Simultaneous determination of free-radical propagation and transfer rates from a novel type of PLP-SEC experiment

A novel type of pulsed laser polymerization (PLP)-size exclusion chromatography (SEC) experiment is presented in which laser pulse sequences are applied at considerable dark time intervals between each pulse package. The pulse sequences give rise to the characteristically structured molecular weight distribution (MWD) from which k(p) may be derived. Polymer produced during the extended dark time intervals determines the MWD at high molecular weights and allows for the measurement of chain transfer rates. The method by which propagation and transfer rates are accessible from one experiment is illustrated by simulations using the program package PREDICI.