Metal-Free Synthesis of Hydrophobic and Dielectric Poly(propylene carbonate) via CO₂/PO/TF-PO Terpolymerization:...

To overcome the inherent drawbacks of poly(propylene carbonate) (PPC), such as poor thermal stability, low mechanical strength, and high surface energy, this study introduced, for the first time, 1,1,1-trifluoro-2,3-epoxypropane (TF-PO) as a third monomer into the metal-free TEB/PPNCl catalytic system for the terpolymerization with carbon dioxide (CO₂) and propylene oxide (PO), successfully synthesizing a series of fluorinated PPC (PPCF). The optimal polymerization conditions (60 °C, 2.0 MPa, 12 h, n(PO):n(TF-PO) = 100:4) were determined through systematic optimization. Comprehensive structural characterization (FT-IR, NMR, XPS) confirmed the successful incorporation of TF-PO into the polymer backbone. Property evaluation revealed that the PPCF materials exhibited substantial improvements in thermal stability, mechanical strength, hydrophobicity, and dielectric properties compared to unmodified PPC. The optimal sample, PPCF4, achieved a 5% weight-loss temperature (Td,-5%) of 242 °C, a glass transition temperature (Tg) of 42 °C, a tensile strength of 21.5 MPa, and a Young modulus of 296 MPa. With a 5% TF-PO feed ratio, the material's water contact angle increased to 102°, and its dielectric constant reached 6.01 at 104 Hz. Furthermore, density functional theory (DFT) calculations elucidated the Lewis acidity of the TEB catalyst and the reactive sites of the monomers, leading to a proposed mechanism for the ternary alternating copolymerization. This work provides an effective synthetic strategy and theoretical foundation for preparing high-performance and functionalized PPC materials through molecular structure design.