Using PCL oligomers to study the differences in melting behavior between polymers and small molecules crystals

Polymer crystals usually show a completely different melting behavior than small molecules. Instead of starting from the crystal growth front, the lamellar crystals within polymer spherulites always experience a successive thickening process upon heating before they simultaneously melt. However, a systematic comparative study of the different melting behavior of crystals formed by small and large polymer chains is still scarce. In this work, two PCL oligomers with similar molecular weight are selected to study their crystallization and melting behavior. The defect-free oligomer (PCL2.4) exhibits a similar melting behavior as polymeric crystals (where spherulites melt simultaneously). In contrast, the other oligomer (PCL2.0) with a mid-chain defect shows prominent surface melting starting at the spherulite growth front. SAXS, SSA thermal fractionation, and flash DSC results confirm that an extended chain-like crystal structure could form at relatively high crystallization temperatures. According to the Gibbs-Thomson equation, the melting temperature of PCL2.0 crystals at the spherulite growth front is relatively lower than in the inner part due to different surface free energies. On the other hand, the thermal stability of PCL2.4 is enhanced due to melting and recrystallization during heating, and the spherulites show identical melting points and lamellar thicknesses at their growth front centers.