A DFT Study on the Co‐polymerization of CO2 and Ethylene: Feasibility Analysis for the Direct Synthesis of Polyethylene Esters. Issue 13 (20th June 2016)

• Record Type: Journal Article
• Authors: Moha, Verena; Cozzula, Daniela; Hölscher, Markus; Leitner, Walter; Müller, Thomas E.
• Is Part Of: ChemSusChem. Volume 9:Issue 13(2016:Jul.)
• Page Start: 1614
• Page End: 1622
• Publication Date: 2016-06-20
• Subjects: carbon dioxide -- density functional theory -- energy profile -- palladium catalysis -- polyesters; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201501615
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: The co‐polymerization of CO2 with the non‐polar monomer ethylene, though highly desirable, still presents a challenge whereas the palladium‐catalyzed CO/C2 H4 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 /C2 H4 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. Abstract : A dream come true? The copolymerization of a polar (CO2 ) with a non‐polar co‐monomer (ethylene) is a highly desirable reaction as the incorporation of CO2 into polyethylene will give rise to more sustainable materials for which highly exciting properties can be expected. We have taken the analogy to CO–ethylene copolymerization and demonstrated in a comprehensive DFT study that the reaction should be feasible with palladium catalysts, with the key being the choice of an appropriate ligand set.