Global trends for kp? Expanding the frontier of ester side chain topography in acrylates and methacrylates

Haehnel, A. P., Schneider-Baumann, M., Hiltebrandt, K. U., Misske, A. M., & Barner-Kowollik, C. (2013) Global trends for kp? Expanding the frontier of ester side chain topography in acrylates and methacrylates. Macromolecules, 46(1).

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The Arrhenius parameters of the propagation rate coefficient for two linear methacrylates, two branched methacrylates, and two branched acrylates are determined via the pulsed laser polymerization-size exclusion chromatography (PLP-SEC) method. The Mark-Houwink-Kuhn-Sakurada parameters of these polymers are additionally determined via multidetector SEC of narrowly distributed polymer samples obtained through fractionation, allowing for a correct SEC calibration in the PLP-SEC experiment. The data obtained for stearyl methacrylate (SMA, A = 3.45 (-1.17 to +4.46) × 106 L·mol-1·s-1; Ea = 21.49 (-1.59 to +1.90) kJ·mol-1) and behenyl methacrylate (BeMA, A = 2.51 (-0.80 to +3.06) × 106 L·mol-1·s -1; Ea = 20.52 (-1.43 to +1.85) kJ·mol -1) underpin the trend of increasing kp with increasing ester side chain length. Propylheptyl methacrylate (PHMA, A = 2.83 (-0.82 to 3.15) × 106 L·mol-1·s-1; Ea = 21.72 (-1.20 to +1.64) kJ·mol-1) and heptadecanyl methacrylate (C17MA, A = 2.04 (-0.66 to +1.71) × 10 6 L·mol-1·s-1; Ea = 20.72 (-1.42 to +1.38) kJ·mol-1) can be described as a family of branched methacrylates jointly with isodecyl methacrylate and ethylhexyl methacrylate (both published previously), resulting in joint Arrhenius parameters of A = 2.39 (-0.51 to +0.84) × 106 L·mol -1·s-1 and Ea = 21.16 (-0.78 to +0.76) kJ·mol-1. In addition, the corresponding branched acrylates are studied applying high-frequency PLP at a 500 Hz laser repetition rate, resulting in Arrhenius parameters of A = 1.05 (-0.42 to +2.81) × 10 7 L·mol-1·s-1 and Ea = 16.41 (-1.99 to +2.42) kJ·mol-1 for propylheptyl acrylate (PHA) and A = 8.15 (-2.83 to +10.3) × 106 L·mol -1·s-1 and Ea = 14.66 (-1.49 to +1.66) kJ·mol-1 for heptadecanyl acrylate (C17A). © 2012 American Chemical Society.

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ID Code: 99350
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :14
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany; email:
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Keywords: Arrhenius parameters, Exclusion chromatography, Global trends, High frequency HF, Laser repetition rate, Multi-detectors, Polymer samples, Propagation rate coefficient, Side chain lengths, Side-chains, Stearyl methacrylate, Esterification, Esters, Lasers, Polymers, Salts
DOI: 10.1021/ma302319z
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 29 Sep 2016 22:48

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