Molecular dynamics in precision deuteriomethyl branched polyethylene from solid-state deuterium NMR

Deuterium quadrupolar echo NMR was applied to precision CD3 branched polyethylene at temperatures ranging from below the glass transition up to the melting point. The CD3 branches were placed on every 15th or 21st carbon with zero variation in the branch spacing by acyclic diene metathesis polymerization chemistry. The deuterium lineshapes were simulated and fit to the experimental spectrum assuming appropriate models that approximate the motions in the amorphous and crystalline phases. Spectral contributions of each phase were isolated by T1 fitting. The fitting results comprise the isotropic reorientation correlation time distribution and axial jump angle distribution in these two phases, respectively. The mean jump angle was found to increase monotonically with temperature, approaching 35° near the melting point, consistent with previous carbon-13 NMR results on this same polymer.