eATRP was successfully applied to methyl acrylate in [BMIm][OTf], then the PMMA-Br chain was extended with acrylonitrile under a catalytic halogen exchange.

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The preparation of well‐defined polymers via aqueous atom transfer radical polymerization (ATRP) is challenging due to the high activity and limited stability of ATRP catalysts in water. Optimized conditions previously reported for the ATRP of some water‐soluble monomers cannot be regarded as universal conditions. Indeed, well‐controlled electrochemically mediated ATRP (eATRP) of oligo(ethylene oxide)methyl ether acrylate (OEOA) and 2‐hydroxyethyl methacrylate (HEMA) were achieved by adjusting the conditions in relation to the solubility and reactivity of these monomers and corresponding polymers. Importantly, PEOA with low dispersity and predetermined molecular weight was obtained even with low catalyst loading and high monomer content (up to 50 vol %). Moreover, >90% conversion of HEMA was obtained within 6–7 h, giving PHEMA with dispersity 1.2–1.3. This work confirms eATRP as a versatile, clean technique applicable to a range of water‐soluble, biocompatible monomers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 114–123

Due to environmental concerns, more attention has been given to the development of bio-based materials for substitution of fossil-based ones. Moreover, paper use is essential in daily routine and several applications of industrial pulp can be developed. In this study, transparent films were produced by industrial cellulose pulp solubilization in tetramethylguanidine based ionic liquids followed by its regeneration. Films were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), UV/Vis spectroscopy, proton nuclear magnetic resonance (1H-NMR), dynamic scanning calorimetry (DSC), thermal analysis (TG), and X-ray diffraction (XRD). Mechanical tests showed that films have a good elongation property, up to 50%, depending on ionic liquid incorporation. The influence of the conjugated acid and dissolution temperature on mechanical properties were evaluated. These results revealed the potential of this methodology for the preparation of new biobased films.

Electrochemically mediated atom transfer radical polymerization (ATRP) of N,N‐dimethylacrylamide (DMAA) catalyzed by copper complexes with polydentate amine ligands was studied systematically in water, investigating several reaction parameters such as applied potential, catalyst concentration, ligand structure, monomer and initiator concentrations. Electropolymerizations were successfully performed under both potentiostatic and galvanostatic conditions; in both eATRP modes, reactions were fast (monomer conversion >90 % in less than 1 h) and well‐controlled, providing polymers with narrow molecular weight distributions. Despite the low dispersity, chain extension attempts of the obtained polymer were not successful because of partial loss of C−Br chain‐end functionality, due to an intramolecular nucleophilic attack. This is an intrinsic drawback of ATRP of acrylamides and although the electrochemical approach allowed preparation of well‐defined polymers in a very short time (down to ca. 15 min), loss of chain‐end functionality was unavoidable.