A general method for the transformation of “living” carbocationic into “living” radical polymerization, without any modification of chain ends, is reported for the preparation of ABA block copolymers. For example, α,ω-difunctional polyisobutene, capped with several units of styrene, Cl-St-PIB-St-Cl, prepared cationically (Mn = 7800, Mw/Mn = 1.31) was used as an efficient difunctional macroinitiator for homogeneous “living” atom transfer radical polymerization to prepare triblock copolymers with styrene, PSt-PIB-PSt (Mn = 28,800, Mw/Mn = 1.14), methyl acrylate, PMA-PIB-PMA (Mn = 31,810, Mw/Mn = 1.42), isobornyl acrylate, PIBA-PIB-PIBA (Mn = 33,500, Mw/Mn = 1.21), and methyl methacrylate, PMMA-PIB-PMMA (Mn = 33,500, Mw/Mn = 1.47).
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Coca et al. (1997) studied this question.