Cobalt-Mediated Radical Polymerization of Acrylonitrile: Kinetics Investigations and DFT Calculations - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2008

Cobalt-Mediated Radical Polymerization of Acrylonitrile: Kinetics Investigations and DFT Calculations

Résumé

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt‐mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried out starting from a conventional azo‐initiator (V‐70) in the presence of bis(acetylacetonato)cobalt(II) ([Co(acac)2]) but also by using organocobalt(III) adducts. Molar concentration ratios of the reactants, the temperature, and the solvent were tuned, and the effect of these parameters on the course of the polymerization is discussed in detail. The best level of control was observed when the AN polymerization was initiated by an organocobalt(III) adduct at 0 °C in dimethyl sulfoxide. Under these conditions, poly(acrylonitrile) with a predictable molar mass and molar mass distribution as low as 1.1 was prepared. A combination of kinetic data, X‐ray analyses, and DFT calculations were used to rationalize the results and to draw conclusions on the key role played by the solvent molecules in the process. These important mechanistic insights also permit an explanation of the unexpected “solvent effect” that allows the preparation of well‐defined poly(vinyl acetate)‐b‐poly(acrylonitrile) by CMRP.
Fichier principal
Vignette du fichier
254-10.1002-chem.200800371-Accepted.pdf (870.22 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03191507 , version 1 (07-04-2021)

Identifiants

Citer

Antoine Debuigne, Catherine Michaux, Christine Jérôme, Robert Jérôme, Rinaldo Poli, et al.. Cobalt-Mediated Radical Polymerization of Acrylonitrile: Kinetics Investigations and DFT Calculations. Chemistry - A European Journal, 2008, 14 (25), pp.7623-7637. ⟨10.1002/chem.200800371⟩. ⟨hal-03191507⟩
87 Consultations
161 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More