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The interaction between imperfect mixing and cyclic operation is examined for several continuous polymerizations in stirred‐tank reactors. The reactor is represented by a mixed model involving two interconnected ideal stirred vessels. Cyclic fluctuations in the concentration of a chain transfer agent during Ziegler‐catalyzed olefin polymerization can yield molecular weight distributions significantly different from those of a conventional steady state reactor. This result is consistent with the available experimental data. It is especially interesting that the cyclic reactor effluent with a modified molecular weight distribution is of approximately time‐invariant composition when the period of cycling is on the order of the reactor holding time. Imperfect mixing has a lesser effect on cycled reactors for free‐radical and polycondensation polymerization than it has on cycled olefin polymerization reactors.
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Lee et al. (1974) studied this question.
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