A DFT Study on the Co-polymerization of CO2 and Ethylene: Feasibility Analysis for the Direct Synthesis of Polyethylene Esters

The co-polymerization of CO2 with the non-polar monomer ethylene, though highly desirable, still presents a challenge whereas the palladium-catalyzed CO/C2H4 co-polymerization is well understood. Building on this analogy, the goal of this study was to elucidate the feasibility of developing suitable catalysts for co-polymerizing CO2 with ethylene to polyethylene esters. Computational methods based on density functional theory were hereby employed. In the search for new catalyst lead structures, a closed catalytic cycle was identified for the palladium-catalyzed CO2/C2H4 co-polymerization reaction. The computational study on palladium complexes with a substituted anionic 2-[bis(2,4-dimethoxyphenyl)-phosphine]-benzene-2-hydroxo ligand revealed key aspects that need to be considered when designing ligand sets for potential catalysts for the non-alternating co-polymerization of CO2 and ethylene.