Chemical Papers

, Volume 73, Issue 5, pp 1121–1134 | Cite as

Biodegradability of blends based on aliphatic polyester and thermoplastic starch

  • Vesna Ocelić BulatovićEmail author
  • Dajana Kučić Grgić
  • Miroslav Slouf
  • Aleksandra Ostafinska
  • Jiri Dybal
  • Antun Jozinović
Original Paper


In this work, biodegradable aliphatic polyester blends of polycaprolactone and polylactide were melted and blended with a natural and biodegradable thermoplastic starch (TPS). The TPS employed in this study was obtained by plasticization of isolated wheat starch using glycerol as plasticizer. Morphology as well as thermal properties of the blends was investigated, and water vapor permeability as a barrier property was also monitored. The biodegradability of the biodegradable blends was performed by a composting process on laboratory scale. The composting process was conducted in an adiabatic closed reactor for 21 days and during the composting process, the temperature, pH value, % moisture and volatile matter and evolved CO2 were monitored. Biodegradation of the blends was determined by weight loss, as well as monitoring of morphological surface change. The thermophilic phase prevailed in the composting process, indicating intensive biodegradation of substrate as well as biodegradation of investigated ternary blends. Since microorganisms use starch as a carbon source, addition of TPS causes considerable acceleration of biodegradation of ternary blends due to higher water vapor permeability as a result of the hydrophilic nature of starch. The thermoplastic starch was first degraded within the blend, which was facilitated access to the microorganisms of other ingredients in the blend, encouraging the biodegradation of other components.


Aliphatic polyester Thermoplastic starch Biodegradation Composting process 



This study was funded by the University of Zagreb, Croatia (Grant no. 110001/2013). Electron microscopy at the Institute of Macromolecular Chemistry was supported by projects TE01020118 (Technology Agency of the CR) and POLYMAT LO1507 (Ministry of Education, Youth and Sports of the CR, program NPU I).

Compliance with ethical standards

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Supplementary material

11696_2018_663_MOESM1_ESM.pdf (679 kb)
Supplementary material 1 (PDF 678 kb)


