Synthesis and characterization of amorphous octakis-functionalized polyhedral oligomeric silsesquioxanes for polymer nanocomposites

We have synthesized the polyhedral oligomeric silsesquioxane (POSS) derivatives OS-POSS and OA-POSS through the hydrosilylation of styrene and 4-acetoxystyrene, respectively, with octakis(dimethylsiloxy)silsesquioxane (Q8M8H). We then prepared OP-POSS through acetoxyl hydrazinolysis of OA-POSS with hydrazine monohydrate. The chemical structures of these POSS derivatives were characterized using FTIR and 1H NMR spectroscopy and MALDI-TOF mass spectrometry. Unlike Q8M8H, which is crystalline, these three hydrosilylated POSS derivatives are liquids at 25 °C. Through DSC and XRD analyses, we found that they exhibit polymer-like glass transitions and amorphous halos. These octakis-functionalized POSS derivatives can be regarded as amorphous glasses possessing low glass transition temperatures, the values of which depend on the intermolecular interactions of their outer organic groups. To investigate the dispersion of these POSS derivatives in polymer nanocomposites, we blended OS-POSS, OA-POSS, and OP-POSS with polystyrene, poly(4-acetoxystyrene), and poly(4-vinylpyridine), respectively, and investigated the effects of the resulting intermolecular aromatic hydrophobic, dipole-dipole, and hydrogen-bonding interactions, respectively. Dipole-dipole interactions provided the best dispersion of OA-POSS in poly(4-acetoxystyrene), in which the POSS-polymer intermolecular interactions were of similar strength to the POSS-POSS interactions.