Polymer Bulletin

, Volume 73, Issue 12, pp 3485–3502 | Cite as

Polylactic acid and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) nano and microparticles for packaging bioplastic composites

  • Rebeca BouzaEmail author
  • María del Mar Castro
  • Sonia Dopico-García
  • M. Victoria González-Rodríguez
  • Luis F. Barral
  • Birgit Bittmann
Original Paper


Two methods, nanoprecipitation and emulsification/solvent evaporation with different solvents, to prepare nano and microparticles of polylactic acid (PLA) and PHBV are investigated. The obtained particles are characterized in terms of morphology by SEM and thermal properties by DSC and TGA. The objective is the preparation of PLA and PHBV nano and microparticles, with controlled shape and size distribution, for their further inclusion into biopolymer matrices such as PLA, PHBV or thermoplastic starch matrices. The purpose is the use of these biocomposites in the sector of wrapping and packaging. Good thermal properties of the nano and microparticles are important to the posterior processing as extrusion film technique. Although the smallest particles are obtained for PLA using nanoprecipitation technique with THF as solvent, these nanoparticles show a low thermal stability. The emulsification technique using dichloromethane as solvent shows to be a good option to obtain, for PLA and PHBV, spherical particles with controlled size and adequate thermal stability. The reproducibility of the selected method is studied for up-scaling nano and microparticle production to pre-industrial level. This study of reproducibility using statistical analysis shows the robustness of the methodology.


PLA PHBV Nanoprecipitation Emulsification/solvent evaporation SEM DSC TGA 



Financial support was provided from Ministerio de Economía y Competitividad (MAT2013-41892-R, Project NanoCompBioPol) and Xunta de Galicia Government (Autonomous Community Government) and FEDER: Program of Consolidation and Structuring Competitive Research Units (GRC 2014/036).


