https://scholars.lib.ntu.edu.tw/handle/123456789/623916
標題: | The mechanism and thermodynamic studies of CMRP: Different control mechanisms demonstrated by CoII(TMP), CoII(salen?), and CoII(acac)2 mediated polymerization, and the correlation of reduction potential, equilibrium constant, and control mechanism | 作者: | Wang F.-S. Yang T.-Y. Hsu C.-C. Chen Y.-J. Li M.-H. Hsu Y.-J. Chuang M.-C. CHI-HOW PENG |
關鍵字: | cobalt mediated radical polymerization;controlled/living radical polymerization;degenerative transfer;reversible termination;vinyl acetate | 公開日期: | 2016 | 卷: | 217 | 期: | 3 | 起(迄)頁: | 422-432 | 來源出版物: | Macromolecular Chemistry and Physics | 摘要: | The 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. |
URI: | https://www.scopus.com/inward/record.uri?eid=2-s2.0-84956897098&doi=10.1002%2fmacp.201500311&partnerID=40&md5=403f6f31494f1c6d51bf671b10e23b79 https://scholars.lib.ntu.edu.tw/handle/123456789/623916 |
DOI: | 10.1002/macp.201500311 | SDG/關鍵字: | Atom 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 compounds |
顯示於: | 化學系 |
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