(157e) Controllable Synthesis of High Performance Fluorine-Containing Polyarylate By Interfacial Polymerization

Fluorine-containing polyarylates exhibit unique properties compared to their non-fluorinated analogues. However, the inductive effect of fluorine atoms on adjacent hydroxyl groups lowers the reactivity of diols which cause difficulty to obtain high molecular weight polymers. Furthermore, differences in reactivity between fluorinated and non-fluorinated monomers, along with the complex reaction mechanisms in interfacial polymerization, pose challenges in tuning the microstructure of polymeric chains. In this study, a series of fluorine-containing polyarylates were synthesized from bisphenol A, isophthaloyl dichloride, paraphthaloyl dichloride and their fluorinated analogues, bisphenol AF, tetrafluoroisophthaloyl dichloride and tetrafluoroparaphthaloyl dichloride via interfacial polymerization. The effects of monomer type, concentration, solvents, compatibilizers, phase transfer agents, reaction temperature, time and stirring rates on the reaction yields, the molecular weights and their distributions of the as-prepared polymers were systematically investigated. An in-situ Raman spectroscopy method was developed to elucidate the reaction mechanism and to monitor the reaction process. By adopting different monomer feeding strategies, copolymers with random, quasi-alternating and quasi-block microstructures were prepared and the molecular weight showed a ten-fold difference with the highest at 250,000. The copolymers demonstrate improved optical properties (91.2% transmittance at 400 nm) and thermal stability (452 ^oC-T5%) while maintaining the mechanical properties.