A phenoxy-imine titanium catalyst (FI-catalyst) for selective ethylene trimerization was immobilized on methyl aluminoxane (MAO) pretreated silica and its activity and selectivity was compared with that of the corresponding homogeneous catalyst system. The homogeneous and heterogeneous ethylene oligomerization was conducted in the presence of different aluminum alkyls, commonly used as scavengers during olefin polymerization to remove residual oxygen and moisture from the reaction medium. Both the homogeneous and heterogeneous catalysts were strongly affected by the presence of scavenger in the reaction medium. Upon activation with R3Al/MAO (R= Et, nOct, iBu), the homogeneous catalyst switches selectivity from ethylene trimerization to polymerization. NMR spectroscopic investigations indicate that this change of selectivity can be attributed to ligand exchange between the precatalyst and the aluminum alkyl and reduction of the titanium species. The thereby formed ligand-free and/or reduced titanium alkyls act as polymerization catalysts and are responsible for the increasing polymer formation. Using the heterogeneous catalyst, the scavenger employed during ethylene trimerization was found to be of crucial influence regarding the activity of the catalyst and the occurrence of reactor fouling. Employing aluminum alkyls like iBu3Al and nOct3Al resulted in catalyst leaching and homogeneous polymer formation. The latter was prevented using Me3Al or Et3Al as scavengers; however, in general the supported catalyst was poisoned by aluminum alkyls, resulting in a low overall activity. It was found to be beneficial for the heterogeneous trimerization system to employ silica-supported scavengers. By physical separation of the catalyst and the scavenger this poisoning effect was effectively prevented, resulting in a highly active heterogeneous catalyst.
- selective ethylene oligomerization
- supported catalyst
- phenoxy-imine titanium catalyst
- aluminum alkyls