This article summarizes fundamental and general aspects of carbocationic polymerizations, with a historical overview and up-to-date references. Following general considerations, the basic elements of carbocationic polymerization, such as monomers, initiating systems, solvents, and temperature, are discussed. Special attention is given to carbocation stability and monomer nucleophilicity, and dynamic interactions. The section on the kinetics of carbocationic polymerization presents current understanding of the elementary reactions—initiation, propagation, termination, and transfer reactions, and copolymerization. Controlled (living) carbocationic polymerization is discussed in a separate section. Finally, industrial carbocationic polymerizations are reviewed.
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