Skip to main content
Article
Licensed
Unlicensed Requires Authentication

Reaction mechanisms of furfuryl alcohol polymer with wood cell wall components

  • , , , , EMAIL logo and EMAIL logo
Published/Copyright: August 2, 2021
Holzforschung
From the journal Holzforschung Volume 75 Issue 12

Abstract

Wood properties of furfurylation can be altered by reaction mechanisms of furfuryl alcohol polymer (PFA) and cell walls. Although chemical reactions between PFA and lignin have been studied, reaction mechanisms between PFA and cell wall components, including lignin, cellulose and hemicellulose are still not comprehensively understood. In order to elucidate chemical reactions regarding PFA with wood cell walls, model compounds of main cell wall components were used to investigate its reactions with PFA by 13C NMR spectroscopy and differential scanning calorimetry (DSC). Results showed that there was no chemical bonding of PFA with either cellulose or hemicellulose. Condensations of uncrowded ring positions (meta, ortho and para) and side chains (α–C, β–C, β–OH, and γ–OH) of lignin with PFA did occur based on 13C NMR spectra. Reaction enthalpy and activation energy also confirmed the condensation reactions between lignin and PFA. This study could provide design guidelines to control the chemical reactions of PFA in cell walls and lignin and, therefore, improve the properties of furfurylated wood.

Keywords: cellulose; chemical reaction; furfurylation; hemicellulose; lignin; wood cell walls
Corresponding authors: Sheng Yang and Fuxiang Chu, Research Institute of Wood Industry, Chinese Academy of Forestry, Xiangshan Road, Haidian District, Beijing 100091, China, E-mail: ,

Funding source: National Key Research and Development Program of China

Award Identifier / Grant number: 2017YFD0600202

Funding source: National Key Research and Development Program of China

Award Identifier / Grant number: 2017YFD0600203

  1. Author contributions: X. S. and S. Y. designed the experiment. X. S. and P. J. performed experiments and analyzed data. All authors contributed to the writing and review of manuscript. All authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was financially supported by the National Key Research and Development Program of China (2017YFD0600202) and National Key Research and Development Program of China (2017YFD0600203).

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

References

Barsberg, S. and Thygesen, L.G. (2009). Poly (furfuryl alcohol) formation in neat furfuryl alcohol and in cymene studied by ATR-IR spectroscopy and density functional theory (B3LYP) prediction of vibrational bands. Vib. Spectrosc 49: 52–63, https://doi.org/10.1016/j.vibspec.2008.04.013.Search in Google Scholar

Barsberg, S.T. and Thygesen, L.G. (2017). A combined theoretical and FT-IR spectroscopy study of a hybrid poly (furfuryl alcohol)-lignin material: basic chemistry of a sustainable wood protection method. ChemistrySelect 2: 10818–10827, https://doi.org/10.1002/slct.201702104.Search in Google Scholar

Baysal, E., Ozaki, S.K., and Yalinkilic, M.K. (2004). Dimensional stabilization of wood treated with furfuryl alcohol catalysed by borates. Wood Sci. Technol. 38: 405–415, https://doi.org/10.1007/s00226-004-0248-2.Search in Google Scholar

Beck, G., Strohbusch, S., Larnøy, E., Militz, H., and Hill, C. (2017). Accessibility of hydroxyl groups in anhydride modified wood as measured by deuterium exchange and saponification. Holzforschung 72: 17–23, https://doi.org/10.1515/hf-2017-0059.Search in Google Scholar

Chen, C., Kuang, Y., Zhu, S., Burgert, I., Keplinger, T., Gong, A., Li, T., Berglund, L., Eichhorn, S.J., and Liangbing Hu, L. (2020). Structure-property-function relationships of natural and engineered wood. Nat. Rev. Mater. 5: 1–25, https://doi.org/10.1038/s41578-020-0195-z.Search in Google Scholar

Choura, M., Belgacem, N.M., and Gandini, A.J.M. (1996). Acid-catalyzed polycondensation of furfuryl alcohol: mechanisms of chromophore formation and cross-linking. Macromolecules 29: 3839–3850, https://doi.org/10.1021/ma951522f.Search in Google Scholar

