Chapter Three - Exploiting the pulsed laser polymerization-size exclusion chromatography technique to retrieve kinetic parameters in radical polymerization: State-of-the-art and future challenges.

Pulsed laser polymerization (PLP) has emerged as a leading technique to determine radical polymerization characteristics. Here we present a concise overview of the potential of this polymerization technique mainly in combination with size exclusion chromatography (SEC) analysis. Focus is not only on the traditional determination of intrinsic propagation reactivities for radical polymerizations with one dominant macroradical type based on inflection point data but also on (i) the determination of such intrinsic reactivities if multiple dominant radical types are present (e.g. , for radical polymerization with branch formation and copolymerization); and (ii) the exploitation of the complete SEC trace to obtain information on the quantum yield, chain initiation and (apparent) termination reactivity. General guidelines are provided how to increase the accuracy of PLP-SEC measurements and to combine such measurements with advanced kinetic modeling and ab initio calculations to further increase our understanding of radical polymerization chemistry and to construct chemical structure-reactivity relationships. [ABSTRACT FROM AUTHOR]