Rate Enhancement by Carboxylate Salts in the CuCl, Cu₂O, and Cu(0) Catalyzed “Living” Radical Polymerization of Butyl Methacrylate Initiated with Sulfonyl Chlorides

Copper(0)‐Mediated Living Radical Polymerization of Methyl Methacrylate in a Non‐polar Solvent

“…It is well established that Cu(0) reacts with activated alkyl halides to produce an alkyl radical and Cu(I)X/L. [20,21] If it does not instantaneously disproportionate, this Cu(I)X/L species can react with an additional alkyl halide to generate Cu(II)X 2 /L and another radical. Therefore, the number of radicals produced will be higher than the number of Cu(II)X 2 /L deactivating species.…”

Low-fluorinated homopolymer from heterogeneous ATRP of 2,2,2-trifluoroethyl methacrylate mediated by copper complex with nitrogen-based ligand

“…In other words, after a few minutes, the dissolved Cu II is constant and high enough to minimize termination events, as a result a controlled polymerization with a low fraction of dead polymer chains is expected. Secondly, the initially added solid CuBr 2 does not dissolve well [74] and as a result will not contribute to the control of the polymerization leading to a similar kinetic plot to that without CuBr 2 . However, for PMDETA or Me 6 TREN system, although the solubilization coefficients (k sol ) are high enough judging by the fast change of color after mixing all the reactants, the deactivation rate of growing TFEMA chains is not fast enough in comparison with PFEMA propagation.…”

Synthesis of aromatic carboxyl functionalized polymers by atom transfer radical polymerization

“…However, upon the addition of stoichiometric amounts of benzoic acid relative to initiator, the rate of polymerization was enhanced with concomitant broadening of the molecular weight distribution, indicating the poisoning of the copper–ligand catalyst system and low initiation efficiency. Also, reports by Perceo and co‐workers13 show that the addition of sodium benzoate to the CuCl/bpy catalysed living radical polymerization initiated by p ‐methoxybenzene sulfonyl chloride enhances the rate of polymerization of butyl acrylate in diphenyl ether. However, poor control of molecular weight is observed, and polymers with broad molecular weight distribution are formed.…”

“…In the classical ATRP process, neither the polymerization of carboxylic acid containing monomers nor the synthesis of carboxyl functionalized polymers are considered synthetically viable, because poisoning of the transition metal–ligand catalyst complex system is observed due to the rapid reversible formation of copper(I) carboxylates 11–16. In addition, the presence of copper(I) carboxylates and carboxylic acids influences the rate of polymerization of the metal catalysed controlled radical polymerization of styrene 11–16. Haddleton et al 12 reported that the 2‐bromoisobutyrate initiated polymerization of methyl methacrylate, catalysed by the ( N‐n ‐butyl‐2‐pyridylmethanimine) copper(I) bromide system, proceeded with good control of molecular weight and molecular weight distribution.…”

“…Thus, literature results indicate that the carboxylic acid group plays an active role in the metal‐catalysed living radical polymerization of styrene and acrylate monomers, especially at high concentrations. The initial role of the carboxylic acid is to complex with the copper(I) centre, displacing the ligand, thereby creating a coordination site on the cuprate intermediate for propagation to occur 12–16…”