Mechanism and kinetics of poly(ether ether ketone) (PEEK) sulfonation in concentrated sulfuric acid at room temperature. Part 1. Qualitative comparison between polymer and monomer model compound sulfonation

The sulfonation kinetics of fluorine ended poly(ether ether ketone) (PEEK) in solution in 95.9% and 96.8% concentrated sulfuric acid was studied with the help of a model compound representative of the PEEK chain repeat unit. The reaction rate of the model compound sulfonation was found to be first order with respect to the aromatic ring to be sulfonated. Consequently, PEEK kinetic data were treated following a first order with respect to the unsulfonated repeat unit concentration. Two rate-slowing effects were detected. They were attributed to 'long range' electronic effects resulting from the inductive nature of the fluorine atom, and from the electron-withdrawing character of the grafted sulfonic acid group. (C) 2001 Society of Chemical Industry