Classical radical polymerization has led to the creation of robust materials such as Styrofoam and Plexiglas, which have made significant impacts on modern society. A fundamental element of this process is the creation of polymers with non-degradable, all-carbon backbones. A method to alter this paradigm has long existed through radical ring-opening polymerization (rROP). This method is attractive, as it enables new types of functional groups to be incorporated into the backbone of radical polymers, such as esters, that permit degradation; however, poor reactivity with many important monomer families (styrene, acrylates, and acrylamides) has limited the adoption of this polymerization strategy in next-generation materials. In this work, we have developed a new class of rROP monomers that uses a thiocarbonyl as a reversible radical acceptor to overcome classical issues of monomer reactivity and compatibility with living polymerization techniques. Further, the modular design of the thionolactone monomer allows for easy structural modifications to tune the stability of the propagating radical species. This has resulted in a versatile method to copolymerize challenging monomer families and yields thioester copolymers that are chemically and photochemically degradable.

Thiocarbonyl platform for degradable radical polymerization

2019 Spring National Meeting

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