The role of intermolecular interactions on the crystallization

Crystalline properties of polyesters have attracted great interest since they can be obtained from sustainable sources and are biodegradable. The study of crystalline properties is of great relevance since it affects the final performance of the material, including mechanical properties and barrier properties. Nevertheless, the effect of intermolecular interactions has not been studied systematically. In this work, a series of polyesters that contain additional ester and amide groups have been studied. In addition to the presence of functional groups, the effect of the number of methylene groups and the position of the functional group in the repeating unit of the polymer in the crystalline properties is studied. We demonstrate how the presence of additional ester and amide groups widens the melt memory effect and hinders the crystallization process leading to higher undercoolings due to intermolecular interactions. The incorporation of additional ester groups, however, does not significantly modify the melting and crystallization temperature. Therefore, this work can shed light on understanding how the intermolecular interactions can modify the thermal properties. This would allow to tune melt memory, crystallization kinetic or thermal parameters (T_m or T_c) independently.