Cited by 125biodegradable polymer synthesis and propertiesAdvanced Polymer Synthesis and CharacterizationCarbon dioxide utilization in catalysis

Metal-Based Catalysts for Controlled Ring-Opening Polymerization of Macrolactones: High Molecular Weight and Well-Defined Copolymer Architectures

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Bouyahyi, Miloud, Duchateau, Rob·2014·Macromolecules

Abstract

This contribution describes our recent results regarding the metal-catalyzed ring-opening polymerization of pentadecalactone and its copolymerization with ε-caprolactone involving single-site metal complexes based on aluminum, zinc, and calcium. Under the right conditions (i.e., monomer concentration, catalyst type, catalyst/initiator ratio, reaction time, etc.), high molecular weight polypentadecalactone with M n up to 130 000 g mol –1 could be obtained. The copolymerization of a mixture of ε-caprolactone and pentadecalactone yielded random copolymers. Zinc and calcium-catalyzed copolymerization using a sequential feed of pentadecalactone followed by ε-caprolactone afforded perfect block copolymers. The blocky structure was retained even for prolonged times at 100 °C after full conversion of the monomers, indicating that transesterification is negligible. On the other hand, in the presence of the aluminum catalyst, the initially formed block copolymers gradually randomized as a result of intra- and intermolecular transesterification reactions. The formation of homopolymers and copolymers with different architectures has been evidenced by HT-SEC chromatography, NMR, DSC and MALDI-ToF-MS.

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Crossref · 10.1021/ma402072t

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Authors
Bouyahyi, M., & Duchateau, R.
Affiliations
Saudi Arabia Basic Industries (Netherlands) (NL)
Corresponding author
Duchateau, Rob
Venue
Macromolecules
Published
2014-01-14
Volume
47
Issue
2
Pages
517-524
ISSN
  • 0024-9297 (ISSN-L)
  • 1520-5835
OpenAlex
W2068108623
Cited by
125
References
59
Citations by year
2026: 10 · 2025: 10 · 2024: 15 · 2023: 7 · 2022: 5 · 2021: 4 · 2020: 12 · 2019: 12 · 2018: 11 · 2017: 7 · 2016: 9 · 2015: 13 · 2014: 10
FWCI
4.93
Type
journal article
Language
en
Open access
Licence
other-oa
Locations
  • Macromolecules (publishedVersion)
  • TU/e Research Portal (publishedVersion, other-oa)
  • TU/e Research Portal (submittedVersion)
  • University of Groningen research database (University of Groningen / Centre for Information Technology) (submittedVersion)
  • TU/e Research Portal (submittedVersion, other-oa)
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, macrolactones, ε-caprolactone, block copolymers, random copolymers, aluminum catalyst, zinc catalyst, calcium catalyst, transesterification, copolymer architecture, high molecular weight polymers, controlled radical polymerization

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