Entropically driven ring-opening copolymerization of mixtures of a fraction of cyclic oligo(hexamethylene terephthalate)s composed of cycle sizes from 2 to 5 and p-dioxanone was used to prepare random copolyesters covering a range of aromatic (HT) to aliphatic (DO) units ratios from 9 to 1.3. The composition and microstructure of the copolyesters were accurately determined by 1H and 13C NMR, respectively. The copolyesters showed thermal degradation and glass transition temperatures in good agreement with their comonomeric composition and microstructure, and they crystallized for contents in DO less than 30%, adopting the same crystal structure as poly(hexamethylene terephthalate). The copolyesters appeared to be sensitive to hydrolytic degradation, which was observed to take place superficially with the generation of non-water-soluble degraded fragments and with the release of water-soluble dioxanoic acid to the aqueous medium.

Peer Reviewed