Ether Bond Formation in Waste Biomass–Derived, Value-Added Technical Hardwood Kraft Lignin Using Glycolic Acid
DOI:
https://doi.org/10.6000/1929-5995.2023.12.14Keywords:
Waste black liquor, hardwood kraft lignin, bio-materials, bio-adhesives, eco-friendly products, sustainabilityAbstract
Ether bond formation in technical hardwood kraft lignin (THKL) by crosslinking using glycolic acid was investigated for bio-adhesive applications. Industrial hardwood kraft black liquor was used to extract the THKL utilized by acidification. Chemical and thermal properties of the THKL with and without crosslinking were analyzed by Fourier transform infrared (FTIR) spectroscopy, solid-state 13C cross-polarization/magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). FTIR results revealed a new peak corresponding to the ether bond and hemiacetal formation due to crosslinking at 1075 cm-1 and 1324 cm-1. 13C CP/MAS NMR spectra revealed the presence of a higher number of ether bonds due to the reduced aromatic and aliphatic hydroxyl groups in THKL and new bonds formed at 62-64 ppm and 168-191 ppm due to crosslinking. XPS results revealed that new bonds were formed between glycolic acid and THKL, leading to increased atomic oxygen percentage and carbon–oxygen bonds in crosslinked THKL detected by peak intensity changes at 287.7 and 288.8 related to O–C–O and O–C=O. Also, the oxygen content increased from 14.88% to 31.76% due to bond formation. GPC confirmed a higher molecular weight and broader molecular-weight distribution of THKL. DSC and TGA curves of crosslinked THKL revealed exothermic behavior, high thermal stability, and low thermal degradation rate. Owing to a significant amount of kraft black liquor being generated by wood pulp industries and attractive chemical properties of THKL, THKL demonstrates promise as a raw material to produce green, sustainable bio-adhesives via the crosslinking of its different hydroxyl groups using glycolic acid.
References
Suota MJ, da Silva TA, Zawadzki SF, Sassaki GL, Hansel FA, Paleologou M, Ramos LP. Chemical and Structural Characterization of Hardwood and Softwood Lignoforce™ Lignins. Ind Crops and Prod 2021; 173: 114138. https://doi.org/10.1016/j.indcrop.2021.114138 DOI: https://doi.org/10.1016/j.indcrop.2021.114138
Lawoko M, Samec JSM. Kraft lignin valorization: Biofuels and thermoset materials in focus. Curr Opin Green Sustain Chem 2023; 40: 100738. https://doi.org/10.1016/j.cogsc.2022.100738 DOI: https://doi.org/10.1016/j.cogsc.2022.100738
Giummarella N, Lindén PA, Areskogh D, Lawoko M. Fractional Profiling of Kraft Lignin Structure: Unravelling Insights on Lignin Reaction Mechanisms. ACS Sustain Chem Eng 2020; 8: 1112-1120.
http://dx.doi.org/10.1021/acssuschemeng.9b06027 DOI: https://doi.org/10.1021/acssuschemeng.9b06027
Crestini C, Lange H, Sette M, Argyropoulos DS. On the Structure of Softwood Kraft Lignin. Green Chem 2017; 19: 4104-4121. https://doi.org/10.1039/C7GC01812F DOI: https://doi.org/10.1039/C7GC01812F
Van Nieuwenhove I, Renders T, Lauwaert J, De Roo T, De Clercq J, Verberckmoes A. Biobased Resins Using Lignin and Glyoxal. ACS Sustain Chem Eng 2020; 8: 18789-18809. https://doi.org/10.1021/acssuschemeng.0c07227 DOI: https://doi.org/10.1021/acssuschemeng.0c07227
Zheng L, Tao L, Li Y, Zhang X, Xu Y, Li J, Gao Q. Performance of soybean protein adhesive cross-linked by lignin and cuprum. J Clean Prod 2022; 366: 132906. https://doi.org/10.1016/j.jclepro.2022.132906 DOI: https://doi.org/10.1016/j.jclepro.2022.132906
Ding C, Li N, Chen Z, Zhang Y. Preparation of highly water-resistant wood adhesives using ECH as a crosslinking agent. e-polymers 2022; 22:99-107. https://doi.org/10.1515/epoly-2022-0010 DOI: https://doi.org/10.1515/epoly-2022-0010
De Hoyos-Martínez PL, Robles E, Khoukh A, Charrier-El Bouhtoury F, Labidi J. Formulation of Multifunctional Materials Based on the Reaction of Glyoxalated Lignins and a Nanoclay/Nanosilicate. Biomacromolecules 2019; 20: 3535-3546. https://doi.org/10.1021/acs.biomac.9b00799 DOI: https://doi.org/10.1021/acs.biomac.9b00799
Ammar M, Khiari R, Belgacem MN, Elalou E. Thermal characterization and comparisons of lignin-formaldehyde and lignin-glyoxal adhesives. Mediterr J Chem 2014; 2: 731-737.
