ω-Pentandecalactone Polymerization and ω-Pentadecalactone/ε-Caprolactone Copolymerization Reactions Using Organic Catalysts
Abstract
The catalytic behavior of several inexpensive and simple N-heterocyclic organic catalysts in ring-opening polymerization (ROP) of ω-pentadecalactone (PDL) and ε-caprolactone (CL) has been studied. The polymerization reactions, carried out in bulk monomer and in toluene solution at 100 °C, identified 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) in combination with benzyl alcohol (BnOH) as initiator as the only active catalyst for the ring-opening polymerization of PDL and for the copolymerization of PDL and CL. The guanidine N -methyl-TBD (MTBD), 1,2,3-triisopropylguanidine, the amidine 1,8-diazabicycloundec-7-ene (DBU), and other N-heterocyclic organic catalysts such as dialkylaminopyridine (DMAP), imidazole, indoles, and N-heterocyclic carbenes (NHC’s) tested in this study proved to be inactive in the ROP of PDL even for the long reaction times. The polymerization mechanism, kinetic studies, temperature, and monomer concentration effects were investigated both in solution and in bulk monomer. The pseudoliving character of the TBD/BnOH system has been proven by kinetic studies in both toluene solution and bulk monomer. By varying the experimental conditions and the monomer feed composition, highly crystalline poly(PDL- co -CL) random copolymers of various compositions have been prepared using the binary system TBD/ROH as catalyst/initiators. Thermal analysis and 13 C NMR spectroscopy show a linear relation of the variation of the random copolymers melting temperatures as a function of comonomer content.
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ROP of a few macrolactones (ring size = 14, 16) has been successfully applied to prepare long-chain polyesters with similar structures but higher and more predictable molecular weights than those obtained from the polycondensation of fatty acids.
“ROP of a few macrolactones (ring size = 14, 16) have been successfully applied to prepare longchain polyesters with similar structures but higher and more predictable molecular weights than the ones obtained from the polycondensation of fatty acids.[279][280][281]”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [281]
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- Authors
- Bouyahyi, M., Pepels, M. P. F., Heise, A., & Duchateau, R.
- Affiliations
- Eindhoven University of Technology (NL)
- Dublin City University (IE)
- Corresponding author
- Duchateau, Rob
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-04-09
- Volume
- 45
- Issue
- 8
- Pages
- 3356-3366
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2045887715
- Cited by
- 157
- References
- 49
- Citations by year
- 2026: 8 · 2025: 11 · 2024: 12 · 2023: 7 · 2022: 4 · 2021: 6 · 2020: 12 · 2019: 10 · 2018: 16 · 2017: 10 · 2016: 12 · 2015: 17 · 2014: 18 · 2013: 10 · 2012: 3
- FWCI
- 6.23
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- TU/e Research Portal (submittedVersion)
- University of Groningen research database (University of Groningen / Centre for Information Technology) (submittedVersion)
- 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 › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Keywords
- ε-caprolactone, ring-opening polymerization, copolymerization, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, benzyl alcohol initiator, polymerization kinetics, random copolymers, crystallinity, melting point, N-heterocyclic carbenes
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