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Photoinduced Iron-Catalyzed Atom Transfer Radical Polymerization with ppm Levels of Iron Catalyst under Blue Light Irradiation

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Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh 15213, Pennsylvania United States
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, China
*E-mail: [email protected] (K.M.).
Cite this: Macromolecules 2017, 50, 20, 7967–7977
Publication Date (Web):October 5, 2017
https://doi.org/10.1021/acs.macromol.7b01708
Copyright © 2017 American Chemical Society

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    Abstract

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    Photoinduced atom transfer radical polymerization (ATRP) has been mainly explored using copper-based catalytic systems. Recently developed iron-catalyzed photochemical ATRP employed high amounts of iron catalysts under high-energy UV light irradiation. Herein, a successful photoinduced iron-catalyzed ATRP mediated under blue light irradiation with ppm amounts (100–400 ppm) of iron(III) bromide/tetrabutylammonium bromide as the catalyst is reported. Several methacrylate monomers were polymerized with excellent control providing molecular weight in good agreement with theoretical values and low dispersity (Đ < 1.20). Near-quantitative monomer conversions (∼95%) enabled in situ chain extension and block copolymerization, indicating high retention of chain-end functionality. Notably, this system can tolerate oxygen, enabling synthesis of well-defined polymers with good chain-end functionality in the presence of air.

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