The viscosities of a number of monodisperse polystyrene melts have been measured using a capillary rheometer. The materials covered a molecular weight range of 43,000–460,000. Shear rates of 1.54–1540 sec.−1 and temperatures of 350–450°F. were studied. The effect of molecular weight distribution of polydisperse polystyrene was also measured. It was found that while low shear viscosity was dependent on Mw, higher shear melt viscosities depended on averages between Mw and Mn until at 1000–2000 sec.−1, Mn controlled viscosity. Agreement with the 3.4‐power dependence of zero shear viscosity was good. Similar exponential relationships were found, with higher rates of shear, corresponding to smaller values of the exponent. Constant values of the exponent were found at constant shear stress but not at constant shear rate. Agreement with the constancy of the activation energy for viscous flow for various molecular weights and distributions at constant shear stress was good. However at constant shear rate, ΔE decreased as the molecular weight average increased and as the distribution broadened. Viscosity versus shear rate master curves were constructed by using the Buehe‐Harding procedure. All monodisperse polystyrenes showed excellent fit with the master curve. Other molecular weight distributions did not. Master curves also were constructed for measurements of dynamic viscosity versus frequency for monodisperse polystyrene. These curves when compared to steady state viscosities failed to confirm the correspondence of ηa to either |η*| or to η′.

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The rational design of a reaction system to produce a desired polymer is more feasible today by virtue of mathematical tools which permit one to predict product distribution as affected by reactor type and conditions. New analytical tools such as gel permeation chromatography are beginning to be used to check technical predictions and to aid in defining molecular parameters as they affect product properties. The vast majority of work concerns bulk or solution polymerization in isothermal batch or continuous stirred tank reactors. There is a clear need to develop techniques to permit fuller application of reaction engineering to realistic nonisothermal systems, emulsion systems, and systems at high conversion found industrially. A mathematical framework is also needed which will start with carefully planned experimental data and efficiently indicate a polymerization mechanism and statistical estimates of kinetic constants rather than vice-versa./^wing to a recent increase in theoretical treatments of polymerization kinetics, processes, and reactor design, chemical engineers are becoming increasingly active in a field where physical chemists primarily published. This paper reviews the theoretical tools now available and attempts to identify the work needed to make a fundamental approach more useful in practice. The broader field of chemical reactor engineering is itself relatively new, with the first modern text by Brotz (10) and by Walas (56) appearing in 1958 and 1959, respectively. Of the several thousand pages that have appeared since 1958, however, only a few deal with polymerization reactors, hardly sufficient recognition of their commercial importance. The recent activity seems triggered by the avail-'Also staff member,

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