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Phenol-formaldehyde resins with suitable bonding strength synthesized from “less-reactive” hardwood lignin fractions

  • Tainise V. Lourençon ORCID logo EMAIL logo , Sami Alakurtti , Tommi Virtanen , Anna-Stiina Jääskeläinen , Tiina Liitiä , Mark Hughes , Washington L.E. Magalhães , Graciela I.B. Muniz and Tarja Tamminen EMAIL logo
Published/Copyright: May 24, 2019
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Holzforschung
From the journal Holzforschung Volume 74 Issue 2

Abstract

The substitution of phenol by lignin in phenol-formaldehyde (PF) resins is one of the most promising end uses of lignin valorization. Lignin from grasses and softwood has been the focus of the studies in this field as they present a higher number of theoretical reactive sites for resin synthesis. Herein we examined the composition and chemical reactivity of “less-reactive” hardwood lignin fractions and their performance in PF resins, synthesized by substituting 50 wt% of the phenol with lignin. Before resin synthesis, the samples were hydroxymethylated and the maximum formaldehyde consumption was recorded. By doing so, we observed that hardwood fractions consumed formaldehyde close to the theoretical calculation, whereas the reference softwood lignin consumed only about ¼ of the theoretical value. In the resin synthesis, we added formaldehyde to the formulation according to the measured maximum formaldehyde consumption. Thus, low values of free formaldehyde in lignin-PF (LPF) resins were achieved (<0.23%). Moreover, the resin bonding strength displayed similar performance irrespective of whether the LPF resins were made with softwood or hardwood lignin (range of 3.4–4.8 N mm−2 at 150°C and 45–480 s of press time). Furthermore, we concluded that hardwood kraft lignins present no disadvantage compared to softwood lignins in PF resin applications, which have significant practical implications.

Keywords: formaldehyde consumption; kraft; phenolic resins; reactive sites; technical lignin

Acknowledgments

We acknowledge the technical personnel who helped with the analyses. Atte Mikkelson (VTT) is acknowledged especially for providing the novel method for formaldehyde determination.

[Correction statement: The second sentence of the Acknowledgment was added after online publication on 4 January, 2020.]

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: The authors would like to thank BBI Horizon 2020 project SmartLi – Smart Technologies for the Conversion of Industrial Lignins into Sustainable Materials – for the received funding; and the Brazilian agencies CNPq and CAPES for the scholarships.

  3. Employment or leadership: None declared.

  4. Honorarium: None declared.

  5. Conflict of interest: None declared.

References

Balakshin, M., Capanema, E. (2015) On the quantification of lignin hydroxyl groups with P and C NMR spectroscopy. J. Wood Chem. Technol. 35:220–237.10.1080/02773813.2014.928328Search in Google Scholar

Balakshin, M., Capanema, E. (2016) Rethinking biorefinery lignins: breaking dogmas. In: European Workshop on Lignocellulosics and Pulp. Autrans, France.Search in Google Scholar

Chaouch, M., Diouf, P.N., Laghdir, A., Yin, S. (2014) Bio-oil from whole-tree feedstock in resol-type phenolic resins. J. Appl. Polym. Sci. 131:1–6.10.1002/app.40014Search in Google Scholar

Doherty, W.O.S., Mousavioun, P., Fellows, C.M. (2011) Value-adding to cellulosic ethanol: lignin polymers. Ind. Crops Prod. 33:259–276.10.1016/j.indcrop.2010.10.022Search in Google Scholar

Gardziella, A., Pilato, L., Knop, A. Phenolic Resins: Chemistry, Applications, Standardization, Safety and Ecology, 2nd ed. Springer-Verlag, Berlin, Heidelberg, 2000.10.1007/978-3-662-04101-7Search in Google Scholar

Ghorbani, M., Liebner, F., Van Herwijnen, H.W.G., Pfungen, L., Krahofer, M., Budjav, E., Konnerth, J. (2016) Lignin phenol formaldehyde resoles: the impact of lignin type on adhesive properties. BioResources 11:6727–6741.10.15376/biores.11.3.6727-6741Search in Google Scholar

Goldschmid, O. (1971) Ultraviolet spectra. In: Lignins: Occurrence, Formation, Structure and Reactions. Eds. SArkanen, K.V., Ludwig, C.H. John Wiley & Sons, Inc., New York. pp. 241–298.Search in Google Scholar

Granata, A., Argyropoulos, D. (1995) 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, a reagent for theaccurate determination of the uncondensed and condensed phenolic moietiesin lignins. J. Agric. Food Chem. 43:1538–1544.10.1021/jf00054a023Search in Google Scholar

