Wang F.-S.Yang T.-Y.Hsu C.-C.Chen Y.-J.Li M.-H.Hsu Y.-J.Chuang M.-C.CHI-HOW PENG2022-10-212022-10-212016https://www.scopus.com/inward/record.uri?eid=2-s2.0-84956897098&doi=10.1002%2fmacp.201500311&partnerID=40&md5=403f6f31494f1c6d51bf671b10e23b79https://scholars.lib.ntu.edu.tw/handle/123456789/623916The mechanism study of cobalt mediated radical polymerization (CMRP) is performed with CoII(TMP), CoII(salen?), and CoII(acac)2 at 60 C to demonstrate that the control of vinyl acetate radical polymerization is achieved via a degenerative transfer pathway when CoII(TMP) and CoII(salen?) are used but via a reversible termination process with equilibrium constant (Keq) equal to 1.4 ? 106 m-1 when CoII(acac)2 is the mediator. Given by the measured Keq in CMRP with varied cobalt complexes and the reduction potential (E1/2) of the corresponding cobalt complexes, a linear correlation between log(Keq), and E1/2 is found and can be used to estimate the Keq of other CMRP systems. With the enriched database of Keq values, the control mechanisms of CMRP are quantitatively defined by CoII/CoIII equilibrium constant. The connection of reduction potential, equilibrium constant, and control mechanism would contribute to the in-depth understanding of CMRP process. The control mechanisms in cobalt mediated radical polymerization (CMRP) are quantitatively defined by the CoII/CoIII equilibrium constants, which are either measured by following the cobalt concentration or derived from the reduction potentials of corresponding cobalt species using the linear correlation of log(Keq) and E1/2. The difference of control mechanisms in CMRP is demonstrated by vinyl acetate polymerization mediated by varied cobalt complexes as well. ? 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.cobalt mediated radical polymerization;controlled/living radical polymerization;degenerative transfer;reversible termination;vinyl acetateAtom transfer radical polymerization;Cobalt;Equilibrium constants;Polymerization;Polyvinyl acetates;Thermomechanical pulping process;Controlled/living radical polymerization;Degenerative transfer;In-depth understanding;Linear correlation;Reduction potential;Reversible termination;Thermodynamic studies;Vinyl acetates;Cobalt compoundsjournal article10.1002/macp.2015003112-s2.0-84956897098