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Journal of Polymer Science Part A: Polymer Chemistry, Vol.37, No.14, 2285-2293, 1999
Living cationic polymerization of olefins. How did the discovery come about?
The tortuous road to living carbocationic polymerizations is chronicled. The impetus for this project was my conviction that, just as living anionic polymerizations have started with a critical insight, a similar breakthrough will also be possible with cations. Upon retrospect, the facts show a three-step progression to the objective: Discovery of 1) controlled initiation, 2) reversible termination (quasiliving systems), and 3) controlled chain transfer. But what good is the discovery of a process without demonstrating its usefulness in terms of desirable products? Thus, a section concerns unique microarchitectures obtainable only by this technique: functional liquids, telechelics, thermoplastic elastomers, etc. The marketing of some of these products has already started, and the fundamental exploration of the promises of this technique is in progress worldwide.
Keywords:living carbocationic polymerizations;cationic olefin polymerization;boron trichloride;titanium tetrachloride;polyisobutylene;polystyrene;tailor-made microarchitectures;telechelics;thermoplastic elastomers