Pulsed initiation polymerization as a means of obtaining propagation rate coefficients in free-radical polymerizations. II Review up to 2000

The application of the pulsed initiation polymerization technique (PIP) to determine propagation rate coefficients has evolved into a valuable tool. T he number of monomers studied has rapidly increased since 1987. Besides hom opropagation rate coefficients also copolymerizations are studied extensive ly. The calibration of the size exclusion chromatography is still a limitin g factor in studying delicate differences in reactivities, for example in f amilies of monomers like that of the methacrylates. In studying solvent eff ects in propagation, PIP is capable of disclosing even small solvent effect s, typically in the order of magnitude of plus or minus 20%. For some famil ies of monomers PIP does not result in reliable parameters. The reasons for the breakdown of the PIP technique with the acrylates are discussed.