The scale-up of electrochemically mediated atom transfer radical polymerization without deoxygenation

Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

“…4D). 20). A sample was then taken from the postpolymerization mixture and used without further purication to prepare an ATRP "cocktail" with OEOMA 300 monomer (DP T ¼ 250).…”

“…This inspired researchers to harness Cu I /Cu II catalysis to function also as an oxygen scavenger. [17][18][19][20][21][22] The continuous reduction of Cu II /L back to Cu I /L makes the ATRP inherently resistant to oxygen (Fig. 1).…”

Polymer-modified regenerated cellulose membranes: following the atom transfer radical polymerization concepts consistent with the principles of green chemistry

“…Low catalyst loading methods offer more environmentally benign and industrially scalable reaction conditions compared to "classical" ATRP but also provide an option to prepare polymers with designed dispersity, defined by the catalyst content (Discekici et al 2018(Discekici et al , 2016(Discekici et al , 2017Lu et al 2019;Matyjaszewski 2012a;Parkatzidis et al 2020;Treat et al 2014). The new low ppm ATRP methods regenerate the activator by the use of a chemical reducing agent as a radical initiator in initiators for continuous activator regeneration (ICAR) ATRP (Konkolewicz et al 2012;Luan et al 2022), chemical compounds (Luo et al 2022;Matyjaszewski et al 2007;Min et al 2007) and silver (Williams et al 2015) in activators regenerated by electron transfer (ARGET) ATRP-used a few times for membrane modification (Bhut et al 2012;Worthley et al 2011), zerovalent metals in supplemental activator and reducing agent (SARA) ATRP (Chmielarz et al 2015a;Konkolewicz et al 2014Konkolewicz et al , 2013, external stimuli as an electrical current in electrochemically mediated ATRP (eATRP) (Chmielarz 2017;Chmielarz et al 2015b;De Bon et al 2022;Han et al 2022;Park et al 2015;Zhao et al 2022), light in metal-free (Soly et al 2022;Su et al 2022;Treat et al 2014) or photochemically mediated ATRP (photo-ATRP) (Fu et al 2021;Huang et al 2017;Tasdelen et al 2011), mechanical forces in mechanically induced ATRP (mechano-ATRP) (Liu et al 2022a;Mohapatra et al 2018;Wang et al 2019), ultrasound in ultrasonication-induced atom tran...…”

Atom Transfer Radical Polymerization: A Mechanistic Perspective

“…When one adjusted the reaction volume to diminish the headspace as well as judiciously selected the ratios between the various ATRP components, it was possible to obtain well-controlled polymerizations without deoxygenation . Robust oxygen-tolerant ATRP was recently developed by means of enzymatic degassing, via light irradiation combined with sodium pyruvate in photoinduced ICAR (PICAR) ATRP, or by modulating electrical currents in the presence of sodium pyruvate in e ATRP …”

“…26 Robust oxygen-tolerant ATRP was recently developed by means of enzymatic degassing, 27 via light irradiation combined with sodium pyruvate in photoinduced ICAR (PICAR) ATRP, 28 or by modulating electrical currents in the presence of sodium pyruvate in eATRP. 29 These advances were made possible by an in-depth investigation of the ATRP mechanism and by defining expressions and correlations to predict ATRP outcomes. The next section of this Perspective discusses the fundamental characteristics of an ATRP catalyst, namely, its ability to activate dormant species and deactivate propagating radicals and its selectivity toward these processes.…”