Unravelling the para- and ortho-benzene substituent effect on the glass transition of renewable wholly (hetero-)aromatic polyesters bearing 2,5-furandicarboxylic moieties

abstract

High-glass transition thermoplastic polymers have dawned much attention in recent years due to their typical stiffness, enhanced thermal properties, and more importantly the emerging need to replace commercial fossil-based products by more sustainable alternatives, derived from renewable resources. In this regard we engineer here for the first time the design of wholly (hetero-)aromatic polyesters based on a key-platform chemical2,5-furandicarboxylic acid (FDCA) and commercially-available catechol, or hydroquinone, whose structures were characterized by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR). Both polymers had a high glass transition (T-g up to 167 degrees C) detected by differential scanning calorimetry (DSC) and has excellent thermal stability according to thermogravimetric analysis (TGA). The para- and ortho- substitution in hydroquinone and catechol, respectively, affected crystallinity, which was typically higher for poly (1,4-phenylene-2,5-furandicarboxylate) (PHQF) favouring a stiffer and close packing structure. Also, the thermal properties were higher for PHQF.

keywords

THERMOTROPIC POLYESTERS; COPOLYESTERS; ACID; POLY(ETHYLENE-TEREPHTHALATE); CRYSTALLIZATION; RESOURCES; FILMS

subject category

Polymer Science

authors

Zaidi, S; Soares, MJ; Bougarech, A; Thiyagarajan, S; Guigo, N; Abid, S; Abid, M; Silvestre, AJD; Sousa, AF

Groups

G4 - Renewable Materials and Circular Economy

Projects

European network of FURan based chemicals and materials FOR a Sustainable development (FUR4Sustain)

CICECO - Aveiro Institute of Materials (UIDB/50011/2020)

CICECO - Aveiro Institute of Materials (UIDP/50011/2020)

Rede Nacional de Ressonância Magnética Nuclear (PTNMR)

acknowledgements

This work is based upon work from COST Action FUR4Sustain-European network of FURan based chemicals and materials FOR a Sustainable development, CA18220, supported by COST (European Cooperation in Science and Technology); and also developed within the scope of the ERASMUS + ICM project (Ref. 2017-1-PTO1-KA107-035493) between the University of Sfax and the University of Aveiro; This work was supported within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the FCT-Fundacao para a Ciencia e a Tecnologia/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. This research is also sponsored by FEDER funds through the program COMPETE-Programa Operacional Factores de Competitividade-and by national funds through FCT under the project UID/EMS/00285/2020. The costs resulting from the FCT hiring of AFS were funded by national funds (OE), through FCT, IP, in the scope of the framework contract foreseen in numbers 4, 5, and 6 of article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19. The authors would also like to acknowledge the financial support of the Ministry of Higher Education and Scientific Research in Tunisia. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project N. 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC).