Effect of the Intramolecular Chain Transfer to Polymer on PLP/SEC Experiments of Alkyl Acrylates

Pulsed‐laser polymerization (PLP) has been adopted by IUPAC as the method of choice for the determination of propagation rate constants ( k p ). 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 k p 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. image Pulsed‐laser polymerization of BA in bulk at temperatures between −41 and +40 °C: Simulated MWD trace.