Linear and star block copolymers of styrenic macromonomers by anionic polymerization

Aggelos Vazaios, David J. Lohse*, Nikos Hadjichristidis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

50 Scopus citations


We describe the synthesis of a number of linear and star block copolymers where at least one block consists of a polymacromonomer (molecular brush). The key to this general technique is the use of styrene-tipped macromonomers, which polymerize in a manner similar to styrene monomer. By this means well-defined styrenic macromonomers of polyisoprene, PI (sMMI), polybutadiene, PB (sMMB), and poly(styrene-b-isoprene), PSI (sMMSI), have been prepared by selective reaction of PILi, PBLi, and PSILi with the chlorine of 4-(chlorodimethylsilyl)styrene. These macromonomers and conventional monomers (styrene, isoprene, and butadiene) were homopolymerized or block copolymerized, by anionic polymerization high-vacuum techniques, to synthesize the following structures: PsMM-b-PM, PS-b-PsMM-b-PM, and PsMM1-b-PsMM2 where PsMM is PsMMI or PsMMB and PM is PS, PI, or PB. Furthermore, by utilizing the chlorosilane method, star polymers of the (PSMPsMMB) and (PsMMI-e-PDa type were synthesized. Attempts to prepare A 3 and A 4 star polymers with polymacromonomer arms were not entirely successful. All materials were characterized by size exclusion chromatography (SEC) with DRI and UV detectors, SEC with two-angle-laser-light- scattering detector (SEC/TALLS), and NMR spectroscopy. It was concluded that macromonomers can be used much like the conventional monomers under appropriate experimental conditions.

Original languageEnglish (US)
Pages (from-to)5468-5474
Number of pages7
Issue number13
StatePublished - Jun 28 2005
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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