[en] Designing novel polyfluoropolymer architectures is attractive for the development of new applications, such as advanced coatings, purification membranes, or materials for
energy. Nevertheless, controlling the radical polymerization of fluoroalkenes is very challenging due to the high reactivity of the propagating fluorinated macroradicals. This study aims at exploring the controlled copolymerization of perfluoro- hexylethylene (PFHE) and vinyl acetate (VAc) in order to prepare a range of well-defined statistical poly(PFHE-stat-VAc) copolymers with different compositions. Cobalt-mediated radical polymerization demonstrated to be active at 40 °C starting from an alkylcobalt(III) initiator, and copolymers with a fluorinated monomer content as high as ca. 80 wt % were successfully prepared. Reactivity ratios were determined to be rVAc = 0.18 and rPFHE = 0 at 40 °C and emphasized a clear tendency for alternation. Unprecedented PFHE/VAc containing block copolymers were also prepared via a single-step approach or through
sequential copolymerizations. Finally, hydrolysis of the pendant ester groups of these copolymers led to the corresponding fluorinated copolymers bearing vinyl alcohol (VOH). A preliminary solution behavior study, carried out by dynamic light scattering and transmission electron microscopy on block copolymers composed of PFHE and VAc or VOH units, evidenced a marked amphiphilicity of the copolymer composed of an extremely hydrophobic PFHE block associated with a highly hydrophilic PVOH segment.
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 :
Demarteau, Jérémy ; University of Liège - ULiège > Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Améduri, Bruno; Institut Charles Gerhardt, Ingénierie et Architectures Macromoléculaires, CNRS, UM, ENSCM, Montpellier, France
Ladmiral, Vincent; Institut Charles Gerhardt, Ingénierie et Architectures Macromoléculaires, CNRS, UM, ENSCM, Montpellier, France
Mees, Maarten A.; Ghent University, Supramolecular Chemistry Group, Department of Organic and Macromolecular Chemistry
Hoogenboom, Richard; Ghent University, Supramolecular Chemistry Group, Department of Organic and Macromolecular Chemistry
Debuigne, Antoine ; 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 :
Controlled synthesis of fluorinated copolymers via cobalt-mediated radical copolymerization of perfluorohexylethylene and vinyl acetate
Publication date :
23 May 2017
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
50
Issue :
10
Pages :
3750-3760
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique ANR - Agence Nationale de la Recherche
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