Discrete Metal‐Based Catalysts for the Copolymerization of CO2 and Epoxides: Discovery, Reactivity, Optimization, and Mechanism
Abstract
Most synthetic polymers are made from petroleum feedstocks. Given the non‐renewable nature of these materials, there is increasing interest in developing routes to polymeric materials from renewable resources. In addition, there is a growing demand for biodegradable polymeric materials. Polycarbonates made from CO 2 and epoxides have the potential to meet these goals. Since the discovery of catalysts for the copolymerization of CO 2 and epoxides in the late 1960's by Inoue, a significant amount of research has been directed toward the development of catalysts of improved activity and selectivity. Reviewed here are well‐defined catalysts for epoxide–CO 2 copolymerization and related reactions.
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Upcycling of waste gases such as CO2 to useful and valuable plastics has long been of interest, and the ROCP of epoxides and CO2 represents one of the most successful examples of CO2 utilization in polymer synthesis.
“Upcycling of waste gases such as CO2 to useful and valuable plastics has long been of interest to researchers, and the ROCP of epoxides and CO2 represents one of the most successful examples of CO2 utilization in polymer synthesis.83,[344][345][346][347][348][349][350][351][352]”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [344]
Although the exact mechanism for each catalytic system may vary, ROCP of epoxide with CO2 or cyclic anhydride generally follows the coordination-insertion mechanism.
“Although the exact mechanism for each catalytic system may vary, ROCP of epoxide with CO2 or cyclic anhydride generally follows the coordination-insertion mechanism shown in Scheme 14. 344”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [344]
The polymerization is initiated by the nucleophilic attack of a ligand (X) or an exogenous nucleophile onto a coordinated epoxide.
“The polymerization is initiated by the nucleophilic attack of a ligand (X) or an exogenous nucleophile onto a coordinated epoxide.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [344]
Chain propagation proceeds by the alternative insertion of epoxide and CO2 (or cyclic anhydride) to the metal-oxygen chain end, which leads to the desired formation of polycarbonate (or polyesters) backbones.
“Chain propagation proceeds by the alternative insertion of epoxide and CO2 (or cyclic anhydride) to the metal-oxygen chain end, which leads to the desired formation of polycarbonate (or polyesters) backbones.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [344]
This leads to a metal bound alkoxide to which CO2 (or cyclic anhydride) readily inserts to form a metal carbonate (or carboxylate) species.
“This leads to a metal bound alkoxide to which CO2 (or cyclic anhydride) readily inserts to form a metal carbonate (or carboxylate) species.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [344]
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- Authors
- Coates, G. W., & Moore, D. R.
- Affiliations
- Cornell University (US)
- Corresponding author
- Coates, Geoffrey W.
- ORCID
- Coates, Geoffrey W.
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2004-12-08
- Volume
- 43
- Issue
- 48
- Pages
- 6618-6639
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W2161652710
- Cited by
- 1,154
- References
- 168
- Citations by year
- 2026: 19 · 2025: 27 · 2024: 36 · 2023: 50 · 2022: 54 · 2021: 52 · 2020: 63 · 2019: 59 · 2018: 67 · 2017: 69 · 2016: 69 · 2015: 82 · 2014: 78 · 2013: 94 · 2012: 70
- FWCI
- 30.88
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Angewandte Chemie International Edition (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Keywords
- CO2/epoxide copolymerization, metal catalysts, polycarbonate, biodegradable polymers, renewable raw materials, catalyst discovery, catalyst reactivity, reaction mechanism, catalyst optimization
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