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Propagation rate coefficient (kp) data for radical polymerization of methyl acrylate (MA) in the bulk are critically evaluated and a benchmark dataset is put forward by a task-group of the IUPAC Subcommittee on Modeling of Polymerization Kinetics and Processes. This dataset comprises previously published results from three laboratories as well as new data from a fourth laboratory. Not only do all these values of kp fulfill the recommended consistency checks for reliability, they are also all in excellent agreement with each other. Data have been obtained employing the technique of pulsed-laser polymerization (PLP) coupled with molar-mass determination by size-exclusion chromatography (SEC), where PLP has been carried out at pulse-repetition rates of up to 500 Hz, enabling reliable kp to be obtained through to 60 °C. The best-fit – and therefore recommended – Arrhenius parameters are activation energy EA = 17.3 kJ mol−1 and pre-exponential (frequency) factor A = 1.41 × 107 L mol−1 s−1. These hold for secondary-radical propagation of MA, and may be used to calculate effective propagation rate coefficients for MA in situations where there is a significant population of mid-chain radicals resulting from backbiting, as will be the case at technically relevant temperatures. The benchmark dataset reveals that kp values for MA obtained using PLP in conjunction with MALDI-ToF mass spectrometry are accurate. They also confirm, through comparison with previously obtained benchmark kp values for n-butyl acrylate, methyl methacrylate and n-butyl methacrylate, that there seems to be identical family-type behavior in n-alkyl acrylates as in n-alkyl methacrylates. Specifically, kp for the n-butyl member of each family is about 20% higher than for the corresponding methyl member, an effect that appears to be entropic in origin. Furthermore, each family is characterized by an approximately constant EA, where the value is 5 kJ mol−1 lower for acrylates.

Critically evaluated rate coefficients in radical polymerization – 7. Secondary-radical propagation rate coefficients for methyl acrylate in the bulk