Application of SSA thermal fractionation and X-ray diffraction to elucidate comonomer inclusion or exclusion from the crystalline phases in poly(butylene succinate-ran-butylene azelate) random copolymers

Poly(butylene succinate-ran-butylene azelate) random copolyesters were thermally fractionated by successive self-nucleation and annealing (SSA). The samples before and after SSA were analyzed by differential scanning calorimetry (DSC) and X-ray diffraction (WAXS and SAXS). WAXS results indicate that a small degree of comonomer inclusion is present in the crystalline phases that are formed in the copolymers depending on composition: a PBS-like unit cell or/and a PBAz-like unit cell, thus confirming the isodimorphic behavior of the samples. SSA on the other hand demonstrated that the degree of comonomer exclusion during crystallization is far larger than comonomer inclusion, as judged by the increase in fractionation degree with compositions leading to the pseudo-eutectic point. Furthermore, WAXS, SAXS, and SSA results show that the isodimorphic behavior is not highly dependent on kinetic factors, as the degree of comonomer inclusion or exclusion in the samples was not significantly altered by SSA thermal fractionation, a thermal treatment that promotes annealing and molecular segregation of defects to the amorphous regions of the material.