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Hydrogen Bond Donor Catalyzed Cationic Polymerization of Vinyl Ethers
Author(s) -
Kottisch Veronika,
Jermaks Janis,
Mak JoeYee,
Woltornist Ryan A.,
Lambert Tristan H.,
Fors Brett P.
Publication year - 2021
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.202013419
Subject(s) - cationic polymerization , polymerization , chemistry , polymer chemistry , monomer , chain transfer , living cationic polymerization , polymer , vinyl polymer , hydrogen bond , catalysis , reagent , ionic polymerization , ring opening polymerization , photochemistry , organic chemistry , molecule , radical polymerization
Abstract The synthesis of high‐molecular‐weight poly(vinyl ethers) under mild conditions is a significant challenge, since cationic polymerization reactions are highly sensitive to chain‐transfer and termination events. We identified a novel and highly effective hydrogen bond donor (HBD)–organic acid pair that can facilitate controlled cationic polymerization of vinyl ethers under ambient conditions with excellent monomer compatibility. Poly(vinyl ethers) of molar masses exceeding 50 kg mol −1 can be produced within 1 h without elaborate reagent purification. Modification of the HBD structure allowed tuning of the polymerization rate, while DFT calculations helped elucidate crucial intermolecular interactions between the HBD, organic acid, and polymer chain end.