Abstract
AbstractThis paper discusses recent developments in living cationic polymerization of vinyl monomers, specifically focusing on (a) new initiating systems, (b) kinetics and mechanism, and (c) controlled polymer synthesis. The new initiating systems were based on nucleophilic stabilization of the growing carbocations, either by counteranions (as in phosphate/ZnI2 and Me3SiI/ZnI2 systems) or by added Lewis bases (as 2,6‐dimethylpyridine for EtAlCl2). The kinetic study included the determination of the lifetime of living cationic polymers. The controlled polymer synthesis by living cationic processes led to not only end‐ and pendant‐functionalized polymers of narrow molecular weight distributions but also star‐shaped polymers and sequence‐regulated vinyl ether oligomers with functional groups.
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