Devi, R.R., Ali, I., and Maji, T. (2003). Chemical modification of rubber wood with styrene in combination with a crosslinker: effect on dimensional stability and strength property. Bioresour. Technol. 88: 185–188, https://doi.org/10.1016/s0960-8524(03)00003-8.Search in Google Scholar

Domínguez, J.C., Grivel, J.C., and Madsen, B. (2012). Study on the non-isothermal curing kinetics of a polyfurfuryl alcohol bioresin by DSC using different amounts of catalyst. Thermochim. Acta 529: 29–35, https://doi.org/10.1016/j.tca.2011.11.018.Search in Google Scholar

Dong, C., Zhang, S., Wang, J., and Chui, Y.H. (2020). Static bending creep properties of furfurylated poplar wood. Construct. Build. Mater. 269: 1–10, https://doi.org/10.1016/j.conbuildmat.2020.121308.Search in Google Scholar

Ehmcke, G., Pilgård, A., Koch, G., and Richter, K. (2017). Topochemical analyses of furfuryl alcohol-modified radiata pine (Pinus radiata) by UMSP, light microscopy and SEM. Holzforschung 71: 821–831, https://doi.org/10.1515/hf-2016-0219.Search in Google Scholar

Emmerich, L., Bollmus, S., and Militz, H. (2019). Wood modification with DMDHEU (1.3-dimethylol-4.5-dihydroxyethyleneurea)-state of the art, recent research activities and future perspectives. Wood Mater. Sci. Eng. 14: 3–18, https://doi.org/10.1080/17480272.2017.1417907.Search in Google Scholar

Eranna, P.B. and Pandey, K.K. (2012). Solvent-free chemical modification of wood by acetic and butyric anhydride with iodine as catalyst. Holzforschung 66: 967–971, https://doi.org/10.1515/hf-2011-0223.Search in Google Scholar

Falco, G., Guigo, N., Vincent, L., and Sbirrazzuoli, N. (2018). FA polymerization disruption by protic polar solvents. Polymers 10: 1–12, https://doi.org/10.3390/polym10050529.Search in Google Scholar PubMed PubMed Central

Ferdosian, F., Yuan, Z., Anderson, M., and Xu, C.C. (2015). Sustainable lignin-based epoxy resins cured with aromatic and aliphatic amine curing agents: curing kinetics and thermal properties. Thermochim. Acta 618: 48–55, https://doi.org/10.1016/j.tca.2015.09.012.Search in Google Scholar

Frihart, C.R., Hunt, C.G., and Moon, R.J. (Eds.) (2009). International conference of wood adhesives proceedings, September 28–30, 2009: characterizing polymeric methylene diphenyl diisocyanate reactions with wood: 2. Nano-Indentation. For. Prod. Soc., Wisconsin.Search in Google Scholar

Gobakken, L.R. and Westin, M. (2008). Surface mould growth on five modified wood substrates coated with three different coating systems when exposed outdoors. Int. Biodeterior. Biodegrad. 62: 397–402, https://doi.org/10.1016/j.ibiod.2008.03.004.Search in Google Scholar

Guigo, N., Mija, A., Vincent, L., and Sbirrazzuoli, N. (2007). Chemorheological analysis and model-free kinetics of acid catalysed furfuryl alcohol polymerization. Phys. Chem. Chem. Phys. 9: 5359–5366, https://doi.org/10.1039/b707950h.Search in Google Scholar PubMed

Hadi, Y.S., Herliyana, E.N., Mulyosari, D., Abdillah, I.B., Pari, R., and Hiziroglu, S. (2020). Termite resistance of furfuryl alcohol and imidacloprid treated fast-growing tropical wood species as function of field test. Appl. Sci. 10: 6101, https://doi.org/10.3390/app10176101.Search in Google Scholar

