5-Hydroxymethyl-2-furancarboxylic acid (HFCA), a promising biomonomer from renewable resources, was used to synthesize two bio-based plasticizers, namely, hexyl 5-((hexanoyloxy)­methyl)-2-furancarboxylate (HHMFC) and dihexyl 5,5′-(oxybis­(methylene))­bis­(furan-2-carboxylate) (DHOBFC). The chemical structures of these prepared plasticizers were confirmed using Fourier transform infrared and nuclear magnetic resonance, and then, their plasticization effects on poly­(vinyl chloride) (PVC) were also studied. As a result, HFCA-based plasticizers were miscible with PVC and exhibited excellent plasticization performances, compared with commercial dioctyl phthalate. It was noted that HHMFC had a much better plasticizing effect on the PVC film than DHOBFC; however, it displayed a poorer volatility resistance and exudation resistance, which could be attributed to its smaller molecular weight. Besides, because each rigid furan ring of the synthesized plasticizers contained one oxygen atom, the polarity of HFCA-based plasticizers was improved, which inhibited them from migrating from the PVC matrix into nonpolar solvents. Therefore, the HFCA-based plasticizers have good potential as primary plasticizers for PVC.

A series of bio‐based diester plasticizers with various alkyl chain asymmetry and the same molecular weight were designed and synthesized, using renewable 5‐hydroxymethyl‐2‐furancarboxylic acid (HFCA) as the raw material. The chemical structures of the HFCA‐based plasticizers were characterized by Fourier transform infrared and nuclear magnetic resonance (1H NMR and 13C NMR). Besides, the influence of alkyl chain asymmetry on plasticization properties of the HFCA‐based plasticizers in poly(vinyl chloride) (PVC) blends was also investigated. It was found that increasing the alkyl chain asymmetry of the diester plasticizer and keeping the molecular weight unchanged simultaneously could further improve its plasticizing efficiency, without sacrificing its volatility resistance and exudation resistance. The results showed that this study provided a new approach for further optimizing the overall properties of the asymmetric diester plasticizers.