Journal of Rheology, Vol.54, No.2, 393-406, 2010
Method for obtaining tube model parameters for commercial ethene/alpha-olefin copolymers
We propose a method of obtaining all three key "tube" model parameters, namely, the plateau modulus G(N)(0), the entanglement molecular weight, M-e, and the frictional equilibration time tau(e), from the molecular weight per backbone bond of ethene/alpha-olefin copolymers with longer comonomers, ranging from C4 (butylene) to C26 (hexacosene). G(N)(0) is obtained from a correlation by Fetters [Macromolecules 35, 10096-10101 (2002)] and M-e is obtained from this using the standard tube-model formula, M-e=(4/5)(rho RT/G(N)(0)). The equilibration time tau(e) is obtained from a remarkable finding by Stadler and Muumlnstedt [J. Rheol. 52, 697-712 (2008)] that, at fixed weight-average molecular weight, the zero-shear viscosity of linear ethene/alpha-olefin copolymers is independent of comonomer type and content over a wide range of alpha-olefin comonomers. From this observation, and from the values of G(N)(0) and M-e, we use the tube theory to construct a method for obtaining tau(e) from the comonomer type and content. We show that these a priori values of the tube model parameters, when used in two publicly available models ("hierarchical model" and "branch-on-branch" model) for predicting linear rheology, yield accurate predictions for a wide range of polydisperse copolymers. These results show that a priori predictions of linear rheology of complex commercial polyolefin copolymers are now possible.