Better Together: Photoredox/Copper Dual Catalysis in Atom Transfer Radical Polymerization DOI Creative Commons
Julian Sobieski, Adam Gorczyński, Arman Moini Jazani

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 29, 2024

Abstract Photomediated Atom Transfer Radical Polymerization (photoATRP) is an activator regeneration method, which allows for the controlled synthesis of well‐defined polymers via light irradiation. Traditional photoATRP often limited by need high‐energy ultraviolet or violet light. These could negatively affect control and selectivity polymerization, promote side reactions, may not be applicable to biologically relevant systems. This drawback can circumvented introduction catalytic amount photocatalysts, absorb visible and/or NIR and, therefore, controlled, regenerative ATRP performed with dual‐catalytic cycle. Herein, a critical summary recent developments in field dual‐catalysis concerning Cu‐catalyzed provided. Contributions involved species are examined mechanistically, followed challenges future directions towards next generation advanced functional macromolecular materials.

Language: Английский

Visible light-induced photo-radical ring-opening copolymerization of thionolactone and acrylates DOI Creative Commons
Arman Moini Jazani, Roksana Bernat, Krzysztof Matyjaszewski

et al.

Polymer, Journal Year: 2024, Volume and Issue: 302, P. 127032 - 127032

Published: April 8, 2024

Radical ring-opening (co)polymerization (RROP) provides an accessible method for synthesizing main chain degradable vinyl polymers. Although the applications of reversible deactivation radical polymerization (RDRP) into RROP have been reported, use photo-mediated RDRP methods has received less attention than thermal process. Here, photo-RROP thionolactone dibenzo[c,e]-oxepine-5(7H)-thione (DOT) and methyl acrylate (MA) was studied using photo-iniferter (PI) addition-fragmentation(chain) transfer (RAFT) at ambient temperature without external initiators or photocatalysts. Despite occurrence some side reactions including desulfurization-oxygenation O-S isomerization DOT promoted by photoexcited thiocarbonyl groups, polymers with thioester linkages in backbone were prepared, which degraded presence amines bleach.

Language: Английский

Citations

5
Copper and ZnO Dual-Catalyzed Photo-Assisted depolymerization of Poly(Methyl Methacrylate) without deoxygenation DOI Creative Commons

Martin Cvek,

Arman Moini Jazani,

Ferdinando De Luca Bossa

et al.

European Polymer Journal, Journal Year: 2024, Volume and Issue: 220, P. 113429 - 113429

Published: Sept. 2, 2024

Despite significant advancements in thermal and photothermal depolymerizations, the success of these techniques relies on tedious deoxygenation procedures. Herein, we report development depolymerization technique efficient without prior deoxygenation, which was enabled by copper/ligand complexes inclusion (0.25 wt% relative to solvent) zinc oxide (ZnO) nanocrystals activated UV light. This approach tested for poly(methyl methacrylate) (PMMA) prepared atom transfer radical polymerization (ATRP); effects solvent polarity activity ligands were investigated. Unexpectedly, a low-activity Cu-complex with 2,2'-bipyridyne ligand, combination low-polarity solvent, 1,2,4-trichlorobenzene, relatively high yields less than 1 h at 150 °C. Higher ATRP tris(2-pyridylmethyl)amine (TPMA) N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) ligands, efficient, associated their decomposition and/or excessive formation radicals premature termination chain ends. The presented facile designed be used even partially aerated reactors, opening new avenues depolymerization.

Language: Английский

Citations

4
Unraveling the Roles of Amines in Atom Transfer Radical Polymerization in the Dark DOI Creative Commons
Arman Moini Jazani, Görkem Yılmaz, Mitchell A. Baumer

