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Modelling carbocationic polymerizations: Kinetics of the reactions of carbocations with alkenes
Author(s) -
Mayr Herbert,
Patz Matthias
Publication year - 1996
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.19961070111
Subject(s) - carbocation , kinetics , isobutylene , chemistry , cationic polymerization , photochemistry , polymer chemistry , materials science , organic chemistry , physics , polymer , copolymer , quantum mechanics
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 < 10 7 ‐10 8 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.