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Dual role of lignin in waterborne polymer composites: Reinforcement and stimuli-triggered degradation

Authors

  • Marija Proševa Ss. Cyril and Methodius University in Skopje, Faculty of Technology and Metallurgy, Ruger Boskovic 16 1000 Skopje, R.N.Macedonia https://orcid.org/0000-0003-3966-7120
  • Andrea Petanova Ss. Cyril and Methodius University in Skopje, Faculty of Technology and Metallurgy, Ruger Boskovic 16 1000 Skopje, R.N.Macedonia https://orcid.org/0009-0005-0081-560X
  • Radmila Tomovska POLYMAT and Departamento de Química Aplicada Facultad de Ciencias Químicas University of the Basque Country, Joxe Mari Korta Center - Avda. Tolosa, 72 20018, Donostia-San Sebastian, Spain IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain https://orcid.org/0000-0003-1076-7988
  • Jadranka Blaževska Gilev Ss. Cyril and Methodius University in Skopje, Faculty of Technology and Metallurgy, Ruger Boskovic 16 1000 Skopje, R.N.Macedonia https://orcid.org/0000-0002-0551-7784

DOI:

https://doi.org/10.20450/mjcce.2025.3267

Keywords:

sustainable materials, polymer composites, lignin, UV-triggered degradation

Abstract

Improving the sustainability of polymer composites is a pressing priority, particularly in reducing reliance on fossil-derived components and minimizing environmental impact during synthesis. Lignin, an abundant and renewable natural polymer, offers significant potential as a bio-based additive due to its aromatic structure and intrinsic functionality. Conventional methods for incorporating lignin into polymer matrices often rely on non-sustainable, solvent-based routes, leading to poor dispersion and aggregate formation due to lignin’s incompatibility with polymers. This study presents a more sustainable approach using waterborne, in-situ semicontinuous miniemulsion polymerization to integrate lignin (0.5–1 wt%) into (meth)acrylic matrices. The resulting composite films, formed via water evaporation, exhibited enhanced UV and visible light absorption, improved mechanical strength, particularly at 1 wt% lignin and increased thermal stability even at low loadings. Despite lignin’s hydrophilicity, the composites demonstrated reduced water permeability. UV degradation studies showed that lignin’s chromophoric groups generate free radicals under UV exposure, triggering controlled photodegradation of both lignin and polymer phases. This controlled breakdown combined with the composite’s enhanced structural integrity highlights lignin’s dual function: reinforcing the material under standard conditions while enabling degradation under specific environmental stimuli.

References

(1) Kuan, H. T. N.; Tan, M. Y.; Shen, Y.; Yahya, M. Y. Mechanical properties of particulate organic natural filler-reinforced polymer composite: A review. Composites and Advanced Materials 2021, 30, 1–17. https://doi.org/10.1177/26349833211007502.

(2) Ridho, M. R.; Agustiany, E. A.; Rahmi, D. n. M.; Madyaratri, E. W.; Ghozali, M.; Restu, W. K.; Falah, F.; Rahandi Lubis, M. A.; Syamani, F. A.; Nurhamiyah, Y.; Hidayati, S.; Sohail, A.; Karungamye, P.; Nawawi, D. S.; Iswanto, A. H.; Othman, N.; Mohamad Aini, N. A.; Hussin, M. H.; Sahakaro, K.; Hayeemasae, N.; Ali, M. Q.; Fatriasari, W. Lignin as Green Filler in Polymer Composites: Development Methods, Characteristics, and Potential Applications. Advances in Materials Science and Engineering 2022, 2022, 1–33. https://doi.org/10.1155/2022/1363481.

(3) Sztorch, B.; Brząkalski, D.; Pakuła, D.; Frydrych, M.; Špitalský, Z.; Przekop, R. E. Natural and Synthetic Polymer Fillers for Applications in 3D Printing—FDM Technology Area. Solids 2022, 3 (3), 508–548. https://doi.org/10.3390/solids3030034.

