Conductive films based on composite polymers containing ionic liquids absorbed on crosslinked polymeric ionic-like liquids (SILLPs)

Polymerization of styrenic monomers containing imidazolium subunits in the presence of crosslinking monomers and using ionic liquids (ILs) as porogenic agents provides composite materials with excellent mechanical properties and displaying conductivities that are in the same order of magnitude than those shown by bulk ILs. This approach allows the use of high crosslinking degrees and low IL-loadings without compromising the required properties of the resulting composites. Besides, no appreciable leaching of the bulk IL component is detected.Financial support by Ministerio de Ciencia e Innovacion (CTQ2011-28903-C02-01 and SP-ENE-20120718), Generalitat Valenciana (PROMETEO/2012/020) and Universitat Jaume I (P11B2013-38) is acknowledged.Altava Benito, B.; Compañ Moreno, V.; Andrio Balado, A.; Del Castillo Davila, LF.; Mollá Romano, S.; Burguete, MI.; García-Verdugo Cepeda, E.... (2015). Conductive films based on composite polymers containing ionic liquids absorbed on crosslinked polymeric ionic-like liquids (SILLPs). Polymer. 72:69-81. https://doi.org/10.1016/j.polymer.2015.07.009S69817

Synthesis by RAFT and Ionic Responsiveness of Double Hydrophilic Block Copolymers Based on Ionic Liquid Monomer Units

Three imidazolium-based ionic liquid (IL) monomers, namely, 3-(1-ethyl imidazolium-3-yl)propylmethacrylamido bromide (IL-1), 2-(1-methylimidazolium-3-yl)ethyl methacrylate bromide (IL-2), and 2-(1-ethylimidazolium-3-yl)ethyl methacrylate bromide (IL-3), and methacrylic acid (MAA) were polymerized by the reversible addition fragmentation chain transfer (RAFT) process in methanolic solutions at 70 °C, using either 2-cyanopropyl dithiobenzoate (CTA-1) or (4-cyanopentanoic acid)-4-dithiobenzoate (CTA-2) as chain transfer agents (CTAs). Under these conditions, polymers exhibited molar masses predetermined by the initial molar ratio of the monomers to the dithioester precursor, as evidenced by 1H NMR spectroscopy from chain ends analysis. These hydrophilic polymers were subsequently used as macro-CTAs in chain extension experiments in aqueous or in alcoholic solutions, affording IL-based double hydrophilic block copolymers (DHBCs) of the type PIL-1-b-PAm, PMAA-b-PIL-2 and PMAA-b-PIL-3, where PAm and PIL stand for polyacrylamide and polymeric ionic liquid. These DHBCs could be further manipulated and made to self-assemble in micelle-like structures in water by exchanging the bromide (Br−) counteranion of IL blocks for −N(SO2CF3)2. This anion exchange indeed turned the solution properties of the PIL blocks from hydrophilic to hydrophobic, as verified on the corresponding IL-based homopolymers which were immiscible with water after the anion switch. Investigations by 1H NMR evidenced that the diblock copolymers exhibited salt-responsive behavior in aqueous solutions: anion exchange induced the formation of water-soluble micellar aggregates consisting of hydrophobic − N(SO2CF3)2-based IL blocks at the core stabilized by water-soluble PAm or PMAA at the shell