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Comparative Thermodynamic Study on the Contribution of the Autocondensation and Copolymerization Reactions for the Tannins of the Subspecies of Acacia nilotica

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Abstract

Autocondensation and copolymerization reactions of the Acacia nilotica subspecies tomentosa (Ant) and the subspecies adansonii (Ana) tannins extracts solutions have been studied at several pH values by thermomechanical analyzer. Results of chemical analysis of these tannins revealed that the studied tannins, Ant and Ana contained high percentages of extractable tannins (54 and 57 %) for and polyphenolic materials (78 and 80 %) respectively. Different hardeners such as paraformaldehyde, Urea and pMDI were added at different ratios and their polycondensation reactions was studied and compared with their autocondensation ones. The aim was to evaluate the tannins suitability for the production of commercially and technically viable tannin adhesives with reduced Formaldehyde emission for wood products and to study the interference between the autocondensation and the copolymerization reaction. The obtained results of autocondensation reaction for both of the tannins studied showed that the best Young’s modulus values for Ant (3,500 and 2,750 MPa) and Ana (2,650 and 2,620 MPa) were obtained at pH 5 and 7. The Young’s modulus values obtained by the tannins Ant were higher than those achieved by Ana. This indicates that the Ant is more reactive than Ana. These results were also in line with results achieved by the gel time for both of the tannins. Gel time results indicate that the reactivity of both tannins increased towards alkalinity with Ana being more reactive at alkaline pH. Addition of 8 % of paraformaldehyde was adversely affecting the autocondensation reactions, as the best Young’s modulus values were achieved at pH 4 for Ant tannins. As for Ana the higher Young’s modulus values (2,000 and 2,310 MPa) were achieved at pH 5 and 7. This indicates that autocondensation reaction was contributed to the final network of the copolymerization reaction. When smaller ratio of paraformaldehyde and Urea (5 %) was added to Ant tannins it favors the autocondensation reaction and the best Young’s modulus values were obtained at pH 5 and 7. Addition of pMDI (10–30 %) was found to decrease the temperature of copolymerization and the obtained Young’s modulus values by Ant were lower than those obtained by autocodensation reaction. Best Young’ modulus values were obtained by Ant at pH 5 and 7. Ana gave the best Young’s modulus values at pH 4 and 5 indicating that the autocondensation appears to depress the copolymerization reactions. The obtained results by both reactions were very important from technical and economical point of view as they concluded that it is very possible to produce adhesives system with zero emission depending on the tannins autocondensation reaction and pH values. Reduction of formaldehyde emission was also possible upon addition of smaller amount of paraformaldehyde and Urea.

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References

  1. Moubarik A, Allal A, Pizzi A, Charrier F, Charrier B (2010) Characterization of a formaldehyde-free cornstarch-tannin wood adhesive for interior plywood. Eur J Wood Wood Prod 68(4):427–433

    Article  CAS  Google Scholar 

  2. Chen CM (1996) State of the art report: adhesives from renewable resources. Holzforschung und Holzverwertung 4:58–60

    Google Scholar 

  3. Pizzi A, Stefanou A (1994) Fast vs. slow-reacting non-modified tannin extracts for exterior particleboard adhesives. Holz Roh- Werkstoff 52:218–222

    Article  CAS  Google Scholar 

  4. Kim S, Lee YK, Kim HJ, Lee HH (2003) Physico-mechanical properties of particleboards bonded with pine and wattle tannin-based adhesives. J Adhes Sci Technol 17(14):1863–1875

    Article  CAS  Google Scholar 

  5. Pizzi A, Tekely P (1995) Mechanism of polyphenolic tannin resin hardening by hexamethylenetetramine: CP-MAS 13C-NMR. J Appl Polym Sci 56:1645–1650

    Article  CAS  Google Scholar 

  6. Pena C, De la Caba K, Retegi A, Ocando C, Labidi J, Echeverria JM, Mondragon I (2009) J Therm Anal Calorim 96(2):515–521

    Article  CAS  Google Scholar 

  7. Garcia R, Pizzi A (1998) Polycondensation and autocondensation networks in polyflavonoid tannins. I. Final networks. J Appl Polym Sci 70:1083–1091

    Article  CAS  Google Scholar 

  8. Garcia R, Pizzi A (1998) Polycondensation and autocondensation networks in polyflavonoid tannins. II. Polycondensation versus autocondensation. J Appl Polym Sci 70:1093–1109

    Article  CAS  Google Scholar 

  9. Osman Z (2012) Thermomechanical analysis of tannins Acacia Nilotica spp Nilotica as a rapid tool for the evaluation wood–based adhesives. J Therm Anal Calorim 107:709–716

