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Ultra‐High‐Molecular‐Weight Polymers Produced by the Immortal Phosphine‐Based Catalyst System
Author(s) -
Bai Yun,
He Jianghua,
Zhang Yuetao
Publication year - 2018
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.201811946
Subject(s) - superbase , polymer chemistry , methyl methacrylate , frustrated lewis pair , polymerization , lewis acids and bases , chemistry , catalysis , steric effects , polymer , molar mass distribution , living polymerization , phosphine , imine , methacrylate , organic chemistry , radical polymerization
A strong organophosphorus superbase, N‐(diphenylphosphanyl)‐1,3‐diisopropyl‐4,5‐dimethyl‐1,3‐dihydro‐2H‐imidazol‐2‐imine ( IAP3 ) was combined with a sterically encumbered but modestly acidic Lewis acid (LA), (4‐Me‐2,6‐ t Bu 2 ‐C 6 H 2 O)Al i Bu 2 ((BHT)Al i Bu 2 ), to synergistically promote the frustrated Lewis pair (FLP)‐catalyzed living polymerization of methyl methacrylate (MMA), achieving ultrahigh molecular weight (UHMW) poly(methyl methacrylate) (PMMA) with M n up to 1927 kg mol −1 and narrow molecular weight distribution (MWD) at room temperature (RT). This FLP catalyst system exhibits exceptionally long lifetime polymerization performance even in the absence of free MMA, which could reinitiate the desired living polymerization after the resulting system was held at RT for 24 h.