Synthesis of a novel centipede‐like copolymer of styrene, isoprene, and methyl methacrylate

A well-defined, ABC-type, centipede-like copolymer of styrene, isoprene, and methyl methacrylate (MMA) was synthesized by the combination of living anionic polymerization and atom transfer radical polymerization (ATRP). The synthetic approach involved the coupling reaction of a polystyrene (PS) backbone bearing 1,1-diphenylethene pendant groups, produced by ATRP and Wittig reactions, with living polyisoprenyllithium (PILi) and the subsequent polymerization of the resulting 1,1-diphenylmethyl anions with MMA. The centipede-like copolymer was characterized with 1H NMR, IR, size exclusion chromatography, static light scattering, and differential scanning calorimetry measurements.