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No Apparent Correlation of kp with Steric Hindrance for Branched Acrylates
Authors:Katrin B. Kockler  Alexander P. Haehnel  Friederike Fleischhaker  Maria Schneider‐Baumann  Andrea M. Misske  Christopher Barner‐Kowollik
Affiliation:1. Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany;2. Institut für Biologische Grenzfl?chen, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany;3. Adolphe Merkle Institute, University of Fribourg, Fribourg, Switzerland;4. BASF SE, Registered Office, Ludwigshafen, Germany
Abstract:
The Arrhenius parameters of the propagation rate coefficient, kp, are determined via the pulsed laser polymerization—size exclusion chromatography (PLP‐SEC) method for five branched acrylates (tert‐butyl (tBA), isobornyl (iBoA), benzyl (BnA), 2‐ethylhexyl (EHA), and 2‐propylheptyl acrylate (PHA)) in 1 m solution in butyl acetate (BuAc) to complete the series, published by Haehnel et al. in 2014, of branched acrylates (isononyl (INA‐A), tridecyl (TDA‐A and TDN‐A), heptadecyl (C17A), and henicosyl acrylate (C21A)) in solution that do not show a trend in kp. Furthermore, the propagation rate coefficients of the branched acrylates in 1 m solution are critically compared with the branched acrylates in bulk as well as branched methacrylates. A summary of the trends and family‐type behavior for the linear and branched (meth)acrylates as well as methacrylates with cyclic ester side chains is provided. For the branched acrylates in 1 m solution, no clear trends of the propagation rate coefficients, kp, or Arrhenius parameters A and EA are detectable and—in contrast to the corresponding methacrylates—there is no family‐type behavior observed in solution as well as in bulk.
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Keywords:Arrhenius parameters  free radical polymerization  kinetic studies  PLP‐SEC  propagation rate coefficient
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