Mechanisms and kinetics of thermal degradation of poly(ε-caprolactone)

O. Persenaire, M. Alexandre, P. Degée, P. Dubois

Research output: Contribution to journalArticle

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(ε-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 ε-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 H2O, CO2, and 5-hexenoic acid. The second step leads to the formation of ε-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.

Original languageEnglish
Pages (from-to)288-294
Number of pages7
JournalBiomacromolecules
Volume2
Issue number1
DOIs
Publication statusPublished - 15 Aug 2001
Externally publishedYes

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Pyrolysis
Polyesters
Gases
Spectrometry
Kinetics
Mass spectrometry
Thermogravimetric analysis
Fourier transforms
Monomers
Molecular weight
Infrared radiation
Depolymerization
Gas fuel analysis
Ring opening polymerization
Molecular weight distribution
Aluminum
Esters
Activation energy
Degradation
Catalysts

Cite this

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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(ε-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 ε-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 H2O, CO2, and 5-hexenoic acid. The second step leads to the formation of ε-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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Mechanisms and kinetics of thermal degradation of poly(ε-caprolactone). / Persenaire, O.; Alexandre, M.; Degée, P.; Dubois, P.

In: Biomacromolecules, Vol. 2, No. 1, 15.08.2001, p. 288-294.

Research output: Contribution to journalArticle

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