Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization
Open accessAbstract
The need for polymers for high-end applications, coupled with the desire to mimic nature’s macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design.
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Five-membered lactones such as γBL have traditionally been considered non-polymerizable due to low strain energy and positive Gibbs free energy of polymerization.
“Five-membered lactones such as γBL have traditionally been considered as non-polymerizable due to the low strain energy of the ring and to the positive Gibbs free energy related to the polymerization [32].”
From Coordination ring-opening polymerization of cyclic esters: A critical overview of DFT modeling and visualization of the reaction mechanisms (2019) · cites this paper as [32]
In general, substituted lactones have relatively low polymerizability compared to the unsubstituted ones and are thus potential candidates for thermal recycling.
“In general, substituted lactones have relatively low polymerizability compared to the unsubstituted ones and are thus potential candidates for thermal recycling.”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [275]
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- Dainton F. S.; Ivin K. J. Q. Rev., Chem. Soc. 1958, 12, 61 10.1039/qr9581200061. · DOI
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Catalysis as an Enabling Science for Sustainable Polymers
Zhang, X., Fevre, M., Jones, G. O., & Waymouth, R. M. (2018) · Chemical Reviews · doi:10.1021/acs.chemrev.7b00329 · Cited by 936 · see citing works
Aliphatic Polyester Block Polymer Design
Schneiderman, D. K., & Hillmyer, M. A. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b00211 · Cited by 290 · see citing works
Design principles for intrinsically circular polymers with tunable properties
Shi, C., Reilly, L. T., Phani Kumar, V. S., Coile, M. W., Nicholson, S. R., Broadbelt, L. J., Beckham, G. T., & Chen, E. Y.-X. (2021) · Chem · doi:10.1016/j.chempr.2021.10.004 · Cited by 219 · see citing works
Chemically Recyclable Biobased Polyurethanes
Schneiderman, D. K., Vanderlaan, M. E., Mannion, A. M., Panthani, T. R., Batiste, D. C., Wang, J. Z., Bates, F. S., Macosko, C. W., & Hillmyer, M. A. (2016) · ACS Macro Letters · doi:10.1021/acsmacrolett.6b00193 · Cited by 213 · see citing works
Tang, X., Hong, M., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.6b07974 · Cited by 179 · see citing works
Frenkel-Pinter, M., Haynes, J. W., C, M., Petrov, A. S., Burcar, B. T., Krishnamurthy, R., Hud, N. V., Leman, L. J., & Williams, L. D. (2019) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1904849116 · Cited by 128 · see citing works
Li, X., Clarke, R. W., An, H., Gowda, R. R., Jiang, J., Xu, T., & Chen, E. Y. ‐. (2023) · Angewandte Chemie International Edition · doi:10.1002/anie.202303791 · Cited by 93 · see citing works
Nifant’ev, I., & Ivchenko, P. (2019) · Molecules · doi:10.3390/molecules24224117 · Cited by 72 · see citing works
Jitonnom, J., Molloy, R., Punyodom, W., & Meelua, W. (2016) · Computational and Theoretical Chemistry · doi:10.1016/j.comptc.2016.10.009 · Cited by 33 · see citing works
Huang, H.-Y., Xie, M., Wang, S.-Q., Huang, Y.-T., Luo, Y.-H., Yu, D.-G., Cai, Z., & Zhu, J.-B. (2025) · Journal of the American Chemical Society · doi:10.1021/jacs.4c17703 · Cited by 33 · see citing works
McGuire, T. M., Ning, D., Buchard, A., & Williams, C. K. (2025) · Journal of the American Chemical Society · doi:10.1021/jacs.5c04603 · Cited by 32 · see citing works
Kirchhecker, S., Nguyen, N., Reichert, S., Lützow, K., Eselem Bungu, P. S., Jacobi von Wangelin, A., Sandl, S., & Neffe, A. T. (2023) · RSC Advances · doi:10.1039/d3ra03112h · Cited by 6 · see citing works
- Authors
- Olsén, P., Odelius, K., & Albertsson, A.-C.
- Affiliations
- KTH Royal Institute of Technology , , , ,
- KTH Royal Institute of Technology (SE)
- Corresponding author
- Albertsson, Ann-Christine
- Venue
- Biomacromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-01-21
- Volume
- 17
- Issue
- 3
- Pages
- 699-709
- ISSN
- 1525-7797 (ISSN-L)
- 1526-4602
- PMC
- PMC4793204
- OpenAlex
- W2260769276
- Cited by
- 244
- References
- 111
- Citations by year
- 2026: 27 · 2025: 28 · 2024: 33 · 2023: 35 · 2022: 40 · 2021: 17 · 2020: 22 · 2019: 11 · 2018: 14 · 2017: 9 · 2016: 8
- FWCI
- 0.75
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Locations
- Biomacromolecules (publishedVersion, other-oa)
- Europe PMC (PubMed Central) (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Funders
- European Research Council (246776)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- ring-opening polymerization, lactones, thermodynamic equilibrium, monomer structure, ring size, degree of substitution, monomer conversion, catalytic specificity, polymerization behavior, macromolecular design
- MeSH terms
- Lactones, Thermodynamics, Polymerization
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