Copper(II)/Tertiary Amine Synergy in Photoinduced Living Radical Polymerization: Accelerated Synthesis of ω-Functional and α,ω-Heterofunctional Poly(acrylates)
Athina Anastasaki,Vasiliki Nikolaou,Qiang Zhang,James A. Burns,Shampa R. Samanta,Christopher Waldron,Alice J. Haddleton,Ronan McHale,David J. Fox,Virgil Percec,Paul Wilson,David M. Haddleton +11 more
TLDR
Minimal polymerization in the absence of light confers temporal control and alludes to potential application at one of the frontiers of materials chemistry whereby precise spatiotemporal "on/off" control and resolution is desirable.Abstract:
Photoinduced living radical polymerization of acrylates, in the absence of conventional photoinitiators or dye sensitizers, has been realized in “daylight’”and is enhanced upon irradiation with UV radiation (λmax ≈ 360 nm). In the presence of low concentrations of copper(II) bromide and an aliphatic tertiary amine ligand (Me6-Tren; Tren = tris(2-aminoethyl)amine), near-quantitative monomer conversion (>95%) is obtained within 80 min, yielding poly(acrylates) with dispersities as low as 1.05 and excellent end group fidelity (>99%). The versatility of the technique is demonstrated by polymerization of methyl acrylate to a range of chain lengths (DPn = 25–800) and a number of (meth)acrylate monomers, including macromonomer poly(ethylene glycol) methyl ether acrylate (PEGA480), tert-butyl acrylate, and methyl methacrylate, as well as styrene. Moreover, hydroxyl- and vic-diol-functional initiators are compatible with the polymerization conditions, forming α,ω-heterofunctional poly(acrylates) with unparalleled ...read more
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Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications
TL;DR: A comprehensive survey of photo-CRP reactions can be found in this article, where a large number of methods are summarized and further classified into subcategories based on the specific reagents, catalysts, etc., involved.
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A Robust and Versatile Photoinduced Living Polymerization of Conjugated and Unconjugated Monomers and Its Oxygen Tolerance
TL;DR: A photoinduced living polymerization technique is reported, which is able to polymerize a large range of monomers, including conjugated and unconjugated monomer, using ultralow concentrations of an iridium-based photoredox catalyst and a low energy visible LED as the light source.
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Photoinduced Electron Transfer Reactions for Macromolecular Syntheses
TL;DR: This review paper provides a comprehensive account of the fundamentals and applications of photoinduced electron transfer reactions in polymer synthesis, including traditional photopolymerization methods, namely free radical and cationic polymerizations, and step-growth polymerizations involving electron transfer processes are included.
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Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications
TL;DR: This review provides a comprehensive survey of photocontrolled, living radical polymerizations (photo-CRPs), and a large number of methods are summarized and further classified into subcategories based on the specific reagents, catalysts, etc., involved.
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Photocatalysis in organic and polymer synthesis
TL;DR: This review, with over 600 references, summarizes the recent applications of photoredox catalysis for organic transformation and polymer synthesis to give an overview of this emerging field to organic and polymer chemists as well as materials scientists.
References
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Living free-radical polymerization by reversible addition - Fragmentation chain transfer: The RAFT process
John Chiefari,Y. K. Chong,Frances Ercole,Julia Krstina,Justine Leigh Jeffery,Tam P. T. Le,Roshan T. A. Mayadunne,Gordon Francis Meijs,Catherine Louise Moad,Graeme Moad,Ezio Rizzardo,San H. Thang +11 more
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Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes
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Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris- (triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization
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