  1. Abdul KHPS, Tye YY, Saurabh CK, Leh CP, Lai TK, Chong EWN, Fazita NMR, Mohd HJ, Banerjee A, Syakir MI (2017) Biodegradable polymer films from seaweed polysaccharides: a review on cellulose as a reinforcement material. eXPRESS Polym Lett 11:244–265. CrossRefGoogle Scholar
  2. Ačkar Ð, Babić J, Šubarić D, Kopjar M, Miličević B (2010) Isolation of starch from two wheat varieties and their modification with epichlorohydrin. Carbohydr Polym 81:76–82. CrossRefGoogle Scholar
  3. Antosik AK, Wilpiszewska K (2018) Natural composites based on polysaccharide derivatives: preparation and physicochemical properties. Chem Pap 72:3215–3218. CrossRefGoogle Scholar
  4. Auras R, Harte B, Selke SE (2004) An overview of polylactides as packaging materials. Macromol Biosci 4:835–864. CrossRefGoogle Scholar
  5. Austrian Standards Institute (1986) Austrian standard: analytical methods and quality control for waste compost. ÖNORM S 2023, ViennaGoogle Scholar
  6. Averous L, Moro L, Dole P, Fringant C (2000) Properties of thermoplastic blends: starch-polycaprolactone. Polymer 41:4157–4167. CrossRefGoogle Scholar
  7. Bota J, Lj Kratofil Krehula, Katančić Z, Brozović M, Hrnjak-Murgić Z (2017) Surface characteristics and enhancement of water vapor properties of paperboard coated with polycaprolactone nanocomposites. J Adhes Sci Technol 31:1–21. CrossRefGoogle Scholar
  8. Briški F, Kopčić N, Ćosić I, Kučić D, Vuković M (2012) Biodegradation of tobacco waste by composting: genetic identification of nicotine-degrading bacteria and kinetic analysis of transformations in leachate. Chem Pap 66:1103–1110. Google Scholar
  9. Brody AL (2005) Commercial uses of active food packaging and modified atmosphere packaging systems. In: Han JH (ed) Innovations in food packaging. Elsevier Science, Oxford, pp 457–474CrossRefGoogle Scholar
  10. Broz ME, Vander HDL, Washburn NR (2003) Structure and mechanical properties of poly(d, l-lactic acid)/poly(ϵ-caprolactone) blends. Biomaterials 24:4181–4190. CrossRefGoogle Scholar
  11. Carbonell-Verdu Ferri JM, Dominici F, Boronat T, Sanchez-Nacher L, Balart R, Torre L (2018) Manufacturing and compatibilization of PLA/PBAT binary blends by cottonseed oil-based derivatives. eXPRESS Polym Lett 12:808–823. CrossRefGoogle Scholar
  12. Carmona VB, Correˆ AC, Marconcini JM, Capparelli Mattoso LH (2015) Properties of a biodegradable ternary blend of thermoplastic starch (TPS), poly(e-caprolactone) (PCL) and poly(lactic acid) (PLA). J Polym Environ 23:83–89. CrossRefGoogle Scholar
  13. Carvalho AJF, Zambon MD, Curvelo AAS, Gandini A (2003) Size exclusion chromatography characterization of thermoplastic starch composites 1. Influence of plasticizer and fibre content. Polym Degrad Stab 79:133–138. CrossRefGoogle Scholar
  14. Chen L, Qiu X, Xie Z, Hong Z, Sun J, Chen X, Jing X (2006) Poly(l-lactide)/starch blends compatibilized with poly(l-lactide)-g-starch copolymer. Carbohydr Polym 65:75–80. CrossRefGoogle Scholar
  15. Crescenzi V, ManziniG Calzolari G, Borri C (1972) Thermodynamics of fusion of poly-β-propiolactone and poly-ϵ-caprolactone. Comparative analysis of the melting of aliphatic polylactone and polyester chains. Eur Polym J 8:449–463. CrossRefGoogle Scholar
  16. Curvelo AAS, Carvalho AJF, Agnelli JAM (2001) Thermoplastic starch-cellulosic fibers composites: preliminary results. Carbohydr Polym 45:183–188. CrossRefGoogle Scholar
  17. Davoodi S, Oliaei E, Davachi SM, Hejazi I, Seyfi J, Be S, Ebrahimi H (2016) Preparation and characterization of interface-modified PLA/starch/PCL ternary blends using PLLA/triclosan antibacterial nanoparticles for medical applications. RSC Adv. 6:39870–39882. CrossRefGoogle Scholar
  18. Feng F, Ye L (2011) Morphologies and mechanical properties of polylactide/thermoplastic polyurethane elastomer blends. J Appl Polym Sci 119:2778–2783. CrossRefGoogle Scholar
  19. Ferreira ARV, Alves VD, Coelhoso IM (2016) Polysaccharide-based membranes in food packaging applications. Membranes (Basel) 6:22–39. CrossRefGoogle Scholar
