Enzyme-Deoxygenated Low Parts per Million Atom Transfer Radical Polymerization in Miniemulsion and Ab Initio Emulsion

The development of robust oxygen-tolerant reversible deactivation radical polymerization (RDRP) systems can dramatically simplify synthesis of well-defined polymers without redundant deoxygenation procedures. Herein, we broaden the application of oxygen-tolerant RDRP from homogeneous aqueous and organic solutions to dispersed media. The glucose oxidase (GOx) degassed atom transfer radical polymerization (ATRP) was conducted in miniemulsion and ab initio emulsion systems using various catalyst regeneration methods: ARGET, ICAR, photo, and eATRP. All of these polymerization procedures led to polymers with predetermined molecular weight, low dispersity, and high chain-end functionality. Emulsion ATRP on a larger scale with preserved control was also successful. Circular dichroism (CD) studies demonstrated that the anionic surfactant, sodium dodecyl sulfate (SDS), did not damage the secondary structure of GOx. This confirms the versatility of the GOx system for various low ppm ATRP methods. GOx-assisted oxygen removal in the synthesis of hydrophobic polymers is reported for the first time. The low cost of deoxygenation reagents and the ability to scale up the procedure suggest the potential for industrial production, especially for emulsion polymerization.