Critically Evaluated Rate Coefficients in Radical Polymerization – 8. Propagation Rate Coefficients for Vinyl Acetate in Bulk. Issue 1 (26th September 2016)

• Record Type: Journal Article
• Authors: Barner‐Kowollik, Christopher; Beuermann, Sabine; Buback, Michael; Hutchinson, Robin A.; Junkers, Thomas; Kattner, Hendrik; Manders, Bart; Nikitin, Anatoly N.; Russell, Gregory T.; van Herk, Alex M.
• Is Part Of: Macromolecular chemistry and physics. Volume 218:Issue 1(2017:Jan.)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2016-09-26
• Subjects: kinetics -- pulsed laser polymerization -- radical polymerization -- vinyl acetate; Polymers -- Periodicals; Polymerization -- Periodicals; Synthetic products -- Periodicals; Macromolecules -- Periodicals; 547.7
• DOI: 10.1002/macp.201600357
• Languages: English
• ISSNs: 1022-1352

Abstract

Abstract : Propagation rate coefficient values, k p, reported by several groups for radical polymerization of bulk vinyl acetate are critically evaluated. All data are obtained by the combination of pulsed‐laser polymerization and subsequent polymer analysis by size exclusion chromatography, as recommended by the IUPAC Working Party on Modeling of Polymerization Kinetics and Processes. Although a small (≈15%) increase in k p is observed as laser pulse repetition rate is increased from low (25–100 Hz) to high (300–500 Hz) values, all of the data fulfill the required consistency criteria and thus are combined into a benchmark set covering the temperature range of 5–70 °C. The data are fitted well by an Arrhenius relation resulting in a pre‐exponential factor of 1.35 × 10 7 L mol −1 s −1 and an activation energy of 20.4 kJ mol −1, with 95% confidence ellipsoids for the parameters also presented. Abstract : A benchmark data set of k p values for bulk vinyl acetate is compiled by the IUPAC Working Party on Modeling of Polymerization Kinetics and Processes from six independent pulsed‐laser polymerization studies. The resulting best‐fit Arrhenius parameters provide a firm basis for further kinetic and modeling studies of this important monomer.