Industrial & Engineering Chemistry Research, Vol.53, No.18, 7275-7295, 2014
Evaluation of the Chain Length Distribution in Free-Radical Emulsion Polymerization-The Compartmentalization Problem
In emulsion polymerizations it is sometimes the case that the radical chains inside particles are small enough in number so that the compartmentalization or segregation effect on the chain length distribution (CLD) becomes important such as in 0-1 or 0-1-2 systems. At the other extreme, the numbers of chains per particle are so numerous as to resemble a pseudobulk system so that compartmentalization does not influence the CLD. In the past the low radicals per particle case has been calculated by distinguished distributions of particles in radical live or radical chain lengths. This paper follows the latter approach but attempts various levels of simplification so that one can relatively easily calculate the CLD ranging between the 0-1 and pseudobulk cases all in the same model by introducing "compartmentalization factors". These compartmentalization factor models are arranged in increasing level of difficulty. We also compare results of these models with analytical solutions and previous worker's numerical results. Finally we provide guidance on how to choose a reasonable approach for a given emulsion system.