Mechanistic mapping of (CS2/CO2)/epoxide copolymerization catalysis leads to terpolymers with improved degradability

Sam Neale; Jenny Stephan; Merlin Stuhler; Susanne Rupf; Alex Plajer

doi:10.1016/j.xcrp.2023.101510

Mechanistic mapping of (CS2/CO2)/epoxide copolymerization catalysis leads to terpolymers with improved degradability

Sam Neale, Jenny Stephan, Merlin Stuhler, Susanne Rupf, Alex Plajer

Department of Chemistry

Freie Universität Berlin

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

9 Citations (SciVal)

Abstract

The placement of main-group functionalities within polymers represents a strategy to access a wide catalog of materials but is limited by poor understanding of the catalyst selection criteria and polymerization mechanism when moving down the periodic table. Here, we study a series of new heterobimetallic carbon dioxide and carbon disulfide/epoxide copolymerization catalysts that allow for a comparative mechanistic understanding of two ring-opening copolymerization processes. We reveal that the distinct roles each metal plays are preserved from carbon dioxide to carbon disulfide, maintaining activity and selectivity across copolymerizations. Experimental and computational studies show that carbon disulfide/epoxide copolymerization can be understood as a series of structurally related insertion events that are interlinked by a central oxygen/sulfur scrambling reaction at the propagating chain end. This facilitates the synthesis of new carbon dioxide-/carbon disulfide-/epoxide-derived terpolymers with improved degradability over the parent carbon dioxide/epoxide copolymers at low levels of sulfur incorporation.

Original language	English
Article number	101510
Number of pages	15
Journal	Cell Reports Physical Science
Volume	4
Issue number	8
Early online date	21 Jul 2023
DOIs	https://doi.org/10.1016/j.xcrp.2023.101510
Publication status	Published - 16 Aug 2023

Bibliographical note

The authors declare that the data supporting the findings of this study are available within the article and the supplemental information.
Single-crystal X-ray data are available at the Cambridge Crystallographic Database under the identification codes CCDC: 2243753, 2243925, 2243420, 2242774, 2243903, and 2243785.
All other data are available from the lead contact upon reasonable request.

Funding Information:
The VCI is acknowledged for a Liebig Fellowship to A.J.P. Christian Müller and Prof. Dr. Rainer Haag are thanked for continuous support and valuable discussions. Thomas Rybak and Prof. Dr. Bernhard Schartel (Bundesanstalt für Materialforschung Fachbereich 7.5) are thanked for DSC measurements. J.S. M.R.S. and A.J.P. performed the experiments and analyzed the data. S.M.R. collected and analyzed the XRD data. S.N. performed the DFT calculations. A.J.P. and S.N. wrote the manuscript and supplemental information. A.J.P secured the funding and designed and directed the project. The authors declare no competing interests.

Keywords

degradable polymers
heterobimetallic catalysis
polymerization catalysis
waste utilization

ASJC Scopus subject areas

General Engineering
General Energy
General Physics and Astronomy
General Chemistry
General Materials Science

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10.1016/j.xcrp.2023.101510Licence: CC BY

Cite this

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title = "Mechanistic mapping of (CS2/CO2)/epoxide copolymerization catalysis leads to terpolymers with improved degradability",

abstract = "The placement of main-group functionalities within polymers represents a strategy to access a wide catalog of materials but is limited by poor understanding of the catalyst selection criteria and polymerization mechanism when moving down the periodic table. Here, we study a series of new heterobimetallic carbon dioxide and carbon disulfide/epoxide copolymerization catalysts that allow for a comparative mechanistic understanding of two ring-opening copolymerization processes. We reveal that the distinct roles each metal plays are preserved from carbon dioxide to carbon disulfide, maintaining activity and selectivity across copolymerizations. Experimental and computational studies show that carbon disulfide/epoxide copolymerization can be understood as a series of structurally related insertion events that are interlinked by a central oxygen/sulfur scrambling reaction at the propagating chain end. This facilitates the synthesis of new carbon dioxide-/carbon disulfide-/epoxide-derived terpolymers with improved degradability over the parent carbon dioxide/epoxide copolymers at low levels of sulfur incorporation.",

