Structure-activity relationship in olefin polymerization catalysis: is entropy the key?
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.
Ciancaleoni
Gianluca
G
Dipartimento di Chimica, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy.
Fraldi
Natascia
N
Budzelaar
Peter H M
PH
Busico
Vincenzo
V
Cipullo
Roberta
R
Macchioni
Alceo
A
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*
D000475:Alkenes; D009942:Organometallic Compounds; C013658:propylene; D015040:Zirconium