Synthesis and characterization of a biopolymer of glycerol and macadamia oil

  • Osmar Antonio Baldo Pires
  • Rafael Turra Alarcon
  • Caroline Gaglieri
  • Luiz Carlos da Silva-Filho
  • Gilbert BannachEmail author


The main objective of this work was the synthesis of a polymer using a vegetable and renewable feedstock and following the green chemistry principles. The use of macadamia oil (extracted from Macadamia integrifolia nuts) in a synthesis route was achieved under mild temperature and pressure conditions. The produced material was submitted to a series of characterization techniques. Thermal analysis was used to determine its thermal stability (140.0 °C), its degradation pattern with the involved kinetic, and its glass transition (midpoint at 48.8 °C). Infrared spectrometry found the general mechanism of polymerization of macadamia oil with pre-polymer (glycerol and maleic anhydride) and identified functional groups of the polymer. Some interesting characteristics of the macadamia polymer include good removal of organic dyes from aqueous solutions, which demonstrates the great interaction of its surface with organic molecules that leads to a potential application as an encapsulation material for substances of nutritional and pharmacological interests. This adsorption may be related to the polymer surface that is very rough as shown by scanning electron microscopy images. Another interesting phenomenon demonstrated was the macadamia polymer fluorescence that indicates potential applications in electronic devices.


Macadamia oil Oil polymer Glycerol Thermal analysis Infrared Ultraviolet spectroscopy 



The authors wish to thank CAPES (proc. 024/2012 and 011/2009 Pro-equipment), POSMAT/UNESP, FAPESP (processes: 2013/09022-7, 2015/00615-0, 2016/01599-1, 2017/08820-8 and 2018/03460-6), and CNPq (Processes 302267/2015-8 and 302753/2015-0) for the financial support.

Supplementary material

10973_2018_7922_MOESM1_ESM.tif (85 kb)
Fig. S1 DMA curve of tan delta for macadamia polymer (TIFF 84 kb)
10973_2018_7922_MOESM2_ESM.tif (722 kb)
Fig. S2 Experimental and theoretical data of mass loss obtained for macadamia oil in the heating rates of 5, 10, 15, and 20 °C min−1 and in two temperature intervals (1st, from 250 to 460 °C; 2nd, from 460 to 600 °C) (TIFF 721 kb)
10973_2018_7922_MOESM3_ESM.tif (530 kb)
Fig. S3 Experimental and theoretical data of mass loss obtained for macadamia polymer in the heating rates of 5, 10, 15, and 20 °C min−1 and in two temperature intervals (1st, from 250 to 460 °C; 2nd, from 460 to 600 °C) (TIFF 529 kb)


