Radical Ring-Opening Polymerization: Scope, Limitations, and Application to (Bio)Degradable Materials
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Cyclic monomers bearing either vinyl or exomethylene groups have the ability to be polymerized through a radical pathway via a ring-opening mechanism (addition-fragmentation process), leading to the introduction of functionalities in the polymer backbone. Radical ring-opening polymerization (rROP) combines the advantages of both ring-opening polymerization and radical polymerization, that is the preparation of polymers bearing heteroatoms in the backbone but with the ease and robustness of a radical process. This current review presents a comprehensive description of rROP by detailing: (i) the various monomers that polymerize through rROP; (ii) the main parameters that govern the rROP mechanism; (iii) the copolymerization by conventional or controlled/living radical polymerization between rROP monomers and traditional vinyl monomers to obtain copolymers with advanced properties; (iv) the different applications (low shrinkage materials and preparation of (bio)degradable materials) of rROP monomer-containing materials, and (v) the main alternatives to rROP to induce degradability to materials obtained by a radical polymerization.
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The rROP approach requires delicate design of the cyclic monomer to achieve high reactivity and to control the ratio of ring-opened and cyclic structures.
“However, the rROP approach requires delicate design of the cyclic monomer to achieve high reactivity and to control the ratio of ring-opened and cyclic structures.”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [21]
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Radical Approach to Thioester-Containing Polymers
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Morris, P. T., Olsen, S. C., Santiago, M., Wang, H. M., Denton, E. H., Read de Alaniz, J., Bates, C. M., Albanese, K. R., & Hawker, C. J. (2026) · Journal of the American Chemical Society · doi:10.1021/jacs.5c20808 · Cited by 17 · see citing works
- Authors
- Tardy, A., Nicolas, J., Gigmes, D., Lefay, C., & Guillaneuf, Y.
- Affiliations
- Centre National de la Recherche Scientifique (FR)
- Aix Marseille Univ, CNRS, Institut de Chimie Radicalaire UMR 7273, campus Saint Jérôme, Avenue Escadrille Normandie-Niemen, Case 542, 13397 Marseille Cedex 20, France
- Corresponding author
- Lefay, Catherine
- Guillaneuf, Yohann
- Venue
- Chemical Reviews
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-01-13
- Volume
- 117
- Issue
- 3
- Pages
- 1319-1406
- ISSN
- 0009-2665 (ISSN-L)
- 1520-6890
- OpenAlex
- W2572929162
- Semantic Scholar
- a17f9b1624f724651558ba8c138c5376dee5c14d
- Cited by
- 469
- References
- 392
- Citations by year
- 2026: 68 · 2025: 79 · 2024: 72 · 2023: 58 · 2022: 57 · 2021: 37 · 2020: 39 · 2019: 17 · 2018: 28 · 2017: 14
- FWCI
- 1.56
- Type
- journal article
- Language
- en
- Open access
- green
- amu.hal.science
- Licence
- other-oa
- Locations
- Chemical Reviews (publishedVersion)
- PubMed (publishedVersion)
- HAL (submittedVersion, other-oa)
- Funders
- Agence Nationale de la Recherche (ANR-15-CE08-0019)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Photopolymerization techniques and applications
- Keywords
- radical ring-opening polymerization, cyclic monomers, vinyl monomers, copolymerization, controlled radical polymerization, heteroatom-containing polymers, biodegradable polymers
- MeSH terms
- Molecular Structure, Polymerization
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