Atom transfer radical polymerization with activators regenerated by electron transfer was demonstrated as a convenient strategy to graft functional polymers from a concave surface of ordered mesoporous silica. SBA-15 silica with cylindrical mesopores of diameter 24 nm (nominal BJH pore diameter of 29 nm) was used as a support, and poly(N-isopropylacrylamide) (PNIPAAm) as well as poly(2-(dimethylamino)ethyl methacrylate) as grafted polymers, which are known for their stimuli-responsive properties. Successful polymerizations were performed in small vials without prior deoxygenation. The resulting silica/polymer composites had appreciable specific surface areas of 68–145 m2 g−1 and accessible pores of nominal (BJH) diameters 21–24 nm, with up to 26 wt% polymer loading. PNIPAAm chains cleaved from the silica support had a quite low polydispersity index (∼1.26) throughout the grafting process. Temperature-responsive properties of the silica/PNIPAAm composite were confirmed by using differential scanning calorimetry.
