Thermal Reprocessing and Closed-Loop Chemical Recycling of Styrene-Butadiene Rubber Enabled by Exchangeable and Cleavable Acetal Linkages.

The covalent cross-linking is an essential prerequisite for achieving the unique entropic elasticity of rubber products; however, the formation of a 3D cross-linked network and permanent cross-links makes thermosetting rubbers difficult to be recycled, causing serious environmental pollution at the end of their life. Herein, a facile, green, and promising strategy to introduce the exchangeable and cleavable acetal bonds into the chemically cross-linked networks of diene-typed rubbers is reported. For the first time, the hydroxyl-functionalized styrene-butadiene rubber (ESBR-HEMA) is prepared by introducing 2-hydroxyethyl methacrylate (HEMA) during the emulsion polymerization of styrene-butadiene rubber (ESBR). Then, based on hydroxyl-vinyl ether addition reactions, divinyl ether (DVE) could serve as a cross-linking agent to facilely and effectively cross-link hydroxyl-functionalized rubbers without additional additives, producing exchangeable and hydrolyzable acetal linkages. What's more, the acetal-containing cross-linked network in ESBR-HEMA vulcanizates could rearrange their topologies at elevated temperatures, endowing them with malleable and thermal reprocessing abilities. Moreover, the hydrolyzable acetal bonds could be selectively cleaved into hydroxyl and aldehyde groups in acidic conditions, resulting in a closed-loop chemical recycling of the ESBR-HEMA rubber. Hence, this work provides a facile and green cross-linking strategy for hydroxyl-functionalized rubbers to address the inherent problems brought from the covalent cross-linking of rubbers.

Eco-friendly PVA-LYS fibers for gold nanoparticle recovery from water and their catalytic performance.

In this work, we grafted lysine on PVA electrospun fibers, using a green preparation technique. The resulting fiber mats were proposed for gold nanoparticles (AuNPs) removal from water. The efficiency of three fibers with different lysine amounts (10, 20, and 30%) was investigated. The incorporation of amino groups in PVA fibers was firstly proved by FTIR, SEM, and elemental analysis, confirming the presence of lysine. Among the three different fibers, PVA-LYS 30% has shown the best removal efficiency, reaching 65%, at pH equal to 5. Adsorption isotherms were studied and showed that the Langmuir model is the best model fitting our experimental results, with a maximum adsorption capacity of 20.1 mg g-1. Metal-ligand interactions and electrostatic attraction between protonated amino groups of lysine on the fibers and negatively charged, citrate capped, AuNPs are the main proposed mechanisms for AuNP adsorption on the fibers. Sustainability of AuNPs adsorbed on these fibers has been checked through their reuse as catalyst for the reduction of 4-nitrophenol to 4-aminophenol. The process was completed within 60 min, and their reusability showed more than 99% efficiency after 5 reduction cycles. Our results prove that green PVA-LYS fibers can extract nanoparticles from water, as low cost-effective and eco-friendly adsorbent, and contribute to the promotion of a circular economy approach, through their reuse as catalyst in the reduction of pollutants.

Design of next-generation cross-linking structure for elastomers toward green process and a real recycling loop.

Currently adopted cross-linking methods in rubber industry are suffering from variable persistent issues, including the utilization of toxic curing packages, release of volatile organic compounds (VOCs) and difficulties in the recycling of end-of-life materials. It is of great importance to explore a green cross-linking strategy in the area. Herein, we report a new "green" strategy based on hydrolyzable ester cross-links for cross-linking diene-typed elastomers. As a proof of concept, a commercial carboxylated nitrile rubber (XNBR) is efficiently cross-linked by a bio-based agent, epoxidized soybean oil (ESO), without any toxic additives. ESO exhibits an excellent plasticization effect and excellent scorch safety for XNBR. The cross-linking density and mechanical properties of the ESO-cured XNBR can be manipulated in a wide range by changing simply varying the content of ESO. In addition, zinc oxide (ZnO) performs as a catalyst to accelerate the epoxide opening reaction and improve the cross-linking efficiency, serving as reinforcement points to enhance the overall mechanical properties of the ESO-cured XNBR. Furthermore, the end-of-life elastomer materials demonstrate a closed-loop recovery by selectively cleaving the ester bonds, resulting in very high recovery of the mechanical performance of the recycled composites. This strategy provides an unprecedented green avenue to cross-link diene elastomers and a cost-effective approach to further recycle the obtained cross-linked elastomers at high efficiency.