Rapid and Scalable Access to Sequence‐Controlled DHDM Multiblock Copolymers by FLP Polymerization

An immortal N‐(diphenylphosphanyl)‐1,3‐diisopropyl‐4,5‐dimethyl‐1,3‐dihydro‐2H‐imidazol‐2‐imine/diisobutyl (2,6‐di‐tert‐butyl‐4‐methylphenoxy) aluminum (P(NIiPr)Ph2/(BHT)AliBu2)‐based frustrated Lewis pair (FLP) polymerization strategy is presented for rapid and scalable synthesis of the sequence‐co...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-07, Vol.59 (28), p.11613-11619
Main Authors: Bai, Yun, Wang, Huaiyu, He, Jianghua, Zhang, Yuetao
Format: Article
Language:English
Subjects:
Access control
Aluminum
Catalysts
Chemical synthesis
Copolymers
frustrated Lewis pairs
living polymerization
Molecular weight
multiblock copolymers
organophosphorus superbase
Polymerization
Room temperature
sequence control
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Summary:An immortal N‐(diphenylphosphanyl)‐1,3‐diisopropyl‐4,5‐dimethyl‐1,3‐dihydro‐2H‐imidazol‐2‐imine/diisobutyl (2,6‐di‐tert‐butyl‐4‐methylphenoxy) aluminum (P(NIiPr)Ph2/(BHT)AliBu2)‐based frustrated Lewis pair (FLP) polymerization strategy is presented for rapid and scalable synthesis of the sequence‐controlled multiblock copolymers at room temperature. Without addition of extra initiator or catalyst and complex synthetic procedure, this method enabled a tripentacontablock copolymer (n=53, k=4, dpn=50) to be achieved with the highest reported block number (n=53) and molecular weight (Mn=310 kg mol−1) within 30 min. More importantly, this FLP polymerization strategy provided access to the multiblock copolymers with tailored properties by precisely adjusting the monomer sequence and block numbers. Non‐touching superbase: An organophosphorus superbase‐containing frustrated Lewis pair was employed to achieve sequence‐controlled tripentacontablock copolymer (n=53, k=4, dpn=50) with the highest reported block number (n=53) and molecular weight (Mn=310 kg mol−1) within 30 min.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202004013