Macromolecules, Vol.28, No.8, 2658-2664, 1995
Diffusion in Aqueous-Solutions of Poly(Ethylene Glycol) at Low Concentrations
We have observed the scaling behavior of the diffusion coefficient of poly(ethylene glycol) (PEG) ranging from dimer to n-mer of 14 000 ethylene glycol units in D2O and in a (1:1) mixture of D2O and diethylene glycol, solvents of both low and moderate viscosities. The accepted scaling relationship for diffusion of polymers at infinite dilution is D-0 = KM(-alpha), where a ranges from 0.5 for a Theta solvent to 0.6 for a good solvent, as originally proposed by Flory. Measuring D-0 as the extrapolated value of D versus concentration in a PGSE-NMR experiment, we find a surprisingly good fit to this scaling relationship over the entire molecular weight range for both solvent systems. The values of alpha obtained in D2O at 25 degrees C, D2O at 5 degrees C, and a D2O/diethylene glycol mixture at 25 degrees C were 0.597 +/- 0.020, 0.534 +/- 0.021, and 0.542 +/- 0.058, respectively. The extension of the scaling behavior down to the dimer species is believed to be due to the high local segmental friction coefficient of the ethylene oxide unit.
Keywords:FIELD GRADIENT NMR;NUCLEAR MAGNETIC-RESONANCE;DYNAMIC LIGHT-SCATTERING;DILUTE POLYMER-SOLUTIONS;SLOW-MODE DIFFUSION;SELF-DIFFUSION;OXIDE);WATER;CONFORMATION;POLYSTYRENE