Pressure and trimethylaluminum effects on ethene/1‐hexene copolymerization with methylaluminoxane‐activated (1,2,4‐Me3Cp)2ZrCl2: Trimethylaluminum suppression of standard termination reactions after 1‐hexene insertion

Ethene homopolymerizations and copolymerizations with 1‐hexene were catalyzed by methylaluminoxane‐activated (1,2,4‐Me₃Cp)₂ZrCl₂. Investigations of the effects of various pressures on the homopolymerizations and copolymerizations and of the effects of different concentrations of trimethylaluminum (TMA) on the copolymerizations were performed. The characteristics of the ethene/1‐hexene copolymers agreed with expectations for changes in the ethene concentration: the incorporation of 1‐hexene decreased, whereas the melting point and crystallinity increased, with increasing pressure. The main termination mechanism of the homopolymerizations was β‐hydrogen transfer to the monomer. Termination mechanisms resulting in vinylidene unsaturations dominated in the copolymerizations. Standard termination mechanisms producing vinyl and trans‐vinylene unsaturations occurred in parallel and were not influenced by the ethene or TMA concentration. In addition, some chain transfer to TMA, producing saturated end groups after hydrolysis, occurred. Copolymerizations with different additions of TMA, with the other polymerization conditions kept constant, showed that the catalytic productivity tons of polyethylene/(mol of Zr h)], the 1‐hexene incorporation, and the molecular weight (from gel permeation chromatography) were independent of the TMA concentration. Surprisingly, the vinylidene content decreased almost linearly with increasing TMA concentration. TMA might have coordinated to the catalytic site after 1‐hexene insertion and rotation to the β‐agostic state and, therefore, suppressed the standard termination reactions after 1‐hexene insertion. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2584–2597, 2005