Analysis of a symmetric neopolyol ester

Quantitative thermal analysis was carried out for tetramethyleneoxycarbonyl(2,4,4-trimethyl)pentyl]methane. The ester has a glass transition temperature of 219 K and a melting temperature of 304 K. The heat of fusion is 51.3 kJ mol^?1, and the increase in heat capacity at the glass transition is 250 J K^?1 mol^?1. The measured and calculated heat capacities of the solid and liquid states from 130 to 420 K are reported and a discussion of the glass and melting transitions is presented. The computation of the heat capacity made use of the Advanced Thermal Analysis System, ATHAS, using an approximate group-vibration spectrum and a Tarasov treatment of the skeletal vibrations. The experimental and calculated heat capacities of the solid ester were compared over the whole temperature range to detect changes in order and the presence of large-amplitude motion. An addition scheme for heat capacities of this and related esters was developed and used for the extrapolation of the heat capacity of the liquid state for this ester. The liquid heat capacity for the title ester is well represented by 691.1+1.668T J K^?1 mol^?1]. A deficit in the entropy and enthalpy of fusion was observed relative to values estimated from empirical addition schemes, but no gradual disordering was noted outside the transition region. The final interpretation of this deficit of conformational entropy needs structure and mobility analysis by solid state¹³C NMR and X-ray diffraction. These analyses are reported in part II of this investigation.