Intrachain Interactions Accelerate Access to a Modifiable Fluoro-Polyester Library With End-of Life Fluoride Recyclability

Fluorinated polymers offer outstanding material properties but lack viable end-of-life options. Here we report a general ring-opening copolymerisation strategy that delivers a broad library of fluorinated polyesters with tunable thermal properties, straightforward post-polymerisation modification and quantitative fluorine recovery as sodium fluoride upon degradation. In mapping the scope of this methodology across diverse anhydride partners, we found that fluorination accelerates catalysis mostly when both monomers are aromatic and one is fluorinated. Density functional theory and mechanistic experiments reveal that the rate enhancement does not originate at the catalyst but within the growing polymer chain itself, through intrachain π–π stacking interactions that stabilise the transition state. The polymer chain constructs a structured non-covalent environment around the active centre with every turnover making chain microstructure an unexpected determinant of catalytic rate. These findings reframe how we think about chain-derived effects in polymerisation catalysis, and are accompanied by a modifiable fluoropolyester library spanning glass transition temperatures from below -14 °C to 144 °C, from which fluorine can be recovered upon degradation.