Effect of polymeric diisocyanate addition on bonding performance of a demethylated-pyrolysis-oil-based adhesive

  • Alexandre Santos PimentaEmail author
  • Rosilani Trianoski
  • Antonio Pizzi
  • Francisco Jose Santiago-Medina
  • Elias Costa de Souza
  • Thays Vieira da Costa Monteiro
  • Maíra Fasciotti
  • Renato Vinicius Oliveira Castro


After demethylation, eucalyptus pyrolysis oil has higher reactivity with formaldehyde in alkaline media than the raw oil. The objective of the present work was to evaluate the effect of adding polymeric diphenylmethane diisocyanate (PMDI) on a demethylated oil-based adhesive. Chemical composition of pyrolysis oil was determined by gas chromatography/mass spectrometry. Before and after demethylation, the eucalyptus pyrolysis oil was analyzed by carbon-13 nuclear magnetic resonance spectroscopy (13C NMR) and matrix-assisted laser desorption ionization-time of flight (MALDI-TOF). Demethylated oil-based adhesive was analyzed by MALDI-TOF. Plywood panels were produced with adhesives supplemented with 0, 4, 8, 16 and 20% PMDI and an extra treatment applying a reference phenolic adhesive. The experiment encompassed six treatments with four replicates, totaling 24 panels. As demonstrated by nuclear magnetic resonance analysis, the demethylation reaction was effective in removing methyl groups from the methoxyls of syringol and derivatives, turning them, respectively, into pyrogallol and its derivatives. PMDI was effective as a cross-linking agent, enhancing the mechanical performance of the original demethylated-pyrolysis-oil adhesive. In dry condition and after boiling test, plywood manufactured with formulations adding 16 and 20% PMDI had shear strengths statistically equal to panels bonded with the reference phenolic adhesive.



This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-Brazil (CAPES), finance code 001. We are grateful to Ibiré Negócios Sustentáveis Ltda ( for financial support and as well for supplying analytical material and chemical reagents.


