title: Structure-activity relationship in olefin polymerization catalysis: is entropy the key?
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.
authors.affiliation: Dipartimento di Chimica, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy.
authors.forename: Gianluca
authors.initials: G
authors.lastname: Ciancaleoni
authors.forename: Natascia
authors.initials: N
authors.lastname: Fraldi
authors.forename: Peter H M
authors.initials: PH
authors.lastname: Budzelaar
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Busico
authors.forename: Roberta
authors.initials: R
authors.lastname: Cipullo
authors.forename: Alceo
authors.initials: A
authors.lastname: Macchioni
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003198:Computer Simulation; D019277:Entropy; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D015040:Zirconium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D009942:Organometallic Compounds; C013658:propylene; D015040:Zirconium