A 1D- and 2D-NMR Study of an Anionic Surfactant/Neutral Polymer Complex

NMR chemical shifts and linewidth measurements were examined for mixtures of sodium 10-phenyldecanoate (Na ω-PhDec) in deuterated aqueous solutions in the presence of varying compositions of poly(ethylene oxide) (PEO) polymers of 2000 and 4000 molecular weight. In addition, variable temperature NMR spectra and NMR spin lattice relaxation times (T ₁) were obtained for the PEO-4000/Na ω-PhDec system as a function of varying polymer concentrations. As expected, the polymer/surfactant systems exhibit the behaviour typical of that of an anionic surfactant/neutral polymer system with well defined critical aggregation concentrations (CMC) corresponding to the formation of polymer/surfactant complexes below the CMC of the free surfactant. The ¹H-NMR linewidths acquired for the Na ω-PhDec/PEO-4000 system before and after the CMC region of the surfactant indicate that the maximum in the linewidth of the PEO proton peak is reached at approximately twice the CMC of the free surfactant. 2D-NMR NOESY measurements on this system exhibit cross peaks between the PEO protons and the protons on the surfactant backbone, consistent with the location of the phenyl group in the micellar interior. All these NMR experiments are interpreted in terms of the structure of the polymer/surfactant complexes as a function of the system composition.

Jan C. T. Kwak (Corresponding author)Email: