Abstract
In this study an empirical calculation of the relative reactivities of cyclic ethers, formals, and esters in cationic copolymerizations has been achieved. It is postulated that the apparent propagation reaction consists of two elementary reactions of the nucleophilic coordination of cyclic monomers to a growing cation and of the ionic ring-opening and addition of the broken bond. The former is an equilibrium reaction and its equilibrium constant has been evaluated as KD (or the free energy change, ΔGD) of the intermodular complex formed between the monomer and the deuterium atom of methanol-d as a cation model. The reactivity of the latter has been discussed using the method of activation energy evaluation employing the Morse potential energy function, and the rate constant has been approximately estimated with the radical dissociation energy, Di, of the broken bond. The available experimental data on the reactivities of cyclic monomers are discussed in detail by using these energetic terms. The following empirical formula has been derived to represent the relative reactivities of cyclic ethers
where Δ is the difference from monomer 2 to 1. The treatment proposed is useful for the evaluation of the monomer reactivities of various cyclic ethers in cationic copolymerizations.
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Kagiya, T., Sumida, Y. & Inoue, T. Reactivities of Cyclic Monomers in Cationic Copolymerizations. Nucleophilic Coordination and Ionic Ring-Opening of the Bond. Polym J 1, 312–321 (1970). https://doi.org/10.1295/polymj.1.312
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DOI: https://doi.org/10.1295/polymj.1.312
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