High‐Molecular‐Weight Biodegradable CO2/Propylene Oxide/Epichlorohydrin Terpolymers with Outstanding Gas Barrier Performance Synthesized Using an Organoboron Catalyst

As the sole commercial polycarbonate derived from CO2, poly(propylene carbonate) (PPC) is still hindered by poor thermal stability and a low glass transition temperature. Hererin, we first report the terpolymerization of CO2, propylene oxide (PO) and epichlorohydrin (ECH) to synthesize PPC‐ECH terpolymers via one‐pot and metal‐free method using multi‐nuclear organoboron catalysts. The PPC‐ECH terpolymers with well‐rounded properties can be easily synthesized by adjusting reaction conditions, monomer ratios, catalyst types and loading. The molecular weight of the PPC‐ECH terpolymer can reach up to 59.4 kg/mol, which is the highest known. Notably, the synthesized PPC‐ECH exhibits outstanding barrier performance with oxygen permeability as low as 1.31 cm3·mm/(m2·day) and water vapor permeability as low as 0.016 g·mm/(m2·day), significantly lower than those of pure PPC or other common packaging materials. Importantly, the introduction of a small amount of ECH not only preserves the biodegradability of polycarbonate but also markedly enhances its mechanical properties, glass transition temperature, thermal stability and flame retardancy, offering promising prospects for application in packaging materials.