期刊
MACROMOLECULES
卷 53, 期 4, 页码 1380-1387出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.9b02449
关键词
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资金
- FCT/MEC [UIDB/50011/2020]
- FEDER under the PT2020 Partnership Agreement
- FCT [SFRH/BD/129040/2017, IF/01468/2015]
- national funds (OE), through FCT-Fundacio para a Ciencia e a Tecnologia, I.P.
- Fundação para a Ciência e a Tecnologia [SFRH/BD/129040/2017] Funding Source: FCT
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.
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