Metal-Based Catalysts for Controlled Ring-Opening Polymerization of Macrolactones: High Molecular Weight and Well-Defined Copolymer Architectures
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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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“Their synthesis can be achieved by the ring-opening polymerization (ROP) of the cyclic esters lactide (LA) and ε-caprolactone (CL), respectively [4,5].”
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- Authors
- Bouyahyi, M., & Duchateau, R.
- Affiliations
- Saudi Arabia Basic Industries (Netherlands) (NL)
- Corresponding author
- Duchateau, Rob
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- 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
- green
- research.tue.nl
- 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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