ABSTRACT Polybutadiene elastomers are versatile materials, being employed at several applications from rocket propellant binder to adhesives and sealants. The elastomers derived from hydroxyl-terminated polybutadiene are usually stabilised with antioxidants to prevent degradation. In this study, a comparative assessment among 2,2’-methylene-bis (4-methyl-6-tert-butylphenol) (AO2246), 2,6-di-tert-butyl-4-methylphenol (BHT), p-phenylenediamine (pPDA), and triphenylphosphine (TPP) regarding stabilisation of hydroxyl-terminated polybutadiene binder under accelerated ageing (six months at 65 °C) was carried out. Evaluation of antioxidants effectiveness was examined through Oxidation Induction Time, sol/gel extraction, swelling and mechanical testing, dynamic mechanical analysis, and mass variation measurement. AO2246 yielded the best performance, meanwhile BHT was poorly protective. TPP acted as prooxidant, causing a severe degradation of the binder, and pPDA was not manageable to be assessed due to the lower curing degree of the resulted polyurethane.

Thermal aging of hydroxy-terminated polybutadiene/isophorone diisocyanate (HTPB/IPDI)-based polyurethane was studied as a function of NCO/OH ratio (1.0 and 0.85). Samples were aged in air ovens at 50, 60, 65, and 70 ºC for periods of time from 1 to 34 weeks. Changes in chemical (swelling testing and FT-IR spectroscopy) and mechanical (tension testing and hardness) properties were evaluated throughout the aging assays. Correlation between equilibrium swelling ratio and elastic modulus, coupled with changes in FT-IR spectra, indicated oxidative cross-linking as the dominant mechanism for both molar ratios investigated. However, determination of Arrhenius activation energy resulted in values of (82 ± 10) kJ.mol-1 and (156 ± 30) kJ.mol-1 for 1.0 and 0.85 NCO/OH ratios, respectively, thus revealing faster oxidative degradation kinetics for higher urethane linkage networks.

Abstract: Thermal aging of hydroxy-terminated polybutadiene (HTPB) stabilized with 2,6-di(tert-butyl)hydroxytoluene (BHT) was carried out at 60ºC from 1 to 11 weeks. Samples of 200 mL were stored in sealed 500-mL Erlenmeyer flasks under atmospheric pressure or vacuum and periodically withdrawn for physical and chemical analysis, infrared spectroscopy characterization and measurement of HTPB/IPDI (isophorone diisocyanate) reactivity, expressed as pot life. Mechanical properties of the cured polyurethane, prepared from aged HTPB, were assayed by uniaxial tension tests. Despite the unchanged chemical structure, an increase in HTPB/IPDI binder reactivity was observed, being correlated with BHT depletion measured as color change (yellowing). Aging of HTPB showed no interference on mechanical properties of the cured polyurethane.