Preparation of acylated microcrystalline cellulose using olive oil and its reinforcing effect on poly(lactic acid) films for packaging application

  • Ravindra D. Kale
  • Vikrant G. Gorade


A novel poly(lactic acid) (PLA) based composite, reinforced by microcrystalline cellulose (MCC) was prepared. MCC was modified by esterification reaction using olive oil for improving the compatibility with PLA matrix. The acylated microcrystalline cellulose (AMCC) exhibited reduced polarity in comparison to unmodified MCC. AMCC/ PLA composite films were prepared using solvent casting technique. The effects of the MCC surface modification on morphological, mechanical, physical, thermal, biodegradability and barrier properties of the PLA based MCC composites were studied. FTIR analysis confirmed acylation reaction of MCC. Scanning electron microscopy analysis exhibited a uniform distribution of AMCC in PLA matrix. Barrier properties of AMCC based composites were improved as compared to MCC based composites. The tensile strength and tensile modulus of composite films (at 2 wt.% AMCC) were improved about 13% and 35% as much as those of the pure PLA films, respectively. These biodegradable composite films can be a sustainable utilization of olive oil and microcrystalline cellulose in the food packaging application.


Bioresource Microcrystalline cellulose Olive oil Surface acylation Ultraviolet protection Biodegradability 



One of the authors Vikrant G. Gorade is indebted to World Bank-funded TEQIP-II - CoE in Process Intensification, for the scholarship support during the Ph.D. course. The authors would like to thank the DST-FIST for providing testing facilities.

Author contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ‡Vikrant G. Gorade contributed equally to this work.

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interest.


