Precision synthesis of poly(ionic liquid)-based block copolymers by cobalt-mediated radical polymerization and preliminary study of their self-assembling properties
[en] A poly(ionic liquid)-based block copolymer (PIL BCP), namely, poly(vinyl acetate)-b-poly(N-vinyl-3-butylimidazolium bromide), PVAc-b-PVBuImBr, is synthesized by sequential cobalt-mediated radical polymerization (CMRP). A PVAc precursor is first prepared at 30 °C in bulk by CMRP of VAc, using bis(acetylacetonato)cobalt(II), Co(acac)2, and a radical source (V-70). Growth of PVBuImBr from PVAc-Co(acac)2 is accomplished by CMRP in DMF/MeOH (2:1, v/v). This PIL BCP self-assembles in the sub-micron size range into aggregated core–shell micelles in THF, whereas polymeric vesicles are observed in water, as evidenced by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Thin-solid sample cut from raw materials analyzed by TEM shows an ordered lamellar organization by temperature-dependent synchrotron small-angle X-ray scattering (SAXS). Anion exchange can be accomplished to achieve the corresponding PIL BCP with bis(trifluorosulfonyl)imide (Tf2N−) anions, which also gives rise to an ordered lamellar phase in bulk samples. A complete suppression of SAXS second-order reflection suggests that this compound has a symmetric volume fraction (f ≈ 0.5). SAXS characterization of both di- and triblock PIL BCP analogues previously reported also shows a lamellar phase of very similar behavior, with only an increase of the period by about 8% at 60 °C.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Coupillaud, Paul; University of the Basque Country, Institute for Polymer Materials (POLYMAT) > University of Bordeaux and Centre National de la Recherche Scientifique > Laboratoire de Chimie des Polymères Organiques
Fèvre, Maréva; University of Bordeaux and Centre National de la Recherche Scientifique > Laboratoire de Chimie des Polymères Organiques
Wirotius, Anne-Laure; University of Bordeaux and Centre National de la Recherche Scientifique > Laboratoire de Chimie des Polymères Organiques
Aissou, Karim; University of Bordeaux and Centre National de la Recherche Scientifique > Laboratoire de Chimie des Polymères Organiques
Fleury, Guillaume; University of Bordeaux and Centre National de la Recherche Scientifique > Laboratoire de Chimie des Polymères Organiques
Debuigne, Antoine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Mecerreyes, David; University of the Basque Country > Institute for Polymer Materials (POLYMAT)
Vignolle, Joan; University of Bordeaux and Centre National de la Recherche Scientifique > Laboratoire de Chimie des Polymères Organiques
Taton, Daniel; University of Bordeaux and Centre National de la Recherche Scientifique > Laboratoire de Chimie des Polymères Organiques
Language :
English
Title :
Precision synthesis of poly(ionic liquid)-based block copolymers by cobalt-mediated radical polymerization and preliminary study of their self-assembling properties
FP7 - 229036 - ORION - ORDERED INORGANIC-ORGANIC HYBRIDS USING IONIC LIQUIDS FOR EMERGING APPLICATIONS
Funders :
The French Ministry of Education and Research CNRS - Centre National de la Recherche Scientifique [FR] The European Commission in the frame of the ORION project F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE] BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique CE - Commission Européenne [BE]
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