Oxygen‐enhanced superoxido copper‐catalyzed <scp>ATRP</scp> accelerated by light

Casa, Sina Della; Parkatzidis, Kostas; Truong, Nghia P.; Anastasaki, Athina

doi:10.1002/pol.20230479

Cited by 7 publications

(6 citation statements)

References 64 publications

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“…These systems are considered oxygen-resistant because, although they perform better in the absence of oxygen, they can still function in the presence of a certain level of oxygen that is consumed by the reagents used. This approach contrasts with the recently developed “oxygen-enhanced″ − or “oxygen-demanded″ − polymerizations. In these cases, oxygen is not intolerable; rather, it is an essential component.…”

Section: Introductionmentioning

confidence: 95%

Zinc Phthalocyanine Covalent Polymers as Recyclable Catalysts for NIR-Photocontrolled RAFT Polymerization in Water

Sun,

Zhao,

Zhang

et al. 2024

Macromolecules

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An excellent catalyst plays key roles and is always pursued by researchers for various controlled polymerizations. In this work, flexible triethylene glycol is used for the first time to bridge zinc phthalocyanine to form zinc phthalocyanine covalent polymers (ZnPc-CPs) as highly efficient heterogeneous photocatalysts for the generation of singlet oxygen ( 1 O 2 ) and thereafter to catalyze an aqueous reversible addition−fragmentation chain transfer polymerization under irradiation with near-infrared (NIR) LED light (λ max = 730 nm) at room temperature. The oxygen content is crucial to the polymerization. Trace oxygen in the polymerization produces an active hydrogen peroxide initiator to accelerate the polymerization, while a large amount of oxygen will terminate the polymerization. Additionally, benefiting from the high penetrating power of NIR light, the polymerization can still proceed in the presence of barriers. More importantly, compared to homogeneous photocatalysts, heterogeneous ZnPc-CPs can be reused by simple post-treatment and recycled without a significant decrease in the catalytic efficiency. The significant advantages, including employing NIR LED light irradiation, water as a solvent, a recyclable heterogeneous photocatalyst, and no need of prior deoxygenation, make this polymerization system not only easy to manipulate but also highly economical and environmentally beneficial.

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Section: Introductionmentioning

confidence: 95%

Zinc Phthalocyanine Covalent Polymers as Recyclable Catalysts for NIR-Photocontrolled RAFT Polymerization in Water

Sun,

Zhao,

Zhang

et al. 2024

Macromolecules

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“…These approaches cannot replace the commonly used solvents in ATRP like dimethylformamide (DMF), − dimethyl sulfoxide (DMSO), − anisole, tetrahydrofuran (THF), , N -methyl-2-pyrrolidone (NMP), , toluene, or dimethyl acetate (DMAc), which are the most frequently used reaction environments for fully controlled polymerizations of both hydrophilic and hydrophobic monomers. Nevertheless, these solvents are also restricted by Registration, Evaluation, Authorization, and Restriction of Chemicals (REACH) regulation, and therefore, their application in industrial processes is significantly limited.…”

Section: Introductionmentioning

confidence: 99%

Controlled Polymer Synthesis Toward Green Chemistry: Deep Insights into Atom Transfer Radical Polymerization in Biobased Substitutes for Polar Aprotic Solvents

Zaborniak,

Klamut,

Warne

et al. 2024

ACS Sustainable Chem. Eng.

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Cyrene (dihydrolevoglucosenone) and its derivative Cygnet 0.0, recognized as eco-friendly alternatives to polar aprotic solvents, were utilized in atom transfer radical polymerization (ATRP) of a wide range of both hydrophobic and hydrophilic (meth)acrylates. The detailed kinetics study and electrochemical experiments of the catalytic complex in these solvents reveal the opportunities and limitations of their use in controlled radical polymerization. Both solvents produce precisely controlled polymers using supplemental activator and reducing agent (SARA) ATRP. They offer an efficient reaction medium for crafting well-defined branched architectures from naturally derived cores such as riboflavin, β-cyclodextrin, and troxerutin, thereby significantly expanding the application scope of these solvents. Notably, Cygnet 0.0 significantly reduces side reactions between the solvent and the catalyst compared to Cyrene, allowing the catalyst complex to be used at a reduced concentration down to 75 ppm. The effective mass yield values achieved in Cyrene and Cygnet 0.0 underscore a substantial advantage of these solvents over DMF in generating processes that adhere to the principles of green chemistry. Furthermore, the copper residue in the final polymers was several hundred times lower than the permissible daily exposure to orally administered copper in pharmaceuticals. As a result, the resulting polymeric materials hold immense potential for various applications, including the pharmaceutical industry.

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“…[12] In this context, detecting a persistent end-on superoxido copper(II) complex using the ligand Me 6 tren under ambient conditions in an atom transfer radical polymerization (ATRP) was notably unexpected. [13,14] ATRP is one of the most prevalent techniques in reversible deactivation radical polymerization (RDRP). [15][16][17][18] It relies on the dynamic equilibrium between active and dormant states of polymers.…”

Section: Introductionmentioning

confidence: 99%

Unusual Stability of an End‐on Superoxido Copper(II) Complex under Ambient Conditions

Campi,

Parkatzidis,

Anastasaki

et al. 2024

Chemistry A European J

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Superoxido copper complexes play an important role as usually short‐lived intermediates in biology and chemistry. The unusual stability of an end‐on superoxido copper complex observed in an oxygen‐enhanced atom transfer radical polymerization (ATRP) led to a detailed mechanistic investigation of the formation of [CuII(Me6tren)(O2•−)]+ (Me6tren = tris(2‐dimethyl‐aminoethyl)amine) under ambient conditions. The persistence of the superoxido copper complex could be explained by a reaction cycle including the peroxido complex [(Me6tren)2CuII2(O2)]2+ together with [CuI(Me6tren)(DMSO)]+ and [CuII(Me6tren)(OH)]+ in the overall reaction.

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Oxygen‐enhanced superoxido copper‐catalyzed ATRP accelerated by light

Cited by 7 publications

References 64 publications

Zinc Phthalocyanine Covalent Polymers as Recyclable Catalysts for NIR-Photocontrolled RAFT Polymerization in Water

Zinc Phthalocyanine Covalent Polymers as Recyclable Catalysts for NIR-Photocontrolled RAFT Polymerization in Water

Controlled Polymer Synthesis Toward Green Chemistry: Deep Insights into Atom Transfer Radical Polymerization in Biobased Substitutes for Polar Aprotic Solvents

Unusual Stability of an End‐on Superoxido Copper(II) Complex under Ambient Conditions

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