Advertisement

Polymer Bulletin

, Volume 76, Issue 1, pp 423–445 | Cite as

Long- and short-term stability of plasticized poly(lactic acid): effects of plasticizers type on thermal, mechanical and morphological properties

  • Mehmet KodalEmail author
  • Humeyra Sirin
  • Guralp Ozkoc
Original Paper
  • 92 Downloads

Abstract

In this work, PLA was plasticized with poly(ethylene glycol) (PEG) having different molecular weights such as 400, 8000 and 35,000 g/mol at various concentrations ranging from 5 to 20%. In addition, a new plasticizer, PEG-functionalized polyhedral oligomeric silsesquioxane (PEG-POSS), was used for comparison. The short- and long-term mechanical, thermal, and morphological properties of PLA and plasticized PLA were determined by tensile tests, differential scanning calorimetry, and scanning electron microscopy (SEM), respectively. All the blends were found to be miscible in the entire composition range, since a single Tg was observed. Blending with PEGs and PEG-POSS decreased the tensile modulus and yield strength and increased the elongation at break. The plasticized samples were stored under ambient conditions of temperature and humidity for 4 months and 1 and 2 years to determine their long-term properties. Physical aging was only seen in PEG-400-plasticized PLA samples for 4 months after production. It was found that glass transition temperature, tensile modulus and yield strength increased and the elongation at break decreased for 1-year-old samples. Migration of plasticizers with time was proved by SEM analysis.

Keywords

Poly(lactic acid) Plasticization Mechanical stability Thermal stability Morphological stability 

Notes

Acknowledgements

This study is granted by the research foundation of Kocaeli University (Project No: 2011/83) and the Scientific and Technological Research Council of Turkey (Project No: 111M514).

Supplementary material

289_2018_2388_MOESM1_ESM.docx (676 kb)
Supplementary material 1 (DOCX 675 kb)

