Design and Synthesis of Functional Graft Copolymers with Complex Architectures by Controlled Radical Polymerization Methods

Functional graft copolymers with star and bottlebrush topologies were prepared by using controlled radical polymerization methods, mainly by atom transfer radical polymerization (ATRP) but also by reversible addition fragmentation (RAFT) polymerization. A general introduction on some applications of graft copolymers with star and bottlebrush topologies were given in Chapter 1. Chapter 2 introduces a new approach to prepare star copolymers by using oligomeric macroinitiators as star cores via grafting from synthesis. Chapter 3 describes the preparation of typical molecular bottlebrush macromolecules. The importance of copper removal on the stability of multifunctional bottlebrush macromolecules were shown. Also, the use of SARA-ATRP and ICAR-ATRP for preparation of molecular bottlebrushes by using ppm amounts of catalyst was reported. Chapter 4 reports preparation of functional molecular bottlebrushes. This functionality is introduced in bond level, by introduction of a disulfide bond in the middle of the bottlebrush backbone which was later cleaved by adsorption induced stress; in molecular level by preparing a pH sensitive fluorescent molecular bottlebrushes by copolymerization of a fluorescent monomer with butyl acrylate in brush side chains; in intermolecular level by crosslinking of polystyrene bottlebrushes, using Diels-Alder reactions to produce a nanoporous network. The last part of the thesis, chapter 5 shows the preparation of a macro chain transfer agent for RAFT polymerization. Molecular bottlebrushes with poly(vinyl acetate), poly(N-vinyl pyrrolidone) and poly(N-vinyl pyrrolidone)-b-poly(vinyl acetate) molecular bottlebrushes were prepared.