Ring-opening polymerization of racemic β-butyrolactone promoted by rare earth trisborohydride complexes towards a PHB-diol: an experimental and DFT study

Sophie M. Guillaume (1) , Liana Annunziata (1) , Iker Del rosal (2) , Christophe Iftner (3) , Laurent Maron (2) , Peter W. Roesky , Matthias Schmid

1 ISCR - Institut des Sciences Chimiques de Rennes
2 LPCNO - Laboratoire de physique et chimie des nano-objets
3 MAD - Modélisation, Agrégats, Dynamique (LCPQ)

The ring-opening polymerization (ROP) of racemic β-butyrolactone (BL), catalyzed by the homoleptic lanthanide trisborohydride complexes, [Ln(BH4)3(THF)3] with Ln = La, Nd, and Sm, is reported, together with a DFT study of the polymerization mechanism. Well-defined atactic α,ω-dihydroxytelechelic poly(3-hydroxybutyrate)s (PHBs), PHB diols, are thus synthesized (Mn up to 8000 g mol−1, 1.02 ≤ Đ ≤ 1.10) as evidenced both experimentally and computationally. DFT investigations also emphasize the lack of stereoselectivity of the catalyst although a high activity is energetically evidenced.

Domaines: Chimie

Sophie M. Guillaume, Liana Annunziata, Iker Del rosal, Christophe Iftner, Laurent Maron, et al.. Ring-opening polymerization of racemic β-butyrolactone promoted by rare earth trisborohydride complexes towards a PHB-diol: an experimental and DFT study. Polymer Chemistry, 2013, 4 (10), pp.3077-3087. ⟨10.1039/C3PY00056G⟩. ⟨hal-00844464⟩