He, G. and Riedl, B. (2004). Curing kinetics of phenol formaldehyde resin and wood-resin interactions in the presence of wood substrates. Wood Sci. Technol. 38: 69–81.10.1007/s00226-003-0221-5Search in Google Scholar

He, G., Riedl, B., and Aït-Kadi, A. (2003a). Model-free kinetics: curing behavior of phenol formaldehyde resins by differential scanning calorimetry. J. Appl. Polym. Sci. 87: 433–440, https://doi.org/10.1002/app.11378.Search in Google Scholar

He, G., Riedl, B., and Aït-Kadi, A. (2003b). Curing process of powdered phenol-formaldehyde resol resins and the role of water in the curing systems. J. Appl. Polym. Sci. 89: 1371–1378, https://doi.org/10.1002/app.12417.Search in Google Scholar

Hill, C.A.S. (2006). Wood modification: chemical, thermal and other processes. John Wiley & Sons, Chichester, England.10.1002/0470021748Search in Google Scholar

Hill, C.A.S. and Jones, D. (1996). The dimensional stabilisation of Corsican pine sapwood by reaction with carboxylic acid anhydrides. Holzforschung 50: 457–462, https://doi.org/10.1515/hfsg.1996.50.5.457.Search in Google Scholar

Himmel, S. and Carsten, M. (2015). Effects of acetylation and formalization on the dynamic water vapor sorption behavior of wood. Holzforschung 69: 633–643, https://doi.org/10.1515/hf-2014-0161.Search in Google Scholar

Hosseinpourpia, R., Stergios, A., and Carsten, M. (2016). Dynamic vapour sorption of wood and holocellulose modified with thermosetting resins. Wood Sci. Technol. 50: 165–178, https://doi.org/10.1007/s00226-015-0765-1.Search in Google Scholar

Hughes, M., Hill, C., and Pfriem, A. (2015). The toughness of hygrothermally modified wood-a review. Holzforschung 69: 851–862, https://doi.org/10.1515/hf-2014-0184.Search in Google Scholar

Inoue, M., Norimoto, M., Tanahashi, M., and Rowell, R.M. (1993). Steam or heat fixation of compressed wood. Wood Fiber Sci. 25: 224–235.Search in Google Scholar

Jakes, J.E., Hunt, C.G., Yelle, D.J., Lorenz, L., Hirth, K., Gleber, S.C., Vogt, S., Grigsby, W., and Frihart, C.R. (2015). Synchrotron-based X-ray fluorescence microscopy in conjunction with nanoindentation to study molecular-scale interactions of phenol-formaldehyde in wood cell walls. ACS Appl. Mater. Interfaces 7: 6584–6589, https://doi.org/10.1021/am5087598.Search in Google Scholar PubMed

Jiang, Q. and Singamaneni, S. (2017). Water from wood: pouring through pores. Joule 1: 429–430, https://doi.org/10.1016/j.joule.2017.10.018.Search in Google Scholar

Kong, L., Guan, H., and Wang, X. (2018). In situ polymerization of furfuryl alcohol with ammonium dihydrogen phosphate in poplar wood for improved dimensional stability and flame retardancy. ACS Sustain. Chem. Eng. 6: 3349–3357, https://doi.org/10.1021/acssuschemeng.7b03518.Search in Google Scholar

Lande, S., Eikenes, M., and Westin, M. (2004a). Chemistry and ecotoxicology of furfurylated wood. Scand. J. For. Res. 19: 14–21, https://doi.org/10.1080/02827580410017816.Search in Google Scholar

Lande, S., Westin, M., and Schneider, M. (2004b). Eco-efficient wood protection: furfurylated wood as alternative to traditional wood preservation. Manag. Environ. Qual. Int. J. 15: 529–540, https://doi.org/10.1108/14777830410553979.Search in Google Scholar

Lande, S., Westin, M., and Schneider, M. (2004c). Properties of furfurylated wood. Scand. J. For. Res. 19: 22–30, https://doi.org/10.1080/0282758041001915.Search in Google Scholar

