Abstract
Pulsed-laser polymerization (PLP) in conjunction with polymer analysis by size-exclusion chromatography (SEC) is the IUPAC-recommended method for measuring propagation rate coefficients, kp, of radical polymerization. Pulse repetition rate, vrep, and photoinitiator concentration need to be adjusted to the termination rate of the monomer, preferably via the quantity β, the fraction of radicals terminating prior to applying the successive laser pulse. By PREDICI simulation, the prerequisites for successful PLP-SEC work are demonstrated. Slow termination, as with fully ionized monomers, is specifically addressed. Both very high and very low vrep are not suitable for accurate kp measurements.
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