  1. ASTM D1084-1997. Standard test methods for viscosity of adhesives. American Society for Testing and Materials. ASTM International, West Conshohocken, PA, USAGoogle Scholar
  2. ASTM 1490-01-2006. Standard test method for nonvolatile content of urea-formaldehyde resin solutions. American Society for Testing and Materials – ASTM International, West Conshohocken, PA, USAGoogle Scholar
  3. ASTM D7261-2017. Standard test method for determining water separation characteristics of diesel fuels by portable separometer. American Society for Testing and Materials. ASTM International, West Conshohocken, PA, USAGoogle Scholar
  4. ASTM D 4052-1988. Standard test method for density and relative density of liquids by digital density meter. American Society for Testing and Materials. ASTM International, Easton, MD, USAGoogle Scholar
  5. ASTM D 445-1988. Standard test method for kinematic viscosity of transparent and opaque liquids (and the calculation of dynamic viscosity). American Society for Testing and Materials. ASTM International, Easton, MD, USAGoogle Scholar
  6. Athanassiadou E, Tsiantzi S, Nakos P (2002) Wood adhesives made with pyrolysis oils. ACM Wood Chemicals, technical reportGoogle Scholar
  7. Ayrilmis N, Özbay G (2017) Technological properties of plywood bonded with phenol-formaldehyde resol resin synthesized with bio-oil. Cerne 23(4):493–500CrossRefGoogle Scholar
  8. Bhatt MV, Kulkarni SU (1983) Cleavage of ethers. Synthesis 6:249–282CrossRefGoogle Scholar
  9. Chan F, Riedl B, Wang XM, Lu X, Amen-Chen C, Roy C (2002) Performance of oil-based wood adhesives in OSB. For Prod J 52(4):31–38Google Scholar
  10. Cheng S, Yuan Z, Anderson M, Leitch M, Xu C (2012) Synthesis of biobased phenolic resins/adhesives with methylolated wood-derived bio-oil. J Appl Polym Sci 126:E430–E440CrossRefGoogle Scholar
  11. Chum H, Diebold J, Scahill J, Thompson D, Black S, Schroeder H, Kreibich RE (1989) Biomass pyrolysis oil feedstocks for phenolic adhesives. In: Hemingway RW et al (eds) Adhesives from renewable resources. American chemical society symposium series, vol 385, pp 135–151Google Scholar
  12. Doassans-Carrère N, Ferasse J-H, Boutin O, Mauviel G, Lédé J (2014) Comparative study of biomass fast pyrolysis and direct liquefaction for bio-oils production: products yields and characterizations. Energy Fuels 28:5103–5111CrossRefGoogle Scholar
  13. EN 314-2 (2002) Plywood—bonding quality—Part 2: requirements. European Committee for Standardization, BrusselsGoogle Scholar
  14. Fang Z, Zhou G, Zheng S, He G, Li J, He L, Bei D (2007) Lithium chloride catalyzed selective demethylation of aryl-methyl ethers under microwave irradiation. J Mol Catal A: Chem 274:16–23CrossRefGoogle Scholar
  15. Frihart CR, Hunt CG. (2010) Adhesives with wood materials: bond formation and performance. Forest Products Laboratory, general technical report FPL-GTR-190, Chap. 10, pp 1–24Google Scholar
  16. Gagnon M, Roy C, Riedl B (2004) Adhesives made from isocyanates and pyrolysis oils for wood composites. Holzforschung 58:400–407CrossRefGoogle Scholar
  17. Garro-Galvez JM, Riedl B (1997) Pyrogallol-formaldehyde thermosetting adhesives. J Appl Polym Sci 65(2):399–408CrossRefGoogle Scholar
  18. Karas M, Hillenkamp F (1988) Laser desorption ionization of proteins with molecular masses exceeding 10,000 Daltons. Anal Chem 60(20):2299–2301. CrossRefPubMedGoogle Scholar
  19. Kato Y, Kohnosu T, Enomoto R, Akazawa M, Yoon S-L, Kojima Y (2014) Chemical properties of bio-oils produced by fast pyrolysis of bamboo. Trans Mater Res Soc Jpn 39(4):491–498CrossRefGoogle Scholar
  20. Li D, Berruti F, Briens C (2016) Adhesives from biomass pyrolysis. In: Proceedings of 5th international congress on green process engineering (GPE 2016). Engineering conferences international-ECI digital archivesGoogle Scholar
  21. Lúcio DM, Pimenta AS, Castro RVO, Costa FSL, Santos RC, Lima KMG (2017) Phenolic adhesives based on eucalyptus pyrolysis oil: effect of urea addition on synthesis and properties. Int J Adhes Adhes 75:57–65CrossRefGoogle Scholar
  22. Lyu G, Wu S, Zhang H. (2015) Estimation and comparison of bio-oil components from different pyrolysis conditions. Front Energy Res 3, article 28Google Scholar
  23. Mo XF, Fan DB, Qin TF, Chu FX (2015) Curing characteristics and adhesion performance of phenol-formaldehyde resins with composite additives. J Trop For Sci 27:248–254Google Scholar
  24. Mullen C, Boateng A (2011) Production and analysis of fast pyrolysis oils from proteinaceous biomass. Bioenergy Res. CrossRefGoogle Scholar
