Abstract
Thermal and photosensitized cationic polymerizations of N-vinylcarbazole (VCZ) induced by silver (I) perchlorate were investigated in benzene at 30°C. Cationic propagation was confirmed by means of the additive effect of inhibitors. The following kinetic expressions for the polymerization rate (Rp) were obtained:
For thermal polymerization:
For photopolymerization: .
In the thermal polymerization, Rp saturated with an increase in monomer concentration. The dependence of Rp of photopolymerization on monomer concentration was examined in two systems: at constant optical length and at constant optical density.
; thickness of the cell=1 cm.
; (thickness of the cell)×[VCZ]0=0.25 M cm.
Various kinetic quantities determining the degree of polymerization were calculated from the viscosity-average molecular weights of the polymers. These values are almost identical for both thermal and photosensitized systems. This suggests that propagation in these systems proceeds via the carbonium ion ion-paired with the counter anion of ClO4−.
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Asai, M., Takeda, Y., Tazuke, S. et al. Photoreactions of N-Vinylcarbazole Induced by Metal Salts. IV. Kinetic Studies of the Thermal and Photosensitized Cationic Polymerization Induced by Silver(I) Perchlorate in Benzene. Polym J 7, 359–365 (1975). https://doi.org/10.1295/polymj.7.359
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DOI: https://doi.org/10.1295/polymj.7.359