A Fatty Acid-Inspired Tetherable Initiator for Surface-Initiated Atom Transfer Radical Polymerization

A universal tetherable initiator, derived from the structure of fatty acids, for surface-initiated atom transfer radical polymerization (SI-ATRP) from metal oxide surfaces was prepared. A simple amidation between 2-bromoisobutyryl bromide and omega-aminolauric acid allowed preparation of 12-(2-bromoisobutyramido)dodecanoic acid (BiBADA). After facile purification, BiBADA was used as a tetherable initiator for a broad range of metal oxide nanoparticles. The modified nanoparticles were grafted with methyl methacrylate or n-butyl acrylate via SI-ATRP with a high grafting density. This is the first report of successful SI-ATRP from a selection of different metal oxide nanoparticles. Sub-10 nm Fe3O4 nanoparticles with an intrinsically tethered initiator were also prepared using BiBADA as a surfactant template: Additional experiments demonstrated successful modification of an aluminum foil surface with polymer brushes using BiBADA as a tetherable initiator.