[en] A straightforward strategy is proposed for the derivatization of poly(epsilon-caprolactone) (PCL). First, statistical copolymerization of alpha-chloro-epsilon-caprolactone (alpha-Cl-epsilon-CL) with epsilon-caprolactone (epsilon-CL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP). In a second step, pendent chlorides were converted into azides by reaction with sodium azide. Finally, duly substituted terminal alkynes were reacted with pendent azides by copper-catalyzed Huisgen's 1,3-dipolar cycloaddition, thus a "click" reaction. According to this strategy, pendent hydroxyl and acrylate groups and atom transfer radical polymerization (ATRP) initiators were successfully attached to PCL. Similarly, amphiphilic graft copolymers were prepared by cycloaddition of an alkyne end-capped poly(ethylene oxide) (PEO) onto the azide substituents of the copolyester. The dependence of the grafting yield on the experimental conditions of the "click" reaction, i.e., temperature, solvent, and catalyst, was investigated. This strategy is very versatile because a large variety of aliphatic polyesters can be easily synthesized from a single precursor, easily prepared from commercially available compounds, merely by changing the alkyne involved in the Huisgen's 1,3-dipolar cycloaddition. Last but not least, PCL subsituted by azide groups does not have to be isolated after substitution of chlorides by sodium azide, and the "click" reaction can be carried out in a "one-pot" process.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Riva, Raphaël ; Université de Liège - ULiège > Centre d'études et de rech. sur les macromolécules (CERM)
Schmeits, Stéphanie
Jérôme, Christine ; Université de Liège - ULiège > Centre d'études et de rech. sur les macromolécules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Centre d'études et de rech. sur les macromolécules (CERM)
Lecomte, Philippe ; Université de Liège - ULiège > Centre d'études et de rech. sur les macromolécules (CERM)
Language :
English
Title :
Combination of ring-opening polymerization and "click chemistry": Toward functionalization and grafting of poly(epsilon-caprolactone)
Publication date :
20 February 2007
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
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