Torsional Strain Enabled Ring-Opening Polymerization towards Axially Chiral Semiaromatic Polyesters with Chemical Recyclability.

The development of new chemically recyclable polymers via monomer design would provide a transformative strategy to address the energy crisis and plastic pollution problem. Biaryl-fused cyclic esters were targeted to generate axially chiral polymers, which would impart new material performance. To overcome the non-polymerizability of the biaryl-fused monomer DBO, a cyclic ester Me-DBO installed with dimethyl substitution was prepared to enable its polymerizability via enhancing torsional strain. Impressively, Me-DBO readily went through well-controlled ring-opening polymerization, producing polymer P(Me-DBO) with high glass transition temperature (T >100 °C). Intriguingly, mixing these complementary enantiopure polymers containing axial chirality promoted a transformation from amorphous to crystalline material, affording a semicrystalline stereocomplex with a melting transition temperature more than 300 °C. P(Me-DBO) were capable of depolymerizing back to Me-DBO in high efficiency, highlighting an excellent recyclability.