Visible Light‐ATRP Driven by Tris(2‐Pyridylmethyl)Amine (TPMA) Impurities in the Open Air

Jazani, Arman Moini; Schild, Dirk; Sobieski, Julian; Hu, Xiaolei; Matyjaszewski, Krzysztof

doi:10.1002/marc.202200855

Cited by 12 publications

(12 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…15 Photoinduced ATRP (photoATRP) employs the photochemical reaction of excited Cu(II)/L deactivators with electron donors, such as amines (including also excess Nbased ligands). 18,19 Alternatively, organic dyes, such as eosin Y, 20 upon excitation can form strongly reducing species that can directly reduce Cu(II) deactivators by outer sphere electron transfer (OSET) in the oxidative quenching process. Also, the excited photocatalysts can first react with electron donors and form radical anion species, which can transfer an electron and reduce Cu(II) species to Cu(I) activators.…”

Section: Introductionmentioning

confidence: 99%

Comparison of Mechano- and PhotoATRP with ZnO Nanocrystals

et al. 2023

Self Cite

View full text Add to dashboard Cite

Zinc oxide (ZnO) was previously reported as an excellent cocatalyst for mechanically controlled atom transfer radical polymerization (mechanoATRP), but its photocatalytic properties in photoinduced ATRP (photoATRP) have been much less explored. Herein, well-defined ZnO nanocrystals were prepared via microwave-assisted synthesis and applied as a heterogeneous cocatalyst in mechano- and photoATRP. Both techniques yielded polymers with outstanding control over the molecular weight, but ZnO-cocatalyzed photoATRP was much faster than analogous mechanoATRP (conversion of 91% in 1 h vs 54% in 5 h). The kinetics of photoATRP was tuned by loadings of ZnO nanocrystals. PhotoATRP with ZnO did not require any excess of ligand versus Cu, in contrast to mechanoATRP, requiring an excess of ligand, acting as a reducing agent. ZnO-cocatalyzed photoATRP proceeded controllably without prior deoxygenation, since ZnO was involved in a cascade of reactions, leading to the rapid elimination of oxygen. The versatility and robustness of the technique were demonstrated for various (meth)acrylate monomers with good temporal control and preservation of end-group functionality, illustrated by the formation of tailored block copolymers.

show abstract

Section: Introductionmentioning

confidence: 99%

Comparison of Mechano- and PhotoATRP with ZnO Nanocrystals

et al. 2023

Self Cite

View full text Add to dashboard Cite

show abstract

“…Then, the generated activator Cu I /L reacts with a C(sp 3 )–X polymer chain end to form a carbon radical and the X–Cu II /L deactivator. Oxygen tolerance in this approach can be achieved using an excess ligand. − However, photoinduced Cu-catalyzed ATRP typically requires the use of biocidal UV light. ,, In organocatalyzed ATRP (O-ATRP), the dormant polymer chain is directly activated by electron transfer from a photoredox catalyst (PC) in the excited state (Figure b). − O-ATRP is compatible with a wide range of visible light but is mainly limited to methacrylates and organic solvents. − ATRP with dual catalysis uses copper complexes to attain a controlled radical propagation and PCs to trigger and drive polymerization (Figure c). ,− The photoredox/copper dual catalysis overcomes the challenges of using biocidal UV light, poor oxygen tolerance, and limited monomer scope.…”

Section: Introductionmentioning

confidence: 99%

Fully Oxygen-Tolerant Visible-Light-Induced ATRP of Acrylates in Water: Toward Synthesis of Protein-Polymer Hybrids

