Thermally Stable Metallic Nanoparticles Prepared via Core-Cross-linked Block Copolymer Micellar Nanoreactors.

Thermally stable metallic nanoparticles (MNPs) are highly desirable for the melt processing of polymer nanocomposites. However, due to the high surface energy penalty and decreased melting temperature, MNPs are easy to agglomerate and lose their unique properties if there is no protection or confinement layer. In this work, we report a facile and efficient way to synthesize thermally stable MNPs using core-cross-linked polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) reverse micelles as nanoreactors. From infrared results, gold, silver, and palladium ions exhibited distinctive coordination to the 4VP groups with varying chelation strengths. Compared to the non-cross-linked micelles, 1,4-dibromobutane (DBB)-cross-linking of the P4VP cores provided several advantages. First, it prevented severe swelling of the P4VP cores caused by the reducing agents and subsequent merger of swollen micelles. Second, the quaternized P4VP with hydrophilicity enhanced the uptake speed of precursor metal ions into the cores. Third, the cross-linked cores greatly stabilized the MNPs against the high-temperature environment (e.g., 110 °C for 40 h in toluene). In addition, the solubility of the reducing agents also played an important role. Anhydrous hydrazine could swell the P4VP cores and concentric core-shell particle morphology was obtained. On the contrary, triethylsilane could not swell the P4VP cores and thus eccentric core-shell particle morphology was observed. Only the concentric core-shell MNPs exhibited good thermal stability, whereas the eccentric core-shell MNPs did not. This work suggested that these thermally stable MNPs could be good candidates for the melt processing of functional polymer nanocomposites.