  1. 1.
    Mukherjee T, Sani M, Kao N et al (2013) Improved dispersion of cellulose microcrystals in polylactic acid (PLA) based composites applying surface acetylation. Chem Eng Sci 101:655–662. CrossRefGoogle Scholar
  2. 2.
    Guo W, Bao F, Wang Z (2013) Biodegradability of wood fiber/poly(lactic acid) composites. J Compos Mater 47:3573–3580. CrossRefGoogle Scholar
  3. 3.
    Tunç S, Duman O (2011) Preparation of active antimicrobial methyl cellulose/carvacrol/montmorillonite nanocomposite films and investigation of carvacrol release. LWT-Food Sci Technol 44:465–472. CrossRefGoogle Scholar
  4. 4.
    Kumar S, Koh J (2014) Physiochemical and optical properties of chitosan based graphene oxide bionanocomposite. Int J Biol Macromol 70:559–564. CrossRefGoogle Scholar
  5. 5.
    Çetin NS, Özmen Çetin N, Harper DP (2015) Vinyl acetate-modified microcrystalline cellulose-reinforced HDPE composites prepared by twin-screw extrusion. Turk J Agric For 39:39–47. CrossRefGoogle Scholar
  6. 6.
    Dubief D, Samain E, Dufresne A (1999) Polysaccharide microcrystals reinforced amorphous poly(β-hydroxyoctanoate) nanocomposite materials. Macromolecules 32:5765–5771. CrossRefGoogle Scholar
  7. 7.
    Ten E, Turtle J, Bahr D et al (2010) Thermal and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/cellulose nanowhiskers composites. Polymer (Guildf) 51:2652–2660. CrossRefGoogle Scholar
  8. 8.
    Habibi Y, Dufresne A (2008) Highly filled bionanocomposites from functionalized polysaccharide nanocrystals. Biomacromolecules 9:1974–1980. CrossRefGoogle Scholar
  9. 9.
    Ruiz MM, Cavaillé JY, Dufresne A et al (2000) Processing and characterization of new thermoset nanocomposites based on cellulose whiskers. Compos Interfaces 7:117–131. CrossRefGoogle Scholar
  10. 10.
    Garcia de Rodriguez NL, Thielemans W, Dufresne A (2006) Sisal cellulose whiskers reinforced polyvinyl acetate nanocomposites. Cellulose 13:261–270. CrossRefGoogle Scholar
  11. 11.
    Chazeau L, Cavaillé JY, Terech P (1999) Mechanical behaviour above T(g) of a plasticised PVC reinforced with cellulose whiskers; a SANS structural study. Polymer (Guildf) 40:5333–5344. CrossRefGoogle Scholar
  12. 12.
    Chazeau L, Paillet M, Cavaillé JY (1999) Plasticized PVC reinforced with cellulose whiskers. I. Linear viscoelastic behavior analyzed through the quasi-point defect theory. J Polym Sci Part B Polym Phys 37:2151–2164.<2151::AID-POLB17>3.0.CO;2-V CrossRefGoogle Scholar
  13. 13.
    Liu D, Zhong T, Chang PR et al (2010) Starch composites reinforced by bamboo cellulosic crystals. Bioresour Technol 101:2529–2536. CrossRefGoogle Scholar
  14. 14.
    Marcovich NE, Auad ML, Bellesi NE et al (2006) Cellulose micro/nanocrystals reinforced polyurethane. J Mater Res 21:870–881. CrossRefGoogle Scholar
  15. 15.
    Bondeson D, Oksman K (2007) Polylactic acid/cellulose whisker nanocomposites modified by polyvinyl alcohol. Compos A Appl Sci Manuf 38:2486–2492. CrossRefGoogle Scholar
  16. 16.
    Petersson L, Kvien I, Oksman K (2007) Structure and thermal properties of poly(lactic acid)/cellulose whiskers nanocomposite materials. Compos Sci Technol 67:2535–2544. CrossRefGoogle Scholar
  17. 17.
    Oksman K, Mathew AP, Bondeson D, Kvien I (2006) Manufacturing process of cellulose whiskers/polylactic acid nanocomposites. Compos Sci Technol 66:2776–2784. CrossRefGoogle Scholar
  18. 18.
    Kale G, Auras R, Singh SP (2006) Degradation of commercial biodegradable packages under real composting and ambient exposure conditions. J Polym Environ 14:317–334. CrossRefGoogle Scholar
  19. 19.
    Mohammed L, Ansari MNM, Pua G et al (2015) A review on natural fiber reinforced polymer composite and its applications. Int J Polym Sci 2015:1–15. CrossRefGoogle Scholar
  20. 20.
    Peydecastaing J, Vaca-Garcia C, Borredon E (2011) Bi-acylation of cellulose: determining the relative reactivities of the acetyl and fatty-acyl moieties. Cellulose 18:1015–1021. CrossRefGoogle Scholar
  21. 21.
