The glass transition temperatures of amorphous linear aliphatic polyesters

•Wholly amorphous linear aliphatic polyesters were synthesized.•Tgs increase linearly with ester to methylene ratio.•Conformational entropy Sconf ∝ 1/Tg.

A series of wholly amorphous linear aliphatic co- and tetra-polyesters were synthesized via bulk melt step-growth polymerization. Their glass transition temperatures were determined using DSC and were essentially unaffected by crystallinity. The glass transition temperatures of the polyesters increase linearly with the ratio of ester groups per methylene group. Extrapolations of the ratio to zero ester group content gave a reliable value for the Tg of amorphous polyethylene (PE). The experimental Tgs manifest a steeper slope on the Tgvs. ester group content plot compared to those calculated using Van Krevelen's group contribution method. The intramolecular equilibrium flexibilities were evaluated through the calculation of conformational entropies of individual polymer chains approximated by considering solely the short-range interactions between neighboring groups, as embodied in their RIS conformational models. Their calculated conformational entropies, Sconf, decrease linearly with increasing ester group content, leading to the observation that Sconf∝1/Tg.

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