Modeling molecular weight development of gas-phase α-olefin copolymerization



A comprehensive kinetic model developed for molecular weight calculations of ethylene axsnd α-olefin copolymerizations in the context of a terminal model accounts for multiple-type active centers of the catalyst, detailed elementary chemical reactions, and catalyst composition. The moments of copolymer chain distributions are defined considering molecular weights of comonomer units so that copolymer molecular weight averages can be directly calculated from those moments. A double Z-transformation is introduced for the derivation of differential equations of the moments. Model simulations are carried out based on ethylene and 1-butene copolymerizations in a gas-phase fluidized-bed reactor. Polydisperity of accumulated copolymer depends on catalyst composition and kinetic characteristics of the catalyst. For a catalyst with specified kinetic characteristics, the polydispersity depends on the mole fraction of each type of active center. For a catalyst with two types of active centers, the maximum polydispersity of copolymer occurs at 50 wt. % of the total copolymer if polydispersities of the copolymers generated at each active site are the same. Polydispersity of accumulated copolymer is sensitive to propagation reactions and chain transfer to hydrogen reactions. Differences in chain transfer to cocatalyst and monomers and in spontaneous deactivation rates for different types of active centers may play minor roles in controlling molecular weight development in the presence of hydrogen. This model can be used for catalyst composition design, simulation of commercial olefin copolymerization processes, and kinetic parameter estimation.