(4) Ramesh, M.; Rajeshkumar, L.; Srinivasan, N.; Kumar, D.; Balaji, D. Influence of filler material on properties of fiber-reinforced polymer composites: A review. e-Polymers 2022, 22, 898–916. https://doi.org/10.1515/epoly-2022-0080.

(5) Gaspar, R.; Fardim, P. Lignin-based materials for emerging advanced applications. Current Opinion in Green and Sustainable Chemistry 2023, 41, 100834. https://doi.org/10.1016/j.cogsc.2023.100834.

(6) Fabbri, F.; Bischof, S.; Mayr, S.; Gritsch, S.; Jimenez Bartolome, M.; Schwaiger, N.; Guebitz, G. M.; Weiss, R. The Biomodified Lignin Platform: A Review. Polymers 2023, 15 (17), 1694. https://doi.org/10.3390/polym15071694.

(7) Horizon Databook. Lignin Market Size, Share & Trend Analysis Report By Product (Lignosulfonates, Kraft Lignin, Organosolv Lignin, Others), By Application, By Region, And Segment Forecasts 2024 – 2030. Report ID: 978-1-68038-422-2.

(8) Liao, J. J.; Latif, N. H. A.; Trache, D.; Brosse, N.; Hussin, M. H. Current advancement on the isolation, characterization and application of lignin. Int. J. Biol. Macromol. 2020, 162, 985–1024. https://doi.org/10.1016/j.ijbiomac.2020.06.168.

(9) Zhang, Y.; Naebe, M. Lignin: A Review on Structure, Properties, and Applications as a Light-Colored UV Absorber. ACS Sustainable Chem. Eng. 2021, 9 (4), 1427–1442. https://doi.org/10.1021/acssuschemeng.0c06998.

(10) Sadeghifar, H.; Ragauskas, A. Lignin as a UV Light Blocker—A Review. Polymers 2020, 12 (5), 1134. https://doi.org/10.3390/polym12051134.

(11) Jędrzejczak, P.; Collins, M. N.; Jesionowski, T.; Klapiszewski, L. The role of lignin and lignin-based materials in sustainable construction – A comprehensive review. Int. J. Biol. Macromol. 2021, 187, 624–650. https://doi.org/10.1016/j.ijbiomac.2021.07.125.

(12) Gadioli, R.; Morais, J. A.; Waldman, W. R.; De Paoli, M.-A. The role of lignin in polypropylene composites with semi-bleached cellulose fibers: Mechanical properties and its activity as antioxidant. Polymer Degradation and Stability 2014, 108, 23–34. https://doi.org/10.1016/j.polymdegradstab.2014.06.005.

(13) Gadioli, R.; Waldman, W. R.; De Paoli, M.-A. Lignin as a green primary antioxidant for polypropylene. J. Appl. Polym. Sci. 2016, 133 (45), 43558. https://doi.org/10.1002/app.43558.

(14) Avelino, F.; de Oliveira, D. R.; Mazzetto, S. E.; Lomonaco, D. Poly(methyl methacrylate) films reinforced with coconut shell lignin fractions to enhance their UV-blocking, antioxidant and thermo-mechanical properties. Int. J. Biol. Macromol. 2019, 125, 171–180. https://doi.org/10.1016/j.ijbiomac.2018.12.043.

(15) Huang, W.; Wu, M.; Liu, W.; Hua, Z.; Wang, Z.; Zhou, L. Value-adding of organosolv lignin: Designing mechanically robust UV-resistant polymeric glass via ARGET ATR. Applied Surface Science 2019, 475, 302–311. https://doi.org/10.1016/j.apsusc.2018.12.266.

(16) Yang, W.; Rallini, M.; Wang, D.-Y.; Gao, D.; Dominici, F.; Torre, L.; Kenny, J. M.; Puglia, D. Role of lignin nanoparticles in UV resistance, thermal and mechanical performance of PMMA nanocomposites prepared by a combined free-radical graft polymerization/masterbatch procedure. Composites: Part A 2018, 107, 61–69. https://doi.org/10.1016/j.compositesa.2017.12.030.

