Revolutionizing photocatalysis: Synthesis of innovative poly(N-tertiary-butylacrylamide)-graft-hydroxypropyl cellulose polymers for thermo-responsive applications via metal-free organic photoredox catalysis

In this study, we present a groundbreaking approach utilizing metal-free, visible light-mediated organic photoredox catalyzed atom transfer radical polymerization (O-ATRP) to synthesize cellulose-based stimuli-responsive polymers. Our method resulted in the successful synthesis of innovative metal-free poly(N-tertiary-butylacrylamide)-graft-hydroxypropyl cellulose (PNTBAM-g-HPC) polymers with exceptional control over molecular weight and narrow dispersity index (Đ) and explored their applications in organo-photocatalytic reactions. This approach addresses the limitations of traditional atom transfer radical polymerization method, which suffer from metal contamination and toxicity related problems. O-ATRP and organic photoredox catalysts have been sought to address these difficult challenges. In this study, we synthesized organic compound; 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile (4DPIPN), which served as an organic photoredox catalyst, enabling the synthesis and application study of PNTBAM-g-HPC polymers via organic photoredox catalysis. Furthermore, by employing 4DPIPN, three different types of PNTBAM-g-HPC polymers were synthesized. Through thorough characterization techniques including FTIR, NMR, UV/Visible spectroscopy, TGA, and GPC analysis, we confirmed the successful synthesis of photocatalyst and three different types of PNTBAM-g-HPC polymers under O-ATRP conditions. By adjusting the molar ratios of PNTBAM side chains, we fine-tuned the LCST of HTA-20 polymers to 37.3 °C, demonstrating their thermoresponsive behavior. This synthetic approach shows great potential for applications in biosensors, pharmaceuticals, biomedical engineering, and drug delivery systems.