Polystyrene-block-poly(methyl methacrylate): Initiation issues with block copolymer formation using ARGET ATRP

Tony Aitchison, Milena Ginic-Markovic, Stephen Clarke, Suresh Valiyaveettil

    Research output: Contribution to journalArticlepeer-review

    9 Citations (Scopus)


    The synthesis, kinetics, and characterization of polystyrene and poly(methyl methacrylate) block copolymers produced by ARGET ATRP are discussed. Halogen exchange is used and the polymerization appears to be living in the generation of the second block. On further investigation, the GPC traces exhibit a shoulder, which suggests poor initiation of the macroinitiator. Previous reports suggest that to increase the initiation efficiency of the second block, 10% styrene monomer should be added to the mixture. Upon adding the 10% styrene for the second block ARGET ATRP polymerization, the appearance of a well-initiated polymer is observed. However, at greater conversions the results clearly demonstrate the production of a homopolymer/block copolymer mixture. A comprehensive exploration of ARGET ATRP for use in the formation of block copolymers is described. With polystyrene as the first block, the more reactive monomer methyl methacrylate is used to generate a second block using the halogen exchange technique and 10% comonomer. Issues with initiation efficiency and additional effects in the comonomer technique are discovered.

    Original languageEnglish
    Pages (from-to)79-86
    Number of pages8
    JournalMacromolecular Chemistry and Physics
    Issue number1
    Publication statusPublished - 16 Jan 2012


    • atom transfer radical polymerization
    • block copolymers
    • living polymerization
    • poly(methyl methacrylate)
    • polystyrene


    Dive into the research topics of 'Polystyrene-block-poly(methyl methacrylate): Initiation issues with block copolymer formation using ARGET ATRP'. Together they form a unique fingerprint.

    Cite this