Polyoctadecyl methacrylate brushes via surface‐initiated atom transfer radical polymerization

Abstract

The synthesis of poly(octadecyl methacrylate) brushes on planar Si substrates using surface‐initiated atom transfer radical polymerization (SI‐ATRP) is reported. SI‐ATRP of octadecyl methacrylate from a silane initiator‐modified Si substrate yielded well‐defined homopolymer brushes of varying molar mass (5000–38 000 g mol −1 ) and film thickness from around 2 to 20 nm. Correlation of both free polymer molar mass and brush thicknesses confirmed controlled surface‐initiated ATRP from these modified surfaces. By optimization of brush molar mass, film thickness and thin‐film processing, we observed side chain crystallization of tethered poly(octadecyl methacrylate) chains, resulting in the formation of lamellar morphologies with high‐aspect‐ratio nanofibers. Copyright © 2013 John Wiley & Sons, Ltd.