Overcoming oxygen sensitivity is a well-known challenge in the field of controlled radical polymerizations (CRP). Previous work on non-degassed CRP mainly relies on additives – such as enzymes, photocatalysts, or sacrificial reductants – to scrub the oxygen both in solution and in the headspace of a closed reaction vessel before polymerization can proceed. Limited examples in open vessels have been reported. We developed an additive-free iniferter polymerization utilizing high-intensity blue (450 nm) light to generate excess radicals to deplete the local oxygen concentration, allowing for the controlled polymerization of acrylates and acrylamides in completely open vials. Living behavior is demonstrated through control over molecular weight, narrow molecular weight distributions, chain extension, and block copolymer synthesis. The origin of oxygen tolerance and future applications will be discussed.

Open-to-air and additive-free photocontrolled radical polymerization of acrylates and acrylamides

2019 Fall National Meeting

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