Our first paper of 2022 with the title "Towards novel lignin-based aromatic polyesters: In-depth study of the thermal degradation and crystallization of poly(propylene vanillate)" has just been published in Thermochimica Acta! As part of our work on biobased vanillate polysters, we studied the crystallization kinetics of poly(propylene vanillate) (PPV) using advanced analysis methods and the thermal degradation with isoconversional methods and model fitting analysis.
We first reported the synthesis and characterization of PPV in early 2021, which has very interesting properties, similar to its terephthalate counterpart. Afterwards, we investigated its molecular mobility with advanced methods. This work is part of the phD thesis of Eleftheria Xanthopoulou, under the supervision of Asoc. Professor George Papageorgiou of University of Ioannina.
The study of these biobased polyesters are part of the work for the Fur4Sustain COST action, which aims to identify and support solutions for the successful market introduction of sustainable, furan-based products. Finally, the Fur4Sustain action is an open platform for collaboration and networking, fostering the development of intersectorial knowledge. BikiarisLab has a prominent role in the project, as leader of Working Group 2 and an important number of publications that resulted from collaborations in the context of the project. Via the Fur4Sustain action, our phD students Lazaros Papadopoulos and Eleftheria Xanthopoulou had the unique opportunity to strengthen their international collaborations. More specifically, Lazaros was granted two Mobility Grants, that allowed him to perform part of his work in the Fraunhofer Institute for Wood Research in, Braunschweig, Germany, while Eleftheria was the holder of a Virtual Mobility Grant, that allowed her to initiate a collaboration with Dr Nathanaël Guigo of University of Nice Sophia Antipolis, aiming on the in-depth characterization of the crystallization properties of polyesters.
More information on Fur4Sustain and the role of BikiarisLab can be found here!
Abstract
The growing environmental concerns over the excessive emissions of greenhouse gases and the accumulation of synthetic plastics in terrestrial and aqueous recipients have driven the public, academic and industrial awareness towards the production of novel bio-based polymeric materials. Within this frame, poly(propylene vanillate) (PPV) is an alipharomatic engineering polyester with promising thermal and mechanical properties, produced via a two-step melt polycondensation of 4-(3-hydroxypropoxy)-3-methoxybenzoic acid, a monomer derived from the potentially lignin-based vanillic acid. Herein, a systematic investigation of the non-isothermal crystallization, the thermal stability and the decomposition mechanism of PPV was performed, with the implementation of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass spectroscopy (Py-GC/MS), respectively. The Lauritzen-Hoffman parameters (K and U*) of crystallization were calculated using a combination of the Lauritzen-Hoffman theory and isoconversional methods. The determination of the activation energy, using isoconversional methods, along with the model fitting analysis of mass loss data have led to a first assumption about the thermal degradation profile of the synthesized polyester. Furthermore, decomposition products revealed the two different main degradation mechanisms take place: heterolytic β-hydrogen scission and α-homolytic scission.
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Acknowledgments
This publication is based upon work from COST Action FUR4Sustain, CA18220, supported by COST (European Cooperation in Science and Technology).
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