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Investigating Cu(0)‐Mediated Polymerizations: New Kinetic Insights Based on a Comparison of Kinetic Modeling with Experimental Data
Author(s) -
Haehnel Alexander P.,
Fleischmann Sven,
Hesse Pascal,
Hungenberg KlausDieter,
BarnerKowollik Christopher
Publication year - 2013
Publication title -
macromolecular reaction engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 32
eISSN - 1862-8338
pISSN - 1862-832X
DOI - 10.1002/mren.201200030
Subject(s) - kinetic energy , kinetics , polymer , thermodynamics , polymerization , chemistry , offset (computer science) , materials science , polymer chemistry , physics , organic chemistry , computer science , quantum mechanics , programming language
A kinetic model is developed mimicking experimental results obtained via detailed kinetic investigation of Cu 0 ‐mediated LRP processes of butyl acrylate in variable solvents at 50 °C. In all polymerizations, a pronounced offset in the $\overline {M} _{{\rm n}} $ versus conversion profile is observed. The kinetic modeling predicts that conventional FRP is responsible for a high molecular weight fraction of terminated polymer. The initial $\overline {M} _{{\rm n}} $ offset is congruent with a relatively slow establishment of the controlling equilibrium. Kinetic modeling and experiments demonstrate that the conversion versus time data cannot be adequately described by a first‐order kinetic analysis. For selected rate coefficients ( k a , k d , and k dis_cu ) a range is assigned, which affords a well controlled polymerization.