    Lu J, Askeland P, Drzal LT (2008) Surface modification of microfibrillated cellulose for epoxy composite applications. Polymer (Guildf) 49:1285–1296. CrossRefGoogle Scholar
  22. 22.
    Paul A, Joseph K, Thomas S (1997) Effect of surface treatments on the electrical properties of low-density polyethylene composites reinforced with short sisal fibers. Compos Sci Technol 57:67–79. CrossRefGoogle Scholar
  23. 23.
    Kabir MM, Wang H, Lau KT, Cardona F (2012) Chemical treatments on plant-based natural fibre reinforced polymer composites: an overview. Compos Part B Eng 43:2883–2892. CrossRefGoogle Scholar
  24. 24.
    Lindqvist J, Malmström E (2006) Surface modification of natural substrates by atom transfer radical polymerization. J Appl Polym Sci 100:4155–4162. CrossRefGoogle Scholar
  25. 25.
    Kim DY, Nishiyama Y, Kuga S (2002) Surface acetylation of bacterial cellulose. Cellulose 9:361–367. CrossRefGoogle Scholar
  26. 26.
    Ismail H, Rusli A, Rashid AA (2005) Maleated natural rubber as a coupling agent for paper sludge filled natural rubber composites. Polym Test 24:856–862. CrossRefGoogle Scholar
  27. 27.
    Yuan H, Nishiyama Y, Wada M, Kuga S (2006) Surface acylation of cellulose whiskers by drying aqueous emulsion. Biomacromolecules 7:696–700. CrossRefGoogle Scholar
  28. 28.
    Hidayat A, Tachibana S (2012) Characterization of polylactic acid (PLA)/kenaf composite degradation by immobilized mycelia of Pleurotus ostreatus. Int Biodeterior Biodegrad 71:50–54. CrossRefGoogle Scholar
  29. 29.
    Hao Y, Peng J, Li J et al (2009) An ionic liquid as reaction media for radiation-induced grafting of thermosensitive poly (N-isopropylacrylamide) onto microcrystalline cellulose. Carbohydr Polym 77:779–784. CrossRefGoogle Scholar
  30. 30.
    Dankovich TA, Hsieh YL (2007) Surface modification of cellulose with plant triglycerides for hydrophobicity. Cellulose 14:469–480. CrossRefGoogle Scholar
  31. 31.
    Phillips DL, Liu H, Pan D, Corke H (1999) General application of Raman spectroscopy for the determination of level of acetylation in modified starches. Cereal Chem 76:439–443. CrossRefGoogle Scholar
  32. 32.
    Namazi H, Dadkhah A (2010) Convenient method for preparation of hydrophobically modified starch nanocrystals with using fatty acids. Carbohydr Polym 79:731–737. CrossRefGoogle Scholar
  33. 33.
    Gunti R, Ratna Prasad AV, Gupta AVSSKS (2016) Mechanical and degradation properties of natural fiber reinforced PLA composites: jute, sisal, and elephant grass. Polym Compos.
  34. 34.
    Almasi H, Ghanbarzadeh B, Dehghannya J et al (2015) Novel nanocomposites based on fatty acid modified cellulose nanofibers/poly(lactic acid): morphological and physical properties. Food Packag Shelf Life 5:21–31. CrossRefGoogle Scholar
  35. 35.
    American Society for Testing and Materials (2010) ASTM E96/E96M-10 standard test methods for water vapor transmission. Annu B ASTM Stand 4:1–12. Google Scholar
  36. 36.
    Keshk SMAS, Yousef E, Omran A (2015) Preparation and characterization of starch /cellulose composite. Indian J Fibre Text Res 40:190–194Google Scholar
  37. 37.
    Vlachos N, Skopelitis Y, Psaroudaki M et al (2006) Applications of Fourier transform-infrared spectroscopy to edible oils. Anal Chim Acta 573–574:459–465. CrossRefGoogle Scholar
  38. 38.
    Liang P, Chen C, Zhao S et al (2013) Application of fourier transform infrared spectroscopy for the oxidation and peroxide value evaluation in virgin walnut oil. J Spectrosc:1:1–1:5.
  39. 39.
    Kale RD, Gorade VG, Bhor S (2017) Preparation of self-reinforced cellulose composite using microcrystalline cellulose. Indian. J Sci Res 16:3–6Google Scholar
  40. 40.
    Mukherjee T, Tobin MJ, Puskar L et al (2017) Chemically imaging the interaction of acetylated nanocrystalline cellulose (NCC) with a polylactic acid (PLA) polymer matrix. Cellulose 24:1717–1729. CrossRefGoogle Scholar
  41. 41.
    Kale RD, Bansal PS, Gorade VG (2017) Extraction of microcrystalline cellulose from cotton sliver and its comparison with commercial microcrystalline cellulose. J Polym Environ 26:355–364. CrossRefGoogle Scholar
