Abstract
AbstractBulk polymerization data of methyl methacrylate, ethyl methacrylate, ethyl acrylate, n‐propyl acrylate, vinyl acetate, and styrene were compared with the predictions of the theory proposed in the earlier parts of this series (I‐III). This theory of polymerization kinetics uses the concepts of free volume and chain entanglements to describe the relationship between chain mobility and chain length dependent termination reactions. Excellent agreement was found between the predictions of the theory and the polymerization rate and molecular weight data of the six polymerization systems studied. Emphasis was placed on the ability to explain the development of higher order molecular weight averages (M̄w, M̄z, etc.) because they provide the most crucial tests for such a model. No changes were required in the model as it was applied to the different polymerization systems for a variety of reaction conditions. The theory offers a unified understanding of the diverse polymerization behavior displayed by such systems.
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