Polymer Bulletin

, Volume 69, Issue 7, pp 757–763 | Cite as

Precipitation polymerization of ε-caprolactone in water using metal triflates as catalysts

Original Paper


The precipitation polymerization of ε-caprolactone has been assessed in water using various commercial metal triflates as catalysts. The reaction is quantitative at 70 and 100 °C, leading to number-average molecular weights up to 5,400 g/mol and dispersities around 1.5–2.0. A polycondensation mechanism operating from in situ generated 6-hydroxyhexanoic acid is proposed. Among various salts, aluminum and tin(II) triflates lead to the higher molecular weight after 24 h reaction at 70 °C.


Triflates Poly(ε-caprolactone) 6-Hydroxyhexanoic acid Water 


  1. 1.
    Barrere M, Landfester K (2003) Polyester synthesis in aqueous miniemulsion. Polymer 44:2833–2841CrossRefGoogle Scholar
  2. 2.
    Taden A, Antonietti M, Landfester K (2003) Enzymatic polymerization toward biodegradable polyester nanoparticles. Macromol Rapid Commun 24:512–516CrossRefGoogle Scholar
  3. 3.
    Tanaka H, Kurihashi T (2003) Synthesis of polyesters by emulsion polycondensation reaction in water. Polym J 35:359–363CrossRefGoogle Scholar
  4. 4.
    Takasu A, Takemoto A, Hirabayashi T (2006) Polycondensation of dicarboxylic acids and diols in water catalyzed by surfactant-combined catalysts and successive chain extension. Biomacromolecules 7:6–9CrossRefGoogle Scholar
  5. 5.
    Kobayashi S, Uyama H, Namekawa S (1998) In vitro biosynthesis of polyesters with isolated enzymes in aqueous systems and organic solvents. Polym Deg Stab 59:195–201CrossRefGoogle Scholar
  6. 6.
    Namekawa S, Uyama H, Kobayashi S (1998) Lipase catalyzed ring-opening polymerization in water. Polym J 30:269–271CrossRefGoogle Scholar
  7. 7.
    Kobayashi S, Uyama H, Suda S, Namekawa S (1997) Dehydration polymerization in aqueous medium catalyzed by lipase. Chem. Letters 1997 105Google Scholar
  8. 8.
    Nallani M, de Hoog HPM, Cornelissen JJLM, Palmans ARA, van Hest JCM, Nolte RJM (2007) Polymersomes nanoreactors for enzymatic ring-opening polymerization. Biomacromolecules 8:3723–3728CrossRefGoogle Scholar
  9. 9.
    Nomura N, Taira A, Tamioka T, Okada M (2000) A catalytic approach for cationic living polymerization: Sc(OTf)3-catalyzed ring-opening polymerization of lactones. Macromolecules 33:1497–1499CrossRefGoogle Scholar
  10. 10.
    Moeller M, Kange R, Hedrick JL (2000) Sn(OTf)2 and Sc(OTf)3: efficient and versatile catalysts for the controlled polymerization of lactones. J Polym Sci Polym Chem 38:2067–2074CrossRefGoogle Scholar
  11. 11.
    Takasu A, Oishi Y, Iio Y, Inai Y, Hirabayashi T (2003) Synthesis of aliphatic polyesters by direct polyesterification of dicarboxylic acids with diols under mild conditions catalyzed by reusable rare earth triflate. Macromolecules 36:1772–1774CrossRefGoogle Scholar
  12. 12.
    Yashiro T, Kricheldorf HR, Huijser S (2009) Synthesis of polyesters from succinic anhydride and various diols catalyzed by metal triflates. Macromol Chem Phys 210:1607–1616CrossRefGoogle Scholar
  13. 13.
    Kobayashi S, Nagayama S, Busujima T (1998) Lewis acid catalysts stable in water. Correlation between catalytic activity in water and hydrolysis constants and exchange rate constants for substitution of inner sphere water ligands. J Am Chem Soc 120:8287–8288CrossRefGoogle Scholar
  14. 14.
    Save M, Schappacher M, Soum A (2002) Controlled ring-opening polymerization of lactones and lactide initiated by lanthanum isopropoxide, 1. General aspects and kinetics. Macromol Chem Phys 203:889–899CrossRefGoogle Scholar
  15. 15.
    Niehausa DE, Jackson C (2000) Size exclusion chromatography of step-growth polymers with cyclic species: theoretical model and data analysis method. Polymer 41:259–268CrossRefGoogle Scholar
  16. 16.
    Kawaguchi S, Ito K (2005) Dispersion polymerization. Adv Polym Sci 175:299–328Google Scholar

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  1. 1.Université Lille Nord de FranceLilleFrance
  2. 2.ENSCL, UCCS, CCMVilleneuve d’AscqFrance
  3. 3.USTL, UCCS, CCMVilleneuve d’AscqFrance
  4. 4.CNRS, UMR 8181Villeneuve d’AscqFrance

Personalised recommendations