Organoaluminum Initiators: Influence of Al Coordination on Polymerization and Product Properties

Summary Alkyl aluminum halides are well established initiators for cationic polymerizations. They enable homogeneous polymerization processes in nonchlorinated hydrocarbon processes. Activity and polymer properties can be significantly affected by the choice of the compound used for activating the organoaluminum halide. Three examples of organoaluminum chloride based initiator systems for cationic polymerizations are presented here illustrating different stages of a workflow established for the development and optimization of such initiators and corresponding polymerization processes. Initiator formation via addition of protic compounds to organoaluminum chloride precursors is studied by multiple spectroscopic techniques, in particular IR‐spectroscopy. Differently prepared initiators are tested in lab scale batch polymerizations and continuous mini‐plant polymerizations. The influence of aluminum coordination on polymer properties like molecular weights is analyzed.