Poly(dimethylsiloxane-b-methylvinylsiloxane) (PDMS-b-PMVS) diblock copolymers were synthesized via anionic living polymerization with controlled molecular weights and narrow molecular weight distributions. Targeted molecular weights agreed well with experimental values determined by 1H NMR, 29Si NMR, and GPC. Morphologies were investigated by DSC to analyze glass transition temperatures. Only one Tg was observed for each PDMS-b-PMVS block copolymer suggesting that the blocks were miscible in bulk. Tg's ranged from approximately -126 to -128 °C and were between the Tg's of the PDMS (-123 °C) and PMVS (-137 °C) homopolymers. The PMVS blocks were functionalized with trimethoxysilethyl or triethoxysilethyl pendent groups via hydrosilations to yield poly(dimethylsiloxane-b-[poly(methylvinyl)-co-(methyl-(2-trimethoxysilethyl)siloxane)] (PDMS-b-[PMVS-co-PMTMS]) or poly(dimethylsiloxane-b-[poly(methylvinyl)-co-(methyl-(2-triethoxysilethyl)siloxane)] (PDMS-b-[PMVS-co-PMTES]) copolymers, respectively. The PMVS blocks were either derivatized with the functional groups or half of the repeat units were functionalized. The fully hydrosilated materials were diblock copolymers, and the materials that were 50% hydrosilated had a random sequence of methylvinylsiloxy units and methyl-(trialkoxysilethyl)siloxy units. The PDMS-b-[PMVS-co-PMTES] block copolymers had Tg's ranging from -124 to -126 °C and only one Tg was observed. Surface tension measurements suggested that PDMS-b-[PMVS-co-PMTES] copolymers formed aggregates in toluene. Stable suspensions of superparamagnetic cobalt nanoparticles were prepared in toluene in the presence of PDMS-b-[PMVS-co-PMTMS] or PDMS-b-[PMVS-co-PMTES] copolymers via thermolysis of Co2(CO)8. It is hypothesized that the block copolymers functioned as micellar templates for the cobalt nanoparticles. TEM micrographs showed non-aggregated cobalt nanoparticles coated with copolymers that had mean particle diameters ranging from ≥10-15 nm. Specific saturation magnetizations of these cobalt-copolymer complexes ranged from 90-110 emu g-1 Co, comparable to literature values for this particle size. / Master of Science

Polylactide-siloxane triblock copolymers with pendent carboxylic acid functional groups have been designed and synthesized for study as magnetite nanoparticle dispersion stabilizers. Magnetic nanoparticles are of interest in a variety of biomedical applications, including magnetic field-directed drug delivery and magnetic cell separations. Small magnetite nanoparticles are desirable due to their established biocompatibility and superparamagnetic (lack of magnetic hysteresis) behavior. For in-vivo applications it is important that the magnetic material be coated with biocompatible organic materials to afford dispersion characteristics or to further modify the surfaces of the complexes with biospecific moieties. The synthesis of the triblock copolymers is comprised of three reactions. Difunctional, controlled molecular weight polymethylvinylsiloxane oligomers with either aminopropyl or hydroxybutyl endgroups were prepared in ring-opening redistribution reactions. These oligomers were utilized as macroinitiators for ring-opening L-lactide to provide triblock materials with polymethylvinylsiloxane central blocks and poly(L-lactide) endblocks. The molecular weights of the poly(L-lactide) endblocks were controlled by the mass of L-lactide relative to the moles of macroinitiator. The vinyl groups on the polysiloxane center block were further functionalized with carboxylic acid groups by adding mercaptoacetic acid across the pendent double bonds in an ene-thiol free radical reaction. The carboxylic acid functional siloxane central block was designed to bind to the surfaces of magnetite nanoparticles, while the poly(L-lactide)s served as tailblocks to provide dispersion stabilization in solvents for the poly(L-lactide). The copolymers were complexed with magnetite nanoparticles by electrostatic adsorption of the carboxylates onto the iron oxide surfaces and these complexes were dispersible in dichloromethane. The poly(L-lactide) tailblocks extended into the dichloromethane and provided steric repulsion between the magnetite-polymer complexes. / Master of Science