Abstract
The effect of molecular weight on the thermal degradation of poly(ε-caprolactone) (PCL) was investigated by thermogravimetric analysis in combination with differential thermal analysis and Fourier transform infrared spectroscopy (TGA/DTA/FT-IR). The measurements were made in the temperature range 40–720 °C and it was found that PCL undergoes completely different degradation processes in nitrogen and oxygen atmosphere. Thus, in nitrogen atmosphere low molecular weight (<i>M</i><sub>n</sub> = 10 000 g/mol) PCL (PCL<sup>10k</sup>) decomposed in a three-step mechanism. The evolved gases detected by FT-IR spectroscopy were identified as ε-caprolactone, 5-hexenoic acid, CO<sub>2</sub>, and methyl pentanoate and traces of H<sub>2</sub>O. In the case of high molecular weight (<i>M</i><sub>n</sub> = 80 000 g/mol) PCL (PCL<sup>80k</sup>) only a two-step degradation was observed. By FT-IR spectroscopy 5-hexenoic acid, CO<sub>2</sub>, H<sub>2</sub>O, and methyl pentanoate were detected as decomposition products. In an oxygen environment, similar degradation products were detected for the different molecular-weight PCLs. The recorded FT-IR spectra of the evolved gases were identified as CO<sub>2</sub>, CO, H<sub>2</sub>O, and short-chain carboxylic acids.
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