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Living carbocationic polymerization

XXXIII. Living polymerization of isobutylene by tertiary hydroxyl/boron trichloride/electron pair donor systems

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Abstract

Tert-alcohols in conjunction with BCl3 plus strong electron pair donors (EDs), such as dimethyl sulfoxide (DMSO) and dimethyl acetamide (DMA), have been found efficiently to initiate the living polymerization of isobutylene (IB) in methyl chloride diluent yielding narrow molecular weight distribution (MWD) polyisobutylenes (PIBs). For example, the aliphatic diol 2, 6-dihydroxy-2,4,4,6-tetramethylheptane/BCl3/ IB/DMA/−45°C system yields lineartert-chlorine telechelic\(\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{t} Cl - PIB - Cl\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{t} s\) with Mw/Mn = 1.12 at Mn = 2500, and the aromatic triol 1,3,5-tri (2-hydroxyisopropyl)benzene/BCl3/IB/DMA/−50°C system produces three-arm startert-chlorine telechelic\(\begin{gathered} \underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{t} Cl - \mathop {PIB}\limits_| - Cl\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{t} \hfill \\ Cl\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{t} \hfill \\ \end{gathered} \) with Mw/Mn = 1.15 at Mn = 2000. Premixing experiments suggest that in the presence of excess BCl3 thetert-alcohols are rapidly transformed totert-chlorides, and that the latters are the true initiating species. Due to reversible termination the products are capped bytert-chlorines.

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Author notes

  1. Gabor Kaszas & Judit E. Puskas

    Present address: Polysar Ltd., 1265 Vidal St. South, P.O. Box 3001, N7T 7M2, Samia, ONT, Canada

Authors and Affiliations

  1. Institute of Polymer Science, University of Akron, 44325-3909, Akron, OH, USA

    C. Charles Chen, Gabor Kaszas, Judit E. Puskas & Joseph P. Kennedy

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  1. C. Charles Chen
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  2. Gabor Kaszas
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  3. Judit E. Puskas
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Chen, C.C., Kaszas, G., Puskas, J.E. et al. Living carbocationic polymerization. Polymer Bulletin 22, 463–470 (1989). https://doi.org/10.1007/BF00718920

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