Determination of Propagation Rate Coefficient of Free-Radical Polymerization of N-Vinylcarbazole by Pulsed-Laser Polymerization

Abstract

Pulsed-laser polymerization in conjunction with molecular weight distribution measurement was adopted for determining the propagation rate coefficient kp in the free radical solution polymerization of N-vinylcarbazole (VCZ). A photoinitiator which absorbs up to ca. 410 nm was selected to exclude the excitation of VCZ. We measured the effects of light intensity, pulse frequency and the concentration of VCZ on the rate coefficients. The value kp=4.16×103 L mol−1 s−1 was obtained in benzene at 30°C. The values of kp were well fitted by the Arrhenius equation in the range of 30–70°C. The values evaluated by using the non-linear least-squares fitting for determination of Arrhenius parameters were A=2.20×108 L mol−1 s−1 and EA=27.4 kJ mol−1. We obtained the 95% joint confidence interval for the Arrhenius parameters.