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 (\({\rm{VL}}^{{\rm{R}}_{2}}\)), 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 (\({\rm{PVL}}^{{\rm{R}}_{2}}\)) 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 \({\rm{PVL}}^{{\rm{R}}_{2}}\), this work establishes a simple circular, high-performance polyester platform based on \({\rm{VL}}^{{\rm{R}}_{2}}\) and highlights the importance of synergistic utilization of gem-disubstitution for enhancing both chemical recyclability and materials performance of sustainable polyesters.

环状单体的双取代是提高其聚合物的化学可回收性的有效策略，但它仅用于该目的并且通常以牺牲性能为代价。在这里，我们展示了可用的大规模生物基 δ-戊内酯的 gem-α,α-二取代的协同使用，以产生 gem-二烷基取代的戊内酯 ( \({\rm{VL}}^{{\rm{R }}_{2}}\)），生成的聚合物不仅解决了不良的化学可回收性，而且解决了母体聚（δ-戊内酯）的低熔融温度和机械性能；宝石二取代聚酯 ( \({\rm{PVL}}^{{\rm{R}}_{2}}\)) 因此不仅表现出完全的化学可回收性，而且表现出与聚乙烯相媲美或超过的热、机械和运输性能。通过一项基本的结构-性质研究，揭示了烷基链长度对\({\rm{PVL}}^{{\rm{R}}_{2}}\)材料性能的有趣影响，这项工作建立了一个基于\({\rm{VL}}^{{\rm{R}}_{2}}\)的简单圆形高性能聚酯平台，并强调了协同利用宝石二取代对增强两种化学物质的重要性可持续聚酯的可回收性和材料性能。