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No Apparent Correlation of k p with Steric Hindrance for Branched Acrylates
Author(s) -
Kockler Katrin B.,
Haehnel Alexander P.,
Fleischhaker Friederike,
SchneiderBaumann Maria,
Misske Andrea M.,
BarnerKowollik Christopher
Publication year - 2015
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.201500140
Subject(s) - methacrylate , acrylate , arrhenius equation , steric effects , polymer chemistry , polymerization , chemistry , acrylate polymer , butyl acrylate , materials science , activation energy , organic chemistry , polymer , copolymer
The Arrhenius parameters of the propagation rate coefficient, k p , are determined via the pulsed laser polymerization—size exclusion chromatography (PLP‐SEC) method for five branched acrylates ( tert ‐butyl (tBA), isobornyl ( i BoA), 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 k p . 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, k p , or Arrhenius parameters A and E A are detectable and—in contrast to the corresponding methacrylates—there is no family‐type behavior observed in solution as well as in bulk.