Unraveling Sequence Effect on Glass Transition Temperatures of Discrete Unconjugated Oligomers

Sequence plays a critical role in enabling unique properties and functions of natural biomolecules, which has promoted the rapid advancement of synthetic sequence-defined polymers in recent decades. Particularly, investigation of short chain sequence-defined oligomers (also called discrete oligomers) on their properties has become a hot topic. However, most studies have focused on discrete oligomers with conjugated structures. In contrast, unconjugated oligomers remain relatively underexplored. In this study, three pairs of discrete oligomers with the same composition but different sequence for each pair are employed for investigating their glass transition temperatures (T(g)s). The resultant T(g)s of sequenced oligomers in each pair are found to be significantly different (up to 11.6 degrees C), attributable to variations in molecular packing as demonstrated by molecular dynamics and density function theory simulations. Intermolecular interaction is demonstrated to have less impact on T(g)s than intramolecular interaction. The mechanistic investigation into two model dimers suggests that monomer sequence caused the difference in intramolecular rotational flexibility of the sequenced oligomers. In addition, despite having different monomer sequence and T(g)s, the oligomers have very similar solubility parameters, which supports their potential use as effective oligomeric plasticizers to tune the T(g)s of bulk polymer materials.

Automated summary

Sequence plays a critical role in determining the unique properties of discrete oligomers, as demonstrated by the significant differences in glass transition temperatures (T(g)s) of oligomers with the same composition but different sequences. Molecular packing variations were found to be the main factor influencing T(g)s, with intramolecular interactions playing a more significant role than intermolecular interactions. Despite differences in monomer sequences and T(g)s, the oligomers showed very similar solubility parameters, suggesting their potential use as effective plasticizers for bulk polymer materials.