Direct access to dithiobenzoate RAFT agent fragmentation rate coefficients by ESR spin-trapping

Ranieri, K., Delaittre, G., Barner-Kowollik, C., & Junkers, T. (2014) Direct access to dithiobenzoate RAFT agent fragmentation rate coefficients by ESR spin-trapping. Macromolecular Rapid Communications, 35(23).

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Abstract

The β-scission rate coefficient of tert -butyl radicals fragmenting off the intermediate resulting from their addition to tert-butyl dithiobenzoate-a reversible addition-fragmentation chain transfer (RAFT) agent-is estimated via the recently introduced electron spin resonance (ESR)- trapping methodology as a function of temperature. The newly introduced ESR-trapping methodology is critically evaluated and found to be reliable. At 20 °C, a fragmentation rate coefficient of close to 0.042 s-1 is observed, whereas the activation parameters for the fragmentation reaction- determined for the first time-read EA = 82 ± 13.3 kJ mol-1 and A = (1.4 ± 0.25) × 1013 s-1. The ESR spin-trapping methodology thus efficiently probes the stability of the RAFT adduct radical under conditions relevant for the pre-equilibrium of the RAFT process. It particularly indicates that stable RAFT adduct radicals are indeed formed in early stages of the RAFT polymerization, at least when dithiobenzoates are employed as controlling agents as stipulated by the so-called slow fragmentation theory. By design of the methodology, the obtained fragmentation rate coefficients represent an upper limit. The ESR spin-trapping methodology is thus seen as a suitable tool for evaluating the fragmentation rate coefficients of a wide range of RAFT adduct radicals.(Figure Presented). © 2014 Wiley-VCH Verlag GmbH & Co. KGaA.

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ID Code: 99399
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :4
Export Date: 5 September 2016
CODEN: MRCOE
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, Germany
Chemicals/CAS: Polymers
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Keywords: Electron spin resonance, Fragmentation rate, Kinetics, Polymer reactions, Reversible addition-fragmentation chain transfer, Spin-trapping, Chains, Electrospinning, Enzyme kinetics, Free radical polymerization, Living polymerization, Magnetic moments, Paramagnetic resonance, Spin dynamics, Activation parameter, Fragmentation reactions, Fragmentation theory, Polymer Reaction, RAFT adduct radicals, Reversible addition fragmentation chain transfer (RAFT), Electron spin resonance spectroscopy, polymer, chemistry, procedures, Polymers
DOI: 10.1002/marc.201400518
ISSN: 10221336
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 28 Sep 2016 01:42

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