Recent Synthetic Developments in Miktoarm Star Polymers with More than Three Different Arms

Akira Hirao*, Mayumi Hayashi, Tomoya Higashihara, Nikos Hadjichristidis

*Corresponding author for this work

Research output: Chapter in Book/Report/Conference proceedingChapterpeer-review

14 Scopus citations


This chapter reviews the precise synthesis of multiarmed and multicomponent asymmetric star-branched polymers, the so-called 'miktoarm star polymers'. Most of the miktoarm star polymers introduced herein are those having more than three different arms and have emerged since 2000. For the synthesis of such complex star polymers, we propose a novel and quite versatile stepwise iterative methodology based on living anionic polymerization. In this methodology, the reaction system is designed in such a way that the same reaction site is always regenerated after the introduction of an arm segment in each iterative process and this 'arm introduction-regeneration of the reaction site' synthetic sequence is repeatable. Accordingly, a series of miktoarm star polymers can be successively and, in principle, limitlessly synthesized by repeating the synthetic sequence. This iterative methodology with the regeneration of reaction sites has been widely developed so far, allowing access to a wide variety of miktoarm star polymers that are well defined in architecture and precisely controlled in arm segments. Furthermore, miktoarm star polymers synthesized since 2000 by other methodologies based on living anionic polymerization and living/controlled radical polymerization are also described.

Original languageEnglish (US)
Title of host publicationComplex Macromolecular Architectures
Subtitle of host publicationSynthesis, Characterization, and Self-Assembly
PublisherJohn Wiley and Sons
Number of pages36
ISBN (Print)9780470825136
StatePublished - May 3 2011
Externally publishedYes


  • 1,1-diphenylethylene chemistry
  • Four-arm ABCD star
  • Iterative methodology
  • Living anionic polymerization
  • Living/controlled radical polymerization
  • Miktoarm star-branched polymer
  • Multiarmed and multicomponent miktoarm star
  • Precise synthesis
  • Star-branched polymer
  • Three-arm ABC star

ASJC Scopus subject areas

  • General Chemistry


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