Synthesis and Characterization of New Multifunctional Initiators for Anionic Polymerization and the Use of Poly(4-hydroxystyrene) as a Template for new Polymers

This dissertation explores the synthesis and use of multifunctional anionic polymerization initiators for the purpose of opening the gateway to the synthesis of polymer architectures of greater complexity. First the multifunctional oxyanion initiator generated by reacting poly(4-hydroxystyrene) with sodium hydride was used to synthesize a previously unknown polymer containing an aryl halide functional group. The homopolymer solution self-assembly behavior of poly(4-hydroxystyrene) and the newly synthesized poly (4-bromo-phenyloxystyrene) were both investigated. This is followed by the synthesis and characterization of multifunctional alkyne core molecules and random copolymers of polystyrene-co-poly(4-hydroxystyrene) which served as templates for the synthesis of new random copolymers of polystyrene-co-poly(4-propynyloxy)styrene. The newly formed multifunctional alkyne core molecules and alkyne functionalized random copolymers served as polymer backbones in a “grafting to” strategy. Previously prepared azide terminated polymers were grafted to the multifunctional alkyne core molecules and polymer backbones by copper (I) catalyzed alkyne-azide cycloaddition reactions. Lastly, the synthesis of a new hydrocarbon soluble multifunctional initiator was undertaken. The resulting molecule was shown to be an efficient initiator of anionic polymerization in non-polar solvent in the absence of polar additives, necessary in all previous attempts to combat large scale aggregation of such multifunctional initiator. This new initiator will open the way to facile synthesis of well-defined star polymers, star-block copolymers, and more complex polymer architectures.