Abstract
AbstractAs a method for overcoming the challenge of rigorous deoxygenation in copper‐mediated controlled radical polymerization processes [e.g., atom‐transfer radical polymerization (ATRP)], reported here is a simple Cu0‐RDRP (RDRP=reversible deactivation radical polymerization) system in the absence of external additives (e.g., reducing agents, enzymes etc.). By simply adjusting the headspace of the reaction vessel, a wide range of monomers, namely acrylates, methacrylates, acrylamides, and styrene, can be polymerized in a controlled manner to yield polymers with low dispersities, near‐quantitative conversions, and high end‐group fidelity. Significantly, this approach is scalable (ca. 125 g), tolerant to elevated temperatures, compatible with both organic and aqueous media, and does not rely on external stimuli which may limit the monomer pool. The robustness and versatility of this methodology is further demonstrated by the applicability to other copper‐mediated techniques, including conventional ATRP and light‐mediated approaches.
Highlights
As a method for overcoming the challenge of rigorous deoxygenation in copper-mediated controlled radical polymerization processes [e.g., atom-transfer radical polymerization (ATRP)], reported here is a simple Cu0-RDRP (RDRP = reversible deactivation radical polymerization) system in the absence of external additives
The robustness and versatility of this methodology is further demonstrated by the applicability to other copper-mediated techniques, including conventional ATRP and light-mediated approaches
The integrity and precision of these materials can be compromised by potential oxygen contamination during the polymerization as it can irreversibly react with the reaction components, leading to terminated polymer chains and/
Summary
By adjusting the headspace of the reaction vessel, a wide range of monomers, namely acrylates, methacrylates, acrylamides, and styrene, can be polymerized in a controlled manner to yield polymers with low dispersities, near-quantitative conversions, and high end-group fidelity. We focused on Cu0-wire-mediated RDRP, a system consisting of a number of components which could play the role of the reducing agent/oxygen scavenger such as the initiator, the N-containing ligand, and the Cu0 wire which can consume oxygen by oxidation into CuI or CuII.[7] Initial experiments involved preparing a Cu0-wirecatalyzed polymerization in a 28 mL unsealed vial, wherein the total reaction volume was 8 mL, with methyl acrylate (targeting DPn = 50) as the monomer, ethyl a-bromoisobutyrate (EBiB) as the initiator, tris(2-(dimethylamino)ethyl)amine (Me6Tren) as the ligand, and dimethyl sulfoxide (DMSO) as the solvent, in the absence of any commonly employed deoxygenation procedures (i.e., nitrogen sparging or freeze-pump-thaw).
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