We synthesized a ferrocene-based burning rate catalyst, 2-(ferrocenylpropyl) dimethylsilane (FPDS). FPDS-grafted hydroxyl-terminated polybutadiene (FPDS-g-HTPB) was synthesized using hydrosilylation with a Pt catalyst. The structures of FPDS and FPDS-g-HTPB were investigated by Fourier transform infrared spectroscopy and nuclear magnetic resonance. HTPB-based polyurethanes were prepared from HTPB, ,6-hexamethylenediisocyanate (HDI), and HDI-trimer. Polyurethane network was prepared with an (NCO)/(OH) ratio of 1.05 and an [isocyanate trimer]/[total NCO] ratio of 0.3 then subjected to accelerated aging at 80 degrees C. The thermal behaviors of the polyurethane network were compared using differential scanning calorimetry and thermal gravity analysis. The glass transition temperatures (T(g)) of HTPB and FPDS-g-HTPB were -76 degrees C and -47 degrees C, respectively. The value of T(g) for the networked polyurethane was not influenced by HDI-trimer content but by FPDS content. The decomposition temperature of the neat HTPB-based polyurethane network was lower than that of the FPDS-g-HTPB-based polyurethane networks. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 3560-3568, 2011