From grafting to to grafting from

The aim of this work is to obtain block copolymer brushes by a combined grafting to and grafting from approach. A new strategy was employed in which the second block re-growths starting from a homopolymer brush layer obtained by the grafting to approach. In detail, polystyrene samples with molecular weight ranging from 2.5 to 13 kg/mol and narrow molar mass distribution were synthesized by nitroxide-mediated-polymerization (NMP) using N-tert-butyl-N-[1-diethylphosphono(2,2-dimetylpropyl)] nitroxide (SG1/DEPN) as polymerization controller. Such polymers were grafted onto a silicon oxide surface by Rapid Thermal Processing (RTP) at different temperatures. As thermolabile groups deriving from the terminal SG1 are located at the silica surface, they could allow a synthesis of block copolymers via the grafting from approach by surface initiated NMP. Preliminary experiments of regrowth from surface were conducted with deuterated styrene and 4-vinylpyridine. The corresponding block copolymer brushes were obtained and their characteristics discussed as a function of the relevant reaction parameter.