Activation parameters for propene polymerization mediated by a bis(phenoxyamine)Zr-dibenzyl catalyst in combination with MAO have been measured experimentally and calculated by DFT; experiment and calculation consistently indicate that the entropic term is the most important reason for the low chain propagation rate with this system. Based on this finding and a review of literature data on a variety of olefin polymerization catalysts, we propose a strong correlation between the propagation rate and how catalysts deal with the entropy loss of monomer capture.
Structure-Activity Relationship in Olefin Polymerization Catalysis: Is Entropy the Key? / Ciancaleoni, G.; Fraldi, N.; Budzelaar, Petrus Henricus Maria; Busico, Vincenzo; Cipullo, Roberta; Macchioni, A.. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - ELETTRONICO. - 132:(2010), pp. 13651-13653. [10.1021/ja105965x]
Structure-Activity Relationship in Olefin Polymerization Catalysis: Is Entropy the Key?
BUDZELAAR, Petrus Henricus Maria;BUSICO, VINCENZO;CIPULLO, ROBERTA;
2010
Abstract
Activation parameters for propene polymerization mediated by a bis(phenoxyamine)Zr-dibenzyl catalyst in combination with MAO have been measured experimentally and calculated by DFT; experiment and calculation consistently indicate that the entropic term is the most important reason for the low chain propagation rate with this system. Based on this finding and a review of literature data on a variety of olefin polymerization catalysts, we propose a strong correlation between the propagation rate and how catalysts deal with the entropy loss of monomer capture.File | Dimensione | Formato | |
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