[en] [Tris(hexamethyldisilyl)amide] yttrium is a catalyst for the controlled ring-opening polymerization of epsilon-caprolactone when reacted with an excess of alcohol. Up to an alcohol-to-yttrium molar ratio of 50, the chain transfer to the alcohol is quantitative, and the molecular weight of the chains can be predicted from the monomer-to-alcohol molar ratio. At alcohol-to-yttrium ratios higher than 100, the alcohol is quantitatively consumed provided that 1,1,1,3,3,3-hexamethyldisilazane, which is formed as a byproduct, is removed from the reation medium. Depending on the structure of the alcohol, end-functional polyesters can be prepared (e.g., with N-pyrrolyl and 3-thienyl end groups). Well-defined block and random copolymers of epsilon-CL with lactides and gamma-bromo-epsilon-caprolactone, respectively, have also been synthesized. Compared to aluminum alkoxides, the in situ formed yttrium alkoxides have the advantage of a much faster polymerization kinetics while preserving control.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Martin, Eric; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Dubois, Philippe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
In situ formation of yttrium alkoxides: A versatile and efficient catalyst for the ROP of epsilon-caprolactone
Publication date :
12 August 2003
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
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Bibliography
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Fréchet, J. M. J. Science 1994, 263, 1710.
Martin, B.; Dubois, P.; Jérôme, R. Macromolecules 2000, 33, 1530.
Detrembleur, C.; Mazza, M.; Halleux, O.; Lecomte, P.; Mecerreyes, D.; Hedrick, J. L.; Jérôme, R. Macromolecules 2000, 33, 14.
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