Modelling carbocationic polymerizations: Kinetics of the reactions of carbocations with alkenes

Reactions of carbocations with olefins and related π-nucleophiles follow second order kinetics, first order with respect to carbocation and first order with respect to olefin. The rate constants are equal for paired and non-paired ions and independent of the nature of the negative counter-ions. Rate constants k < 10⁷-10⁸ L mol⁻¹ s⁻¹ can be calculated by lg k(20 °C) = s (N+E), where E represents the strengths of the electrophiles, while nucleophiles are characterized by the slope parameter s and the nucleophilicity parameter N. These parameters can be used for selecting initiators for carbocationic polymerizations and for designing copolymers.