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 (k(p)) 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 k(p) value was obtained by the RSP-SEC method in the low temperature range of 9-30degreesC and was compared with the value obtained previously by the pulse laser polymerization-SEC method (PLP-SEC). The k(p) value obtained by the RSP-SEC method in the range of 9-30degreesC were in good agreement with the Arrhenius equation with A = 2.20 x 10(8) L mol(-1) s(-1), E-a = 27.4 kJ mol(-1) determined previously by the PLP-SEC method in the range of 30-70degreesC. The solvent effects on kp were also studied and the results were discussed in terms of a growing radical-solvent interaction.