Vanillin, as a promising aromatic aldehyde, possesses worthy structural and bioactive properties useful in the design of novel sustainable polymeric materials. Its versatility and structural similarity to terephthalic acid (TPA) can lead to materials with properties similar to conventional poly(ethylene terephthalate) (PET). In this perspective, a symmetrical dimethylated dialkoxydivanillic diester monomer (DEMV) derived from vanillin was synthesized via a direct-coupling method. Then, a series of poly(ether-ester)s were synthesized via melt-polymerization incorporating mixtures of phenyl/phenyloxy diols (with hydroxyl side-chains in the 1,2-, 1,3- and 1,4-positions) and a cyclic diol, 1,4-cyclohexanedimethanol (CHDM). The polymers obtained had high molecular weights (M_w = 5.3–7.9 × 10⁴ g.mol⁻¹) and polydispersity index (Đ) values of 1.54–2.88. Thermal analysis showed the polymers are semi-crystalline materials with melting temperatures of 204–240 °C, and tunable glass transition temperatures (T_g) of 98–120 °C. Their 5% decomposition temperature (T_d,5%) varied from 430–315 °C, which endows the polymers with a broad processing window, owing to their rigid phenyl rings and trans-CHDM groups. These poly(ether-ester)s displayed remarkable impact strength and satisfactory gas barrier properties, due to the insertion of the cyclic alkyl chain moieties. Ultimately, the synergistic influence of the ester and ether bonds provided better control over the behavior and mechanism of in vitro degradation under passive and enzymatic incubation for 90 days. Regarding the morphology, scanning electron microscopy (SEM) imaging confirmed considerable surface degradation in the polymer matrices of both polymer series, with weight losses reaching up to 35% in enzymatic degradation, which demonstrates the significant influence of ether bonds for biodegradation.

In this work, the feasibility of replacing petroleum-based poly(ethylene terephthalate) (PET) with fully bio-based copolyesters derived from dimethyl 2,5-thiophenedicarboxylate (DMTD), dimethyl 2,5-dimethoxyterephthalate (DMDMT), and polysaccharide-derived 1,6-hexanediol (HDO) was investigated. A systematic study of structure-property relationship revealed that the properties of these poly(thiophene–aromatic) copolyesters (PHS(20–90)) can be tailored by varying the ratio of diester monomers in the reaction, whereby an increase in DMTD content noticeably shortened the reaction time in the transesterification step due to its higher reactivity as compared with DMDMT. The copolyesters had weight-average molar masses (Mw) between 27,500 and 38,800 g/mol, and dispersity Đ of 2.0–2.5. The different polarity and stability of heterocyclic DMTD provided an efficient mean to tailor the crystallization ability of the copolyesters, which in turn affected the thermal and mechanical performance. The glass transition temperature (T_g) could be tuned from 70–100 °C, while the tensile strength was in a range of 23–80 MPa. The obtained results confirmed that the co-monomers were successfully inserted into the copolyester chains. As compared with commercial poly(ethylene terephthalate), the copolyesters displayed not only enhanced susceptibility to hydrolysis, but also appreciable biodegradability by lipases, with weight losses of up to 16% by weight after 28 weeks of incubation.