keywords = "degradable polymers, heterobimetallic catalysis, polymerization catalysis, waste utilization",

author = "Sam Neale and Jenny Stephan and Merlin Stuhler and Susanne Rupf and Alex Plajer",

note = "The authors declare that the data supporting the findings of this study are available within the article and the supplemental information. Single-crystal X-ray data are available at the Cambridge Crystallographic Database under the identification codes CCDC: 2243753, 2243925, 2243420, 2242774, 2243903, and 2243785. All other data are available from the lead contact upon reasonable request. Funding Information: The VCI is acknowledged for a Liebig Fellowship to A.J.P. Christian M{\"u}ller and Prof. Dr. Rainer Haag are thanked for continuous support and valuable discussions. Thomas Rybak and Prof. Dr. Bernhard Schartel (Bundesanstalt f{\"u}r Materialforschung Fachbereich 7.5) are thanked for DSC measurements. J.S. M.R.S. and A.J.P. performed the experiments and analyzed the data. S.M.R. collected and analyzed the XRD data. S.N. performed the DFT calculations. A.J.P. and S.N. wrote the manuscript and supplemental information. A.J.P secured the funding and designed and directed the project. The authors declare no competing interests. ",

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N1 - The authors declare that the data supporting the findings of this study are available within the article and the supplemental information. Single-crystal X-ray data are available at the Cambridge Crystallographic Database under the identification codes CCDC: 2243753, 2243925, 2243420, 2242774, 2243903, and 2243785. All other data are available from the lead contact upon reasonable request. Funding Information: The VCI is acknowledged for a Liebig Fellowship to A.J.P. Christian Müller and Prof. Dr. Rainer Haag are thanked for continuous support and valuable discussions. Thomas Rybak and Prof. Dr. Bernhard Schartel (Bundesanstalt für Materialforschung Fachbereich 7.5) are thanked for DSC measurements. J.S. M.R.S. and A.J.P. performed the experiments and analyzed the data. S.M.R. collected and analyzed the XRD data. S.N. performed the DFT calculations. A.J.P. and S.N. wrote the manuscript and supplemental information. A.J.P secured the funding and designed and directed the project. The authors declare no competing interests.

PY - 2023/8/16

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N2 - The placement of main-group functionalities within polymers represents a strategy to access a wide catalog of materials but is limited by poor understanding of the catalyst selection criteria and polymerization mechanism when moving down the periodic table. Here, we study a series of new heterobimetallic carbon dioxide and carbon disulfide/epoxide copolymerization catalysts that allow for a comparative mechanistic understanding of two ring-opening copolymerization processes. We reveal that the distinct roles each metal plays are preserved from carbon dioxide to carbon disulfide, maintaining activity and selectivity across copolymerizations. Experimental and computational studies show that carbon disulfide/epoxide copolymerization can be understood as a series of structurally related insertion events that are interlinked by a central oxygen/sulfur scrambling reaction at the propagating chain end. This facilitates the synthesis of new carbon dioxide-/carbon disulfide-/epoxide-derived terpolymers with improved degradability over the parent carbon dioxide/epoxide copolymers at low levels of sulfur incorporation.

AB - The placement of main-group functionalities within polymers represents a strategy to access a wide catalog of materials but is limited by poor understanding of the catalyst selection criteria and polymerization mechanism when moving down the periodic table. Here, we study a series of new heterobimetallic carbon dioxide and carbon disulfide/epoxide copolymerization catalysts that allow for a comparative mechanistic understanding of two ring-opening copolymerization processes. We reveal that the distinct roles each metal plays are preserved from carbon dioxide to carbon disulfide, maintaining activity and selectivity across copolymerizations. Experimental and computational studies show that carbon disulfide/epoxide copolymerization can be understood as a series of structurally related insertion events that are interlinked by a central oxygen/sulfur scrambling reaction at the propagating chain end. This facilitates the synthesis of new carbon dioxide-/carbon disulfide-/epoxide-derived terpolymers with improved degradability over the parent carbon dioxide/epoxide copolymers at low levels of sulfur incorporation.

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Mechanistic mapping of (CS2/CO2)/epoxide copolymerization catalysis leads to terpolymers with improved degradability

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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