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

Hutchinson, R. and Beuermann, S.

Pure and Applied Chemistry, 2019

Volume 91, Issue 11, pp. 1883-1888

https://doi.org/10.1515/pac-2018-1108

Arrhenius parameters capturing the temperature dependence of radical polymerization propagation rate coefficients, kp, 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 kp 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 kp values seen between the major monomer families.

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