Geminal disubstitution of cyclic monomers is an effective strategy to enhance the chemical recyclability of their polymers, but it is utilized for that purpose alone and often at the expense of performance properties. Here we present synergistic use of gem-α,α-disubstitution of available at-scale, bio-based δ-valerolactones to yield gem-dialkyl-substituted valerolactones ([Formula: see text]), which generate polymers that solve not only the poor chemical recyclability but also the low melting temperature and mechanical performance of the parent poly(δ-valerolactone); the gem-disubstituted polyesters ([Formula: see text]) therefore not only exhibit complete chemical recyclability but also thermal, mechanical and transport properties that rival or exceed those of polyethylene. Through a fundamental structure-property study that reveals intriguing impacts of the alkyl chain length on materials performance of [Formula: see text], this work establishes a simple circular, high-performance polyester platform based on [Formula: see text] and highlights the importance of synergistic utilization of gem-disubstitution for enhancing both chemical recyclability and materials performance of sustainable polyesters.
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