Cited by 40biodegradable polymer synthesis and propertiesOrganometallic Complex Synthesis and CatalysisCarbon dioxide utilization in catalysis

Tuning the Thiolen: Al(III) and Fe(III) Thiolen Complexes for the Isoselective ROP of rac-Lactide

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Stewart, Jack A., McKeown, Paul, Driscoll, Oliver J., Mahon, Mary F., Ward, Benjamin D., Jones, Matthew D.·2019·Macromolecules

Abstract

A series of five iron and aluminum complexes bearing {ONSO} imine thiobis(phenolate) ligands have been prepared and applied to the ring-opening polymerization (ROP) of rac -lactide. Fe( 1 )Cl produced polylactide with a very strong isotactic bias ( P m = 0.79–0.89) and well-defined melting temperatures ( T m = 154–181 °C). The polymers have been characterized by a combination of 1 H{ 1 H} NMR, 13 C{ 1 H} NMR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and powder X-ray diffraction. Fe( 1 )Cl has also been shown to activate CO 2, at atmospheric pressure and concentrations, to form a carbonato-bridged dimer. Fe( 2 – 5 )Cl and Al( 1 – 5 )Me were also active for lactide ROP demonstrating good-molecular-weight control ( Đ = 1.04–1.12) and moderate isotactic preference ( P m = 0.56–0.72), with polymerization outcome correlating with ligand substituents.

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Crossref · 10.1021/acs.macromol.9b01205

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Authors
Stewart, J. A., McKeown, P., Driscoll, O. J., Mahon, M. F., Ward, B. D., & Jones, M. D.
Affiliations
  • University of Bath (GB)
  • Cardiff University (GB)
Corresponding author
Jones, Matthew D.
Venue
Macromolecules
Published
2019-07-31
Volume
52
Issue
15
Pages
5977-5984
ISSN
  • 0024-9297 (ISSN-L)
  • 1520-5835
OpenAlex
W2965222898
Cited by
40
References
80
Citations by year
2026: 4 · 2025: 6 · 2024: 5 · 2023: 7 · 2022: 9 · 2021: 4 · 2020: 2 · 2019: 3
FWCI
1.28
Type
journal article
Language
en
Locations
  • Macromolecules (publishedVersion)
  • ORCA Online Research @Cardiff (Cardiff University) (acceptedVersion)
  • ORCA Online Research @Cardiff (Cardiff University) (submittedVersion)
  • Pure (University of Bath) (submittedVersion, other-oa)
Funders
Engineering and Physical Sciences Research Council (EP/P016405/1, EP/L016443/1)
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
ring-opening polymerization, rac-lactide, polylactic acid, iron(III) complexes, aluminum(III) complexes, isotacticity, ligand substituent effects, CO2 activation, molecular weight control, stereoselective polymerization

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