Preparation, Properties, and Structure‐Performance Relationship of Bio‐Based Polyester Plasticizers

ABSTRACT Conventional phthalate plasticizers face significant challenges due to their migration potential and associated health risks, making the development of environmentally friendly, high‐performance alternatives a current research hotspot. Polyester plasticizers have garnered considerable attention for their excellent migration resistance and compatibility; however, the intrinsic relationship between their molecular structure and plasticizing performance remains insufficiently systematic. In this study, a series of polyester plasticizers with tunable chain structures were prepared by modulating the structures of dicarboxylic acids and diols (with different chain lengths, branching, ether linkages). The influence of these structural parameters on the thermal stability, mechanical properties, resistance to liquid migration, and volatility loss of plasticized polyvinyl chloride (PVC) films was investigated. The results demonstrate that, compared to traditional dioctyl phthalate (DOP), the polyester plasticizers significantly enhance the thermal stability, elongation at break, and toughness of PVC, while exhibiting superior migration resistance and lower volatility. This research establishes a clear structure‐performance relationship between the molecular structure of polyester plasticizers and their plasticizing properties, revealing a synergistic plasticization mechanism involving polar interactions, physical entanglement, and molecular structure regulation. These findings provide theoretical guidance for the rational design of high‐performance, environmentally friendly plasticizers.