Abstract
The kinetics of the polymerization of 3-methyl-3-chloromethyloxetane with the i-Bu3Al–H2O catalyst system and the molecular-weight characteristics of the resulting polymer have been investigated. The main feature of this process is the ability for self-regulation of the size of the macromolecules with the formation of a polymer of high molecular weight (∼106) and narrow molecular-weight distribution (Mw/Mn=1.30±0.05) which do not depend on conversion and initial monomer and catalyst concentrations. A kinetic scheme for the polymerization involves a slow initiation stage, rapid propagation via the preliminary stage of monomer complexation with active centres, spontaneous monomolecular termination as a result of intramolecular interaction of the active centre with a fragment of its own polymer chain and the inhibition stage due to the deactivation of the unconsumed catalyst by the polymer. The mathematical description of this scheme enabled us to calculate the rate constants for elementary reactions of the process at 20°C: the propagation-rate constant is (1.9±0.3)×103 min−1; the initiation-rate constant is (6.9±0.3)×104 l mol−1 min−1 and the termination-rate constant is (0.16±0.02) min−1.
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Aleksiuk, G., Shamanin, V., Podolsky, A. et al. Polymerization of Oxetanes with Organoaluminium Catalysts. I. Kinetics of the Polymerization of 3-Methyl-3-chloromethyloxetane with the i-Bu3Al–H2O Catalyst System. Polym J 13, 23–31 (1981). https://doi.org/10.1295/polymj.13.23
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DOI: https://doi.org/10.1295/polymj.13.23