[en] Well-defined poly(lactide)-based block copolymers were synthesized by a heterogeneous solvent and metal-free green approach by using organocatalysts in supercritical carbon dioxide (scCO2). We first report on the homopolymerization of both L- and D,L- lactide by organocatalyzed Ring-Opening Polymerization (o-ROP) by using a bicomponent organocatalyst composed of a thiourea derivative and various tertiary amines as cocatalysts. Control over the molar mass and dispersity is achieved until high monomer conversion although the polylactides are insoluble in the polymerization medium. The precision synthesis of PLA-based block copolymers from various CO2-phobic hydroxyl end-capped macroinitiators such as polyethylene glycol, polycaprolactone, polybutylene succinate and polyphosphoester was then reported. Merging scCO2 with this organocatalytic system provides therefore a unique tool for the design under solvent-free conditions of poly(lactide)-based block copolymers that are insoluble in scCO2.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM) CESAM Complex and Entangled Systems from Atoms to Materials (CESAM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Grignard, Bruno ; University of Liège - ULiège > Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
De Winter, Julien; University of Mons (UMONS), Mass Spectrometry Research Group, Interdisciplinary Center of Mass Spectrometry (CISMa)
Gerbaux, Pascal; University of Mons (UMONS), Mass Spectrometry Research Group, Interdisciplinary Center of Mass Spectrometry (CISMa)
Gilbert, Bernard ; University of Liège (ULg), Department of Chemistry, Analytic Chemistry and Electrochemistry
Jérôme, Christine ; University of Liège - ULiège > Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; University of Liège - ULiège > Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Merging supercritical carbon dioxide and organocatalysis for the precision and green synthesis of poly(lactide)-based (co)polymers
Publication date :
October 2017
Journal title :
European Polymer Journal
ISSN :
0014-3057
eISSN :
1873-1945
Publisher :
Elsevier Science
Volume :
95
Pages :
635-649
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique F.R.S.-FNRS - Fonds de la Recherche Scientifique The Walloon Region and the FEDER in the frame of the Sinopliss and Polytiss programs
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