Controlling Polymer Architecture and Monomer Sequence Using Confined Space and Unequal Reactivity

Explored in this dissertation are methods for controlling monomer sequence, molecular weight and polydispersity of branched and linear copolymers. In Chapter 1, an overview of polymer control methods, recent advancements, and a brief discussion about the scope of structures and relevant materials is presented. Following this is a detailed description of the methods and materials proposed in the subsequent chapters. In Chapter 2, copolymerization of monomer and AB* inimer in heterogeneous media by atom transfer radical polymerization is investigated for the controlled synthesis of one-polymer-per-latex nano-plastics. Also included is the introduction of organic photocatalyst, replacing traditional transition metal based mediating species, into hyperbranched polymerization in solution and microemulsion to improve biocompatibility of the polymer particles. In Chapter 3, acid-catalyzed Friedel-Crafts hydroxyalkylation polymerization of 1,4-disubstituted benzene and benzaldehyde derivatives is used to obtain multisegmented block copolymers. This polymerization takes advantage of the intriguing unequal reactivity in step-growth polymerization to control the structure and produce block copolymers from carefully tuned oligomers.