Stable dispersions of hybrid nanoparticles induced by stereocomplexation between enantiomeric poly(lactide) star polymers

We report the formation and characterization of stable dispersions of hybrid nanoparticles in solution formed via stereocomplexation of enantiomeric poly(lactide) hybrid star polymers. The hybrid starlike polymers, having polyhedral oligomeric silsesquioxane (POSS) nanocages as the core and either poly(L-lactide) (PLLA) or poly(D-lactide) (PDLA) as the arms, are synthesized via ring-opening polymerization of lactide using octafunctional POSS as the macroinitiator. In the solid state, differential scanning calorimetry and wide-angle X-ray scattering measurements confirmed the formation of the stereocomplex in the mixture of POSS-star-PLLA and POSS-star-PDLA (50:50, wt %). In a solution of the same mixture in tetrahydrofuran (THF), sterocomplexation leads to formation of hybrid nanaoparticles. Detailed accounts of the nanoparticle formation and influence of aging and concentration have been presented. It was observed that at low concentration the stereocomplexed nanaoparticles remain stable over 45 days and are not sensitive to dilution, suggesting the formation of a stable hybrid nanoparticle dispersion in solution. In contrast, the aggregates of the individual POSS-star-PLLA or POSS-star-PDLA in THF, formed via weak solvophobic interactions, tended to disintegrate into smaller aggregates on dilution. Exploiting the PLLA-PDLA stereocomplexation with an appropriate molecular design can be a versatile route to develop stable organic/inorganic hybrid nanoparticle dispersions.