Synthesis of new functional polymers by living cationic polymerization

This paper covers three major areas of the synthetic applications of living cationic polymerization of vinyl ethers initiated by the hydrogen iodide/iodine (HI/I 2 ) system; namely, the synthesis of (a) pendant‐functionalized polymers, (b) end‐functionalized polymers, and (c) amphiphilic block polymers with a unique structure. In area (a), more than 25 vinyl ethers with a functional pendant were found to undergo living polymerization to give a variety of pendant‐functionalized polymers:In area (b), terminally monofunctional and telechelic polymers (including macromonomers) were prepared by living polymerization using a functional initiating system (CH 3 ‐CHI‐OCH 2 CH 2 ‐X/I 2 ) and/or by end‐capping of the HI/I 2 ‐initiated living polymer ends with a functional nucleophile (:Nu‐X):In area (c), amphiphilic block polymers of vinyl ethers were obtained and characterized, the hydrophilic segment of which carried highly branched bulky substituents with a large number of hydroxyl groups (six per pendant):