Cationic polymerization of N‐vinylcarbazole by tropylium salts at low temperatures

Abstract Cationic polymerizations of N‐vinylcarbazole (NVC) in methylene dichloride containing approximately 1% nitromethane were studied by adiabatic calorimetry at temperatures between −40 and −70°C. Tropylium salts containing AsF , SbF and SbCl counterions were used as initiators. Reaction halflives ranged from 2 to 80 seconds and first‐order plots displayed induction periods. Evidence indicated that the majority of the initiator was consumed, permitting estimation of propagation rate constants. For polymerizations involving the SbF counterion, these rate constants were found to be relatively insensitive to the concentration of initiator or excess anion and the conclusion is drawn that paired and unpaired PNVC+ SbF ions have similar reactivities at low temperatures. Correlation of the present results with those from previous work at 20 and 0°C yielded an Arrhenius exponential factor for propagation by unpaired ions of 30±9 kJ mol−1. The degree of polymerization approached the ratio [M]0/[1]0 at −70°C. At higher temperatures, molecular weights appeared to be governed by transfer reactions. The absence of significant chlorine content in polymer samples precluded the possibility of chain transfer to solvent.