Prediction of linear viscoelastic response for entangled polyolefin melts from molecular weight distribution

The linear viscoelastic properties of polymer melts depend strongly and systematically on the molecular weight distribution. A molecular theory relating dynamic modulus acid molecular weight distribution for linear polymers, developed and confirmed earlier with data for three other polymer species, is applied here to commercial samples of isotactic polypropylene and high density polyethylene. Experimental master curves are compared with predictions based on only the fundamental rheological parameters of the species and molecular weight distributions as obtained by the methods of size exclusion chromatography. Agreement is fairly good for the two polypropylene samples, about the same as had been found earlier for the other species, but it is highly variable for the ten polyethylene samples. We attribute this variability to differences among high density polyethylenes in the frequency, length, and type of long-chain branching. However, we could find surprisingly little supporting evidence for this from such supposed signatures of long branches in polyethylene as the flow activation energy E(alpha). Measured values of E(alpha) agreed well with the literature results for linear polyethylene; none showed the elevation in E(alpha) that would be expected for polyethylene with long branches.