Abstract
A kinetic model has been derived based upon multiple catalyst sites of differing reactivities for the Ziegler-Natta copolymerization of olefins. The kinetic scheme accounts for the formation, initiation and deactivation of active sites, as well as for spontaneous transfer and for transfer reactions to hydrogen, monomer and organometallics. The model predicts the rate of polymerization, the copolymer composition and the molecular-weight distribution of the polymer produced. The model accounts for the observed broad copolymer composition and molecular-weight distributions. A method for the estimation of the model parameters via temperature-rising elution fractionation, gel permeation chromatography and nuclear magnetic resonance is discussed. Some simple calculations are performed to demonstrate that the observed broad copolymer composition and molecular-weight distributions can be predicted by this model.
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