Branching Regulation in Olefin Polymerization via Lewis Acid Triggered Isomerization of Monomers.
Angew Chem Int Ed Engl
; 59(12): 4743-4749, 2020 Mar 16.
Article
em En
| MEDLINE
| ID: mdl-31881118
ABSTRACT
We present a new strategy to regulate branching in chain-walking olefin polymerization by triggering a rapid isomerization of 1-alkene monomers into internal olefins by adding a Lewis acid. Polymerization of internal alkenes proceeds via chain-walking to give polymers with much higher branching than 1-alkene analogues. The utility of this approach is exemplified by synthesis of well-defined block copolymers with distinct branching characteristics per block by addition of Lewis acid midway through a reaction. We propose a novel mechanism whereby Lewis acid undergoes a counterion swap with the complex which favors isomerization as well as forming adducts with ancillary ligands, freeing coordination sites for internal alkene coordination polymerization.
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MEDLINE
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En
Ano de publicação:
2020
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Article