Cu(0)-mediated living radical polymerization: recent highlights and applications; a perspective

Abstract

Cu(0)-mediated living radical polymerization or single electron transfer living radical polymerization (Cu(0)-mediated LRP or SET-LRP) is a versatile polymerization technique that has attracted considerable interest during the past few years for the facile preparation of advanced materials.

Universal Conditions for the Controlled Polymerization of Acrylates, Methacrylates, and Styrene via Cu(0)-RDRP

“…In order to circumvent this, a number of different "variations" of ATRP and SET-LRP have recently been developed, including use of free radical initiators (initiators for continuous activator regeneration (ICAR) ATRP) 20 , reducing agents (activators regenerated by electron transfer (ARGET) and AGET ATRP) 21,22 , electrochemical (eATRP) 23 and light stimuli (light ATRP), [24][25][26][27][28][29][30] as well as Cu(0)-wire and Cu(0) particle mediated processes. 31,32 The latter two approaches have demonstrated high end group fidelity even at near-quantitative conversions as exemplified by the in situ synthesis of multiblock copolymers. [33][34][35][36][37][38][39] Moreover, to the best of our knowledge, in situ chain extensions with copper mediated polymerization approaches have only been reported for relatively high kp monomers such as acrylates, as methacrylates are more susceptible to termination, chain transfer and side reactions.…”

Functionalisation of MWCNTs with poly(lauryl acrylate) polymerised by Cu(0)-mediated and RAFT methods

“…It has been demonstrated that Cu(0)-mediated polymerisation is highly efficient in allowing facile synthesis of well-defined, high molar mass polymers at ambient temperatures with low molar mass dispersity whilst retaining high end group fidelity. [10][11][12] In particular, Cu(0)-mediated polymerisation has shown to provide impressive control of monomers containing long hydrophobic side chains e.g. lauryl acrylate.…”

Heteroatom‐Doped Carbon Dots (CDs) as a Class of Metal‐Free Photocatalysts for PET‐RAFT Polymerization under Visible Light and Sunlight

“…[1] Recently,t he integration of photo-mediated synthesis with reversible-deactivation radical polymerization (RDRP), including nitroxide-mediated polymerization (NMP), atom-transfer radical polymerization (ATRP), and reversible addition-fragmentation chain-transfer (RAFT) polymerization, is as ignificant advancement in this field. [3] So far, in this field, great progress has been made in the groups led by Hawker and Fors, [4] Matyjaszewski, [5] Yagci, [6] Miyake, [7] Boyer, [8][9][10] Qiao, [11] Haddleton and Anastasaki, [12] Johnson, [13,14] Boydston, [15] Egap, [16] and many others. [3] So far, in this field, great progress has been made in the groups led by Hawker and Fors, [4] Matyjaszewski, [5] Yagci, [6] Miyake, [7] Boyer, [8][9][10] Qiao, [11] Haddleton and Anastasaki, [12] Johnson, [13,14] Boydston, [15] Egap, [16] and many others.…”

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Ak ey challenge of photoregulated living radical polymerization is developing efficient and robust photocatalysts.Now carbon dots (CDs) have been exploited for the first time as metal-free photocatalysts for visible-light-regulated reversible addition-fragmentation chain-transfer (RAFT) polymerization. [3] So far, in this field, great progress has been made in the groups led by Hawker and Fors, [4] Matyjaszewski, [5] Yagci, [6] Miyake, [7] Boyer, [8][9][10] Qiao, [11] Haddleton and Anastasaki, [12] Johnson, [13,14] Boydston, [15] Egap, [16] and many others. PET-RAFT polymerization of various monomers with temporal control, narrowdispersity ( % 1.04), and chain-endfidelity was achieved.Besides,itwas demonstrated that the CD-catalyzed PET-RAFT polymerization was effectively performed under natural solar irradiation.

Inspired by the solar-driven biosynthesis of proteins with high chain end fidelity and sequence control, macromolecular research has been focused on the exploitation of light to regulate modern polymer synthesis for ab etter control over the polymerization process.

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