Effect of Monomer Feeding Strategy on the Sequence and Properties of Fluorine-Containing Polyarylates via Interfacial Polycondensation

Fluorine-containing polyarylates (F-PARs) were synthesized via interfacial polycondensation of hexafluorobisphenol A (BPAF), bisphenol A (BPA), and two acyl chloride monomers under four feeding strategies. Sequential feeding affords the highest Mw (2.02 × 105 g/mol) and high alternating sequence content; the one-pot method gives intermediate Mw and a random sequence; and segmented and parallel methods yield lower-Mw polymers and pseudo-block sequences. Time-resolved GPC results reveal that the concentration of -CF3-activated acyl chloride termini during chain propagation controls the subsequent chain propagation and, thus, the final Mw. Consequently, sequential feeding delivers the highest Tg (215 °C) and stiffness (2.51 GPa) for thermal–mechanical loads; the one-pot protocol maximizes optical clarity (T450 = 85%) for transparent films. Systematic variation in the BPAF/BPA ratio via sequential feeding further reveals that higher BPAF content increases Mw, enhances thermal stability, and blue-shifts UV absorption, whereas BPA-rich compositions improve the tensile strength and modulus. These findings provide a quantitative roadmap for the rational design of F-PAR chain architectures, enabling on-demand tuning of thermal, mechanical, and optical properties without additional synthetic complexity.