References

  1. 1.
    Gumus S, Ozkoc G, Aytac A (2012) Plasticized and unplasticized PLA/organoclay nanocomposites: short- and long-term thermal properties, morphology, and nonisothermal crystallization behavior. J Appl Polym Sci 123:2837–2848CrossRefGoogle Scholar
  2. 2.
    Kodal M, Sirin H, Ozkoc G (2014) Effects of reactive and nonreactive POSS types on the mechanical, thermal, and morphological properties of plasticized poly(lactic acid). Polym Eng Sci 54:264–275CrossRefGoogle Scholar
  3. 3.
    Yuan Y, Hu Z, Fu X, Jiang L, Xiao Y, Hu K, Yan P, Lei J (2016) Poly(lactic acid) plasticized by biodegradable glyceryl lactate. J Appl Polym Sci 133:43460Google Scholar
  4. 4.
    Qin Y, Wang Y, Wu Y, Zhang Y, Li H, Yuan M (2015) Effect of hexadecyl lactate as plasticizer on the properties of poly(l-lactide) films for food packaging applications. J Polym Environ 23:374–382CrossRefGoogle Scholar
  5. 5.
    Yang X, Hakkarainen M (2015) Migration resistant glucose esters as bioplasticizers for polylactide. J Appl Polym Sci 132:41928Google Scholar
  6. 6.
    Yang Y, Xiong Z, Zhang L, Tang Z, Zhang R, Zhu J (2016) Isosorbide dioctoate as a “green” plasticizers for poly(lactic acid). Mater Design 91:262–268CrossRefGoogle Scholar
  7. 7.
    Xing C, Matuana LM (2016) Epoxidized soybean oil-plasticized poly(lactic acid) films performance as impacted by storage. J Appl Polym Sci 133:43201CrossRefGoogle Scholar
  8. 8.
    Darie-Nita RN, Vasile C, Irimia A, Lipşa R, Rapa M (2016) Evaluation of some eco-friendly plasticizers for PLA films processing. J Appl Polym Sci 133:43223CrossRefGoogle Scholar
  9. 9.
    Tee YB, Talib RA, Abdan K, Chin NL, Basha RK, Yunus KFM (2016) Comparative study of chemical, mechanical, thermal and barrier properties of poly(lactic acid) plasticized with epoxidized soybean oil and epoxidized palm oil. BioResources 11:1518–1540CrossRefGoogle Scholar
  10. 10.
    Wang Y, Qin Y, Zhang Y, Yuan M, Li H, Yuan M (2014) Effects of N-octyl lactate as plasticizer on the thermal and functional properties of extruded PLA-based films. Int J Biol Macromol 67:58–63CrossRefGoogle Scholar
  11. 11.
    Tanrattanakul V, Bunkaew P (2014) Effect of different plasticizers on the properties of bio-based thermoplastic elastomer containing poly(lactic acid) and natural rubber. Express Polym Lett 8:387–389CrossRefGoogle Scholar
  12. 12.
    Martin O, Averous L (2001) Poly(lactic acid): plasticization and properties of biodegradable multiphase systems. Polymer 42:6209–6219CrossRefGoogle Scholar
  13. 13.
    Maiza M, Benaniba MT, Quintard G, Massardier-Nageotte V (2015) Biobeased additive plasticizing poly(lactic acid). Polimeros 25:581–590CrossRefGoogle Scholar
  14. 14.
    Harte I, Birkinshaw C, Jones E, Kennedy J, DeBarra E (2013) The effect of citrate ester plasticizers on the thermal and mechanical properties of poly(dl-lactide). J Appl Polym Sci 127:1997–2003CrossRefGoogle Scholar
  15. 15.
    Biardo M, Frisoni G, Scandola M, Rimelen M, Lips D, Ruffieux K, Wintermantel E (2003) Thermal and mechanical properties of plasticized poly(l-lactic acid). J Appl Polym Sci 90:1731–1738CrossRefGoogle Scholar
  16. 16.
    Ferri JM, Samper MD, Garcia-Sanoguera D, Reig MJ, Fenollar O, Balart R (2016) Plasticizing effect of biobased epoxidized fatty acid esters on mechanical and thermal properties of poly(lactic acid). J Mater Sci 51:5356–5366CrossRefGoogle Scholar
  17. 17.
    Sungsanit K, Kao N, Bhattacharya SN (2012) Properties of linear poly(lactic acid)/polyethylene glycol blends. Polym Eng Sci 52:108–116CrossRefGoogle Scholar
  18. 18.
    Yu Y, Cheng Y, Ren J, Cao E, Fu X, Guo W (2015) Plasticizing effect of poly(ethylene glycol)s with different molecular weights in poly(lactic acid)/starch blends. J Appl Polym Sci 132:41808Google Scholar
  19. 19.
    Sheth M, Kumar RA, Dave V, Gross RA, Mccarthy SP (1997) Biodegradable polymer blends of poly(lactic acid) and poly (ethylene glycol). J Appl Polym Sci 66:1495–1505CrossRefGoogle Scholar
  20. 20.
    Pivsa-Art W, Fujii K, Nomura K, Aso Y, Ohara H, Yamane H (2016) The effect of poly(ethylene glycol) as plasticizer in blends of poly(lactic acid) and poly(butylene succinate). J Appl Polym Sci 133:43044CrossRefGoogle Scholar
  21. 21.
