Catalytic Ring-Opening Polymerisation of Cyclic Ethylene Carbonate: Importance of Elementary Steps for Determining Polymer Properties Revealed via DFT-MTD Simulations Validated Using Kinetic Measurements.

The production of CO-containing polymers is still very demanding in terms of controlling the synthesis of products with pre-defined CO content and molecular weight. An elegant way of synthesising these polymers is via CO-containing building blocks, such as cyclic ethylene carbonate (cEC), via catalytic ring-opening polymerisation. However, to date, the mechanism of this reaction and control parameters have not been elucidated.

A DFT-metadynamics study disclosing key properties of ring-opening polymerization catalysts to produce polyethercarbonate polyols from cyclic ethylene carbonate as part of an emerging CCU technology.

The ring opening polymerization of cyclic carbonates made from epoxide and CO to CO-containing polymers constitutes an emerging technology of particular industrial interest. Considering the reaction of ring-opening polymerization of cyclic ethylene carbonate to produce polyethercarbonate polyols, several types of catalysts were tested experimentally and mechanistic pathways were proposed, but a detailed analysis of structure property relationship including the CO-liberation pathways is still lacking. This contribution is using computational methods to investigate reported benchmark catalysts with the lead structure AMO (A: alkali metal or alkyl, M: main group element or transition metal) that are particularly approved as effiecient catalysts for industrial purpose.

Toolbox of Nonmetallocene Lanthanides: Multifunctional Catalysts in Group-Transfer Polymerization.

Herein, we present a fundamental study of isostructural 2-methoxyethylamino-bis(phenolate)-lanthanide complexes [(ONOO)M(X)(THF)] (M = Lu, Y; R = Bu, CMePh, X = CHTMS, collidine; THF = tetrahydrofuran; TMS = trimethylsilyl) for rare-earth metal-mediated group-transfer polymerization (GTP). This analysis includes the differentiation of electron-donating and nondonating vinyl monomers and two metal centers with regard to the ionic radius (yttrium and lutetium). In addition, highly nucleophilic alkyl initiators are compared with electron-donating heteroaromatic initiators.