An experimental study of the bulk polymerization of styrene has been carried out. The rate of polymerization, molecular weight, and flow patterns around agitators as a function of conversion have been observed. The rate data are interpreted in terms of free-radical polymerization kinetics. Duerksen and Hamielec's modified termination rate constant and initiator efficiency relations are generally consistent with our data. The flow patterns were interpreted in terms of the mechanics of viscoelastic liquids and observations for nonreacting systems. Specifically, at low conversions for spheres and similar agitators, the flow patterns are dominated by centrifugal forces with fluid drawn in at the poles and expelled at the equator for spherical agitators. At higher conversions, normal stresses interact with the centrifugal forces causing segregated secondary flow regions adjacent to the sphere. At very high concentrations, normal stresses dominate, yielding Weissenberg effects.
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