ATRP is a powerful method for the synthesis of polymeric materials with well controlled architectures, molecular weight and polydispersity. The control is ensured by an equilibrium between the dormant species and the propagating radical, catalyzed by copper complexes with polydentate amine ligands. The equilibrium is strongly shifted toward the dormant species, so the concentration of the radical is very low, thus sharply reducing the rate of termination reactions. The activation reaction plays a crucial role in the polymerization process and it is strongly affected by the reaction medium. In particular, the rate constant of the activation reaction depends on the nature of the copper complex, on the solvent and on the monomer. In this thesis project, several electrochemical metods will be employed to provide insights onto the kinetics of the activation reaction, by analysing different catalysts in a range of solvents, both with and without (i) some monomers, (ii) small amounts of water and (iii) halide ions.

Effetto dell'acqua sulla reazione di attivazione nella polimerizzazione radicalica per trasferimento d'atomo

Pavan, Paola
2019/2020

Abstract

ATRP is a powerful method for the synthesis of polymeric materials with well controlled architectures, molecular weight and polydispersity. The control is ensured by an equilibrium between the dormant species and the propagating radical, catalyzed by copper complexes with polydentate amine ligands. The equilibrium is strongly shifted toward the dormant species, so the concentration of the radical is very low, thus sharply reducing the rate of termination reactions. The activation reaction plays a crucial role in the polymerization process and it is strongly affected by the reaction medium. In particular, the rate constant of the activation reaction depends on the nature of the copper complex, on the solvent and on the monomer. In this thesis project, several electrochemical metods will be employed to provide insights onto the kinetics of the activation reaction, by analysing different catalysts in a range of solvents, both with and without (i) some monomers, (ii) small amounts of water and (iii) halide ions.
2019-09-19
147
ATRP, chronoamperometry, ciclic voltammetry, kinetics, methyl acrylate, electrocatalysis, initiator
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.12608/23095