We report a fully oxygen photoinduced RDRP system, independent of any externally added oxygen quenchers, enzymes, reducing agents or deoxygenation methods. The efficient elimination of headspace gives access to a range of monomer families, such as methyl acrylate (MA) even in molecular weights as high as ~ 53,000, ethylene glycol methyl ether acrylate (EGA) and the hydrophilic poly(ethylene glycol methyl ether acrylate) (PEGA480). Moreover, the hydrophobic monomers such as n-butyl acrylate (n-BA) and hexyl acrylate (HA), as well as the protected and expansively functionalized tert-butyl acrylate (t-BA) are polymerized in different solvents. Additionally, utilizing 2,2,2-trifluoroethanol (TFE) as solvent, the semi-fluorinated poly(2,2,2-trifluoroethyl acrylate) (PTFEA) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) are obtained. Surprisingly, this approach is efficiently scalable from extremely low volumes such as 5 μL, to high scale reactions of 0.5 L. The experimental data generating from the oxygen probe demonstrate preliminary insights into the oxygen consumption mechanism and the role of the different components that comprise a deoxygenation-free polymerization.

Copper mediated living radical polymerisation in the presence of oxygen

2019 Fall National Meeting

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