http://dx.doi.org/10.13171/mjc.2.6.2014.20.03.11 DOI: https://doi.org/10.13171/mjc.2.6.2014.20.03.11
Roy R, Jadhav B, Rahman MDS, Raynie DE. Characterization of residue from catalytic hydrothermal depolymerization of lignin. CRGSC 2021; 4: 100052. https://doi.org/10.1016/j.crgsc.2020.100052 DOI: https://doi.org/10.1016/j.crgsc.2020.100052
Sequeiros A, Serrano L, Briones R, Labidi L. Lignin Liquefaction Under Microwave Heating. J Appl Polym Sci 2013; 130: 3292-3298. https://doi.org/10.1002/app.39577 DOI: https://doi.org/10.1002/app.39577
Zhang Y, Zhu W, Lu Y, Gao Z, Gu J. Nano-scale blocking mechanism of MMT and its effects on the properties of polyisocyanate-modified soybean protein adhesive. Ind Crops Prod 2014; 57: 35-42. https://doi.org/10.1016/j.indcrop.2014.03.027 DOI: https://doi.org/10.1016/j.indcrop.2014.03.027
Ribca I, Jawerth ME, Brett JC, Lawoko M, Schwartzkopf M, Chumakov A, Roth SV, Johansson M. Exploring the Effects of Different Cross-Linkers on Lignin-Based Thermoset Properties and Morphologies. ACS Sustain Chem Eng 2021; 9: 1692-1702. https://doi.org/10.1021/acssuschemeng.0c07580 DOI: https://doi.org/10.1021/acssuschemeng.0c07580
Navarrete P, Pizzi A, Pasch H, Delmotte L. Study on Lignin-Glyoxal Reaction by MALDI-TOF and CP-MAS13C-NMR. J Adhes Sci Technol 2012; 26: 1069-1082. https://doi.org/10.1163/016942410X550030 DOI: https://doi.org/10.1163/016942410X550030
Wibowo ES, Park BD. The Role of Acetone-Fractionated Kraft Lignin Molecular Structure on Surface Adhesion to Formaldehyde-Based Resins. Int J Biol Macromol 2023; 225: 1449-1461. https://doi.org/10.1016/j.ijbiomac.2022.11.202 DOI: https://doi.org/10.1016/j.ijbiomac.2022.11.202
Lisperguer J, Perez P, Urizar S. Structure and Thermal Properties of Lignins: Characterization by Infrared Spectroscopy and Differential Scanning Calorimetry. J Chil Chem Soc 2009; 54: 460-463.
http://dx.doi.org/10.4067/S0717-97072009000400030 DOI: https://doi.org/10.4067/S0717-97072009000400030
Gordobil O, Egüés I, Llano-Ponte R, Labidi J. Physicochemical Properties of PLA Lignin Blends. Polym Degrad Stab 2014; 108: 330-338. https://doi.org/10.1016/j.polymdegradstab.2014.01.002 DOI: https://doi.org/10.1016/j.polymdegradstab.2014.01.002
Assumpção NRL, Lona LMF. Effect of Lignin without Surface Treatment in In Situ Methyl Methacrylate Miniemulsion Polymerization. ACS Sustain Chem Eng 2022; 10: 3219-3226. https://doi.org/10.1021/acssuschemeng.1c07467 DOI: https://doi.org/10.1021/acssuschemeng.1c07467
Zhen X, Cui X, Al-Haimi AANM, Wang X, Liang H, Xu Z, Wang Z. Fully bio-based epoxy resins from lignin and epoxidized soybean oil: Rigid-flexible, tunable properties and high lignin content. Int J Biol Macromol 2024; 254: 127760. https://doi.org/10.1016/j.ijbiomac.2023.127760 DOI: https://doi.org/10.1016/j.ijbiomac.2023.127760
Khan MA, Ashraf SM. Studies on Thermal Characterization of Lignin Substituted Phenol Formaldehyde Resin as Wood Adhesives. J Therm Anal 2007; 89: 993–1000. https://doi.org/10.1007/s10973-004-6844-4 DOI: https://doi.org/10.1007/s10973-004-6844-4
Downloads
Published
How to Cite
Issue
Section
License
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
Policy for Journals/Articles with Open Access
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work
Policy for Journals / Manuscript with Paid Access
Authors who publish with this journal agree to the following terms:
- Publisher retain copyright .
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work .