Journal ArticleDOI
Solvent Choice Differentiates SET-LRP and Cu-Mediated Radical Polymerization with Non-First-Order Kinetics
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TLDR
In this article, the role of solvent mediating the disproportionation of Cu(I)X into Cu(0) and Cu(II)X2 during SET-LRP, a series of polymerizations of methyl acrylate initiated with methyl 2-bromopropionate and catalyzed by Cu( 0)/Me6-TREN at 25 °C in DMSO, MeCN, and their mixtures were investigated.Abstract:
In order to assess the role of the solvent mediating the disproportionation of Cu(I)X into Cu(0) and Cu(II)X2 during SET-LRP, a series of polymerizations of methyl acrylate initiated with methyl 2-bromopropionate and catalyzed by Cu(0)/Me6-TREN at 25 °C in DMSO, MeCN, and their mixtures were investigated. These polymerizations proceed in a dissimilar manner. SET-LRP of MA in DMSO, a solvent that mediates disproportionation, was exemplary of “ultrafast living radical polymerization” with complete conversion in 45 min following the expected first-order kinetics and providing perfect fidelity of the structure of the polymer chain ends. When the polymerization was performed in MeCN, a solvent in which Cu(I)X species do not disproportionate, it displayed nonlinear first-order kinetics with a poor retention of the bromine chain end functionality. The lack of first-order kinetics and decrease of chain end functionality with conversion indicate a nonliving polymerization in MeCN. Increasing the concentration of D...read more
Citations
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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.
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.
Journal ArticleDOI
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.
Journal ArticleDOI
Copper-Mediated Living Radical Polymerization (Atom Transfer Radical Polymerization and Copper(0) Mediated Polymerization): From Fundamentals to Bioapplications
Cyrille Boyer,Nathaniel Corrigan,Kenward Jung,Diep Nguyen,Thuy-Khanh Nguyen,Nik Nik M. Adnan,Susan Oliver,Sivaprakash Shanmugam,Jonathan Yeow +8 more
TL;DR: Radical Polymerization and Copper(0) Mediated polymerization): From Fundamentals to Bioapplications
Journal ArticleDOI
Precision Polymer Synthesis by Degenerative Transfer Controlled/Living Radical Polymerization Using Organotellurium, Organostibine, and Organobismuthine Chain-Transfer Agents
TL;DR: Shigeru Yamago received his B.S. and Ph.D in chemistry from Tokyo Institute of Technology in 1986 and 1991, under the supervision of Professor Eiichi Nakamura and then moved to Kyoto University in 1995 in the group of Professor Jun-ichi Yoshida, where he holds Professorship.
References
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Journal ArticleDOI
The persistent radical effect: a principle for selective radical reactions and living radical polymerizations.
Journal ArticleDOI
Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates, methacrylates, and vinyl chloride mediated by SET at 25 degrees C.
Virgil Percec,Tamaz Guliashvili,Janine S. Ladislaw,Anna Finne Wistrand,Anna Stjerndahl,Monika J. Sienkowska,Michael J. Monteiro,Sangrama Sahoo +7 more
TL;DR: It is reported that polarsolvents such as H(2)O, alcohols, dipolar aprotic solvents, ethylene and propylene carbonate, and ionic liquids instantaneously disproportionate Cu(I)X into Cu(0) and Cu(II)X(2), facilitating an ultrafast LRP in which the free radicals are generated by the nascent and extremely reactive Cu( 0) atomic species.
Journal ArticleDOI
Five-Coordinated High-Spin Complexes of Bivalent Cobalt, Nickel, andCopper with Tris(2-dimethylaminoethyl)amine
M. Ciampolini,N. Nardi +1 more
Journal ArticleDOI
Aqueous Room Temperature Metal-Catalyzed Living Radical Polymerization of Vinyl Chloride
Virgil Percec,Anatoliy V. Popov,Ernesto Ramirez-Castillo,Michael J. Monteiro,Bogdan Barboiu,Oliver Weichold,A. D. Asandei,Catherine M. Mitchell +7 more
TL;DR: The room-temperature living radical polymerization (LRP) of vinyl chloride in H2O/THF in the presence of Cu0 or CuI salts as catalysts, tren or PEI as ligands, and iodoform as initiator is described.
Journal ArticleDOI
The Persistent Radical effect in controlled radical polymerizations
TL;DR: In this article, the basic kinetic features of living polymerizations controlled and regulated by persistent radicals or related species and by reversible atom transfer are described, and analytical equations for the polymerization rates and for the polydispersities of the resulting polymers are presented, and important requirements for reaction rate constants leading to control are outlined.
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