    Article  CAS  Google Scholar 

  10. Osman Z, Pizzi A, Alamin IH (2009) Comparative properties of agrofiber based particle boards using newly developed bonding materials. J Biobased Mater Bioenergy 3(3):1–7

    Article  Google Scholar 

  11. Society of leather Trade Chemists (1965). Official Methods of Analysis, S.T.C. Redboure, pp 225

  12. Yazaki Y, Zheng G, Searle S (1990) Exytractive yields and polyphenolic contents from Acacia mernsii barks in Australia. Aust For 53(3):148–153

    Article  Google Scholar 

  13. DIN ISO 16916

  14. 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(2):2157–2170

    Article  CAS  Google Scholar 

  15. Probst F, Laborie MP, Pizzi A, Merlin A, Deglise X (1997) Molecular mechanics/experimental methods applied to varnish/primer/wood interactions. Holzforschung 51(5):459–467

    Article  CAS  Google Scholar 

  16. Fechtal M, Riedl B, Calve L (1993) Holzforschung 47:419–424

    Article  CAS  Google Scholar 

  17. Ali AR, Low CK, Ahmed AS (1981) Malays For 44(1):87–92

    Google Scholar 

  18. Pizzi A (1994) Advanced Wood Adhesives Technology. Chapter 5, Marcel Dekker, New York, 289

  19. Pizzi A (1982) Holz als roh–und Werkstoff 40:293

  20. Pizzi A, Mittal KL (1983) Handb Adhesives technol 347–358

  21. Garcia R, Pizzi A (1998) Crosslinked and entanglement networks in thermomechanical analysis of polycondensation resins. J Appl Polym Sci 70:1111–1119

    Article  CAS  Google Scholar 

  22. Osman Z, Pizzi A (2002) Comparison on gelling reaction effectiveness of procyanidin tannins for wood adhesives. Hoz Roh werkstoff 60(5):328

    Article  CAS  Google Scholar 

  23. Pizzi A, Stephanou J (1994) Appl Polym Sci 51:2109

    Article  CAS  Google Scholar 

  24. Pizzi A, Stephanou J (1994) Holz Roh Werkst 52:214

    Google Scholar 

  25. European Standard EN 312 (2004) Panels for interior applications (including furniture) in dry areas (P2). CEN European Committee for Standardisation

  26. Newman RH, Porter L (1992) J and Hemingway ED. Plenum Press, New York

    Google Scholar 

  27. Paola Navarrete, Pizzi A, Bertaud S, Rigolet F (2011). Condensed tannin reactivity inhibition by internal rearrangements: detection by CP-MAS 13CNMR. Maderas. Ciencia y tecnologia 13(1)

  28. Pichelin F, Pizzi A (1999) European commission contract, FAIR TC95-0137, Final report

  29. Pizzi A, Stephanou A (1998) Mechanisms of tannin rearrangement in thermosetting tannin adhesives for particleboard: In Adhesives Technology and Bonded Tropical Wood Products, TFRI 96

  30. Pizzi A (1983) Wood Adhesives: Chemistry and Technology, chap. 4, Marcel Dekker, New York

  31. Pizzi A, Valenzuela J, Westermayer C (1993) Emulsifiable, waterbased, mixed diisocyanate adhesive systems for exterior plywood. Hozforshung 47(1):68

    Google Scholar 

  32. Pizzi A, Walton T (1992) Non-emulsifiable, water-based, mixed diisocyanate adhesive systems for exterior plywood. Part I: novel reaction mechanisms and their chemical evidence. Holzforschung 46:541–547

    Article  CAS  Google Scholar 

  33. Osman Z, Pizzi A, Kantner W, Triboulot MC (2005) PUF panel adhesives depoted with additional urea and reinforced by isocyanate. HolzRoh Werkstoff 63:53–56

    Google Scholar 

  34. Merlin A, Pizzi A (1996) An ESR study of the silica-induced autocondensation of polyflavonoid tannins. J Appl Polym Sci 59(6):945–952

    Article  CAS  Google Scholar 

  35. Pizzi A, Stephanou A (1993) Holzforschung, holsverwert 45(2):30–33

    Google Scholar 

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Acknowledgments

The author wishes to thank the French embassy, Sudan for the Grant supplied for this research work, which has been carried out in collaboration with the National Center for Research, Sudan. Thanks are also extended to LERMAB laboratories, University of Nancy1, France.

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Osman, Z. Comparative Thermodynamic Study on the Contribution of the Autocondensation and Copolymerization Reactions for the Tannins of the Subspecies of Acacia nilotica . J Polym Environ 21, 1100–1108 (2013). https://doi.org/10.1007/s10924-013-0611-1

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