Tunable and recyclable polyesters from CO2 and butadiene

Rachel M. Rapagnani; Rachel J. Dunscomb; Alexandra A. Fresh; Ian A. Tonks

doi:10.1038/s41557-022-00969-2

Tunable and recyclable polyesters from CO₂ and butadiene

Rachel M. Rapagnani
, Rachel J. Dunscomb
, Alexandra A. Fresh
, Ian A. Tonks

Chemistry (Twin Cities)

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

98 Scopus citations

Abstract

Carbon dioxide is inexpensive and abundant, and its prevalence as waste makes it attractive as a sustainable chemical feedstock. Although there are examples of copolymerizations of CO 2 with high-energy monomers, the direct copolymerization of CO 2 with olefins has not been reported. Here an alternative route to functionalizable, recyclable polyesters derived from CO 2, butadiene and hydrogen via an intermediary lactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one, is described. Catalytic ring-opening polymerization of the lactone by 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields polyesters with molar masses up to 13.6 kg mol -1 and pendent vinyl side chains that can undergo post-polymerization functionalization. The polymer has a low ceiling temperature of 138 °C, allowing for facile chemical recycling, and is inherently biodegradable under aerobic aqueous conditions (OECD-301B protocol). These results show that a well-defined polyester can be derived from CO 2, olefins and hydrogen, expanding access to new polymer feedstocks that were once considered unfeasible.

Original language	English (US)
Pages (from-to)	877-883
Number of pages	7
Journal	Nature Chemistry
Volume	14
Issue number	8
DOIs	https://doi.org/10.1038/s41557-022-00969-2
State	Published - Aug 2022

Bibliographical note

Funding Information:
The funding for this work was provided by the NSF Center for Sustainable Polymers (no. CHE-1901635 to I.A.T.) at the University of Minnesota. Instrumentation for the University of Minnesota Chemistry NMR facility was supported by a grant through the National Institutes of Health (no. S10OD011952).

Publisher Copyright:
© 2022, The Author(s), under exclusive licence to Springer Nature Limited.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 12 Responsible Consumption and Production

Keywords

Butadienes
Carbon Dioxide/chemistry
Hydrogen
Lactones/chemistry
Polyesters/chemistry

PubMed: MeSH publication types

Journal Article
Research Support, U.S. Gov't, Non-P.H.S.
Research Support, N.I.H., Extramural

Publisher link

10.1038/s41557-022-00969-2

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Cite this

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title = "Tunable and recyclable polyesters from CO2 and butadiene",

abstract = "Carbon dioxide is inexpensive and abundant, and its prevalence as waste makes it attractive as a sustainable chemical feedstock. Although there are examples of copolymerizations of CO 2 with high-energy monomers, the direct copolymerization of CO 2 with olefins has not been reported. Here an alternative route to functionalizable, recyclable polyesters derived from CO 2, butadiene and hydrogen via an intermediary lactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one, is described. Catalytic ring-opening polymerization of the lactone by 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields polyesters with molar masses up to 13.6 kg mol -1 and pendent vinyl side chains that can undergo post-polymerization functionalization. The polymer has a low ceiling temperature of 138 °C, allowing for facile chemical recycling, and is inherently biodegradable under aerobic aqueous conditions (OECD-301B protocol). These results show that a well-defined polyester can be derived from CO 2, olefins and hydrogen, expanding access to new polymer feedstocks that were once considered unfeasible. ",

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note = "Funding Information: The funding for this work was provided by the NSF Center for Sustainable Polymers (no. CHE-1901635 to I.A.T.) at the University of Minnesota. Instrumentation for the University of Minnesota Chemistry NMR facility was supported by a grant through the National Institutes of Health (no. S10OD011952). Publisher Copyright: {\textcopyright} 2022, The Author(s), under exclusive licence to Springer Nature Limited.",

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