High-performance cyclopolyester thermoplastics from CO2 and 1,3-butadiene

Exploiting carbon dioxide (CO 2 ) to produce sustainable and high-performance polymeric materials from commodity feedstocks such as olefins has long been an attractive yet challenging goal. Here, we present a new strategy to create cyclopolyester thermoplastics derived from CO 2 and 1,3-butadiene via ring-opening polymerization of α - alkyl-α,δ-divinyl-δ-valerolactone (DVL R ) monomers, followed by polymer backbone editing via ring-closing metathesis. Ultra-high-molecular-weight (MW) (absolute MW up to 768.4 kg/mol) polyester PDVL R s are synthesized using N -heterocyclic carbene and urea binary catalysts. Ring-closing metathesis of PDVL R s is employed to construct cyclopolyester PCHEL R s (CO 2 content up to 32 wt %) with a hindered cyclohexene structure incorporated into the backbone. These PCHEL R s are degradable and amorphous with tunable glass transition temperatures of 30.1°C–56.2°C, which behave as tough thermoplastics with ultimate tensile strength up to 31.1 MPa and elongation at break up to 333.5%. This work paves the way for polyester thermoplastics from CO 2 and highlights the potential of sustainable feedstocks in polymeric materials.