Asymmetric Monomer, Amorphous Polymer? Structure-Property Relationships in 2,4-FDCA and 2,4-PEF
authors Nolasco, MM; Araujo, CF; Thiyagarajan, S; Rudic, S; Vaz, PD; Silvestre, AJD; Ribeiro-Claro, PJA; Sousa, AF
nationality International
journal MACROMOLECULES
keywords POLY(ETHYLENE 2,5-FURANDICARBOXYLATE); CRYSTAL-STRUCTURE; ACID; POLYESTER; TOSCA; COPOLYESTERS; MOBILITY
abstract 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.
publisher AMER CHEMICAL SOC
issn 0024-9297
isbn 1520-5835
year published 2020
volume 53
issue 4
beginning page 1380
ending page 1387
digital object identifier (doi) 10.1021/acs.macromol.9b02449
web of science category Polymer Science
subject category Polymer Science
unique article identifier WOS:000517351100027
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