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Versatile Pathways for In Situ Polyolefin Functionalization with Heteroatoms: Catalytic Chain Transfer
Author(s) -
Amin Smruti B.,
Marks Tobin J.
Publication year - 2008
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200703310
Subject(s) - polyolefin , metallocene , surface modification , catalytic chain transfer , polymerization , polymer chemistry , chain transfer , chemistry , heteroatom , materials science , organic chemistry , combinatorial chemistry , alkyl , radical polymerization , polymer , layer (electronics)
Chain‐transfer processes represent highly effective chemical means to achieve selective, in situ d‐ and f‐block‐metal catalyzed functionalization of polyolefins. A diverse variety of electron‐poor and electron‐rich chain‐transfer agents, including silanes, boranes, alanes, phosphines, and amines, effect efficient chain termination with concomitant carbon–heteroelement bond formation during single‐site olefin‐polymerization processes. High polymerization activities, control of polyolefin molecular weight and microstructure, and selective chain functionalization are all possible, with distinctly different mechanisms operative for the electron‐poor and electron‐rich reagents. A variety of metal centers (early transition metals, lanthanides, late transition metals) and single‐site ancillary ligand arrays (metallocene, half‐metallocene, non‐metallocene) are able to mediate these selective chain‐termination/functionalization processes.