Thermal degradation of biobased polyesters: Kinetics and decomposition mechanism of polyesters from 2,5-furandicarboxylic acid and long-chain aliphatic diols

• Published in: Journal of analytical and applied pyrolysis Vol. 117; pp. 162 - 175
• Main Authors: Terzopoulou, Zoe, Tsanaktsis, Vasilios, Nerantzaki, Maria, Achilias, Dimitris S., Vaimakis, Tiverios, Papageorgiou, George Z., Bikiaris, Dimitrios N.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.01.2016
• Subjects: chemical structure; chromatography; Decomposition mechanism; glycols; mass spectrometry; molecular weight; nuclear magnetic resonance spectroscopy; Poly(alkylene 2,5-furan dicarboxylate) polyesters; Poly(decylene 2,5-furanoate); Poly(dodecylene 2,5-furanoate); Poly(octylene 2,5-furanoate); polyesters; pyrolysis; Thermal degradation kinetics; thermal stability; thermogravimetry; Poly(octylene 2,5-furanoate); Poly(decylene 2,5-furanoate); Thermal degradation kinetics; Poly(alkylene 2,5-furan dicarboxylate) polyesters; Decomposition mechanism; Poly(dodecylene 2,5-furanoate)
• ISSN: 0165-2370; 1873-250X
• DOI: 10.1016/j.jaap.2015.11.016

[Display omitted] •New poly(alkylene 2,5-furan dicarboxylate) polyesters were prepared.•Thermal stability and decomposition kinetics of such polyesters are presented.•All polyesters are thermostable materials.•Decomposition takes place mainly via β- and α-hydrogen bond scission. In the present study, biobased furan dicarboxylate polyesters have been prepared using 2,5-furandicarboxylic acid (FDCA) and diols with high number of methylene groups (long chain diols), namely 8, 10 and 12, which are named as poly(octylene 2,5-furanoate) (POF), poly(decylene 2,5-furanoate) (PDeF) and poly(dodecylene 2,5-furanoate) (PDoF), respectively. Semi-crystalline polyesters with number average molecular weight ranging from 34,000 to 39,000g/mol have been prepared and their chemical structure was proved by 1H NMR spectroscopy. A systematic investigation of the thermal stability and decomposition kinetics of these polyesters was performed, using thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass spectroscopy (Py-GC/MS). From TGA curves it was found that all polyesters have high thermal stability since their decomposition starts around 340°C and completes near 500°C. The decomposition mechanism of the prepared polyesters was also studied with pyrolysis-gas chromatography/mass spectroscopy (Py-GC/MS). From the identified decomposition products after pyrolysis at 350 and 450°C, it was found that the decomposition of these polyesters is taking place mainly via β-hydrogen bond scission and in lower extent with homolytic >CC< radical decomposition and with α-hydrogen scission.