Beyond Stereoselectivity, Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters
Abstract
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.
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As opposed to step-growth polymerizations, ROP allows for a fine degree of control over several important macromolecular parameters including molecular weight, polydispersity, end-group fidelity, regio- and stereoselectivity, and architecture.
“As opposed to step-growth polymerizations, ROP allows for a fine degree of control over several important macromolecular parameters including molecular weight, polydispersity, end-group fidelity, regio-and stereoselectivity, and architecture (block, cyclic, star, etc). 267,268”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [267]
The use of switchable metal catalysts to strategically modulate the rate and monomer selectivity of ROP is emerging.
“Recently, the use of switchable metal catalysts to strategically modulate the rate and monomer selectivity of ROP is emerging.267”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [267]
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- Authors
- Guillaume, S. M., Kirillov, E., Sarazin, Y., & Carpentier, J.
- Affiliations
- Centre National de la Recherche Scientifique (FR)
- Corresponding author
- Carpentier, Jean‐François
- Venue
- Chemistry – A European Journal
- Publisher
- Wiley
- Published
- 2015-04
- Volume
- 21
- Issue
- 22
- Pages
- 7988-8003
- ISSN
- 0947-6539 (ISSN-L)
- 1521-3765
- OpenAlex
- W2022523714
- Cited by
- 251
- References
- 68
- Citations by year
- 2026: 3 · 2025: 8 · 2024: 18 · 2023: 15 · 2022: 7 · 2021: 17 · 2020: 25 · 2019: 34 · 2018: 35 · 2017: 41 · 2016: 40 · 2015: 8
- FWCI
- 14.97
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Chemistry - A European Journal (publishedVersion)
- PubMed (publishedVersion)
- HAL (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- ring-opening polymerization, cyclic esters, switchable catalysis, stereoselectivity, lactide, stereoblock copolymers, metal catalysts, organocatalysis, chemical stimuli, tacticity
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