Pulsed‐laser polymerization (PLP) has been adopted by IUPAC as the method of choice for the determination of propagation rate constants (kp). However, the method has failed in the polymerization of alkyl acrylates at temperatures above 30 °C. In this work, the PLP experiments were analyzed by simulation using a Monte Carlo algorithm. It was found that the experimental difficulties encountered to accurately determine kp at temperatures above 30 °C were caused by extensive intramolecular chain transfer. This mechanism is not operative at lower temperatures because of its high activation energy.
Pulsed‐laser polymerization of BA in bulk at temperatures between −41 and +40 °C: Simulated MWD trace.