Machado, G., Leon, S., Santos, F., Lourega, R., Dullius, J., Mollmann, M.E., and Eichler, P. (2016). Literature review on furfural production from lignocellulosic biomass. Nat. Resour. 7: 115–129, https://doi.org/10.4236/nr.2016.73012.Search in Google Scholar

Mantanis, G.I., Young, R.A., and Rowell, R.M. (1994). Swelling of wood. Wood Sci. Technol. 28: 119–134, https://doi.org/10.1007/bf00192691.Search in Google Scholar

Moghaddam, M.S., Van den Bulcke, J., Wålinder, M.E., Claesson, P.M., Van Acker, J., and Swerin, A. (2017). Microstructure of chemically modified wood using X-ray computed tomography in relation to wetting properties. Holzforschung 71: 119–128, https://doi.org/10.1515/hf-2015-0227.Search in Google Scholar

Nordstierna, L., Lande, S., Westin, M., Karlsson, O., and Furo, I. (2008). Towards novel wood-based materials: chemical bonds between lignin-like model molecules and poly (furfuryl alcohol) studied by NMR. Holzforschung 62: 709–713, https://doi.org/10.1515/hf.2008.110.Search in Google Scholar

Norimoto, M. and Gril, J. (1993). Structure and properties of chemically treated woods. In: Shiraishi, N., Kajita, H., and Norimoto, M. (Eds.), Recent research on wood and wood-based materials. Elsevier, Barking, UK, pp. 135–154.10.1016/B978-1-4831-7821-9.50019-8Search in Google Scholar

Norimoto, M., Gril, J., and Rowell, R.M. (1992). Rheological properties of chemically modified wood: relationship between dimensional and creep stability. Wood Fiber Sci. 24: 25–35.Search in Google Scholar

Ozawa, T. (1992). Estimation of activation energy by isoconversion methods. Thermochim. Acta 203: 159–165, https://doi.org/10.1016/0040-6031(92)85192-x.Search in Google Scholar

Ralph, S.A., Ralph, J., and Landucci, L. (2004). NMR database of lignin and cell wall model compounds, Available at: <https://www.glbrc.org/databases_and_software/nmrdatabase/NMR_DataBase_2009_Complete.pdf>.10.1201/EBK1574444865-c5Search in Google Scholar

Rowell, R.M. and Dickerson, J.P. (2014). Acetylation of wood. In: Schultz, T., Goodell, B., and Nicholas, D. (Eds.), Deterioration and protection of sustainable biomaterials. ACS Symposium Series 1158. American Chemical Society, Washington, DC, USA, pp. 301–327.10.1021/bk-2014-1158.ch018Search in Google Scholar

Sejati, P.S., Imbert, A., Gérardin-Charbonnier, C., Dumarçay, S., Fredon, E., Masson, E., Nandika, D., Priadi, T., and Gérardin, P. (2017). Tartaric acid catalyzed furfurylation of beech wood. Wood Sci. Technol. 51: 379–394, https://doi.org/10.1007/s00226-016-0871-8.Search in Google Scholar

Shen, X., Jiang, P., Guo, D., Li, G., Chu, F., and Yang, S. (2021). Effect of furfurylation on hierarchical porous structure of poplar wood. Polymers 13: 1–9.10.3390/polym13010032Search in Google Scholar PubMed PubMed Central

Shen, X., Zou, X., Li, G., Wang, X., and Liu, J. (2019). Modified poplar wood with the mixture of prepolymer and monomer of furfuryl alcohol. Sci. Silvae Sin. 55: 197–204.Search in Google Scholar

Thygesen, L.G., Barsberg, S., and Venås, T.M. (2010). The fluorescence characteristics of furfurylated wood studied by fluorescence spectroscopy and confocal laser scanning microscopy. Wood Sci. Technol. 44: 51–65, https://doi.org/10.1007/s00226-009-0255-4.Search in Google Scholar

Tu, K., Wang, X., Kong, L., and Guan, H. (2018). Facile preparation of mechanically durable, self-healing and multifunctional superhydrophobic surfaces on solid wood. Mater. Des. 140: 30–36, https://doi.org/10.1016/j.matdes.2017.11.029.Search in Google Scholar

