RESUMEN
[2π + 2π]-photocycloadditions and their ability to trigger controlled and reversible photoligation through disparate wavelengths provide an attractive platform to unlock advanced functionalities in soft materials. Yet, among the limited amount of functional motifs enabling reversible photoreactions, cyclability is often overlooked due to poor reaction yield and orthogonality. In this study, the advantageous photocharacteristics of the previously underexplored N-methyl-quinolinone photoresponsive motif are leveraged to create a covalent gated system, enabling controlled formation and cleavage of covalent bonds on demand. A systematic evaluation of individual cycloadditions and reversions on the molecular scale, including reaction rates, conversions, and photoproducts, allows identification of the required conditions for generating controlled photoreactions with a remarkable degree of cyclability; while, maintaining high reaction yields. Ultimately, these controlled and cyclable reactions are translated to a macromolecular scale, showcasing a comparable performance in initiating reversible photoligation, as observed at the molecular level. In addition, it is also shown that this progressive methodology can be leveraged to gain a comprehensive understanding of cyclability and clarify the factors contributing to its decreasing yield. Overall, unlocking the potential of quinolinone derivatives through this step-by-step approach lays the foundation for the development of highly controlled and responsive polymer materials with unprecedented potential.
RESUMEN
Ultra-high-molecular-weight, water-soluble polyelectrolytes are commonly employed as flocculants for solid-liquid separation via colloidal destabilization, enabling the rapid and efficient removal of particulate matter from wastewater streams. A drive toward more sustainable and less polluting industrial practices, coupled with the desire to reduce freshwater usage and improve closed-loop systems, demands the development of flocculants with ever-higher dewatering dose performance. Herein, the use of trithiocarbonate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization under either blue LED (λmax = 470 nm) or UV (λmax = 365 nm) irradiation, known as photoiniferter polymerization, was successfully utilized to generate ultra-high-molecular-weight (Mn > 1,000,000 g mol-1) polyelectrolyte copolymer flocculants with narrow molecular weight distributions (Mw/Mn < 1.2). Cationic and anionic polyelectrolyte flocculants were synthesized containing various monomer compositions of acrylamide (AM), dimethylacrylamide (DMA), 3-(acryloyloxyethyll)trimethylammonium chloride (DMAEAq), 3-(acrylamidopropyl)trimethylammonium chloride (APTAC), sodium acrylate (NaAA), and sodium 2-(acrylamido)-2-methylpropylsulfonate (NaATBS) with high monomer conversion using simple experimental apparatus. The narrow molecular weight distribution cationic polyelectrolytes showed improved flocculation efficiency in the clarification of kaolin suspensions of up to 50% in comparison to a broad polydispersity (Mw/Mn > 5.0) commercial benchmark with an equivalent number average molecular weight. The improved performance of the narrow-polydispersity copolymers is attributed to the reduction in the content of the lower-molecular-weight polymer chains, which impart lower flocculation performance.