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2005-04-19 - Article/Dans un journal avec peer-review - Anglais - 10 page(s)

Coulembier Olivier , Degée Philippe, Gerbaux Pascal , Wantier Pascale, Barbaud Christel, Flammang Robert, Guerin P., Dubois Philippe , "Synthesis of amphiphilic poly([R,S]b-malic acid-graft-poly(e-caprolactone) graft copolymer: the “grafting from” and “grafting through” approaches" in Macromolecules, 38, 8, 3141-3150

  • Edition : American Chemical Society, Washington (DC)
  • Codes CREF : Chimie macromoléculaire (DI1315), Catalyses hétérogène et homogène (DI1334), Chimie organique (DI1313)
  • Unités de recherche UMONS : Matériaux Polymères et Composites (S816), Chimie organique (S836)
  • Instituts UMONS : Institut de Recherche en Science et Ingénierie des Matériaux (Matériaux)
Texte intégral :

Abstract(s) :

(Anglais) The synthesis of novel amphiphilic graft copolyesters based on hydrophobic poly(e-caprolactone) (PCL) segments grafted all along a hydrophilic poly((R,S)-ß-malic acid) (PMLA) backbone is proposed. These PMLA-g-PCL graft copolymers have been prepared in a controlled way using either the “grafting through” or the “grafting from” technique. Both approaches involve two different well-controlled ring-opening polymerization (ROP) mechanisms: anionic ROP of ß-lactones, i.e., benzyl or allyl ß-malolactonate (MLABz or MLAAllyl), and living ROP of e-caprolactone (CL) through a so-called coordination-insertion mechanism. The grafting through approach relies upon the anionic copolymerization of MLABz and ?-malolactonate-PCL macromonomer as initiated by potassium carboxylic acid salt in the presence of 1 equiv of 18-crown-6 ether. The second route follows a four-step synthesis involving the anionic ROP of MLABz and MLAAllyl, the conversion of allylic groups into pendant hydroxyl functions owing to a free-radical reaction with thioethanol in the presence of 2,2‘-azobis(2-methylpropionitrile), and then the CL polymerization as initiated from these pendant -OH groups after adequate activation into aluminum alkoxide active species. Whatever the synthetic approach, the final step consists of the deprotection of the MLABz repeating units along the backbone via a soft catalytic hydrogenation reaction. The amphiphilic character of the so-prepared graft copolyesters has been evidenced by some preliminary interfacial tension experiments using the pendant drop method.

Notes :
  • (Anglais) Publié en ligne le 16 mars 2005
Identifiants :
  • DOI : 10.1021/ma047928m