Organocatalyzed ring-opening polymerization (ROP) of functional beta-lactones: new insights into the ROP mechanism and poly(hydroxyalkanoate)s (PHAs) macromolecular structure - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Polymer Chemistry Année : 2020

Organocatalyzed ring-opening polymerization (ROP) of functional beta-lactones: new insights into the ROP mechanism and poly(hydroxyalkanoate)s (PHAs) macromolecular structure

Résumé

The organocatalyzed ring-opening polymerization (ROP) of various 4-alkoxymethylene-beta-propiolactones (BPL(OR)s; R = CH2CH=H-2 (All), CH2Ph (Bn), (CH2)(3)CH3 (Bu-n), (SiMe2Bu)-Bu-t (TBDMS)) towards the formation of the corresponding poly(hydroxyalkanoate)s (PHAs; poly(BPLOR)s (PBPL(OR)s)) is investigated under mild operating conditions (neat, 60 degrees C), simply using basic organocatalysts of the guanidine (1,5,7-triazabicyclo [4.4.0]dec-5-ene, TBD), amidine (1,8-diazabicyclo[5.4.0]-undec-7-ene, DBU) or phosphazene (2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2diazaphosphorine, BEMP) type. The polymerization proceeds basically at the same rate as the alike organocatalyzed ROP of related beta-lactones (especially the ubiquitous beta-butyrolactone (BL) and alkyl beta-malolactonates (MLA(R)s)), with BEMP being significantly more active than TBD and DBU. Insights into the polymerization mechanisms are gained through detailed 1D/2D NMR spectroscopy and MALDI-ToF mass spectrometry analyses of the resulting PBPL(OR)s and in particular through the identification of the nature of the end-capping groups. Each of the three organobases promotes the polymerization in its own way, as dictated by either its basic, nucleophilic or dual behavior.

Domaines

Chimie Polymères
Fichier principal
Vignette du fichier
Shakaroun et al-2020-Organocatalyzed ring-opening polymerization.pdf (4.94 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-02562365 , version 1 (27-05-2020)

Identifiants

Citer

Rama M. Shakaroun, Philippe Jehan, Ali Alaaeddine, Jean-François Carpentier, Sophie M. Guillaume. Organocatalyzed ring-opening polymerization (ROP) of functional beta-lactones: new insights into the ROP mechanism and poly(hydroxyalkanoate)s (PHAs) macromolecular structure. Polymer Chemistry, 2020, 11 (15), pp.2640-2652. ⟨10.1039/d0py00125b⟩. ⟨hal-02562365⟩
44 Consultations
368 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More