  1. 1.
    Nilsson C, Birnbaum S, Nilsson S (2007) Use of nanoparticles in capillary and microchip electrochromatography. J Chromatogr A 1168:212–224CrossRefGoogle Scholar
  2. 2.
    Mora-Huertas CE, Fessi H, Elaissari A (2010) Polymer-based nanocapsules for drug delivery. Int J Pharm 385:113–142CrossRefGoogle Scholar
  3. 3.
    Lu X, Zhang W, Wang C, Wen TC, Wei Y (2010) One-dimensional conducting polymer nanocomposites: synthesis, properties and applications. Prog Polym Sci 36:671–712CrossRefGoogle Scholar
  4. 4.
    Dhillon GS, Kaur S, Verma M, Brar SK (2010) Biopolymer-based nanomaterials: potential applications in bioremediation of contaminated wastewaters and soils. Compr Anal Chem 59:91–129CrossRefGoogle Scholar
  5. 5.
    Rao JP, Geckeler KE (2011) Polymer nanoparticles: preparation techniques and size-control parameters. Prog Polym Sci 36:887–913CrossRefGoogle Scholar
  6. 6.
    Legrand P, Lesieur S, Bochot A, Gref R, Raatjes W, Barratt G, Vauthiera C (2007) Influence of polymer behaviour in organic solution on the production of polylactide nanoparticles by nanoprecipitation. Int J Pharm 344:33–43CrossRefGoogle Scholar
  7. 7.
    Vauthier C, Bouchemal K (2009) Methods for the preparation and manufacture of polymeric nanoparticles. Pharm Res 26:1025–1058CrossRefGoogle Scholar
  8. 8.
    Lassalle V, Luján M (2007) PLA nano- and microparticles for drug delivery: an overview of the methods of preparation. Macromol Biosci 6:767–783CrossRefGoogle Scholar
  9. 9.
    Piñón-Segundo E, Nava-Arzaluz M, Lechuga-Ballesteros D (2012) Pharmaceutical polymeric nanoparticles prepared by the double emulsion- solvent evaporation technique. Recent Pat Drug Deliv Formul 6:224–235CrossRefGoogle Scholar
  10. 10.
    Horn D, Rieger J (2001) Organic nanoparticles in aqueous phase. Angew Chem Int 40:4330–4361CrossRefGoogle Scholar
  11. 11.
    Colombo P, Briançon S, Lieto J, Fessi H (2001) Project, design, and use of a pilot plant for nanocapsule production. Drug Dev Ind Pharm 27:1063–1072CrossRefGoogle Scholar
  12. 12.
    Galindo-Rodríguez S, Puel F, Briançon S, Allémann E, Doelker E, Fessi H (2005) Comparative scale-up of three methods for producing ibuprofen-loaded nanoparticles. Eur J Pharm Sci 25:357–367CrossRefGoogle Scholar
  13. 13.
    Musyanovych A, Schmitz-Wienke J, Mailänder V, Walther P, Landfester K (2008) Preparation of biodegradable polymer nanoparticles by miniemulsion technique and their cell interactions. Macromol Biosci 8:127–139CrossRefGoogle Scholar
  14. 14.
    Fessi H, Piusieux F, Devissaguet JP, Ammoury N, Benita S (1989) Nanocapsule formation by interfacial polymer deposition following solvent displacement. Int J Pharm 55:R1–R4CrossRefGoogle Scholar
  15. 15.
    Rescignano N, Amelia M, Credi A, Kenny JM, Armentano I (2012) Morphological and thermal behavior of porous biopolymeric nanoparticles. Eur Poly J 48:1152–1159CrossRefGoogle Scholar
  16. 16.
    Zambaux MF, Bonneaux F, Gref R, Maincent P, Dellacherie E, Alonso MJ, Labrude P, Vigneron C (1998) Influence of experimental parameters on the characteristics of poly(lactic acid) nanoparticles prepared by a double emulsion method. J Control Release 50:31–40CrossRefGoogle Scholar
  17. 17.
    Kelsch A, Tomcin S, Rausch K, Barz M, Mailänder V, Schmidt M, Landfester K, Zentel R (2012) HPMA Copolymers as surfactants in the preparation of biocompatible nanoparticles for biomedical application. Biomacromolecules 13:4179–4187CrossRefGoogle Scholar
  18. 18.
    Müller RH, Wallis KH (1993) Surface modification of i.v. injectable biodegradable nanoparticles with poloxamer polymers and poloxamine 908. Int J Pharm 89:25–31CrossRefGoogle Scholar
  19. 19.
    Leimann FV, Biz MH, Musyanovych A, Sayer C, Landfester K, Hermes de Araújo PH (2013) Hydrolysis of poly(hydroxybutyrate- co -hydroxyvalerate) nanoparticles. J Appl Polym Sci 128:3093–3098CrossRefGoogle Scholar
  20. 20.
    Errico C, Bartoli C, Chiellini F, Chiellini E (2009) Poly(hydroxyalkanoates)-based polymeric nanoparticles for drug delivery. J Biomed Biotechnol 2009:571–702CrossRefGoogle Scholar
  21. 21.
    Poletto FS, Fiel LA, Donida B, Re MI, Guterres SS, Pohlmann AR (2008) Controlling the size of poly(hydroxybutyrate-co-hydroxyvalerate) nanoparticles prepared by emulsification-diffusion technique using ethanol as surface agent Colloid. Surf. A: Physicochem Eng Aspects 324:105–112CrossRefGoogle Scholar
