Four different samples of ferrocene-grafted hydroxyl-terminated polybutadiene (Fc-HTPB), containing 0.20, 0.52, 0.90, and 1.50 wt % iron, were synthesized by the Friedel-Crafts alkylation of ferrocene with hydroxyl-terminated polybutadiene (HTPB) in the presence of AlCl3 as a (Lewis acid) catalyst. The effects of the reaction conditions on the extent of ferrocene substitution were investigated. The Fc-HTPBs were characterized by IR, ultraviolet-visible, H-1-NMR, and C-13-NMR spectra. The iron content and number of hydroxyl groups were estimated, and the properties, including thermal degradation, viscosity, and propellant burning rates (BRs), were also studied. The thermogravimetric data indicated two major weight loss stages around 395 and 500 degrees C. These two weight losses were due to the depolymerization and decomposition of the cyclized product, respectively, with increasing temperature. The Fc-HTPB was cured with toluene diisocyanate and isophorone diisocyanate separately with butanediol-trimethylolpropane crosslinker to study their mechanical properties. Better mechanical properties were obtained for the gumstock of Fc-HTPB polyurethanes with higher NCO/OH ratios. The BRs of the ammonium perchlorate (AP)-based propellant compositions having these Fc-HTPBs (without dilution) as a binder were much higher (8.66 mm/s) than those achieved with the HTPB/AP propellant (5.4 mm/s). (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 2517-2524, 2011