Hyperbranched polymers as scaffolds for multifunctional reversible addition-fragmentation chain-transfer agents: A route to polystyrene-core-polyesters and polystyrene-block-poly(butyl acrylate)-core-polyesters

Martin Jesberger, Leonie Barner, Martina H. Stenzel, Eva Malmström, Thomas P. Davis, Christopher Barner-Kowollik

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142 Citations (Scopus)


Polydisperse hyperbranched polyesters were modified for use as novel multifunctional reversible addition-fragmentation chain-transfer (RAFT) agents. The polyester-core-based RAFT agents were subsequently employed to synthesize star polymers of n-butyl acrylate and styrene with low polydispersity (polydispersity index < 1.3) in a living free-radical process. Although the polyester-core-based RAFT agent mediated polymerization of n-butyl acrylate displayed a linear evolution of the number-average molecular weight (Mn) up to high monomer conversions (>70%) and molecular weights [Mn > 140,000 g mol-1, linear poly(methyl methacrylate) equivalents)], the corresponding styrene-based system reached a maximum molecular weight at low conversions (≈30%, Mn = 45,500 g mol-1, linear polystyrene equivalents). The resulting star polymers were subsequently used as platforms for the preparation of star block copolymers of styrene and n-butyl acrylate with a polyester core with low polydispersities (polydispersity index < 1.25). The generated polystyrene-based star polymers were successfully cast into highly regular honeycomb-structured microarrays.

Original languageEnglish
Pages (from-to)3847-3861
Number of pages15
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number23
Publication statusPublished - 1 Dec 2003
Externally publishedYes


  • Dendrimers
  • Honeycomb-structured arrays
  • Hyperbranched
  • Kinetics (polym.)
  • Reversible addition-fragmentation chain transfer (RAFT)

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