  20. Ferri JM, Fenollar O, Jorda-Vilaplana A, García-Sanoguera D, Balart R (2016) Effect of miscibility on mechanical and thermal properties of poly(lactic acid)/polycaprolactone blends. Polym Int 65:453–463. CrossRefGoogle Scholar
  21. Fortelny I, Slouf M, Sikora A, Hlavata D, Hasova V, Mikesova J, Jacob C (2006) The effect of the architecture and concentration of styrene-butadiene compatibilizers on the morphology of polystyrene/low-density polyethylene blends. J Appl Polym Sci 100:2803–2816. CrossRefGoogle Scholar
  22. Fox PG, Fuller KNG (1971) Thermal mechanism for craze formation in brittle amorphous polymers. Nat Phys Sci 234:13–14. CrossRefGoogle Scholar
  23. Garcia-Campo MJ, Quiles-Carrillo L, Masia J, ReigPérez MJ, Montanes N, Balart R (2017) Environmentally friendly compatibilizers from soybean oil for ternary blends of poly(lactic acid)-PLA, poly(epsilon-caprolactone)-PCL and poly(3-hydroxybutyrate)-PHB. Materials 10:1339/1–1339/19. CrossRefGoogle Scholar
  24. Ghasemlou M, Aliheidari N, Fahmi R, Shojaee-Aliabadi S, Keshavarz B, Cran MJ, Khaksar R (2013) Physical, mechanical and barrier properties of corn starch films incorporated with plant essential oils. Carbohydr Polym 98:1117–1126. CrossRefGoogle Scholar
  25. Gumede TP, Luyt AS, Müller AJ (2018) Review on PCL, PBS, and PCL/PBS blends containing carbon nanotubes. eXPRESS Polym Lett 12:505–529. CrossRefGoogle Scholar
  26. Hosseini SF, Rezaei M, Zandi M, Ghavi FF (2013) Preparation and functional properties of fish gelatin–chitosan blend edible films. Food Chem 136:1490–1495. CrossRefGoogle Scholar
  27. Huang SJ (2005) Poly(lactic acid) and copolyesters. In: Bastioli C (ed) Handbook of biodegradable polymers. Rapra Technology Litmited, Shawbury, pp 287–297Google Scholar
  28. Huang M, Yu J, Ma X (2005) Ethanolamine as a novel plasticiser for thermoplastic starch. Polym Degrad Stab 90:501–507. CrossRefGoogle Scholar
  29. Jayasekara R, Harding I, Bowater I, Lonergan G (2005) Biodegradability of a selected range of polymers and polymer blends and standard methods for assessment of biodegradation. J Polym Environ 13:231–251. CrossRefGoogle Scholar
  30. Jiang W, Qiao X, Sun K (2006) Mechanical and thermal properties of thermoplastic acetylated starch/poly(ethylene-co-vinyl alcohol) blends. Carbohydr Polym 65:139–143. CrossRefGoogle Scholar
  31. Kolthoff IM, Sandel EB (1951) Inorganic quantitative analysis. Školska knjiga, Zagreb, pp 347–352Google Scholar
  32. Kostakova EK, Meszaros L, Maskova G, Blazkova L, Turcsan T, Lukas D (2017) Crystallinity of electrospun and centrifugal spun polycaprolactone fibers: a comparative study. J Nanomater. Google Scholar
  33. Kučić D, Kopčić N, Briški F (2013) Zeolite and potting soil sorption of CO2 and NH3 evolved during co-composting of grape and tobacco waste. Chem Pap 67:1172–1180. Google Scholar
  34. Labet M, Thielemans W (2009) Synthesis of polycaprolactone: a review. Chem Soc Rev 38:3484–3504. CrossRefGoogle Scholar
  35. Lu X, Zhao J, Yang X, Xiao P (2017) Morphology and properties of biodegradable poly (lactic acid)/poly (butylene adipate-co-terephthalate) blends with different viscosity ratio. Polym Test 60:58–67. CrossRefGoogle Scholar
  36. Mittal V, Akhtar T, Matsko N (2015) Mechanical, thermal, rheological and morphological properties of binary and ternary blends of PLA, TPS and PCL. Macromol Mater Eng 300:423–435. CrossRefGoogle Scholar
  37. Musioł M, Sikorska W, Janeczek H, Wałach W, Hercog A, Johnston B, Rydz J, Rydz J (2018) (Bio)degradable polymeric materials for a sustainable future—part 1. Organic recycling of PLA/PBAT blends in the form of prototype packages with long shelf-life. Waste Manag 77:447–454. CrossRefGoogle Scholar
  38. Nair LS, Laurencin CT (2007) Biodegradable polymers as biomaterials. Prog Polym Sci 32:762–798. CrossRefGoogle Scholar
  39. Neto BAM, Fornari Junior CCM, da Silva EGP, Franco M, Reis NS, Bonomo RCF, de Almeida PF, Pontes KV (2017) Biodegradable thermoplastic starch of peach palm (Bactris gasipaes Kunth) fruit: production and characterisation. Int J Food Prop 20:S2429–S2440. CrossRefGoogle Scholar
