Re-evaluation of Propagation Rate Coefficient of Free-Radical Polymerization of N-Vinylcarbazole by the Rotating-Sector Technique

Rotating sector polymerization in conjugation with a size exclusion chromatography (RSP–SEC) was adopted to determine the propagation rate coefficient (kp) in free radical solution polymerization of N-vinylcarbazole (VCZ). A photoinitiator whose absorption edge is up to ca. 415 nm was selected to reduce the light excitation of VCZ. The kp value was obtained by the RSP–SEC method in the low temperature range of 9–30 °C and was compared with the value obtained previously by the pulse laser polymerization–SEC method (PLP–SEC). The kp value obtained by the RSP–SEC method in the range of 9–30 °C were in good agreement with the Arrhenius equation with A=2.20×108 L mol−1 s−1, Ea=27.4 kJ mol−1 determined previously by the PLP–SEC method in the range of 30–70 °C. The solvent effects on kp were also studied and the results were discussed in terms of a growing radical–solvent interaction.