Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts

Daniel Stasiw, Anna M. Luke, Tomer Rosen, Aaron B. League, Mukunda Mandal, Benjamin D. Neisen, Chris Cramer, Moshe Kol, William B Tolman

Research output: Contribution to journalArticle

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Abstract

The ring-opening transesterification polymerization (ROTEP) of rac-lactide (rac-LA) using LXZn catalysts (LX = ligand having phenolate, amine, and pyridine donors with variable para substituents X on the bound phenolate donor; X = NO2, Br, t-Bu, OMe) was evaluated through kinetics experiments and density functional theory, with the aim of determining how electronic modulation of the ligand framework influences polymerization rate, selectivity, and control. After determination that zinc-ethyl precatalysts required 24 h of reaction with benzyl alcohol to convert to active alkoxide complexes, the subsequently formed species proved to be active and fairly selective, polymerizing up to 300 equiv of rac-LA in 6-10 min while yielding isotactic (Pm = 0.72-0.78) polylactide (PLA) with low dispersities: = 1.06-1.17. In contrast to previous work with aluminum catalysts for which electronic effects of ligand substituents were significant (Hammett ρ = +1.2-1.4), the LXZn systems exhibited much less of an effect (ρ = +0.3). Density functional calculations revealed details of the initiation and propagation steps, enabling insights into the high isotacticity and the insensitivity of the rate on the identity of X.

Original languageEnglish (US)
Pages (from-to)14366-14372
Number of pages7
JournalInorganic Chemistry
Volume56
Issue number22
DOIs
StatePublished - Nov 20 2017

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alkoxides
Zinc
polymerization
zinc
Polymerization
Ligands
catalysts
ligands
Catalysts
Density functional theory
Benzyl Alcohol
Transesterification
Aluminum
electronics
Amines
pyridines
amines
alcohols
selectivity
Modulation

Cite this

Stasiw, D., Luke, A. M., Rosen, T., League, A. B., Mandal, M., Neisen, B. D., ... Tolman, W. B. (2017). Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts. Inorganic Chemistry, 56(22), 14366-14372. https://doi.org/10.1021/acs.inorgchem.7b02544

Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts. / Stasiw, Daniel; Luke, Anna M.; Rosen, Tomer; League, Aaron B.; Mandal, Mukunda; Neisen, Benjamin D.; Cramer, Chris; Kol, Moshe; Tolman, William B.

In: Inorganic Chemistry, Vol. 56, No. 22, 20.11.2017, p. 14366-14372.

Research output: Contribution to journalArticle

Stasiw, D, Luke, AM, Rosen, T, League, AB, Mandal, M, Neisen, BD, Cramer, C, Kol, M & Tolman, WB 2017, 'Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts', Inorganic Chemistry, vol. 56, no. 22, pp. 14366-14372. https://doi.org/10.1021/acs.inorgchem.7b02544
Stasiw D, Luke AM, Rosen T, League AB, Mandal M, Neisen BD et al. Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts. Inorganic Chemistry. 2017 Nov 20;56(22):14366-14372. https://doi.org/10.1021/acs.inorgchem.7b02544
Stasiw, Daniel ; Luke, Anna M. ; Rosen, Tomer ; League, Aaron B. ; Mandal, Mukunda ; Neisen, Benjamin D. ; Cramer, Chris ; Kol, Moshe ; Tolman, William B. / Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 22. pp. 14366-14372.
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