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Page de résumé pour ULgetd-05302007-140034

Auteur : Riva, Raphael
E-mail de l'auteur : raphael.riva@ulg.ac.be
URN : ULgetd-05302007-140034
Langue : Anglais/English
Titre : Functionalization of poly(epsilon-caprolactone) and its macromolecular engineering
Intitulé du diplôme : Doctorat en sciences
Département : FS - Département de chimie
Jury :
Nom : Titre :
Detrembleur, C. Membre du jury/Committee Member
Dijkstra, P. Membre du jury/Committee Member
Du Prez, F. Membre du jury/Committee Member
Lecomte, P. Membre du jury/Committee Member
Luxen, André Président du jury/Committee Chair
Jérôme, Robert Promoteur/Director
Mots-clés :
  • aliphatic polyesters/polyesters aliphatiques
  • PCL
  • functionalization/fonctionalisation
  • graft copolymers/polymères greffés
  • lactones
  • ATRA
  • Click chemistry
  • antimicrobial polymer/ polymère antibactérien
Date de soutenance : 2007-04-20
Type d'accès : Restreint/Intranet
Résumé :

Macromolecular engineering is one of the most powerful tools to control the molecular parameters, including architecture of polymers, and to improve their performances or to impart them new properties.

This contribution aims at reporting on a novel strategy for the macromolecular engineering of poly-ε-caprolactone (PCL) which is based on the use of functional ε-caprolactone, the α-chloro-ε-caprolactone (αClεCL). Indeed, αClεCL is a precursor of polymers and copolymers with εCL that bear pendant activated chlorides well suited to “grafting from” reaction. These (co)polyesters have been used as macroinitiators for the Atom Transfer Radical Polymerization (ATRP) of methyl methacrylate leading to the corresponding graft copolymer. They have also been involved in an Atom Transfer Radical Addition (ATRA) reaction with a series of olefins bearing different functional groups (hydroxyl, carboxylic acid and epoxy group) in order to functionalize the polyester backbone without deleterious degradation. ATRA of PEO chains with an unsaturation end groups has also been carried out in order to prepare PCL-g-PEO of different compositions to be used as stabilizers of polyester nanoparticles.

Combination of ring-opening polymerization of ε-caprolactone and the copper-catalyzed Huisgen’s [3+2] cycloaddition is a novel strategy for going a step further in the macromolecular engineering of poly-ε-caprolactone (PCL). This ‘click” reaction is very well-suited to the chemical modification of aliphatic polyesters because, its implementation under very mild conditions prevents chain degradation from occurring. Indeed, alkynes were cycloadded onto azide containing PCL at low temperature (35°C) in an organic solvent (DMF or THF). Originally, α-chloro-ε-caprolactone and ε-caprolactone were randomly copolymerized in toluene at room temperature followed by reaction of the activated chlorides with sodium azide.

In order to make a wide range of functional aliphatic polyesters available, poly(α-azide-ε-caprolactone-co-ε-caprolactone) copolyesters were reacted with a series of alkynes substituted by a functional group, e.g., hydroxyl, acrylate and quaternary ammonium salts, This strategy turned out to be efficient to synthesize for instance hydrophilic, photo-cross-linkable and hydrosoluble PCL. Moreover, a variety of graft copolymers were prepared by both the “grafting from” and the “grafting onto” techniques. Indeed, an ATRP initiator was attached onto PCL followed by polymerization of vinyl monomers, whereas alkyne end–capped PEO was cycloadded onto azide-containing PCL with formation of amphiphilic PCL-g-PEO copolymers.

Last but not least, the “click” chemistry was very instrumental in imparting an antimicrobial activity to PCL or for the preparation of new functionalized caprolactones.

Autre version :
Fichiers :
Nom du fichier Taille Temps de chargement évalué (HH:MI:SS)
Modem 56K ADSL
[Restreint/Intranet] Aims.pdf 25.32 Kb 00:00:03 < 00:00:01
[Restreint/Intranet] Chapter3.pdf 489.40 Kb 00:01:09 00:00:02
[Restreint/Intranet] Chapter4.pdf 221.36 Kb 00:00:31 00:00:01
[Restreint/Intranet] Chapter5.pdf 480.49 Kb 00:01:08 00:00:02
[Restreint/Intranet] Chapter6.pdf 306.97 Kb 00:00:43 00:00:01
[Restreint/Intranet] Chapter7.pdf 296.47 Kb 00:00:42 00:00:01
[Restreint/Intranet] Chapter8.pdf 291.33 Kb 00:00:41 00:00:01
[Restreint/Intranet] Chapter9.pdf 117.36 Kb 00:00:16 < 00:00:01
[Restreint/Intranet] Conclusions.pdf 22.80 Kb 00:00:03 < 00:00:01
[Restreint/Intranet] Cover.pdf 195.82 Kb 00:00:27 00:00:01
[Restreint/Intranet] Remerciements.pdf 10.09 Kb 00:00:01 < 00:00:01
[Restreint/Intranet] Tabledesmatieres.pdf 42.76 Kb 00:00:06 < 00:00:01
[Restreint/Intranet] Tableofabbreviations.pdf 15.14 Kb 00:00:02 < 00:00:01
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