Cyclic voltammetric studies of copper complexes catalyzing atom transfer radical polymerization

Qiu, Jian; Matyjaszewski, Krzysztof; Thouin, Laurent; Amatore, Christian

doi:10.1002/1521-3935(20000901)201:14<1625::aid-macp1625>3.0.co;2-9

Cited by 238 publications

(209 citation statements)

References 22 publications

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“…115 In a detailed study, Cu I Cl and Cu I Br complexes of bpy, dNbpy, BPMOA, BPMODA, TPMA, PMDETA, and Me 6 TREN were all characterized by CV and the measured redox potentials were correlated with the activity of the complexes in the ATRP of MA initiated by ethyl 2-bromopropionate (EBP). 209 The logarithm of the apparent ATRP equilibrium constant (determined from the slope of the time dependence of ln(…”

Section: Experimental Determination Of the Equilibrium Constant K Atrmentioning

confidence: 99%

“Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

2007

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Section: Experimental Determination Of the Equilibrium Constant K Atrmentioning

confidence: 99%

“Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

2007

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“…the redox potential, the higher is the catalytic activity. [20,21] A broad spectrum of nitrogen-based ligands has been successfully employed in copper-mediated ATRP. [19] Tetradentate nitrogen ligands, including branched aliphatic tetramines, especially tris [2-(dimethylamino)ethyl]amine (Me 6 TREN) copper complexes, currently form one of the most active class of catalysts for the ATRP of certain monomers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and ATRP Activity of New TREN‐Based Ligands

Gromada

Spanswick

Matyjaszewski

2004

Macro Chemistry & Physics

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Summary: Ligands suitable for atom transfer radical polymerization (ATRP) were prepared by the Michael addition of several acrylates (allyl, benzyl, butyl, 2‐ethylhexyl, and 3‐(dimethoxymethylsilyl)propyl acrylates) with tris(2‐aminoethyl)amine (TREN). These ligands, readily prepared from inexpensive precursors, were used for the preparation of catalyst complexes suitable for polymerization of (meth)acrylates and styrene, providing activity comparable to catalysts currently used for these monomers. Catalysts containing ligands with a dimethoxymethylsilyl substituent were examined for copper removal after the reaction mixture was contacted with silica gel.magnified image

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“…Indeed, CuBr complexed by tetradentate ligands such as tris [2-(dimethylamino)ethyl]amine (Me 6 TREN) and tris(2-pyridylmethyl)amine (TPMA) is 10 3 -10 5 times more active than the originally used CuBr/bipyridine complexes. [31][32][33][34][35] However, the catalyst concentration can not simply be reduced by 10 3 (from a concentration equimolar with the initiator (i.e., 1 mol % vs. monomer) to 10 ppm vs. monomer) owing to the radical termination and concurrent irreversible oxidation of the catalyst (Cu I to Cu II ). All Cu I species would be converted to Cu II when less than 1 % of the growing chains terminate.…”

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confidence: 99%

Activators Regenerated by Electron Transfer for Atom‐Transfer Radical Polymerization of (Meth)acrylates and Related Block Copolymers

2006

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Atom-transfer radical polymerization (ATRP) is a controlled or living radical polymerization (CRP) technique [1,2] that enables the preparation of new nanostructured materials that are not accessible by conventional free-radical polymerization (FRP). Reported herein is the ATRP of polar monomers such as (meth)acrylates and related block copolymers by means of a new initiating/catalytic method based on activators regenerated by electron transfer (ARGET) with ppm (10 À4 mol % vs. monomer) amounts of Cu catalyst. [3] ATRP [4][5][6][7] provides a simple route to many well-defined (co)polymers with precisely controlled functionalities, topologies, and compositions. [8][9][10] It has been very successfully applied to the preparation of many nanocomposites, hybrids, and bioconjugates. [11][12][13][14][15][16][17][18][19][20][21][22][23] The advantages of ATRP, in comparison with other CRP processes, include the large range of available monomers and (macro)initiators, the simplicity of reaction setup, and the ability to conduct the process over a large range of temperatures, solvents, and dispersed media. [6,7,24] ATRP (Scheme 1) is a repetitive atom-transfer process between a macromolecular alkyl halide P n ÀX and a redoxactive transition-metal complex Cu I ÀX/ligand in which P n C radicals propagate (rate constant of propagation k p ) and are reversibly formed (rate constants k a and k da ). The growing radicals also terminate by coupling or disproportionation (rate constant k t ).An inherent feature, but also a limitation of ATRP, is the presence of a catalyst (a transition-metal complex with Scheme 1. Mechanism for ATRP.

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Cyclic voltammetric studies of copper complexes catalyzing atom transfer radical polymerization

Cited by 238 publications

References 22 publications

“Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

“Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

Synthesis and ATRP Activity of New TREN‐Based Ligands

Activators Regenerated by Electron Transfer for Atom‐Transfer Radical Polymerization of (Meth)acrylates and Related Block Copolymers

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