Structure-performance relationships in lignin-based transesterification vitrimers: The role of lignin structural features

Karoki, Peter K.; Kemefa, Christian O.; Kousika, Rohit; Pu, Yunqiao; Cai, Charles M.; Ragauskas, Arthur J.

doi:10.1016/j.indcrop.2025.122108

Structure-performance relationships in lignin-based transesterification vitrimers: The role of lignin structural features

Journal Article · Fri Oct 24 00:00:00 EDT 2025 · Industrial Crops and Products

DOI:https://doi.org/10.1016/j.indcrop.2025.122108· OSTI ID:3011553

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Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of California, Riverside, CA (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Lignin has been hailed as an ideal renewable alternative for petrochemical-based prepolymers in material synthesis for a sustainable and circular economy, due to its abundant aromatic network and high carbon content. However, the properties and performance of lignin-derived macromolecules are strongly influenced by the lignin itself. While numerous studies have explored the impact of lignin content on the thermomechanical performance of lignin-based vitrimers, literature on how the inherent structural features of lignin affect these properties is scanty. In this study, hardwood organosolv lignin was fractionated in ethyl acetate, ethanol, and acetone to obtain lignin fractions with varying structural characteristics. These fractions were then modified through carboxylation and crosslinked with epoxidized soybean oil (ESO) at a hydroxyl to epoxy group ratio of 1:1 to produce lignin-based transesterification vitrimers (LVs). The thermal properties (i.e. glass transition temperature and thermal stability), tensile strength, storage modulus, and stress relaxation behavior of the LVs were studied and carefully related to the structural features of lignin. The results revealed a positive relationship between strong hydroxyl content in modified lignin and the tensile strength (5.10–9.71 MPa), storage modulus (1099.4 – 1372.8 MPa), crosslinking density, and stress relaxation of the LVs. Additionally, both the storage modulus and tensile strength exhibited a positive relationship with the ratio of rigid linkages in modified lignin, while lignin molecular weight was found to significantly impact the thermal properties of LVs (i.e Tg and thermal stability). This study not only highlights the valorization of lignin in vitrimer synthesis but also provide insights for designing lignin-based materials with tailored properties for specific applications.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 3011553

Journal Information:: Industrial Crops and Products, Journal Name: Industrial Crops and Products Vol. 237; ISSN 0926-6690

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Structure-performance relationships in lignin-based transesterification vitrimers: The role of lignin structural features

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