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Formation of Octameric Methylaluminoxanes by Hydrolysis of Trimethylaluminum and the Mechanisms of Catalyst Activation in Single-Site α-Olefin Polymerization Catalysis
Ist Teil von
Chemphyschem, 2014-09, Vol.15 (13), p.2732-2742
Ort / Verlag
Weinheim: WILEY-VCH Verlag
Erscheinungsjahr
2014
Link zum Volltext
Quelle
Wiley Online Library Journals Frontfile Complete
Beschreibungen/Notizen
Hydrolysis of trimethylaluminum (TMA) leads to the formation of methylaluminoxanes (MAO) of general formula (MeAlO)n(AlMe3)m. The thermodynamically favored pathway of MAO formation is followed up to n=8, showing the major impact of associated TMA on the structural characteristics of the MAOs. The MAOs bind up to five TMA molecules, thereby inducing transition from cages into rings and sheets. Zirconocene catalyst activation studies using model MAO co‐catalysts show the decisive role of the associated TMA in forming the catalytically active sites. Catalyst activation can take place either by Lewis‐acidic ion of an alkyl or halide ligand from the precatalyst or by reaction of the precatalyst with an MAO‐derived AlMe2+ cation. Thermodynamics suggest that activation through AlMe2+ transfer is the dominant mechanism because sites that are able to release AlMe2+ are more abundant than Lewis‐acidic sites. The model catalyst system is demonstrated to polymerize ethene.
Modeling MAOs: Hydrolysis of trimethylaluminum forms methylaluminoxanes with general formula (AlOMe)n(AlMe3)m. The process is computationally followed until the formation of octameric structures. By using model co‐catalysts, associated trimethylaluminum is shown to be responsible for the cocatalytic activity of the methylaluminoxanes.