Summary: Propagation rate coefficients, kp, for free-radical polymerization of butyl acrylate (BA) previously reported by several groups are critically evaluated. All data were determined by the combination of pulsed-laser polymerization (PLP) and subsequent polymer analysis by size exclusion (SEC) chromatography. The PLP-SEC technique has been recommended as the method of choice for the determination of kp by the IUPAC Working Party on Modeling of Polymerization Kinetics and Processes. Application of the technique to acrylates has proven to be very difficult and, along with other experimental evidence, has led to the conclusion that acrylate chain-growth kinetics are complicated by intramolecular transfer (backbiting) events to form a mid-chain radical structure of lower reactivity. These mechanisms have a significant effect on acrylate polymerization rate even at low temperatures, and have limited the PLP-SEC determination of kp of chain-end radicals to low temperatures (<20 °C) using high pulse repetition rates. Nonetheless, the values for BA from six different laboratories, determined at ambient pressure in the temperature range of −65 to 20 °C mostly for bulk monomer with few data in solution, fulfill consistency criteria and show excellent agreement, and are therefore combined together into a benchmark data set. The data are fitted well by an Arrhenius relation resulting in a pre-exponential factor of 2.21 × 107 L · mol−1 · s−1 and an activation energy of 17.9 kJ · mol−1. It must be emphasized that these PLP-determined kp values are for monomer addition to a chain-end radical and that, even at low temperatures, it is necessary to consider the presence of two radical structures that have very different reactivity. Studies for other alkyl acrylates do not provide sufficient results to construct benchmark data sets, but indicate that the family behavior previously documented for alkyl methacrylates also holds true within the alkyl acrylate family of monomers.
Arrhenius plot of propagation rate coefficients, kp, for BA as measured by PLP-SEC.