Abstract
AbstractFactors which affect and broaden molecular weight distributions are investigated for polymerizations in catalyst particles which are accumulating polymer, such as Ziegler polymerizations of olefins. Expressions for the Q value, or ratio of weight‐average to number‐average molecular weight, are derived for simple, but important linear models. These expressions are of the form Q = FSX for a kinetic scheme in which polymer chains have an infinite growing lifetime, and Q = 2FGSX for a kinetic scheme in which termination by hydrogen is dominant and each site produces many chains. The factors F, G, S, and X are equal to or greater than unity: F depends on particle geometry and the nature of diffusion and reaction; G depends on environmental history of the particle; S depends on the distribution of site activities; and X depends on the distribution of particle sizes. Effects of reactor type are also studied quantitatively.
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