    Chieng BW, Ibrahim NA, Yunus WMZW, Hussein MZ (2013) Plasticized poly(lactic acid) with low molecular weight poly(ethylene glycol): mechanical, thermal, and morphology properties. J Appl Polym Sci 130:4576–4580Google Scholar
  22. 22.
    Ljunberg N, Wesslen B (2003) Tributyl citrate oligomers as plasticizers for poly(lactic acid): thermo-mechanical film properties and aging. Polymer 44:7679–7688CrossRefGoogle Scholar
  23. 23.
    Burgos N, Martino VP, Jimenez A (2013) Characterization and ageing study of poly(lactic acid) films plasticized with oligomeric lactic acid. Polym Degrad Stabil 98:651–658CrossRefGoogle Scholar
  24. 24.
    Goncalves CMB, Tome LC, Coutinho JAP, Marrucho IM (2011) Addition of α-tocopherol on poly(lactic acid): thermal, mechanical, and sorption properties. J Appl Polym Sci 119:2468–2475CrossRefGoogle Scholar
  25. 25.
    Zubrowska A, Piorkowska E, Kowalewska A, Cichorek M (2015) Novel blends of polylactide with ethylene glycol derivatives of POSS. Colloid Polym Sci 293:23–33CrossRefGoogle Scholar
  26. 26.
    Cangialosi D, Boucher VM, Alegria A, Colmenero J (2013) Physical aging in polymers and polymer nanocomposites: recent results and open questions. Soft Matter 9:8619–8630CrossRefGoogle Scholar
  27. 27.
    Mohamed EHA (2011) The effect of annealing treatments on spherulitic morphology and physical ageing on glass transition of poly lactic acid (PLLA). Mater Sci Appl 2:439–443Google Scholar
  28. 28.
    Hu Y, Rogunova M, Topolkaraev V, Hiltner A, Baer E (2003) Aging of poly(lactide)/poly(ethylene glycol) blends. Part 1. Poly(lactide) with low stereoregularity. Polymer 44:5701–5710CrossRefGoogle Scholar
  29. 29.
    Hu Y, Hu YS, Topolkaraev V, Hiltner A, Baer E (2003) Aging of poly(lactide)/poly(ethylene glycol) blends. Part 2. Poly(lactide) with low stereoregularity. Polymer 44:5711–5720CrossRefGoogle Scholar
  30. 30.
    Pluta M, Paul MA, Alexandre M, Dubois P (2006) Plasticized polylactide/clay nanocomposites. II. The effect of aging on structure and properties in relation to the filler content and the nature of its organo-modification. J Polym Sci Pol Phys 44:312–325CrossRefGoogle Scholar
  31. 31.
    Qiu Z, Pan H (2010) Preparation, crystallization and hydrolytic degradation of biodegradable poly(L-lactide)/polyhedral oligomeric silsesquioxanes nanocomposite. Compos Sci Technol 70:1089–1094CrossRefGoogle Scholar
  32. 32.
    Yu J, Qiu Z (2011) Effect of low octavinyl- polyhedral oligomeric silsesquioxanes loadings on the melt crystallization and morphology of biodegradable poly(L-lactide). Thermochim Acta 519:90–95CrossRefGoogle Scholar
  33. 33.
    Jung CH, Hwang IT, Jung CH, Choi JH (2014) Preparation of flexible PLA/PEG-POSS nanocomposites by melt blending and radiation crosslinking. Radiat Phys Chem 102:23–28CrossRefGoogle Scholar
  34. 34.
    Turan D, Sirin H, Ozkoc G (2011) Effects of POSS particles on the mechanical, thermal and morphological properties of PLA and plasticized PLA. J Appl Polym Sci 121:1067–1075CrossRefGoogle Scholar
  35. 35.
    Migliaresi C, Cohn D, De Lollis A, Fambri L (1991) Dynamic mechanical and calorimetric analysis of compression-molded PLLA of different molecular weights: effect of thermal treatments. J Appl Polym Sci 43:83–95CrossRefGoogle Scholar
  36. 36.
    Pan P, Liang Z, Zhu B, Dong T, Inoue Y (2008) Roles of physical aging on crystallization kinetics and induction period of poly(L-lactide). Macromolecules 41:8011–8019CrossRefGoogle Scholar
  37. 37.
    Constantinos T, Bokaris EP (1993) Enthalpy relaxation studies in isotactic polystyrene. Effects of crystallinity. Polym Bull 30:609–616CrossRefGoogle Scholar
  38. 38.
    Santhoskumar AU, Ramkumar A (2014) Preparation/characterization of plasticized poly(lactic acid) for packaging applications. Firat Univ Turkish J Sci Technol 9:73–79Google Scholar
  39. 39.
    Alperstein D, Knani D, Goichman A, Narkis M (2012) Determination of plasticizsers efficiency for nylon by molecular modeling. Polym Bull 68:1977–1998CrossRefGoogle Scholar
  40. 40.
    Rasal RM, Janorkar AV, Hirt DE (2010) Poly(lactic acid) modifications. Prog Polym Sci 35:338–356CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Chemical EngineeringKocaeli UniversityIzmitTurkey

Personalised recommendations