TY - JOUR
T1 - Undiscovered Potential
T2 - Ge Catalysts for Lactide Polymerization
AU - Rittinghaus, Ruth D.
AU - Tremmel, Jakub
AU - Ruzicka, Ales
AU - Conrads, Christian
AU - Albrecht, Pascal
AU - Hoffmann, Alexander
AU - Ksiazkiewicz, Agnieszka N.
AU - Pich, Andrij
AU - Jambor, Roman
AU - Herres-Pawlis, Sonja
N1 - Funding Information:
R.D.R. thanks the DBU (Deutsche Bundesstiftung Umwelt) for funding. The authors acknowledge funding by the Deutsche Forschungsgemeinschaft in the framework of the SFB985, TACR (project no. TH02010197) and thank Total Corbion for lactide donations. We furthermore thank the Paderborn Center for Parallel Computing, PC2, for providing computing time on the High-Performance Computing (HPC) system OCuLUS as well as support.
Publisher Copyright:
© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
PY - 2020/1/2
Y1 - 2020/1/2
N2 - Polylactide (PLA) is a high potential bioplastic that can replace oil-based plastics in a number of applications. To date, in spite of its known toxicity, a tin catalyst is used on industrial scale which should be replaced by a benign catalyst in the long run. Germanium is known to be unharmful while having similar properties as tin. Only few germylene catalysts are known so far and none has shown the potential for industrial application. We herein present Ge complexes in combination with zinc and copper, which show amazingly high polymerization activities for lactide in bulk at 150 degrees C. By systematical variation of the complex structure, proven by single-crystal XRD and DFT calculations, structure-property relationships are found regarding the polymerization activity. Even in the presence of zinc and copper, germanium acts as the active site for polymerizing probably through the coordination-insertion mechanism to high molar mass polymers.
AB - Polylactide (PLA) is a high potential bioplastic that can replace oil-based plastics in a number of applications. To date, in spite of its known toxicity, a tin catalyst is used on industrial scale which should be replaced by a benign catalyst in the long run. Germanium is known to be unharmful while having similar properties as tin. Only few germylene catalysts are known so far and none has shown the potential for industrial application. We herein present Ge complexes in combination with zinc and copper, which show amazingly high polymerization activities for lactide in bulk at 150 degrees C. By systematical variation of the complex structure, proven by single-crystal XRD and DFT calculations, structure-property relationships are found regarding the polymerization activity. Even in the presence of zinc and copper, germanium acts as the active site for polymerizing probably through the coordination-insertion mechanism to high molar mass polymers.
KW - bioplastics
KW - germanium
KW - lactide
KW - ring-opening polymerization
KW - zinc
KW - RING-OPENING POLYMERIZATION
KW - UNSUPPORTED SILVER-GERMANIUM
KW - ZETA VALENCE QUALITY
KW - BOND COVALENT RADII
KW - ZINC-COMPLEXES
KW - BASIS-SETS
KW - STRUCTURAL-CHARACTERIZATION
KW - EXPANSION POLYMERIZATIONS
KW - EPSILON-CAPROLACTONE
KW - ALKOXIDE COMPLEXES
U2 - 10.1002/chem.201903949
DO - 10.1002/chem.201903949
M3 - Article
C2 - 31587400
SN - 0947-6539
VL - 26
SP - 212
EP - 221
JO - Chemistry: a European journal
JF - Chemistry: a European journal
IS - 1
ER -