Nitroxide-mediated polymerization

Nicolas, Julien; Guillaneuf, Yohann; Lefay, Catherine; Bertin, Denis; Gigmès, Didier; Charleux, Bernadette

doi:10.1016/j.progpolymsci.2012.06.002

Cited by 1,196 publications

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“…In contrast to Ir(ppy) 3 and traditional metal-catalyzed ATRP processes, a unique feature of PTH is its highly reducing excited state, which may allow a wider selection of functional groups to be tolerated during the polymerization. We sought to take advantage of this feature by polymerizing monomer types that were inaccessible with the Ir-based system.…”

Section: ■ Discussionmentioning

confidence: 99%

“…The test vehicle chosen was 2-(dimethylamino)ethyl methacrylate (DMAEMA), a monomer utilized ubiquitously for its stimuli-responsive properties. 29−32 In the presence of Ir(ppy) 3 under the previously optimized conditions, very broad polydispersities were observed (Supporting Information Table S1, M w /M n > 3). We surmised that the uncontrolled polymerization was a result of radical formation through oxidation of the amine; this is a well-known reaction pathway for photoredox catalysts.…”

Section: ■ Discussionmentioning

confidence: 99%

“…The presence of bromo chain-ends suggests potential orthogonality for combining metal-free ATRP with other controlled radical processes, increasing the range of block copolymers that can be prepared. To demonstrate the ability of metal-free ATRP to be combined with other catalyst systems, the starting PMMA homopolymer (M n = 3600 g/mol, M w /M n = 1.19) was used to polymerize methyl acrylate under Ir(ppy) 3 catalyst conditions. 20 Significantly, a well-defined block copolymer (Figure 4, M n = 20 200 g/mol, M w /M n = 1.24) with virtually no tailing in the homopolymer regime of the SEC trace was obtained.…”

Section: ■ Discussionmentioning

confidence: 99%

“…Although the emergent field of photoredox catalysis has primarily utilized transition metals (i.e., iridium and ruthenium), 23 organic catalysts have recently attracted significant attention 24 and, in some cases, have been shown to be more efficient than metalbased systems. 25 We saw this as an opportunity to establish a metal-free ATRP process by developing an organic-based catalyst that could replace Ir(ppy) 3 in photomediated, controlled radical polymerizations. The ultimate aim is an organic photoredox system that is reducing in the excited state and effectively catalyzes controlled radical polymerization processes in an analogous manner to traditional ATRP systems (Scheme 1).…”

Section: ■ Introductionmentioning

confidence: 99%

“…The majority of organic-based dyes, currently used as photoredox catalysts, are oxidizing in the excited state and would not possess the desired reduction potentials required to reduce the alkyl bromide initiator or subsequent polymer chain ends to a propagating radical. We therefore reasoned that an organic catalyst is needed that has an excited state reduction potential on par with Ir(ppy) 3 , as well as a stable radical cation species, which is formed after reduction of the alkyl bromide ( Figure 1). After surveying a range of possible organic dyes, phenothiazine derivatives were chosen as candidates for our initial studies due to the desired photophysical properties (vide supra), low cost, ready availability, and facile modification chemistry.…”

Section: ■ Introductionmentioning

confidence: 99%

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Metal-Free Atom Transfer Radical Polymerization

et al. 2014

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Overcoming the challenge of metal contamination in traditional ATRP systems, a metal-free ATRP process, mediated by light and catalyzed by an organic-based photoredox catalyst, is reported. Polymerization of vinyl monomers are efficiently activated and deactivated with light leading to excellent control over the molecular weight, polydispersity, and chain ends of the resulting polymers. Significantly, block copolymer formation was facile and could be combined with other controlled radical processes leading to structural and synthetic versatility. We believe that these new organic-based photoredox catalysts will enable new applications for controlled radical polymerizations and also be of further value in both small molecule and polymer chemistry.

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Section: ■ Discussionmentioning

confidence: 99%

Section: ■ Discussionmentioning

confidence: 99%

Section: ■ Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Metal-Free Atom Transfer Radical Polymerization

et al. 2014

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Copolymers

Ballard

2023

Kirk-Othmer Encyclopedia of Chemical Technology

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This article provides an overview of the preparation, properties, use, and characterization of synthetic copolymers. The range of different copolymer structures that can be synthesized using current methods is detailed and the current IUPAC‐recommended nomenclature for naming these structures is explained. Techniques for the production of copolymers are discussed, with an emphasis on the types of copolymers and copolymer structures attainable through each polymerization technique. Industrially important random, alternating, block, graft, star, and hyperbranched copolymers are described in terms of the processes used to produce them and the properties achieved. Their main uses and major producers are also detailed.

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Poly(2‐oxazoline)s

Verbraeken

Lava

Hoogenboom

2014

Encyclopedia of Polymer Science and Technology

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Research in the field of poly(2‐oxazoline)s (PAOx) is rapidly expanding as this polymer class combines high synthetic versatility and biocompatibility, opening up the way to highly functional (biocompatible) materials. PAOx are prepared by living cationic ring‐opening polymerization (CROP) of 2‐oxazolines. The variety of 2‐oxazoline monomers that are readily available or can easily be synthesized allows for tuning of polymer properties and introduction of diverse functionalities. Moreover, thanks to the living nature of CROP, well‐defined polymers with narrow molar mass distribution and high end group fidelity can be obtained. This article covers all aspects of PAOx ranging from the synthesis of 2‐oxazoline monomers, via in‐depth discussion on the CROP mechanism to the synthesis and properties of functional PAOx (co)polymers. The presented research demonstrates that owing to their structural adaptability and the so‐called “stealth” behavior, PAOx are well suited for a range of biomedical applications, including polymer therapeutics, scaffolds for three‐dimensional cell culture, surface modification, matrix excipient for solid dispersions, and antimicrobial agents.

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Nitroxide-mediated polymerization

Cited by 1,196 publications

References 1,061 publications

Metal-Free Atom Transfer Radical Polymerization

Metal-Free Atom Transfer Radical Polymerization

Copolymers

Poly(2‐oxazoline)s

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