(17) Hararak, B.; Wanmolee, W.; Wijaranakul, P.; Prakymoramas, N.; Winotapun, C.; Kraithong, W.; Nakason, K. Physicochemical properties of lignin nanoparticles from softwood and their potential application in sustainable pre-harvest bagging as transparent UV-shielding films. Int. J. Biol. Macromol. 2023, 229, 575–588. https://doi.org/10.1016/j.ijbiomac.2022.12.270.

(18) Xin, Q.; Li, H.; Sun, W.; Li, X.; Lu, X.; Zhao, J. Lignin-xylan nanospheres prepared by green and quick method from lignocellulose and used as additive in PVA films. Int. J. Biol. Macromol. 2024, 164, 129762. https://doi.org/10.1016/j.ijbiomac.2024.129762.

(19) Fan, D.; Chen, J.; Kong, M.; Lv, Y.; Huang, Y.; Li, G. Valorization of enzymatic hydrolysis lignin for the multifunctional stabilization of polypropylene. Ind. Crops Prod. 2022, 187, 115443. https://doi.org/10.1016/j.indcrop.2022.115443.

(20) Yang, H.; Yu, B.; Xu, H.; Bourbigot, S.; Wang, H.; Song, P. Lignin-derived Bio-based Flame Retardants toward High-Performance Sustainable Polymeric Materials. Green Chem. 2020, 22 (7), 2129–2161. https://doi.org/10.1039/D0GC00449A.

(21) Mandlekar, N.; Cayla, A.; Rault, F.; Giraud, S.; Salaün, F.; Malucelli, G.; Guan, J.-P. An Overview on the Use of Lignin and Its Derivatives in Fire Retardant Polymer Systems, in: M. Poletto (Ed.), Lignin - Trends and Applications, InTech. 2018. Available at: http://dx.doi.org/10.5772/intechopen.72963.

(22) Chollet, B.; Lopez-Cuesta, J.-M.; Laoutid, F.; Ferry, L. Lignin Nanoparticles as A Promising Way for Enhancing Lignin Flame Retardant Effect in Polylactide. Materials 2019, 12 (13), 2132. https://doi.org/10.3390/ma12132132.

(23) Zhang, S.; Meng, X.; Bhagia, S.; Ji, A.; Dean Smith, M.; Wang, Y.-Y.; Liu, B.; Yoo, C. G.; Harper, D. P.; Ragauskas, A. J. 3D printed lignin/polymer composite with enhanced mechanical and anti-thermal-aging performance. Chem. Eng. J. 2024, 481, 148449. https://doi.org/10.1016/j.cej.2023.148449.

(24) Podkościelna, B.; Wnuczek, K.; Goliszek, M.; Klepka, T.; Dziuba, K. Flammability Tests and Investigations of Properties of Lignin-Containing Polymer Composites Based on Acrylates. Molecules 2020, 25 (24), 5947. https://doi.org/10.3390/molecules25245947.

(25) Klapiszewski, L.; Podkościelna, B.; Goliszek, M.; Kubiak, A.; Młynarczyk, K.; Jesionowski, T. Synthesis, characterization and aging tests of functional rigid polymeric biocomposites with kraft lignin. Int. J. Biol. Macromol. 2021, 178, 344–353. https://doi.org/10.1016/j.ijbiomac.2021.02.193.

(26) Domínguez-Robles, J.; Larrañeta, E.; Fong, M. L.; Martin, N. K.; Irwin, N. J.; Mutjé, P.; Tarrés, Q.; Delgado-Aguilar, M. Lignin/poly(butylene succinate) composites with antioxidant and antibacterial properties for potential biomedical applications. Int. J. Biol. Macromol. 2020, 145, 92–99. https://doi.org/10.1016/j.ijbiomac.2019.12.146.

