AB-type monomers for the preparation of perfluorocycloalkene (PFCA) aryl ether polymers

•A synthetic protocol was developed for AB-type monomers.•Optically transparent perfluorocycloalkene aryl ether polymers were prepared.•Fluoride-catalyzed rearrangement resulted in allyl-substitution.•Method was more efficient than previously developed trifluorovinyl aryl ether synthesis.

A method for the preparation of AB-type monomers with complimentary fluoro-olefin and phenol functionalities is described. The three-step process is amenable to commercial scale up and uses widely-available, commercial reagents including bisphenols and perfluorocycloalkene (PFCA) compounds. Title compounds and intermediates were characterized via multi-nuclear NMR and FT-IR spectroscopy providing structural and mechanistic elucidation of PFCA step-growth polymerizations. The formation of vinyl and allyl substituted products were quantified and shown to be dependent on PFCA ring size and reaction medium. Nearly equal amounts of vinyl- and allyl-substituted products were observed with perfluorocyclohexene (PFCH) while 2–11% allyl-substitution was observed with perfluorocyclopentene (PFCP), depending on reaction medium polarity. Previous PFCA research and characterization of title compounds suggests that fluoride-catalyzed rearrangement is primarily responsible the formation of two substitution products. Polymerization of an AB-type monomer derived from bisphenol A is demonstrated and was shown to reproducibly result in film-forming polymers with higher molecular weights than previously described methods.

Graphical abstractA facile three-step synthesis for the preparation of AB-type monomers with complimentary fluorinated alkene and phenol functionalities is described and characterized. Polycondensation of AB-type monomers affords optically transparent, film-forming polymers.Figure optionsDownload full-size imageDownload as PowerPoint slide