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
Author:
Brüggemann Daniel12ORCID, Machat Martin R.23ORCID, Schomäcker Reinhard1ORCID, Heshmat Mojgan3
Affiliation:
1. Institut für Chemie—Technische Chemie, Technische Universität Berlin, Straße des 17. Juni 124, D-10623 Berlin, Germany 2. Covestro Deutschland AG, Kaiser-Wilhelm-Alle 60, D-51373 Leverkusen, Germany 3. Institute of Technical and Macromolecular Chemistry, CAT Catalytic Center, RWTH Aachen Universität, Worringerweg 2, D-52074 Aachen, Germany
Abstract
The production of CO2-containing polymers is still very demanding in terms of controlling the synthesis of products with pre-defined CO2 content and molecular weight. An elegant way of synthesising these polymers is via CO2-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. In this work, using DFT-metadynamics simulations for exploiting the potential of the polymerisation process, we aim to shed more light on the mechanisms of the interaction between catalysts (in particular, the catalysts K3VO4, K3PO4, and Na2SnO3) and the cEC monomer in the propagation step of the polymeric chain and the occurring CO2 release. Confirming the simulation results via subsequent kinetics measurements indicates that, depending on the catalyst’s characteristics, it can be attached reversibly to the polymeric chain during polymerisation, resulting in a defined lifetime of the activated polymer chain. The second anionic oxygen of the catalyst can promote the catalyst’s transfer to another electrophilic cEC monomer, terminating the growth of the first chain and initiating the propagation of the new polymer chain. This transfer reaction is an essential step in controlling the molecular weight of the products.
Funder
RWTH-HPC BMBF Federal Ministry of Education and Research
Subject
Polymers and Plastics,General Chemistry
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