Kinetic studies on the polymerization of 1.3‐dioxolane catalyzed by triethyl oxonium tetrafluoroborate

The kinetics of the polymerization of 1.3‐dioxolane with triethyl oxonium tetrafluoroborate has been studied in methylene chloride solution. The polymerization was preceded by an induction period. The addition of water to the system prolonged the induction period and decreased both rate of polymerization and molecular weight of the polymer. The induction period was found to be proportional to reciprocal of the initial catalyst concentration but to be independent of initial monomer concentration. Therefore it would appear that the induction period is mainly due to a reaction of the catalyst with water. A near linear relationship between the degree of polymerization and the conversion suggested that the polymerization proceeds essentially without termination and chain transfer reactions to an equilibrium conversion in the absence of water. The rate constant of propagation was estimated to be 4.3·10 −2 l./ mole sec in methylene chloride at 30°C.