Intramolecular activation of hydrocarbyls to form metallacyclic complexes is a relatively fast process in cationic hafnocene catalysts bearing propyl-substituted Cp ligands. The resulting metallacycles are effective 1-hexene polymerization catalysts with activities comparable to that of the nonmetalated precursor. Ad hoc polymerizations of 1-hexene, using (CpPr)2HfMe2 as catalyst precursor, allow the isolation and characterization, via nuclear magnetic resonance (NMR) and matrix-assisted laser desorption ionization (MALDI) techniques, of polymers containing (CpCH2-CH2-CR3)2HfCl2 (R = H or polymeryl) units. The polymeryl substitutions arise from irreversible incorporation of polymer chains onto the cyclopentadienyl ligand substituent(s) via metallacycle intermediates. As a consequence of such "selfmodification", multiple active sites are generated by a nominally single-site catalyst; this may explain the broadening of the molecular weight distribution (MWD) and chemical composition distribution (CCD) observed in olefin polymerization. (Chemical Equation Presented). © 2016 American Chemical Society.
C–H Activation and Olefin Insertion as Sources of Multiple Sites in Olefin Polymerization Catalyzed by CpAlkylHf(IV) Complexes
ZUCCACCIA, Cristiano
;TENSI, LEONARDO;MACCHIONI, Alceo
2017
Abstract
Intramolecular activation of hydrocarbyls to form metallacyclic complexes is a relatively fast process in cationic hafnocene catalysts bearing propyl-substituted Cp ligands. The resulting metallacycles are effective 1-hexene polymerization catalysts with activities comparable to that of the nonmetalated precursor. Ad hoc polymerizations of 1-hexene, using (CpPr)2HfMe2 as catalyst precursor, allow the isolation and characterization, via nuclear magnetic resonance (NMR) and matrix-assisted laser desorption ionization (MALDI) techniques, of polymers containing (CpCH2-CH2-CR3)2HfCl2 (R = H or polymeryl) units. The polymeryl substitutions arise from irreversible incorporation of polymer chains onto the cyclopentadienyl ligand substituent(s) via metallacycle intermediates. As a consequence of such "selfmodification", multiple active sites are generated by a nominally single-site catalyst; this may explain the broadening of the molecular weight distribution (MWD) and chemical composition distribution (CCD) observed in olefin polymerization. (Chemical Equation Presented). © 2016 American Chemical Society.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
