Atom transfer radical polymerization in aqueous dispersed media

This thesis describes the extension of a valuable polymerization technique, atom transfer radical polymerization (ATRP), to economically viable and environmentally benign aqueous dispersed media. Several criteria for ATRP to be carried out in aqueous dispersed media, including the selection of surfactant and catalyst, are discussed in Chapter I. In Chapter II, various initiation techniques are evaluated for ATRP to be successfully carried out in aqueous dispersed media. In particular, a new initiation technique, named as activators generated by electron transfer (AGET), was recently developed and proved beneficial for ATRP in aqueous dispersed media. Chapter III focuses on the application of ATRP in miniemulsion for preparation of polymers with various compositions and architectures, including gradient copolymers, (star) block copolymers, molecular brushes and hybrid nanoparticles. Chapter IV presents the example of synthesis of microgel, degradable microgel and dual-crosslinked microgel by copolymerizing monomer and crosslinker using ATRP in miniemulsion. Chapter V discusses a further extension of ATRP to microemulsion, resulting in production of translucent microlatex and nanogel if crosslinker is involved in polymerization. Chapter VI reports the development of the successful ATRP in an emulsion process which is created by using a two-stage approach, where a microemulsion ATRP is initiated before the addition of the second batch monomer. The feasibility of ATRP in emulsion for synthesis of hairy nanoparticles is also examined in Chapter VI. Chapter VII investigates atom transfer radical dispersion polymerization by using a two-stage reverse ATRP. This approach resulted in the preparation of uniform micron-sized particles.