Ubiquitous Nature of Rate Retardation in Reversible Addition-Fragmentation Chain Transfer Polymerization
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Description
Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most powerful reversible deactivation radical polymerization (RDRP) processes. Rate retardation is prevalent in RAFT and occurs when polymerization rates deviate from ideal conventional radical polymerization kinetics. Herein, we explore beyond what was initially thought to be the culprit of rate retardation: dithiobenzoate chain transfer agents (CTA) with more active monomers (MAMs). Remarkably, polymerizations showed that rate retardation occurs in systems encompassing the use of trithiocarbonates and xanthates CTAs with varying monomeric activities. Both the simple slow fragmentation and intermediate radical termination models show that retardation of all these systems can be described by using a single relationship for a variety of monomer reactivity and CTAs, suggesting rate retardation is a universal phenomenon of varying severity, independent of CTA composition and monomeric activity level.
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| ID Code: | 229131 | ||
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| Item Type: | Contribution to Journal (Journal Article) | ||
| Refereed: | Yes | ||
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| Additional Information: | Funding Information: This work was partially supported by the National Science Foundation under Grant No. (DMR- 1749730) to D.K. for supporting polymerization experiments and scaling law development; 400 MHz NMR instrumentation at Miami University is supported through funding from the National Science Foundation under grant number (CHE-1919850). D.K. acknowledges equipment support from Miami University through startup funding and the Robert H. and Nancy J. Blayney Professorship. A.A. gratefully acknowledges ETH Zurich for aid in designing reaction conditions. C.B.-K. acknowledges the Australian Research Council (ARC) for funding to aid kinetic analysis in the context of a Laureate Fellowship as well as the Queensland University of Technology (QUT) for continued support, including through its Centre for Materials Science. | ||
| Measurements or Duration: | 9 pages | ||
| DOI: | 10.1021/jacs.1c08654 | ||
| ISSN: | 0002-7863 | ||
| Pure ID: | 107333929 | ||
| Divisions: | Current > Research Centres > Centre for Materials Science Current > Research Centres > Centre for a Waste Free World Current > QUT Faculties and Divisions > Faculty of Science Current > Schools > School of Chemistry & Physics |
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| Funding Information: | This work was partially supported by the National Science Foundation under Grant No. (DMR- 1749730) to D.K. for supporting polymerization experiments and scaling law development; 400 MHz NMR instrumentation at Miami University is supported through funding from the National Science Foundation under grant number (CHE-1919850). D.K. acknowledges equipment support from Miami University through startup funding and the Robert H. and Nancy J. Blayney Professorship. A.A. gratefully acknowledges ETH Zurich for aid in designing reaction conditions. C.B.-K. acknowledges the Australian Research Council (ARC) for funding to aid kinetic analysis in the context of a Laureate Fellowship as well as the Queensland University of Technology (QUT) for continued support, including through its Centre for Materials Science. | ||
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| Copyright Owner: | 2021 American Chemical Society | ||
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| Deposited On: | 29 Mar 2022 03:13 | ||
| Last Modified: | 19 Jul 2024 12:04 |
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