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

Research output: Contribution to journal › Article › peer-review

60 Citations (SciVal)

595 Downloads (Pure)

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 Sept 2017

Keywords

catalysis
guanidine
poly(lactide)
ring-opening polymerization
zinc

ASJC Scopus subject areas

Environmental Chemistry
General Chemical Engineering
General Materials Science
General Energy

Access to Document

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

Cite this

@article{5f58633defd5497d92d0e5f36673263c,

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.",

keywords = "catalysis, guanidine, poly(lactide), ring-opening polymerization, zinc",

author = "Sch{\"a}fer, {Pascal M} and Martin Fuchs and Andreas Ohligschl{\"a}ger and Ruth Rittinghaus and Paul McKeown and Enver Akin and Maximilian Schmidt and Alexander Hoffmann and Liauw, {Marcel A.} and Matthew Jones and Sonja Herres-Pawlis",

year = "2017",

month = sep,

day = "22",

doi = "10.1002/cssc.201701237",

language = "English",

volume = "10",

pages = "3547--3556",

journal = "ChemSusChem",

issn = "1864-5631",

publisher = "Wiley-VCH Verlag",

number = "18",

}

TY - JOUR

T1 - Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide

AU - Schäfer, Pascal M

AU - Fuchs, Martin

AU - Ohligschläger, Andreas

AU - Rittinghaus, Ruth

AU - McKeown, Paul

AU - Akin, Enver

AU - Schmidt, Maximilian

AU - Hoffmann, Alexander

AU - Liauw, Marcel A.

AU - Jones, Matthew

AU - Herres-Pawlis, Sonja

PY - 2017/9/22

Y1 - 2017/9/22

N2 - 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.

AB - 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.

KW - catalysis

KW - guanidine

KW - poly(lactide)

KW - ring-opening polymerization

KW - zinc

UR - http://www.scopus.com/inward/record.url?scp=85029761225&partnerID=8YFLogxK

U2 - 10.1002/cssc.201701237

DO - 10.1002/cssc.201701237

M3 - Article

C2 - 28779508

AN - SCOPUS:85029761225

SN - 1864-5631

VL - 10

SP - 3547

EP - 3556

JO - ChemSusChem

JF - ChemSusChem

IS - 18

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Avance III 400 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (9West)

Avance NEO 400 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)

Raman confocal microscope RENISHAM INVIA

Cite this

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

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Equipment

Avance III 400 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (9West)

Avance NEO 400 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)

Raman confocal microscope RENISHAM INVIA

Cite this