  40. Ortega-Toro R, Morey I, Talens P, Chiralt A (2015) Active bilayer films of thermoplastic starch and polycaprolactone obtained by compression molding. Carbohydr Polym 127:282–290. CrossRefGoogle Scholar
  41. Palsikowski PA, Kuchnier CN, Pinheiro IF, Morales AR (2018) Biodegradation in soil of PLA/PBAT blends compatibilized with chain extender. J Polym Environ 26:330–334CrossRefGoogle Scholar
  42. Perotti GF, Kijchavengkul T, Auras RA, Constantino VRL (2017) Nanocomposites based on cassava starch and chitosan. Modified clay: physico-mechanical properties and biodegradability in simulated compost soil. J Braz Chem Soc 28:649–658. Google Scholar
  43. Plichta A, Lisowska P, Kundys A, Zychewicz A, Debowski M, Florjanczyk Z (2014) Chemical recycling of poly(lactic acid) via controlled degradation with protic (macro)molecules. Polym Degrad Stab 108:288–296. CrossRefGoogle Scholar
  44. Rhim J-W, Lee JH, Ng Perry KW (2007) Mechanical and barrier of biodegradable soy protein isolate-based films coated with polylactic acid. LWT Food Sci Technol 40:232–238. CrossRefGoogle Scholar
  45. Sarazin P, Li G, Orts WJ, Favis BD (2008) Binary and ternary blends of polylactide, polycaprolactone and thermoplastic starch. Polymer 49:599–609. CrossRefGoogle Scholar
  46. Selke SE (2000) Plastics recycling and biodegradable plastics. In: Harper CA (ed) Modern plastics handbook. McGraw-Hill, New York, pp 12.1–12.108Google Scholar
  47. Selke SE, Culter JD, Hernandez RJ (2004) Plastics packaging: properties, processing, applications, and regulations. Hanser, Cincinnati, pp 448–467Google Scholar
  48. Shogren R (1997) Water vapor permeability of biodegradable polymers. J Environ Polym Degrad 5:91–95. CrossRefGoogle Scholar
  49. Siracusa V, Rocculi P, Romani S, Rosa MD (2008) Biodegradable polymers for food packaging: a review. Trends Food Sci Technol 19:634–643. CrossRefGoogle Scholar
  50. Slouf M, Kolarik J, Fambri L (2004) Phase morphology of PP/COC blends. J Appl Polym Sci 91:253–259. CrossRefGoogle Scholar
  51. Sorrentino A, Gorrasi G, Vittoria V (2007) Potential perspectives of bio-nanocomposites for food packaging applications. Trends Food Sci Technol 18:84–95. CrossRefGoogle Scholar
  52. Su J, Chen L, Li L (2012) Characterization of polycaprolactone and starch blends for potential application within the biomaterials field. Afr J Biotechnol 11:694–701. Google Scholar
  53. Sun H, Xiao A, Yu B, Bhat G, Zhu F (2017) Effect of PCL and compatibilizer on the tensile and barrier properties of PLA/PCL films. Polymer (Korea) 4:181–188. CrossRefGoogle Scholar
  54. Taggort P (2004) Starch as an ingredient: manufacture and applications. In: Eliasson AC (ed) Starch in food: structure, function and applications. Woodhead Publishing Limited, Cambridge, pp 363–392CrossRefGoogle Scholar
  55. Thakur VK, Thakur MK (2016) Handbook of sustainable polymers: processing and applications. Pan Stanford Publishing, SingaporeCrossRefGoogle Scholar
  56. Tumwesigye KS, Oliveira JC, Sousa-Gallagher MJ (2016) New sustainable approach to reduce cassava borne environmental waste and develop biodegradable materials for food packaging applications. Food Packag Shelf Life 7:8–19. CrossRefGoogle Scholar
  57. Vertuccio L, Gorrasi G, Sorrentino A, Vittoria V (2009) Nano clay reinforced PCL/starch blends obtained by high energy ball milling. Carbohydr Polym 75:172–179. CrossRefGoogle Scholar
  58. Yu L, Dean K, Li L (2006) Polymer blends and composites from renewable resources. Prog Polym Sci 31:576–602. CrossRefGoogle Scholar
  59. Zembouai I, Kaci M, Bruzaud S, Benhamida A, Corre Y-M, Grohens Y (2013) A study of morphological, thermal, rheological and barrier properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/polylactide blends prepared by melt mixing. Polym Test 32:842–851. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2018

Authors and Affiliations

  1. 1.Faculty of Chemical Engineering and TechnologyUniversity of ZagrebZagrebCroatia
  2. 2.Institute of Macromolecular Chemistry, Academy of Sciences of the Czech RepublicPrague 6Czech Republic
  3. 3.Faculty of Food TechnologyUniversity of Josip Juraj Strossmayer OsijekOsijekCroatia

Personalised recommendations