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Journal of Applied Polymer Science, Vol.65, No.2, 209-215, 1997
Viscoelastic Properties of Poly(Ethylene-Co-Styrene) Copolymers
The viscoelastic properties of narrowly distributed linear poly( ethylene-co-styrene) copolymers with different mole fractions of styrene (x(s) = 0-20.5 mol%) and molecular weights (M-w = 64-214 kg/mol) were analyzed in the molten state at different temperatures by means of oscillatory rheometry. Analyzing the thermorheological properties of the polymers, we found that the time temperature superposition principle is fulfilled. The corresponding shift factors follow up to 16.5 mol% of styrene units the Arrhenius behavior of neat polyethylene. For a styrene content of about 20 mol%, the polymers no longer crystallize and a transition from Arrhenius to WLF behavior of pure polystyrene was observed. The zero shear viscosity, eta(0), of the polymers was derived from the master curves. The determination of the plateau modulus by the well-known tan delta-min criterion is not possible due to the beginning crystallization in the corresponding temperature range. An approximate calculation of this value is based on the characteristic relaxation time lambda(x) = 1/w(x), corresponding to the crossover of G’ and G ". Indeed, the characteristic modulus G(px) calculated as eta(0)/lambda(x) is a good approximation for the plateau modulus G(p). The viscosity-molecular weight and relaxation time-molecular weight scaling relations were established for three copolymers with different molecular weights and nearly the same styrene content. For both material parameters, the scaling exponent is around 3.4, confirming the linear architecture of the investigated polymers. The mixing rules describing the change of such material parameters like zero shear viscosity or plateau modulus independent of styrene content are of logarithmic linear character using the weight fraction of styrene units instead of the mole fraction. The relations found allow the prediction of melt state properties for polymers with arbitrary styrene content. In the future, when catalysts with sufficient activity for the synthesis of high styrene content copolymers are available, these predictions will have to be checked.