Designing Macromolecules on Nanoparticle Surfaces: In Situ Formation of Silica Grafted with Star Chains

Fatimah Aldakheel, Konstantinos Ntetsikas*, Arief Yudhanto, Gilles Lubineau, Nikos Hadjichristidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Herein, we report the synthesis and characterization of asymmetric 3-arm homostar (3h-star) and 3-miktoarm star (3μ-star) chains grafted on silica nanoparticles simultaneously with the formation of silica. We employed high-vacuum anionic polymerization techniques to synthesize well-defined ω-triethoxysilyl (TEOS)-terminated (PS)2PS, (PS)2PI, and (PS)2PI-b-PS macromonomers (polystyrene (PS) and polyisoprene (PI)), which upon hydrolysis/condensation of the terminal TEOS yielded the grafted silica nanoparticles. The molecular characteristics of the precursors (PS)2PS-TEOS, (PS)2PI-TEOS, and (PS)2PI-b-PS-TEOS were determined by proton nuclear magnetic resonance (NMR) spectroscopy and size-exclusion chromatography (SEC). The formation of 3h-star and 3μ-star@SiO2 nanoparticles was demonstrated by Fourier transform infrared spectroscopy, 29Si solid-state NMR, transmission electron microscopy, thermogravimetry, and dynamic light scattering. Blends of 3h-star and 3μ-star@SiO2 with a thermoplastic elastomer (TPE) (PS-b-PI-b-PS), synthesized by anionic polymerization, were obtained by the evaporation of solutions containing the TPE and the grafted nanoparticles. The role of 3h-star and 3μ-star@SiO2 in the mechanical properties and morphological features of the polymer matrices was examined by tensile testing and scanning electron microscopy. This synthetic methodology controls the molecular characteristics, particle size, and grafting density of nanoparticles and enhances the mechanical properties of the final nanocomposites.

Original languageEnglish (US)
Pages (from-to)9721-9731
Number of pages11
JournalACS Applied Polymer Materials
Issue number12
StatePublished - Dec 8 2023


  • anionic polymerization
  • homostar polymers
  • in situ formation of polymer@SiO
  • mechanical properties
  • miktoarm star polymers
  • morphology

ASJC Scopus subject areas

  • Process Chemistry and Technology
  • Polymers and Plastics
  • Organic Chemistry


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