Abstract
The mechanisms of initiation reactions of carbocationic polymerizations determine the nature of the counter-ions and then to a large extent the stability of the active centres and the importance of chain transfer. The fate of the initiator is examined in chemically initiated carbocationic polymerizations initiated with protonic acids and with Friedel Crafts catalysts. In this last case, the criteria proposed to distinguish between direct and cocatalysed initiation are discussed. This is related to the mechanisms of synthesis of block and graft copolymers and of polymers with well defined end groups. A discussion of the types of species active for polymer growth is then made. This is linked to the possible occurrence of pseudocationic polymerizations, to the existence of visible and invisible species and to the observations of polymodal molecular weight distributions. In the last part, the stability of the active centres is examined, and also the various assumptions made to explain the growth of molecular weight with conversion in several systems. The occurrence of living or “quasiliving” polymerizations and other possible explanations are discussed.
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Sigwalt, P. Recent Results in Proton-Initiated and Non Proton-Initiated Cationic Polymerizations. Polym J 17, 57–71 (1985). https://doi.org/10.1295/polymj.17.57
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DOI: https://doi.org/10.1295/polymj.17.57