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Single‐Site, Organometallic Aluminum Catalysts for the Precise Group Transfer Polymerization of Michael‐Type Monomers
Author(s) -
Weger Michael,
Giuman Marco M.,
Knaus Maximilian G.,
Ackermann Maximilian,
Drees Markus,
Hornung Julius,
Altmann Philipp J.,
Fischer Roland A.,
Rieger Bernhard
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201802075
Subject(s) - polymerization , polymer chemistry , copolymer , monomer , chemistry , living polymerization , cationic polymerization , lewis acids and bases , ionic polymerization , catalysis , radical polymerization , organic chemistry , polymer
Unlike different types of Lewis pairs as polymerization catalysts for acrylic monomers, organometallic aluminum(III) compounds are reported that show a surprisingly high polymerization activity even without an additional Lewis base.[1][, ] DFT calculations, end group analysis and kinetic investigations clearly suggest a main group element (MGE) group transfer polymerization (GTP) mechanism analogous to the known metal‐mediated GTP mechanism. The novel catalysts perform a precision polymerization of a broad variety of monomers, ranging from 2‐isopropenyl‐2‐oxazoline to tert ‐butylmethacrylate and N , N ‐dimethylacrylamide. Additionally, extended Michael‐type structures like 4‐vinyl pyridine are accessible. Especially the Al(III) half‐metallocenes show an almost quantitative initiator efficiency, and, combined with the living character of the polymerization reactions, they enable the synthesis of block copolymers, even with unconventional monomers like vinyl phosphonates.