Wilding, C.Y.P. orcid.org/0000-0002-2441-9741, Knox, S.T. orcid.org/0000-0001-5276-0085, Bourne, R.A. orcid.org/0000-0001-7107-6297 et al. (1 more author) (2023) Development and Experimental Validation of a Dispersity Model for In Silico RAFT Polymerization. Macromolecules, 56 (4). pp. 1581-1591. ISSN 0024-9297
Abstract
The exploitation of computational techniques to predict the outcome of chemical reactions is becoming commonplace, enabling a reduction in the number of physical experiments required to optimize a reaction. Here, we adapt and combine models for polymerization kinetics and molar mass dispersity as a function of conversion for reversible addition fragmentation chain transfer (RAFT) solution polymerization, including the introduction of a novel expression accounting for termination. A flow reactor operating under isothermal conditions was used to experimentally validate the models for the RAFT polymerization of dimethyl acrylamide with an additional term to accommodate the effect of residence time distribution. Further validation is conducted in a batch reactor, where a previously recorded in situ temperature monitoring provides the ability to model the system under more representative batch conditions, accounting for slow heat transfer and the observed exotherm. The model also shows agreement with several literature examples of the RAFT polymerization of acrylamide and acrylate monomers in batch reactors. In principle, the model not only provides a tool for polymer chemists to estimate ideal conditions for a polymerization, but it can also automatically define the initial parameter space for exploration by computationally controlled reactor platforms provided a reliable estimation of rate constants is available. The model is compiled into an easily accessible application to enable simulation of RAFT polymerization of several monomers.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2023 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 17 Oct 2023 12:39 |
Last Modified: | 17 Oct 2023 12:39 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.macromol.2c01798 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:204256 |