Odd-Even Effect of Polyesters' Cyclic Oligomers and the Definition of Oligomers Based on Physicochemical Properties

This work explores the definition and characterization of synthetic polymeric oligomers, chemical substances comprising a small number of repeated organic molecules. It highlights the lack of clarity surrounding the range of repeated units that can be classified as an oligomer, and how this definition is field-dependent. The present study focused on PET cyclic oligomers and revealed that the progression of the ring length from smaller to longer oligomers followed the well-known odd-even effect. This phenomenon affects the physical and chemical properties of oligomers and can also be observed with analytical techniques such as differential scanning calorimetry (DSC), high resolution mass spectrometry (HR-MS) and NMR. Similarities between PET and PBT oligomers were also observed, and an alternative potential definition for oligomers in the polymeric field is suggested based on physical behaviour of the longer cyclic oligomers.