(27) Buzarovska, A.; Blazevska-Gilev, J.; Perez-Martnez, B. T.; Balahura, L. R.; Gradisteanu Pircalabioru, G.; Dinescu, S.; Costache, M. Poly(l-lactic acid)/alkali lignin composites: properties, biocompatibility, cytotoxicity and antimicrobial behavior. J. Mater. Sci. 2021, 56, 13785–13800. https://doi.org/10.1007/s10853-021-06185-6.

(28) Xu, C.; Liu, L.; Renneckar, S.; Jiang, F. Chemically and physically crosslinked lignin hydrogels with antifouling and antimicrobial properties. Ind. Crops Prod. 2021, 170, 113759. https://doi.org/10.1016/j.indcrop.2021.113759.

(29) Jiang, C.; Wang, X.; Qin, D.; Da, W.; Hou, B.; Hao, C.; Wu, J. Construction of magnetic lignin-based adsorbent and its adsorption properties for dyes. J. Hazard. Mater. 2019, 369, 50–61. https://doi.org/10.1016/j.jhazmat.2019.02.021.

(30) Şimşek, S. Adsorption properties of lignin containing bentonite–polyacrylamide composite for ions. Desalination and Water Treatment 2016, 57 (50), 23790–23799. https://doi.org/10.1080/19443994.2015.1135478.

(31) Meng, X.; Scheidemantle, B.; Li, M.; Wang, Y.; Zhao, X.; Toro-González, M.; Singh, P.; Pu, Y.; Wyman, C. E.; Ozcan, S.; Cai, C. M.; Ragauskas, A. J. Synthesis, Characterization, and Utilization of a Lignin-Based Adsorbent for Effective Removal of Azo Dye from Aqueous Solution. ACS Omega 2020, 5 (6), 2865–2877. https://doi.org/10.1021/acsomega.9b03717.

(32) Kayan, G. O.; Kayan, A. Composite of Natural Polymers and Their Adsorbent Properties on the Dyes and Heavy Metal Ions. J. Polym. Environ. 2021, 39, 3477–3496. http://dx.doi.org/10.1007/s10924-021-02154-x.

(33) Aldajani, M.; Alipoormazandarani, N.; Kong, F.; Fatehi, P. Acid hydrolysis of kraft lignin-acrylamide polymer to improve its flocculation affinity. Sep. Purif. Technol. 2021, 258, 117964. http://dx.doi.org/10.1016/j.seppur.2020.117964.

(34) Hu, C.; Zhao, M.; Li, Q.; Liu, Z.; Hao, N.; Meng, X.; Li, J.; Lin, F.; Li, C.; Fang, L.; Dai, S. Y.; Ragauskas, A. J.; Sue, H. J.; Yuan, J. S. Phototunable Lignin Plastics to Enable Recyclability. ChemSusChem 2021, 14 (19), 4260–4269. https://doi.org/10.1002/cssc.202101040.

(35) Chaochanchaikul, K.; Jayaraman, K.; Rosarpitak, V.; Sombatsompop, N. Influence of lignin content on photodegradation in wood/HDPE composites under UV weathering. BioResources 2012, 7 (1), 38–55. http://dx.doi.org/10.15376/biores.7.1.38-55.

(36) Goliszek, M.; Podkościelna, B.; Sevastyanova, O.; Fila, K.; Chabros, A.; Pączkowski, P. Investigation of accelerated aging of lignin-containing polymer materials. Int. J. Biol. Macromol. 2019, 123, 910–922. https://doi.org/10.1016/j.ijbiomac.2018.11.141.

(37) Tang, Y.; Ye, Z.; Jean, M. Influence of lignin accessibility on chemical and biological decomposition of lignin/polyethylene composite thermoplastics. Can. J. Chem. Eng. 2020, 98 (1), 104–118. https://doi.org/10.1002/cjce.23623.

