Journal of Polymers and the Environment

, Volume 26, Issue 3, pp 970–979 | Cite as

Determination of In Situ Esterification Parameters of Citric Acid-Glycerol Based Polymers for Wood Impregnation

  • Marc-Andre Berube
  • Diane Schorr
  • Richard J. Ball
  • Veronic Landry
  • Pierre BlanchetEmail author
Original Paper


The development of wood treatments is of increasing industrial importance. A novel technique for improving the properties of lodgepole pine and white pine through modification of the microstructure is described. The present investigation is devoted to the synthesis and determination of in situ parameters of citric acid and glycerol based polymers for wood impregnation. This solvent free approach is environmentally friendly and achieved through an esterification condensation reaction under acidic conditions. Crude glycerol and citric acid reactants were cross-linked via a curing process at 160 °C creating a polymer with only water as the byproduct. The ester bonds and crosslinking levels were controlled using different catalysts and citric acid contents and related to the reaction time and temperature. The nature of bonding within the polymers and at the wood cell walls was determined by FT-IR analysis. The thermal properties such as glass transition temperature (Tg) were studied using TGA/DSC and the effect of citric acid content and catalyst type determined. Dimensional stability of impregnated wood samples improved above 50% for each sample with HCl and p-TSA catalysts compared to control samples. FTIR spectra were studied to show the presence of the ester linkages of the polymer in situ at the wood cell walls. Bonding between the polymer and wood macromolecules were observed by scanning electron microscopy and interpreted as evidence of chemical bonds at the wood cells. When prepared using a catalyst, the polymer was intimately incorporated into wood structure significantly improving the substrate dimensional stability. Enhanced stability makes this approach of particular interest for exterior wood products especially as a green renewable option for the wood industry.


Crude glycerol Citric acid Polymerisation Wood impregnation Wood dimensional stability 



The authors are grateful to Natural Sciences and Engineering Research Council of Canada for the financial support through its IRC and CRD programs (IRCPJ 461745-12 and RDCPJ 445200-12) (MSc CRD 14) as well as the industrial partners of the NSERC industrial chair on eco-responsible wood construction (CIRCERB). Thanks are also due to Ursula Potter and Dr Philip Fletcher from the Microscopy and Analyse Suite, University of Bath for help given for scanning electron microscopy and Dr Martin Ansell, Department of Architecture and Civil Engineering, University of Bath for helpful discussions. Acknowledgement is also due to the Canadian Queen Elizabeth II Diamond Jubilee scholarship scheme and the Ministry of Economy, Science and Innovation of the Province of Quebec in its Research Support Program PSR-SIIRI.


  1. 1.
    Salminen E, Valo R, Korhonen M, Jernlås R (2014) Wood preservation with chemicals: best available techniques. Nordic Council of Ministers, CopenhagenCrossRefGoogle Scholar
  2. 2.
    Xiaoli G, Lan S, Guozhen L, Chaoqun Y, Chun Kan KC, Jianfeng Y (2015) Wood Res 60:247–254Google Scholar
  3. 3.
    Zhu S, Zhu Y, Gao X, Mo T, Zhu Y, Li Y (2013) Bioresour Technol 130:45–51CrossRefGoogle Scholar
  4. 4.
    Molinero L, Ladero M, Tamayo JJ, García-Ochoa F (2014) Chem Eng J 247:174–182CrossRefGoogle Scholar
  5. 5.
    Essoua Essoua GG, Blanchet P, Landry V, Beauregard R (2016) BioResourses 11:3049Google Scholar
  6. 6.
    Halpern JM, Urbanski R, Weinstock AK, Iwig DF, Mathers RT, von Recum HA (2014) J Biomed Mater Res A 102:1467–1477CrossRefGoogle Scholar
  7. 7.
    Pramanick D, Ray TT (1988) Polym Bull 19:365–370CrossRefGoogle Scholar
  8. 8.
    Bodirlau R, Teaca C (2009) Rom J Phys. 54:93–104Google Scholar
  9. 9.
    Kwak JCT (1998) Polymer-surfactant systems. CRC Press, New YorkGoogle Scholar
  10. 10.
    Garcia PS, Grossmann MVE, Shirai MA, Lazaretti MM, Yamashita F, Muller CMO, Mali S (2014) Ind Crops Prod 52:305–312CrossRefGoogle Scholar
  11. 11.
    Shi R, Zhang Z, Liu Q, Han Y, Zhang L, Chen D, Tian W (2007) Carbohydr Polym 69:748–755CrossRefGoogle Scholar
  12. 12.
    Dou B, Dupont V, Williams PT, Chen H, Ding Y (2009) Bioresour Technol 100:2613–2620CrossRefGoogle Scholar
  13. 13.
    Franklin DS, Guhanathan S (2015) Ecotoxicol Environ Saf 121:80CrossRefGoogle Scholar
  14. 14.
    Barbooti MM, Al-Sammerrai DA (1986) Thermochim Acta 98:119–126CrossRefGoogle Scholar
  15. 15.
    Thomas LV, Nair PD (2011) Biomatter 1:81–90CrossRefGoogle Scholar
  16. 16.
    Wiedenbeck J, Hofmann K, Peralta P, Skaar C, Kock P (1990) Wood Fiber Sci 22:229–245Google Scholar
  17. 17.
    Rice RW, Donofrio M (1996) Wood Fiber Sci 28:301–308Google Scholar
  18. 18.
    Šefc B, Trajković J, Hasan M, Katović D, Bischof Vukušić S, Frančić M (2009) Drvna industrija 60:23–26Google Scholar
  19. 19.
    Schramm C, Rinderer B (1999) Coloration Technol 115:306–311CrossRefGoogle Scholar
  20. 20.
    Li G-Y, Huang L-H, Hse C-Y, Qin T-F (2011) Carbohydr Polym 85:560–564CrossRefGoogle Scholar
  21. 21.
    Owen N, Thomas D (1989) Appl Spectrosc 43:451–455CrossRefGoogle Scholar
  22. 22.
    Cogulet A, Blanchet P, Landry V (2016) J Photochem Photobiol B 158:184–191CrossRefGoogle Scholar
  23. 23.
    Budhavaram NK, Barone JR (2008) Simple esters of crude glycerol and citric acid, in 2008 Providence, Rhode Island, June 29–July 2Google Scholar

Copyright information

© Springer Science+Business Media New York 2017

Authors and Affiliations

  • Marc-Andre Berube
    • 1
    • 2
  • Diane Schorr
    • 1
    • 2
  • Richard J. Ball
    • 3
  • Veronic Landry
    • 1
    • 2
  • Pierre Blanchet
    • 1
    • 2
    Email author
  1. 1.Department of Wood and ForestUniversité LavalQuebec CityCanada
  2. 2.CIRCERB NSERC Industrial Research Chair on Ecoresponsible Wood ConstructionUniversité LavalQuebec CityCanada
  3. 3.Department of Architecture and Civil Engineering, BRE Center for Innovative Construction MaterialsUniversity of BathBathUK

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