Synthesis of nanostructured organic/inorganic hybrid materials using controlled/living radical polymerization

The objective of this thesis was the synthesis and characterization of nanocomposite organic/inorganic hybrid materials. This research demonstrated that well-defined organic polymers could be covalently attached to inorganic substrates using controlled/living radical polymerization. In particular, the use of atom transfer radical polymerization (ATRP) allowed for a wide range of organic (co)polymers to be introduced to organ ichnorganic hybrid copolymers, colloids and flat surfaces. Hybrid copolymers were prepared using either a one-pot copolymerization of organic and inorganic monomers, or chain extension from a preformed macroinitiator. Reactive hybrid copolymers were also prepared using a combination of living anionic polymerization and ATRP. Subsequent attachment of the hybrid copolymer via a “grafting to” approach resulted in the synthesis of an ABC triblock copolymer brush. Finally, hybrid nanoparticles, composed of an inorganic core and a shell of end-tethered organic (co)polymers, were prepared from initiation from colloidal surfaces using the “grafting from” methodology. From this approach, spherical brushes and multilayered core-shell colloids were prepared by the tethering of homopolymers, or block copolymers to inorganic colloidal initiators, respectively.; Chapter 1 of this thesis summarized the various kinds of hybrid materials that have been prepared using controlled/living radical polymerization (CRP) techniques.; In chapters 2 and 3, the synthesis and characterization of homopolymers, statistical and block copolymers containing polyhedral oligomeric silsesquioxanes (POSS) side chain groups are discussed.; In chapter 4, the synthesis of an ABC triblock copolymer brush is discussed.; In chapter 5, the synthesis of hybrid nanoparticles containing an inorganic core of polysilsesquioxane and organic shells of either polystyrene (pS) (M _n = 5,260), or polystyrene-block-poly(benzyl acrylate) (pS-b-pBzA) (M_n = 26,790 g/mol) is described.; In chapter 6, synthesis and characterization of silica-graft -polystyrene (SiO₂-g-pS) hybrid nanoparticles is presented.; In chapter 7, the kinetics of styrene, n-butyl acrylate and methyl methacrylate (MMA) ATRP reactions from silica colloidal initiators were studied. (Abstract shortened by UMI.)...