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The errors incurred in free‐radical chain addition polymerizations through the use of the popular quasi‐stationary state approximation (QSSA) under severe, but fairly common, reaction conditions are examined in detail, and simple, useful criteria for applicability of the QSSA are proposed. The conditions examined are “dead end” polymerization, polymerization with hindered termination and nonisothermal polymerization. It is concluded that the proposed criteria are reasonably accurate and that in most known free‐radical polymerizations only hindered termination might possibly lead to appreciable errors through application of the QSSA.
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Biesenberger et al. (1972) studied this question.
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