The synthesis of the novel inimer (initiator-monomer) 4-(1,2-oxirane-isopropyl)styrene EPOIM and the copolymerization of this inimer with isobutylene (IB) to form arborescent polyisobutylene (PIB) is described. Polymerizations were accomplished by use of TiCl4 coinitiator and the effect of reaction conditions was investigated. Size exclusion chromatography (SEC) was used demonstrate EPOIM incorporation across the whole molecular weight distribution. The average number of branch points (B) per chain measured by use of selective link destruction increased with increasing EPOIM/IB ratio and decreased with [TiCl4]. Large scale polymerizations were carried out based on results from small scale polymerizations. Architecture analysis carried out through use of branching parameters based on the radii of gyration R-g and hydrodynamic radii Rh measured by multidetector SEC corroborated the proposed arborescent architecture. (c) 2007 Wiley Periodicals, Inc.