Conformation of oligo(ethylene glycol) grafted polystyrene in dilute aqueous solutions

Temperature induced conformational changes of poly(p-oligo(ethylene glycol) styrene) (POEGS) in aqueous solutions were investigated by small angle neutron scattering (SANS), neutron transmission and dynamic light scattering (DLS). The molecular weight of the polymer studied was 9400 g/mol with a polydispersity index of 1.18 and each repeat unit of the polymer had four ethylene glycol monomer segments. The polymer was water soluble due to the hydrophilicity of the OEG side chains and these solutions showed lower critical solution temperature (LCST) depending on the concentration of the polymer. Measurements of solution behavior were made as a function of temperature in the range of 25-55 °C for three polymer concentrations (0.1 wt%, 0.3 wt%, and 1.8 wt%). Neutron transmission measurements were used to monitor the amount of polymer which precipitated or remained in solution above the cloud point temperature (TCP). DLS revealed the presence of large clusters in all solutions both below and above TCP while SANS provided information on the structure and interactions between individual chains. It was found that in the homogeneous region below TCP the shape of individual polymers in solution was close to ellipsoidal with the dimensions Ra = 37 Å and Rb = 14 Å and was virtually independent of temperature. The SANS data taken for the most concentrated solution studied (1.8 wt%) were fit to the ellipsoidal model with attractive interactions which were approximated by the Ornstein-Zernike function with a temperature-dependent correlation length in the range of 24-49 Å. The collapse of individual polymers to spherical globules with the radius of 15 Å above TCP was observed.