Partially Biosourced Poly(1,2,3-triazolium)-Based Diblock Copolymers Derived from Levulinic Acid Amira Kallel Elloumi, †,‡ Imen Abdelhedi Miladi, ‡ Anatoli Serghei, † Daniel Taton, § Karim Aissou, § Hatem Ben Romdhane, ‡ and Eric Drockenmuller* ,† † Univ Lyon, Université Lyon 1, CNRS, Ingé nierie des Maté riaux Polymè res, UMR 5223, F-69003, Lyon, France ‡ Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie (Bio)Organique Structurale et de Polymè res - Synthè se et Etudes Physicochimiques (LR99ES14), 2092 El Manar, Tunisia § Laboratoire de Chimie des Polymè res Organiques, Université de Bordeaux IPB-ENSCBP, CNRS, F-33607 Pessac Cedex, France * S Supporting Information ABSTRACT: Partially biobased poly(1,2,3-triazolium)s are synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of tailor-made 1,2,3- triazole-functionalized (meth)acrylate monomers derived from levulinic acid, followed by N-alkylation of the 1,2,3-triazole moieties by methyl iodide (CH 3 I) and subsequent anion exchange with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI). Chain extension of a 1,2,3-triazole-functionalized polymethacrylate by RAFT polymerization of styrene followed by N-alkylation with CH 3 I and anion exchange with LiTFSI affords two poly(1,2,3-triazole)- and two poly(1,2,3-triazolium)-based diblock copolymers (BCPs) with different weight fractions of each block. Discussion of the structure/properties relationships of all obtained materials is based on NMR spectroscopy, size exclusion chromatography, differential scanning calorimetry, thermogravimetric analysis, and broadband dielectric spectroscopy. The morphological and self-assembling properties of neutral and charged BCPs in bulk and in thin films are investigated by small-angle X-ray scattering and atomic force microscopy experiments, respectively. ■ INTRODUCTION Poly(ionic liquid)s (PILs) are macromolecular analogues of ionic liquids (ILs) that ideally combine the best attributes of ILs (e.g., high thermal, chemical, electrochemical stabilities and enhanced ionic conductivity, ...) with those of polymer materials (e.g., processability, viscoelasticity, adhesion, film- forming properties, and macromolecular design, ...). 1-6 So far, a broad variety of PILs has been developed using many combinations of cations (e.g., ammonium, pyridinium, pyrrolidinium, imidazolium, phosphonium, thiazolium, 1,2,3- triazolium, 1,2,4-triazolium, ...) and anions (e.g., carboxylates, sulfonates, phosphates, halides, inorganic fluorides, perfluori- nated sulfonimides, ...). Besides this, PILs with diverse microstructures (e.g., random, gradient, block copolymers, (hyper)branched polymers, chemical and physical networks, ...) and broad chemical variety (e.g., polystyrenics, poly(meth)- acrylates, poly(vinyl ester)s, poly(vinyl imidazolium)s, poly- esters, polyimides, polyurethanes, ...) have been obtained using several step growth or chain growth polymerizations as well as postpolymerization chemical modification approaches. Many of those PILs have shown promising potential in numerous applications, including thermoresponsive polyelectrolytes, 7 self-assembled colloids, 8-11 catalysis, 12-14 dye sensitized solar cells, 15,16 electrochromic devices, 17 electrolyte-gated transis- tors, 18 gas separation membranes, 19-21 sensors and actua- tors, 22,23 anion exchange membranes for fuel cells, 24,25 batteries, 26-28 and supercapacitors. 29 PIL-based diblock copolymers (BCPs) have also attracted a lot of attention as they merge the properties of PILs (e.g., ionic conductivity and electrochemical stability) with the well-known phase separa- tion of BCPs into nanostructured morphologies either in bulk, in thin films or in dispersed media. 9,11,18,30-34 Their inherent anisotropic transport properties have for instance been applied to electrolyte-gated transistors, 18 actuators, 22 or gas separation membranes. 33,35 Because of the programmed depletion of fossil resources polymer materials issued from renewable feedstocks are attracting increasing attention. 36-41 Biobased ILs having the cation and/or the anion moieties derived from sustainable building blocks have been applied as green solvents for the processing of lignocellulose, as catalysts for the production of biodiesel, as well as reaction solvents, organocatalysts and media for metal extraction, for CO 2 absorption, or for the chiral recognition of carboxylic acids. 42-47 Conversely, the synthesis of PILs issued from renewable feedstocks has been scarcely investigated. For instance, Mecerreyes and co-workers have developed partially biobased supramolecular ionic networks using citric acid and different geminal dicationic ILs. 48 They have further extended this approach to fully biobased analogues using a fatty diamine and different naturally occurring dicarboxylic acids. 49 Furthermore, they have developed the synthesis of partially biobased amphiphilic Received: May 5, 2018 Revised: July 6, 2018 Article pubs.acs.org/Macromolecules Cite This: Macromolecules XXXX, XXX, XXX-XXX © XXXX American Chemical Society A DOI: 10.1021/acs.macromol.8b00962 Macromolecules XXXX, XXX, XXX-XXX Downloaded via DURHAM UNIV on July 25, 2018 at 13:21:12 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.