Vanadium-Catalyzed Terpolymerization of α,ω-Dienes with Ethylene and Cyclic Olefins: Ready Access to Polar-Functionalized Polyolefins - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Macromolecules Année : 2021

Vanadium-Catalyzed Terpolymerization of α,ω-Dienes with Ethylene and Cyclic Olefins: Ready Access to Polar-Functionalized Polyolefins

Résumé

α,ω-Dienes are an important class of monomers due to their utility in the synthesis of cyclopolyolefins and reactive polyolefin intermediates. In this contribution, the terpolymerization of two α,ω-dienes (i.e., 1,5-hexadiene and 1,7-octadiene) with ethylene and various cyclic olefins [i.e., norbornene (NB), 5-ethylidene-2-norbornene (ENB), and dicyclopentadiene (DCPD)] catalyzed by a chelated imido vanadium complex has been examined. The ENB and DCPD diene termonomers provide additional sites for post-polymerization functionalization. Vanadium-catalyzed terpolymerization of the investigated α,ω-dienes yields polyolefins with a high molecular weight (Mw up to 200 × 103 g mol–1), unimodal and narrow molecular weight distribution, subambient glass transition temperatures (−30 < Tg °C < −3), and a proper content of C═C bonds. Comprehensive NMR investigation of the obtained polymers revealed that subtle changes in the α,ω-diene size have important effects on the numerous combinations of insertion paths (ring closure vs ring opening), from which different repeating units with a C═C bond in the side or main polymer chain and cyclic units are installed. Finally, the poly(ethylene-ter-1,5-hexadiene-ter-NB) was subjected to thiol-ene addition using thioglycolic acid, methyl thioglycolate, and N-acetyl-l-cysteine to access polar-functionalized polyolefins with a degree of functionalization and properties dependent on the thiol substitution.
Fichier principal
Vignette du fichier
Palucci, Vanadium−Catalyzed Terpolymerization, 2021.pdf (1.19 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03518735 , version 1 (14-10-2022)

Identifiants

Citer

Benedetta Palucci, Giorgia Zanchin, Giovanni Ricci, Laure Vendier, Christian Lorber, et al.. Vanadium-Catalyzed Terpolymerization of α,ω-Dienes with Ethylene and Cyclic Olefins: Ready Access to Polar-Functionalized Polyolefins. Macromolecules, 2021, 54 (23), pp.10700-10711. ⟨10.1021/acs.macromol.1c02142⟩. ⟨hal-03518735⟩
27 Consultations
49 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More