TFAA chemical derivatization and XPS. Analysis of OH and NHx polymers

The determination of functional groups on complex polymer surfaces by X‐ray photoelectron spectroscopy (XPS) can be improved considerably by derivatization reactions. Simple polymers containing hydroxyl groups or amino groups were investigated as reference materials for the derivatization with trifluoroacetic anhydride (TFAA). ‐1 Poly(vinyl alcohol) (PVA), poly(hydroxyethyl methacrylate) (PHEMA), poly(vinyl butyral) (PVB), poly(allylamine) (PAAm), and poly(diallyl amine) (PDAAm) were derivatized using TFAA and analyzed with XPS. Polyethylene (PE) was used as an independent external reference for the binding energy (BE). Applying this procedure, the BE scales of all measurements were referenced to the carbon atoms of PE. It was found that the BE of the CF 3 component in the C1s region is different when bonded as an acetate or as an amide. The CF 3 BE is also influenced by the density of these groups in the polymer molecule. In TFAA‐PVA, where every second main chain carbon atom carries a trifluoroacetate (TFAc) group, the BE is 294.3 eV while in TFAA‐PVB with only isolated groups, the BE is 293.6 eV. The BE of the CF 3 component in the trifluoroacetamides (TFAAms) prepared from PAAm and PDAAm was found to be 292.5 and 292.3 eV, respectively. Compared with the analog fluorine free compounds, the BE is shifted toward higher values also for the ester carbon atom, the amide carbon atom, and the carbon atom to which the ester or amide is bonded. The data suggest that the gas phase reaction of TFAA with a polymer surface is diffusion limited. The actual ester or amide formation is a fast reaction and runs as a wave into the surface. Copyright © 2009 John Wiley & Sons, Ltd.