  1. 1.
    Monteiro RCP, do Sul JAI, Costa MF. Plastic pollution in islands of the Atlantic Ocean. Environ Pollut. 2018;238:103–10.CrossRefGoogle Scholar
  2. 2.
    Anastas PT, Warner JC. Green chemistry: theory and practice. 1st ed. Oxford: University Press; 1998.Google Scholar
  3. 3.
    Kaur G, Uisan K, Ong KL, Lin CSK. Recent trends in green and sustainable chemistry and waste valorisation: rethinking plastics in a circular economy. Curr Opin Green Sust Chem. 2018;9:30–9.CrossRefGoogle Scholar
  4. 4.
    Feldman D. Polymer history. Des Monomers Polym. 2008;11:1–15.CrossRefGoogle Scholar
  5. 5.
    No SY. Application of straight vegetable oil from triglyceride based biomass to IC engines—a review. Renew Sustain Energy Rev. 2017;69:80–97.CrossRefGoogle Scholar
  6. 6.
    Khatuna R, Rezaa MIH, Moniruzzam M, Yaakob Z. Sustainable oil palm industry: the possibilities. Renew Sustain Energy Rev. 2017;76:608–19.CrossRefGoogle Scholar
  7. 7.
    Adekunle KF. A review of vegetable oil-based polymers: synthesis and applications. Open J Polym Chem. 2015;5:34–40.CrossRefGoogle Scholar
  8. 8.
    Sun HS, Chiu YC, Chen WC. Renewable polymeric materials for electronic applications. Polym J. 2017;49:61–73.CrossRefGoogle Scholar
  9. 9.
    Quispe CAG, Coronado CJR, Carvalho JA Jr. Glycerol: production, consumption, prices, characterization and new trends in combustion. Renew Sustain Energy Rev. 2013;27:475–93.CrossRefGoogle Scholar
  10. 10.
    Tan HW, Aziz ARA, Aroua MK. Glycerol production and its applications as a raw material: a review. Renew Sustain Energy Rev. 2013;27:118–27.CrossRefGoogle Scholar
  11. 11.
    Monteiro MR, Kugelmeier CL, Pinheiro RS, Batalha MO, César AS. Glycerol from biodiesel production: technological paths for sustainability. Renew Sustain Energy Rev. 2018;88:109–22.CrossRefGoogle Scholar
  12. 12.
    Alarcon RT, Almeida MV, Bannach G. Processo de obtenção de um biopolímero a partir do subproduto glicerol gerado na produção de biodiesel. BR 10 2016 01805-6. 2016.Google Scholar
  13. 13.
    Alarcon RT, de Almeida MV, Rinaldo D, Bannach G. Synthesis and thermal study of polymers from soybean, sunflower, and grape seed maleinated oil. Eur J Lipid Sci Technol. 2017;119:1–6.CrossRefGoogle Scholar
  14. 14.
    de Almeida MV, Alarcon RT, Bannach G. Synthesis and thermal studies of new soybean and grape seed oil based polymers: clean and efficient pathway using green chemistry principles. Braz J Therm Anal. 2016;5:16–20.CrossRefGoogle Scholar
  15. 15.
    Alarcon RT, Gaglieri C, Bannach G. Dimethacrylate polymers with different glycerol content. J Therm Anal Calorim. 2018;132:1–13.CrossRefGoogle Scholar
  16. 16.
    Wallace HM, Walton DA. Macadamia (Macadamia integrifolia, Macadamia tetraphylla and hybrids). In: Yahia EM, editor. Postharvest biology and technology of tropical and subtropical fruits. Cambridge: Woodhead Publishing; 2011. p. 450–74.CrossRefGoogle Scholar
  17. 17.
    Azad AK, Rasul MG, Khan MMK, Sharma SC. Biodiesel from queensland bush nut (Macadamia integrifolia). In: Rasul MG, Azad AK, Sharma SC, editors. Clean energy for sustainable development. Cambridge: Academic; 2017. p. 419–39.CrossRefGoogle Scholar
  18. 18.
    Kaijser A, Dutta P, Savage G. Oxidative stability and lipid composition of macadamia nuts grown in New Zealand. Food Chem. 2000;71:67–70.CrossRefGoogle Scholar
  19. 19.
    Aquino-Bolaños EN, Mapel-Velazco L, Martín-del-Campo ST, Chávez-Servia JL, Martínez AJ, Verdalet-Guzmán I. Fatty acids profile of oil from nine varieties of Macadamia nut. Int J Food Prop. 2017;20:1262–9.CrossRefGoogle Scholar
  20. 20.
    Navarro SLB, Rodrigues CEC. Macadamia oil extraction methods and uses for the defatted meal byproduct. Trends Food Sci Technol. 2016;54:148–54.CrossRefGoogle Scholar
  21. 21.
    Vyadzovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA, Popescu C, Sbirrazzuoli N. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. 2011;520:1–19.CrossRefGoogle Scholar
  22. 22.
    Kayalvizhi M, Vakees E, Suresh J, Arun A. Synthesis and characterization of polyurethane-urea-amide based on functionalized polystyrene. Des Monomers Polym. 2015;18:734–44.CrossRefGoogle Scholar
  23. 23.
    Dweck J, Sampaio CMS. Analysis of the thermal decomposition of commercial vegetable oils in air by simultaneous TG/DTA. J Therm Anal Calorim. 2004;75:385–91.CrossRefGoogle Scholar
  24. 24.
    Vecchio S, Campanella L, Nuccilli A, Tomassetti M. Kinetic study of thermal breakdown of triglycerides contained in extra-virgin olive oil. J Therm Anal Calorim. 2008;91:51–6.CrossRefGoogle Scholar
  25. 25.
    Mellan I. Polyhydric alcohols. Washington, DC: Spartan Books; 1962.Google Scholar
  26. 26.
    American Society for Testing and Materials-ASTM. ASTM-E1356: standard test method for assignment of the glass transition temperatures by differential calorimetry. West Conshohocken: ASTM; 2014.Google Scholar
  27. 27.
    Friedman HL. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci. 1964;6:183–95.Google Scholar
  28. 28.
    Moukhina E. Determination of kinetic mechanisms for reactions measured with thermoanalytical instruments. J Therm Anal Calorim. 2012;109:1203–14.CrossRefGoogle Scholar
  29. 29.
    Peterson JD, Vyadzovkin S, Wight CA. Kinetics of the thermal and thermo-oxidative degradation of polystyrene, polyethylene and poly(propylene). Macromol Chem Phys. 2001;202:775–84.CrossRefGoogle Scholar
  30. 30.
    Miller JN, Miller JC. Statistics and chemometrics for analytical chemistry. 6th ed. Harlow: Pearson Education Limited; 2010.Google Scholar
  31. 31.
    Monagle JJ. Carbodiimides III: conversion of isocyanates to carbodiimides catalyst studies. J Org Chem. 1962;27:3851–5.CrossRefGoogle Scholar
  32. 32.
    Opfermann J. Kinetic analysis using a multivariate nonlinear regression. J Therm Anal Calorim. 2000;60:641–58.CrossRefGoogle Scholar
  33. 33.
    Gupta MC, Deshmukh VG. Thermal oxidative degradation of poly-lactic acid. Coll Polym Sci. 1982;260:308–11.CrossRefGoogle Scholar
  34. 34.
    Burke J. The kinetics of phase transformations in metals. London: Pergamon Press Ltd; 1965.Google Scholar
  35. 35.
    de Moura A, Gaglieri C, Alarcon RT, Ferreira PO, Magdalena AG, Bannach G. Non-isothermal kinetic study of andiroba and babassu oils. Braz J Therm Anal. 2017. Scholar
  36. 36.
    Brown ME, Glass BD. Pharmaceutical applications of the Prout–Tompkins rate equation. Int J Pharm. 1999;190:129–37.CrossRefGoogle Scholar
  37. 37.
    Jacobs PWM. Formation and growth of nuclei and the growth of interfaces in the chemical decomposition of solids: new insights. J Phys Chem. 1997;101:10086–93.CrossRefGoogle Scholar
  38. 38.
    Silverstein RM, Webster FX, Kiemle DJ. Spectrometric identification of organic compounds. 7th ed. New York: Wiley; 2005.Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Chemistry Department, School of ScienceSão Paulo State University (UNESP)BauruBrazil

Personalised recommendations