Catalytical and Radical Polymerization by P. C. Barbe

By P. C. Barbe

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2 Number of Active Centers and Values of the Propagation Rate Constants In Ziegter-Natta catalysts, quantitative information about the number of active centers is very important. Together with kinetic data and polymer microstructural and stereochemical analyses, they contribute to the formulation of the most likely reaction mechanism and to the understanding of the roles the different catalyst system components play. C. Barb6 et al. even more important as it makes it possible to establish the reason why these catalysts are more active than the traditional ones.

A rough model could, for example, be made up of the following equilibria (where C a t - [ ] indicates a free site on the catalytic surface) : 1 CAT-EB + A1Et3 ~ AIEt 3 - EB + CAT-I-q 2 CAT-IT + AtEt a ~ C A T • A1Et 3 3 A1Et 3 + MPT ~ A1Et 3 • M P T ( ~ degradation) 4 CAT-[-] + AIEt 3 - M P T ~ C A T • M P T + AIEt 3 In fact, equilibria 1 and 2 account for the displacement of EB and its replacement with A1 which can be observed in Fig. 25, while equilibrium 3, with the subsequent degradation reaction, by removing AIEt z from equilibrium 1, explains the fact that the addition o f M P T to the system attenuates the EB extraction.

Based on the independence of IVlw/IVl" on the hydrogen concentration, as well as kinetic evidence concerning an inhibition of the polymerization rate by CO, a surface heterogeneity dependence of the propagation rate constant has been proposed. As mentioned above, the electron donor has no effect on the polymer IVlw/1VI.. The polydispersity of the overall polymer only changes as a result of a variation of the relative quantity of atactic and isotactic polymer. Thus, the donor does not participate in the formation of active centers having different if,I and MWD.

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