[en] The organometallic-mediated radical polymeriza- tion (OMRP) of vinylidene fluoride (VDF) using an alkyl cobalt(III) compound as initiator was recently proven successful for the controlled synthesis ofPVDF (Angew. Chem., Int. Ed. 2018, 57, 2934−2937). However, the required synthesis of the organometallic initiator renders this method labor-intensive and time-consuming. This article reports the straightforward synthesis of well-defined poly(VDF) and its block copolymers via OMRP performed using a two-component initiating system from readily available compounds. First, PVDF was obtained by redox initiation using the combination of a peroxide initiator and bis(acetylacetonato)cobalt(II) (Co(acac)2). This step was optimized in terms of the initiator choice, polymerization temperature, and reactant molar ratio. The best results regarding the molar mass control and the dispersities were obtained using bis(tert-butylcyclohexyl) peroxydicarbonate as initiator at 60 °C. The polymerization followed first-order kinetics, and the molar masses ofPVDF increased linearly up to a 27% conversion to reach 11 800 g/mol with low dispersities (Đ = 1.35). Chain extension of the resulting PVDF-Co(acac)2 with vinyl acetate (VAc) led to three diblock copolymers of various chain lengths.
Research Center/Unit :
CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège Center for Education and Research on Macromolecules (CERM)
Ladmiral, Vincent; University of Montpellier, Institut Charles Gerhardt, France
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)
Poli, Rinaldo; University of Toulouse, CNRS, Laboratoire de Chimie de Coordination, France > Institut Universitaire de France, Paris, France
Ameduri, Bruno; University of Montpellier, Institut Charles Gerhardt, France
Language :
English
Title :
Straightforward synthesis of well-defined poly(vinylidene fluoride) and its block copolymers by cobalt-mediated radical polymerization
Publication date :
12 February 2019
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society, United States - District of Columbia
Volume :
52
Issue :
3
Pages :
1266-1276
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique ANR - Agence Nationale de la Recherche
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