Heats and entropies of fusion of linear aliphatic polyesters. I. Experimental determinations

Poly(ethylene adipate), poly(ethylene suberate), and poly(ethylene sebacate) were synthesized by a modified ester interchange procedure. Polydispersity was reduced and low molecular weight material removed by fractional crystallization. Samples of 50–60% crystallinity were prepared by bulk crystallization and annealing. Melting points and amorphous densities were obtained by dilatometry. Melting points were 7–12°C higher than previously reported. Heats of fusion were measured by differential scanning calorimetry and extrapolated to 100% crystallinity by using measured amorphous densities and recently redetermined crystalline densities. Entropies of fusion were calculated and separated for the first time into volume expansion and conformational contributions.