Sol–Gel Preparation of Initiator Layers for Surface-Initiated ATRP: Large-Scale Formation of Polymer Brushes Is Not a Dream

We demonstrated for the first time a facile and reproducible preparation of large-scale (∼40 m2) initiator layers for surface-initiated atom transfer radical polymerization (SI-ATRP) using a simple sol–gel solution of (p-chloromethyl)­phenyl­trimethoxysilane and tetraethoxysilane. Highly smooth and transparent initiator layers could be formed on various inorganic/organic substrates via a spin-, wire-bar-, or roll-to-roll-coating without any marked change in surface morphology or bulk properties at room temperature. Combining the advantages of this sol–gel approach and subsequent “paint on” SI-ATRP using a variety of waterborne monomers, we have succeeded in the formation of polymer brushes on large-scale real-life substrates (i.e., maximum 50 × 50 cm2) under ambient conditions (room temperature and open to the air) without any complicated apparatus or harsh reaction conditions.