Abstract
Initiated by an organic molecule trifluoromethanesulfonimide (HNTf2) without any Lewis acid or Lewis base stabilizer, cationic polymerization of isobutyl vinyl ether (IBVE) takes place rapidly and the polymerization is proved to be in a controlled/living manner. The conversion of IBVE could easily achieve 99% in seconds. The product poly(isobutyl vinyl ether) is narrowly distributed and its molecular weight increases linearly with time and fits well with the corresponding theoretical value. This single-molecular initiating system also works well in the living cationic polymerization of ethyl vinyl ether. HNTf2 is considered playing multiple roles which include initiator, activator, and stabilizer in the polymerization. It is quite different from the hydrogen halide-catalyzed polymerizations of vinyl ethers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1373-1377
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