Propagation rate coefficients of isobornyl acrylate, tert-butyl acrylate and 1-ethoxyethyl acrylate: A high frequency PLP-SEC study

Bart Dervaux, Thomas Junkers, Maria Schneider-Baumann, Filip E. Du Prez, Christopher Barner-Kowollik

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Abstract

Pulsed laser polymerization (PLP) coupled to size exclusion chromatography (SEC) is considered to be the most accurate and reliable technique for the determination of absolute propagation rate coefficients, kp. Herein, kp data as a function of temperature were determined via PLP-SEC for three acrylate monomers that are of particular synthetic interest (e.g., for the generation of amphiphilic block copolymers). The high-Tg monomer isobornyl acrylate (iBoA) as well as the precursor monomers for the synthesis of hydrophilic poly(acrylic acid), tert-butyl acrylate (tBuA), and 1-ethoxyethyl acrylate (EEA) were investigated with respect to their propagation rate coefficient in a wide temperature range. By application of a 500 Hz laser repetition rate, data could be obtained up to a temperature of 80 °C. To arrive at absolute values for kp, the Mark-Houwink parameters of the polymers have been determined via on-line light scattering and viscosimetry measurements. These read: K = 5.00 × 105 dL g-1, α = 0.75 (piBoA), K = 19.7 × 105 dL g-1, a = 0.66 (ptBA) and K = 1.53 × 105 dL g-1, α = 0.85 (pEEA). The bulky iBoA monomer shows the lowest propagation rate coefficient among the three monomers, while EEA is the fastest. The activation energies and Arrhenius factors read: (iBoA): log(A/L mol-1 s -1) = 7.05 and EA = 17.0 kJ mol-1; (tBuA): log(A/L mol-1 s-1) = 7.28 and EA = 17.5 kJ mol-1 and (EEA): log(A/L mol-1 s-1) = 6.80 and EA = 13.8 kJ mol -1.

Original languageEnglish
Pages (from-to)6641-6654
Number of pages14
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume47
Issue number23
DOIs
Publication statusPublished - 1 Dec 2009
Externally publishedYes

Keywords

  • 1-ethoxyethyl acrylate
  • Activation energy
  • High frequency pulsed laser polymerization (PLP)
  • Isobornyl acrylate
  • Kinetics (polym.)
  • Liquid chromatography
  • Propagation rate coefficient
  • Size exclusion chromatography (SEC)
  • Tert-butyl acrylate

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