Tandem Living Insertion and Controlled Radical Polymerization for Polyolefin–Polyvinyl Block Copolymers

Practical synthesis of polyolefin–polyvinyl block copolymers remains a challenge for transition‐metal catalyzed polymerizations. Common approaches functionalize polyolefins for post‐radical polymerization via insertion methods, yet sacrifice the livingness of the olefin polymerization. This work ide...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-03, Vol.61 (10), p.e202112742-n/a
Main Authors: Keyes, Anthony, Dau, Huong, Matyjaszewski, Krzysztof, Harth, Eva
Format: Article
Language:English
Subjects:
Block Copolymer
Block copolymers
Chemical synthesis
Copolymers
Coupling
Functionalization
Insertion
Living Polymerization
Nitroxide
Polymerization
Polyolefin
Polyolefins
Radical Coupling
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Summary:Practical synthesis of polyolefin–polyvinyl block copolymers remains a challenge for transition‐metal catalyzed polymerizations. Common approaches functionalize polyolefins for post‐radical polymerization via insertion methods, yet sacrifice the livingness of the olefin polymerization. This work identifies an orthogonal radical/spin coupling technique which affords tandem living insertion and controlled radical polymerization. The broad tolerance of this coupling technique has been demonstrated for diverse radical/spin traps such as 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide (TIPNO), 1‐oxyl‐(2,2,6,6‐tetramethylpiperidine) ‐4‐yl‐α‐bromoisobutyrate (TEMPO‐Br), and N‐tert‐butyl‐α‐phenylnitrone (PBN). Subsequent controlled radical polymerization is demonstrated with nitroxide‐mediated polymerization (NMP) and atom transfer radical polymerization (ATRP), yielding polyolefin–polyvinyl di‐ and triblock copolymers (Đ
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202112742