Summary
Low molecular weight (¯Mn ∼900–5000) narrow molecular weight distribution (MWD; ¯Mw/Mn = 1.1–1.2)tert.-chlorine telechelic polyisobutylenes (PIBs) have been synthesized by the use of thetrans-2,5-dimethyl-2,5-diacetoxy-3-hexene (DiOAcDMeH6)/BCl3 initiating system in the presence of the electron donor (ED) dimethyl sulfoxide (DMSO) in methyl chloride diluent at −30°C. The living character of the polymerization was demonstrated by linear Mn versus Wp (weight of polymer) plots starting at the origin with the slope of 1/[Io] (where [Io] = initiator concentration). DMSO reduces the overall rate of polymerization, however, it increases the initiator efficiency (Ieff) to ∼100%. The number averagetert.-chlorine end functionality is -Fn=1.97±0.04, by1H NMR spectroscopy. Polymerization mechanistic details are discussed. This is the first time narrow MWDtert.-chlorine telechelic PIB has been prepared close to the reflux temperature of methyl chloride.
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Paper XXVII in the series on Living Carbocationic Polymerization. For paper XXVI see Kaszas et al., J. Macromol. Sci. Chem. to appear (1989)
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Zsuga, M., Kennedy, J.P. Electron donors in carbocationic polymerization. Polymer Bulletin 21, 5–12 (1989). https://doi.org/10.1007/BF00700261
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DOI: https://doi.org/10.1007/BF00700261