Novel epoxy-terminated macromonomers and their polymerization for synthesis of bottle-brush type amphiphilic block copolymers

Architecture of polymers has vital implications for their physical properties and applications. In this study, synthesis of a series of novel epoxy-terminated macromonomers namely Ep-DEGMME, Ep-TEGMME, Ep-EGMEE, Ep-EGMBE, and Ep-EGMHE is reported. The synthesized macromonomers vary in number of ethylene oxide units and length of the alkyl group. These macromonomers are first homopolymerized by anionic ring-opening polymerization for synthesis of homopolymers of a molar mass range. Subsequently, these macromonomers with different lengths of two segments (alkyl group and ethylene oxide units) are copolymerized with other monomers for synthesis of bottle-brush type architectures. In the first case, di- and tri-block copolymers of Ep-EGMBE are synthesized while using MeO-PEG or PEG as a macroinitiator; the resulting block copolymers have hydrophilic handle and hydrophobic brush. On the same lines, block copolymers of Ep-TEGMME with ε-caprolactone have hydrophobic handle and hydrophilic brush. The synthesized block copolymers are comprehensively characterized by SEC and liquid chromatography at critical conditions. The analysis reveals the successful synthesis of block copolymers while providing information on relative total molar mass, and individual block lengths of the block copolymers, along with amount of unwanted homopolymers in the sample.