Synthesis of macroporous poly(acrylic acid)–carbon nanotube composites by frontal polymerization in deep-eutectic solvents

Deep Eutectic Solvents (DESs) formed between Acrylic Acid (AA) and Choline Chloride (CCl) exhibit certain properties of ionic liquids (e.g. high viscosity) that make them suitable for frontal polymerization (FP). The use of DESs not only as a monomer but also as the solvent prevents the use of additional solvents (i.e. typically of organic nature) and offers a green tool for the synthesis of functional composites. We have recently explored this approach for the preparation of poly(acrylic acid) (PAA) and poly(methacrylic acid). In this work, we have taken advantage of the outstanding capability of DESs to solubilize and/or disperse a number of substances to incorporate – in a homogeneous fashion – carbon nanotubes (in this particular case, N-doped MWCNT – CNxMWCNTs) in the polymerizable DES. Interestingly, CNxMWCNTs also played the role of an inert filler in FP. The resulting PAA–CNxMWCNT composites exhibited some distinct features as compared to previous PAA also obtained via DES-assisted FP. For instance, PAA–CNxMWCNT composites can undergo swelling depending on the pH, as bare PAA. However, the presence of CNxMWCNTs allows the formation of a macroporous structure after submission to a freeze-drying process, the achievement of which was not possible in bare PAA. The combination of structural (e.g. macroporosity) and functional (e.g. stimuli responsive) properties exhibited by these materials besides an eventually high biocompatibility – coming from the green character of the DES-assisted synthesis – should make the resulting macroporous PAA–CNxMWCNT composites excellent candidates for their future application as biomaterials.