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

Multidentate amines have been widely used as ligands (L) for Cu-catalysts in atom transfer radical polymerization (ATRP) and electron donors photochemically induced polymerizations. However, mechanistic aspects of the role ATRP dark remained elusive. Herein, structure-activity relationship related reactions with Br-CuII/L complexes and/or alkyl bromides (R-Br) were investigated 25 amines. Amines function reducing agents via an outer sphere (OSET) mechanism, enabling slow but continuous generation CuI/L activators inducing controlled ATRP. two amines, diazabicyclo(5.4.0)undec-7-ene (DBU) 1,1,3,3-tetramethylguanidine (TMG), reduced faster, suggesting inner (ISET) process. ATRP, starting initial deactivators (Br-CuII/L) species, proceeded presence excess tertiary such tris[2-(dimethylamino)ethyl]amine (Me6TREN), 1,4-diazabicyclo[2.2.2]octane (DABCO), TMG at room temperature afforded polymers low dispersities (Đ ≤ 1.15). With copper(II) triflate complex (CuII/L+2, -(OTf)2), which has a more positive reduction potential, several inexpensive secondary including triethylamine (TEA) dimethylethanolamine (DMAE). Interestingly, multidentate also served direct R-Br elevated temperatures (60 °C). In all cases, chains initiated not by amine cations byproducts transfer. enabled residual air flasks large headspace, underpinning them robust accessible agent practical applications.

Language: Английский

Citations

0
Better Together: Photoredox/Copper Dual Catalysis in Atom Transfer Radical Polymerization DOI Creative Commons
Julian Sobieski, Adam Gorczyński, Arman Moini Jazani

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 29, 2024

Abstract Photomediated Atom Transfer Radical Polymerization (photoATRP) is an activator regeneration method, which allows for the controlled synthesis of well‐defined polymers via light irradiation. Traditional photoATRP often limited by need high‐energy ultraviolet or violet light. These could negatively affect control and selectivity polymerization, promote side reactions, may not be applicable to biologically relevant systems. This drawback can circumvented introduction catalytic amount photocatalysts, absorb visible and/or NIR and, therefore, controlled, regenerative ATRP performed with dual‐catalytic cycle. Herein, a critical summary recent developments in field dual‐catalysis concerning Cu‐catalyzed provided. Contributions involved species are examined mechanistically, followed challenges future directions towards next generation advanced functional macromolecular materials.

Language: Английский

Citations

2
Interfacial and ion-pairing catalysis for oxygen-tolerant large-scale ATRP in ab initio emulsion DOI Creative Commons
Francesco De Bon, Ana B. Barbosa,

Teresa J. Lourenço Bernardino

et al.

European Polymer Journal, Journal Year: 2024, Volume and Issue: 214, P. 113142 - 113142

Published: May 16, 2024

A cooperative interfacial and ion-pairing catalysis, coupled with a molecular oxygen reduction reaction (ORR), to scale up an Atom Transfer Radical Polymerization of n-butyl acrylate (BA) from 20 mL 10 L (scale-up factor = 500) in ab initio emulsion conditions is introduced. The polymerization driven by the regeneration [CuIL]+ through CuII/Cu0 comproportionation. simultaneously converts O2 H2O2 (which then degraded sodium pyruvate) drives butyl acrylate. anionic surfactant dodecyl sulfate (SDS) facilitates catalyst transport inside outside micelles catalysis. n-Butyl polymerizations are investigated on small Cu0 wire larger powder. On scale, yielded controlled PBA-Br (Mn 32.3 × 103; Ð 1.39, ∼1.64 kg) after 9 h. Chain extension macroinitiators proved their livingness. An on-line electrochemical monitoring was also introduced determine instantaneous CuI CuII concentrations at surface during polymerization.

Language: Английский

Citations

0
Better Together: Photoredox/Copper Dual Catalysis in Atom Transfer Radical Polymerization DOI Creative Commons
Julian Sobieski, Adam Gorczyński, Arman Moini Jazani

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 29, 2024

Abstract Photomediated Atom Transfer Radical Polymerization (photoATRP) is an activator regeneration method, which allows for the controlled synthesis of well‐defined polymers via light irradiation. Traditional photoATRP often limited by need high‐energy ultraviolet or violet light. These could negatively affect control and selectivity polymerization, promote side reactions, may not be applicable to biologically relevant systems. This drawback can circumvented introduction catalytic amount photocatalysts, absorb visible and/or NIR and, therefore, controlled, regenerative ATRP performed with dual‐catalytic cycle. Herein, a critical summary recent developments in field dual‐catalysis concerning Cu‐catalyzed provided. Contributions involved species are examined mechanistically, followed challenges future directions towards next generation advanced functional macromolecular materials.

Language: Английский

Citations

0