  22. 22.
    Vilos C, Morales FA, Solar PA, Herrera NS, Gonzalez-Nilo FD, Aguayo DA, Mendoza HL, Comer J, Bravo ML, Gonzalez PA, Kato S, Cuello MA, Alonso C, Bravo EJ, Bustamante EI, Owen GI, Velasquez LA (2013) Paclitaxel-PHBV nanoparticles and their toxicity to endometrial and primary ovarian cancer cells. Biomaterials 34:4098–4108CrossRefGoogle Scholar
  23. 23.
    Lightfoot S, Rojas C, Bouza R, Pérez M, Haensgen A, González M (2016) Synthesis and characterization of polyhydroxybutyrate-co-valerate nanoparticles for encapsulation of quercetin. J Bioact Compat Polym. doi: 10.1177/0883911516635839 Google Scholar
  24. 24.
    Li F, Tian F, Liu CJ (2010) Effect of additives on characteristics of poly(3-hydroxybutyrate) microspheres. Adv Mate Res 160:54–59CrossRefGoogle Scholar
  25. 25.
    Zhao Y, Tian F, Liu C, Li F, Xing N (2008) Preparation and evaluation of poly (3-hydroxybutyrate) microspheres containing bovine serum albumin for controlled release. J Appl Polym Sci 110:3826–3835CrossRefGoogle Scholar
  26. 26.
    Boufarguine M, Guinault A, Miquelard-Garnier G, Sollogoub C (2013) PLA/PHBV films with improved mechanical and gas barrier properties. Macromol Mater Eng 298:1065–1073Google Scholar
  27. 27.
    Bittmann B, Bouza R, Barral L, Diez J, Ramirez C (2013) Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/clay nanocomposites for replacement of mineral oil based materials. Polym Compos 34:1033–1040CrossRefGoogle Scholar
  28. 28.
    Bittmann B, Bouza R, Barral L, Gonzalez-Rodriguez MV, Abad MJ (2012) Nanoclay-reinforced poly(butylene adipate-co-terephthalate) biocomposites for packaging applications. Polym Compos 33:2022–2028CrossRefGoogle Scholar
  29. 29.
    Bittmann B, Bouza R, Barral L, Castro-Lopez M, Dopico-Garcia S (2015) Morphology and thermal behavior of poly (3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(butylene adipate-co-terephthalate)/clay nanocomposites. Polym Compos 36:2051–2058CrossRefGoogle Scholar
  30. 30.
    Bittmann B, Bouza R, Barral L, Bellas R, Cid A (2016) Effect of environmental factors on Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(butylene adipate-co-terephthalate)/montmorillonite nanocomposites with antimicrobial agents. Polym Compos. doi: 10.1002/pc.24018 Google Scholar
  31. 31.
    Dopico-García S, Ares-Pernas A, Otero-Canabal J, Mar Castro-López, López-Vilariño JM, González-Rodríguez V, Abad-López MJ (2013) Insight into industrial PLA aging process by complementary use of rheology, HPLC, and MALDI. Polym Adv Tech 24:723–731CrossRefGoogle Scholar
  32. 32.
    Fortunati E, Armentano I, Zhou Q, Iannoni A, Saino E, Visai L, Berglund LA, Kenny JM (2012) Multifunctional bionanocomposite films of poly(lactic acid), cellulose nanocrystals and silver nanoparticles. Carb Polym 87:1596–1605CrossRefGoogle Scholar
  33. 33.
    Javadi A, Srithep Y, Lee J, Pilla S, Clemons C, Gong S, Turng LT (2010) Processing and characterization of solid and microcellular PHBV/PBAT blend and its RWF/nanoclay composites. Comp Part A: Appl Sci Manuf 41:982–990CrossRefGoogle Scholar
  34. 34.
    Song KC, Lee HS, Choung IY, Cho KI, Ahn Y, Choi EJ (2006) The effect of type of organic phase solvents on the particle size of poly(d, l-lactide-co-glycolide) nanoparticles. Colloid Surf A Physicochem Eng Asp 276:162–167CrossRefGoogle Scholar
  35. 35.
    Mainardes RM, Evangelista RC (2005) Praziquantel-loaded PLGA nanoparticles: preparation and characterization. J Microencapsul 22:13–24CrossRefGoogle Scholar
  36. 36.
    Chin SF, Pang SC, Tay SH (2011) Size controlled synthesis of starch nanoparticles by a simple nanoprecipitation method. Carbohydr Polyms 86:1817–1819CrossRefGoogle Scholar
  37. 37.
    Lee I, Yoo Y, Cheng Z, Jeong HK (2008) Generation of monodisperse mesoporous silica microspheres with controllable size and surface morphology in a microfluidic device. Adv Funct Mat 18:4014–4021CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Rebeca Bouza
    • 1
    Email author
  • María del Mar Castro
    • 1
  • Sonia Dopico-García
    • 1
  • M. Victoria González-Rodríguez
    • 1
  • Luis F. Barral
    • 1
  • Birgit Bittmann
    • 2
  1. 1.Grupo de Polímeros, Departamento de Físicam, Escuela Universitaria PolitécnicaUniversidad de A CoruñaFerrolSpain
  2. 2.Institut für Verbundwerkstoffe GmbHKaiserslauternGermany

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