Ultra-Fast, One-Pot Synthesis of Nanofibers by Lewis Pair Polymerization-Induced Self-Assembly

Owing to their wide application potentials resulting from high aspect ratio, morphologically pure nanofibers attract intense attention but remain challenging to synthesize due to their narrow synthetic experimental window. Here, we employed strong nucleophilic N-heterocyclic olefin (NHO) as a Lewis base (LB) and a bulky organoaluminum compound as a Lewis acid (LA) to construct a Lewis pair (LP), which can rapidly prepare a series of diblock copolymers (di-BCPs), poly(trifluoroethyl methacrylate)-b-poly(heptadecafluorodecyl methacrylate) (PTFEMA-b-PHDFDMA), through the sequential monomer addition method. The liquid-crystalline characteristics of PHDFDMA, in combination with Lewis pair polymerization-induced self-assembly (LP-PISA) strategy, enable ultrafast, one-pot synthesis of di-BCPs with fiber morphologies (dimeters = 11.7–25.1 nm) across a wide experimental window and solid contents (up to 20% w/w). These di-BCPs are structurally characterized by 1H nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and small-angle X-ray scattering and morphologically analyzed by transmission electron microscopy. This LP-PISA strategy provides the possibility of achieving the desired morphology with well-defined structure and purity through precise control over the evolution parameters.