Mechanistic and Kinetic Insights into the Interfacial Polymerization of Fluorine-Containing Polyarylate

The interfacial polymerization of fluorine-containing polyarylates (F-PAR) represents an important synthetic route for advanced polymeric materials. This work presents a comprehensive mechanistic investigation through integrated kinetic analysis and macromolecular characterization. The polymerization for both F-PAR and its non-fluorinated analogue (M-PAR) follows a two-stage, second-order kinetic profile, with the F-PAR system exhibiting a lower initial rate constant. Kinetic modeling revealed a dynamic reaction locus, transitioning from the bulk organic phase to an indistinguishable regime. The fluorinated system exhibits distinct stage-dependent behavior: initial retardation due to fluorine-induced "nucleophilicity penalty" on bisphenol monomer followed by a kinetic crossover where the growth rate of F-PAR surpasses M-PAR through enhanced oligomer electrophilicity. The terminal stage reveals fundamental divergence, while flexible M-PAR chains sustain accelerated growth via efficient chain-chain coupling, rigid F-PAR chains reach a molecular weight plateau. The incorporation of fluorine enhances thermal stability and optical transparency due to the low polarizability of C-F bonds. This study provides a complete mechanistic roadmap of fluorine's dynamic role in polymer architecture control.