Abstract
AbstractThis work deals with the cationic ring‐opening polymerization of a cyclic thiocarbonate, 5,5‐dimethyl‐1,3‐dioxane‐2‐thione (1). The polymerization was carried out with 2 mol% of trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, boron trifluoride etherate, or triethyloxonium tetrafluoroborate as an initiator to afford the polythiocarbonate with the narrow molecular weight distribution (Mn = 11200‐31000, Mw/Mn = 1.04‐1.15). The molecular weight of the obtained polymer could be controlled by the feed ratio of the monomer to the initiator and increased when the second monomer was added to the polymerization mixture after quantitative consumption of 1 in the first stage, supporting that the cationic ring‐opening polymerization of 1 proceeded via a living process.
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