Fast living cationic polymerization of vinyl ethers with iron(III) chloride in the presence of a cyclic ether: Most active and environmentally benign catalyst for the living cationic polymerization of vinyl ethers

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Abstract

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The fast living cationic polymerization of isobutyl vinyl ether was demonstrated with FeCl3 as a Lewis acid catalyst in the presence of a cyclic ether. The reaction was completed in 15 s even under mild conditions and was 5 or 1000 times faster than the reaction with SnCl4 or EtAlCl2, respectively, in the presence of 1,4-dioxane. The faster reaction was attributed to the superior ability of FeCl3 to extract Cl in comparison with the other two acids. In addition, the molecular weight distributions of the product polymers were invariably very narrow (weight-average molecular weight/number-average molecular weight < 1.1). Through the reduction of the basicity of a cyclic ether (e.g., 1,3-dioxolane), ultrafast living polymerization (97% in 3 s) was achieved.

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