Controlled synthesis of an ABC miktoarm star-shaped copolymer by sequential ring-opening polymerization of ethylene oxide, benzyl beta-malolactonate, and epsilon-caprolactone
English
Rieger, Jutta[University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Coulembier, Olivier[University of Mons-Hainaut (UMH) > > Laboratory of Polymeric and Composite Materials > >]
Dubois, Philippe[University of Mons-Hainaut (UMH) > > Laboratory of Polymeric and Composite Materials > >]
Bernaerts, Katrien V.[University of Ghent > Department of Organic Chemistry > Polymer Chemistry Research Group > >]
Du Prez, Filip E.[University of Ghent > Department of Organic Chemistry > Polymer Chemistry Research Group > >]
Jérôme, Robert[University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Jérôme, Christine[University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
[en] This paper reports on the synthesis of an amphiphilic miktoarm ABC star-shaped copolymer, s[(PEO)(PMLABz)(PCL)], consisting of biocompatible/bioresorbable arms. Indeed, PEO is a hydrophilic biocompatible poly(ethylene oxide) arm, PMLABz is a poly(benzyl beta-malolactonate) arm precursor of a pH-sensitive bioresorbable poly(beta-malic acid) block, and PCL is a hydrophobic bioresorbable poly(epsilon-caprolactone) arm. Each constitutive arm was prepared by ring-opening polymerization. A double-headed PEO macroinitiator [PEO-(OH)-COO-K+] was first prepared by selective hydrolysis of the alpha-lactone (2-oxepanone) end group of PEO chains end-capped by a omega-methoxy group. The anionic polymerization of benzyl beta-malolactonate (MLABz) was selectively initiated by the alpha-potassium carboxylate end group of PEO in the presence of 18-crown-6 ether. The polymerization of epsilon-caprolactone (epsilon-CL) was initiated by the hydroxyl group left at the junction of the two blocks of the as-prepared PEO-b-PMLABz diblock copolymer, in the presence of tin(II) bis(2-ethylhexanoate) (Sn(Oct)(2)). The macroinitiator, the intermediate diblock, and the final miktoarm. star-shaped copolymer were analyzed by H-1 NMR spectroscopy and size exclusion chromatography.
Center for Education and Research on Macromolecules (CERM)
Fonds de la Recherche Scientifique (Communauté française de Belgique) - F.R.S.-FNRS ; Politique Scientifique Fédérale (Belgique) = Belgian Federal Science Policy ; Fonds Wetenschappelijk Onderzoek - FWO ; Fonds pour la formation à la Recherche dans l'Industrie et dans l'Agriculture (Communauté française de Belgique) - FRIA ; The Région Wallonne and Fonds Social Européen in the frame of Objectif 1-Hainaut: Materia Nova program