Facile one-step synthesis of three-dimensional network-structured polyester plasticizers with superior migration resistance in poly(vinyl chloride)

Phthalate plasticizers are gradually restricted in PVC products due to the escalating demand for health and environmental safeguards. Here, novel poly(glycerol ester) plasticizers(PGE), were synthesized utilizing biomass-derived glycerol and 1,4-cyclohexanedicarboxylic acid as raw materials via an esterification condensation reaction, with n -octanoic acid serving as an end-capping agent, adjustment of reactant ratios yielded PGE-1 and PGE-0.75, subsequently evaluated for their efficacy in PVC applications. FT-IR and GPC analyses elucidated potential structures and molecular weight distributions of the plasticizers, revealing oligomeric PGE with molecular weights spanning 1000–2000 g mol −1 . Mechanical properties, thermal stability, dynamic mechanical analysis, and migration resistance of PVC plasticized with PGE-1 and PGE-0.75 were compared against those employing conventional plasticizers, including di(2-ethylhexyl) phthalate (DEHP), dioctyl terephthalate (DOTP), and acetyl tributyl citrate (ATBC). The hyperbranched network structure and high molecular weight of PGE conferred superior thermal stability and migration resistance to the plasticized PVC samples. Notably, the T 50% of PGE-1/PVC film surpassed that of films plasticized with DEHP, DOTP and ATBC by 107.92, 95.17 and 111.14 °C, respectively. The weight loss of PGE/PVC film in distilled water, anhydrous alcohol and petroleum ether was below 2 wt% during 48 h. Furthermore, the weight loss of each PVC film was below the safety value (5 wt%) during 10 d in three different food simulants. Overall, the obtained poly(glycerol ester) plasticizers exhibit promise as phthalate replacements, owing to their favourable attributes in human health and environmental protection. Graphical abstract The poly(glycerol ester) plasticizers derived from biomass glycerol, 1,4-CHDA and n -octanoic acid exhibited superb thermal stability and migration resistance far more than commercial plasticizers in PVC, resulting from the hyperbranched network structure.