et al. 2023

Self Cite

View full text Add to dashboard Cite

Over the last decade, photoinduced ATRP techniques have been developed to harness the energy of light to generate radicals. Most of these methods require the use of UV light to initiate polymerization. However, UV light has several disadvantages: it can degrade proteins, damage DNA, cause undesirable side reactions, and has low penetration depth in reaction media. Recently, we demonstrated green-light-induced ATRP with dual catalysis, where eosin Y (EYH 2 ) was used as an organic photoredox catalyst in conjunction with a copper complex. This dual catalysis proved to be highly efficient, allowing rapid and well-controlled aqueous polymerization of oligo(ethylene oxide) methyl ether methacrylate without the need for deoxygenation. Herein, we expanded this system to synthesize polyacrylates under biologically relevant conditions using Cu II /Me 6 TREN (Me 6 TREN = tris[2-(dimethylamino)ethyl]amine) and EYH 2 at ppm levels. Water-soluble oligo(ethylene oxide) methyl ether acrylate (average M n = 480, OEOA 480 ) was polymerized in open reaction vessels under green light irradiation (520 nm). Despite continuous oxygen diffusion, high monomer conversions were achieved within 40 min, yielding polymers with narrow molecular weight distributions (1.17 ≤ D̵ ≤ 1.23) for a wide targeted DP range (50−800). In situ chain extension and block copolymerization confirmed the preserved chain end functionality. In addition, polymerization was triggered/halted by turning on/off a green light, showing temporal control. The optimized conditions also enabled controlled polymerization of various hydrophilic acrylate monomers, such as 2-hydroxyethyl acrylate, 2-(methylsulfinyl)ethyl acrylate), and zwitterionic carboxy betaine acrylate. Notably, the method allowed the synthesis of well-defined acrylate-based protein-polymer hybrids using a straightforward reaction setup without rigorous deoxygenation.

show abstract

“…Incorporating photochemistry into reversible-deactivation radical polymerization (RDRP) has become a subject of increased interest, which offer a new opportunity for precise polymeric materials synthesis under a spatiotemporal controllable manner and mild condition. − Atom transfer radical polymerization (ATRP) is one of the most intensively utilized RDRP methods. − Until now, several photoATRP systems have shown extraordinary control over activation–deactivation equilibrium. In Cu-mediated photoATRP, Cu II /L first accessed the excited state by absorbing an ultraviolet or violet light (<400 nm) photon.…”

Section: Introductionmentioning

confidence: 99%

Hybrid of Organophotoredox- and Cu-Mediated Pathways Enables Atom Transfer Radical Polymerization with Extremely Low Catalyst Loading

Ti,

Fang,

Bai

et al. 2023

Macromolecules

View full text Add to dashboard Cite

The rise of photoredox catalysis has extended the landscape of reversible-deactivation radical polymerization. Recently, visible-light-driven photoredox/Cu dual catalyzed atom transfer radical polymerization (photoATRP) has become an emerging trend, providing well-defined polymer under low copper catalyst loading. In this work, we described a dual catalyzed ATRP using CuBr2/tris(2-pyridinylmethyl)amine (TPMA) and donor–acceptor-type organophotoredox catalysts (OPCs) with visible light absorption. The excited state OPC can reduce both dormant polymer chain-end and CuBr2/TPMA, generating propagating radical species and CuBr/TPMA, respectively. This indicates that the mechanism is a hybrid of organophotoredox-mediated and Cu-mediated ATRP. The photoATRP driven by 425 nm light irradiation produced a series of well-defined polymethacrylates under extremely low catalyst loadings (5 or 10 ppm CuBr2 and 1 ppm OPC relative to monomer). The method also showed excellent temporal control over polymerization and oxygen tolerance.

show abstract

Visible Light‐ATRP Driven by Tris(2‐Pyridylmethyl)Amine (TPMA) Impurities in the Open Air

Cited by 12 publications

References 53 publications

Comparison of Mechano- and PhotoATRP with ZnO Nanocrystals

Comparison of Mechano- and PhotoATRP with ZnO Nanocrystals

Fully Oxygen-Tolerant Visible-Light-Induced ATRP of Acrylates in Water: Toward Synthesis of Protein-Polymer Hybrids

Hybrid of Organophotoredox- and Cu-Mediated Pathways Enables Atom Transfer Radical Polymerization with Extremely Low Catalyst Loading

Contact Info

Product

Resources

About