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• W2066136262 endingPage "2028" @default.
• W2066136262 startingPage "2023" @default.
• W2066136262 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." @default.
• W2066136262 created "2016-06-24" @default.
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• W2066136262 date "2014-10-30" @default.
• W2066136262 modified "2023-10-12" @default.
• W2066136262 title "Direct Access to Dithiobenzoate RAFT Agent Fragmentation Rate Coefficients by ESR Spin-Trapping" @default.
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• W2066136262 doi "https://doi.org/10.1002/marc.201400518" @default.
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