Critically evaluated propagation rate coefficients for radical polymerizations: acrylates and vinyl acetate in bulk (IUPAC Technical Report)

Arrhenius parameters capturing the temperature dependence of radical polymerization propagation rate coefficients, k(p), for methyl acrylate, butyl acrylate, and vinyl acetate in bulk are reported, based on the fitting of benchmark data sets compiled from independent laboratories using the pulsed-laser polymerization/size exclusion chromatography method. The reported k(p) values for acrylates hold for secondary-radical propagation and are needed to calculate effective propagation rate coefficients in situations where there is a significant population of mid-chain acrylate radicals resulting from backbiting, as will be the case at technically relevant temperatures. The results are compared to those previously reported for styrene and methacrylates to highlight the large differences in k(p) values seen between the major monomer families.