Mechanisms and Kinetics of Thermal Degradation of Poly(ε-caprolactone)
Abstract
Thermogravimetric analysis (TGA) simultaneously coupled with mass spectrometry (MS) and Fourier transform infrared spectrometry (FTIR) was developed as an original technique to study the thermal modification/degradation of poly(epsilon-caprolactone) (PCL) through in depth analysis of the evolved gas. Perfectly well-defined PCL samples with controlled end groups, predictable molecular weight, and narrow molecular weight distribution were synthesized by living "coordination-insertion" ring-opening polymerization of epsilon-caprolactone initiated by aluminum triisopropoxide. TGA analyses carried out on purified PCL samples, deprived from any residual catalyst or monomer, highlighted a two-step thermal degradation. Evolved gas analysis by both MS and FTIR showed that the first process implies a statistical rupture of the polyester chains via ester pyrolysis reaction. The produced gases were identified as H(2)O, CO(2), and 5-hexenoic acid. The second step leads to the formation of epsilon-caprolactone (cyclic monomer) as result of an unzipping depolymerization process. The influence of parameters such as polyester molecular weight, nature of the PCL end groups, and presence of catalytic residues as well as the type of purge gas were investigated. The activation energy of the thermal degradation was also studied.
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The presence of ε-caprolactone monomer unit in the second-stage degradation is due to depolymerization via an unzipping mechanism occurring at a temperature above 440 °C.
“The presence of this monomer unit in the second-stage degradation stage is due to the depolymerization via an unzipping mechanism occurring at a temperature above 440 °C.66”
Decomposition of SBS occurs by a free-radical mechanism according to scission of the polymer.
“It can be found that the decomposition of SBS occurs by a free-radical mechanism according to the scission of the polymer.66,67”
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- Authors
- Persenaire, O., Alexandre, M., Degée, P., & Dubois, P.
- Affiliations
- University of Mons (BE)
- Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc, 20-7000 Mons, Belgium
- Venue
- Biomacromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2001-02-16
- Volume
- 2
- Issue
- 1
- Pages
- 288-294
- ISSN
- 1525-7797 (ISSN-L)
- 1526-4602
- OpenAlex
- W2051603731
- Cited by
- 444
- References
- 10
- Citations by year
- 2026: 20 · 2025: 23 · 2024: 26 · 2023: 21 · 2022: 21 · 2021: 23 · 2020: 31 · 2019: 27 · 2018: 29 · 2017: 26 · 2016: 17 · 2015: 14 · 2014: 18 · 2013: 12 · 2012: 15
- FWCI
- 4.87
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Biomacromolecules (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Materials Chemistry › Thermal and Kinetic Analysis
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer Science and PVC
- Keywords
- polycaprolactone, thermal degradation, degradation kinetics, ester pyrolysis, depolymerization, end groups, molecular weight effects, activation energy, evolved gas analysis, thermogravimetric analysis
- MeSH terms
- Chromatography, Gel, Gases, Hot Temperature, Kinetics, Molecular Weight, Magnetic Resonance Spectroscopy, Polyesters, Molecular Structure, Spectroscopy, Fourier Transform Infrared
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