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Living carbocationic polymerization

XXXII. Living polymerization of isobutylene by tertiary alcohol/boron trichloride systems

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Abstract

Mono- and bifunctionaltert-alcohols, i.e., cumyl alcohol (CumOH), 2,4,4-trimethyl-2-pentanol (TMPOH), 2,6-dihydroxy-2,4, 4, 6-tetramethylheptane (TMHDiOH), in conjunction with BCl3 have been shown to be efficient initiating systems for the living polymerization of isobutylene (IB) in CH3Cl or CH2Cl2 solvents in the −10° to −80°C range. The living nature of the polymerizations was demonstrated by linear Mn versus amount of polyisobutylene (PIB) formed (WPIB) plots starting at the origin and corresponding horizontal number of PIB moles formed (N) versus WPIB plots. Quenching with methanol producestert-chlorine terminated PIBs. Quantitative dehydrochlorination of the latter products yields exo-olefin (isopropylidene) end groups. These experiments demonstrate that living carbocationic polymerizations have in fact been conducted in these laboratories long ago (1) without having been recognized as such.

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Author notes

  1. Munmaya K. Mishra

    Present address: Elastomers Research Division, Polysar Inc., 44224, Stow, OH, USA

Authors and Affiliations

  1. Institute of Polymer Science, University of Akron, 44325, Akron, OH, USA

    Munmaya K. Mishra, C. Charles Chen & Joseph P. Kennedy

Authors
  1. Munmaya K. Mishra
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  2. C. Charles Chen
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  3. Joseph P. Kennedy
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Mishra, M.K., Charles Chen, C. & Kennedy, J.P. Living carbocationic polymerization. Polymer Bulletin 22, 455–462 (1989). https://doi.org/10.1007/BF00718919

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  • DOI: https://doi.org/10.1007/BF00718919

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