Well-Defined P III -Terminated Polymers from Phosphorylated Carbodithioate RAFT Agents - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Macromolecules Année : 2021

Well-Defined P III -Terminated Polymers from Phosphorylated Carbodithioate RAFT Agents

Résumé

Five S-alkyl di-tert-butylphosphorylated carbodithioates, Z–C(S)SR, were studied as chain transfer agents (CTAs) in the RAFT polymerization of vinyl monomers. These phosphorus-containing CTAs involve new PIII and PV moieties in the Z group (phosphine-borane or free phosphine). Two of them, with an S-bonded 1-methoxycarbonylethyl group as leaving group, have not previously been described. The CTAs with a PV Z group provide good control over the polymerization of styrene (St) and n-butyl acrylate (nBA). Molar masses are close to theoretical values, and dispersities are consistently low during polymerization. The monitoring of polymerization by 31P NMR spectroscopy supports the controlled character and the integrity of the polymer chain ends. Conversely, they inhibit the polymerization of the less-activated monomer vinyl acetate (VAc). The reactivity of the CTAs with a PIII Z group mainly depends on the reaction medium, and their performance for St, nBA, and VAc was surprising and unexpected. Theoretical calculations were carried out to rationalize their behavior. Finally, an innovative strategy was developed to obtain well-controlled polymers with free phosphine ω-chain ends.
Fichier principal
Vignette du fichier
Paper_tBu2P-serie_RAFT_v11_AK.pdf (1.4 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03200586 , version 1 (16-04-2021)

Identifiants

Citer

Andrii Karpus, Simon Harrisson, Rinaldo Poli, Stéphane Mazières, Eric Manoury, et al.. Well-Defined P III -Terminated Polymers from Phosphorylated Carbodithioate RAFT Agents. Macromolecules, 2021, 54 (6), pp.2627-2636. ⟨10.1021/acs.macromol.0c02805⟩. ⟨hal-03200586⟩
94 Consultations
104 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More