Design of Anti‐Migratory and Thermally Stable Bio‐Plasticizers for Polar Plastics Toward Superior Overall Performance

ABSTRACT Developing bio‐based plasticizers for polyvinyl chloride (PVC) that exhibit effective plasticizing performance, thermal stability, and migration resistance remains a significant challenge. In this work, two plasticizers, acetylated methyl oleate citrate (A‐MO‐CAE) and acetylated n‐butyl oleate citrate (A‐NBO‐CAE), were synthesized by using fatty acid esters and citric acid as raw materials and compared with the commercial plasticizer bis(2‐ethyl)hexyl phthalate (DEHP). It was found that the PVC plasticized by A‐MO‐CAE, with a shorter alkane chain, had better overall performance; the alkyl chain of A‐MO‐CAE increases the intermolecular distance of PVC, and the ester group of A‐MO‐CAE interacts with PVC, which results in a good plasticizing effect. The Tg of PVC/50A‐MO‐CAE was 43.3°C; meanwhile, the heat resistance of PVC/50A‐MO‐CAE was better than that of PVC/50DEHP, and PVC/50A‐MO‐CAE did not oxidize and turn black after aging for 1 h at 180°C. The elongation at break (EB) of PVC/50A‐MO‐CAE was 633.3%, which was higher than that of PVC/50A‐NBO‐CAE (456.6%) and PVC/50DEHP (429.2%). More importantly, the weight loss of PVC/50A‐MO‐CAE in volatility and leaching tests was much lower than that of PVC/50A‐NBO‐CAE and PVC/50DEHP. These results indicate that A‐MO‐CAE has the potential to replace DEHP, providing a straightforward and practical way for the preparation of bio‐based plasticizers.