  42. 42.
    Freire CSR, Silvestre AJD, Neto CP et al (2006) Controlled heterogeneous modification of cellulose fibers with fatty acids: effect of reaction conditions on the extent of esterification and fiber properties. J Appl Polym Sci 100:1093–1102. CrossRefGoogle Scholar
  43. 43.
    Tunç S, Duman O (2010) Preparation and characterization of biodegradable methyl cellulose/montmorillonite nanocomposite films. Appl Clay Sci 48:414–424. CrossRefGoogle Scholar
  44. 44.
    Kargarzadeh H, Sheltami RM, Ahmad I et al (2015) Cellulose nanocrystal: a promising toughening agent for unsaturated polyester nanocomposite. Polym (United Kingdom) 56:346–357. Google Scholar
  45. 45.
    Tunç S, Duman O, Polat TG (2016) Effects of montmorillonite on properties of methyl cellulose/carvacrol based active antimicrobial nanocomposites. Carbohydr Polym 150:259–268. CrossRefGoogle Scholar
  46. 46.
    Fortunati E, Peltzer M, Armentano I et al (2012) Effects of modified cellulose nanocrystals on the barrier and migration properties of PLA nano-biocomposites. Carbohydr Polym 90:948–956. CrossRefGoogle Scholar
  47. 47.
    Abdulkhani A, Hosseinzadeh J, Ashori A et al (2014) Preparation and characterization of modified cellulose nanofibers reinforced polylactic acid nanocomposite. Polym Test 35:73–79. CrossRefGoogle Scholar
  48. 48.
    Paralikar SA, Simonsen J, Lombardi J (2008) Poly(vinyl alcohol)/cellulose nanocrystal barrier membranes. J Membr Sci 320:248–258. CrossRefGoogle Scholar
  49. 49.
    Zafar MT, Maiti SN, Ghosh AK (2016) Effect of surface treatments of jute fibers on the microstructural and mechanical responses of poly(lactic acid)/jute fiber biocomposites. RSC Adv 6:73373–73382. CrossRefGoogle Scholar
  50. 50.
    Frone AN, Berlioz S, Chailan JF et al (2011) Cellulose fiber-reinforced polylactic acid. Polym Compos 32:976–985. CrossRefGoogle Scholar
  51. 51.
    Lin N, Chen G, Huang J et al (2009) Effects of polymer-grafted natural nanocrystals on the structure and mechanical properties of poly(lactic acid): a case of cellulose whisker-graft-polycaprolactone. J Appl Polym Sci 113:3417–3425. CrossRefGoogle Scholar
  52. 52.
    Lin N, Huang J, Chang PR et al (2011) Surface acetylation of cellulose nanocrystal and its reinforcing function in poly(lactic acid). Carbohydr Polym 83:1834–1842. CrossRefGoogle Scholar
  53. 53.
    Yu T, Ren J, Li S et al (2010) Effect of fiber surface-treatments on the properties of poly(lactic acid)/ramie composites. Compos A Appl Sci Manuf 41:499–505. CrossRefGoogle Scholar
  54. 54.
    Suchaiya V, Aht-Ong D (2014) Microwave-assisted modification of cellulose as a compatibilizer for PLA and MCC biocomposite film: effects of side chain length and content on mechanical and thermal properties. Polym Polym Compos 22:613–624Google Scholar
  55. 55.
    Tee YB, Talib RA, Abdan K et al (2013) Thermally grafting aminosilane onto kenaf-derived cellulose and its influence on the thermal properties of poly(lactic acid) composites. Bioresources 8:4468–4483. CrossRefGoogle Scholar
  56. 56.
    Wang Y, Tong B, Hou S et al (2011) Transcrystallization behavior at the poly(lactic acid)/sisal fibre biocomposite interface. Compos A Appl Sci Manuf 42:66–74. CrossRefGoogle Scholar
  57. 57.
    Martins IMG, Magina SP, Oliveira L et al (2009) New biocomposites based on thermoplastic starch and bacterial cellulose. Compos Sci Technol 69:2163–2168. CrossRefGoogle Scholar
  58. 58.
    Auras R, Harte B, Selke S (2004) An overview of polylactides as packaging materials. Macromol Biosci 4:835–864. CrossRefGoogle Scholar
  59. 59.
    Goriparthi BK, Suman KNS, Nalluri MR (2012) Processing and characterization of jute fiber reinforced hybrid biocomposites based on polylactide/polycaprolactone blends. Polym Compos 33:237–244. CrossRefGoogle Scholar

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© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Fibres and Textile Processing TechnologyInstitute of Chemical TechnologyMumbaiIndia

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