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Abstract In an effort to synthesize chemically recyclable thermoplastic elastomers, a redox‐switchable catalytic system was developed to synthesize triblock copolymers containing stiff poly(lactic acid) (PLA) end blocks and a flexible poly(tetrahydrofuran‐co‐cyclohexene oxide) (poly(THF‐co‐CHO) copolymer as the mid‐block. The orthogonal reactivity induced by changing the oxidation state of the iron‐based catalyst enabled the synthesis of the triblock copolymers in a single reaction flask from a mixture of monomers. The triblock copolymers demonstrated improved flexibility compared to poly(l‐lactic acid) (PLLA) and thermomechanical properties that resemble thermoplastic elastomers, including a rubbery plateau in the range of −60 to 40 °C. The triblock copolymers containing a higher percentage of THF versus CHO were more flexible, and a blend of triblock copolymers containing PLLA and poly(d‐lactic acid) (PDLA) end‐blocks resulted in a stereocomplex that further increased polymer flexibility. Besides the low cost of lactide and THF, the sustainability of this new class of triblock copolymers was also supported by their depolymerization, which was achieved by exposing the copolymers sequentially to FeCl₃and ZnCl₂/PEG under reactive distillation conditions. 

We describe the theory and application of SEC-MALS with minimal equations and a focus on synthetic polymer characterization. 

We report a polymeric version of Piloty's acid where the release rate of HNO can be tuned by changing the block ratios of PEG- b -poly(Piloty's acid) in a block copolymer system. The poly(Piloty's acid) block was derived from poly(styrene sulfonate), and HNO release from the block copolymers varied by as much as an order of magnitude via increasing the length of the poly(Piloty's acid) block. We anticipate this study will guide the development of HNO-releasing polymers to measure the effects of sustained HNO delivery in biological systems.