Controlled free radical polymerization of styrene initiated from the alkoxyamine-functionalized silicon surface

We describe a new method of fabricating a brush-like polystyrene layer anchored on the surface of the silicon substrate, which involves three steps, namely (i) the attachment of 3-methacryloxypropyltrimethoxysilane onto the silicon surface; (ii) the reaction of vinyl moiety at another extremity of the anchored 3-methacryloxypropyltrimethoxysilane to 4-Hydroxyl-2, 2, 6, 6-tetramethyl-1-piperidinyloxy (HTEMPO·) catalyzed by azobisisobutyronitrile (AIBN); (iii) living free radical grafting polymerization of styrene in the presence of HTEMPO·. The controllable living free radical polymerization permits accurate control of both the molecular weight and the polydispersity. X-photoelectron spectroscopy measurement proved that the alkoxyamine initiator layer forms on the silicon surface. XPS and Ellipsometry measurements showed that the polystyrene chains were covalently anchored onto the silicon surface. The thickness of the grafted polymer layer can be accurately manipulated by altering the polymerization time. The new method allows synthesizing random copolymer and block copolymers by the sequential growth of monomers from the substrate surface.