Sequence-Structure–Property Relationships in Short-Chain Polyesters: How Primary Structure Governs Macroscopic Performance

Abstract

While polymer properties are fundamentally linked to their nanostructure, the influence of monomer sequence remains less understood than stereochemical factors like tacticity. This study examines how sequence distribution affects the thermal behavior and morphology of homo- and copolyesters, specifically comparing polymers derived from constitutionally identical monomers but with varying degrees of sequence regularity depending on monomer structure or polymerization selectivity. Our findings show that increasing sequence defects progressively diminish thermal stability, crystallinity, melting temperatures, and morphological order. As new materials become more compositionally complex, this work underscores the importance of sequence control in the design of advanced polymers for emerging applications.