Controlled cationic polymerization of furfuryl alcohol

CuCl/N,N,N′,N″,N″-pentamethyldiethylenetriamine catalyst system was used successfully in the controlled cationic polymerization of furfuryl alcohol initiated with benzyl bromide in acetonitrile. Polymerizations were carried out at 110 °C open to air. The effect of reaction time, amount of initiator and solvent on the rate of polymerization was studied. The linear kinetic plot of ln([M]o/[M]) versus polymerization time, linear dependence of the molecular weight on the monomer conversion and low polydispersity of the polymers (1.07–1.50) showed the characteristics of the controlled polymerization. Soluble polymers with Mn up to 6.6 kg/mol were obtained. The structural analysis of the polymer was carried out by 1H NMR, 13C NMR, FTIR and UV–VIS spectroscopies. Formation of carbonyl groups and single bondCH2single bondOsingle bondCH2single bond bridges on poly(furfuryl alcohol) chains were observed. Thermal properties of the polymer were studied by DSC and TGA analyses.