Abstract
Rate constants for the reactions of carbocations with substituted ethylenes can be determined when the reactions terminate at the [1:1]-product stage. Correlation equations are presented which allow one to derive rate constants for these reactions from the electrophilicity parameters (E) of the carbocations and the nucleophilicity (N) and slope parameters (s) of the yn-systems. Since the slope s is usually close to 1, initiation and propagation rate constants of carbocationic polymerizations can be estimated from the data presented in Schemes 7–11. The special features of fast reactions (e.g., propagations), which do not have enthalpic barriers, are discussed.
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Mayr, H. (1999). Rate Constants and Reactivity Ratios in Carbocationic Polymerizations. In: Puskas, J.E., Michel, A., Barghi, S. (eds) Ionic Polymerizations and Related Processes. NATO Science Series, vol 359. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-4627-2_7
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DOI: https://doi.org/10.1007/978-94-011-4627-2_7
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