  25. Nuryawan A, Alamsyah (2018) A review of isocyanate wood adhesive: a case study in Indonesia. In: Applied adhesive bonding in science and technology, Chap. 5. Google Scholar
  26. Pasa VMD, Otani C, Carazza F (1993) Wood tar pitch as phenolic resin precursor. In: Proceedings of the 3rd Brazilian symposium of lignins and other wood components, vol 4. Belo Horizonte, BrazilGoogle Scholar
  27. Carazza F, Pereira MOS, Pereira, NS, Alcântara MFC, Braga JV, Faix O, Meier D (1990) Fine chemicals from syringyl rich fraction of tar obtained from Eucalyptus sp. Wood. In: Proceedings of the 1st European workshop on lignocellulosics and pulp (EWLP)—utilization and analysis of lignins. Hamburg, vol 68, pp 207–212Google Scholar
  28. Pimenta AS, Vital BR, Della Lucia RM, Silva EH (1996) Eucalyptus tar and creosote based adhesives for flakeboard production. Revista Árvore 20(3):343–360Google Scholar
  29. Pimenta AS, Vital BR, Fujiwara FY (1997) Wood adhesives from eucalyptus tar and creosote. Quim Nova 20(4):365–371CrossRefGoogle Scholar
  30. Pimenta AS, Bayona JM, García MT, Solànas AM (2000) Evaluation of acute toxicity of liquid products from pyrolysis of Eucalyptus grandis wood. Arch Environ Contam Toxicol 38:169–175CrossRefGoogle Scholar
  31. Pimenta AS, Ganem FR, Araújo SO, Vital BR (2002) Adesivos à base de creosoto vegetal desmetilado: efeito dos compostos não fenólicos na eficiência da colagem de madeira [Wood adhesives based on demethylated oil: effect of non-phenolics on wood bonding performance]. Floresta e Ambiente 9(1):01–08Google Scholar
  32. Pimenta AS, Monteiro TVC, Fasciotti M, Braga RM, Souza EC, Lima KMG (2018) Fast pyrolysis of trunk wood and stump wood from a Brazilian eucalyptus clone. Ind Crops Prod 125:630–638CrossRefGoogle Scholar
  33. Pizzi A, Stephanou A (1993) On the chemistry, behavior, and cure acceleration of phenol formaldehyde resins under very alkaline conditions. J Appl Polym Sci 49:2157–2170CrossRefGoogle Scholar
  34. Pizzi A, Walton T (1999) Non-emulsifiable, water-based, mixed diisocyanate adhesive systems for exterior plywood—Part I. Novel reaction mechanisms and their chemical evidence. Holzforsch Int J Biol Chem Phys Technol Wood 46:541–547Google Scholar
  35. Pizzi A, Valenzuela J, Westermeyer C (1993) Non-emulsifiable, water-based, mixed diisocyanate adhesive systems for exterior plywood. Part II. Theory application and industrial results. Holzforsch Int J Biol Chem Phys Technol Wood 47:68–71Google Scholar
  36. Ramirez JA, Brown RJ, Rainey TJ (2015) A review of hydrothermal liquefaction bio-crude properties and prospects for upgrading to transportation fuels. Energies 8:6765–6794. CrossRefGoogle Scholar
  37. Ren X, Cai H, Du H, Chang J (2017) The preparation and characterization of pyrolysis bio-oil-resorcinol-aldehyde resin cold-set adhesives for wood construction. Polymers 9:232–244CrossRefGoogle Scholar
  38. Santos CG, Laranjeira DA, Carazza F (1988) Utilização de alcatrão vegetal na produção de resinas fenólicas [Wood tar for phenolic resin production]. Quim Nova 11(3):284–288Google Scholar
  39. Standard EN 314:1 (2004) Plywood—bonding-quality—Part 1: test methods. European Committee for Standardization, BrusselsGoogle Scholar
  40. Zhang S, Yang X, Zhang H, Chu C, Zheng K, Meiting J (2019) Liquefaction of biomass and upgrading of bio-oil: a review. Molecules 24:2250. CrossRefPubMedCentralGoogle Scholar
  41. Zhao C, Pizzi A, Garnier S (1999) Fast advancement and hardening acceleration of low-condensation alcaline PF resins by esters and copolymerized urea. J Appl Polym Sci 74:359–378CrossRefGoogle Scholar
  42. Zhou X, Du G (2019) Applications of tannin resin adhesives in the wood industry. In: Tannins—structural properties, biological properties and current knowledge. IntechOpen-Open Access Books. Accessed 30 July 2019Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Agricultural Sciences Academic Unit, Forest EngineeringFederal University of Rio Grande do Norte (UFRN)NatalBrazil
  2. 2.Laboratory of Wood Panels, Department of Forest EngineeringFederal University of Paraná (UFPR)CuritibaBrazil
  3. 3.Ecole Nationale Supérieure des Technologies et Industries du Bois (ENSTIB-LERMAB)University of LorraineÉpinalFrance
  4. 4.Laboratory of Organic AnalysisNational Institute of Metrology, Quality and TechnologyDuque de CaxiasBrazil
  5. 5.Department of Agricultural SciencesFederal University of São João del-Rei (UFSJ)São João del-ReiBrazil

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