Hong, S., Gu, Z., Chen, L., Zhu, P., Lian, H. (2018) Synthesis of phenol formaldehyde (PF) resin for fast manufacturing laminated veneer lumber (LVL). Holzforschung 72:745–752.10.1515/hf-2017-0184Search in Google Scholar

IBÁ (2016) Indústria Brasileira de Árvores (IBÁ).Search in Google Scholar

ICIS Chemical Business (2017) Outlook big Brand. -become bio-based partners. URL https://www.icis.com (accessed 1.1.17).Search in Google Scholar

Jääskeläinen, A., Liitiä, T., Mikkelson, A., Tamminen, T. (2017) Aqueous organic solvent fractionation as means to improve lignin homogeneity and purity. Ind. Crop. Prod. 103:51–58.10.1016/j.indcrop.2017.03.039Search in Google Scholar

Kalami, S., Arefmanesh, M., Master, E., Nejad, M. (2017) Replacing 100% of phenol in phenolic adhesive formulations with lignin. J. Appl. Polym. Sci. 134:2–10.10.1002/app.45124Search in Google Scholar

Khan, M.A., Marghoob, S.A., Malhotra, V.P. (2004) Development and characterization of a wood adhesive using bagasse lignin. Int. J. Adhes. Adhes. 24:485–493.10.1016/j.ijadhadh.2004.01.003Search in Google Scholar

Lee, W., Chang, K., Tseng, I. (2011) Properties of phenol-formaldehyde resins prepared from phenol-liquefied lignin. J. Appl. Polym. Sci. 124:4782–4788.10.1002/app.35539Search in Google Scholar

Lin, S.Y., Dence, C.W. Methods in Lignin Chemistry. Springer-Verlag, Berlin Heidelberg, 1992.10.1007/978-3-642-74065-7Search in Google Scholar

Lorente, E., Torras, C., Berrueco, C., Salvado, J. (2017) Transformation of lignin from bioethanol production for phenol substitution in resins. Wood Sci. Technol. 51:1209–1225.10.1007/s00226-017-0911-zSearch in Google Scholar

Lourençon, T.V., Hansel, F.A., Da Silva, T.A., Ramos, L.P., De Muniz, G.I.B., Magalhães, W.L.E. (2015) Hardwood and softwood kraft lignins fractionation by simple sequential acid precipitation. Sep. Purif. Technol. 154:82–88.10.1016/j.seppur.2015.09.015Search in Google Scholar

El Mansouri, N., Salvadó, J. (2006) Structural characterization of technical lignins for the production of adhesives : application to lignosulfonate, kraft, soda-anthraquinone, organosolv and ethanol process lignins. Ind. Crop. Prod. 24:8–16.10.1016/j.indcrop.2005.10.002Search in Google Scholar

Nassar, M., MacKay, G. (1984) Mechanism of thermal decomposition of lignin. Wood Fiber Sci. 16:441–453.Search in Google Scholar

NREL standard (2008) Determination of structural carbohydrates and lignins in biomass. Laboratory analytical procedure (LAP).Search in Google Scholar

Pang, B., Yang, S., Fang, W., Yuan, T., Argyropoulos, D.S., Sun, R.-C. (2017) Structure-property relationships for technical lignins for the production of lignin-phenol-formaldehyde resins. Ind. Crop. Prod. 108:316–326.10.1016/j.indcrop.2017.07.009Search in Google Scholar

Schorr, D., Diouf, P.N., Stevanovic, T. (2014) Evaluation of industrial lignins for biocomposites production. Ind. Crops Prod. 52:65–73.10.1016/j.indcrop.2013.10.014Search in Google Scholar

Stark, N.M., White, R.H., Mueller, S.A., Osswald, T.A. (2010) Evaluation of various fire retardants for use in wood flour-polyethylene composites. Polym. Degrad. Stab. 95:1903–1910.10.1016/j.polymdegradstab.2010.04.014Search in Google Scholar

Tejado, A., Peña, C., Labidi, J., Echeverria, J.M., Mondragon, I. (2007) Physico-chemical characterization of lignins from different sources for use in phenol-formaldehyde resin synthesis. Bioresour. Technol. 98:1655–1663.10.1016/j.biortech.2006.05.042Search in Google Scholar PubMed

Yang, S., Wen, J.-L., Yuan, T.-Q., Sun, R.-C. (2014) Characterization and phenolation of biorefinery technical lignins for lignin–phenol–formaldehyde resin adhesive synthesis. RSC Adv. 4:57996–58004.10.1039/C4RA09595BSearch in Google Scholar

