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• W2893130872 abstract "The chemical kinetics for a series of three zirconium amine bis(phenolate) catalysts for poly 1-hexene polymerization have been examined as a function of temperature. Detailed modeling of the experimental data has yielded the activation parameters for many of the reaction rate constants, including those for propagation, initiation, chain transfer, and monomer misinsertion and recovery. While existing literature is sparse, the results herein generally agree with previously published values; specifically, for the propagation rate constant, the magnitude of the enthalpy of activation is low (12 kcal mol–1 and below), and the magnitude of the entropy of activation is moderate (up to −27 cal mol–1 K–1). With regard to the remaining rate constants, Arrhenius behavior is observed in most cases despite the complexity of the temperature dependence in the two-step adsorption/insertion kinetics. The rate expression for these reactions approaches an Arrhenius form in certain limiting cases of the relative elementary rate constants. The reaction rate data are compared against these limiting cases, leading to the conclusion that docking, with an early transition state, is rate limiting for propagation and placing bounds on the interpretation of most of the remaining constants. The challenges encountered in assigning temperature-dependent rate constants for the polymerization reactions are indicative of both the significant complexity in modeling a reaction in which thousands of species are present and the extreme care that is required in generating reproducible data." @default.
• W2893130872 created "2018-10-05" @default.
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• W2893130872 date "2018-09-27" @default.
• W2893130872 modified "2023-10-06" @default.
• W2893130872 title "Quantitative Modeling of the Temperature Dependence of the Kinetic Parameters for Zirconium Amine Bis(Phenolate) Catalysts for 1-Hexene Polymerization" @default.
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• W2893130872 doi "https://doi.org/10.1021/acscatal.8b01989" @default.
• W2893130872 hasPublicationYear "2018" @default.
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