Macromolecules, Vol.48, No.24, 8858-8866, 2015
Branch-Induced Heterogeneous Chain Motion in Precision Polyolefins
The effect of branching on the chain dynamics of model branched polyethylene was studied by solid state H-2 and C-13 NMR. Methyl branched polyethylene models with branches at every 15th (PE15) and 21st (PE21) chain carbon were synthesized with deuterons placed either at the carbon alpha to the branching point or in the middle of the chain between branches. Line shape analysis of the temperature-dependent 2H spectra revealed that the distribution of motional amplitudes in the solid state is homogeneous along the crystalline chain but heterogeneous in the less constrained amorphous phase. The C-13 and H-2 longitudinal spin relaxation data obtained at different positions along the chain are explained in terms of the segmental dynamics as a function of branch incorporation into the crystals. A detailed analysis of the chain dynamics in the confonnationally disordered phase exhibited in PE15 is also provided.