Quantitative nuclear magnetic resonance characterization of long-range chain dynamics: Polybutadiene, polyethylene-oxide solution

We report two sets of independent nuclear magnetic resonance (NMR) measurements of self-diffusion and proton transverse relaxation in molten cis1,4-polybutadiene (PB) performed in order to investigate chain dynamics properties. Self-diffusion coefficients were measured as a function of temperature and of molecular weight (M) over the range 104 to 6.7×104 g/mol. The crossover from the Rouse-type behavior (D≈M−1) to the reptation one was found to occur for MCross≈3×104 g/mol; for M>MCross the data were consistent with the scaling dependence: D≈M−2.4±0.05, in agreement with the data analysis recently reported in the literature. The thorough analysis of the transverse relaxation of protons attached to highly entangled PB chains (6.7×104⩽M⩽43×104 g/mol) gave evidence for the dynamics partition of one chain into two end-submolecules and one inner part clearly discriminated from one another. The number NEnd of monomeric units in one end-submolecule, independent of M, is shown to be closely related to the monomeric friction coefficient ζ0 measured from short chain diffusion over the temperature range 25 to 85 °C. The interpretation both of diffusion results and of proton relaxation of inner monomeric units lead to the definition of an effective friction coefficient ζ0Eff≈ζ0(M/NEnd)0.4 associated with the curvilinear diffusion of one chain in its tube. The friction coefficient ζLoc associated with local monomeric rotations is discriminated from ζ0 from its weaker temperature dependence. This approach was applied to polyethylene-oxide chains in solution (dimethyl formamide, 0.18⩽c⩽1, w/w) where the segmental size of end-submolecules was found to vary as 1/c. Experimental results are well matched by this specific NMR approach which accounts for the novel properties of the proton relaxation function.