NMR Analysis of Thermally‐Oxidized Hydroxyl‐Terminated Polybutadiene (HTPB)

Abstract

Nuclear magnetic resonance spectroscopy was employed to monitor the change in chemical structures, olefin units (cis, trans and vinyl) and hydroxyl value on stabilized Hydroxyl‐terminated polybutadiene (HTPB) under accelerated ageing condition. Thermal ageing of HTPB was carried out at 65 °C for 10‐weeks and periodically withdrawn sample for NMR analysis. 1H and 13C NMR spectroscopy provided detailed structural information for all HTPB samples, including the quantification of olefin units and the determination of hydroxyl value. The analysis revealed a decrease in signal intensity, particularly for the olefin near or at the molecular end, suggesting that they were oxidized before those in the middle position within the chain. The quantitative assessment of olefin units indicates a slight decrease of 2 % in 1,2‐vinyl unit after 10‐weeks of ageing. The NMR spectra did not show any detectable signals corresponding to epoxides, peroxides or alcohols in any HTPB samples. However, a slight increase in the OH value was observed after 8 and 10 weeks of ageing, suggesting the possible incorporation of new hydroxyl groups due to thermal‐oxidation. The antioxidants used to stabilize HTPB exhibited limited effectiveness in preventing degradation reactions, even after 4 weeks of ageing at 65 °C.