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Alk‐1‐ene Polymerization in the Presence of a Monocyclopentadienyl Zirconium( IV ) Acetamidinate Catalyst: Microstructural and Mechanistic Insights
Author(s) -
Busico Vincenzo,
Carbonniere Philippe,
Cipullo Roberta,
Pellecchia Roberta,
Severn John R.,
Talarico Giovanni
Publication year - 2007
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.200700098
Subject(s) - tacticity , living polymerization , polymerization , chain transfer , propene , copolymer , ene reaction , polymer chemistry , polymer , catalysis , materials science , zirconium , reversible addition−fragmentation chain transfer polymerization , chemistry , radical polymerization , organic chemistry , metallurgy , composite material
Suitably activated, (Cp*){N( t Bu)C(Me)N(Et)}ZrMe 2 is known to initiate the ‘living’ and isotactic‐selective polymerization of alk‐1‐enes, and it can be used to synthesize block copolymers and stereoblock polymers. We report a full molecular kinetic investigation of propene, but‐1‐ene, and hex‐1‐ene polymerization with a MAO‐activated catalyst system. By combining NMR microstructural polymer analysis with QM modeling of the active species, the complicated regio‐ and stereochemistry of the polyinsertion process, as well as the active chain‐transfer pathways, are investigated. The perspectives and limitations of this catalyst for application in (stereo)block polymerizations are discussed.