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

doi:10.1002/cssc.201701237

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

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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 (M_w=69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant k_p. 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 language	English
Pages (from-to)	3547-3556
Number of pages	10
Journal	ChemSusChem
Volume	10
Issue number	18
DOIs	https://doi.org/10.1002/cssc.201701237
Publication status	Published - 22 Sep 2017

Keywords

catalysis
guanidine
poly(lactide)
ring-opening polymerization
zinc

ASJC Scopus subject areas

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

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10.1002/cssc.201701237

ChemSusChem paper-rerevision0208_MDJ_PURE
This is the peer reviewed version of the following article: P. M. Schäfer, M. Fuchs, A. Ohligschläger, R. Rittinghaus, P. McKeown, E. Akin, M. Schmidt, A. Hoffmann, M. A. Liauw, M. D. Jones, S. Herres-Pawlis, ChemSusChem 2017, 10, 3547., which has been published in final form at https://doi.org/10.1002/cssc.20170123. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
Accepted author manuscript, 1 MB

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

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.",

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AU - McKeown, Paul

AU - Akin, Enver

AU - Schmidt, Maximilian

AU - Hoffmann, Alexander

AU - Liauw, Marcel A.

AU - Jones, Matthew

AU - Herres-Pawlis, Sonja

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KW - catalysis

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

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