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Title: Lignin-Based Polyurethanes from Unmodified Kraft Lignin Fractionated by Sequential Precipitation

Abstract

In this work, lignin-based polyurethanes were synthesized from three unmodified softwood Kraft lignin fractions as the primary hydroxyl group providers which constituted >40% of the polymeric materials. High-, medium-, and low-molecular-weight Kraft lignin fractions were prepared by sequential precipitation from the acetone–methanol cosolvent by adding hexane as an antisolvent. A polyether, poly(ethylene glycol), and a polyester, poly(trimethylene glutarate), were selected as secondary polyols to form the soft segments in the lignin-based network. At a fixed NCO/OH ratio (1:1), the effects of lignin macromolecular features and their intermolecular interactions with the secondary polyols on mechanical and thermal properties of the lignin-based polyurethanes were investigated by tensile tests, DMA, SEM, and TGA. Because of the unique association behavior of macromolecular lignin, the sequential precipitation method was able to produce Kraft lignin fractions possessing very high molecular weights. The morphological study showed that the polyurethane network was assembled by cross-linking nanosized lignin complexes through urethane links. It was discovered that the mechanical properties of the lignin-based polyurethanes can be tuned by lignin molecular weight and the incorporation of a secondary polyol. Compared to poly(trimethylene glutarate), poly(ethylene glycol) interacts strongly with associated lignin complexes through hydrogen bonding. It promoted dissociation of the lignin complexesmore » and consequently improved reactivity between lignin and diisocyanate. Moreover, at PEG/lignin = 1:4 (w/w), the soft segments formed by PEG enhanced the stiffness of the lignin-based polyurethanes; when the PEG content was increased to PEG/lignin = 2:3 (w/w), plastic deformation can be observed for the stress–strain curves of all corresponding lignin-based polyurethanes.« less

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1545197
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Polymer Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 7; Journal ID: ISSN 2637-6105
Publisher:
ACS Publications
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; lignin-based polyurethane; lignin refinery and valorization; nanoparticles; mechanical properties; intermolecular interactions

Citation Formats

Wang, Yun-Yan, Wyman, Charles E., Cai, Charles M., and Ragauskas, Arthur J.. Lignin-Based Polyurethanes from Unmodified Kraft Lignin Fractionated by Sequential Precipitation. United States: N. p., 2019. Web. https://doi.org/10.1021/acsapm.9b00228.
Wang, Yun-Yan, Wyman, Charles E., Cai, Charles M., & Ragauskas, Arthur J.. Lignin-Based Polyurethanes from Unmodified Kraft Lignin Fractionated by Sequential Precipitation. United States. https://doi.org/10.1021/acsapm.9b00228
Wang, Yun-Yan, Wyman, Charles E., Cai, Charles M., and Ragauskas, Arthur J.. Tue . "Lignin-Based Polyurethanes from Unmodified Kraft Lignin Fractionated by Sequential Precipitation". United States. https://doi.org/10.1021/acsapm.9b00228. https://www.osti.gov/servlets/purl/1545197.
@article{osti_1545197,
title = {Lignin-Based Polyurethanes from Unmodified Kraft Lignin Fractionated by Sequential Precipitation},
author = {Wang, Yun-Yan and Wyman, Charles E. and Cai, Charles M. and Ragauskas, Arthur J.},
abstractNote = {In this work, lignin-based polyurethanes were synthesized from three unmodified softwood Kraft lignin fractions as the primary hydroxyl group providers which constituted >40% of the polymeric materials. High-, medium-, and low-molecular-weight Kraft lignin fractions were prepared by sequential precipitation from the acetone–methanol cosolvent by adding hexane as an antisolvent. A polyether, poly(ethylene glycol), and a polyester, poly(trimethylene glutarate), were selected as secondary polyols to form the soft segments in the lignin-based network. At a fixed NCO/OH ratio (1:1), the effects of lignin macromolecular features and their intermolecular interactions with the secondary polyols on mechanical and thermal properties of the lignin-based polyurethanes were investigated by tensile tests, DMA, SEM, and TGA. Because of the unique association behavior of macromolecular lignin, the sequential precipitation method was able to produce Kraft lignin fractions possessing very high molecular weights. The morphological study showed that the polyurethane network was assembled by cross-linking nanosized lignin complexes through urethane links. It was discovered that the mechanical properties of the lignin-based polyurethanes can be tuned by lignin molecular weight and the incorporation of a secondary polyol. Compared to poly(trimethylene glutarate), poly(ethylene glycol) interacts strongly with associated lignin complexes through hydrogen bonding. It promoted dissociation of the lignin complexes and consequently improved reactivity between lignin and diisocyanate. Moreover, at PEG/lignin = 1:4 (w/w), the soft segments formed by PEG enhanced the stiffness of the lignin-based polyurethanes; when the PEG content was increased to PEG/lignin = 2:3 (w/w), plastic deformation can be observed for the stress–strain curves of all corresponding lignin-based polyurethanes.},
doi = {10.1021/acsapm.9b00228},
journal = {ACS Applied Polymer Materials},
number = 7,
volume = 1,
place = {United States},
year = {2019},
month = {6}
}

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    Works referencing / citing this record:

    Effects of some material parameters on lignin biopolymer liquefaction by microwave heating
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