Enhancing Biopolyester Backbone Rigidity with an Asymmetric Furanic Monomer

Woroch, Cristian P. [Stanford Univ., CA (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000246016222); Addison, Bennett [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000307633137); Stovall, Alexandra [National Renewable Energy Laboratory (NREL), Golden, CO (United States)]; Rognerud, Erik [National Renewable Energy Laboratory (NREL), Golden, CO (United States)]; Lincoln, Clarissa Lydia [National Renewable Energy Laboratory (NREL), Golden, CO (United States)]; Miscall, Joel [National Renewable Energy Laboratory (NREL), Golden, CO (United States)]; Rosetto, Gloria [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0009000971167258); Kanan, Matthew W. [Stanford Univ., CA (United States)] (ORCID:0000000259326289); Rorrer, Nicholas A. [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000191345853); Beckham, Gregg T. [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:000000023480212X)

doi:10.1021/acssuschemeng.5c07913

DOE OSTI · 3000213

Enhancing Biopolyester Backbone Rigidity with an Asymmetric Furanic Monomer

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Abstract

Biobased furanic polyesters can exhibit performance advantages over petroleum-derived polyesters, primarily due to their rigid furan-containing backbones. Herein, we develop two strategies to polymerize methyl 5-hydroxymethyl furanoate to poly(5-hydroxymethyl furanoate) (PHMF), a furan-based polyester with even greater backbone rigidity than poly(ethylene furanoate). Thermal, spectroscopic, and computational investigations of PHMF alongside analogous furan-based and phenyl-based polyesters suggest that the high furan content of PHMF leads to its high glass transition temperature, slow crystallization kinetics, and low amorphous mobility. Molecular dynamics simulations suggest that while the backbone of PHMF is exceptionally rigid, its amorphous phase is denser than its phenyl analog due to noncovalent interchain interactions. Together, these results highlight how asymmetric furan-based monomers can modulate key properties in biobased polyesters.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY 42 ENGINEERING chain mobility crystallization kinetics furan polyester hydroxyester polycondensation molecular dynamics performance-advantaged bioplastic

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Woroch, Cristian P. [Stanford Univ., CA (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000246016222), Addison, Bennett [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000307633137), Stovall, Alexandra [National Renewable Energy Laboratory (NREL), Golden, CO (United States)], Rognerud, Erik [National Renewable Energy Laboratory (NREL), Golden, CO (United States)], Lincoln, Clarissa Lydia [National Renewable Energy Laboratory (NREL), Golden, CO (United States)], Miscall, Joel [National Renewable Energy Laboratory (NREL), Golden, CO (United States)], Rosetto, Gloria [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0009000971167258), Kanan, Matthew W. [Stanford Univ., CA (United States)] (ORCID:0000000259326289), Rorrer, Nicholas A. [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000191345853), Beckham, Gregg T. [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:000000023480212X). 2025-10-08. Enhancing Biopolyester Backbone Rigidity with an Asymmetric Furanic Monomer. https://doi.org/10.1021/acssuschemeng.5c07913

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