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Ubiquitous Nature of Rate Retardation in Reversible Addition–Fragmentation Chain Transfer Polymerization

Year: 2021
Type: article
Abstract: 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.
DOI: 10.1021/jacs.1c08654
Authors: Kate G. E. Bradford, Leilah M. Petit, Richard Whitfield, Athina Anastasaki, Christopher Barner-Kowollik, Dominik Konkolewicz
Language: English
Field: Chemistry
Open Access status: green
Funders: National Science Foundation, University of Miami, Queensland University of Technology, Eidgenössische Technische Hochschule Zürich, Australian Research Council, Division of Materials Research, Division of Chemistry
Awards: G3745203787, G4448408980, G5210186636, G7196358480, MRI: Acquisition of a 400 MHz Nuclear Magnetic Resonance (NMR) Spectrometer at Miami University, G7834648152, CAREER: Dynamic Polymer Materials with Advanced Polymer Architecture and Carbon Nanotube Reinforcements
OpenAlex ID: W3205397113
FWCI: 4.46
Cites: 51
Cited by: 65
Related to: 10