Functional Nano-Objects Prepared via Living Anionic Polymerization-Induced Self-Assembly (LAPISA) of Polar Vinyl Monomers

The living anionic polymerization-induced self-assembly (LAPISA) process, possessing the common merits of both LAP and PISA techniques, facilitated and promoted research on self-assembly. However, the limited monomers available for the LAPISA process significantly restricted the preparation and application of the corresponding nano-objects. Herein, polar monomers were appended to the LAPISA system, and functional nano-objects were targeted. By optimizing 1,1-diphenylhexane lithium (DPH–Li+) and potassium bis(trimethylsilyl) amide (KHMDS) as a co-initiation system and tri-isobutylaluminum (iBu3Al) as an additive, the sequential LAP of tert-butyl methacrylate (tBMA) and LAPISA of 4-vinylpyridine (4VP) were successfully realized at room temperature of 25 °C. By adjusting [KHMDS]0/[DPH–Li+]0, [iBu3Al]0/[4VP]0, targeted Mn,P4VP/Mn,PtBMA, and toluene content in toluene/tetrahydrofuran (wt %Tol), nano-objects with different morphologies, including spheres, worms, and vesicles, were prepared. The PtBMA-b-P4VP diblock copolymer and nano-objects were prepared in a controlled manner. The crosslinking reaction between the pyridine groups on P4VP and 1,4-dibromobutane was performed via the quaternization reaction, which enabled the stabilization of the nano-objects. Using the functional pyridine groups in the core region, silver ions (Ag+) and metal (Ag0) were introduced into the nano-objects by sequential complexation and reduction reactions, and the Ag0 content could be well controlled by modulating the [Ag+]0/[4VP]0. The successful LAPISA of polar monomers provided an efficient and alternate route to functional nano-objects and organic/inorganic nanocomposites.