Mechanistic Studies of ε-Caprolactone Polymerization by (salen)AlOR Complexes and a Predictive Model for Cyclic Ester Polymerizations
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Aluminum alkoxide complexes (2) of salen ligands with a three-carbon linker and para substituents having variable electron-withdrawing capabilities (X = NO2, Br, OMe) were prepared, and the kinetics of their ring-opening polymerization (ROP) of ε-caprolactone (CL) were investigated as a function of temperature, with the aim of drawing comparisons to similar systems with two-carbon linkers investigated previously (1). While 1 and 2 exhibit saturation kinetics and similar dependences of their ROP rates on substituents X (invariant Keq, similar Hammett ρ = +1.4(1) and 1.2(1) for k2, respectively), ROP by 2 was significantly faster than for 1. Theoretical calculations confirm that, while the reactant structures differ, the transition state geometries are quite similar, and by analyzing the energetics of the involved distortions accompanying the structural changes, a significant contribution to the basis for the rate differences was identified. Using this knowledge, a simplified computational method for evaluating ligand structural influences on cyclic ester ROP rates is proposed that may have utility for future catalyst design.
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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 [45]
The Introduction discusses how ligand linker length and substituents affect ring-opening polymerization rates, but does not say whether alkyl substituent size and location have been systematically studied for bulk polymerization. The Results describe kinetics measured in toluene-d8, not in bulk. Searches for bulk or solvent-free polymerization and alkyl substituent size or location found no passage addressing the claimed research gap; page numbers were unavailable in our copy. (LLM, conf=0.75)
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- Authors
- Marlier, E. E., Macaranas, J. A., Marell, D. J., Dunbar, C. R., Johnson, M. A., DePorre, Y., Miranda, M. O., Neisen, B. D., Cramer, C. J., Hillmyer, M. A., & Tolman, W. B.
- Affiliations
- University of Minnesota (US)
- Corresponding author
- Cramer, Christopher J.
- Hillmyer, Marc A.
- Tolman, William B.
- ORCID
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-01-21
- Volume
- 6
- Issue
- 2
- Pages
- 1215-1224
- ISSN
- 2155-5435 (ISSN-L)
- PMC
- PMC4749094
- OpenAlex
- W2292390022
- Cited by
- 60
- References
- 7
- Citations by year
- 2026: 4 · 2024: 3 · 2023: 5 · 2022: 6 · 2021: 5 · 2020: 5 · 2019: 5 · 2018: 7 · 2017: 12 · 2016: 8
- FWCI
- 4.36
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Locations
- ACS Catalysis (publishedVersion, other-oa)
- Europe PMC (PubMed Central) (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Institutes of Health (S10OD011952)
- Division of Chemistry (CHE-1229400, CHE-1413862)
- 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 › Organometallic Complex Synthesis and Catalysis
- Keywords
- ε-caprolactone, ring-opening polymerization, cyclic ester polymerization, transition state structure, Hammett substituent effects, polymerization kinetics, catalyst design, electron-withdrawing substituents
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