Abstract
A systematic investigation of the factors that influence cyclic oligomer formation in the polymerizations of oxetane initiated by triethyloxonium salts or ethyl trifluoromethanesulfonate is reported. In addition to the cyclic tetramer and polymer, which were previously reported, cyclic trimer was unexpectedly found. No higher cyclic oligomers were observed. Cyclic oligomer formation is a concurrent process with polymerization and not the result of a backbiting reaction with depolymerization or termination. The amount and type of cyclic oligomer obtained is very dependent on counter-ion, temperature, and solvent. Polymerizations initiated by triethyloxonium tetrafluoroborate resulted in as much as 35-% conversion to oligomer at complete conversion. Cyclic tetramer was predominant. Other oxonium salts (PF6−, SbF6−, and SbCl6−) produced insignificant conversion to cyclic oligomers. Polymerizations initiated by ethyl trifluoromethanesulfonate led to as much as 15-% cyclic oligomer, almost exclusively cyclic trimer. Below 50°C little oligomer was observed. Higher temperatures favored cyclic oligomer formation. The effect of solvent depended on the counter-ion and cyclic oligomer under consideration.
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Dreyfuss, P., Dreyfuss, M. The Formation of Cyclic Oligomers Accompanying the Polymerization of Oxetane. Polym J 8, 81–87 (1976). https://doi.org/10.1295/polymj.8.81
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DOI: https://doi.org/10.1295/polymj.8.81