Prof. Athina Anastasaki, ETH Zurich

Making and Unmaking Polymers by Controlled Radical Polymerization

Controlled radical polymerization is widely used to prepare a broad range of polymeric materials for diverse applications in various fields. A common misconception in the field is that high end-group fidelity and high dispersity are typically mutually exclusive characteristics. This is a significant limitation as both high and low dispersity polymers exhibit unique properties and functions and as such dispersity is a key parameter in material design. In this talk I will present a straightforward and versatile batch method based on reversible addition-fragmentation chain transfer (RAFT) polymerization to tailor molecular weight distributions for a wide range of monomer classes. Although high end-group fidelity is crucial to facilitate the synthesis of well-defined block copolymers, it has rarely been exploited to reverse controlled radical polymerization and regenerate the starting materials. In the second part of the talk I will discuss a near-quantitative and catalyst-free depolymerization of various linear, bulky, crosslinked, and functional polymethacrylates made by RAFT polymerization. Importantly, the depolymerization product can be utilized to either reconstruct the linear polymer or create an entirely new insoluble gel that can also be subjected to depolymerization.