No Apparent Correlation of kp with Steric Hindrance for Branched Acrylates. Issue 14 (12th June 2015)

• Record Type: Journal Article
• Authors: Kockler, Katrin B.; Haehnel, Alexander P.; Fleischhaker, Friederike; Schneider‐Baumann, Maria; Misske, Andrea M.; Barner‐Kowollik, Christopher
• Is Part Of: Macromolecular chemistry and physics. Volume 216:Issue 14(2015:Jul.)
• Page Start: 1573
• Page End: 1582
• Publication Date: 2015-06-12
• Subjects: Polymers -- Periodicals; Polymerization -- Periodicals; Synthetic products -- Periodicals; Macromolecules -- Periodicals; 547.7
• DOI: 10.1002/macp.201500140
• Languages: English
• ISSNs: 1022-1352

Abstract

<abstract abstract-type="main" xml:lang="en"> <title> <x xml:space="preserve">Abstract</x> </title> <p>The Arrhenius parameters of the propagation rate coefficient, <italic>k</italic><sub>p</sub>, are determined via the pulsed laser polymerization—size exclusion chromatography (PLP‐SEC) method for five branched acrylates (<italic>tert</italic>‐butyl (tBA), isobornyl (<italic>i</italic>BoA), benzyl (BnA), 2‐ethylhexyl (EHA), and 2‐propylheptyl acrylate (PHA)) in 1 <sc>m</sc> 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 <italic>k</italic><sub>p</sub>. Furthermore, the propagation rate coefficients of the branched acrylates in 1 <sc>m</sc> 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 <sc>m</sc> solution, no clear trends of the propagation rate coefficients, <italic>k</italic><sub>p</sub>, or Arrhenius parameters <italic>A</italic> and <italic>E</italic><sub>A</sub> are detectable and—in contrast to the corresponding methacrylates—there is no family‐type behavior observed in solution as well as in bulk.<graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgj22d5jqsj" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></p> </abstract>