Functionalized poly(ether ether ketone) analogs via reactivity ratio controlled polycondensation

Abstract

A route for the introduction of functional groups to poly(ether ether ketone) analogues, via a reactivity ratio controlled polycondensation process, has been developed. The reactivity differences, toward nucleophilic aromatic substitution reactions, of the three electrophilic sites in 3,4',5-trifluorobenzophenone, 1, affords the opportunity to prepare functionalized B 2-type monomers in situ, followed by polycondensation with the appropriate bisphenol to prepare the corresponding linear polymer. The reactivity differences in 1 were probed via a combination of 13 C and 19 F NMR spectroscopy along with model reactions using m-cresol as the nucleophile. Reaction of 1 with 1.03 molar equivalents of a series of phenols provided the desired B 2-type monomers in high selectivity. The B 2-type monomers were then converted to the linear polymers by reaction with Bisphenol-A and their structures were confirmed via NMR spectroscopy. The thermal properties were evaluated by a combination of thermogravimetric analysis and differential scanning calorimetry.

Introduction to the special issue of Polymer on “Macromolecular Engineering” dedicated to Professor Krzysztof Matyjaszewski on the occasion of his 65th birthday

“…The next section of the issue is comprised of papers describing primarily various synthetic methodologies. The section starts with Fossum's paper [50] which provides examples of reactivity ratio-controlled polycondensation reactions and their use in the synthesis of functional polyethers. In his paper, Siegwart [51] demonstrates the utility of sequential thiobutyrolactone aminolysis and thiol-ene reactions in the preparation of biodegradable polymers with applications in nucleic acid delivery.…”