Engineering High-Performance Renewable Polyesters via Monomer Skeleton Control

Creating novel polymers from diverse feedstocks through innovative biobased monomers is essential to address environmental challenges and enable a sustainable, low-carbon future. However, the systematic influence of the monomer skeleton on the properties of biomass-derived polyesters remains underexplored. Herein, we report a novel W-shaped rigid tricyclic diol (TCDO) derived from inedible furfural. A comparative study was conducted with linear 1,4-butanediol (BDO), aromatic diol (PBDO), and N-shaped bicyclic diol (BCDO) to investigate the influence of the monomer skeleton on polyester synthesis and properties. The cyclization kinetics of BCDO and TCDO were studied to inform the synthesis of high-molecular-weight biobased polyesters from diols with varying spatial configurations and linear diacids. Notably, both the glass transition temperature and tensile strength of the amorphous polyesters exhibit the same changing trend: aromatic ring < N-shaped ring < W-shaped ring. Remarkably, the W-shaped TCDO and succinic acid yielded a polyester with a T g of 88 °C, comparable to commercial petroleum-based amorphous copolyester poly(1,4-cyclohexylene dimethylene terephthalate glycol) (PCTG). Furthermore, the TCDO/glutaric acid polyester exhibited an excellent tensile strength of 44.0 MPa, outperforming previously reported biobased polyesters from cyclic diols and matching the strength of commercial poly(trimethylene terephthalate) (PTT) and poly(butylene succinate) (PBS) despite being amorphous. This work establishes a monomer skeleton-driven design strategy for developing high-performance biobased polyesters with excellent thermal and mechanical properties.