Polymer Bulletin

, Volume 67, Issue 9, pp 1751–1760 | Cite as

Novel triazole-based aluminum complex for ring-opening polymerization of lactones

  • Soňa HermanováEmail author
  • Monica M. Moya Cabrera
  • Zdeňka Vyroubalová
  • Lucy Vojtová
Original Paper


Novel triazole-based aluminum complex {O,O′-[4,5-P(O)Ph2tz]-AlMe2 was studied as the catalyst for the ring-opening polymerization of caprolactone (ε-CL) in chlorobenzene. In the presence of methanol, isopropanol, and bifunctional poly(ethylene glycol), the catalytic system produced polymers with high conversion (81–85 %) but broader distribution (M w/M n = 1.5–1.8). The system of catalyst and benzyl alcohol produced relative monodisperse PCLs (M w/M n ~ 1.2) with defined molecular weight at 1/1ratio, 60 °C and an initial concentration of ε-CL equal to 0.5 mol/L.


Aluminum Polycaprolactone Ring-opening polymerization 



This work was supported by the Ministry of Education of the Czech Republic under the project no. MSM 0021630501 and by the CONACyT (grant 058484). The authors thank J. Alcántara and N. Zavala for their technical assistance.


  1. 1.
    Gref R, Minamitake Y, Peracchia MT, Trubetosky V, Trochilin V, Langer R (1994) Biodegradable long-circulating polymeric nanospheres. Science 263:1600–1603. doi: 10.1126/science.8128245 CrossRefGoogle Scholar
  2. 2.
    Allen C, Han J, Yu Y, Maysinger D, Eisenberg AJ (2000) Polycaprolactone-b-poly(ethylene oxide) copolymer micelles as a delivery vehicle for dihydrotestosterone. Control Rel 63:275–286. doi: 10.1016/S0168-3659(99)00200-X CrossRefGoogle Scholar
  3. 3.
    Jérome Ch, Lecomte P (2008) Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization. Adv Drug Deliv Rev 60:1056–1076. doi: 10.1016/j.addr.2008.02.008 CrossRefGoogle Scholar
  4. 4.
    Ouhadi T, Stevens C, Teyssié P (1975) Mechanism of ε-caprolactone polymerization by aluminum alkoxides. Makromol Chem Suppl 1:191–201. doi: 10.1002/macp.1975.020011975112 CrossRefGoogle Scholar
  5. 5.
    Hamitou A, Teyssié P (1977) Soluble bimetallic μ-oxoalkoxides. IX. ε-caprolactone and β-propiolactone block copolymerization. J Polym Sci Polym Chem Ed 15:1035–1041. doi: 10.1002/pol.1977.170150502 CrossRefGoogle Scholar
  6. 6.
    Akatsuka M, Aida T, Inoue S (1995) Alcohol/methylaluminium diphenolate systems as novel, versatile initiators for synthesis of narrow molecular weight distribution polyester and polycarbonate. Macromolecules 28:1320–1322. doi: 10.1021/ma00108a075 CrossRefGoogle Scholar
  7. 7.
    Ko BT, Lin CC (1999) Efficient “living” and “immortal” polymerization of lactones and diblock copolymer of ε-CL and δ-VL catalyzed by aluminium alkoxides. Macromolecules 32:8296–8300. doi: 10.1021/ma991055s CrossRefGoogle Scholar
  8. 8.
    Chen HL, Ko BT, Huang BH, Lin Ch-Ch (2001) Reactions of 2,2′-methylenebis(4-chloro-6-isopropyl-3-methylphenol) with trimethylalumium: highly efficient catalysts for the ring-opening polymerization of lactones. Organometallics 20:5076–5083. doi: 10.1021/om010425+ CrossRefGoogle Scholar
  9. 9.
    Liu YCH, Ko BT, Lin ChCh (2001) A highly efficient catalyst for the “living” and “immortal” polymerization of ε-caprolactone and l-lactide. Macromolecules 34:6196–6201. doi: 10.1021/ma0104579 CrossRefGoogle Scholar
  10. 10.
    Endo M, Aida T, Inoue S (1987) “Immortal” polymerization of ε-caprolactone initiated by aluminium porphyrin in the presence of alcohol. Macromolecules 20:2982–2991. doi: 10.1021/ma00178a005 CrossRefGoogle Scholar
  11. 11.
    Lewinski J, Horeglad P, Dranka M, Justyniak I (2004) Simple generation of cationic aluminium alkyls and alkoxides based on the pendant arm tridentate schiff base. Inorg Chem 43:5789–5791. doi: 10.1021/ic049337i CrossRefGoogle Scholar
  12. 12.
    Chen ChT, Huang ChA, Huang BH (2004) Aluminium complexes supported by tridentate aminophenoxide ligand as efficient catalyst for ring-opening polymerization of ε-caprolactone. Macromolecules 37:7968–7973. doi: 10.1021/ma0492014 CrossRefGoogle Scholar
  13. 13.
    Chen ChT, Huang ChA, Huang BH (2003) Aluminium metal complexes supported by amine bis-phenolate ligands as catalysts for ring-opening polymerization of ε-caprolactone. Dalton Trans 2003:3799–3803. doi: 10.1039/b307365c CrossRefGoogle Scholar
  14. 14.
    Amgoune A, Lavanant L, Thomas ChM, Chi Y, Welter R, Dagorne S, Carpentier JF (2005) An aluminium komplex supported by a fluorous diamino-dialkoxide ligand for the highly productive ring-opening polymerization of ε-caprolactone. Organometallics 24:6279. doi: 10.1021/om050512s CrossRefGoogle Scholar
  15. 15.
    Nomura N, Aoyama T, Ishii R, Kondo T (2005) Salicylaldimine-aluminium complexes for the facile and efficient ring-opening polymerization of ε-caprolactone. Macromolecules 38:5363–5366. doi: 10.1021/ma050606d CrossRefGoogle Scholar
  16. 16.
    Iwasa N, Fujiki M, Nomura K (2008) Ring-opening polymerization of various cyclic esters by Al complex catalysts containing a series of phenoxy-imine ligands: effect of the imino substituents for the catalytic activity. J Mol Catal A 292:67–75. doi: 10.1016/j.molcata.2008.06.009 CrossRefGoogle Scholar
  17. 17.
    Iwasa N, Katao S, Liu J, Fujiki M, Furukawa Y, Nomura K (2009) Notable effect of fluoro substituents in the imino group in ring-opening polymerization of ε-caprolactone by Al complexes containing phenoxyimine ligands. Organometallics 28:2179–2187. doi: 10.1021/om8011882 CrossRefGoogle Scholar
  18. 18.
    Moya-Cabrera M et al (2009) Coordination diversity of aluminum centers molded by triazole based chalcogen ligands. Inorg Chem 48:5874–5883. doi: 10.1021/ic900166u CrossRefGoogle Scholar
  19. 19.
    Milione S, Grisi F, Centore R, Tuzi A (2006) Neutral and cationic heteroscorpionate aluminium complexes: synthesis, structure, and ring-opening polymerization of ε-caprolactone. Organometallics 25:266. doi: 10.1021/om050902e CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Soňa Hermanová
    • 1
    Email author
  • Monica M. Moya Cabrera
    • 2
  • Zdeňka Vyroubalová
    • 1
  • Lucy Vojtová
    • 1
  1. 1.Institute of Materials Chemistry, Faculty of ChemistryBrno University of TechnologyBrnoCzech Republic
  2. 2.Centro Conjunto de Investigación en Química Sustentable UAEM-UNAMTolucaMéxico

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