The melting behavior and crystallization kinetics of poly(thiodiethylene adipate) (PSDEA) were investigated with differential scanning calorimetry and hot-stage optical microscopy. The observed multiple endotherms, commonly displayed by polyesters, were influenced by the crystallization temperature (T-c) and ascribed to melting and recrystallization processes. Linear and nonlinear treatments were applied to estimate the equilibrium melting temperature for PSDEA with the corrected values of the melting temperature. The nonlinear estimation yielded a higher value by about 9 degreesC. Isothermal crystallization kinetics were analyzed according to Avrami's treatment. Values of Avrami's exponent close to 3 were obtained, independently of T-c, in agreement with a crystallization process originating from predetermined nuclei and characterized by three-dimensional spherulitic growth. As a matter of fact, space-filling spherulites were observed by optical microscopy at all T-c's. The rate of crystallization became lower as T-c increased, as usual at a low undercooling, the crystallization process being controlled by nucleation. Moreover, the crystal structure of PSDEA was determined from powder X-ray diffraction data by full profile fitting. A triclinic unit cell containing two polymer chains arranged parallel to the c axis was found. (C) 2003 Wiley Periodicals, Inc.