Wen, J.L., Sun, S.L., Xue, B.L., and Sun, R.C. (2013). Recent advances in characterization of lignin polymer by solution-state nuclear magnetic resonance (NMR) methodology. Materials 6: 359–391, https://doi.org/10.3390/ma6010359.Search in Google Scholar PubMed PubMed Central

Westin, M., Rapp, A., and Nilsson, T. (2006). Field test of resistance of modified wood to marine borers. Wood Mater. Sci. Eng. 1: 34–38, https://doi.org/10.1080/17480270600686978.Search in Google Scholar

Xie, Y., Fu, Q., Wang, Q., Xiao, Z., and Militz, H. (2013). Effects of chemical modification on the mechanical properties of wood. Eur. J. Wood Wood Prod. 71: 401–416, https://doi.org/10.1007/s00107-013-0693-4.Search in Google Scholar

Yang, H., Yan, R., Chen, H., Lee, D.H., and Zheng, C.J.F. (2007). Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel 86: 1781–1788, https://doi.org/10.1016/j.fuel.2006.12.013.Search in Google Scholar

Yang, T., Cao, J., and Ma, E. (2019). How does delignification influence the furfurylation of wood? Ind. Crop. Prod. 135: 91–98, https://doi.org/10.1016/j.indcrop.2019.04.019.Search in Google Scholar

Yao, M., Yang, Y., Song, J., Yu, Y., and Jin, Y. (2017). Lignin-based catalysts for Chinese fir furfurylation to improve dimensional stability and mechanical properties. Ind. Crop. Prod. 107: 38–44, https://doi.org/10.1016/j.indcrop.2017.05.038.Search in Google Scholar

Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/hf-2020-0271).

Received: 2020-12-28
Accepted: 2021-06-11
Published Online: 2021-08-02
Published in Print: 2021-12-20

© 2021 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Original Articles
  3. Near-infrared spectroscopy and hyperspectral imaging can aid in the prediction and mapping of polyploid acacia hybrid wood properties in tree improvement programs
  4. Monitoring imbibition dynamics at tissue level in Norway spruce using X-ray imaging
  5. Influence of the applied pressure of the transducer on the propagation speed of the ultrasonic wave in wood
  6. Prediction of shear strength parallel to grain in clear wood of oak (Quercus robur L.) on the basis of shear plane orientation, density and anatomical traits
  7. Sound absorption characteristics of three species (binuang, balsa and paulownia) of low density hardwood
  8. Thermal conductivity of untreated and chemically treated poplar bark and wood
  9. Sorption behavior and swelling of citric acid and sorbitol (SorCA) treated wood
  10. Reaction mechanisms of furfuryl alcohol polymer with wood cell wall components
https://doi.org/10.1515/hf-2020-0271
Keywords for this article
cellulose; chemical reaction; furfurylation; hemicellulose; lignin; wood cell walls

Articles in the same Issue

  1. Frontmatter
  2. Original Articles
  3. Near-infrared spectroscopy and hyperspectral imaging can aid in the prediction and mapping of polyploid acacia hybrid wood properties in tree improvement programs
  4. Monitoring imbibition dynamics at tissue level in Norway spruce using X-ray imaging
  5. Influence of the applied pressure of the transducer on the propagation speed of the ultrasonic wave in wood
  6. Prediction of shear strength parallel to grain in clear wood of oak (Quercus robur L.) on the basis of shear plane orientation, density and anatomical traits
  7. Sound absorption characteristics of three species (binuang, balsa and paulownia) of low density hardwood
  8. Thermal conductivity of untreated and chemically treated poplar bark and wood
  9. Sorption behavior and swelling of citric acid and sorbitol (SorCA) treated wood
  10. Reaction mechanisms of furfuryl alcohol polymer with wood cell wall components
Downloaded on 1.5.2026 from https://www.degruyterbrill.com/document/doi/10.1515/hf-2020-0271/html?lang=en
Scroll to top button