Journal of Polymer Research

, 20:275 | Cite as

Synthesis of poly (l-lactide) in supercritical carbon dioxide with PDMS based stabilizers

  • Song Zhang
  • Shiping Zhan
  • Qicheng Zhao
  • Shuhua Chen
  • Zhijun Liu
  • Jinjun Deng
Original Paper


The dispersion polymerization of poly (L-lactide)(PLLA) in supercritical carbon dioxide (ScCO2) with stannous octoate (Sn(Oct)2) as a catalyst and n-butanol as an initiator was studied. An amphiphilic triblock copolymer was synthesized by the ring-opening polymerization ofε-caprolactone (ε-CL) with the hydroxylpropyl-terminated polydimethylsiloxane (HTPDMS) as the macromolecule initiator and then chosen as the stabilizer in the synthesis of PLLA. With the concentrations of 3 wt % (stabilizer/monomer), fine powder formed PLLAs were obtained. The effects of operating parameters such as pressure, temperature and stirring rate on the properties of the synthesized PLLAs were investigated. The results showed that the temperature had the greatest effect on the conversion and the stirring rate was the most important factor which determined the morphology of the products. An obvious increase of conversion was observed when the temperature increased from 80 °C to 100 °C. The influence of stirring rate on the morphology was achieved through the anchoring of the stabilizer with the growing polymer chains. The stirring rate of 300 rpm was turned out to be necessary and adequate. When the stirring rate increased or decreased out of the range of (300 ± 100)rpm, only agglomerates were obtained.


Poly (l-lactide) Dispersion polymerization Supercritical carbon dioxide Triblock copolymer stabilizer 



The authors are much indebted to the Natural Science foundation of China (Project Nos. 21176032) for financial support.


  1. 1.
    Duda A, Penczek S, Kowalski A, Libiszowski J (2000) Polymerizations of ε-Caprolactone and L, L-dilactide initiated with stannous octoate and stannous butoxide― a comparison. Macromol Symp 153:41–53CrossRefGoogle Scholar
  2. 2.
    Mazarro R, de Lucas A, Gracia I (2008) Copolymerization of D,L-lactide and glycolide in supercritical carbon dioxide with zinc octoate as catalyst. J Biomed Mater Res B Appl Biomater 85B:196–203CrossRefGoogle Scholar
  3. 3.
    Hile DD, Pishko MV (2001) Emulsion copolymerization of D,L-lactide and glycolide in supercritical carbon dioxide. J Polym Sci A Polym Chem 39:562–570CrossRefGoogle Scholar
  4. 4.
    Allcock HR, Chang J-Y (1991) Poly(organophosphazenes) with oligopeptides as side groups: prospective biomaterials. Macromolecules 24:993–999CrossRefGoogle Scholar
  5. 5.
    Grignard B, Stassin F, Calberg C, Jérôme R, Jérôme C (2008) Synthesis of biodegradable poly-ε-caprolactone microspheres by dispersion ring-opening polymerization in supercritical carbon dioxide. Biomacromolecules 9:3141–3149CrossRefGoogle Scholar
  6. 6.
    Mikos AG, Temenoff JS (2001) Injectable biodegradable materials for orthopedic tissue engineering. Electron J Biotechnol 21:114–119Google Scholar
  7. 7.
    Kricherdorf HR (2001) Syntheses and application of polylactides. Chemosphere 43:49–54CrossRefGoogle Scholar
  8. 8.
    de Rosario Mazarro A, Lucas LI, Cabezas (2010) Influence of the operative conditions on the characteristics of poly (D, L-lactide-co-glycolide) synthesized in supercritical carbon dioxide. Macromol Symp 287:111–118CrossRefGoogle Scholar
  9. 9.
    Stassin F, Halleux O, Jérôme R (2001) Ring-opening polymerization of ε-Caprolactone in supercritical carbon dioxide. Macromolecules 34:775–781CrossRefGoogle Scholar
  10. 10.
    Cabezas LI, Fernández V, Mazarro R (2012) Production of biodegradable porous scaffolds impregnated with Indomethacin in supercritical CO2. J Supercrit Fluids 63:155–160CrossRefGoogle Scholar
  11. 11.
    Minami H, Tanaka A, Kagawa Y (2012) Preparation of poly (acrylic acid)–b–polystyrene by two step atom transfer radical polymerization in supercritical carbon dioxide. J Polym Sci A Polym Chem 50:2578–2584CrossRefGoogle Scholar
  12. 12.
    Cooper AI (2000) Polymer synthesis and processing using supercritical carbon dioxide. J Mater Chem 10:207–234CrossRefGoogle Scholar
  13. 13.
    Bratton D, Brown M, Howdle SM (2003) Suspension polymerization ofl-Lactide in supercritical carbon dioxide in the presence of a triblock copolymer stabilizer. Macromolecules 36:5908–5911CrossRefGoogle Scholar
  14. 14.
    Ganapathy HS, Hwang HS, Jeong YT (2007) Ring-opening polymerization of L-lactide in supercritical carbon dioxide using PDMS based stabilizers. Eur Polym J 43:119–126CrossRefGoogle Scholar
  15. 15.
    Yılmaz M, Eğri S, Yıldız N et al (2011) Dispersion polymerization of L-lactide in supercritical carbon dioxide. J Polym Res 18:975–982CrossRefGoogle Scholar
  16. 16.
    Dechy-Cabaret O, Martin-Vaca B, Bourissou D (2004) Controlled ring-opening polymerization of lactide and glycolide. Chem Rev 104:6147–6176CrossRefGoogle Scholar
  17. 17.
    Xu Z, Zheng S (2007) Morphology and thermomechanical properties of nanostructured thermosetting blends of epoxy resin and poly(ɛ-caprolactone)-block-polydimethylsiloxane-block-poly(ɛ-caprolactone)triblock copolymer. Polymer 48:6134–6144CrossRefGoogle Scholar
  18. 18.
    Zhang XY, Li QF (2004) Investigation of stabilizer-free dispersion polymerization process of styrene and maleic anhydride copolymer microspheres. Scientific experimental methods of polymers. Chemical Industry Press, BeijingGoogle Scholar
  19. 19.
    Witzke DR, Narayan R (1997) Reversible kinetics and thermodynamics of the homopolymerization of L-Lactide with 2-Ethylhexanoic acid Tin(II)Salt. Macromolecules 30:7075–7085CrossRefGoogle Scholar
  20. 20.
    Bratton D, Brown M, Howdle SM (2005) Novel fluorinated stabilizers for ring-opening polymerization in supercritical carbon dioxide. J Polym Sci A Polym Chem 43:6573–6585CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  • Song Zhang
    • 1
    • 2
  • Shiping Zhan
    • 2
  • Qicheng Zhao
    • 2
  • Shuhua Chen
    • 2
  • Zhijun Liu
    • 1
  • Jinjun Deng
    • 1
    • 2
    • 3
  1. 1.Institute of Fluid and Powder EngineeringDalian University of TechnologyDalianChina
  2. 2.College of Environment & Chemical EngineeringDalian UniversityDalianChina
  3. 3.Department of Chemistry & Chemical EngineeringDaqing Normal UniversityDaqingChina

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