Structure-Activity Relationships In Group IV Bis (Phenoxide) Amine and Diamine Olefin Polymerization Catalysts: A DFT and Kinetic Analysis

While olefin polymerization is a well established industrial process, very little kinetic data is available to characterize these catalytic processes.  Even less is know about the relationships between catalyst structure and polymerization kinetics.  Here we present a detailed electronic DFT-based analysis of a variety of Group IV bis(phenoxide) amine and diamine catalysts used for the polymerization of 1-butene.   By comparing both electronic and structural descriptors, we reveal several important insights into the effect of salen ligand character on (1) initiation, (2) propagation, and (3) chain-transfer kinetics.  These DFT results, combined with a unique quantitative kinetic modeling approach involving multi-response data (i.e. the time evolution of the following species: monomer consumption, molecular weight distribution, etc.) provide a consistent characterization of this class of polymerization catalysts, and opens the way to full model-based prediction of polymerization activity and permormance.