Controlled cationic polymerization of furfuryl alcohol

► Furfuryl alcohol was polymerized with BzBr-CuCl/PMDETA in acetonitrile at 110 °C. ► Polymerization showed the characteristics of a controlled polymerization. ► A soluble polymer with Mn 6600 g/mol was obtained before crosslinking. ► Carbonyl groups and CH2OCH2 bridges are formed on poly(furfuryl alcohol) chains. ► A polymerization mechanism proceeding via HBr formation is proposed.