Unpublished conference/Abstract (Scientific congresses and symposiums)
Macromolecular engineering of cyclic aliphatic polyesters by ring-opening polymerization and "click" chemistry
Lecomte, Philippe; Li, Haiying; Riva, Raphaël et al.
200718th International Symposium on Ionic Polymerization (IP 2007)
 

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Keywords :
ring-opening polymerization (ROP); lactone; click chemistry; copper-mediated Huisgen's cycloaddition; polymer functionalization
Abstract :
[en] The last decades have witnessed a steadily increasing progress in the macromolecular engineering of the main families of synthetic polymers. Ring-shaped copolymers show a unique topology due to the absence of any chain-end and exhibit distinct properties from their linear counterparts, such as glass transition temperature, order-disorder transition, reduced viscosity, lower hydrodynamic volumes. This communication aims at reporting on a novel route to biodegradable cyclic polyesters. Our strategy is based on the work of Prof. Kricheldorf who initiated the ring-opening polymerization of ε-caprolactone by cyclic tin dialkoxides, e.g., 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP) in order to obtain “living” macrocyclic PCL, still containing two endocyclic tin-oxygen bonds. In this work, the resumption of polymerization by a few units of ε-caprolactone substituted by an acrylic unit, e.g., 1-(2-oxooxepan-3-yl)ethyl prop- 2-enoate, followed by intramolecular photo-crosslinking of pendant unsaturations and finally by hydrolysis gave rise to macrocyclic PCL. As a rule, this strategy is very well-suited for the synthesis of high molecular weight PCL. Moreover, tin alkoxides were kept untouched after the cross-linking step and remained thus available for further macromolecular engineering. The process was extended to the synthesis of other architectures such as sun-shaped, two-tail tadpoleshaped, and eight-shaped copolyesters. The second part of the lecture, it will be shown that the copper(I)-catalyzed Huisgen’s [3+2] cycloaddition, which is the most popular “Click" reaction, is very efficient to graft alkynes, duly substituted by functional groups or chains, onto aliphatic copolyesters bearing pendant azides. Interestingly enough, mild conditions were found and no degradation was observed during the “click” derivatization of copolyesters of PCL. The “click” reactions of alkynes onto pendant azides of copolyesters of PLA, by far more sensitive than PCL, was also successfully carried out without any detectable degradation. ”Click” chemistry is very versatile because this reaction was successfully implemented to graft functional groups or chains directly onto ω-azido-ε-caprolactone, without any ring-opening of the lactone, in order to make available a new range of functional caprolactones. Finally, the “click” grafting of PEO onto the tails of tadpole-shaped copolymers will be shown to be a route to amphiphilic copolymers with an original architecture.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry
Materials science & engineering
Author, co-author :
Lecomte, Philippe  ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Li, Haiying ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Riva, Raphaël ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Schmeits, Stephanie ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Christine  ;  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 :
Macromolecular engineering of cyclic aliphatic polyesters by ring-opening polymerization and "click" chemistry
Publication date :
04 September 2007
Number of pages :
1
Event name :
18th International Symposium on Ionic Polymerization (IP 2007)
Event organizer :
Axel Müller
Event place :
Kloster Banz, Germany
Event date :
2/09/2007 - 7/09/2007
By request :
Yes
Audience :
International
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
Commentary :
This oral communication was presented by Philippe Lecomte
Available on ORBi :
since 22 September 2009

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