Polymers are paramount to our global population as materials that impact every facet of our daily lives. It is estimated that over 300 million tons of plastic are produced each year with approximately 4% of global energy being used for the production of these materials. Due to the growing demand for polymers, the development of more energy-efficient polymerization processes will be critical for ensuring the sustainability of our economy and environment. The aim of this work has been focused on the development of organocatalyzed atom transfer radical polymerization (O-ATRP). Photoinduced O-ATRP uses organic photoredox catalysts for the synthesis of well-defined polymers. As a photoredox catalyzed method, O-ATRP embodies the principles of sustainable chemistry by allowing for improved atom economy through the use of catalysts over stoichiometric additives and by enabling reactions to be driven using sunlight as a renewable energy source. In contrast to many other photoredox catalyzed methods which employ catalysts containing rare metals such as iridium and ruthenium, O-ATRP is catalyzed by organic molecules which further improves the sustainability of this approach.<br/><br/><br/>Through this work, phenoxazine-based organic photoredox catalysts have been developed as sustainable alternatives to commonly used precious metal-containing catalysts. Characterization of the photophysical and redox properties of these phenoxazine catalysts was used to establish structure-property relationships for catalyst design. Application of these catalysts in O-ATRP allowed for the synthesis of polymers of target molecular weights and narrow molecular weight distributions using light to drive the process. In pursuit of making O-ATRP systems more facile to adopt across academia and industry, the ability to use minimal purification of the starting materials and carry out the reaction in the presence of air was demonstrated. Together, the advances in metal-free catalyst design and the development of O-ATRP systems achieved through this work provides new opportunities for polymer synthesis for a sustainable future.

Organocatalyzed atom transfer radical polymerization: Sustainable polymer synthesis

2019 Fall National Meeting

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