Journal ArticleDOI
Understanding atom transfer radical polymerization: effect of ligand and initiator structures on the equilibrium constants.
Wei Tang,Yungwan Kwak,Wade A. Braunecker,Nicolay V. Tsarevsky,Michelle L. Coote,Krzysztof Matyjaszewski +5 more
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TLDR
Equilibrium constants in Cu-based atom transfer radical polymerization (ATRP) were determined for a wide range of ligands and initiators in acetonitrile at 22 degrees C and excellent correlations of the equilibrium constants with the Cu(II/I) redox potentials and the carbon-halogen bond dissociation energies were observed.Abstract:
Equilibrium constants in Cu-based atom transfer radical polymerization (ATRP) were determined for a wide range of ligands and initiators in acetonitrile at 22 °C. The ATRP equilibrium constants obtained vary over 7 orders of magnitude and strongly depend on the ligand and initiator structures. The activities of the CuI/ligand complexes are highest for tetradentate ligands, lower for tridentate ligands, and lowest for bidentate ligands. Complexes with tripodal and bridged ligands (Me6TREN and bridged cyclam) tend to be more active than those with the corresponding linear ligands. The equilibrium constants are largest for tertiary alkyl halides and smallest for primary alkyl halides. The activities of alkyl bromides are several times larger than those of the analogous alkyl chlorides. The equilibrium constants are largest for the nitrile derivatives, followed by those for the benzyl derivatives and the corresponding esters. Other equilibrium constants that are not readily measurable were extrapolated from t...read more
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Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives
TL;DR: The current status and future perspectives in atom transfer radical polymerization (ATRP) are presented in this paper, with a special emphasis on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP.
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Transition metal-catalyzed living radical polymerization : toward perfection in catalysis and precision polymer synthesis
TL;DR: Catalytic Solvents: Catalyst Disproportionation 4981 2.2.1.
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Macromolecular Engineering by Atom Transfer Radical Polymerization
TL;DR: This Perspective presents recent advances in macromolecular engineering enabled by ATRP with emphasis on various catalytic/initiation systems that use parts-per-million concentrations of Cu catalysts and can be run in environmentally friendly media, e.g., water.
Journal ArticleDOI
Single-Electron Transfer and Single-Electron Transfer Degenerative Chain Transfer Living Radical Polymerization
Brad M. Rosen,Virgil Percec +1 more
TL;DR: In this article, the authors present the latest progress in two related polymerization methodologies that rely on singleelectron transfer (SET), single-electron-transfer degenerative chain transfer living radical polymerization (SET-DTLRP), and single-Electron Transfer Living Radical Poly(SET-LRP) for the synthesis of tailored polymers.
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Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes
Justin Orazio Zoppe,Nariye Cavusoglu Ataman,Piotr Mocny,Jian Wang,John Moraes,Harm-Anton Klok +5 more
TL;DR: The generation of polymer brushes by surface-initiated controlled radical polymerization (SI-CRP) techniques has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering as mentioned in this paper.
References
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Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes
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"Green" atom transfer radical polymerization: from process design to preparation of well-defined environmentally friendly polymeric materials.
TL;DR: “Green”
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The persistent radical effect: a principle for selective radical reactions and living radical polymerizations.
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Controlled/“Living” Radical Polymerization. Kinetics of the Homogeneous Atom Transfer Radical Polymerization of Styrene
TL;DR: The homogeneous atom transfer radical polymerization (ATRP) of styrene using solubilizing 4,4'dialkyl substituted 2,2'bipyridines yielded well-defined polymers with Mw/Mn ≤ 1.10 as mentioned in this paper.