Abstract
A complex relationship between chain length and the concentration dependence of polymer self-diffusion, Dp(c)/Dp(0), is revealed from analysis of polystyrene (PS) and oligostyrene self-diffusion in solution. Pulsed-field-gradient NMR measurements of PS self-diffusion in styrene and toluene were compared with literature results for PS self-diffusion in benzene, tetrahydrafuran, toluene, and carbon tetrachloride. An empirical relationship was used to correlate Dp(c)/Dp(0) to the concentration dependence of solvent self-diffusion, Ds(c)/Ds(0): Dp(c)/Dp(0) = [Ds(c)/Ds(0)]β where β quantifies the relationship between chain length and the concentration dependence of Dp. (This power law, with a chain-length-independent β, may be justified from Vrentas−Duda free volume theory.) Accounting for differences in the free volume contribution of the solvent species, β values obtained in the five solvents can be normalized to a single solvent, styrene, revealing universality in the relationship between chain length and ...
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