Nano-Hydroxyapatite Particle Brushes via Direct Initiator Tethering and Surface-Initiated Atom Transfer Radical Polymerization for Dual Responsive Pickering Emulsion.

Well-defined polymer-grafted solid inorganic nanoparticles (NPs) are imperative for practical applications in various fields based on the prerequisite of facile initiator immobilization. Direct atom transfer radical polymerization (ATRP) initiator-tethered solid NPs are described using 2-bromo-2-methylpropionic acid as a tetherable initiator. To illustrate the versatility of the proposed strategy, nano-hydroxyapatite (n-HAP) nanocrystals (NCs) were selected to demonstrate the morphology-controlled synthesis of 2-bromo-2-methylpropionate (2-BrMP) group-immobilized n-HAP (n-HAP-Br) NCs. When water was employed as the sole solvent, the continually introduced 2-BrMP groups altered the surface hydrophobic capacity of the n-HAP-Br NC and thus led to unavoidable aggregation of n-HAP-Br NCs. The synthesis of individually dispersed n-HAP-Br NCs was achieved by rational adjusting polarity of the aqueous medium through adding a portion of water-miscible organic solvents. The type and concentration of added water-miscible organic solvents had critical effects on the morphology and particle size of n-HAP-Br NCs. To verify the efficiency of the tethered initiator, n-HAP-g-poly2-(dimethylamino) ethyl methacrylate (n-HAP-g-PDMAEMA), n-HAP-g-polyacrylonitrile (n-HAP-g-PAN), and n-HAP-g-polymethyl methacrylate (n-HAP-g-PMMA) were fabricated by surface-initiated ATRP (SI-ATRP). Acting as a solid particle emulsifier, the designed n-HAP-g-PDMAEMA-stabilized Pickering emulsion displayed dual pH and temperature response with reversible behaviors. This work presents a versatile and simple way for the fabrication of initiator-immobilized solid NPs (e.g., n-HAP NCs, gibbsite nanoplatelets, and γ-FeOOH nanofibers) ready for polymer grafting and thus enables promising performance in widespread applications.