Unraveling the Catalytic Synergy between Ti(3+) and Al(3+) Sites on a Chlorinated Al2 O3 : A Tandem Approach to Branched Polyethylene.

An original step-by-step approach to synthesize and characterize a bifunctional heterogeneous catalyst consisting of isolated Ti(3+) centers and strong Lewis acid Al(3+) sites on the surface of a chlorinated alumina has been devised. A wide range of physicochemical and spectroscopic techniques were employed to demonstrate that the two sites, in close proximity, act in a concerted fashion to synergistically boost the conversion of ethylene into branched polyethylene, using ethylene as the only feed and without any activator. The coordinatively unsaturated Al(3+) ions promote ethylene oligomerization through a carbocationic mechanism and activate the Ti(3+) sites for the traditional ethylene coordination polymerization.