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

Mariela M. Nolasco; Catarina F. Araujo; Shanmugam Thiyagarajan; Svemir Rudić; Pedro D. Vaz; Armando J.D. Silvestre; Paulo J.A. Ribeiro-Claro; Andreia F. Sousa

doi:10.1021/acs.macromol.9b02449

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

Mariela M. Nolasco^*, Catarina F. Araujo, Shanmugam Thiyagarajan, Svemir Rudić, Pedro D. Vaz, Armando J.D. Silvestre, Paulo J.A. Ribeiro-Claro, Andreia F. Sousa^*

^*Corresponding author for this work

BBP Sustainable Chemistry & Technology

Research output: Contribution to journal › Article › Academic › peer-review

27 Citations (Scopus)

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···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···O stabilization, the ordered crystalline arrangement is disfavored and polymer chains - adopting several quasi iso-energetic structures - prefer to solidify into an amorphous mess.

Original language	English
Pages (from-to)	1380-1387
Journal	Macromolecules
Volume	53
Issue number	4
DOIs	https://doi.org/10.1021/acs.macromol.9b02449
Publication status	Published - 5 Feb 2020

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@article{697eb3d9ce694971996cf29fdc53e5a6,

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

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···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···O stabilization, the ordered crystalline arrangement is disfavored and polymer chains - adopting several quasi iso-energetic structures - prefer to solidify into an amorphous mess.",

author = "Nolasco, {Mariela M.} and Araujo, {Catarina F.} and Shanmugam Thiyagarajan and Svemir Rudi{\'c} and Vaz, {Pedro D.} and Silvestre, {Armando J.D.} and Ribeiro-Claro, {Paulo J.A.} and Sousa, {Andreia F.}",

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doi = "10.1021/acs.macromol.9b02449",

language = "English",

volume = "53",

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journal = "Macromolecules",

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T1 - Asymmetric Monomer, Amorphous Polymer? Structure-Property Relationships in 2,4-FDCA and 2,4-PEF

AU - Nolasco, Mariela M.

AU - Araujo, Catarina F.

AU - Thiyagarajan, Shanmugam

AU - Rudić, Svemir

AU - Vaz, Pedro D.

AU - Silvestre, Armando J.D.

AU - Ribeiro-Claro, Paulo J.A.

AU - Sousa, Andreia F.

PY - 2020/2/5

Y1 - 2020/2/5

N2 - 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···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···O stabilization, the ordered crystalline arrangement is disfavored and polymer chains - adopting several quasi iso-energetic structures - prefer to solidify into an amorphous mess.

AB - 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···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···O stabilization, the ordered crystalline arrangement is disfavored and polymer chains - adopting several quasi iso-energetic structures - prefer to solidify into an amorphous mess.

U2 - 10.1021/acs.macromol.9b02449

DO - 10.1021/acs.macromol.9b02449

M3 - Article

AN - SCOPUS:85079513110

SN - 0024-9297

VL - 53

SP - 1380

EP - 1387

JO - Macromolecules

JF - Macromolecules

IS - 4

ER -

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

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