Controlled Polymer Photosynthesis

Current polymer science research is moving towards the study of well-defined macromolecules with greater applications such as in biological systems, hybrid materials or photonics. Underlying to this move are synthesis methodologies which are robust, operate under mild reaction conditions and are chemoselective, while maintaining the control over various possible parameters of macromolecular structure (i.e., molecular weight distribution, end groups, architecture, composition and sequence). This is part of a broader scientific endeavour of making synthetic macromolecules increasingly resemble those found in living systems with various emergent properties. Photochemistry represents an attractive means toward this end because of its energy efficiency, unique reactivity patterns and stimulus orthogonality. Specifically, we were intrigued with using heterogeneous photocatalysis, namely by metal oxides. Not only are the catalytic materials very easily sourced, but the catalysts can also be used in a massive variety of solvents, they can be removed from a reaction solution by centrifugation, and even recycled. The research outlined in this thesis concerns the application of heterogeneous photocatalysis to controlled polymer synthesis. Throughout, we were able to unravel novel methodologies based around a standard reaction used to control molecular weight, namely, reversible addition fragmentation chain-transfer (RAFT) polymerisation. We found that different layers of control of polymer synthesis could be achieved inherent to the reactions themselves