Premium
Deactivation Kinetics of Metallocene‐Catalyzed Ethene Polymerization at High Temperature and Elevated Pressure
Author(s) -
Dornik Hans Peter,
Luft Gerhard,
Rau Alexander,
Wieczorek Thomas
Publication year - 2004
Publication title -
macromolecular materials and engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.913
H-Index - 96
eISSN - 1439-2054
pISSN - 1438-7492
DOI - 10.1002/mame.200300316
Subject(s) - metallocene , thermostability , activation energy , catalysis , kinetics , ternary operation , polymerization , materials science , polymer chemistry , ligand (biochemistry) , chemistry , organic chemistry , polymer , biochemistry , physics , receptor , quantum mechanics , computer science , programming language , enzyme , composite material
Summary: The kinetics of ethene polymerization with metallocene/[Me 2 PhNH] + [B(C 6 F 5 ) 4 ] − /Al i Bu 3 (ternary systems) and metallocene/methylaluminoxan (MAO) systems respectively has been investigated at 100–140 °C and 7 MPa. Overall, eight different unbridged and ansa ‐metallocenes were tested. The effect of ligand structure, cocatalyst and catalyst concentration on the thermostability and the activation energy of deactivation were studied. Deactivation with respect to the catalyst concentration followed a first order reaction. The half‐life as well as the activation energy of the ternary systems depended strongly on ligand structure while the ligand structure of MAO‐activated metallocenes merely influenced the half‐life. The half‐life associated with MAO activation is approximately twice as high as that in ternary activation. Based on these results, conclusions about the deactivation reactions have been drawn.Influence of catalyst concentration on deactivation.