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Showing papers by "Armando Gennaro published in 2021"


Journal ArticleDOI
TL;DR: In this article, the stability of Cu complexes with tris(2-(dimethylamino)ethyl)amine (Me6TREN) and tris (2-pyridylmethyl)amines (TPMA) was investigated in DMF, DMSO, and MeCN by cyclic voltammetry, UV-vis-NIR spectroscopy and controlled-potential eATRP.

9 citations


Journal ArticleDOI
TL;DR: In this article, the mechanism of ATRP activation, thermodynamic parameters, determination of activation and deactivation rate constants, SARA ATRP vs SET-LRP dispute, and electrochemically-mediated ATRP.
Abstract: Atom Transfer Radical Polymerization (ATRP) is the most powerful and most employed technology of Controlled Radical Polymerization (CRP) to produce polymers with well-defined architecture, that is, composition, topology, and functionality. Several hundreds of papers are published every year on ATRP processes, mainly based on empiric experimental procedures. Electrochemistry powerfully entered in the field of ATRP about 10 years ago, providing important contributions both to the further development of the process and to a better understanding of its mechanism. Five main issues took advantage of electrochemistry and/or its synergism with ATRP: i) understanding the mechanism of ATRP activation; ii) determination of thermodynamic parameters; iii) determination of activation and deactivation rate constants; iv) the SARA ATRP vs SET-LRP dispute: the role of Cu0 ; v) electrochemically-mediated ATRP.

9 citations




Journal ArticleDOI
TL;DR: The target ATRP process catalyzed by CuCl2/tris(2-pyridylmethyl)amine (TPMA) (1/1) in ethyl acetate/ethanol (EtOAc/E) was described in this paper.
Abstract: “Activator regenerated by electron transfer” “atom transfer radical polymerization” (ARGET ATRP) process catalyzed by CuCl2/tris(2-pyridylmethyl)amine (TPMA) (1/1) in ethyl acetate/ethanol (EtOAc/E

4 citations


Journal ArticleDOI
TL;DR: Combined cHE/SARA ATRP is therefore a simple and potent polymerization tool for the copolymerization of a wide range of monomers allowing the production of tailored block copolymers.
Abstract: Synthesis of block copolymers (BCPs) by catalytic halogen exchange (cHE) is reported, using supplemental activator and reducing agent Atom Transfer Radical Polymerization (SARA ATRP). The cHE mechanism is based on the use of a small amount of a copper catalyst in the presence of a suitable excess of halide ions, for the synthesis of block copolymers from macroinitiators with monomers of mismatching reactivity. cHE overcomes the problem of inefficient initiation in block copolymerizations in which the second monomer provides dormant species that are more reactive than the initiator. Model macroinitiators with low dispersity are prepared and extended to afford well-defined block copolymers of various compositions. Combined cHE/SARA ATRP is therefore a simple and potent polymerization tool for the copolymerization of a wide range of monomers allowing the production of tailored block copolymers.

4 citations


Journal ArticleDOI
TL;DR: In this article, a voltammetric comparison of substituted bromothiophenes vs bromobenzenes highlights the combined effects of the aromatic or heteroaromatic ring substituents and the sulphur atom on both the intrinsic reactivity (accounted for by experiments on a glassy carbon electrode, assumed to have negligible specific interactions) and the reactivity in the presence of electrocatalytic effects.

1 citations