Synthesis and characterization of styrene/butyl acrylate linear and star block copolymers via atom transfer radical polymerization

Jinyu Hucing, Shijun Jia, Daniel J. Siegwart, Tomasz Kowalewski, Krzysztof Matyjaszewski

Research output: Contribution to journalArticlepeer-review

13 Scopus citations


Well-defined styrene (S) and butyl acrylate (BA) linear and star-like block copolymers are synthesized via atom transfer radical polymerization (ATRP) using di- and trifunctional alkyl halide initiators employing the Cu/ PMDETA (N,N,N′N″,N″-pentamethyldiethylenetriamine) catalyst system. Initial addition of CuII deactivator and utilization of halogen exchange techniques suppresses the coupling of radicals and improves cross-propagation to a large extent, which results in better control over the polymerization. Two types of star-like PBA/PS block copolymers are prepared by using core-first techniques: a trifunctional PBA or PS macroinitiator extended with the other monomer. Block copolymers with a well-defined structure and low polydispersity (PDI=M̄w/M̄n) are obtained in both cases. A trifunctional PBA3 macroinitiator with M̄n = 136 000 g · mol-1 and PDI= 1.15 is extended to (PBA-PS)3 star-like block copolymer with M̄n = 171 100 g · mol -1 and PDI = 1.15. A trifunctional PS3 macroinitiator with M̄n = 27 000 g · mor-1 and PDI= 1.16 g-mol-1 is extended to (PS-PBA)3 with M̄n = 91 500 g · mol -1 and PDI = 1.40. The individual star-like macromolecules as well as their aggregates are visualized by atomic force microscopy (AFM) where the PS and PBA adopt the globular and extended conformation, respectively. For the PBA core star block copolymers, PS segments tend to aggregate either intramolecularly or intermolecularly. PS core star block copolymers form aggregates with a PS core and emanating PBA chains. Most aggregates have 'n × 3' arms but minor amounts of 'defective' stars with 4,5,8, or 11 arms are also observed. The AFM analysis shows that PS core star block copolymers contain about 92% threearm block copolymers, and the efficiency of cross-propagation is 97.3%.

Original languageEnglish (US)
Pages (from-to)801-811
Number of pages11
JournalMacromolecular Chemistry and Physics
Issue number9
StatePublished - May 2 2006


  • Atom transfer radical polymerization (ATRP)
  • Atomic force microscopy (AFM)
  • Butyl acrylate: Styrene
  • Triblock/star block copolymers

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry


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