Open-Air Chemical Recycling: Fully Oxygen-Tolerant ATRP Depolymerization.

While oxygen-tolerant strategies have been overwhelmingly developed for controlled radical polymerizations, the low radical concentrations typically required for high monomer recovery render oxygen-tolerant solution depolymerizations particularly challenging. Here, an open-air atom transfer radical polymerization (ATRP) depolymerization is presented, whereby a small amount of a volatile cosolvent is introduced as a means to thoroughly remove oxygen. Ultrafast depolymerization (i.e., 2 min) could efficiently proceed in an open vessel, allowing a very high monomer retrieval to be achieved (i.e., ∼91% depolymerization efficiency), on par with that of the fully deoxygenated analogue. Oxygen probe studies combined with detailed depolymerization kinetics revealed the importance of the low-boiling point cosolvent in removing oxygen prior to the reaction, thus facilitating effective open-air depolymerization. The versatility of the methodology was demonstrated by performing reactions with a range of different ligands and at high polymer loadings (1 M monomer repeat unit concentration) without significantly compromising the yield. This approach provides a fully oxygen-tolerant, facile, and efficient route to chemically recycle ATRP-synthesized polymers, enabling exciting new applications.

Chemical recycling of bromine-terminated polymers synthesized by ATRP.

Chemical recycling of polymers is one of the biggest challenges in materials science. Recently, remarkable achievements have been made by utilizing polymers prepared by controlled radical polymerization to trigger low-temperature depolymerization. However, in the case of atom transfer radical polymerization (ATRP), depolymerization has nearly exclusively focused on chlorine-terminated polymers, even though the overwhelming majority of polymeric materials synthesized with this method possess a bromine end-group. Herein, we report an efficient depolymerization strategy for bromine-terminated polymethacrylates which employs an inexpensive and environmentally friendly iron catalyst (FeBr2/L). The effect of various solvents and the concentration of metal salt and ligand on the depolymerization are judiciously explored and optimized, allowing for a depolymerization efficiency of up to 86% to be achieved in just 3 minutes. Notably, the versatility of this depolymerization is exemplified by its compatibility with chlorinated and non-chlorinated solvents, and both Fe(ii) and Fe(iii) salts. This work significantly expands the scope of ATRP materials compatible with depolymerization and creates many future opportunities in applications where the depolymerization of bromine-terminated polymers is desired.

Responsive Polyesters with Alkene and Carboxylic Acid Side-Groups for Tissue Engineering Applications.

Main chain polyesters have been extensively used in the biomedical field. Despite their many advantages, including biocompatibility, biodegradability, and others, these materials are rather inert and lack specific functionalities which will endow them with additional biological and responsive properties. In this work, novel pH-responsive main chain polyesters have been prepared by a conventional condensation polymerization of a vinyl functionalized diol with a diacid chloride, followed by a photo-induced thiol-ene click reaction to attach functional carboxylic acid side-groups along the polymer chains. Two different mercaptocarboxylic acids were employed, allowing to vary the alkyl chain length of the polymer pendant groups. Moreover, the degree of modification, and as a result, the carboxylic acid content of the polymers, was easily tuned by varying the irradiation time during the click reaction. Both these parameters, were shown to strongly influence the responsive behavior of the polyesters, which presented adjustable pKα values and water solubilities. Finally, the difunctional polyesters bearing the alkene and carboxylic acid functionalities enabled the preparation of cross-linked polyester films by chemically linking the pendant vinyl bonds on the polymer side groups. The biocompatibility of the cross-linked polymers films was assessed in L929 fibroblast cultures and showed that the cell viability, proliferation, and attachment were greatly promoted on the polyester surface, bearing the shorter alkyl chain length side groups and the higher fraction of carboxylic acid functionalities.