Precision Synthesis of Poly(Ionic Liquid)-Based Block Copolymers by Cobalt-Mediated Radical Polymerization and Preliminary Study of Their Self-Assembling Properties

Abstract : 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 degrees 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 approximate to 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 degrees C.
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Submitted on : Wednesday, September 21, 2016 - 2:56:49 PM
Last modification on : Thursday, January 11, 2018 - 6:28:09 AM

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Paul Coupillaud, Maréva Fèvre, Anne-Laure Wirotius, Karim Aissou, Guillaume Fleury, et al.. Precision Synthesis of Poly(Ionic Liquid)-Based Block Copolymers by Cobalt-Mediated Radical Polymerization and Preliminary Study of Their Self-Assembling Properties . Macromolecular Rapid Communications, Wiley-VCH Verlag, 2014, 35 (4), pp.422-430. ⟨10.1002/marc.201300776 ⟩. ⟨hal-01369764⟩

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