Cobalt Nanoparticle-Macromolecular Complexes and Their Conversion to Oxidatively Stable Entities

The goal of the research presented in this dissertation was to synthesize novel macromolecular materials that would afford oxidative stability to magnetic cobalt nanoparticles under ambient conditions. The cobalt nanoparticles were formed via the thermolysis of Co2(CO)8 in concentrated solutions of toluene containing the macromolecular dispersion stabilizers. The copolymers were designed to encapsulate the nanoparticles with a number of thin protective coatings to prevent their undesirable oxidation under ambient condtions. Cobalt nanoparticles encased with an organic glass were synthesized by stabilizing cobalt nanoparticles with poly(methyl methacrylate-co-2-vinylpyridine-g-dimethylsiloxane) whereas nanoparticles encapsulated with triazine networks were formed via the thermal treatment of cobalt particles complexed with poly(styrene-b-4-vinylphenylcyanate). Cobalt nanoparticles coated with a combination of carbonaceous and silica char were obtained by pyrolyzing cobalt particles stabilized with poly (4-vinylphenoxyphthalonitrile-co-4-vinylphenoxytriethoxysilane-g-dimethylsiloxane) graft copolymers. Moreover, cobalt nanoparticles encapsulated with either phthalonitrile networks or graphitic char were prepared via the thermal treatment of nanoparticles stabilized with poly(styrene-b-4-vinylphenoxyphthalonitrile).

Oxidatively-stable, magnetic cobalt nanoparticle complexes may be prepared by heating cobalt nanoparticles encapsulated in poly(styrene-b-4-vinylphenoxyphthalonitrile) block copolymers at elevated temperatures. The block copolymers were synthesized through the sequential anionic polymerization of styrene and tert-butyldimethylsilyloxystyrene. The silyl ether protecting groups on the second block were hydrolyzed under acidic conditions to afford poly(styrene-b-4-vinylphenol), and the pendent phenols of the diblock copolymer were chemically modified with 4-nitrophthalonitrile to afford poly(styrene-b-4-vinylphenoxyphthalonitrile). Stable suspensions of ~8-10 nm diameter cobalt metal nanoparticles were formed by thermolysis of dicobalt octacarbonyl in solutions of toluene containing poly(styrene-b-4-vinylphenoxyphthalonitrile). The cobalt-polymer nanoparticle complexes were pyrolyzed under argon to afford highly magnetic cobalt nanoparticles encased in graphitic coatings. Magnetic susceptibility measurements indicate that the cobalt-graphitic particles are oxidatively-stable and retain their high saturation magnetizations (~ 95-100 emu g-1) for at least a year under ambient conditions.