Synthesis of model polycyclohexylene/polyethylene miktoarm star copolymers with three and four arms

Thodoris Tsoukatos, Nikos Hadjichristidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

37 Scopus citations


The synthesis of well-defined 3- and 4-miktoarm star copolymers of the A2B and A3B types is described, where A is 1,4-polybutadiene and B is poly(1,3-cyclohexadiene). The synthetic approach involves the reaction of poly(1,3-cyclohexadienyl)-lithium with an excess of methyltrichlorosilane or tetrachlorosilane followed, after the removal of excess silane, by a small excess of polybutadienyllithium. Characterization was carried out by size exclusion chromatography, low-angle laser light scattering, laser differential refractometry, and NMR spectroscopy. The complete heterogeneous catalytic hydrogenation of the A2B and A3B miktoarm stars, with a calcium carbonate-supported palladium catalyst, leads to the formation of A2B and A3B miktoarm stars with one amorphous polycyclohexylene arm with an extremely high glass-transition temperature and two or three crystalline polyethylene arms. Differential scanning calorimetry was used to determine the glass-transition temperature of the amorphous blocks of the starting and hydrogenated stars and the melting temperature of polyethylene. Solid-state 13C NMR spectroscopy was performed to ensure the complete saturation of the polycyclohexadiene and polybutadiene arms.

Original languageEnglish (US)
Pages (from-to)2575-2582
Number of pages8
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number15
StatePublished - Aug 1 2002
Externally publishedYes


  • 1,3-cyclohexadiene
  • Anionic polymerization
  • Butadiene
  • Chlorosilanes
  • Glass-transition temperature (T)
  • Hydrogenation
  • Melting temperature (T)
  • Miktoarm stars
  • Nonlinear block copolymers
  • Polycyclohexylene/polyethylene stars
  • Solid state NMR

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry


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