Unimolecular Nanoparticles via Carbon‐Carbon “Click” Chemistry for All‐Polymer Nanocomposites

Abstract

AbstractSummary: We report for the first time the synthesis of unimolecular polystyrene‐based nanoparticles (PS‐NPs) under normal air atmosphere by direct carbon‐carbon “click” chemistry (i.e., “self‐click” chemistry). First, statistical poly(styrene‐co‐4‐vinylbenzyl chloride) copolymers synthesized by RAFT polymerization were decorated in a facile manner with alkyne groups by reaction with potassium propiolate, providing well‐defined nanoparticle precursors (PS‐Prec). Next, individual PS‐Prec chains were collapsed irreversibly to unimolecular nanoparticles of ca. 12 nm in size by intrachain Cu(II)‐catalyzed alkyne dimerization under high‐dilution conditions, as revealed by SEC, H1‐NMR, DLS and TEM measurements. Based on predictions from a recent compressible thermodynamic model, the resulting nanoparticles could be promising materials for the development of homogeneous, miscible PS‐NPs / polycarbonate all‐polymer nanocomposites.