Abstract
The polymerization of isobutylene inn-hexane at −78°C under the action of the superacid HBr·2A1Br3 as well as acetyl complexes MeCOBr·AlBr3 and MeCOBr·2AlBr3 in the presence of HBr·AlBr3 and HBr·2AlBr3, respectively, was studied. Unlike the superacid providing a quantitative yield of polyisobutylene (PIB) due to protonogenic initiation, the acetyl complexes suppress the proton initiation. In the presence of a mixture of both complexes with the superacid, only macromolecules with the head acetyl fragments MeC(O) are formed, which is evidence for a carbocationic initiation. The data obtained are explained by trapping of protons by the carbonyl groups to form ionic structures of the\(\begin{gathered} [Me - \mathop C\limits_\parallel - PIB][Al_2 Br_7 ]^ - \hfill \\ HO^ + \hfill \\ \end{gathered} \) type (where PIB is polyisobutylene) and to suppress the ionization of the superacids due to the common ion effect.
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For Part 7, see Ref. 1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 974–978, May, 1997.
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Murachev, V.B., Ezhova, E.A., Nesmelov, A.I. et al. Cationic polymerization of hydrocarbon monomers induced by complexes of acyl halides with Lewis acids. Russ Chem Bull 46, 934–938 (1997). https://doi.org/10.1007/BF02496122
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DOI: https://doi.org/10.1007/BF02496122