Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide

Pascal M Schäfer, Martin Fuchs, Andreas Ohligschläger, Ruth Rittinghaus, Paul McKeown, Enver Akin, Maximilian Schmidt, Alexander Hoffmann, Marcel A. Liauw, Matthew Jones, Sonja Herres-Pawlis

Research output: Contribution to journalArticle

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Abstract

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl2(DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (Mw=69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant kp. Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use.

Original languageEnglish
Pages (from-to)3547-3556
Number of pages10
JournalChemSusChem
Volume10
Issue number18
DOIs
Publication statusPublished - 22 Sep 2017

Fingerprint

Ring opening polymerization
Guanidine
polymerization
Zinc
zinc
catalyst
Catalysts
Polymerization
Molar mass
X ray crystallography
Polydispersity
Raman spectroscopy
Rate constants
Catalyst activity
crystallography
Monomers
Impurities
dilactide
rate

Keywords

  • catalysis
  • guanidine
  • poly(lactide)
  • ring-opening polymerization
  • zinc

ASJC Scopus subject areas

  • Environmental Chemistry
  • Chemical Engineering(all)
  • Materials Science(all)
  • Energy(all)

Cite this

Schäfer, P. M., Fuchs, M., Ohligschläger, A., Rittinghaus, R., McKeown, P., Akin, E., ... Herres-Pawlis, S. (2017). Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide. ChemSusChem, 10(18), 3547-3556. https://doi.org/10.1002/cssc.201701237

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide. / Schäfer, Pascal M; Fuchs, Martin ; Ohligschläger, Andreas ; Rittinghaus, Ruth ; McKeown, Paul; Akin, Enver; Schmidt, Maximilian ; Hoffmann, Alexander; Liauw, Marcel A.; Jones, Matthew; Herres-Pawlis, Sonja.

In: ChemSusChem, Vol. 10, No. 18, 22.09.2017, p. 3547-3556.

Research output: Contribution to journalArticle

Schäfer, PM, Fuchs, M, Ohligschläger, A, Rittinghaus, R, McKeown, P, Akin, E, Schmidt, M, Hoffmann, A, Liauw, MA, Jones, M & Herres-Pawlis, S 2017, 'Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide', ChemSusChem, vol. 10, no. 18, pp. 3547-3556. https://doi.org/10.1002/cssc.201701237
Schäfer PM, Fuchs M, Ohligschläger A, Rittinghaus R, McKeown P, Akin E et al. Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide. ChemSusChem. 2017 Sep 22;10(18):3547-3556. https://doi.org/10.1002/cssc.201701237
Schäfer, Pascal M ; Fuchs, Martin ; Ohligschläger, Andreas ; Rittinghaus, Ruth ; McKeown, Paul ; Akin, Enver ; Schmidt, Maximilian ; Hoffmann, Alexander ; Liauw, Marcel A. ; Jones, Matthew ; Herres-Pawlis, Sonja. / Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide. In: ChemSusChem. 2017 ; Vol. 10, No. 18. pp. 3547-3556.
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