, Volume 19, Issue 1, pp 43-50

Living carbocationic polymerization

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Summary

The synthesis of the first four-arm star polyisobutylenes (PIB) capped by t-chlorine and isopropylidene groups has been accomplished by the 3,3′,5,5′-tetra(2-acetoxy-isopropyl)biphenyl/BCl3 initiating system. The polymerizations yield tertchlorine capped arms which have been quantitatively dehydrochlorinated to isopropylidene end-groups. Homogeneous polymerization conditions seem to be mandatory for the synthesis of well-defined products. The polymers were characterized by GPC and 1H NMR spectroscopy and product homogeneity was demonstrated by KSN plots. The number average end functionality was found to be Fn=4.06 ± 0.4.