Mechanistic Investigations of the Stereoselective Rare Earth Metal-Mediated Ring-Opening Polymerization of β-Butyrolactone.
Poly(3-hydroxybutyrate) (PHB) is produced by numerous bacteria as carbon and energy reserve storage material. Whereas nature only produces PHB in its strictly isotactic (R) form, homogeneous catalysis, when starting from racemic (rac) β-butyrolactone (BL) as monomer, can in fact produce a wide variety of tacticities. The variation of the metal center and the surrounding ligand structure enable activity as well as tacticity tuning. However, no homogeneous catalyst exists to date that is easy to modify, highly active, and able to produce PHB with high isotacticities from rac-β-BL. Therefore, in this work, the reaction kinetics of various 2-methoxyethylamino-bis(phenolate) lanthanide (Ln=Sm, Tb, Y, Lu) catalysts are examined in detail. The order in monomer and catalyst are determined to elucidate the reaction mechanism and the results are correlated with DFT calculations of the catalytic cycle. Furthermore, the enthalpies and entropies of the rate-determining steps are determined through temperature-dependent in situ IR measurements. Experimental and computational results converge in one specific mechanism for the ring-opening polymerization of BL and even allow us to rationalize the preference for syndiotactic PHB.
Technische Universität München, WACKER-Lehrstuhl für Makromolekulare Chemie, Lichtenbergstrasse 4, 85748 Garching (Germany).
Peter T
PT
Altenbuchner
Technische Universität München, WACKER-Lehrstuhl für Makromolekulare Chemie, Lichtenbergstrasse 4, 85748 Garching (Germany).
Alexander
A
Kronast
Technische Universität München, WACKER-Lehrstuhl für Makromolekulare Chemie, Lichtenbergstrasse 4, 85748 Garching (Germany).
Stefan
S
Kissling
Technische Universität München, WACKER-Lehrstuhl für Makromolekulare Chemie, Lichtenbergstrasse 4, 85748 Garching (Germany).
Sergei I
SI
Vagin
Technische Universität München, Lehrstuhl für Anorganische Chemie Lichtenbergstrasse 4, 85748 Garching (Germany).
Eberhardt
E
Herdtweck
Technische Universität München, Lehrstuhl für Anorganische Chemie Lichtenbergstrasse 4, 85748 Garching (Germany).
Alexander
A
Pöthig
BASF SE, GM 67056 Ludwigshafen (Germany).
Peter
P
Deglmann
BASF SE, GM 67056 Ludwigshafen (Germany).
Robert
R
Loos
Technische Universität München, WACKER-Lehrstuhl für Makromolekulare Chemie, Lichtenbergstrasse 4, 85748 Garching (Germany). rieger@tum.de.
Bernhard
B
Rieger
density functional calculations; kinetics; polymers; rare earths; ring-opening polymerization