane-12 {MMAO-12}, heptane) producing a mixture of hexenes (61 wt%; 79% 1-hexene), and polyethylene (16 wt%) with an activity of 2403 g g_Cr ^-1 h^-1. The observed product distribution is rationalised by two competing processes: trimerisation via a supported metallacycle-based mechanism and polymerisation through a classical Cossee-Arlman chain-growth pathway. This is supported by the indirect observation of two distinct chromium environments at the surface of the oxide support by a solid-state ²⁹Si NMR spectroscopic study of the Cr{N(SiMe₃)₂}_x/SiO_2-600 pro-initiator.