<p> Polymers and block copolymers have been grafted from hard and soft polymer micro-spheres by atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP). The hard and soft micro-spheres were prepared by precipitation polymerization of divinylbenzene-80 (DVB80), and of DVB80/hydroxyethylmethacrylate (HEMA), respectively, in neat acetonitrile.</p> <p> Residual vinyl groups in the hard, poly(DVB80) micro-spheres were hydrochlorinated to form benzyl chloride groups that subsequently served as ATRP initiators for poly(styrene) and poly(styrene-block-4-methylstyrene) grafts. Hydrophilic poly(HEMA) and poly(2-( dimethylamino)ethyl methacrylate) poly(DMAEMA) were also grafted from hard micro-spheres containing bromopropionates, using ATRP in the presence of CuBr/Me4Cyclam.</p> <p> Hydroxy groups in soft, poly(DVB80-co-HEMA) micro-spheres were used directly as initiators for ring opening polymerization of ε-caprolactone catalyzed by aluminum compounds. In the addition, they were reacted with α-bromopropionyl bromide to form ATRP initiators.</p> <p> Several combinations of ATRP-ATRP and ROP-ATRP with different monomers were carried out using these initiator micro-spheres. In particular, the soft micro-spheres grafted with poly(methacrylic acid), poly(methylmethacrylate), poly(methylmethacrylate-block-dimethylaminoethylmethacrylate), poly(methylmethacrylate-block-trimethylammoniumethylmethacrylate), poly(methylmethacrylate-block-HEMA), poly(methylmethacrylate-block-glycidylmethacrylate), poly(ε-caprolactone-block- methylmethacrylate), poly(ε-caprolactone-block-dimethylaminoethylmethacrylate).</p> <p> The internal morphology of these homo and block copolymer grafted microspheres was studied using electron microscopy and x-ray microspectroscopy.</p> / Thesis / Doctor of Philosophy (PhD)

Polymers possess bulk elastic properties due to entanglement of the polymer chains, not due to an inherit elasticity found within the monomers. An appropriately disubstituted bicyclo[8.8.8]hexacosane monomer should impart inherit elasticity when utilized in a polymer. A stochastic search of disubstituted bicyclo[m.m.m]alkanes demonstrated that these systems will adopt an out,out configuration and bicycles with medium and large values of m possess variable bridgehead-bridgehead distances. A stochastic search of disubstituted bicyclo[8.8.n]alkanes demonstrated an even-odd effect within the bite-angle of the bicycle. Two model compounds with methyl and hydroxyl groups at the bridgehead carbons were synthesized that demonstrated solid-state structures that correlated extremely well with the computational search. The solid-state structures were observed with both an out,out configuration and variable bridgehead-bridgehead distances. To investigate this hypothesis, polyurethanes will be made from the following diol monomers: 1,10-decanediol, a monocyclic diol, and a bicyclo[8.8.8]hexacosane diol.