Synthesis, Characterization, and Application of High-Molecular-Weight Polyethylene-like Polycarbonates: Toward Sustainable and Recyclable Fibers

Abstract

Polyethylene-like materials, such as polyethylenelike polycarbonates (PLPCs), have garnered widespread attention because they can compensate for the nondegradability of polyethylene while maintaining mechanical properties resembling polyethylene. Although substantial efforts have been invested to develop synthetic methods of PLPCs, a long-pursued goal is to apply these polymers that either functionally replace or exhibit performance advantages relative to incumbent polymers. Herein, we presented a scalable synthesis of PLPCs from long-chain α,ωdiols and diphenyl carbonate, studied the relationship between the structure and properties, and expanded their practical applications as high-strength and high-toughness fibers. These PLPCs were prepared using equivalent biobased aliphatic diols and diphenyl carbonate via melt polycondensation using NaOH/PPh 4 OPh as catalysts at ppm levels, showing high molecular weight (92,000− 121,000 g/mol) and narrow distribution (1.69−1.80) with high yield (∼99%). The influence of the carbonate unit density on thermodynamic properties, morphology, and mechanical performance was systematically studied. The fibers prepared from longermethylene-sequence PLPCs (PC10, PC12, and PC14) show reliable mechanical properties such as satisfactory tensile modulus and yield stress as well as toughness, while the fibers of shorter-methylene-sequence PC6 and PC8 present compromised mechanism properties due to the higher carbonate densities influencing the packed crystalline structure. These affordable and easy-to-prepare PLPC materials also show excellent chemical and physical recovery capabilities, holding great potential for further practical applications.