Yang, S., Wu, J., Zhang, Y., Yuan, T., Sun, R. (2015) Preparation of lignin-phenol-formaldehyde resin adhesive based on active sites of technical lignins. J. Biobased Mater. Bioenergy 9:1–7.10.1166/jbmb.2015.1514Search in Google Scholar

Yelle, D., Ralph, J. (2016) Characterizing phenol–formaldehyde adhesive cure chemistry within the wood cell wall. Int. J. Adhes. Adhes. 70:26–36.10.1016/j.ijadhadh.2016.05.002Search in Google Scholar

Zhang, W., Ma, Y., Wang, C., Li, S., Zhang, M., Chu, F. (2013) Preparation and properties of lignin – phenol – formaldehyde resins based on different biorefinery residues of agricultural biomass. Ind. Crop. Prod. 43:326–333.10.1016/j.indcrop.2012.07.037Search in Google Scholar

Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/hf-2018-0203).

Received: 2018-09-12
Accepted: 2019-04-03
Published Online: 2019-05-24
Published in Print: 2020-02-25

©2020 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Editorial
  3. The 15th European Workshop on Lignocellulosics and Pulp (EWLP) in Aveiro, Portugal (June 26–29, 2018)
  4. Review
  5. Extractives and biological activities of Lamiaceae species growing in Uzbekistan
  6. Original Articles
  7. New drum-chipping technology for a more uniform size distribution of wood chips
  8. Characterization of enzyme-resistant xylooligosaccharides extracted from hardwood chips by pre-hydrolysis and further depolymerized by enzymatic treatment
  9. Stabilising mannose using sodium dithionite at alkaline conditions
  10. Xylan accessibility of bleached eucalypt pulp in alkaline solutions
  11. Investigation of eucalypt and pine wood acid-soluble lignin by Py-GC-MS
  12. The reaction of lignin model compounds during enzymatic bleaching with a Curvularia verruculosa haloperoxidase: impact on chlorination
  13. Molecular weight-based fractionation of lignin oils by membrane separation technology
  14. Phenol-formaldehyde resins with suitable bonding strength synthesized from “less-reactive” hardwood lignin fractions
  15. Impact of birch xylan composition and structure on film formation and properties
  16. Gram-scale economical synthesis of trans-coniferyl alcohol and its corresponding thiol
  17. Lignosulfonate-based polyurethane materials via cyclic carbonates: preparation and characterization
  18. Bioconversion of pine stumps to ethanol: pretreatment and simultaneous saccharification and fermentation
  19. Selective recovery of polyphenols from MDF process waters by adsorption on a macroporous, cross-linked pyrrolidone-based resin
  20. Short Note
  21. Lignin analysis with benchtop NMR spectroscopy
https://doi.org/10.1515/hf-2018-0203
Keywords for this article
formaldehyde consumption; kraft; phenolic resins; reactive sites; technical lignin

Articles in the same Issue

  1. Frontmatter
  2. Editorial
  3. The 15th European Workshop on Lignocellulosics and Pulp (EWLP) in Aveiro, Portugal (June 26–29, 2018)
  4. Review
  5. Extractives and biological activities of Lamiaceae species growing in Uzbekistan
  6. Original Articles
  7. New drum-chipping technology for a more uniform size distribution of wood chips
  8. Characterization of enzyme-resistant xylooligosaccharides extracted from hardwood chips by pre-hydrolysis and further depolymerized by enzymatic treatment
  9. Stabilising mannose using sodium dithionite at alkaline conditions
  10. Xylan accessibility of bleached eucalypt pulp in alkaline solutions
  11. Investigation of eucalypt and pine wood acid-soluble lignin by Py-GC-MS
  12. The reaction of lignin model compounds during enzymatic bleaching with a Curvularia verruculosa haloperoxidase: impact on chlorination
  13. Molecular weight-based fractionation of lignin oils by membrane separation technology
  14. Phenol-formaldehyde resins with suitable bonding strength synthesized from “less-reactive” hardwood lignin fractions
  15. Impact of birch xylan composition and structure on film formation and properties
  16. Gram-scale economical synthesis of trans-coniferyl alcohol and its corresponding thiol
  17. Lignosulfonate-based polyurethane materials via cyclic carbonates: preparation and characterization
  18. Bioconversion of pine stumps to ethanol: pretreatment and simultaneous saccharification and fermentation
  19. Selective recovery of polyphenols from MDF process waters by adsorption on a macroporous, cross-linked pyrrolidone-based resin
  20. Short Note
  21. Lignin analysis with benchtop NMR spectroscopy
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