Understanding the Mechanism of Polymerization of ε-Caprolactone Catalyzed by Aluminum Salen Complexes
Abstract
Studies of the kinetics of polymerization of ε-caprolactone (CL) by salen-aluminum catalysts comprising ligands with similar steric profiles but different electron donating characteristics (R = OMe, Br, or NO2) were performed using high initial monomer concentrations (2 M Br > NO2. Density functional theory (DFT) calculations were performed to characterize mechanistic pathways at a microscopic level of detail. Lowest energy transition-state structures feature incipient bonding of the nucleophile to the lactone carbonyl that is approaching the metal ion, but a distinct CL adduct is not an energy minimum on the reaction pathway, arguing against Keq being associated with coordination of monomer according to the typical coordination-insertion mechanism. An alternative hypothesis is presented associating Keq with "nonproductive" coordination of substrate in a manner that inhibits the polymerization reaction at high substrate concentrations.
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The effect of alkyl substituent size and location on bulk polymerization rate has not been systematically studied.
“The e ff ect of alkyl substituent size and location on bulk polymerization rate has not been systematically studied.”
From Aliphatic Polyester Block Polymer Design (2016) · cites this paper as [44]
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- Authors
- Miranda, M. O., DePorre, Y., Vazquez-Lima, H., Johnson, M. A., Marell, D. J., Cramer, C. J., & Tolman, W. B.
- Affiliations
- University of Minnesota (US)
- Department of Chemistry, Center for Sustainable Polymers, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
- Corresponding author
- Cramer, Christopher J.
- Tolman, William B.
- Venue
- Inorganic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2013-11-12
- Volume
- 52
- Issue
- 23
- Pages
- 13692-13701
- ISSN
- 0020-1669 (ISSN-L)
- 1520-510X
- OpenAlex
- W1982906494
- Cited by
- 79
- References
- 2
- Citations by year
- 2026: 1 · 2025: 2 · 2024: 2 · 2023: 5 · 2022: 4 · 2021: 5 · 2020: 2 · 2019: 10 · 2018: 8 · 2017: 10 · 2016: 14 · 2015: 4 · 2014: 12
- FWCI
- 3.82
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Inorganic Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- ε-caprolactone polymerization, polymerization kinetics, catalytic rate constant, Hammett substituent effects, thermodynamic parameters, reaction mechanism, transition state structure, coordination-insertion mechanism, polycaprolactone
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