[en] Homopolymerization of the unsaturated cyclic ester, 6,7-dihydro-2(5H)-oxepinone (DHO), and copolymerization with epsilon-caprolactone (epsilon-CL) are an easy way to produce unsaturated aliphatic polyesters in a controlled manner, Polymerization of DHO initiated by Al((OPr)-Pr-i)(3) in toluene at room temperature proceeds by a coordination-insertion mechanism and is living as certified by the agreement between the experimental molecular weight at total monomer conversion and the value predicted from the initial monomer to initiator molar ratio. The polydispersity is also low (Mw/Mn less than or equal to 1.2). Random copolymerization of DHO and epsilon-CL leads to the same conclusion. Beyond the complete monomer conversion, the poly(DHO) chains experience mainly intermolecular transesterification reactions at the same rate as poly(epsilon CL) under the same conditions. The livingness of the ROP of both DHO and epsilon-CL allows diblock copolymers to be synthesized with predicted composition and molecular weight. Homopoly(DHO) is semicrystalline with Tm at 35°C and Tg at -50°C. Tm and thermal stability can be modulated by copolymerization of DHO with epsilon-CL.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Lou, Xudong; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Lecomte, 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 :
Living ring-opening (co)polymerization of 6,7-dihydro-2(5H)-oxepinone into unsaturated aliphatic polyesters
Publication date :
14 August 2001
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
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Bibliography
Odian G. Principles of Polymerization, 2nd ed., Wiley-Interscience: New York; 1970.
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