Abstract
Cationic copolymerization of 1,3-dioxolane (DOL) with tetrahydrofuran (THF) was carried out in chloroform at 0°C with methyl fluorosulfate (CH3OSO2F) and triethyloxonium tetrafluoroborate (Et3OBF4) as initiators. The gas chromatographic determination of the residual monomers during the copolymerization revealed that both DOL and THF were consumed concurrently from the initial stage of the polymerization with CH3OSO2F. With Et3OBF4, on the other hand, only THF was consumed at first, followed by the rapid consumption of DOL after an induction period. The fractionation of the reaction products and the microstructural analysis by 1H and 13C NMR spectroscopy showed that the products obtained with CH3OSO2F were real copolymers containing an appreciable ammount of cross-over diads, while those with Et3OBF4 were block copolymers and/or mixtures of homopolymers. The structures and reactivities of the growing species in these two copolymerization systems are discussed on the basis of these findings.
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Yokoyama, Y., Okada, M. & Sumitomo, H. Cationic Copolymerization of 1,3-Dioxolane with Tetrahydrofuran Initiated with Methyl Fluorosulfate. Polym J 11, 629–639 (1979). https://doi.org/10.1295/polymj.11.629
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DOI: https://doi.org/10.1295/polymj.11.629