Asymmetric Monomer, Amorphous Polymer? Structure-Property Relationships in 2,4-FDCA and 2,4-PEF


The biobased polyester poly(ethylene 2,4-furanoate) (2,4-PEF) is a potentially interesting yet insufficiently studied polymer whose resistance to crystallization fundamentally stems from the asymmetric nature of the 2,4-furandicarboxylic acid monomer. A combination of vibrational spectroscopy (infrared, Raman and inelastic neutron scattering) and ab initio calculations has been used to assess the conformational and regiochemistry preferences of 2,4-PEF. The latter polymerizes following a random distribution of monomer orientation, thereby rendering the formation of periodic interchain C-H center dot center dot center dot O contacts wholly unfeasible and ultimately favoring the formation of randomly coiled chains based on gauche-ethylene glycol segments. In the absence of C-H center dot center dot center dot O stabilization, the ordered crystalline arrangement is disfavored and polymer chains-adopting several quasi isoenergetic structures-prefer to solidify into an amorphous mess.



subject category

Polymer Science


Nolasco, MM; Araujo, CF; Thiyagarajan, S; Rudic, S; Vaz, PD; Silvestre, AJD; Ribeiro-Claro, PJA; Sousa, AF

our authors


This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 UIDP/50011/2020, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. FCT is gratefully acknowledged for funding a PhD grant to C.F.A. (SFRH/BD/129040/2017) and a researcher contract to M.M.N. (IF/01468/2015) under the program IF 2015. The STFC Rutherford Appleton Laboratory is thanked for access to neutron beam facilities. The costs resulting from the FCT hiring of A.F.S. were funded by national funds (OE), through FCT-Fundacio para a Ciencia e a Tecnologia, I.P., 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.

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