New initiating systems for living cationic polymerization: Design and mechanism

This paper concerns the recent progress in our search for new initiating systems for living cationic polymerization and the mechanisms involved therein, specifically focusing on: (a) Protonic acid/Lewis acid initiating systems for vinyl ethers; (b) Initiating systems for living cationic polymerization of styrene; (c) Multi‐functional initiating systems. In area (a), the design of counteranions was discussed relative to the principles of living cationic polymerization; in area (b), the first truly living cationic polymerization of styrene is described; and in area (c), the multi‐functional initiating systems led to tri‐armed polymers of vinyl ethers and p ‐alkoxystyrenes with amphiphilic arm chains of uniform lengths.