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

作者：Campos Raymond; Mansur Aleksander A; Cook Chloe H; Batchelor Benjamin; Iacono Scott T^*; Smith Dennis W Jr

来源：Journal of Fluorine Chemistry, 2014, 166: 60-68.

DOI：10.1016/j.jfluchem.2014.07.013

• AB type monomers
• Perfluorocycloalkene
• Fluoroolefin monomers
• Semi-fluorinated polymers
• Step-growth polymerization
• Nucleophilic vinylic substitution

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. Published by Elsevier B.V.

• 出版日期2014-10