Anionic polymerization of styrenic macromonomers of polyisoprene, polybutadiene, and polystyrene

Aggelos Vazaios, Nikos Hadjichristidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

29 Scopus citations


Anionic polymerization and high-vacuum techniques were used to prepare a series of well-defined polyisoprene, polybutadiene, and polystyrene polymacromonomers. The procedure involved (1) the synthesis of styrenic macromonomers in benzene by the selective reaction of the corresponding macroanion with the chlorine of 4-(chlorodimethylsilyl)styrene (CDMSS) and (2) the in situ anionic polymerization of the macromonomer without previous isolation. The synthesis of the macromonomers [polyisoprene macromonomer: 11 samples, weight-average molecular weight (Mw) = 1000-18,000; polybutadiene macromonomer: 5 samples, Mw = 2000-4000; and polystyrene macromonomer: 2 samples, Mw = 1300 and 3600] was monitored by size exclusion chromatography with refractive index/ultraviolet detectors. Selectivity studies with CDMSS indicated that polybutadienyllithum had the highest selectivity, and polystryryllithium the lowest. From kinetic studies it was concluded that the polymerization half-life times were longer but comparable to those of styrene, and they appeared to only slightly depend on the molecular weight of the macromonomer chain (at least for low degrees of polymerization of the polymacromonomer and for Mw < 7000 for the macromonomer side chain). Dependence on the polymerization degree of the polymacromonomer product was also observed. All the prepared polymacromonomers were characterized by size exclusion chromatography with refractive index, ultraviolet and two-angle laser light scattering detectors, and NMR spectroscopy.

Original languageEnglish (US)
Pages (from-to)1038-1048
Number of pages11
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number5
StatePublished - Mar 1 2005
Externally publishedYes


  • 4-(chrorodimethylsilyl)styrene
  • Anionic polymerization
  • Kinetics (polym.)
  • Macromonomers
  • Polymacromonomers

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry


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