(38) Prosheva, M.; Ehsani, M.; Joseph, Y.; Tomovska, R.; Blazhevska Gilev, J. Waterborne polymer composites containing hybrid graphene/carbon nanotube filler: Effect of graphene type on properties and performance. Polymer Composites 2023, 44 (8), 5188–5200. https://doi.org/10.1002/pc.27483.

(39) Prosheva, M.; Aboudzadeh, M. A.; Leal, G. P.; Blazevska Gilev, J.; Tomovska, R. High-performance UV protective waterborne polymer coatings based on hybrid graphene/carbon nanotube radicals scavenging filler. Part. Part. Syst. Charact. 2019, 36 (7), 1800555. https://doi.org/10.1002/ppsc.201800555.

(40) Moreno, A.; Morsali, M.; Liu, J.; Sipponen, M. H. Access to tough and transparent nanocomposites via Pickering emulsion polymerization using biocatalytic hybrid lignin nanoparticles as functional surfactants. Green Chem. 2021, 23 (8), 3001–3014. https://doi.org/10.1039/D1GC00103E.

(41) Faucheu, J.; Gauthier, C.; Chazeau, L.; Cavaillé, J.; Mellon, V.; Lami, E. B. Miniemulsion polymerization for synthesis of structured clay/polymer nanocomposites: Short review and recent advances. Polymer 2009, 51 (1), 6–17. https://doi.org/10.1016/j.polymer.2009.11.044.

(42) El-Aasser, M. S.; Sudol, E. D. Miniemulsions: Overview of Research and Applications. JCT Research 2004, 1 (1), 20–31.

(43) Assumpção, N. R. L.; Lona, L. M. F. Effect of Lignin without Surface Treatment in In Situ Methyl Methacrylate Miniemulsion Polymerization. ACS Sustainable Chem. Eng. 2022, 10 (10), 3219–3226. https://doi.org/10.1021/acssuschemeng.1c07467.

(44) Messmer, N. R.; Guerrini, L. M.; Oliveira, M. P. Effect of unmodified kraft lignin concentration on the emulsion and miniemulsion copolymerization of styrene with n-butyl acrylate and methacrylic acid to produce polymer hybrid latex. Polym. Adv. Technol. 2018, 29 (3), 1094–1106. https://doi.org/10.1002/pat.4221.

(45) Prosheva, M.; Ozmen-Monkul, B.; Gumus, G.; Taskin, D. K.; Trajcheva, A.; Blazevska-Gilev, J.; Tomovska, R. Waterborne advanced optical coatings based on polymer composite with hybrid graphene-metal phthalocyanine nanofiller. Prog. Org. Coat. 2025, 204, 109260. https://doi.org/10.1016/j.porgcoat.2025.109260.

(46) Tham, W. L.; Poh, B. T.; Mohd Ishak, Z. A.; Chow, W. S. Characterisation of Water Absorption of Biodegradable Poly(lactic Acid)/Halloysite Nanotube Nanocomposites at Different Temperatures. J. Eng. Sci. 2016, 12, 13–25.

(47) Argaiz, M.; Aguirre, M.; Tomovska, R. Strategies towards improved performance of waterborne coatings through multiplying the ionic interparticle interactions. Prog. Org. Coat. 2023, 183, 107731. https://doi.org/10.1016/j.porgcoat.2023.107731.

(48) Chen, K.; Dong, W.; Huang, Y.; Wang, F.; Zhou, J. L.; Li, W. Photocatalysis for sustainable energy and environmental protection: A review on advanced surface engineering strategies and emerging synthesis methods. J. Environ. Chem. Eng. 2025, 13, 117529. https://doi.org/10.1016/j.jece.2025.117529.

(49) Rozman, H.; Tan, K.; Kumar, R.; Abubakar, A.; Ishak, Z. M.; Ismail, H. The effect of lignin as a compatibilizer on the physical properties of coconut fiber–polypropylene composites. Eur. Polym. J. 2000, 36 (7), 1483–1494. https://doi.org/10.1016/s0014-3057(99)00200-1.

