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

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Abstract
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.
Funding Information
  • Deutsche Forschungsgemeinschaft
  • Fonds der Chemischen Industrie