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A series of ABA triblock copolymers, consisting of double-bond-containing poly(phenoxyallene) (PPOA), poly(methyl methacrylate) (PMMA), or poly(butyl acrylate) (PBA) segments, were synthesized by sequential free radical polymerization and atom transfer radical polymerization (ATRP). A new bifunctional initiator bearing azo and halogen-containing ATRP initiating groups was first prepared followed by initiating conventional free radical homopolymerization of phenoxyallene with cumulated double bond to give a PPOA-based macroinitiator with ATRP initiating groups at both ends. Next, PMMA- b -PPOA- b -PMMA and PBA- b -PPOA- b -PBA triblock copolymers were synthesized by ATRP of methyl methacrylate and  n -butyl acrylate initiated by the PPOA-based macroinitiator through the site transformation strategy. These double-bond-containing triblock copolymers are stable under UV irradiation and free radical circumstances.

Double-bond-containing polyallene-based triblock copolymers via phenoxyallene and (meth)acrylate