(50) Sameni, J.; Jaffer, S. A.; Sain, M. Thermal and mechanical properties of soda lignin/HDPE blends. Compos. Part A Appl. Sci. Manuf. 2018, 115, 104–111. https://doi.org/10.1016/j.compositesa.2018.09.016.

(51) Thielemans, W.; Wool, R. P. Butyrated kraft lignin as compatibilizing agent for natural fiber reinforced thermoset composites. Compos. Part A Appl. Sci. Manuf. 2004, 35 (3), 327–338. https://doi.org/10.1016/j.compositesa.2003.09.011.

(52) Bilgina, S.; Tomovska, R.; Asua, J. M. Effect of ionic monomer concentration on latex and film properties for surfactant-free high solids content polymer dispersions. Eur. Polym. J. 2017, 93, 480–494. http://dx.doi.org/10.1016/j.eurpolymj.2017.06.029.

(53) Mandlekar, N.; Cayla, A.; Rault, F.; Giraud, S.; Salaün, F.; Malucelli, G.; Guan, J. Thermal Stability and Fire Retardant Properties of Polyamide 11 Microcomposites Containing Different Lignins. Ind. Eng. Chem. Res. 2017, 56 (46), 13704–13714. https://doi.org/10.1021/acs.iecr.7b03085.

(54) Soygun, K.; Şimşek, S.; Yılmaz, E.; Bolayır, G. Investigation of Mechanical and Structural Properties of Blend Lignin-PMMA. Adv. Mater. Sci. Eng. 2013, 2013, 435260. http://dx.doi.org/10.1155/2013/435260.

(55) Park, C.-W.; Youe, W.-J.; Kim, S.-J.; Han, S.-Y.; Park, J.-S.; Lee, E.-A.; Kwon, G.-J.; Kim, Y.-S.; Kim, N.-H.; Lee, S.-H. Effect of Lignin Plasticization on Physico-Mechanical Properties of Lignin/Poly(Lactic Acid) Composites. Polymers 2019, 11 (12), 2089. https://doi.org/10.3390/polym11122089.

(56) Nikafshar, S.; Nejad, M. Evaluating efficacy of different UV-stabilizers/absorbers in reducing UV-degradation of lignin. Holzforschung 2022, 76 (3), 235–244. https://doi.org/10.1515/hf-2021-0147.

(57) Cogulet, A.; Blanchet, P.; Landry, V. Wood degradation under UV irradiation: A lignin characterization. J. Photochem. Photobiol. B 2016, 158, 184–191. https://doi.org/10.1016/j.jphotobiol.2016.02.030.

(58) Kaczmarek, H.; Kamińska, A.; van Herk, A. Photooxidative degradation of poly(alkyl methacrylate)s. Eur. Polym. J. 2000, 36 (4), 767–777. https://doi.org/10.1016/S0014-3057(99)00125-1.

(59) Vu, T.; Chaffee, A.; Yarovsky, I. Investigation of Lignin-water interactions by molecular simulation. Mol. Simul. 2002, 28 (10–11), 981–991. https://doi.org/10.1080/089270204000002610.

(60) Shankar, S.; Reddy, J. P.; Rhim, J. Effect of lignin on water vapor barrier, mechanical, and structural properties of agar/lignin composite films. Int. J. Biol. Macromol. 2015, 81, 267–273. https://doi.org/10.1016/j.ijbiomac.2015.08.015.

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2025-12-12 — Updated on 2025-12-12

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Proševa, M., Petanova, A. ., Tomovska, R., & Blaževska Gilev, J. . (2025). Dual role of lignin in waterborne polymer composites: Reinforcement and stimuli-triggered degradation. Macedonian Journal of Chemistry and Chemical Engineering, 44(2). https://doi.org/10.20450/mjcce.2025.3267

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Vol. 44 No. 2 (2025)

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Materials Engineering

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Copyright (c) 2025 Marija Proševa, Andrea Petanova, Radmila Tomovska, Jadranka Blaževska Gilev

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