Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization

Halil Ibrahim Coskun; Thomas Votruba-Drzal; Hanshu Wu; Steffen Jockusch; Gorkem Yilmaz; Krzysztof Matyjaszewski

doi:10.1002/macp.202400323

Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization

Halil Ibrahim Coskun
, Thomas Votruba-Drzal
, Hanshu Wu
, Steffen Jockusch
, Gorkem Yilmaz^*
, Krzysztof Matyjaszewski^*

^*Bu çalışma için yazışmadan sorumlu yazar

Carnegie Mellon University
Bowling Green State University

Araştırma sonucu: Dergiye katkı › Makale › bilirkişi

Özet

The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr₂/Me₆TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr₂/Me₆TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to M_n ≈ 129 000 g·mol⁻¹) with low dispersity (Đ ≤ 1.16) are prepared, and chain-end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me₆TREN (83%, under [CuBr₂]/[Me₆TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations.

Orijinal dil	İngilizce
Dergi	Macromolecular Chemistry and Physics
DOI'lar	https://doi.org/10.1002/macp.202400323
Yayın durumu	Kabul Edilmiş/Basında - 2024
Harici olarak yayınlandı	Evet

Bibliyografik not

Publisher Copyright:
© 2024 The Author(s). Macromolecular Chemistry and Physics published by Wiley-VCH GmbH.

Belgeye Erişim

10.1002/macp.202400323

Diğer Dosyalar ve Linkler

Link to publication in Scopus

Alıntı Yap

@article{93da7611dcbe4de78660d9292141257d,

title = "Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization",

abstract = "The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr2/Me6TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr2/Me6TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to Mn ≈ 129 000 g·mol−1) with low dispersity ({\D} ≤ 1.16) are prepared, and chain-end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me6TREN (83\%, under [CuBr2]/[Me6TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations.",

keywords = "ATRP, photocatalyst, photopolymerization, riboflavin",

author = "Coskun, \{Halil Ibrahim\} and Thomas Votruba-Drzal and Hanshu Wu and Steffen Jockusch and Gorkem Yilmaz and Krzysztof Matyjaszewski",

note = "Publisher Copyright: {\textcopyright} 2024 The Author(s). Macromolecular Chemistry and Physics published by Wiley-VCH GmbH.",

year = "2024",

doi = "10.1002/macp.202400323",

language = "English",

journal = "Macromolecular Chemistry and Physics",

issn = "1022-1352",

}

TY - JOUR

T1 - Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization

AU - Coskun, Halil Ibrahim

AU - Votruba-Drzal, Thomas

AU - Wu, Hanshu

AU - Jockusch, Steffen

AU - Yilmaz, Gorkem

AU - Matyjaszewski, Krzysztof

PY - 2024

Y1 - 2024

N2 - The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr2/Me6TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr2/Me6TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to Mn ≈ 129 000 g·mol−1) with low dispersity (Đ ≤ 1.16) are prepared, and chain-end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me6TREN (83%, under [CuBr2]/[Me6TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations.

AB - The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr2/Me6TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr2/Me6TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to Mn ≈ 129 000 g·mol−1) with low dispersity (Đ ≤ 1.16) are prepared, and chain-end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me6TREN (83%, under [CuBr2]/[Me6TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations.

KW - ATRP

KW - photocatalyst

KW - photopolymerization

KW - riboflavin

UR - https://www.scopus.com/pages/publications/85206660115

U2 - 10.1002/macp.202400323

DO - 10.1002/macp.202400323

M3 - Article

AN - SCOPUS:85206660115

SN - 1022-1352

JO - Macromolecular Chemistry and Physics

JF - Macromolecular Chemistry and Physics

ER -

Riboflavin-Catalyzed Photoinduced Atom Transfer Radical Polymerization

Özet

Bibliyografik not

Belgeye Erişim

Diğer Dosyalar ve Linkler

Parmak izi

Alıntı Yap