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The Mechanism and Thermodynamic Studies of CMRP: Different Control Mechanisms Demonstrated by Co II (TMP), Co II (salen*), and Co II (acac) 2 Mediated Polymerization, and the Correlation of Reduction Potential, Equilibrium Constant, and Control Mechanism
Author(s) -
Wang FuSheng,
Yang TsungYao,
Hsu ChingChun,
Chen YaJo,
Li MingHan,
Hsu YuJie,
Chuang MinChieh,
Peng ChiHow
Publication year - 2016
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201500311
Subject(s) - chemistry , cobalt , equilibrium constant , polymerization , polymer chemistry , cobalt mediated radical polymerization , medicinal chemistry , radical polymerization , polymer , inorganic chemistry , organic chemistry
The mechanism study of cobalt mediated radical polymerization (CMRP) is performed with Co II (TMP), Co II (salen*), and Co II (acac) 2 at 60 °C to demonstrate that the control of vinyl acetate radical polymerization is achieved via a degenerative transfer pathway when Co II (TMP) and Co II (salen*) are used but via a reversible termination process with equilibrium constant (K eq ) equal to 1.4 × 10 6 m −1 when Co II (acac) 2 is the mediator. Given by the measured K eq in CMRP with varied cobalt complexes and the reduction potential (E 1/2 ) of the corresponding cobalt complexes, a linear correlation between log(K eq ), and E 1/2 is found and can be used to estimate the K eq of other CMRP systems. With the enriched database of K eq values, the control mechanisms of CMRP are quantitatively defined by Co II /Co III equilibrium constant. The connection of reduction potential, equilibrium constant, and control mechanism would contribute to the in‐depth understanding of CMRP process.