HTPB Heat of Formation: Literature Survey, Group Additive Estimations, and Theoretical Effects

Hydroxyl-terminated polybutadiene (HTPB) is a common ingredient in rocket propellants, but its thermochemical properties (composition, density, and heat of formation) are not well defined. A survey of the literature and thermochemical databases indicated wide ranges for these properties, especially heat of formation. Six group additive schemes were used to estimate the heat of formation of HTPB and analyze the effects of hydroxyl functionalization and curing reactions. Good agreement is observed between the methods for HTPB isomer units, but cumulative differences result in significant disparities for larger, practical polymers. Increased hydroxyl functionality and the curing reaction are predicted to yield nonnegligible decreases in the heat of formation. The heat of formation of propellant-grade, isophorone-diisocayante-cured HTPB R-45M (C213.8H323.0O4.6N2.3) was computed as 342 kJ/mol or 114 kJ/kg. Chemical equilibrium analyses were completed for solid propellants composed of ammonium perchlorate and HTPB, and for hybrid rocket engines based on HTPB burning with liquid oxygen or nitrous oxide, where the heat of formation of HTPB was varied within a reasonable range. The chemical equilibrium analysis computations indicated that combustion gas properties and theoretical propellant performance can vary up to 5% within practical operating conditions for the range of HTPB heats of formation implemented.